Flowserve Pump Application Manual

Applications Manual Volume 1 Table of Contents Section 1

Corn Wet Milling and Refining Applications

Section 2

Chlor-Alkali Industries Applications

Section 3

Mineral Acids Applications

Section 4

PTA Applications

Section 5

Titanium Dioxide

Section 6

Hydrocracking Applications

Section 7

Delayed Coker Applications

Section 8

Combined Cycle Unit Applications


Table of Contents Page Number 1.

Introduction 1.1 1.2 1.3

2.

Market Drivers and Growth Competition

2-1 2-2

Flowserve Experience 3.1 3.2 3.3 3.4 3.5

4.

1-1 1-2 1-4

Market Profile 2.1 2.2

3.

Rationale and Methodology Raw Materials and Derivatives Corn Wet Milling and Refining Process

Flowserve Sales Decision Makers Competitive Advantages of Durco Process Pumps Guidelines for Seals Plant and Pump Details

3-1 3-3 3-4 3-5 3-5

Pump Recommendations 4.1 4.2 4.3 4.4 4.5 4.6 4.7

Steep House Mill House Germ Plant Feed House Modification (Mod) House Syrup Refinery Auxiliary Pumps

Appendix A Appendix B Appendix C Appendix D

4-3 4-8 4 - 15 4 - 20 4 - 23 4 - 24 4 - 31

Profile of End-Users OEMS and Engineering Contractors Master List of Pump Applications Conversion Factors: Alloys, Volumes and Temperatures

i

A- 1 B-1 C-1 D-1


Exhibits Page Number 1.

Components of a Corn Kernel

1-2

2.

Derivatives of Corn

1-2

3.

Other Raw Materials Used in Milling and Refining

1-3

4.

Upstream Processes in Corn Milling and Refining

1-4

5.

Corn Derivatives in the United States

2-1

6.

Flowserve Sales of Durco Process Pumps in Corn Wet Milling and Refining

3-1

7.

Flowserve Customers

3-2

8.

Plant Organizational Chart

3-3

9.

Typical Plant Layout

3-6

10.

Pumps Used in Corn Wet Milling and Refining

3-7

11.

Pump Applications List: Corn Wet Milling and Refining

4-2

12.

Pump Applications List: Steep House

4-3

13.

Pump Applications List: Mill House

4-8

14.

Pump Applications List: Germ Plant

4 - 15

15.

Pump Applications List: Feed House

4 - 20

16.

Pump Applications List: Syrup Refinery

4 - 25

17.

Pump Applications List: Auxiliary Pumps

4 - 31

D.1

Alloy Conversions

D-1

D.2

Volume Conversions

D-1

D.3

Temperature Conversions

D-1

ii


1.

Introduction

1.1

Rationale and Methodology

Over the last twenty years, Flowserve’s Durco Process Pump business has developed a leading presence in the corn1 wet milling and refining industry. Although technically part of the food and beverage segment, the industry requires chemical process pumps for abrasive corn slurries and numerous other applications. Driving this market today are the corn syrups produced from corn starch. Demand has been on the rise around the world because these corn syrups are 1.) economical sugar substitutes, and 2.) important ingredients for processed foods and beverages, notably soft drinks. In response to increasing opportunities around the world, a global consolidation is underway in corn wet milling and refining. Whereas many small local producers once existed, a handful of large producers are emerging. Most have well established operations in North America and West Europe, and are now expanding via acquisitions and joint ventures in developing regions. Given Flowserve’s experience serving corn wet millers in developed regions, as well as this new growth potential in developing areas, it seemed logical to create an applications manual specifically for the wet milling and refining processes. The purpose of the manual is therefore twofold: Introduce Flowserve sales personnel to the market as a preparation to pursue new pump business, especially in Asia Pacific, East Europe and Latin America Consolidate and share Flowserve’s modular pump experience in this market so that all sales personnel can offer proven pump solutions. This manual represents the collective work of numerous Flowserve sales engineers and other personnel who have knowledge of the industry. Resources for further information include Corn Refiners Association (Washington, DC USA), the Association Des Amidonnieries De Cereales De L’UE (Brussels, Belgium), and the textbook Technology of Corn Wet Milling.2

1

Corn wet milling, as it is known in North America, is referred to as maize wet milling in Europe and other parts of the world. In addition to corn, other starchy grains, fruits and vegetables are wet milled.

2

Paul Harwood Blanchard, Technology of Corn Wet Milling, Elsevier Science Publishers BV, Amsterdam, The Netherlands, 1992.

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1.2

Raw Materials and Derivatives

Each corn kernel is composed of four materials: 1.) germ, where oil is found 2.) hull, a fibrous material 3.) gluten, a protein 4.) starch EXHIBIT 1 Components of a Corn Kernel

By wet milling corn, the kernels are broken down and the four component parts separated. Water is used throughout the milling process to soften and transport the corn, hence the term “wet” milling. After the four components have been milled, they are refined to make value-added products. Exhibit 2 illustrates the types of products which can be made from corn. EXHIBIT 2 Derivatives of Corn

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In addition to corn, numerous other agricultural products are wet milled and refined into similar value-added products. EXHIBIT 3 Other Raw Materials Used in Milling and Refining OTHER RAW MATERIALS Arrowroot

COMMENTS Tropical American plant; root contains starch

Barley

Cereal grass; seed contains starch

Cassava

Tropical plant; root contains starch

Manioc

Tropical plant; similar to cassava

Potato

Primarily milled in Europe

Rice

Cereal grass; seed contains starch

Sago

Palm plant; pith contains starch

Sorghum

Tropical grass; similar to corn

Tapioca

Also called cassava (see above)

Wheat

Cereal grass; seed contains starch; primarily milled in Europe; more abrasive than corn

Other raw materials are used in parts of the world where corn is less abundant or more expensive. The milling process is generally the same, but there can be differences, such as Method of milling (dry and wet) Number and nature of separation steps Hardness of raw material (abrasion concern) For example, wheat milling involves dry and wet processes. In the dry process, some starch burns and must be removed from the rest of the starch. This is done via a wetted centrifugal separation, but unlike the slurries in corn wet milling, the separation is difficult because the specific gravity of burned and unburned starch is similar. To adjust for this, the suction pressures at the inlet of the pump tend to be higher.

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1.3

Corn Wet Milling and Refining Process

“Corn wet milling and refining” is a term used to describe numerous processes involved in converting corn into value-added products. During “milling,” corn is separated into its four components (germ, hull, gluten, starch). The components are then “refined” into any number of derivatives (food ingredients, chemicals, fuels, etc.).3 A corn wet milling and refining plant will consist of numerous sub-plants. At a minimum, most plants include the facilities and upstream processes highlighted in Exhibit 4: EXHIBIT 4 Upstream Processes in Corn Wet Milling and Refining

For recommended pump specifications used in these upstream processes, see Section 4, Pump Recommendations. A corn wet milling and refining plant can include various other downstream processing facilities which also require large numbers of process pumps. These facilities may be owned by the corn wet miller, or by one of its customers which uses corn derivatives as feedstock. Although not covered in detail in this manual, a few examples of downstream facilities and/or products are: - Citric Acid - Itaconic Acid - Mono Sodium Glutamate - Vitamin E

3

- Erythritol - Lactic Acid - Polyol

- Ethanol Fuel - Lysine - Sorbitol

Most plants include both milling and refining processes, but are often referred to jointly as simply “corn wet milling.”

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2.

Market Profile

2.1

Market Drivers and Growth

The corn wet milling market is driven by demand for its derivatives. The situation in the United States, where the industry is well developed, shows that corn syrups are the largest derivative: EXHIBIT 5 Corn Derivatives in the United States

Corn syrups are part of the 5.3 billion bushel (135 million tonnes) per year sweeteners market. Seventy-nine percent of this market is found in developing regions of the world, so economic development there drives much of the demand for sweeteners. With moderate economic growth expected during 1998, the sweetener market is set to expand 2%. Higher growth is anticipated in the longer term as economic development and population growth rates accelerate. Corn syrups are an expanding part of the world sweeteners market. Representing about 20% of the world sweeteners market, corn syrups are found predominantly in processed foods and beverages. As standards of living increase around the world, so too has demand for these food products and the corn syrups used to make them. Corn syrup production has historically been more significant in North America than in other parts of the world. In Europe, Asia Pacific and Latin America, protected sugar industries have supplied most of the sweetener requirements. Smaller corn wet milling and refining facilities do exist, yet their production has been limited. Despite this there are still significant expansion and upgrade projects in progress today, with even greater potential expected soon as trade barriers are relaxed and economic development proceeds.

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One reason the outlook for global corn syrup consumption is so promising: Processed food producers are expanding around the world, “pulling” their suppliers along to ensure global product uniformity. One important example comes for the soft drink industry. High fructose corn syrup (HFCS 55) is increasingly used in place of sugar in soft drinks. Increasing worldwide demand means that as companies like Coca Cola® and Pepsi Cola® expand production facilities, corn wet millers are purchasing, upgrading and constructing corn syrup production capacity around the world to support their customers. Other products which are made from corn syrups impact corn syrup demand. Ethanol, an environmentally friendly fuel, basic chemicals such as citiric and lactic acid, animal feed additives, pharmaceuticals and biodegradable plastics are all made from corn syrup. The latter, biodegradable plastics, is a product opportunity still in its infancy, but one which may yield considerable demand for corn wet milling and refining in the future. 2.2

Competition

Competitors in corn wet milling are mostly the same as those found in chemicals processing. Rubber-lined and high chrome iron pumps often found in mining may also be used in some highly erosive applications. In the United States, ITT Goulds is often the main competition. Galigher, ITT Allis Chalmers, IDP, Mission and Peerless are involved in the industry as well, although to a lesser extent. In Europe, KSB, Sulzer, Moret and IDP are the main competitors. Based on what is known of the Asia Pacific and Latin American markets, there is a mixture of domestic producers and those global players mentioned above serving the industry. Durco Process Pumps are very competitive in corn wet milling and refining because of numerous unique features and benefits. These are highlighted in Section 3.3.

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3.

Flowserve Experience

3.1

Flowserve Sales

With sales in the tens of millions of US dollars, Durco Process Pumps are becoming a standard around the world for corn wet milling applications. Sales have been historically concentrated in developed regions, but as corn wet millers expand around the globe, so too have sales of Durco Process Pumps. EXHIBIT 6 Flowserve Sales of Durco Process Pumps in Corn Wet Milling and Refining

Many major corn wet millers use Durco Process Pumps; three of them are amongst the largest forty customers for Durco Process Pumps. Some of Flowserve RED’s customers in corn wet milling include:

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EXHIBIT 7 Flowserve Customers COMPANY

AFFILIATES

HOME BASE

MARKETS

Bang Il Industry

South Korea

Asia Pacific

Cargill

USA

Global

Corn Products International Cerestar

formerly CPC Corn Products Eridania Beghin Say (parent) National Starch & ICI (parent) Chemical Roquette

USA

Global

France

Global

USA

Samyang Genex

South Korea

Europe, North America Europe, North America Asia Pacific

Sewon

South Korea

Asia Pacific

UK

Global

Tate & Lyle (parent)

France

AE Staley (USA), Amylum (Belgium)

Some of the best opportunities to sell Durco pumps will come from leveraging these existing relationships with customers who are expanding in new markets. There are numerous other companies in the industry with which Flowserve has no or limited experience. These too represent considerable potential and should be targeted as new customer opportunities. Examples by region are: Asia Pacific Europe Latin America USA/Canada

Asia Modified Starch, Corn India, Doosan Food, Thai Roun, Shin Dong Bang ABR Foods, ADM, Agrana Staerke, Avebe, Crespel & Dieters, Raisio, Remy Amido Glucose, Alimodones Y Glocosa, Aranal Comercial, Arancia, Delmaiz, Grupo Xacur, Industria de Maiz, Maffessoni Comercio e Industria, Molinos ADM, Grain Processors, Midwest Grain, Minnesota Grain Processing, Penford

Detailed profiles of these and other producers are found in Appendix A, Profile of End-Users.

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3.2

Decision Makers

The parties with decision making responsibilities will differ depending on the type of business, new project or MRO For new projects, the plant engineering manager often has the final say, but others are involved in the process. When a project is approved, a project team is formed. The team is often headed up by the plant engineering manager and consists of project engineers and/or an outside engineering firm. The plant engineering manager (or team leader) makes the final decision on all major equipment purchases based on information assimilated from the team. For MRO business, the decision is dominated by the plant maintenance manager. Within each main processing area in the plant (e.g. steep house, mill house, etc.) there is usually one engineer responsible for maintenance activities there. When equipment is needed, the area maintenance engineer seeks approval from either the area manager or the plant maintenance manager. So for MRO sales it is important to establish relations with the plant maintenance manager, area maintenance managers and area mangers. Not only does the plant maintenance manager oversee MRO purchases, but he is also usually consulted prior to any major equipment purchases, including project work.

EXHIBIT 8 Plant Organizational Chart

While these individuals are usually the decision makers, the purchasing office is an important contact as the gateway to those in the plant.

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3.3

Competitive Advantages of Durco Process Pumps

Flowserve is especially competitive in corn wet milling and refining because of features designed to prolong pump life and maximize Mean Time Between Planned Maintenance. Whereas much of the competition promotes CF-8M (cast 316) wet-end material and double seals with forced-air circulation, features unique to the Durco Process Pumps are particularly well suited to handle the erosion and sealing issues involved in corn wet milling and refining. Some of the highly competitive features of Durco Process Pumps include: Reverse vane impeller CD4M material SealSentry FML seal chamber Sealmatic option Reinforced baseplates (types B, C and D) The reverse vane impeller is particulary well suited to corn wet milling applications. Many services contain solids, so limiting wear to the rear cover extends the life of the casing. The ability to remachine a rear cover versus buying new wet-end parts is an added cost advantage. Another benefit is the ability to set the impeller clearance and mechanical seal without the casing. Flowserve’s CD4M material, a duplex stainless steel, also brings advantages. More erosionresistant than stainless steel, it prolongs the life of wet-end parts significantly with little additional cost. Corn wet milling and refining customers standardize almost exclusively on CD4M given numerous corrosive and erosive services in the plant, ease of stocking one metallurgy and Flowserve’s ability to support with quick deliveries. The SealSentry FML seal chamber provides customer cost savings. With the FML, more single seals can be used in place of double seals. This means there are fewer external flush requirements (seal pots) and less water entering the process. This is beneficial since all flush water must be removed; the less water added, the greater the savings. The Sealmatic pump option is promoted for many continuous services found in corn wet milling and refining. The dynamically sealing repeller eliminates the need for conventional mechanical seals, and is advantageous in corn milling where sealing is difficult and flush undesirable. Reinforced baseplate types B (Polybase Polymer Concrete), C (Reinforced, Stilt-mounted), and D (Medium Duty Reinforced) are preferred because of rigidity. Stilt mounting is well accepted because costly grout is not needed and alignment to piping is made simple.

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3.4

Guidelines for Seals

Many of the fluids found in corn wet milling and refining contain solids and/or have a high viscosity, so it can be difficult to keep the seal clean and intact. Yet, any water added to the process via the seal support system must be removed, which adds cost to the process. Based on Flowserve experience, the following guidelines can contribute to improved seal life: - For single and double seals, use SealSentry FML seal chamber to purge heat and solids (i.e., FML might completely replace flush arrangements) - For single seal quench, use clean water instead of dirty process water - For all single seals, locate seal faces beyond seal gland and in process fluid - Use hard seal faces as recommended in Section 4, Pump Recommendations - Where double seals are specified in Secion 4, Pump Recommendations, use in tandem execution if contamination is a concern.

3.5

Plant and Pump Details

A broad overview of a corn wet milling and refining plant is illustrated in Exhibit 9 on the next page. A more detailed view of select subplants and pump applications follows in Exhibit 10. The pump application numbers in Exhibit 10 correspond to those found throughout Section 4, Pump Recommendations.

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4.

Pump Recommendations

The recommendations that follow are general guidelines. They are based on specifications which have performed well in the field, and are intended to raise awareness of issues associated with particular applications. Other specifications not addressed in this manual may be equally or more acceptable, depending on variables associated with the application. These guidelines should not take the place of any manufacturer’s recommended specification for a given application. A qualified pump engineer must still be involved in the specification of any pump, and manufacturers of components/accessories are to be consulted for detailed specifications as well.

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EXHIBIT 11 Pump Applications List: Corn Wet Milling and Refining FACILITY

PROCESS PUMP QUANTITY4

SEE PAGE

STEEP HOUSE

22-26

4-3

MILL HOUSE

62-65

4-8

GERM PLANT

20

4 - 15

FEED HOUSE

11 30-40

4 - 20 4 - 23

128-130

4 - 24

46-56

4 - 31

320-350

--

MODIFICATION (MOD) HOUSE SYRUP REFINERY AUXILIARY TOTAL PROCESS PUMPS

An alphabetical list of pumps found in these upstream processes is found in Appendix C, Master List of Pump Applications.

4

Based on a grind rate of 170,000 bushels (4300 tonnes) per day, which represents an average-sized plant in the USA. Plants in Europe have an average grind of 55,000 bushels (1400 tonnes) per day .

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4.1

STEEP HOUSE Objective

Soften clean, hard corn in preparation for further processing.

Description

Clean corn is transported from storage to the steep house, where it is deposited into large steep tanks. A sulphuric acid solution (0.2% concentration) is added and the corn soaks in this “steep water” for up to 48 hours. The steep is complete when the corn kernel is sufficiently broken down to be milled. EXHIBIT 12 Pump Applications List: Steep House

APPLICATION NUMBER

PUMP APPLICATION

SEE PAGE

2

4-4

16-20

4-5

SH1

Presteep Corn Pump

SH2

Steep Water Recirculation Pump

SH3

Light Steep Water Pump

2

4-6

SH4

Sluice Pump

2

4-7

22-26

--

TOTAL PROCESS PUMPS

5


Based on a grind rate of 170,000 bushels (4300 tonnes) per day, which represents an average-sized plant in the USA. Plants in Europe have an average grind of 55,000 bushels (1400 tonnes) per day.

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PUMP LOCATION PUMP APPLICATION APPLICATION NUMBER QUANTITY OF PUMPS

Steep House Presteep Corn Pump* SH1 2

DESCRIPTION Clean corn is transported in water through pipelines to one tank in the steep tank battery. Since corn is steeped at 120-127°F (49-53°C), the water may be heated to preheat the corn. Tanks are filled one at a time and it takes about 2 hours to fill each tank.

CONDITIONS Fluid Temperature

Clean corn slurry (abrasive with 60% solids) 120-127°F (49-53°C)

PUMP RECOMMENDATION Pump Size Seal Seal Support Materials Impeller Miscellaneous

Group 3 (C) Single seal FML seal chamber and flush High-chrome iron†, CD-4MCu with hard coating Front vane open Recessed impeller pump

COMMENTS * †

Application is suitable for process pump only if corn transported as a slurry. In some cases corn is conveyed dry from storage to steep house. High-chrome iron is preferable. Contact Flowserve RED Marketing regarding availability.

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Steep House Steep Water Recirculation Pump SH2 16-20

DESCRIPTION The steep house consists of batteries of steep tanks. A battery cosists of 8-10 tanks, with each tank requiring one pump. The pumps recirculate steep water within one tank. As steeping is completed, the pumps transport the steep water to the next tank, where it is reused.


Steep water (abrasive with 25-30% solids) 120-127°F (49-53°C)


Group 3 (C) Sealmatic pump and single static seal* FML seal chamber CD-4MCu Reverse Vane Durco Power Monitor (model KW941) †

COMMENTS * †

With high suction pressures, use single seal with FML seal chamber. Application where pump runs dry as fluid in steep tank empties.

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Steep House Light Steep Water Pump SH3 2

DESCRIPTION As the steep process is completed, the remaining steep water contains little acid (0.02%) and about 5% solids. Some of this “light” steep water is transported to a holding tank (SH3) where it is combined with other surplus process water and prepared for use as steep acid once again. Some of the light steep water is evaporated (FH1), concentrating the solids for use in feed products.


Light steep water 120-127°F (49-53°C)


Group 2 (B) Single seal FML seal chamber CD-4MCu Reverse vane Durco Power Monitor (model KW941)

COMMENTS *

A Sealmatic pump can be considered for this application.

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Steep House Sluice Pump SH4 2

DESCRIPTION After the steep water is drawn off, softened corn exits through the bottom of the tank. The corn slurry gathers in a trough or pipeline, is gravity fed into a sluice pump, and pumped to the mill house. Because each sluice pump handles the corn from one steep tank battery (8-10 tanks), it operates continuously.


Corn slurry (abrasive with 30-35% solids) 120-127°F (49-53°C)


Group 3 (C) Single seal FML seal chamber and flush High-chrome iron*, CD-4MCu with hard coating Reverse vane or front vane open Durco Power Monitor (model KW941)

COMMENTS *

High-chrome iron is preferable. Contact Flowserve RED Marketing regarding availability.

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4.2

MILL HOUSE Objective

Separate softened corn kernel into component parts, including germ (oil), hull (fiber), gluten (protein) and starch.

Description

In the mill house, the corn slurry passes through a series of dewatering, grinding, and separating processes. There are three distinct separation processes in the mill house: 1) germ removal, 2.) hull removal, and 3.) gluten removal. A starch slurry remains. All four components are transported to other process units for further processing. EXHIBIT 13 Pump Applications List: Mill House

APPLICATION NUMBER

PUMP APPLICATION

SEE PAGE

MH1

Corn Slurry Pump

24

4-9

MH2

Fiber Slurry Pump

11

4 - 10

MH3

Millstream Slurry Pump

9-11

4 - 11

MH4

Gluten Wash Pump

6

4 - 12

MH5

Gluten Pump

1-2

4 - 13

MH6

Hydroclone Pump

11

4 - 14

62-65

--

TOTAL PROCESS PUMPS

6

PUMP QUANTITY6

Based on a grind rate of 170,000 bushels (4300 tonnes) per day, which represents an average-sized plant in the USA. Plants in Europe have an average grind of 32,000 bushels (800 tonnes) per day, although newer plants are larger.

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Mill House Corn Slurry Pump MH1 24

DESCRIPTION Corn slurry is dewatered, passes over a screen to open the kernel, and is gravity-fed into the first grind mill. The ground corn slurry falls in a tank and is then pumped into each of two cyclones for germ removal. The entire process is repeated in a second grind mill to ensure all germ is removed. In a 170,000 bushel per day plant, there can be four sets of first and second grind mills, each processing a quarter of the corn slurry. Each set requires approximately 6 pumps. CONDITIONS Fluid Temperature

Corn slurry (20-30% solids) 130°F (54°C)


Group 3 (C) Single seal with hard faces FML seal chamber CD-4MCu Reverse vane

COMMENTS

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Mill House Fiber Wash Pump MH2 11

DESCRIPTION With germ removed, the corn slurry enters the third grind mill. The ground slurry (“fiber slurry”) falls into one of three tanks and is pumped to a series of six to eight fiber wash screens. Each fiber wash screen consists of a screen (to remove gluten and protein), a tank (to collect remaining fiber slurry) and a pump (to transport fiber slurry to next screen). CONDITIONS Fluid Temperature

Fiber slurry (20-30% solids) 130°F (54°C)


Group 3 (C) Single seal FML seal chamber High-chrome iron*, CD-4MCu with hard coating Reverse vane

COMMENTS *


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Mill House Millstream Slurry Pump MH3 9-11

DESCRIPTION Millstream slurry consists of a gluten and starch slurry coming from the fiber wash screens. The germ and hull have been removed. Pumps carry the millstream from three holding tanks to a set of two hydrocyclones. Here, the gluten and starch are separated. There may be four sets of hydrocyclones.


Millstream slurry 130°F (54°C)


Group 3 (C) Single seal FML seal chamber High-chrome iron*, CD-4MCu with hard coating Reverse vane

COMMENTS *


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Mill House Gluten Wash Pump MH4 6

DESCRIPTION Gluten is washed in a series of six screens to remove any traces of starch. Like the fiber wash screens, each gluten wash screen consists of a screen, a holding tank and a pump.


Gluten slurry (20-30% solids) 130°F (54°C)


Group 2 and 3 (B and C) Single seal if <30% solids, double seal if >30% solids Quench if single CD-4MCu Reverse vane

COMMENTS *

Solids may be referred to as “dry substance” or DS.

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Mill House Gluten Pump MH5 1-2

DESCRIPTION Gluten slurry is pumped from the gluten thickener.


Gluten slurry (>30% solids) 130°F (54°C)


Group 2 (B) Double seal FML seal chamber CD-4MCu Reverse vane

COMMENTS

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Mill House Hydrocyclone Pump MH6 11

DESCRIPTION After millstream separation, the starch slurry collects in a holding tank and is then pumped to starch washing hydrocyclones to remove any remaining gluten or other impurities. In a 170,000 bushel per day plant, there is one bank of 10 hydroclyclones. A pump feeds each hydrocyclone and to transport clean starch slurry to a holding tank.


Starch slurry* 130°F (54°C)


Group 3 (C) Single (if < 28% DS), double (if > 28% DS) FML seal chamber and quench (if < 28% DS), seal pot and API plan 52 (if > 28% DS)† CD-4MCu Reverse vane ◊

COMMENTS * † ◊

Fluid passing through the first two-thirds of battery will have < 28% solids or dry substance; in the last third of battery, fluid is > 28% solids, or DS. As hydrocyclones operate most efficiently at high pressures, stuffing box pressure will be high. Pressures and flows throughout the starch washing hydrocyclone battery must be identical. Some competitive pumps (KSB, Sulzer, etc.) have wear rings, which become worn in high DS applications. This alters flow rates and the battery may clog.

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4.3

Germ Plant Objective

Extract oil from the germ

Description

Germ separated from the corn slurry during milling is sent to the germ plant for further processing. Using hexane extraction, the oil is removed from the germ. Crude oil is sold to an oil refinery. At smaller corn wet milling facilities, it may not be economical to process the small quantities of germ into oil. Therefore, some producers sell germ to larger extraction plants. Exhibit 14 Pump Applications List: Germ Plant

APPLICATION NUMBER

PUMP APPLICATION

SEE PAGE

GP1

Hexane Pump

3

4 - 16

GP2

Extractor Pump

6

4 - 17

GP3

Finishing Pump

10

4 - 18

GP4

Agitator Pump

1

4 - 19

20

--

TOTAL PROCESS PUMPS

7

PUMP QUANTITY7


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Germ Plant Hexane Pump* GP1 3

DESCRIPTION Hexane is pumped to and from a holding tank in the germ plant. CONDITIONS Fluid Temperature

Hexane (explosive) 190°F (88°C)


Group 2 (B) Single seal† CBL seal chamber, ANSI flush plan 11 DCI† Reverse vane

COMMENTS * †

Pumps may be sourced as part of an OEM system. See Appendix B, OEMs and Engineering Contractors. A Guardian magnetic drive pump is a secondary option.

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Germ Plant Oil Extractor Pump* GP2 6

DESCRIPTION Germ is conveyed to extractor in the germ plant, where it is showered with hexane. A 90% hexane/10% oil fluid collects in the bottom of the extractor. This fluid is pumped to the top, where it again passes over germ to yield 50% hexane/50% oil mixture. This continues until the mixture consists of about 80% oil.


Corn oil and hexane 190°F (88°C)


Group 2 (B) Single seal with hard faces FML seal chamber DCI† Reverse vane◊

COMMMENTS * † ◊

Pumps may be sourced as part of an OEM system. See Appendix B, OEMs and Engineering Contractors. CD-4MCu may be specified for plant standardization and better wear life. CD-4MCu impeller is preferable.

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Germ Plant Finishing Pump GP3 10

DESCRIPTION After hexane is boiled off, the 100% corn oil is finished.


Corn oil 190°F (88°C)


Group 2 (B) Single seal FML seal chamber DCI* Reverse vane †

COMMENTS * †

CD-4MCu may be specified for plant standardization and better wear life. CD-4MCu impeller is preferable.

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PUMP LOCAT ION PUMP APPLICATION APPLICATION NUMBER QUANTITY OF PUMPS

Germ Plant Agitator Pump* GP4 1

DESCRIPTION Finished corn oil is stored in a holding tank. One pump agitates the stored oil continuously.


Corn oil 150°F (66°C)


Group 3 (C) Single seal FML seal chamber DCI Reverse vane

COMMENTS *

Pumps may be sourced as part of an OEM system. See Appendix B, OEMs and Engineering Contractors.

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4.4

Feed House Objective

Process deoiled germ, hulls and gluten into by-products such as animal feeds.

Description

The germ, hulls and gluten are dried by mechanical and/or thermal means, and sold as extracts or processed into feed ingredients. Two feed ingredients include gluten meal (mainly gluten) and gluten feed (mainly hulls with germ and gluten). The high-protein gluten meal commands a higher selling price than the mediumprotein gluten feed, but it is the gluten feed that is usually produced in large volumes. Exhibit 15 Pump Applications List: Feed House

APPLICATION NUMBER

PUMP APPLICATION

SEE PAGE

FH1

Evaporator Pump

8

4 - 21

FH2

Condensate Pump

3

4 - 22

11

--

TOTAL PROCESS PUMPS

8



Flowserve RED 06/98

4-20



Feed House Evaporator Pump FH1 8

DESCRIPTION Light steep water is evaporated, concentrating the solids for use in feed products. Two four-effect evaporators each process half the steep sent to the evaporators. The output is a slurry of 50% solids.


Light steep water 170-230°F (77-110°C)


Group 3 (C) or larger* Double seal FML seal chamber CD-4MCu Reverse vane

COMMENTS *

If larger capacity required, Ahlstrom alliance pumps can be quoted.

Flowserve RED 06/98

4-21



Feed House Condensate Pump FH2 3

DESCRIPTION There are three driers in the feed house, one each for germ, fiber and gluten drying. A steam trap converts the steam to condensate, which is transported to the power house. CONDITIONS Fluid Temperature

Condensate 210°F (99°C)


Group 1 (A) and 2 (B) Single seal with hard faces ANSI flush plan 11 CF-8M (Cast 316)* Reverse vane

COMMENTS *

CD-4MCu may be specified for plant standardization.

Flowserve RED 06/98

4-22


4.5

Modification (Mod) House Objective

Process starch slurry into starch products

Description

Two types of starch products are produced in the mod house: unmodified and modified. Unmodified starch involves a dry process, whereas modified starch is refined in a wet process. Mod house processes tend to be more proprietary than those in milling, so process details can vary widely. A 170,000 bushel (4300 tonnes) per day corn mill which processes about 50% of the slurry into starch requires 30-40 chemical process pumps for various centrifuging, drying and chemical applications. Not all corn wet milling plants produce starch. Some will use all starch to produce corn syrups and derivatives. Other plants will do little syrup refining, and concentrate on starch production.

Flowserve RED 06/98

4-23


4.6

Syrup Refinery Objective

Convert stach slurry to various types of sweeteners, including corn syrups, dextrose and fructose.

Description

Corn syrups are an important food ingredient, found in products such as ice creams and processed meats. Dextrose, another syrup, is widely used as a feedstock in the pharmaceutical industry and for fructose. There are four types of fructose. Three are high fructose corn syrups: 1.) HFCS 42, used in baking and other foods for mild sweetening, 2.) HFCS 55, used in soft drinks, and 3.) HFCS 90, used in reduced calorie foods. The fourth type is crystalline fructose, used in dry foods. Starch-to-syrup conversion involves acid and enzyme reactions. Most corn syrups and dextrose can be produced using either or both reactions, but fructose production requires a specific enzyme reaction. Acid conversion takes place in a reactor at about 175°-195°F (80°90°C). Enzyme conversion involves numerous additional steps, such as liquefaction, dextrinization and saccharification. Corn syrups and dextrose are then purified, cooled and stored. In fructose production, a similar process is used up to purification. At that point, the dextrose syrup is isomerized, yielding a fructose syrup which has about twice the sweetness of dextrose. A syrup refinery may have one multipurpose corn syrup/dextrose process sequence and one fructose process sequence.

Flowserve RED 06/98

4-24


EXHIBIT 16 Pump Applications List: Syrup Refinery APPLICATION NUMBER

PUMP APPLICATION


SEE PAGE

SR1

Hydrochloric Acid Pump

2

4 - 26

SR2

Soda Ash Pump

4-6

4 - 27

SR3

Corn Syrup Pump

100

4 - 28

SR4

Carbon Slurry Pump

6

4 - 29

SR5

Microfiltration Pump

16

4 - 30

128-130

--

TOTAL PROCESS PUMPS

9


Flowserve RED 06/98

4-25



Syrup Refinery Hydrochloric Acid Pump SR1 2

DESCRIPTION In acid coversion process, a hydrochloric acid solution is added to starch slurry before it enters the hydrolysis reactor.


Hydrochloric acid solution (33%) Ambient


Group 2 Single seal CBS seal chamber and external flush if F-Pump FRP (D730) Open F-Pump or unlined L-Pump (group 2 only)*

COMMENTS *

Unlined L-Pump is preferable; if customer desires sealless pump, contact RED Marketing regarding non-metallic magnetic-drive pumps.

Flowserve RED 06/98

4-26



Syrup Refinery Soda Ash Pump SR2 4-6

DESCRIPTION After syrup conversion, wet soda ash is added to the syrup to neutralize any acids. CONDITIONS Fluid Temperature

Soda Ash (35%) 140°F (60°C)


Group 2 (B) Sealmatic with single static seal *, † FML seal chamber and quench CD-4MCu Reverse vane

COMMENTS * †

Packing can be considered instead of a single static seal. A recirculation line from repeller chamber to suction and a DurcoShield are recommended, and a clean water flush may be needed. A less expensive option is a standard Mark III pump with single seal, FML seal chamber and quench. Specified for material standardization.

Flowserve RED 06/98

4-27



Syrup Refinery Corn Syrup Pump SR3 100

DESCRIPTION Corn syrup pumps are used throughout the refinery to transport syrups. The syrups vary from simpler corn syrups (dextrose) to more refined products (high fructose corn syrup).


Corn syrup 180-230°F (82-110°C)


All, mainly Group 2 (B) Double seal* FML seal chamber, seal pot with approximately 1.2 bar on top CD-4MCu Reverse vane 1800 rpm †

COMMENTS * †

Sealmatic pumps or single seals with quench and drain may be suitable for certain corn syrup services. 1800 rpm is recommended to maximize life of the power end; frequent practice is to increase plant capacity by speeding motors to 3600 rpm to the detriment of equipment.

Flowserve RED 06/98

4-28



Syrup Refinery Carbon Slurry Pump SR4 6

DESCRIPTION Corn syrups pass through carbon columns to be purified and to remove any color. Three process pumps transport carbon slurry to and from each of two columns.


Carbon slurry 80-100°F (27-38°C)


Single Group 2 (B) Single seal FML seal chamber High-chrome iron*, CD-4MCu with hard coating Recessed impeller†

COMMENTS * †

High-chrome iron is preferable. Contact Flowserve RED Marketing regarding availability. Reverse vane impeller may be suitable if carbon slurry is very fine.

Flowserve RED 06/98

4-29



Syrup Refinery Microfiltration Pump* SR5 16

DESCRIPTION Microfiltration† removes small particulate from high fructose corn syrup, making it foodgrade quality. The microfiltration system consists of a series of filters with two pumps per filter. A 170,000 bushel (4300 tonnes) per day plant utilizes eight filters and 16 pumps.


Corn syrup 200°F (93°C)


Group 3 (C) Double FML seal chamber and API plan 52 CD-4MCu Reverse vane

COMMENTS * †

Pumps may be sourced as part of an OEM system. See Appendix B, OEMs and Engineering Contractors. Microfiltration may also be referred to as ultrafiltration. Reverse osmosis is a newer filtration technology which may require high pressure pumps.

Flowserve RED 06/98

4-30


4.7

Auxiliary Pumps Description

This section covers pump applications which: 1.) Are not found in the main process units described in this manual or 2.) Are found in more than one of these process units. EXHIBIT 17 Pump Applications List: Auxiliary Pumps

APPLICATION NUMBER

PUMP APPLICATION

SEE PAGE

AU1

Cooling Tower Pump

12

4 - 32

AU2

Syrup Load Out Pump

4

4 - 33

AU3

Lime Slurry Pump

2

4 - 34

AU4

Soda Ash Pump

2

4 - 35

AU5

Sodium Hydroxide Pump

2

4 - 36

AU6

Starch Tank Farm Pump

4

4 - 37

AU7

Sulphuric Acid Pump

2+

4 - 38

AU8

Waste Water Pump

20-30

4 - 39

48-58

--

TOTAL PROCESS PUMPS

10



Flowserve RED 06/98

4-31



Auxiliary Pump (Cooling Tower) Cooling Tower Pump AU1 12

DESCRIPTION


Water Ambient


Group 3 (C) or larger* Single seal FML seal chamber DCI† Reverse vane in CD-4MCu◊ Variable speed driver §

COMMENTS * † ◊ §

If larger capacity required, Ahlstrom alliance pumps can be quoted. Horizontal split case and vertical turbine pumps are also acceptable for this application. DCI is sufficient; CF-8M (Cast 316) and CD-4MCu are specified to standardize plant. CD-4MCu for standardization Allows for flexibility as cooling capacity varies

Flowserve RED 06/98

4-32



Auxiliary Pump Syrup Load Out Pump AU2 4

DESCRIPTION Pumps transport finished high fructose corn syrups into trucks or railcars. There are about four large storage tanks, each requiring one pump for load-out.


Corn Syrup 130°F (54°C)


Group 3 (C) Double seal FML seal chamber CD-4MCu Reverse vane

COMMENTS

Flowserve RED 06/98

4-33



Auxiliary Pump Lime Slurry Pump AU3 2

DESCRIPTION Lime slurry is added to process water for pH control. Application is in waste water treatment facility.


Lime Slurry Ambient


Group 1 (A) Double seal FML seal chamber High-chrome iron*, CD-4MCu with hard coating Open High head application

COMMENTS *

High-chrome iron is preferable. Contact Flowserve RED Marketing for availability.

Flowserve RED 06/98

4-34



Auxiliary Pump Soda Ash Pump AU4 2

DESCRIPTION Soda ash is used to control pH levels in process water. Application is in waste water treatment facility.


Soda Ash Ambient


Group 1 (A) or 2 (B) Sealmatic with double lip seal FML seal chamber CD-4MCu Reverse vane

COMMENTS

Flowserve RED 06/98

4-35



Auxiliary Pump Sodium Hydroxide AU5 2

DESCRIPTION Caustic solutions are used to clean lines and filters throughout the plant. CONDITIONS Fluid Temperature

Sodium Hydroxide 140°F (60°C)


Group 2 (B) Double seal FML seal chamber CD-4MCu Reverse vane

COMMENTS

Flowserve RED 06/98

4-36



Auxiliary Pump Starch Tank Farm Pump AU6 4

DESCRIPTION Pumps transport liquid starch from tanks into the refinery for processing.


Liquid Starch 120-130°F (49-54°C)


Group 3 (C) Single seal FML seal chamber CD-4MCu Reverse vane

COMMENTS

Flowserve RED 06/98

4-37



Auxiliary Pump Sulphuric Acid Pump AU7 2+

DESCRIPTION These pumps deliver sulphuric acid to steep water to sanitize and reduce corn, and to refinery processes to speed reactions and control pH.


Sulphuric acid* 80-105°F (27-41°C)


Group 1 (A) Not applicable Not applicable CN-7M† Reverse vane Sealless magnetic drive pump

COMMENTS * †

Sodium bisulfide may be used in lieu of sulphuric acid, especially when sulphuric acid prices are high. Non-metallic magnetic-drive pumps are another option. Contact RED Marketing regarding availability.

Flowserve RED 06/98

4-38



Auxiliary Pump Waste Water Pump AU8 20-30

DESCRIPTION Sumps collect process waste water throughout facility. From here water is pumped to waste water facility to be treated or back into the process.


Waste water (abrasive) 80-130°F (27-54°C)


Group 2 (B) Single seal FML seal chamber CD-4MCu Open Self-priming pump

COMMENTS

Flowserve RED 06/98

4-39


APPENDIX A Profile of End-Users COMPANY

PLANT LOCATION

ABR Foods Ltd

UK-Northhamptonshire

ADM Food Processing

USA-Illinois, Decatur

PLANT NAME

AFFILIATIONS

GRIND RATE (bushel/ metric tonne per day) 7880 b/ 200 mt

ADM minor interest in Minnesota Grain Processing and Tate & Lyle European plants

USA-Iowa, Cedar Rapids USA-Iowa, Clinton

250000b/ 6250 mt

200000 b/ 5000 mt

USA-New York, Montezuma Agrana Staerke

Austria (five plants) Germany Netherlands

Amido Glucose SA Industria E Comercio

Brazil-Estancia

Alimodones Y Glocosa Mive SA de CV

Mexico-Zapopan

Aranal comercial SA de CV

Mexico-Guadalajara

Aracia CA

Mexico-Guadalajara (two plants) Mexico-San Juan del Rio

Asia Modified Starch Co Ltd.

Thailand-Nokomatchasi

Avebe

France-Haussimont

Arancia-Colibri

JV with Corn Products International

54000b/ 1350 mt

Former Corn Products International partner

Netherlands-Nijmegem Bang Il Industry

South Korea-Inchun

Cargill Foods Corn Milling

Netherlands-Bergen op Zoom

Flowserve RED 06/98

25610 b/ 650 mt Cargill BV

A-1

Corn Wet Milling and Refining Applications COMPANY

Milling

PLANT LOCATION

PLANT NAME

AFFILIATIONS

GRIND RATE (bushel/ metric tonne per day)

Poland Russia Turkey USA-Iowa, Cedar Rapids

100000 b/ 2500 mt

USA-Iowa, Eddyville

320000 b/ 8000 mt

USA-Nebraska, Blair

185000 b/ 4625 mt American Crystal Sugar Co., Minn-Dak Farmers Cooperative and Golden Growers own; Cargill operates

USA-North Dakota, Wahpeton

USA-Ohio, Dayton

100000 b/ 2500 mt

USA-Tennessee, Memphis

200000 b/ 5000 mt

UK-Essex Cerestar

Cargill Plc

Belgium-Brussels

JV with Ulker Group

China

JV with JIFA

Denmark-Holte

Cerestar Scandinavia A/S

France-Haurbourdin France-Neuilly-sur-Seine

Cerestar France SA

Germany-Krefeld

Cerestar Deutschland GmbH

Hungary

Cereol

Italy-Castelmassa Italy-Milano

Flowserve RED 06/98

Netherlands-Sas Van Gent

Cerestar Benelux BV

Spain-Martorell

Cerestar Iberica SA

A-2

32388 b/ 822 mt


PLANT LOCATION

PLANT NAME

AFFILIATIONS


Turkey UK-Manchester

Cerestar UK Ltd

USA-Alabama, Decatur USA-Indiana, Hammond

85000 b/ 2125 mt

USA-Texas, Dimmit Crespel & Dieters

Germany-Ibbenbueren

Companhia Portuguese de Amidos SARL

Portugal-Savacem

Corn India Ltd

India

Corn Products International (CPI) Inc

Argentina-Baradero

Refineries de Mais SAICF

Australia, Lane Cove

Goodman Fielder Mills, Ltd

Brazil-Anastacio

Refinacoes de Milho, Brasil Ltd

Brazil-Balsa Nova


16000 b/ 400 mt

Brazil-Cabo


12000 b/ 300 mt

Brazil-Mogi Guacu


100000 b/ 2500 mt

Canada-Ontario, Cardinal

CASCO Inc

47280 b/ 1200 mt

Canada-Ontario, London

CASCO Inc

34000 b/ 850 mt

Canada-Ontario, Port Colborne

CASCO Inc

31520 b/ 800 mt

Chile-Llay-Llay

Industrias de Mais y Alimentos SA

8000 b/ 200 mt

Columbia-Barranquilla

Industrias de Maiz SA, Maizena SA

5000 b/ 125 mt

Flowserve RED 06/98

A-3

CPI technology license

33000 b/ 825 mt


PLANT LOCATION

PLANT NAME

AFFILIATIONS

Columbia-Cali


Columbia-Medellin


India-Bombay

Corn Products Co (India) Ltd;

CPI major interest

Japan-Tokyo

Nihon Shokuhin Kako (NSK) Co., Ltd.

CPI minor interest

Japan

CNT

CPI and NSK JV

Kenya-Eldoret

18000 b/ 450 mt

CPI and local government interest

Malaysia-Petaling Jaya


Stamford Food Industries Sdn Berhad

CPI 100% interest

New Zealand-Onebunga

New Zealand Starch Products

CPI technology license

Pakistan-Faisalabad

Rafhan Maize Products

CPI majority interest

5000 b/ 125 mt

Mexico-see Arancia

Delmaiz SA

Flowserve RED 06/98

32000 b/ 800 mt

USA-California,Stockton

60000 b/ 1500 mt

USA-Illinois, Summit-Argo

230000 b/ 5750 mt

USA-North Carolina, WinstonSalem

80000 b/ 2000 mt

Venezuela, Agua Viva

Alfonzo Rivas Co., CA

CPI technology/ management agreement

Venezuela, Turmero

Alfonzo Rivas Co., CA (technology management agreement with CPI)

CPI technology/ management agreement

Yugoslavia-Zrenjanin

IPOK

CPI JV

Argentina-Buenos Aires

A-4


PLANT LOCATION

Doosan Food Co Ltd

South Korea-Inchun

Emsland Staerke

Germany-Emlichheim

Finnsugar Ltd Cultor

Finland-Kantvik

Gastaldi Hermanos Saicfei

Argentina-Cordoba

Grain Processors Inc.

PLANT NAME

AFFILIATIONS

Former CPI partner

USA-Iowa, Muscatine

Grupo Xacur SA de CV

Mexico-Merida

Industrias de Maiz SA (IMASA)

Argentina-Chacabuco

GRIND RATE (bushel/ metric tonne per day) 21670 b/ 550 mt

120000 b/ 3000 mt

AE Staley technology agreement

21670 b/ 550 mt

Brazil Chile Jaeckering

Germany-Hamm

Kroener

Germany-Ibbenbueren

Maffessoni Conercio e Industria

Brazil-Centro Cacador

Midwest Grain

USA-Kansas, Atchison

85000 b/ 2125 mt

USA-Illinois, Perkin

85000 b/ 2125

Minnesota Grain Processing

USA-Minnesota, Marshall

ADM minor interest

USA-Nebraska, Columbus

Molinos Canuelas SA

Argentina-Buenos Aires

Molinos y Establecimientos Harineros Bruning SA

Argentina-Sante Fe

National Starch & Chemicals

Germany-Neustadt

Flowserve RED 06/98

230000 b/ 5750 mt 230000 b/ 5750 mt

National Starch & Chemicals GmbH

A-5

ICI acquisition


PLANT LOCATION

PLANT NAME

AFFILIATIONS


UK-Manchester UK-Tilbury USA-Indiana, Hammond USA-Missouri, Kansas City Oriental Brewery Co.

South Korea-Lee Chun

19700 b/ 500 mt

Penford Products Co.

USA-Idaho, Idaho Falls

85000 b/ 2125 mt

USA-Iowa, Cedar Rapids

100000 b/ 2500 mt

Pfiefer & Langen

Germany-Koeln

Primalko

Finland-Koskenkorva

Raisio Group

Finland-Raisio

Remy Industries

Belgium-Wijgmaal-Leuven

Roquette

France-Benheim France-Lestrem France-Lille

Roquette Freres

Owns plant in Romania

France-Vacquemont Italy-Cassano Spinola Spain-Barcelona Romania

Samyang Genex Co. Ltd.

Sewon Ltd.

Flowserve RED 06/98

Owned by Roquette Freres

USA-Iowa, Keokuk

150000 b/ 3750 mt

South Korea-Inchon

39400 b/ 1000 mt

South Korea-Ulsan

23640 b/ 600 mt

South Korea-Kimpo

Former CPI partner

A-6

47280 b/ 1200 mt


PLANT LOCATION

PLANT NAME

South Korea-Pusan

Shin Dong Bang

South Korea-Ansan

SOC Industrial Teofilo Grob SA

Chile-La Union

Tai Roun Product Co Ltd

Taiwan-Yunlin

Tate & Lyle

Flowserve RED 06/98

AFFILIATIONS

Former CPI partner

GRIND RATE (bushel/ metric tonne per day) 39400 b/ 1000 mt 27580 b/ 700 mt

Former CPI partner

Belgium-Aalst

Amylum Belgium NV

Tate & Lyle majority, ADM minority interest

Bulgaria

Amylum Bulgaria AD

Tate & Lyle major, ADM minor interest

China-Guangzhou

Amylum China

Tate & Lyle major interest

Egypt-Cairo

National Company for Maize Products

Government major, Amylum minor interest

France-Bordeaux

Amylum Aquitaine

Tate & Lyle major interest

France-Nesle

Amylum France SA


Greece Thessaloniki

Amylum Hellas SA


Hungary

Hungrana kft

Agrana, Tate & Lyle, ADM interest

India (3 plants)

Bharat Starch

AE Staley JV

Israel

Amylum Israel

Italy

Sedamyl SpA

Morocco

Amylum Megheeb

Netherlands

Amylum Nederland BV

Norway

Amylum Norway

A-7

Tate & Lyle, ADM minor interest


98500 b/ 2500 t

86680 b/ 2200 t


Flowserve RED 06/98

PLANT LOCATION

PLANT NAME

AFFILIATIONS


Romania-Tirgusecuiesc

Amidex

Slovakia

Amylum Slovakia spol


Spain-Zaragoza

Amylum Iberica SA


Turkey

Amylum Nisasta

Tate & Lyle minor interest

UK-Greenwich

Amylum UK Ltd.


USA-Illinois, Decatur

AE Staley

Tate & Lyle, ADM

210000 b/ 5250 t

USA-Indiana, Lafayette

AE Staley

Tate & Lyle, ADM

175000 b/ 4375 t

USA-Indiana, Lafayette

AE Staley

Tate & Lyle, ADM

65000 b/ 1625 t

USA-Tennessee, Loudon

AE Staley

Tate & Lyle, ADM

Vietnam

Amylum Vietnam

A-8

Corn Wet Milling and Refining Applications APPENDIX B OEMS AND ENGINEERING CONTRACTORS COMPANY

LOCATION

PRODUCT

ORIGINAL EQUIPMENT MANUFACTURERS ABB Air Preheater, Inc.

USA (Lisle, IL)

Feed dryers

APV Crepaco, Inc.

USA (Rosemont, IL)

Microfiltration

Barr-Rosin, Inc

USA (Oakbrook Terrace, IL)

Feed dryers

Broadbent Centrifugals

USA (Fort Worth, TX)

Centrifuge

Crown Iron Works

USA (Minneapolis, MN)

Oil extractor

Dedert Corporation

USA (Olympia Fields, IL)

Evaporator, microfiltration

Dorr-Oliver Inc.

Netherlands (Amsterdam) USA (Milford, CT) USA (Oak Brook, IL)

Centrifuges, hydrocyclones

Fluid-Quip Inc.

USA (Springfield, OH)


French Oil

USA (Cincinnati, OH)

Oil Extractor

Graver Separations, Inc.

USA (Newark, DE)

Microfiltration

HPD (Wheelabrator)

USA (Naperville, IL)

Evaporator

Koch Membrane Systems

Germany

Microfiltration

USA (Wilmington, MA) Martech

Belgium (Brussels)


Niro Inc.

USA (Columbia, MD)

Evaporator, microfiltration

PikTek, Inc.

USA (Troy, OH)

Swenson Process Equipment

USA (Harvey, IL)

Tech Sep Groupe

France (Miribel)

US Filter

USA (Palm Desert, CA)

Westfalia Separator, Inc.

USA (Northvale, NJ)

Cyclone Evaporator

Centrifuge

ENGINEERING CONTRACTORS AMG

Corn wet milling, citric acid

Borton, Inc.

USA (Hutchinson, KS)

Coppee

Belgium (Brussels)

Delta T Corporation

USA (Williamsburg, VA)

Fluor Daniel

USA (Greenville, SC)

Flowserve RED 06/98

B-1

Ethanol

Corn Wet Milling and Refining Applications Infilco Degremont

Belgium (Brussels)

Waste Treatment Plant

USA (Richmond, VA) PSI Process Systems, Inc.

USA (Memphis, TN)

Corn wet milling, syrup refining

Raytheon Engineers & Constructors, Inc.

USA (Downers Grove, IL)

Corn wet milling, refining, citric acid, itaconic acid

Simons

USA (Minneapolis, MN)

Biodegradable plastics, vitamin E

Stanley Consultants, Inc.

USA (Muscatine, IA)

Corn wet milling, refining

Starcosa

Germany

Technip

France (Paris)

Ethanol, food-grade alcohol

Vogelbusch

USA (Houston, TX)

Ethanol

Flowserve RED 06/98

B-2

Corn Wet Milling and Refining Applications APPENDIX C MASTER LIST OF PUMP APPLICATIONS Below is an alphabetical list of pump applications found upstream in a corn wet milling and refining plant. The facilities covered include the feed house (FH), germ plant (GP), mill house (MH), steep house (SH) and syrup refinery (SR). Auxiliary pumps (AU) are also included. PUMP APPLICATION

APPLICATION NUMBER


SEE PAGE

Agitator Pump

GP4

1

4 - 19

Carbon Slurry Pump

SR4

6

4 - 29

Condensate Pump

FH2

3

4 - 22

Cooling Tower Pump

AU1

12

4 - 32

Corn Slurry Pump

MH1

24

4-9

Corn Syrup Pump

SR3

100

4 - 28

Evaporator Pump

FH1

8

4 - 21

Extractor Pump

GP2

6

4 - 17

Fiber Slurry Pump

MH2

11

4 - 10

Finishing Pump

GP3

10

4 - 18

Gluten Pump

MH5

1-2

4 - 13

Gluten Wash Pump

MH4

6

4 - 12

Hydrochloric Acid Pump

SR1

2

4 - 26

Hexane Pump

GP1

3

4 - 16

Hydroclone Pump

MH6

11

4 - 14

Light Steep Water Pump

SH3

2

4-6

Lime Slurry Pump

AU3

2

4 - 34

Microfiltration Pump

SR5

16

4 - 30

Millstream Slurry Pump

MH3

9-11

4 - 11

--

30-40

4 - 23

Mod House Pump

11


Flowserve RED 06/98

C-1

Corn Wet Milling and Refining Applications Presteep Corn Pump

SH1

2

4-4

Sluice Pump

SH4

2

4-7

Soda Ash Pump — Auxiliary Pump

AU4

2

4 - 35

Soda Ash Pump — Syrup Refinery

SR2

4-6

4 - 27

Sodium Hydroxide Pump

AU5

2

4 - 36

Starch Tank Farm Pump

AU6

4

4 - 37

Steep Water Recirculation Pump

SH2

16-20

4-5

Sulphuric Acid Pump

AU7

2+

4 - 38

Waste Water Pump

AU8

20-30

4 - 39

PROCESS PUMP TOTAL

Flowserve RED 06/98

321-350

C-2

Corn Wet Milling and Refining Applications APPENDIX D Conversion Factors: Alloys, Volumes and Temperatures EXHIBIT D.1 Alloy Conversions DURCO PROCESS PUMP DESIGNATIONS ASTM (Cast) DESIGNATIONS

DIN (WN) DESIGNATIONS NAME

SYMBOL

60-40-18, A395

DIN 1693, 0.7043

Ductile Iron

DCI

CF-8M, A744

DIN 17445, 1.4408

Durco CF-8M

D4

CD-4MCu12, A890

1.4463

Durcomet 100

CD-4M

CN-7M, A744

1.4500

Durimet 20

D20

Contact Flowserve RED Marketing for availability of high-chrome iron.

EXHIBIT D.2 Volume Conversions MULTIPLY

BY

TO OBTAIN

bushels

56

pounds

bushels

.025

metric tonnes

kilograms

.001

metric tonnes

metric tonnes

39.4

bushels

metric tonnes

1000

kilograms

pounds

.018

bushels

EXHIBIT D.3 Temperature Conversions 1.

Celsius into Fahrenheit

2.

degrees F = 32+9/5 degrees C 12

Fahrenheit into Celsius degrees C= (degrees F-32) 5/9

CD-4MCu designation has changed to CD-4MCuN to indicate presence of nitrogen. Durcomet 100 meets the CD-4MCuN specification.

Flowserve RED 06/98

D-1

Chlor-Alkali Industries Applications Table of Contents Page Number

1. Introduction 1.1 1.2

Rationale and Methodology The Chlor-Alkali Process

1-1 1-2

2. Market Profile 2.1 2.2

Market Drivers and Growth Competition

2-1 2-2

3. Flowserve Experience 3.1 3.2 3.3 3.4 3.5

Flowserve Sales Decision Makers Competitive Advantage of Flowserve Chemical Process Pumps Guidelines for Mechanical Seals Plant and Pump Details

3-1 3-2 3-2 3-3 3-4

4. Pump Recommendations 4.1 4.2 4.3 4.4 4.5

Brine Handling Electrolysis Caustic Handling Chlorine Handling Hydrogen Handling

Appendix A Appendix B Appendix C

4-2 4-3 4-4 4-5 4-6

Profile of End Users Conversion Factors: Alloys, Temperature Other Pump Applications

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Chlor-Alkali Industries Applications Exhibits Page Number 1.

Flow Diagram of Manufacturing Processes

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2.

Global Chlor-Alkali Production

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Chlor-Alkali Industries Applications 1.

Introduction

1.1


The chlor-alkali industries produce some of the most basic and widely used inorganic chemicals including, but not limited to, sodium hydroxide (NaOH, a.k.a. 1 caustic soda, lye), chlorine (Cl2), sodium carbonate (Na2CO3, a.k.a. soda ash), sodium bicarbonate (NaHCO3), sodium chlorite (NaClO 2), sodium hypochlorite (NaOCl, a.k.a. bleach), calcium chloride (CaCl2), hydrochloric acid (HCl), ferric chloride (FeCl3), and hydrogen (H2). Of these, sodium hydroxide and chlorine are the most common and, in fact, rank close to sulfuric acid and ammonia in magnitude of dollar value of use. There are hardly any consumer products that are not dependent on chlorine and sodium hydroxide at some stage in their manufacture. Because of the widespread use of chlorine and sodium hydroxide and, more importantly, because of the broad range of application possibilities for Flowserve chemical process pumps, this manual will focus on these two critical chemicals. Flowserve Corporation has been involved with the chlor-alkali industries almost from the inception of one of its predecessors, The Duriron Company, Inc. Due to the extreme service conditions encountered, there has always been a need for corrosion resistant materials. The material Duriron, and later Durichlor, found widespread use. Later, Durimet 20 met many of the corrosion-resistant needs. Presently, the chlor-alkali industries are using these and other materials including CD-4MCu, titanium, and non-metallics. The chlor-alkali industries have needed, and will continue to need, the broad range of corrosion-resistant materials and the materials application expertise offered by the Flowserve Corporation to solve their severe corrosion problems. The chlor-alkali industries exist worldwide and the plants vary in size from quite small to very large. Some of the smaller plants are actually captive operations producing caustic soda and chlorine for use as basic raw materials for other products. Enterprises involved in the chlor-alkali industries are some of the most recognized global companies including Dow, OxyChem, PPG, Formosa Plastics, Solvay, ICI, Ashai, Bayer, Pioneer, Olin, and Elf Atochem just to name a few. Because of the company’s long involvement with this very basic activity and because of the inherent materials requirements and corrosive nature of the processes, it seemed appropriate to create an applications manual. This manual will explain the basic chlor-alkali manufacturing process and will enumerate the corrosion challenges faced by plant operating personnel. It will further make available the company’s experience in confronting the challenges with its broad range of materials. Finally, in addition to being able to offer solutions to corrosion problems, the Flowserve line of chemical process pumps possess features that can improve overall pumping performance in these difficult services and these features will be highlighted.

1

a.k.a. = also known as

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1.2

The Chlor-Alkali Process

The basis for the chlor-alkali process is the following simple chemical equation: energy

NaCl (salt) + H2O (water) ------→ NaOH (caustic soda) + ½ H2 (hydrogen) + ½ Cl2 (chlorine) The chemical reaction takes place in an electrolytic cell, and caustic soda and hydrogen form at the cathode while chlorine forms at the anode. Exhibit 1 is a simplified schematic showing the three types of chlor-alkali plants. There are five basic areas in these plants: brine handling, electrolysis, caustic handling, chlorine handling, and hydrogen handling. Each of these is discussed below. Brine preparation and purification are critical steps to avoid problems during electrolysis. The brine solution is treated with various chemicals to remove compounds of calcium, iron, and magnesium. After the brine is treated to remove contaminants, it is neutralized with hydrochloric acid. At this stage, the neutral brine is not very corrosive; however, in some plant designs, the brine is used to cool the chlorine gas stream and the resulting hot, chlorinated brine is quite corrosive. Electrolysis is the heart of the process. The different types of chlor-alkali plants are characterized by the electrolysis cell design used. There are basically three cell designs used: mercury, diaphragm, and membrane. There are also many variations of these basic cell designs involving special cathodes, anodes, diaphragms, membranes, etc. These variations, many times, are referred to by the name of process developer and some of the common names are OxyTech, Dow, UHDE, Ashai, Chlorine Engineers (Mitsui), and Oronzio De Nora. Regardless of the cell design or variations, the goal is to keep the anodic and cathodic areas separated. The mercury cell process produces the purest caustic, but extreme controls are required to avoid environmental problems. Mercury cells are practically extinct in the U.S and are actually outlawed in Japan. The potential environmental problems plus advancements in the other technologies have resulted in movement away from mercury cell plants. Diaphragm cell technology replaced the mercury cells but because the diaphragm was made of asbestos, this technology also has drawbacks. Membrane cells comprise the current approach in electrolytic cell technology. Regardless of the cell technology, the basic reaction involved is the same. Purified, saturated brine is fed into the electrolytic cell on the anode side. Electrical energy is applied across the cell and a portion of the brine is eletrolytically decomposed. That portion of the brine not decomposed is sent back to brine purification and recycled. The resulting charged ions migrate to the anode and cathode where the ions combine to form sodium hydroxide, chlorine, and hydrogen. The sodium hydroxide is directed to evaporators and separators for concentrating and purification. The chlorine is sent on for cooling, drying, and liquefaction. The hydrogen can be flared, “packaged” for sale, or used to enhance the calorific value of the plant fuel gases. The sodium hydroxide exiting the electrolysis area is impure and, for diaphragm and membrane cell plants, of a low concentration (typically 12-16% for diaphragm cells and 3035% for membrane cell plants). The caustic handling area of the plant concentrates the sodium hydroxide through evaporators and removes the impurities by precipitation and filtration. The major contaminant is sodium chloride (salt) and this is precipitated and returned Flowserve RED 10/98

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Chlor-Alkali Industries Applications to the brine preparation area. Other contaminants include iron and sodium chlorate. Iron is removed by treating the caustic with calcium carbonate and filtering the mixture. The sodium chlorate and any remaining salt are removed by treating the caustic with ammonia. Sodium hydroxide is generally sold in concentration of about 50%. It is supplied both as a liquid solution and in dry, flake form. For some applications, it goes through an additional evaporator step and is concentrated to about 75%. The chlorine gas exiting from the electrolysis area is hot, wet, and quite corrosive. The gas is first cooled (sometimes using the feed brine) and this removes some of the moisture by condensation, then it is sent to drying towers. The gaseous chlorine is exposed to sulfuric acid and the acid, being hygroscopic, adsorbs the water vapor and dries the chlorine. After drying, the gas is compressed and liquefied. The liquid chlorine is stored and shipped in pressurized cylinders and tank cars. Since chlorine gas is toxic, the tail gases from the drying and liquefaction steps must be captured and treated. Some of the sodium hydroxide produced is used to scrub the tail gases. The reaction of caustic with chlorine produces sodium hypochlorite (bleach). This results in a very corrosive scrubber liquid. Finally, there is the hydrogen gas. In many plants, this gas is flared off. In some plants, the gas is captured, scrubbed, packaged, and sold. In a few plants, the gas is scrubbed and added to the fuel gases in the plant to enhance the calorific value. Chlor-alkali plants are not major sources of commercial hydrogen gas.

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Market Profile

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Chlor-alkali production is driven by demand for sodium hydroxide and chlorine. Below are the major users for these chemicals: Chlorine

Sodium Hydroxide

Plastics (e.g. – vinyls) Water purification Solvents Pulp and paper Pharmaceuticals Bleaching Pesticides/herbicides Refrigerants

Pulp and paper Metallurgical processes Soaps/detergents Pharmaceuticals Foods Dyes Synthetic fibers Petroleum refining Rubber Textiles Chemicals Glass

There are hardly any products or industries that do not use one, or both, of these chemicals sometime during their manufacture. The chlor-alkali process produces these chemicals in the ratio of 1.0 unit of chlorine to 1.1 units of sodium hydroxide. This ratio is relatively fixed; however, the demands for the two chemicals do not necessarily grow together. Therefore, increased demand for one can, and has, resulted in oversupply of the other. For instance, vinyls (e.g., PVC pipe) consume about 25% of the chlorine used. The demand for vinyls has lagged recently, due primarily to the problems in Asia, and production of chlorine has been curtailed. However, there has not been a similar decline in demand for caustic so its supply has tightened. One area of significant, and probably permanent, decline in the use of chlorine is as a bleaching agent particularly in pulp and paper processing. The by-products from these operations are judged to be quite environmentally unsavory and other bleaching agents such as hydrogen peroxide are gaining favor. Because these chemicals are used in so many processes, the growth in demand is expected to be fairly steady and forecast at an annual rate of about 2.7% for the U.S. and 3.4% globally through 2002. New construction is anticipated in North America (a major exporter of these chemicals), the Mideast, Asia, and Latin America. No new capacity is expected in Western Europe. The chlor-alkali industries are somewhat fragmented with regard to manufacturing considerations (supply) and product users (demand). Plant location (supply) is influenced most heavily by two factors; availability of salt and abundant, low cost electricity. These two factors do not weigh heavily in locating plants that use sodium hydroxide and chlorine Flowserve RED 10/98

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Chlor-Alkali Industries Applications (demand). It is reasonable to assume, though, that very large consumers of these chemicals can justify their own captive operations close by or that traditional chlor-alkali producers will be relatively close to their major customers. So, where there are PCV producers or pulp and paper operations, chlor-alkali operations will be in the vicinity. Finally, there is one unifying factor and that is the chlor-alkali technology. Regardless of where the chlor-alkali plants are located, the technology employed is limited to that discussed above. 2.2

Competition

Chlor-alkali production is traditional, basic chemical processing; therefore, all manufacturers of chemical processing pumps are competitors. Of course, the major players are ITT-Goulds, IDP, and KSB with occasional competition from the Sterling Group (Labour, Peerless), Sulzer, and Ebara. Durco Process Pumps have a long and distinguished history in chlor-alkali production. Flowserve’s historical strengths in materials development and materials application expertise have served the company well in this market. Also, Flowserve’s design engineering developments in those areas that enhance pump reliability improve the company’s competitive position. Competitive advantages will be highlighted in Section 3.3.

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3.1

Flowserve Sales

Chlor-alkali production is a global business and it is estimated that 40 million metric tons of chlorine and 44 million metric tons (t) of sodium hydroxide are produced annually. Exhibit 2 below shows the global distribution of the output.

EXHIBIT 2 Global Chlor-Alkali Production

Latin America 6%

North America 33%

Asia Pacific 37% Europe 24%

Flowserve Chemical Process pumps are used worldwide in chlor-alkali plants. Below is a list of the top 10 chlor-alkali producers and their estimated 1997 output (does not reflect China, Russia, and India). These 10 producers account for about 43% of the worldwide production. Four of these 10 are among the top 20 worldwide customers for Flowserve Chemical Process pumps. Company Dow Chemical * OxyChem * PPG Formosa Plastics * Solvay Elf Atochem ICI Bayer * Pioneer Olin * - Top 20 customer

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Chlorine, thousand t 5700 2750 1550 1300 1095 1070 1060 955 950 900

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Sodium hydroxide, thousand t 6270 3025 1705 1430 1205 1177 1166 1050 1045 990

Chlor-Alkali Industries Applications In Appendix A, there are tables for the four regions shown in Exhibit 2 listing the major chloralkali producers. The listings of companies are not exhaustive as there are many small producers and many captive operations; however, they give a good representation of the companies involved in chlor-alkali production and their geographic distribution. The data for North America and Europe are fairly complete and specific regarding individual producers and levels of output. The data for the Asia Pacific region are very incomplete and sketchy so this table shows some output by country only. There are no readily available data for the former Soviet block countries. 3.2

Decision Makers

New plants and major expansions are often handled by an engineering firm and the project manager and rotating equipment expert are key individuals. Many times, end-user personnel are part of the project team and final authority for equipment purchases may fall with the senior end-user person. Also, some plants are designed around licensed technology and the licensor may have key input on equipment purchases, and, in fact, may require the use of specific equipment to maintain the technology guarantee. For in-house projects, the plant engineering manager will be a key individual. Also, there may be a materials or corrosion engineering group that will have input particularly regarding the materials of construction. For MRO2 purchases, plant maintenance is a key area. Again, however, plant materials personnel can be influential particularly if the plant has experienced corrosion problems. Also, some plants receive guidance from a corporate materials group relating to corrosion problems and contact with these individuals can be beneficial. Finally, one can never overlook the purchasing function at the plant level. 3.3

Competitive Advantage of Flowserve Chemical Process Pumps

The principle competitive advantage is the company’s materials expertise. A broad range of corrosion resistant materials, both metallic and nonmetallic, can be offered and the company has the materials application knowledge to assist in selecting the best material for the very difficult services found in chlor-alkali operations. The strengths in this area are unmatched by any of Flowserve’s competitors. The principal Flowserve alloys used in Chlor-alkali processes are listed in Appendix B along with their ASTM designations and DIN equivalents. Other Flowserve Chemical Process pump features that offer advantages to chlor-alkali producers include: • • • • • 2

Mark III reverse vane impeller ANSI 3A power end SealSentry FML seal chamber Sealmatic option Polybase baseplates

MRO = maintenance, repair, operations

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Chlor-Alkali Industries Applications The Mark III reverse vane impeller offers significant operational benefits. Because of the severe nature of many chlor-alkali services, there will be some material removal through corrosion. Because there is only one critical setting for the impeller, optimal pump performance can be restored easily with a simple impeller clearance adjustment. Also, the reverse vane design reduces NPSHR and cavitation problems resulting in much longer pump and mechanical seal life cycles. The atmospheric conditions in some areas of a chlor-alkali plant can be less than ideal due to the presence of chlorine and salt brine vapors. The ANSI 3A power end seals the bearings and bearing lubricant from these potentially harmful vapors thus prolonging bearing life. Some services in chlor-alkali plants contain solids. Also, because of the severe corrosive nature of some of the services, costly mechanical seals are sometimes needed. The SealSentry FML seal chamber provides protection for the mechanical seal and permits the use of single seals without an external flushing system. In the caustic handling area of a chlor-alkali plant, the Sealmatic option is an ideal choice. Sodium hydroxide presents difficulties for a mechanical seal because of crystallization on the seal faces. In addition, one of the operations being performed is evaporation to increase the concentration of the caustic. Since no flush is required, no additional water is added to the caustic thus enhancing the evaporation process. The Polybase baseplate is an ideal choice for the potentially corrosive environment sometimes found in chlor-alkali plants. Corrosion of carbon steel baseplates can be a serious problem and the Polybase design offers a very economical alternative to stainless steel baseplates. 3.4 Guidelines for Mechanical Seals The demands on mechanical seals in chlor-alkali plants can be severe. Services can contain solids, general corrosion attack must be confronted, chloride and caustic induced cracking must be avoided, and elastomer suitability must be considered. Based on Flowserve experience, below are some general guidelines for improved seal life: •

For those services where single seals are suitable, use the SealSentry FML seal chamber. This should eliminate the need for an external flush and, if solids are present, prevent erosion damage.

•

For all single seals in sodium hydroxide service, use a clean water, or steam, quench.

•

For all single seals, locate seal faces beyond the seal gland and in the process liquid.

•

For some services, use hard faces as recommended.

•

For services where environmental concerns are present, consider dual seal arrangements.

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Chlor-Alkali Industries Applications •

Check all seal elastomers for suitability.

Because of the severe nature of many chlor-alkali services, the input of a Flowserve FSD sealing specialist is recommended. 3.5


Exhibit 1 is a general schematic for a typical chlor-alkali plant. Because of the wide range in plant sizes and operational variations, there is no definitive list of pump quantities and designations. Section 4, Pump Recommendations, will present a general overview of the types of applications for chemical process pumps found in chlor-alkali operations. Applications for other types of pumps are shown in Appendix C.

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Pump Recommendations


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Chlor-Alkali Industries Applications 4.1

Brine Handling

4.1.1 Objective This area of the plant is involved in preparation, purification, recycling, storing, and delivering brine to the electrolysis area. 4.1.2 Description Common salt (sodium chloride, NaCl) is dissolved in water to form a saturated brine solution. Because common salt contains many contaminants (primarily calcium, magnesium, barium, sulfates) that are detrimental to the electrolytic cells, the brine must be purified. Purification operations include precipitation, clarification, and filtration. The purified brine is stored and circulated to the electrolytic cells as required. Not all the brine that goes through the cells is decomposed. This brine, called depleted or spent brine, is recycled. This depleted brine must also be purified before it can be returned to the storage area. 4.1.3

Pump Application Guidelines

•

Brine Pumps – neutral and alkaline brines + + + + +

•

Conditions: Neutral or alkaline brine, 100-160°F (38-70°C) Materials: DCI/WCB (to 120°F [50°C] max.), CF-8M, CD-4MCu, FRP (D730) Seals: Single or dual (some brine solutions contain solids, and if solids are present, hard faces are recommended particularly for single seals) Seal Support: FML seal chamber for metallic pumps, flush system for dual seals. Comments: FRP not recommended if solids present. DCI/WCB may not be acceptable because of concern over iron contamination. CD-4MCu is an excellent selection for neutral/alkaline brines. It has excellent corrosion resistance in this service and offers better performance if solids present.

Brine Pumps – acidic brines + + + + +

•

Conditions: Acidic brine, 120-200°F (60-95°C). Materials: Titanium, Palladium stabilized titanium (TiPd), Durichlor (D51M). Seals: Single or dual (seal material selection critical). Seal Support: FML seal chamber, flush system for dual seals. Comments: TiPd recommended above 180°F (82°C)

Reagent Pumps + + + +

Conditions: Typical reagents include sodium sulfite (Na 2SO3), calcium chloride (CaCl3), sodium carbonate (Na2CO3), and sodium hydroxide (NaOH), temperatures less than 120°F (50°C). Materials: CF-8M. Seals: Single or dual. Seal Support: FML seal chamber, flush system for dual seals.

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Hydrochloric Acid Pumps + + + +

•

Purified (demineralized) water + + + +

4.2

Conditions: 32% hydrochloric acid, 95°F (35°C) max. Materials: FRP (D730), Teflon (PFA)-lined. Seals: Single or dual (seal material selection critical) Seal Support: Flush system for dual seals.

Conditions: High purity water, ambient temperature Materials: CF-8M, FRP (D730) Seals: Single Seal Support: FML seal chamber (metallic pumps)

Electrolysis

4.2.1 Objective This area of the plant is involved in the electrolytic decomposition of the brine and the formation of sodium hydroxide, chlorine, and hydrogen. 4.2.2 Description Saturated sodium chloride brine is fed into the anode side of an electrolytic cell. Electrical energy is applied across the cell and the brine is electrolytically decomposed. Sodium hydroxide and hydrogen gas are formed at the cathode and chlorine gas is formed at the anode. 4.2.3


•

Cell Liquor Pumps (diaphragm cell) + + + +

•

Conditions: 10-12% NaOH, 15-17% NaCl. 175-200°F (80-95°C) Materials: CD-4MCu. Seals: Single or dual (seal material selection critical) Seal Support: FML seal chamber, water or steam quench for single seals, flush system for dual seals.

Membrane Cell Caustic + + + +

Conditions: 30-35% NaOH, 175-210°F (80-100°C) Material: CF-8M (less than 200°F [93°C]), CD-4MCu, CN-7M, Seals: Single or dual (seal material selection critical) Seal Support: FML seal chamber, water or steam quench for single seals, flush system for dual seals.

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Mercury Cell Caustic + + + +

•

Depleted Brine + + + + +

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Conditions: 50% NaOH, 175-210°F (80-100°C) Material: CF-8M (less than 200°F [93°C]), CD-4MCu, CN-7M, Seals: Single or dual (seal material selection critical) Seal Support: FML seal chamber, water or steam quench for single seals, flush system for dual seals.

Conditions: 16-22% NaCl and chlorine, 175-212°F (80-100°C). Material: Titanium (Ti), Palladium stabilized titanium (TiPd). Seals: Single or dual (seal material selection critical). Seal Support: FML seal chamber, flush system for dual seals. Comments: TiPd recommended above 180°F (82°C).

Caustic Handling

4.3.1 Objective This area of the plant is involved in reducing impurities, and increasing the concentration of the sodium hydroxide solution coming from the electrolytic cells. 4.3.2 Description Standard commercial grades of caustic are a 50% water-based solution of sodium hydroxide, a 73% solution, and anhydrous sodium hydroxide. Mercury cell caustic is at 50% strength from the cell, is of high purity, and only requires some filtration. Membrane cell caustic is 30-32% sodium hydroxide, is also of high purity, and requires simple evaporation to reach 50% concentration. Diaphragm cell caustic is 10-12% sodium hydroxide, 15-17% sodium chloride, plus other impurities. It requires triple effect evaporation, precipitation of impurities, and filtration to reach a commercial 50% solution. 4.3.2


•

Caustic Pumps + + + + +

+

Conditions: 50% NaOH, ambient-210°F (ambient-100°C). Material: DCI/WCB, CF-8M, CD-4MCu, CN-7M, CZ-100 (cast nickel). Seals: Single or dual (seal material selection critical), Sealmatic option should be considered for continuous duty service. Seal Support: FML seal chamber, water or steam quench for single seals, flush system for dual seals. Comments: DCI/WCB (suitable to 120°F [50°C], possible iron contamination); CF-8M (suitable to 200°F [95°C]); CD-4MCu (suitable to 250°F [120°C], offer better resistance than CF-8M to solids); CN-7M (suitable to 300°F [150°C]); CZ-100 (suitable to boiling point, excellent for maintaining high product purity). Note: This can be a good application for Guardian or Chemstar MD pumps because of the potential for problems with mechanical seals.

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Caustic Pumps + + + + +

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Conditions: 73% NaOH, 150-300°F (65-150°C) Material: CD-4MCu, CN-7M, CZ-100 (cast nickel). Seals: Single or dual (seal material selection critical), Sealmatic option should be considered for continuous duty service. Seal Support: FML seal chamber, water or steam quench for single seals, flush system for dual seals, jacketed seal chamber to avoid solidification of caustic during pump shutdown. Comments: 73% NaOH solidifies at about 150°F (65°C); CD-4MCu (suitable to 250°F [120°C], offer better resistance than CF-8M to solids); CN-7M (suitable to 300°F [150°C]); CZ-100 (suitable to boiling point, excellent for maintaining high product purity).

Chlorine Handling

4.4.1 Objective This area of the plant is involved in cooling, drying, and liquefying the gaseous chlorine. 4.4.2 Description The chlorine gas produced by all the cell types is saturated with water vapor. The gas is cooled in one or two stage heat exchangers to around 50°F (18°C). The gas is then dried in counter-current drying towers using concentrated sulfuric acid (H2SO4). The cool, dry gas can be sent to pipelines for transport or it can be liquefied by compression. The tail gases from the liquefaction process are scrubbed with a caustic solution. 4.4.3


•

Sulfuric Acid Unloading Pump + + + + +

•

Conditions: 98% sulfuric acid, ambient temperature. Material: DCI/WCB, Durimet 20, Durichlor (D51M). Seals: Single or dual. Seal Support: FML for DCI/WCB and Durimet 20, by-pass flush for single seal in D51M pump, flush system for dual seals. Comments: Caution is recommended with DCI/WCB, temperatures above 100°F (38°C) can cause accelerated corrosion.

Sulfuric Acid Recirculating Pump + + + +

Conditions: 96% sulfuric acid, 2% chlorine, 100-125°F (38-52°C) Material: Durimet 20, Durichlor (D51M) Seals: Single or dual Seal Support: FML for Durimet 20, by-pass flush for single seal in D51M pump, flush system for dual seals.

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Sulfuric Acid Recirculating Pump + + + +

•

Scrubber Pump + + + +

•

Conditions: Sodium chloride, sodium hydroxide, sodium hypochlorite, 100-125°F (38-52°C) Material: Titanium, Durichlor (D51M). Seals: Single or dual Seal Support: FML for Titanium pumps, by-pass flush for single seal in D51M pump, flush system for dual seals.

Chilled Water Circulating Pump + + + +

4.5

Conditions: 78% sulfuric acid, 1% chlorine, 100-125°F (38-52°C) Material: Durichlor (D51M), CW-6M, Titanium. Seals: Single or dual Seal Support: FML for CW-6M and Titanium pumps, by-pass flush for single seal in D51M pump, flush system for dual seals.

Conditions: Water, 50-60°F (10-15°C) Material: DCI/WCB, CF-8M Seals: Single Seal Support: FML seal chamber.

Hydrogen Handling

4.5.1 Objective This area of the plant is involved with cooling and compressing the gaseous hydrogen. 4.5.2 Description The hydrogen gas produced by any of the cell types is very pure and requires only cooling. For some special uses, any traces of oxygen must also be removed. 4.5.3


•

Chilled Water Circulating Pump + + + +

Conditions: Water, 50-60°F (10-15°C) Material: DCI/WCB, CF-8M Seals: Single Seal Support: FML seal chamber.

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Appendix A Profile of Major End-Users North America

COMPANY Dow Canada Dow Chemical Elf Atochem Formosa Plastics Georgia Gulf ICI Canada LaRoche Industries Niachlor Olin Corporation

OxyChem

Pioneer PPG Industries Vulcan Materials

Weyerhaeuser

PLANT LOCATION Fort Saskatchewan, Alberta Sarnia, Ontario Freeport, Texas Plaquemine, Louisiana Portland, Oregon Baton Rouge, Louisiana Point Comfort, Texas Plaquemine, Louisiana Becancour, Quebec Cornwall, Ontario Gramercy,Louisiana Niagara Falls, New York Augusta, Georgia Charleston, Tennessee McIntosh, Alabama Convent, Louisiana Corpus Christi, Texas Deer Park, Texas Delaware City, Delaware LaPorte, Texas Mobile, Alabama Muscles Shoals, Alabama Niagara Falls, New York Tacoma, Washington Taft, Louisiana Henderson, Nevada St. Gabriel, Louisiana Lake Charles, Louisiana Natrium, West Virginia Geismar, Louisiana Port Edwards, Wisconsin Wichita, Kansas Longview, Washington

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OUTPUT (chlorine/ sodium hydroxide, thousand tons [metric]) 368/405 235/258 2362/2598 1244/1368 171/188 161/177 500/550 407/447 243/267 47/51 180/198 216/237 96/106 223/246 346/380 284/312 425/468 354/389 128/141 489/538 42/46 135/148 298/328 199/219 592/651 230/253 352/387 1104/1215 349/383 243/267 69/76 238/262 135/148

Chlor-Alkali Industries Applications Appendix A Europe Profile of Major End-Users

COMPANY Akzo Salt Akzo Salt Akzo Salt BASF BASF Bayer Bayer Bayer Bayer Dow Stade Elf Atochem Elf Atochem Elf Atochem Elf Atochem Eng.e Ind. Aragoneas Eng.e Ind. Aragoneas Eng.e Ind. Aragoneas Enichem Enichem Enichem Enichem Enichem Enichem Enichem Enichem ERKIMIA Finnish Chemicals Finnish Chemicals Huls ICI ICI ICI ICI Rhone-Poulenc Rhone-Poulenc Rhone-Poulenc

PLANT LOCATION Delfzijl, The Netherlands Henglo, The Netherlands Rotterdam-Botlek, The Netherlands Antwerpen, Belgium Ludwigshafen, Germany Brunsbuttel, Germany Dormagen, Germany Krefeld 11, Germany Leverkusen, Germany Stade, Germany Fos sur Mer, France Jarrie, France Lavera, France Saint Auban, France Palos de la Frontera, Spain Sabinanigo, Spain Vilaseca, Spain Assemini, Italy Gela, Italy Mantova, Italy Porto Marghera, Italy Porto Torres, Italy Priola,Italy Sant’Eufemia, Italy Pieve -Vergonte, Italy Flix, Spain Joutseno, Finland Kuusankoski, Finland Marl, Germany Fleetwood, United Kingdom Northwich, United Kingdom Runcorn, United Kingdom Wilton, United Kingdom La Madeleine, France Le Pont de Claix, France Chesterfield, United Kingdom

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OUTPUT (chlorine/ sodium hydroxide, thousand tons [metric]) 130/143 70/77 240/264 90/99 260/286 41/45 233/256 162/179 224/246 1100/1210 122/134 292/321 365/401 122/134 80/88 15/17 130/143 80/88 115/126 129/142 185/204 90/99 170/187 35/39 42/47 145/160 80/88 58/64 320/352 90/99 75/83 720/792 170/187 40/44 220/242 52/57

Chlor-Alkali Industries Applications Appendix A Europe Profile of Major End-Users Solvay Solvay Solvay Solvay Solvay Solvay Solvay Solvay Solvay Solvay Tessenderlo Chemie

Hallein, Austria Antwerpen, Belgium Jemeppe sur Sambre, Belgium Tavaux, France Rheinberg, Germany Rosignano, Italy Herten, The Netherlands Martorell, Spain Torrelavega, Spain Zurzach, Switzerland Tessenderlo, Belgium

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50/55 190/209 120/132 325/357 210/231 135/148 135/148 180/198 62/68 50/55 210/231

Chlor-Alkali Industries Applications Appendix A Profile of Major End-Users Asia Pacific

COUNTRY/ COMPANY China, other India, other Indonesia, Asahimas Indonesia, Indochlor Indonesia, other Japan, Ashai Glass Japan, Ashai Glass Japan, Kashima Chlorine Japan, Mitsui Toatsu Japan, Mitsui Toatsu Japan, Mitsui Toatsu Japan, other Japan, Taogosei Chem. Japan, Taogosei Chem. Japan, Tokuyama Soda Japan, Tosoh Japan, Tosoh South Korea, Hanyang Chem. South Korea, Hanyang Chem. South Korea, other Taiwan, China Petro. Taiwan, Formosa Plastics Thailand, other

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Nagoya, Japan Tokushima, Japan Tokuyama, Japan Shin-Nanyo, Japan Yokkaichi, Japan Ulsan, Korea

OUTPUT (chlorine/ sodium hydroxide, thousand tons [metric] ) 4900/5390 2500/2750 120/132 110/121 570/627 191/210 182/200 280/308 70/77 71/78 59/65 2185/2404 85/94 160/176 315/347 440/484 85/94 200/220

Yochon, Korea

400/440

Lin Hai City, Taiwan Jenwu City, Taiwan

300/330 180/198 300/330 350/385

PLANT LOCATION

Serang, Indonesia Serang, Indonesia Ichihara, Japan Kashima, Japan Kashima, Japan Nagoya, Japan Omuta, Japan Takaishi, Japan

A-4

Chlor-Alkali Industries Applications Appendix A Profile of Major End-Users Latin America

COUNTRY/ COMPANY Argentina, Alcalis de la Patagonia Brazil, Carbochloro Brazil, Dow Brazil, other Brazil, Salgama Chile, other Colombia, other Mexico, Chloro de Tahanutepec Mexico, other Mexico, Quimica Ind. del Istmo Peru, Quimpac Venezuela, other

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PLANT LOCATION San Antonio del Oeste, Argentina Cubatao, Brazil Salvador, Brazil

OUTPUT (chlorine/ sodium hydroxide, thousand tons [metric]) 100/110

Tlalnepantla, Mexico

235/259 400/440 270/297 400/440 60/66 35/39 288/317

Monterrey, Mexico

69/76 129/142

Lima, Peru

100/110 120/132

A-5

Chlor-Alkali Industries Applications Appendix B Conversion Factors: Alloys, Temperatures EXHIBIT B.1 Alloy Conversions ASTM (Cast) DESIGNATIONS 60-40-18, A395 WCB, A216 Grade 2, A518 CF-8M, A744 CD-4MCu, A890 CN-7M, A744 CZ-100, A494 CW-6M, A494 Grade C3, B367 Grade 8A, B367

DIN (WN) DESIGNATIONS

DURCO PROCESS PUMP DESIGNATIONS NAME SYMBOL

DIN 1693, 0.7043, GGG 40.3 DIN 17245, 10619, GSC-25N N/A DIN 17445, 1.4408, G-XcrNiMo1810 1.4463, G-X6CrNiMo 24-8-2 1.4500, G-X7CrNiMoCuNb2520 DIN 17730, 2.4170, G-Ni95 2.4883 DIN 17850, 3.7031 DIN 17850, 3.7032

Ductile Iron Carbon Steel Durichlor Durco CF-8M Durcomet 100 Durimet 20 Cast Nickel Chlorimet 3 Titanium Palladium Stabilized Ti

DCI DS D51M D4 CD4M D20 DNI DC3 Ti TiPd

EXHIBIT B.2 Temperature Conversions 1. Celsius to Fahrenheit ° F = (1.8 X ° C) + 32

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2. Fahrenheit to Celsius ° C = (°°F – 32) ÷ 1.8

B-1


Appendix C Other Pump Applications The focus of this manual is on the application of Flowserve chemical process pumps in chlor-alkali operations. However, there are requirements for other types of Flowserve pumps particularly in larger plants. Large vertical turbine pumps are used the handle the large volume of condensate produced by the evaporators. The wastewater system to handle rainwater and runoff water also requires large vertical turbine pumps. In the hydrogen area, high volume vertical turbine or double suction pumps are used. Finally, in plants that use the ammonia process for desalting, the operation is high pressure and API pumps are used.

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Mineral Acids Applications Table of Contents

Page Number 1.

2.

3.

4.

Introduction 1.1 Rationale and Methodology 1.2 Processes

1-1 1-2

Market Profile 2.1 Market Drivers and Growth 2.2 Competition

2-1 2-2

Flowserve Experience 3.1 Flowserve Sales 3.2 Decision Makers 3.3 Competitive Advantage of Flowserve Chemical Process Pumps 3.4 Guidelines for Mechanical Seals 3.5 Plant and Pump Details Pump and Material Recommendations 4.1 Sulfuric Acid 4.2 Phosphoric Acid 4.3 Nitric Acid 4.4 Hydrochloric Acid

Appendix A Appendix B Appendix C Appendix D Appendix E Appendix F

Major Sulfuric Acid Producers Major Phosphoric Acid Producers Major Nitric Acid Producers Major Hydrochloric Acid Producers Conversion Factors: Alloys, Temperatures Other Pump Applications

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3-1 3-1 3-1 3-2 3-3 4-2 4-4 4-5 4-8 A-1 B-1 C-1 D-1 E-1 F-1

Mineral Acids Applications Exhibits

Page Number 1.

Sulfuric Acid Isocorrosion Chart

4-3

2.

Phosphoric Acid Isocorrosion Chart

4-6

3.

Nitric Acid Isocorrosion Chart

4-7

4.

Hydrochloric Acid Isocorrosion Chart

4-10

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Mineral Acids Applications 1.

Introduction

1.1


There are four principal mineral (inorganic) acids: sulfuric (H2SO4), phosphoric (H3PO4), nitric (HNO3), and hydrochloric (HCl). These acids are widely used in a variety of processes and because of the very corrosive nature of these substances, they offer many opportunities for the application of Flowserve chemical process pumps. Flowserve Corporation through one of its predecessors, The Duriron Company, has been supplying equipment to handle mineral acids since its inception. In fact, the material Duriron (durable cast iron), developed early this century, was intended initially to handle concentrated sulfuric and nitric acids in the production of explosives. In 1939, Durimet 20 was introduced. Prior to the development of Durimet 20, sulfuric acid presented severe corrosion problems for the then available stainless steels. With the development of Durimet 20, a ductile, castable, machineable alloy became available to handle sulfuric acid. During the 1960’s, and in conjunction with the Ohio State University, CD-4MCu was introduced. This alloy was particularly well suited to handle the highly oxidizing conditions presented by nitric acid services plus it offered enhanced erosion/corrosion properties needed to produce wet-process phosphoric acid. Finally, the innovative developments introduced with non-metallic materials like fiber-reinforced plastics (FRP) and fluoropolymer (PTFE/PFA) linings were spurred largely by the unique corrosion challenges presented by hydrochloric acid. So, it is safe to say that the mineral acids have been major driving forces behind many of the materials developments introduced over the years and form a large part of the basis for the materials application expertise possessed by Flowserve. The manufacture and use of mineral acids are truly global activities. These acids are used in, and derived from, the manufacture of an extremely broad range of products. Plant sizes vary from extremely large to quite small. Many units are captive operations. Most of the recognized global chemical companies are involved to some degree with either the manufacture or use of mineral acids. This manual was created to bring together the company’s long and successful involvement in providing equipment and materials to handle these very basic chemicals. Some information is presented on the basic processes used in producing these acids and the materials used in their production. However, the requirements for chemical process pumps in the actual production of these acids are somewhat limited. The real corrosion challenges and the opportunities to solve serious customer problems present themselves more in the use of these acids. This is where Flowserve’s materials expertise and unique engineering features can help improve overall pumping performance in these difficult environments and this will be the principal focus of this manual.

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Mineral Acids Applications 1.2

Processes

1.2.1

Sulfuric Acid

The contact process is used to produce almost all sulfuric acid. In very basic terms, this process converts elemental sulfur (S) into sulfur dioxide (SO2) and the sulfur dioxide is catalytically oxidized to produce sulfur trioxide (SO3). The sulfur trioxide is dissolved in 98% sulfuric acid and reacts with the 2% water present forming sulfuric acid. Sulfur dioxide is also formed during the roasting of metal sulfides in smelting operations and during the combustion of hydrogen sulfide. Many times sulfuric acid plants are built adjacent to these sites to make use of the sulfur dioxide by-product. 1.2.2

Phosphoric Acid

Phosphoric acid is produced from phosphate containing rock through either the wet-process or the electric furnace process. The wet-process is more prevalent and involves treating phosphate rock with sulfuric acid forming phosphoric acid and a sulfate. The following chemical reaction is typical 3H2SO4 + Ca(PO4)2 + 6H2O → 2H3PO4 + 3CaSO4•2H2O One important factor not reflected by this equation is the presence of impurities. Most of the phosphate bearing rock contains fluorides and fluosilicates, both of which can contribute to corrosion problems. The electric furnace process produces a purer phosphoric acid, but it also requires a higher grade of rock. In this process, phosphate rock is processed in a furnace to produce elemental phosphorus (P). The elemental phosphorus is oxidized to produce phosphorus pentoxide (P2O5) and this compound is hydrated to produce phosphoric acid. The acid produced by the electric furnace process is quite pure. 1.2.3

Nitric Acid

Nitric acid is produced by the Ammonia Oxidation Process (AOP). Ammonia (NH3) is catalytically oxidized to produce nitrous oxide (NO 2) and this gas is absorbed in water to produce nitric acid. The acid produced by the AOP has a strength of 60-65%. To produce stronger concentrations requires further processing. Demand for acid stronger than 60-65% is quite small. 1.2.4

Hydrochloric Acid

Hydrochloric acid is obtained almost solely as a by-product of the chlorination of hydrocarbons. A typical source is the reaction of chlorine with benzene: C6H6 (benzene) + Cl2 → C6H5Cl (chlorobenzene) + HCl The commercial grade of concentrated acid produced through chlorination is 38% HCl.

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Market Profile

2.1


2.1.1

Sulfuric Acid

Sulfuric acid is, by far, the most widely used industrial chemical. In fact, it has been said that the per capita use of sulfuric acid is an index of the technical development of a nation. Below are the principal users of sulfuric acid: Agricultural fertilizers Chemical processing Mineral extraction Pigments Metallurgical processes Petroleum refining (alkylation) Soaps and detergents Textiles Explosives Annual global production of sulfuric acid exceeds 100 million metric tons (t). Over 50% of this is produced in North America. Appendix A lists some of the major global producers of sulfuric acid, but it should be noted that much of the acid is produced in captive operations. Undeniably, the principal use of sulfuric acid is in the manufacture of agricultural fertilizers. In the U.S., about 60% of the acid used goes into these fertilizers while in the U.K. this figure is about 30%. The demand for fertilizers will generally drive the demand for sulfuric acid. Probably the fastest growing use for sulfuric acid is in copper leaching as part of the solvent extraction, electrowinning process. This is an area where much of the production is from by-product SO2 created in sulfide ore roasting. Global demand for sulfuric acid will probably follow overall GDP growth. Increased production of sulfuric acid from copper smelter generated sulfur dioxide will have a significant influence on the market. By-product producers are not necessarily located near acid markets (fertilizer producers). Also, the economies involved in producing byproduct acid will result in closing of some sulfur burning plants. 2.1.2

Phosphoric Acid

The principal uses of phosphoric acid are: Agricultural fertilizers Soaps and detergents Insecticides Animal feeds Metallurgical processes Sugar refining

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Mineral Acids Applications Refractory bonding Pharmaceuticals Annual global production of phosphoric acid is about 40 million metric tons (t). About one-third of this total is produced in the U.S. Major global producers are listed in Appendix B, but, again, much like sulfuric acid, a great deal of the production capacity is captive. Fully 80% of all phosphoric acid is used in the manufacture of agricultural fertilizers. Because of this, demand should grow with the demand for fertilizers. Plant location is based almost solely on the availability of phosphate rock. 2.1.3

Nitric Acid

The principal uses of nitric acid are: Agricultural fertilizers Explosives Organic synthesis (fibers, plastics, elastomers) Metallurgical processes Photoengraving Pharmaceuticals Precious metals extraction Annual global production of nitric acid is about 35 million metric tons (t). Appendix C lists some of the principal global producers. Nitric acid usage is dependent on agricultural fertilizer output, but to a lesser degree than sulfuric or phosphoric acids. Nitric acid production is a mature industry and growth will be minimal. In fact, in Western Europe demand has declined due to concern over nitrate levels in the groundwater. Plant location is dependent on the availability of ammonia. 2.1.4

Hydrochloric Acid

The principal uses of hydrochloric acid are: Metal cleaning and pickling Petroleum wells Ore reduction Food processing Cleaning solutions Global production of hydrochloric acid is about 15 million metric tons (t) per year. Appendix D lists some of the principal global producers. Growth in demand should be 24% per year and almost all hydrochloric acid is a by-product of hydrocarbon chlorination. 2.2

Competition

Mineral acid production and handling involve serious corrosion problems; therefore, all manufacturers of chemical process pumps are competitors. The principal players are ITT-Goulds, IDP, and KSB with occasional competition from the Sterling Group (Labour, Peerless). Also, there are some specialty type pumps and materials that come into play

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Mineral Acids Applications here. Wet-process production of phosphoric acid involves the handling of rock slurries and rubber-lined pumps are widely used. Labour claims that its R55 alloy offers some advantages in higher temperature mineral acid services. Non-metallics are used quite often in these acids, particularly hydrochloric, so companies like Fybroc will be competitors. Durco Process Pumps have been pumping mineral acids for decades and have performed admirably in these very difficult services. Flowserve can offer a long history of applications expertise and materials knowledge to help customers solve their corrosion problems. Also, Flowserve’s design engineering innovations can enhance overall pump reliability and improve the customer’s competitive position. Competitive advantages will be highlighted in Section 3.3.

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3.1

Flowserve Sales

Mineral acid production and use are truly global activities and Flowserve chemical process pumps are used worldwide to handle these corrosive liquids. Many of the large volume producers of these acids produce mostly, or totally, for their own consumption. For example, there are over 50 significant producers of sulfuric acid in the U.S., but only about half produce for the merchant market. Of the merchant producers, four account for over 50% of the merchant capacity. Three of these are by-product producers (Magnum Metals, Phelps Dodge, Kennecott) and the other is the global company Rhone Poulenc. Appendices A-D show the principal producers for three global regions (North America, Europe, Asia Pacific). There are no readily available data for Latin America. Because these are such highly fragmented markets, the production data are sketchy. For instance, there is a projected production output of 17 million metric tons of sulfuric acid for China for 1998, but there is no list of specific producers. Quite likely, most of the Chinese production is captive. Even though these data are not complete, they give a good representation of the companies involved with mineral acid production and their geographical distribution. 3.2

Decision Makers

Since much mineral acid production is captive and since many of the plants are built in conjunction with other processes to make use of by-product materials, specific projects just involving acid plants may be rare. Instead, they will be part of a larger project and it will be necessary to recognize these needs and offer Flowserve’s expertise. For projects handled by engineering firms, the project manager and rotating equipment expert are key individuals. Also, materials and corrosion engineers are often assigned to these projects and contact with these individuals can be fruitful. For in-house projects, the plant engineering manager is a critical contact. Decision makers involved in acquiring chemical process pumps to handle mineral acids in plant operations include operations and engineering managers, maintenance personnel, and in many plants, materials engineering groups. In plants where corrosion from mineral acids is a constant challenge, MRO1 purchasing must not be overlooked. 3.3

Competitive Advantage of Flowserve Chemical Process Pumps

The principal competitive advantage is the company’s materials expertise. Many of the materials needed to handle mineral acids were developed by Flowserve and the long applications history results in selecting the best materials for these very severe services. In addition, the Flowserve Materials Engineering Group can assist in assessing in-plant corrosion problems and offering proven solutions to these problems. These strengths and capabilities are unmatched by Flowserve’s competitors. In addition to materials, other Flowserve Chemical Process pump features that offer advantages to those handling mineral acids include: 1


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Mineral Acids Applications • • • • •

Mark III reverse vane impeller ANSI 3A power end SealSentry mechanical seal chambers Polybase baseplates Sealless pump technology

The Mark III reverse vane impeller offers significant operational benefits. Because of the severe nature of many mineral acid services, there will be some material removal through corrosion. With only one critical setting for the impeller, optimal pump performance can be restored easily with a simple impeller clearance adjustment. Also, the reverse vane design reduces NPSHR and cavitation problem resulting in much longer pump and mechanical seal life cycles. Finally, the Mark III reverse vane design makes the rear cover/seal chamber the primary wear surface, a much less costly part than the casing which is the wear surface for open impeller designs. The atmospheric conditions in some areas where mineral acids are being handled can be less than ideal. The ANSI 3A power end positively seals the bearings and bearing lubricant from these potentially harmful conditions thus prolonging bearing life. The family of SealSentry seal chambers allows the customer to choose a design to maximize seal life and minimize operating costs. The FM (Flow Modifier) series of seal chambers provides protection for the seal and permits the use of single seals without an external flush. This can be a real advantage in very corrosive services because high alloy materials can result in costly seal flush plans. Some mineral acid services require double seals and the CBL design provides better flushing and cooling of the seals resulting in extended seal life. The Polybase baseplate is an ideal choice for many mineral acid services. Corrosion of carbon steel baseplates can be a serious problem and the Polybase design offers a very economical alternative to stainless steel baseplates. Also, because of the alternate materials available with the Polybase design, the extreme range of corrosive conditions possible with mineral acids can be handled. Many mineral acid applications present some extremely difficult problems for mechanical seals. The Flowserve family of sealless pumps can offer solutions for these difficult sealing problems. In particular, the new Polychem M series pumps offer the advantages of sealless design with innovative non-metallic materials utilization to handle very corrosive services. 3.4

Guidelines for Mechanical Seals

The demands on mechanical seals in mineral acid services are usually severe. Services can lead to severe general corrosion attack on 316 stainless steel, and chloride pitting and cracking can be a problem. Therefore, careful attention must be given to seal selection and configuration. Because of the severe nature of mineral acid services, the recommendations of a Flowserve FSD sealing specialist should be obtained.

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The principal uses of Flowserve chemical process pumps are outside the actual production of mineral acids. For example, in a contact process sulfuric acid plant, there might be only 3-4 chemical process pumps handling sulfuric acid. Therefore, in Section 4, in addition to pumps and materials used in actual manufacture of mineral acids, there will be pump and material guidelines for the general handling of these acids.

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Pump and Material Recommendations


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Sulfuric Acid

4.1.1

Production of Sulfuric Acid

The process for producing sulfuric acid is discussed in Section 1.2.1. In that process, there are essentially three chemical process pumps. Two of these pumps handle 98% sulfuric acid and the other handles oleum (fuming sulfuric acid, concentrated sulfuric acid containing dissolved SO3 sometimes expressed as greater than 100% concentration). Standard horizontal chemical process pumps are normally used for these services and the material of construction is almost always CN-7M. 4.1.2

Materials Recommendations

Selecting the appropriate material for handling sulfuric acid presents a broad range of challenges. Exhibit 1 is an isocorrosion chart showing suitable materials for handling all concentrations of pure sulfuric acid. Suitable materials, depending on concentration and temperature, can range from ductile iron and carbon steel to zirconium. There are a few things worth noting about Exhibit 1. Sulfuric acid is somewhat unique in that below about 70% the liquid will be reducing while above 70% it is oxidizing. Because of this characteristic and particularly in the mid-range concentrations, a higher alloy stainless steel, like CN-7M, or a nickel-base alloy, like CW-6M, is required. Interestingly, at higher concentrations (93-100%), carbon steel and ductile iron are often used. It should be noted that at the very low concentrations, a region for CF-8M is shown outlined with a dashed line. The oxide film that provides protection against corrosion for stainless steels is unstable for CF-8M in dilute sulfuric acid. Behavior of CF-8M in dilute sulfuric acid can be erratic and caution is recommended. CD-4MCu is a much better choice for dilute sulfuric acid. Many typical applications involve handling sulfuric acid containing small amounts of other substances. These substances may be present as contaminants or intentional additions. Chlorides and fluorides are common contaminants and very small quantities can increase the corrosivity of the acid significantly. In general, if the concentration of these substances is less than 200 parts per million (ppm), then the materials shown in Exhibit 1 are suitable. Above 200 ppm, CW -6M is commonly used. For chlorides only, D51M is suitable, but is not suitable if fluorides are present. Finally, chloride and fluoride contaminated sulfuric acid is routinely handled with the fluoropolymers (PTFE/PFA). Reducing agents are commonly present in sulfuric acid services and these substances are also detrimental to the suitability of the stainless steel alloys. Some typical reducing agents are sulfur dioxide (SO2), carbon disulfide (CS2), hydrogen sulfide (H2S), sodium sulfite (Na 2SO3), and compounds containing antimony (Sb) and arsenic (As). When these substances are present above about 200 ppm, then CW-6M or PTFE/PFA are normally used. D51M is not suitable. Oxidizing substances can also be present in sulfuric acid services and these compounds can inhibit corrosion of stainless steels. Some common oxidizing agents are copper sulfate (CuSO4), oxygen (O2), ferric ion (Fe+3), and nitric acid (HNO 3). Even though these substances inhibit corrosion of stainless steels in sulfuric acid, caution should be exercised in depending on these compounds to make an otherwise marginal material suitable.

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Mineral Acids Applications Exhibit 1

SULFURIC ACID ISOCORROSION CHART

Temperature (° C)

Temperature (° F)

(20 mpy lines2)

Percentage of Sulfuric Acid (by wgt) _______________________ 2

Within the temperature-concentration regions where the alloys are shown, general corrosion rates will be ≤ 20 mils per year (1 mil = 0.001 in = 0.0254 mm).

NOTE – See Page E-1 for Alloy cross-references.

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Mineral Acids Applications Another variable influencing material performance in sulfuric acid that merits consideration is liquid velocity. As mentioned above, stainless steels depend on a thin oxide film for protection and even in the absence of solids, excessive velocity of the sulfuric acid can lead to removal of this film. Limiting liquid velocity to less than 8 feet per second (2.4 meters per second) is desirable. Finally, the Polybase finds frequent use with pumps handling sulfuric acid. Because of the highly oxidizing nature of sulfuric acid above 70% concentration, the standard black Polybase should be replaced with the special H2SO4 Red material. 4.1.3

General Guidelines for Mechanical Seals

The main consideration in seal selection is corrosion. Mechanical seal metallic components cannot generally tolerate much corrosion because of thin cross-sections and small size. A corrosion rate of 20 mils per year (mpy) may be acceptable for the pump wet-end parts, but this rate would not be acceptable for mechanical seal components. This is of particular concern in the range of 65-80% acid. CN-7M is suitable for the pump parts, but Alloy 20 is probably not suitable for the seal components. Hastelloy C is generally used in this concentration range and for all concentrations at higher temperatures. The second consideration is the oxidizing nature of sulfuric acid above 70%. These oxidizing conditions make most carbon seal faces unsuitable and silicon carbide is generally used. For all single seal applications, the FM-style seal chamber should be used to provide a more friendly environment for the seal. For dual seals, careful consideration must be given to the barrier fluid. Neither water nor alcohol is suitable since contact between these liquids and the acid can result in very rapid heat generation. Viton is normally suitable for all sulfuric acid concentrations within its acceptable performance temperature range. Because costly materials are required for many mechanical seals in sulfuric acid services, this is an application area where magnetic drive pumps are used. Guardian and ChemStar MD models with CN7M/Alloy 20 construction are used and the PolyChem M series will also be suitable for many applications. This alternative should be considered for many sulfuric acid applications. 4.2

Phosphoric Acid

4.2.1

Production of Phosphoric Acid

There are two principal processes discussed in Section 1.2.2 for producing phosphoric acid. In the wetprocess, there are a number of chemical process pumps handling various concentrations of phosphoric acid. Because of the frequent presence of solids, CD-4MCu is widely used. The presence of fluorides and fluosilicates, and temperatures above 200°F (93°C), may require the use of CW-6M, but these conditions occur infrequently. The electric furnace process produces a high purity acid with little, or no, solids present so CF-8M is most frequently used. 4.2.2


Exhibit 2 is an isocorrosion chart showing suitable materials for handling pure phosphoric acid. This is not a particularly strong acid so most services can be handled with stainless steels. The same precautions Flowserve RED 2/99

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Mineral Acids Applications enumerated in Section 4.1.2 above regarding the presence of chlorides, fluorides, and reducing agents apply to phosphoric acid. 4.2.3


Because this is not a particularly strong acid, mechanical seal selection is not difficult. Most seals used consist of 316 SS metal parts and carbon/ceramic faces. At temperatures greater than 150°F (64°C), Alloy 20 metal parts are usually required. Viton is a suitable elastomer within its acceptable performance temperature range. The presence of solids can influence seal selection. For moderate levels of solids, a single seal with the FM-style seal chamber is suitable. For higher solids loading, dual seals with a water barrier fluid are used. It should be noted that the phosphate industry has used the Sealmatic pump design for many high solids applications, but many of these services experienced problems with the solids packing the repeller chamber during shutdown. When this problem has been experienced, the service was converted to a dual seal. 4.3

Nitric Acid

4.3.1

Production of Nitric Acid

Section 1.2.3 discusses the principal process for producing nitric acid. This is primarily a gaseous process until the nitrous oxide (NO 2) is passed through the absorption column. The acid concentration exiting the column is 60-65% and can be handled with CF-8M. 4.3.2


Exhibit 3 is an isocorrosion chart showing suitable materials for handling pure nitric acid. This acid is very strongly oxidizing and, when uncontaminated, can be handled with stainless steels except at high concentrations and temperatures. Both CF-8 and CF-8M are shown as acceptable materials for handling most nitric acid services. Some feel that CF-8 is the better alloy for this highly oxidizing service; however, testing done at Flowserve and data found in the literature show that if there is a difference, it is so slight as to be insignificant. Many specifications will call for the low carbon grades (CF-3, CF-3M). This could be a factor if any welding will be done without subsequent heat treatment. Because nitric acid is so oxidizing, intergranular corrosion will occur adjacent to welds that have not been heat treated. However, there is no real advantage gained with the low carbon grades over the standard alloys if all parts receive an adequate heat treatment.

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PHOSPHORIC ACID ISOCORROSION CHART

Temperature (° C)

Temperature (° F)

(20 mpy lines2)

Percentage of Phosphoric Acid (by wgt) _______________________ 2



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NITRIC ACID ISOCORROSION CHART

Temperature (° C)

Temperature (° F)

(20 mpy lines2)

Percentage of Nitric Acid (by wgt) _______________________ 2



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Mineral Acids Applications Two common mixed services involve nitric acid. First, there is the mixture of nitric with hydrofluoric acid. This mixture is commonly called a pickling solution and is used to clean metal surfaces, particularly castings. This is a very corrosive mixture. For very intermittent services, CN-7M has given reasonable life. CW-6M is more suitable, particularly for continuous duty; however, even this alloy will suffer attack. Because of the severe nature of this service, the fluoropolymers (PTFE/PFA) are widely used. The second mixture involves nitric with adipic acid. This mixture will attack the CF alloys, but CD-4MCu performs quite well up to about 180°F (82°C). Above this temperature, titanium (Ti) is suitable. The fluoropolymers also find use in nitric/adipic services. There is an area on the isocorrosion chart (Exhibit 3) above 95% that is bounded by a dashed line and does not list any materials. This concentrated acid is very corrosive and is not handled well by any standard alloys. However, Flowserve can offer a material called Durcomet 5 (DV) that works very well. This alloy is essentially CF-3 with about 5% silicon. The Flowserve foundry is the only licensed producer of this material in North America. 4.3.3


For most applications, the metal components of mechanical seals can be made of 316 SS. However, because of the highly oxidizing nature of nitric acid, special consideration must be given to the face and elastomer materials. The acid will attack most common carbon binders so if a carbon face is required, a special grade must be used. Also, the acid will attack the binders in tungsten carbide. Generally, selfsintered silicon carbide faces are used. Viton is not suitable in nitric acid. Either PTFE or Kalrez gasketing and secondary sealing are required. 4.4

Hydrochloric Acid

4.4.1

Production of Hydrochloric Acid

Section 1.2.4 discusses the process for producing hydrochloric acid. This process is gaseous until the hydrogen chloride (HCl) is absorbed in water to form the acid. The acid concentration exiting the column is about 35% and is handled mostly with nickel-base alloys or nonmetallics. 4.4.2


Hydrochloric acid is the most corrosive, by far, of all the acids and extreme care must be taken in material selection. Exhibit 4 is an isocorrosion chart for pure hydrochloric acid. As shown on this chart, stainless steels are not suitable for any hydrochloric acid service. Cleaning and pickling metals are the predominate uses for hydrochloric acid. These operations can introduce ferric (Fe+3) and cupric (Cu+2) ions, both oxidizing agents. N-7M and zirconium (Zr) cannot tolerate the presence of these ions and are unsuitable. In the presence of these ions, titanium (Ti) is suitable up to about 10% acid while D51M is suitable to about 20% acid. In both cases, the temperature is limited to 150°F (65°C). Because all suitable metallic materials are very costly, nonmetallics find wide acceptance for handling hydrochloric acid. These include both the fluoropolymers (PTFE/PFA) and solid fiber reinforced (FRP) epoxy. 4.4.3


Metallic corrosion is the principal concern in mechanical seal selection. The most common metallic material used is Hastelloy C. Carbon/ceramic faces are usually suitable and Viton is an acceptable Flowserve RED 2/99

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Mineral Acids Applications elastomer within its performance temperature range. Dual seals are often used with hydrochloric acid to prevent exposing the metallic parts to the acid.

Because of the very costly mechanical seals required for hydrochloric acid services, the PolyChem M series will find widespread use here. In fact, hydrochloric acid services are some of the principal applications for nonmetallic magnetic drive pumps.

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HYDROCHLORIC ACID ISOCORROSION CHART

Temperature (° C)

Temperature (° F)

(20 mpy lines2)

Percentage of Hydrocholoric Acid (by wgt) _______________________ 2



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Mineral Acids Applications Appendix A Major Sulfuric Acid Producers U.S and Canada Company

Location

Raw Material

Remarks

ASARCO

East Helena, MT El Paso, TX Hayden, AZ Bartow, FL Riverview, FL Bartow, FL Plant City, FL Timmons, Ontario Falconbridge, Ontario Donaldsonville, LA Mulberry, FL Nichols, FL South Pierce, FL Uncle Sam, LA San Manuel, AZ White Springs, FL Baton Rouge, LA

Lead smelter by-product Copper smelter by-product Copper smelter by-product Elemental S Elemental S Elemental S Elemental S Copper/zinc smelter by-product Copper/zinc smelter by-product Elemental S Elemental S Elemental S Elemental S Elemental S Smelter by-product Elemental S 95% sludge & 5% H2S

Mostly captive Partly captive Partly captive Captive Mostly captive Captive Captive Partly captive Partly captive Captive Captive Mostly captive Captive Mostly captive Partly captive Captive Partly captive

Baytown, TX Carson, CA Hammond, IN Houston, TX Martinez, CA Lathrop, CA Pocatello, ID Aurora, NC Fort Meade, FL

100% sludge 100% sludge 40% elemental S & 60% sludge 70% elemental S & 30% sludge 100% sludge Elemental S Elemental S Elemental S Elemental S

Partly captive Partly captive Partly captive Partly captive Partly captive Captive Mostly captive Captive Mostly captive

Cargill Fertilizers C.F. Industries Falconbridge, Ltd. IMC-Agrico

Magma Metals Occidental Chemical Rhone Poulenc

J.R. Simplot Texasgulf U.S. Agri-Chemicals

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Mineral Acids Applications Appendix A Major Sulfuric Acid Producers Asia Pacific Country

Company

Location

Indonesia

Petrokimia Gresik

Japan

Dowa Mining

Gresik, East Java Kosaka Okayama Tamano Naoshima Akita Saganoseki Onahama Toyo Nagoya Annaka Iwaki Takehara Ulsan Yosu Toufen City Kaohsiung City Maptaput

Hibi Kyodo Smelting Mitsubishi Metals Nippon Mining Onahama Smelting Sumitomo Metal Mining Toagosei Chemical Toho Zinc

South Korea Taiwan Thailand

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Dongbu Chemical Korea General Chemical Heng I Chemical Kaohsiung Ammonium Sulfate National Fertilizer

A-2

Mineral Acids Applications Appendix A Major Sulfuric Acid Producers Europe Country Belgium Finland

Company

Location

Bayer Rhone-Poulenc Kemira Agro Kemira TiO2

France

Rhone-Poulenc Chimie

Germany Greece Italy

Norddeutsche Affinerie Sachtleben Chemie Ste. Ind. Chimiques du Nord EniChem

The Netherlands Spain

Kemira Pernis Fesa-Enfersa

United Kingdom

Albright & Wilson ICI

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Raw Material

Antwerpen Gent Kokkola Siilinjärvi Pori

Elemental S Elemental S Pyrite, smelter gas Pyrite Elemental S

Chauny La Madeleine Le Grande Quevilly St. Clair du Rhone Hamburg Duisburg-Homberg Thessaloniki Gela Porto Marghera Rotterdam Cartegena Huelva Whitehaven Billingham Runcorn

Elemental S Elemental S Elemental S Elemental S Copper/lead smelter gas Pyrite Elemental S & pyrite Elemental S Elemental S & pyrite Elemental S Pyrite Pyrite Elemental S Elemental S Elemental S

A-3

Mineral Acids Applications Appendix B Major Phosphoric Acid Producers U.S and Canada Company Arcadia Fertilizer Cargill Fertilizer C.F. Industries Farmland Hydro FMC

IMC-Agrico

Imperial Oil Mulberry Phosphates Occidental Chemical Texasgulf US. Agri-Chemicals

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Location

Process

Geismar, LA Bartow, FL Riverview, FL Bartow, FL Plant City, FL Pierce, FL Green River, WY

Wet Wet Wet Wet Wet Wet Hydrated P2O5

Carteret, NJ Lawernce, KS Newark, CA Donaldsonville, LA Mulberry, FL Nichols, FL South Pierce, FL Uncle Sam, LA Redwater, Alberta Mulberry, FL Piney Point, FL White Springs, FL Aurora, NC Fort Meade, FL

Furnace Furnace Furnace Wet Wet Wet Wet Wet

B-1

Wet Wet Wet Wet Wet

Mineral Acids Applications Appendix B Major Phosphoric Acid Producers Europe Country Belgium Finland France

Company

Location

Soc. Chimique Prayon-Rupel Kemira Agro Grande Paroisse Hydro Azote Germany Hoechst Greece Ste. Ind. Chimiques du Nord Italy Ind. Siciliana Acido Fosforico The Netherlands Hydro Agri Rotterdam Kemira Pernis Spain Fesa-Enfersa United Kingdom Albright & Wilson

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Process

Engis Wet Siilinjärvi Wet Le Petit et le Grand Quevilly Wet Le Havre Wet Hürth-Knapsack Furnace & wet Thessaloniki Wet Gela Wet Vlaardingen Wet Rotterdam Wet Huelva Wet Oldbury Furnace Whitehaven Wet

B-2

Mineral Acids Applications Appendix B Major Phosphoric Acid Producers Asia Pacific Country Indonesia Japan

South Korea

Taiwan Thailand

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Company Petrokimia Gresik Central Glass Co-op Chemical

Location

Gresik, East Java Ube Miyako Niigata-Hidashiko Mitsui Toatsu Chemicals Hikoshima Hokkaido Nippon Phosphoric Acid Kimitsu-gun Dongbu Chemical Ulsan Korea General Chemical Chinhae Yosu Chinese Petroleum Hsiaokang National Fertilizer Maptaput

B-3

Mineral Acids Applications Appendix C Major Nitric Acid Producers U.S. and Canada Company

Location

Remarks

Use

Arcadia Fertilizer

Augusta, GA

Captive

Ammonium nitrate & Caprolactum Ammonium nitrate Ammonium nitrate Ammonium nitrate Ammonium nitrate Ammonium nitrate Ammonium nitrate Ammonium nitrate Nitrobenezene Adipic acid Adipic acid

Clinton, IA Geismar, LA La Platte, NE Wilmington, NC C.F. Industries Donaldsonville, LA Coastal Chemical Battle Mountain, NV Cheyenne, WY Dupont Beaumont, TX Orange, TX Victoria, TX Dyno Nobel Donora, PA Louisiana, MO El Dorado Chemical El Dorado, AR Farmland Industries Beatrice, NE Dodge City, KA Enid, OK Lawrence, KS ICI Canada Beloeil, Quebec Carseland, Alberta Courtright, Ontario Nitrochem Maitland, Ontario Terra Nitrogen Verdigris, OK U.S. Army Baraboo, WI Kingsport, TN Charleston, IN Radford, VA Lawrence, KS Chattanooga, TN Unocal Kennewick, WA West Sacramento, CA

Partly captive Partly captive Partly captive Mostly captive Captive Captive Captive Captive Captive Captive Captive Partly captive Mostly captive Captive Mostly captive Captive Mostly captive

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Captive Captive Captive Captive Captive Captive Captive Captive Captive

Ammonium Ammonium Ammonium Ammonium Ammonium

nitrate nitrate nitrate nitrate nitrate

Ammonium nitrate Explosives Explosives Explosives Explosives Explosives Explosives Nitrate fertilizers Ammonium nitrate

Mineral Acids Applications Appendix C Major Nitric Acid Producers Europe Country Austria Belgium Denmark Finland

France

Germany Greece Ireland Italy The Netherlands

Norway

Spain

Sweden United Kingdom

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Company

Location

Agrolinz Agrarchemikalien Linz BASF Antwerpen Kemira Fredericia Kemira Oulu Siilinjärvi Uusikaupunki Grande Paroisse Le Petit et le Grand Quevilly Mazingarge Monioir de Bretagne Toulouse Hydro Azote Ambés Le Havre Montoir de Bretagne Pardies BASF Ludwigshafen Hoechst Frankfurt Aeval Ptolemais Irish Fertilizer Industries Arklow Agrimont Porto Marghera Enichem Ravenna DSM Meststoffen Gellen Ijmuiden Hydro Agri Sluiskil Sluiskil Norsk Hydro Glomfjord Herøya Rjukan Fesa-Enfersa Avilés Puertollano Sagunto Tablada Hydro Supra Köping Landskrona Hydro Fertilizers Immingham ICI Billingham Severnside Stevenston, Scotland Wilton Kemira Ince

C-2

Mineral Acids Applications Appendix C Major Nitric Acid Producers Asia Pacific Country Indonesia Japan South Korea Taiwan

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Company Multi Nitrotama Kimia Ashai Chemical Sumitomo Chemical Dongbu Chemical Korea General Chemical Taiwan Fertilizer

C-3

Location Nobeoka Niihama Ulsan Yosu Haulien Kaohsiung

Mineral Acids Applications Appendix D Major Hydrochloric Acid Producers U.S. and Canada Company BASF Borden Chemicals Dow

Dow Canada Formosa Plastics Geon Georgia Gulf ICI Materials Miles Occidental

Olin

Oxymar PPG Industries

Vista Chemical Vulcan Materials

Westlake Monomers

Location

Raw Material

Remarks

Geismar, LA Geismar, LA Freeport, TX Midland, MI Oyster Creek, TX Pittsburg, CA Plaquemine, LA Fort Saskatchewan, Alberta Sarnia, Ontario Baton Rouge, LA Port Comfort, TX La Porte, TX Plaquemine, LA Geismar, LA Baytown, TX New Martinsville, WV Deer Park, TX Niagra Falls, NY Tacoma, WA Augusta, GA Charleston, TN Lake Charles, LA Ingleside, TX Barberton, OH Lake Charles, LA Natrium, WV Baltimore, MD Lake Charles, LA Geismar, LA Port Edwards, WI Wichita, KS Calvert City, KY

By-product, isocyanates By-product, vinyl chloride By-product, chlorination By-product, chlorination By-product, vinyl chloride By-product, intermediates By-product, chlorination Chemical reaction Chemical reaction & by-product By-product, vinyl chloride By-product, vinyl chloride By-product, vinyl chloride By-product, vinyl chloride By-product, isocyanates By-product, isocyanates By-product, isocyanates By-product, chlorination By-product, chlorination Thermal reaction Thermal reaction Thermal reaction By-product, isocyanates By-product, vinyl chloride Phosgene By-product, chlorination By-product, chlorination By-product, alkybenzenes By-product, vinyl chloride By-product, chlorination Thermal reaction By-product, chlorination By-product, vinyl chloride

Mostly merchant Captive Captive & merchant Captive Mostly captive Merchant Mostly captive Captive & merchant Captive & merchant Captive Captive Captive Mostly captive Captive & merchant Captive & merchant Captive & merchant Captive Captive Mostly merchant

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Merchant Merchant Captive Mostly merchant Captive Merchant Merchant Captive Captive Mostly merchant Captive & merchant Captive

Mineral Acids Applications Appendix D Major Hydrochloric Acid Producers Europe Country Belgium

France

Germany

Italy

Company

Location

BASF

Antwertpen

Limburgse Vinyl Maatschappij Solvay Tessenderlo Chemie

Tessenderlo Jemeppe sur Sambre Ham Kwaadmechelen Tessenderlo Vilvoorde Jarrie Lavéra Pierre-Bénite Saint Auban Fas sur Mer Tavaux Ludwigshafen Marl Wilhelmshaven Rheinberg Burghausen Bussi sul Tirino Porto Marghera Spinetta-Marengo Assemini Brindisi Porto Marghera Porto Torres Ravenna Rotterdam-Botlek Herøya Vilaseca Martorell Stenungsund Fleetwood Runcorn

Elf-Atochem

Soc. Du Chlorure de Vinyle Solvay BASF Hüls Aktiengesellschaft ICI Solvay Wacker-Chemie Ausimont

EVC

The Netherlands Norway Spain Sweden United Kingdom

ROVIN Norsk-Hydro Aiscondel Viniclor Hydro Plast European Vinyls

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Raw Material By-product, isocyanates & VCM By-product, VCM By-product, chlorination Potassium chloride Potassium & sodium chloride Potassium chloride By-product, chlorination By-product, VCM By-product, fluorocarbons By-product, VCM By-product, VCM Direct synthesis By-product, VCM By-product, VCM By-product, VCM By-product, VCM By-product, VCM By-product, chlorination By-product, fluorocarbons By-product, fluorocarbons By-product, VCM By-product, VCM By-product, VCM By-product, VCM By-product, VCM By-product, VCM By-product, VCM By-product, VCM By-product, VCM By-product, VCM By-product, VCM By-product, VCM

Mineral Acids Applications Appendix D Major Hydrochloric Acid Producers Asia Pacific Country Indonesia Japan

Company Indochlor Perkasa Ashai Denka Kogyo Ashai Glass

Denki Kagadu Kogyo Kanegafuchi Chemical Kanto Denka Kogyo Toagosei Chemical

Tosoh Corp. Tsurumi Soda South Korea Taiwan Thailand

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Kyunggi Chemical Formosa Plastics South East Soda Thai Asahi Caustic Soda

D-3

Location Serang, West Java Kashima Ichihara Kita-Kyushu Yodogawa Omi Takasago Mizushima Shibukawa Nagoya Takaoka Tokushima Shin-Nanyo Yokkaichi Tsurumi Yokohama Ulchu Jenwu City Suao City Bangplakod

Mineral Acids Applications Appendix E Conversion Factors: Alloys, Temperatures EXHIBIT E.1 Alloy Conversions ASTM (Cast) DESIGNATIONS 60-40-18, A395 WCB, A216 Grade 2, A518 CF-8, A744

CW-6M, A494 N-7M, A494 Grade C3, B367 Grade 8A, B367

DIN (WN) DESIGNATIONS DIN 1693, 0.7043, GGG 40.3 DIN 17245, 10619, GSC-25N N/A DIN 17445, 1.4308, G-X6CrNi189 DIN 17445, 1.4408, GXCrNiMo 1810 1.4463, GX6CrNiMo 24-8-2 1.4500, GX7CrNiMoCuNb2520 2.4883 2.4882 DIN 17850, 3.7031 DIN 17850, 3.7032

Grade 702, B752

N/A

CF-8M, A744 CD-4MCu, A890 CN-7M, A744

DURCO PROCESS PUMP DESIGNATIONS NAME SYMBOL Ductile Iron DCI Carbon Steel DS Durichlor D51M (HSI) Durco CF-8 D2 Durco CF-8M

D4

Durcomet 100 Durimet 20

CD-4M D20

Chlorimet 3 Chlorimet 2 Titanium Palladium Stabilized Ti Zirconium

DC3 DC2 Ti TiPd

EXHIBIT E.2 Temperature Conversions 1. Celsius to Fahrenheit °F = (1.8 X °C) + 32

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2. Fahrenheit to Celsius °C = (°F – 32) ÷ 1.8

E-1

Zr

Mineral Acids Applications Appendix F Other Pump Applications The focus of this manual is on the use of Flowserve chemical process pumps for handling mineral acids; however, there are requirements for other types of Flowserve pumps in the manufacture of these acids. One typical application is boiler feedwater pumps. Another is large cooling water circulating pumps. Finally, in the wet-process method for producing phosphoric acid, large axial flow pumps are used with the evaporators.

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PTA Applications Table of Contents

1.

Page Number

Introduction 1.1 Rationale and Methodology 1.2 The PTA Process

2.

1-1 1-1

Market Profiles 2.1 Market Drivers 2.2 Competition

3.

2-1 2-2

Flowserve Experience 3.1 Flowserve Sales 3.2 Decision Makers 3.3 Competitive Advantages of Flowserve Chemical Process pumps 3.4 Guidelines for Mechanical Seals 3.5 Plant and Pump Details

4.

3-1 3-1 3-2 3-3 3-3

Pump Recommendations 4.1 Introduction to Pump Recommendations 4.2 Common Services 4.3 Specific Applications

4-2 4-2 4-6


PTA Producers Alphabetical Listing of Pump Descriptions Other Pump Applications

A-1 B-1 C-1

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PTA Applications Exhibits Page Number 1.

Uses of PTA

2-1

2.

Global PTA Production

3-1

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PTA Applications 1.

Introduction

1.1 Rationale and Methodology Purified terephthalic acid (PTA) is the primary and preferred raw material for production of high-purity polyester resins. These resins are used in a broad range of products ranging from commodity type items to aerospace applications. Demand for the products that use these resins is growing at a significant rate and, therefore, the demand for PTA will grow also. Flowserve chemical process pumps are a standard component in the PTA production process. The broad range of materials available along with a reputation for reliable, dependable operation and excellent after sales support have lead to wide acceptance for Flowserve chemical process pumps in PTA production. In fact, Amoco Chemicals, the leading global producer of PTA, has standardized on Flowserve chemical process pumps. Production of PTA is global with many participants; however, a few major players are dominant. Amoco Chemicals is the giant in the field accounting for about 40% of the world’s total capacity. Other major players include DuPont, Eastman, Mitsui, Mitsubishi, Kohap, Tuntex Petrochemical, and a group of state-owned units in China. Flowserve chemical process pumps have enjoyed widespread application in PTA production. Since significant growth in demand is forecast for PTA, this manual is offered as a tool to increase familiarity with this key chemical. The manual will present the basics of the processes for producing PTA. It will present, in some detail, the applications where Flowserve chemical process pumps have been successfully applied. With this presentation will be included the pump configurations that have proven to offer dependable service. Special emphasis will be given to those features of the configurations that are unique to Flowserve chemical process pumps and the benefits these features offer to the end-user. 1.2 The PTA Process There are three principal steps in the production process for PTA: 1. Mixed xylenes are converted to para-xylene. 2. Para-xylene is oxidized in the presence of a reaction solvent (acetic acid) and a catalyst mixture to produce crude terephthalic acid (TA). 3. The crude TA is purified through catalytic hydrogenation and crystallization to produce purified terephthalic acid (PTA). Much of the process technology involved in producing PTA is proprietary. For example, the catalyst mixture used in the oxidation phase is a closely guarded variable for most producers. All the catalyst systems include cobalt and manganese acetates with a bromine-based promoter; however, the exact make-up is proprietary information. The crude TA is contaminated with 4-carboxyenzaldehyde, a by-product of the oxidation process. This contaminant must be removed by purification because it imparts an undesirable color to the crude TA. The by-product contaminant is removed and the crude TA is purified by catalytic hydrogenation. The catalyst used is platinum based

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PTA Applications and, again, is proprietary. The other parts of the process are involved with recycling the acetic acid and with treating the vent gases through scrubbing and incineration.

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PTA Applications 2.

Market Profile

2.1 Market Drivers and Growth There are four principal product groups that use almost all the PTA produced. The distribution of use by these groups is shown in Exhibit 1. Exhibit 11 Exhibit Exhibit Exhibit 11 Uses of of PTA PTA Uses Uses PTA Uses ofof PTA Engineering plastics 3%

Polyester films 7%

PET bottle resins 15% Polyester fibers 75%

Specific applications within the product groups shown above include: • • • • • • • • • • • • • • • • • •

Easy-care apparel fabrics Blended apparel fabrics Carpeting Upholstery fabrics Soft drink containers Boil-in-bag food pouches Microwavable food containers Blister packaging Lightweight body armor Automotive body panels X-ray and microfilms Magnetic recording tape Electrical insulation Appliance and power tool housings Lawn furniture Tire belting Sporting goods Aerospace parts

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2-1

PTA Applications It is evident that the demand for PTA is driven, in large part, by consumer spending. The overall growth in global GDP will be the principal factor determining the growth in demand for PTA. The mid-1990’s saw a dramatic increase in PTA production capacity. This resulted in significant overcapacity and depressed pricing. However, indications are that the bottom of the market probably occurred in mid-1997 and pricing has started to recover. Several expansion projects were put on hold, but these are becoming active again plus new units are being planned. However, it should be noted that the acquisition of Amoco by BP may have an affect on scheduled expansion projects. Overall, a growth rate of 6-8% in demand for PTA is projected, at least through 2003. One factor that will influence this growth rate is the development of new uses for PET. Test marketing has begun on PET beer bottles. If this application finds market acceptance, PET growth will accelerate. The location of PTA plants is usually determined by the location of polyester resin facilities. Almost all PTA production is captive with Amoco Chemicals being the only significant merchant supplier. Also, most of the planned expansion in PTA production is in the developing regions. 2.2

Competition

The usual competitors for ANSI/ISO business are factors in PTA projects. These include ITT-Goulds, IDP, and KSB with the Sterling Group (Labour, Peerless), Sulzer, and Ebara appearing occasionally. Flowserve chemical process pumps have established a reputation for reliable service in many critical and demanding applications in the PTA production process. With Flowserve’s global presence, the company is well positioned to serve this market in those regions of the world where growth is projected. The PTA market is very competitive and Flowserve chemical process pumps offer unique features that will benefit end-users through improved reliability. The competitive advantages will be highlighted in Section 3.3.

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PTA Applications 3.


3.1 Flowserve Sales PTA production is a global business with estimated annual output of about 14.7 million metric tons (t). Exhibit 2 below shows the global distribution of the output:

Exhibit 22 Exhibit Global PTA Production Global PTA Production

Latin America 6%

Asia Pacific 64%

North America 19%

Europe 11%

In Appendix A, there are tables for the four regions shown in Exhibit 2 listing the global producers of PTA. Two companies, Amoco and DuPont, possess about 48% of the existing production capacity and represent about 38% of the projected expansions. DuPont has become a major player in PTA production through the purchase of ICI’s polyester business. As alliance partners, these companies represent some real potential for Flowserve chemical process pumps. However, it should be noted that in the developing regions, where much of the expansions will take place, the alliances are not rigidly enforced and success will largely depend on local efforts. The tables in Appendix A show planned expansions totalling 8.9 million metric tons (t). Of these planned expansions, 50% (excluding Amoco and DuPont) is located in the Asia Pacific region. This represents both a significant opportunity and a sizeable challenge. 3.2 Decision Makers New plants and major expansions are often handled by an engineering firm and the project manager and rotating equipment expert are key individuals. Many times, enduser personnel are part of the project team and final authority for equipment purchases may fall with the senior end-user person. For in-house projects, the plant engineering manager will be a key individual. Also, there may be a materials or corrosion engineering group that will have input particularly regarding the materials of construction.

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3-1

PTA Applications For MRO1 purchases, plant maintenance is a key area. Again, however, plant materials personnel can be influential particularly if the plant has experienced corrosion problems. Also, some plants receive guidance from a corporate materials group relating to corrosion problems and contact with these individuals can be beneficial. Finally, one can never overlook the purchasing function at the plant level. 3.3 Competitive Advantage of Flowserve Chemical Process Pumps The principal competitive advantage is the company’s in-depth involvement with pump selection and configuration for PTA plants. As the primary supplier of chemical process pumps to Amoco, the recognized leader in PTA production, valuable experience has been obtained. In addition to experience in pump selection and configuration, Flowserve chemical process pumps offer some unique features to assist end-users in extending pump life and improving pump performance. These include: • • • • •

Mark III reverse vane impeller ANSI 3A power end SealSentry mechanical seal chambers Baseline™ Pre-Engineered Baseplates Sealless pump technology

The Mark III reverse vane impeller offers significant operational benefits. With only one critical setting for the impeller, optimal pump performance can be established with a new installation and is easily restored with a simple impeller clearance adjustment. Also, the reverse vane design reduces NPSHR and cavitation problems resulting in much longer pump and mechanical seal life cycles. Finally, the Mark III reverse vane design makes the rear cover/seal chamber the primary wear surface, a much less costly part than the casing which is the wear surface for open impeller designs. The ANSI 3A power end positively seals the bearings and bearing lubricant from any potentially harmful conditions existing in the plant thus prolonging bearing life. The family of SealSentry seal chambers allows the customer to choose a design to maximize seal life and minimize operating costs. The FM (Flow Modifier) series of seal chambers provides protection for the seal and permits the use of single seals without an external flush. The CBL design offers an oversize chamber which permits excellent access to the seal by an external flush which leads to efficient cooling. Baseplate selection is critical to reducing internal pump stress and vibration thus prolonging Mean Time Between Planned Maintenance (MTBPM). Baseline™ PreEngineered Baseplates meets the needs of each customer. For all Amoco PTA plants, the Type E heavy-duty baseplate is used to assist in extending MTBPM in these critical applications. Sealless pumps have not found widespread acceptance, to date, in PTA operations. One reason is the presence of solids in many of the services. However, there are some services where sealless technology would be appropriate. The Flowserve family of sealless pumps can offer operational advantages in many of these services. 1


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3-2

PTA Applications 3.4

Guidelines for Mechanical Seals

Many of the services in PTA production involve liquids with solids present. These seals are normally flushed from an external source. Also, there is concern about emissions and this must be factored into seal selection. Although gas seals have not found widespread use, to date, in PTA plants, there is a trend toward this type seal in the upstream para-xylene operations and this may be extended to include the PTA operations. Secondary elastomeric seals must be suitable for the liquids handled. Many of the liquids will attack Viton and alternate elastomers must be used. Because of the nature of the PTA process, the recommendations of a Flowserve FSD sealing specialist should be sought. 3.5 Plant and Pump Details There are some common services in all PTA plants that require the same type pump configuration (materials, mechanical seals, flush plans, etc.). In Section 4, Pump Recommendations, these services will be listed and proven pump configurations will be presented. Applications for other types of Flowserve pumps will be presented in Appendix B.

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PTA Applications 4.



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PTA Applications 4.1 Introduction to Pump Recommendations There are a number of common services in all PTA plants. These services are shown below with a listing of the major pump options used in these services. Also shown are some common pump descriptions used for these services (Appendix B shows an alphabetical listing). After the common services is a listing of some other specific services found in most plants. 4.2

Common Services

4.2.1 Terephthalic Acid (TA), Acetic Acid (HAC), Water Comment: This service contains solids (usually catalyst); however, it is not considered abrasive. Pump Material: CF-8M (316 SS), Titanium used when temperature exceeds about 270oF (132oC). Casing Modifications: Raised face flanges, casing drain (flanged, socket welded with valve). Seal Chamber: CBL (external flush used), jacketed CBL for higher temperatures. Bearing Housing: ANSI 3A, cooling coil added for higher temperatures. Mechanical Seal: Single cartridge (carbon/silicon carbide faces, Teflon or Kalrez secondary seals, 316 SS or Hastelloy C metal parts). Seal Flush System: ANSI Plan 7332 (injection of clean, cool liquid from external source). Baseplate: Type E (reinforced). Specific TA, HAC, Water Services: Pump Description

Operating Temperature 197 F (91oC) 156oF (68o) 200-218oF (93-103oC) 197oF (91oC) 273oF (133o) 129-149oF (53-65oC) 129-149oF (53-65oC) 90-122oF (32-50 oC) o

TA Filter Feed TA Filtrate Dry Scrubber Circulation Slurry Return Solvent Stripper Circulation (Ti pump) CRU Centrifuge Feed CRU Mother Liquor CRU Condensate Removal

4.2.2 Terephthalic Acid (TA), Water Comment: This service contains solids; however, it is not considered abrasive. Pump Material: CF-8M (316 SS).

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PTA Applications Casing Modifications: Raised face flanges, casing drain (flanged, socket welded with valve). Seal Chamber: CBL (external flush used), jacketed CBL for higher temperatures. Bearing Housing: ANSI 3A. Mechanical Seal: Single cartridge (carbon/silicon carbide faces, Teflon or Kalrez secondary seals, 316 SS or Hastelloy C metal parts), balanced component seal used for high temperature centrifuge feed pumps. Seal Flush System: ANSI Plan 7332 (injection of clean, cool liquid from external source). Baseplate: Type E (reinforced). Specific TA, Water Services: Pump Description PTA Solids Filter Feed Filtered Mother Liquor Residue Vent Scrubber Circulation Pressure Centrifuge Feed (jacket seal chamber) PTA Filter Feed Mother Liquor PTA Filtrate

Operating Temperature 212oF (100oC) 212oF (100oC) 149-230oF (65-110oC) 212oF (100oC) 305oF (151oC) 192oF (88oC) 212oF (100oC) 165oF (73oC)

4.2.3 Acetic Acid (HAC), Water Comment: This service is normally free of solids, but when present an external flush is used. Pump Material: CF-8M (316 SS). Casing Modifications: Raised face flanges, casing drain (flanged, socket welded with valve). Seal Chamber: FML, jacketed for high temperatures, CBL with ANSI Plan 7332. Bearing Housing: ANSI 3A, cooling coil added for higher temperatures. Mechanical Seal: Single cartridge (carbon/silicon carbide faces, Teflon secondary seals, 316 SS or Hastelloy C metal parts). Seal Flush System: ANSI Plan 7321 (by-pass from discharge through orifice and cooler to seal), ANSI Plan 7332 when solids present. Baseplate: Type E (reinforced).

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4-3

PTA Applications Specific HAC, Water Services: Pump Description TA Vacuum Seal Fluid Absorber Circulation Mother Liquor Absorber Top Section Solvent Bottoms (jacketed FML) Dehydration Tower Reflux (Plan 7321) Seal Fluid Dehydrated Solvent PX (para-xylene) Decanter Feed PX Stripper Bottoms (Plan 7321) PTA Acetic Acid Feed

Operating Temperature 131 F (55oC) 104-111oF (40-43oC) 160F (71oC) 90oF (32oC) 241-277oF (116-136oC) 199oF (92oC) 194oF (90oC) 164-194oF (73-90oC) 90oF (32oC) 217oF (102oC) 98oF (36oC) o

4.2.4 Para-xylene Comment: This service is free of solids, but is considered a hazardous fluid. This is a potential application for Guardian and ChemStar MD sealless pumps. Pump Material: CF-8M (316 SS). Casing Modifications: Raised face flanges, casing drain (flanged, socket welded with valve). Seal Chamber: FML. Bearing Housing: ANSI 3A. Mechanical Seal: Double cartridge (carbon/silicon carbide faces, Viton secondary seals, 316 SS metal parts). Seal Flush System: ANSI Plan 7311 (by-pass from discharge through orifice to seal). Baseplate: Type E (reinforced). 4.2.5 Water Comment: There are many types of water services. Some of these contain solids and external seal flushes are used. Pump Material: CF-8M (316 SS), CD-4MCuN. Casing Modifications: Raised face flanges, casing drain (flanged, socket welded with valve). Seal Chamber: FML, jacketed for high temperatures, CBL with ANSI Plan 7332. Bearing Housing: ANSI 3A, cooling coil added for higher temperatures.

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4-4

PTA Applications Mechanical Seal: Single cartridge (carbon/silicon carbide faces, Teflon secondary seals, 316 SS or Hastelloy C metal parts). Seal Flush System: Most water services do not use a seal flush system, ANSI Plan 7321 (by-pass from discharge through orifice and cooler to seal), ANSI Plan 7332 when solids present. Baseplate: Type E (reinforced). Specific Water Services: Pump Description PTA Vacuum Seal Fluid Steam Condensate (CD-4MCuN, jacketed cover) Condensate Collection Wastewater Booster Wastewater Wastewater Feed Wastewater w/NaOH ESW Wastewater Treated Wastewater Wastewater Treatment Cooling Water

Operating Temperature 125oF (51oC) 275oF (135oC) 194-212oF (90-100oC) 126oF (52oC) 80-100oF (26-37 oC) 126-178oF (52-81oC) 110-120oF (43-48oC) 75oF (23oC) 75oF (23oC) 80oF (26oC)

4.2.6 Caustic (Sodium Hydroxide) Comment: There are a number of caustic services with the sodium hydroxide level within the range 5-50%. Caustic is used for wastewater treatment and in scrubbing applications. Caustic services are potential applications for Guardian, ChemStar MD and PolyChem sealless pumps. Pump Material: CF-8M (316 SS). Casing Modifications: Raised face flanges, casing drain (flanged, socket welded with valve). Seal Chamber: FML. Bearing Housing: ANSI 3A. Mechanical Seal: Single cartridge (carbon/silicon carbide faces; Teflon or EPDM secondary seals; 316 SS or Hastelloy C metal parts; flush, vent & drain glands). Seal Flush System: Most caustic services do not use a seal flush system, ANSI Plan 7311 (by-pass from discharge through orifice to seal) used for a few applications, all applications should use a quench to avoid solids accumulation on the faces. Baseplate: Type E (reinforced).

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PTA Applications 4.3 Specific Applications There are a number of specific applications involving only a few pumps. In general, these pumps are of the general configuration shown above. Below is a listing of these pumps with any significant deviation from the general configuration. 4.3.1 Sodium Formate Description: Sodium Formate Transfer, 104oF (40oC) Sodium Formate Charge, 78oF (25oC) Rear cover: FML (no seal flush required). Mechanical Seal: Single cartridge (carbon/silicon carbide faces, Teflon secondary seals, Hastelloy C metal parts). 4.3.2 Sodium Formate, Sodium Bromide, Water Description: Quench Section Recirculation, 162-183oF (72-83oC). Rear cover: FML (no seal flush required). Mechanical Seal: Single balanced (carbon/silicon carbide faces, EPDM secondary seals, Alloy 20 metal parts). 4.3.3 Sodium Formate, Sodium Bromide, Sodium Bicarbonate, Water Description: Scrubbing Section Recirculation, 104oF (40oC). Rear cover: FML (no seal flush required). Mechanical Seal: Single balanced (carbon/silicon carbide faces, EPDM secondary seals, Alloy 20 metal parts). 4.3.4 Hydrobromic Acid Description: HBr Charge, 81oF (27oC). Pump Type: Nonmetallic (Fluoropolymer lined). Mechanical Seal: Double (carbon/tungsten carbide faces, EPDM secondary seals, Hastelloy C metal parts). Seal Flush System: ANSI Plan 54 (circulation of clean liquid from external source). 4.3.5 Lube Oil, Water Description: Compressor Area Oily Sewer, 99oF (37oC). Rear cover: FML (no seal flush required). Mechanical Seal: Single cartridge (carbon/silicon carbide faces, Teflon secondary seals, Hastelloy C metal parts).

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PTA Applications Appendix A PTA Producers North America

COMPANY

PLANT LOCATION

Amoco

Cooper River, SC Decatur, AL Cape Fear, NC Columbia, SC Kingsport, TN Wilmington, NC

DuPont Eastman Hoechst (Cape Ind.)

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OUTPUT (thousands t) Current Expansion 750 1,015 545 270 80 90

500 --115 160 --

PTA Applications Appendix A PTA Producers Latin America OUTPUT (thousands t) Current Expansion

COMPANY

PLANT LOCATION

Amoco-Petrocel (Temex) Amoco/Rhône-Poulenc (Rhodiaco) Rhône-Poulenc (Rhodia-Ster) Petrocel

Cosoleacaque, Mexico

515

90

Paulina, Brazil

130

125

Bahia, Brazil

120

70

Altamira, Mexico

50

--

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PTA Applications Appendix A PTA Producers Europe COMPANY

PLANT LOCATION

Amoco Dupont (ICI) Eastman EniChem Int. Quimica Petkim Petro. Und Kraftstoffe Sabic (Ibn Rushd)

Geel, Belgium Wilton, UK Rotterdam, Netherlands Ottana, Italy San Roque, Spain Aliaga, Turkey Schwedt, Germany Yanbu, Saudia Arabia

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OUTPUT (thousands t) Current Expansion 370 550 -90 200 70 65 350

500 485 290 -150 --350

PTA Applications Appendix A PTA Producers Asia Pacific OUTPUT (thousands t) Current Expansion

COMPANY

PLANT LOCATION

Amoco Amoco (Capco j.v.) Amoco (j.v.) Amoco-Mitsui Amoco-Samsung ATV Petro. Bakrie Kasei Dae Han

Kuantan, Malaysia Kaohsiung, Taiwan Zhuhai, China Merak, Indonesia Ulsan, Korea Utar Pradesh, India Serang, Indonesia Pusan, Korea Tong Yang, Korea Port Quasim, Pakistan Kuannyin, Taiwan

500 1420 --850 120 250 250 --400

100 -250 350 --250 -250 400 500

Llan Hsien, Taiwan Ulsan, Korea Yeochon, Korea Kitakyushu, Japan Matsuyama, Japan Kuga-gun, Japan Rayong, Thailand Mizushima, Japan Palembang, Indonesia Patalganga, India Ulsan, Korea Nanjiing, China Shanghai, China Yizheng, China Urumiqui, China Beijing, China Liaoyang, China Tokai, Japan Tainan, Taiwan Map Ta Phut, Thailand

450 850 480 270 350 550 -155 225 230 -450 250 250 75 35 -250 420 350

250 450 350 ---350 --400 300 -----225 -700 900

ICI DuPont (ICI)-Far East. Textiles Formosa Plastics Kohap Petro. LG-Caltex (Samnam) Mitsubishi Kagaku Mitsui Sekka Mitsui-Siam Cement Mizushima Aroma Pertamina Reliance Samsung General State owned

Toray Industries Tuntex Petro.

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PTA Applications Appendix B Alphabetical Listing of Pump Descriptions Pump Description

Pump Service

Absorber Circulation Absorber Top Section Condensate Collection CRU Centrifuge Feed CRU Condensate Removal CRU Mother Liquor Dehydration Tower Reflux Dry Scrubber Circulation ESW Wastewater Filtered Mother Liquor Mother Liquor Mother Liquor Pressure Centrifuge Feed PTA Acetic Acid Feed PTA Filter Feed PTA Filtrate PTA Solids Filter Feed PTA Vacuum Seal Fluid PX (para-xylene) Decanter Feed PX Stripper Bottoms Residue Slurry Return Solvent Bottoms Solvent Stripper Circulation (Ti pump) Steam Condensate TA Filter Feed TA Filtrate TA Vacuum Seal Fluid Treated Wastewater Vent Scrubber Circulation Wastewater Wastewater Booster Wastewater Feed Wastewater Treatment Cooling Water Wastewater w/NaOH

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HAC, Water HAC, Water Water TA, HAC, Water TA, HAC, Water TA, HAC, Water HAC, Water TA, HAC, Water Water TA, Water TA, Water HAC, Water TA, Water HAC, Water TA, Water TA, Water TA, Water Water HAC, Water HAC, Water TA, Water TA, HAC, Water HAC, Water TA, HAC, Water Water TA, HAC, Water TA, HAC, Water HAC, Water Water TA, Water Water Water Water Water Water

Page No. 4-4 4-4 4-5 4-2 4-2 4-2 4-4 4-2 4-5 4-3 4-3 4-4 4-3 4-4 4-3 4-3 4-3 4-5 4-4 4-4 4-3 4-2 4-4 4-2 4-5 4-2 4-2 4-4 4-5 4-3 4-5 4-5 4-5 4-5 4-5

PTA Applications Appendix C Other Pump Applications The focus of this manual is on the application of Flowserve Chemical Process pumps in PTA operations. However, there are potential applications for other types of Flowserve pumps. There are applications like some of those listed for Flowserve Chemical Process pumps but at higher pressures (1250 psi [90 kg/cm2] discharge pressure) and these applications use API pumps. There are also requirements for very large pumps to handle cooling tower, chiller, and river water plant feed services. Finally, there are typical utilities applications like boiler feed water services.

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Titanium Dioxide (TiO 2) Applications Table of Contents Page Number 1.

Introduction 1.1 Rationale and Methodology 1.2 The PTA Process

2.

1-1 1-1


3.

2-1 2-2

Flowserve Experience 3.1 Flowserve Sales 3.2 Decision Makers 3.3 Competitive Advantages of Flowserve Chemical Process Pumps 3.4 Guidelines for Mechanical Seals 3.5 Plant and Pump Details

4.

3-1 3-1 3-2 3-3 3-3

Pump Recommendations 4.1 Introduction to Pump Recommendations 4.2 Slurry Applications 4.3 Other Applications

4-2 4-2 4-3

Appendix A Appendix B

A-1 B-1

TiO 2 Producers Other Pump Applications

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Titanium Dioxide (TiO 2) Applications Exhibits Page Number 1.

Sulfate Process

1-2

2.

Chloride Process

1-4

3.

Uses of TiO2

2-1

4.

Global Capacity and Demand for TiO2

3-1

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Titanium Dioxide (TiO 2) Applications 1.

Introduction

1.1 Rationale and Methodology Titanium dioxide (TiO 2) is a bright, white powder made from titanium bearing ores that has the power to pigment virtually anything. The properties that make it such a good pigmenting agent include brightness, opacity, and durability. Flowserve chemical process pumps find widespread use in TiO 2 production. The applications found in a typical TiO 2 plant present a broad range of materials and operational challenges including corrosion, erosion, erosion/corrosion, product purity, and control of emissions. Because Flowserve can offer such a broad range of materials and because of the applications expertise acquired through close collaboration with the major TiO 2 producers, Flowserve chemical process pumps are standard components in most TiO 2 production facilities. Production of TiO 2 is global with many participants; however, six producers account for about 70% of the output. These six are: Dupont, Tioxide (part of ICI), Millenium Inorganic Chemicals (formerly SCM Chemicals), Kronos (part of NL Industries), Kemira, and Kerr-McGee. Flowserve chemical process pumps enjoy widespread use in TiO 2 production. Growth in demand for TiO 2 is forecast to be about 3% per year over the next five years and there may not be much expansion since there is excess capacity at this time. However, the processes and services involved in producing TiO 2 result in significant after-market opportunities so this manual is offered as a tool to increase familiarity with this key chemical and its manufacturing technology. Pump configurations that have given dependable service will be given. Finally, features and materials unique to Flowserve chemical process pumps will be highlighted along with the benefits these features provide to end-users. 1.2 Production Processes There are two processes used to produce TiO 2: the sulfate process and the chloride process. Below are brief descriptions and discussions of each. Exhibit 1 is a simplified schematic of the sulfate process. In this process, ilmenite ore is digested in hot concentrated sulfuric acid. The reaction mass consists of soluble sulfates of titanium and iron, and this solution is clarified. Crystallization and filtration remove the iron sulfates, and the titanium sulfate is hydrolyzed to form TiO 2. The TiO 2 is calcined, given various aftertreatments to impart specific properties, dried, ground, and packaged. One major disadvantage of the sulfate process is that it produces large quantities of waste materials. However, much effort has been expended to convert some of the

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Titanium Dioxide (TiO 2) Applications Exhibit 2 Chloride Process

Ilmenite ore

Cinder

Sulfuric acid

Digestion

Clarification

Crystallization

Roasting

Sulfuric Acid

Evaporation

Filtration

Concentration

Filtration

Crystallization

Calcination

Aftertreatment

Drying

Grinding

Shipping

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Packing

Titanium Dioxide (TiO 2) Applications waste materials into useable products and to recycle most of the sulfuric acid. The iron sulfates are processed for use in color pigments, fertilizers, and water treatment chemicals. The sulfuric acid that is not recycled is treated to form gypsum, which is used in building materials, and carbon dioxide, which is used by soft-drink manufacturers. The sulfate process utilizes ilmenite ore, the most abundant titanium bearing ore, and produces both crystalline forms of TiO 2: anatase and rutile. The rutile form is generally preferred for paints because it has less chalking and yellowing tendencies and greater hiding power. However, the anatase form is preferred for paper treatment because it has better optical properties. Exhibit 2 is a simplified schematic of the chloride process. This is essentially a two step process. In the first step, the rutile bearing ore is reacted with chlorine and coke at a very high temperature to form an intermediate compound, titanium tetrachloride (TiCl4). The TiCl4 is oxidized to produce TiO 2. The chlorine is recovered and recycled. The TiO 2 receives various aftertreatments to impart the desired properties, is filtered, dried, ground, and packaged. Reference is made in the chloride process to the “black end” of the plant. The ore used is black and before the separation stage of the operation is considered the “black end” of the process. The disadvantages of the chloride process include the handling of toxic materials (chlorine, TiCl4) and the production of only the rutile form of TiO 2. However, this process is much more environmentally friendly, uses less energy, produces much less waste materials, and produces a superior flame-formed rutile crystal. It is believed that over the long-term most TiO 2 production will be through the chloride process.

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Market Profile

2.1 Market Drivers and Growth There are three principal uses for TiO 2 with a fourth “Other” category of general uses. The distribution of use is shown in Exhibit 3.

Exhibit 3

Other 8%

Uses of TiO2

Paper 13%

Coatings 59%

Plastics 20%

Specific applications for TiO 2 include: • Paints (white and colors) • Plastics • Rubber • Paper • Cosmetics • Floor coverings • Glassware and ceramics • Frits for enameling and glazing • Synthetic fibers • Inks • Welding rod • High temperature transducers The demand for TiO 2 is largely driven by consumer spending, and residential and commercial construction. Global GDP growth will be a principal factor in determining demand for TiO 2. No significant TiO 2 capacity has been added since about 1995. In fact, at the end of 1998, capacity exceeded demand by about 20%. However, the market began showing

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Titanium Dioxide (TiO 2) Applications some life in late 1997 and prices began to rise then. It is estimated that global demand will grow about 3.1% per year through 2003 with the major growth being in the Asia/Pacific region (4.8%). Paintmakers account for such a large part of the demand for TiO 2 that consolidation and globalization in the paint industry has forced consolidation in TiO 2 markets. A growing number of the paintmakers are multinationals and they want to be supplied by the same TiO 2 manufacturer worldwide. In the recent past, Rhone-Poulenc sold its European plants to Millenium Inorganic Chemicals. Bayer sold 80% interest in its German and Belgium operations to Kerr-McGee and its Tibras operation in Brazil to Millenium. In late 1997 ICI announced the sale of its Tioxide business unit to Dupont and Kronos. However, due to strong objections from the U.S. Federal Trade Commission (FTC), the tentative deal has been terminated. Just recently, Kemira has expressed interest in Tioxide; however, no firm deal has been announced. For the short term, there may be some smaller acquisitions, but nothing major seems to be planned. It does seem certain that, with time, worldwide capacity will shift toward the Asia/Pacific region. 2.2 Competition The usual global competitors will be factors in TiO 2 projects. These include ITT-Goulds, IDP, and KSB. Flowserve chemical process pumps have a long history of dependable operation at most plant sites of the major TiO 2 producers. Flowserve’s global presence will allow the company to serve this market as it shifts and grows. TiO 2 operations present some unique pumping challenges and Flowserve chemical process pumps can offer some unique features that will benefit the end-users. The ability to assist TiO 2 producers in improving pump reliability will be key because these operations are under tremendous pressure to improve efficiency. In fact, it has been stated that efficiency now drives this market. The features that provide Flowserve chemical process pumps with competitive advantages will be highlighted in Section 3.3.

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3.1 Flowserve Sales TiO 2 production is a global business with estimated annual capacity of 4.4 million metric tons (t)1 and annual demand of 3.6 metric tons (t). Exhibit 4 below shows the global distribution of capacity and demand:

Exhibit 4 Global Capacity and Demand for TiO2 Demand: 3.6 million t.

Asia-Pacific 20%

Capacity: 4.4 million t.

Latin America 5%

Europe, Middle East, Africa 39%

Asia-Pacific 21% USA & Canada 36%


Latin America 4%

USA & Canada 35%

In Appendix A, there are tables for the four regions shown in Exhibit 4 listing the global producers of TiO 2. Six companies account for 70% of the global production capacity and these companies are all recognized customers for Flowserve chemical process pumps. Table 1 below lists these companies and their share of global capacity. Three of these companies (Dupont, Kemira, Kerr-McGee) are alliance customers and, as such, offer special opportunities. However, as the capacity and demand shifts towards the Asia/Pacific region, future success will depend, in large part, on local efforts. 3.2 Decision Makers New plants and major expansions are often handled by an engineering firm and the project manager and rotating equipment expert are key individuals. Many times, enduser personnel are part of the project team and final authority for equipment purchases may fall with the senior end-user person. 1

metric ton (t) = 2,205 lb (1,000 kg)

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Titanium Dioxide (TiO 2) Applications Table 1 Principal Producers and Share of Capacity Company Dupont Tioxide Millenium Kronos Kemira Kerr-McGee Other Total

Capacity, thousands of t 987 590 473 410 301 241 1,344 4,346

Share of Global Capacity 23% 14% 10% 9% 7% 6% 30% 100%

For MRO1 purchases, plant maintenance is a key area and for the TiO 2 processes aftermarket parts sales are significant. Again, however, plant materials personnel can be influential, and some plants receive guidance from a corporate materials group relating to materials reliability issues and contact with these individuals can be beneficial. Finally, one can never overlook the purchasing function at the plant level. 3.3 Competitive Advantage of Flowserve Chemical Process Pumps Flowserve RED has been a principal supplier of chemical process pumps to the major producers of TiO 2 and has gained a wealth of experience in solving the pumping problems confronted in the two processes used in producing this key chemical. In addition to being able to offer recommendations for improving pump performance based on this experience, Flowserve chemical process pumps have some unique features that will lead to extended pump life. These include: • • • • • •

Mark III and Chemstar reverse vane impeller ANSI 3A power end and Chemstar equivalent SealSentry mechanical seal chambers Baseline Pre-Engineered Baseplates Materials for erosive services Sealless pump technology

The Mark III and Chemstar reverse vane impeller offers many operational benefits in TiO 2 plants. Because of the many slurry services found in these processes, many pumps show some erosive wear with time. With the Mark III reverse vane impeller, a simple impeller clearance adjustment can compensate for this wear and restore pump performance to like-new levels. Also, since the Mark III reverse vane design makes the rear cover/seal chamber the primary wear surface, any erosion that occurs is on this less costly component. The environment in many TiO 2 plants can subject pumps to fairly harsh surroundings. The ANSI 3A power end and ISO equivalent positively seals the bearings and bearing lubricant from these surroundings and prolongs bearing life.

1


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Titanium Dioxide (TiO 2) Applications There are many sealing challenges in TiO 2 operations and the family of SealSentry seal chambers provides choices to create a sealing environment that will maximize seal life and minimize operating costs. The FM (Flow Modifier) seal chambers provide protection for the seal in many of the slurry services and they permit the use of single seals without an external flush. For many of the more severe slurry services, dual seals are utilized and the CBL design is ideal for these services. Baseplate selection is critical in reducing internal pump stress and vibration thus prolonging Mean Time Between Planned Maintenance (MTBPM). Baseline  PreEngineered Baseplates offer a range of options to meet the many requirements found in TiO 2 operations. Because of the harsh surroundings encountered in many applications, the Polybase baseplate finds widespread use. In fact, Kemira has standardized on the Polybase design. Other services utilized reinforced designs. Corrosion, erosion, and erosion/corrosion are critical factors in the production of TiO 2. There are many slurry services and many corrosive chemicals are used in the processes. Selection of the materials of construction will significantly influence pump performance and life. The slurry applications offer the greatest challenge in extending pump life. Flowserve chemical process pumps are available in a broad range of materials, both standard and special. CD4MCu offers excellent performance in mild to moderate erosive services. Special materials like DC8 have proven successful in highly erosive services and hard coatings have also extended component life. Later this year, a number of Mark III and Chemstar pumps will be available in high chrome iron, an extremely erosion resistant material. No other manufacturer routinely offers process pumps in this very hard material and this will provide TiO 2 producers with the proven Flowserve chemic al process pump designs in this very erosion resistant alloy. The chloride process produces an intermediate compound, TiCl4, that is a very hazardous and toxic material. This is a natural application for the Flowserve family of sealless pumps and these pumps have been successfully applied on this critical service. There are other chemicals handled in typical TiO 2 operations that may require the use of sealless pumps. 3.4 Guidelines for Mechanical Seals Because of the many slurry applications in TiO 2 production, there are significant sealing challenges. Many of the older pumps were initially supplied with packing and this arrangement is still in use with some units; however, most applications are being converted to mechanical seals. Standard dual seals with an external flush are used for many slurries, but for the more difficult services, slurry seal designs are used. The Sealmatic design has found some used since this approach avoids introducing flush liquid into the process. Because of the severity of many of the services found in the TiO 2 process, the recommendations of a Flowserve FSD sealing specialist should be sought. 3.5 Plant and Pump Details The principal pump application in TiO 2 operations is handling the slurries found at various stages in the processes. These slurries vary in percent solids and present some real pumping challenges. In addition to slurry handling, there are many other applications involving chemicals used during processing, by-products and waste

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Titanium Dioxide (TiO 2) Applications generated, and aftertreatment reagents added to impart specific properties to the TiO 2. In Section 4, Pump Applications, various pump configurations (materials, sealing methods, flush plans, etc.) that have proven successful in TiO 2 plants will be presented. Applications for other types of Flowserve pumps will be presented in Appendix B.

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Titanium Dioxide (TiO 2) Applications 4.1 Introduction to Pump Recommendations By far, slurry handling is the predominant application for Flowserve chemical process pumps in TiO 2 plants. There are widely varying conditions in these slurry handling applications. Specific gravity can range from about 1.00 up to as high as 2.50. Temperatures are usually within the range of ambient to about 200°F (93°C). Erosive wear is a constant concern, but the problems of handling these slurries are compounded by the presence of contaminants. The most serious contamination problem is encountered in the chloride process where some free chlorine can be present. This results in grave erosion/corrosion problems. In addition to the TiO 2 slurries, there are a number of other services requiring Flowserve chemical process pumps. These services include chemicals required in the main processes such as the sulfuric acid used to digest the ore in the sulfate process. There are also many reagents used at various stages of the processes to improve processing characteristics. At the end of the processes, various chemicals are added to the TiO 2 to impart specific properties. Finally, there are by-products and waste that must be handled. Below is a discussion of various Flowserve chemical process pump configurations that have proven successful in many TiO 2 operations. This information should be helpful in understanding Flowserve’s successful involvement in the manufacture of this important chemical. 4.2 Slurry Applications Erosion is the most serious materials problem confronted in TiO 2 production. TiO 2 slurries must be moved through many processing steps in a typical production cycle. Standard horizontal Flowserve chemical process pumps are routinely used to move these slurries, and the company possesses a wealth of knowledge and expertise regarding materials of construction and pump configurations that have provided reliable service in this difficult environment. Pump selection is a critical factor. Operating speeds should be minimized and the operating point should be as near the best efficiency point (BEP) as possible. Below are some specific guidelines for handling TiO 2 slurry pumps: Materials – For standard materials, CD-4MCu (CD4M) is widely used in handling TiO 2 slurries. This material possesses good hardness for erosion resistance and has the corrosion resistance to handle many contaminants. However CN-7M (D20) finds significant use in contaminated slurries where CD-4MCu has inadequate corrosion resistance. For some highly contaminated slurries, titanium (Ti), palladium-stabilized titanium (TiPd), and high silicon iron (D51M) have found use. Some limited use has been made of DC8, Flowserve’s proprietary cobalt-based alloy. This alloy has very good erosion resistance and has corrosion resistance at least equal to CN-7M (D20); however, its major shortcoming is that machining is very difficult so production of pump parts has been limited primarily to impellers. Finally, some components have been supplied with tungsten carbide coatings, but performance with these has been mixed. In the future, high chrome iron wet-end parts will be available. This material has outstanding erosion resistance but fairly poor corrosion resistance so it will not handle

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Titanium Dioxide (TiO 2) Applications contaminated slurries. However, it should be very suitable for the slurries found in the finishing areas. Although not used for pumping the slurries, another material that has found widespread use with TiO 2 slurry pumps is polymer concrete used to produce the Polybase. The Polybase offers the advantage of excellent rigidity plus outstanding corrosion resistance. Sealing – Many older TiO 2 slurry pumps were supplied, and are still operating, with packing. Both standard and abrasive service designs are used. With time the packing is being changed out to mechanical seals, plus all new pumps are generally supplied this way. For some lower concentration slurries, single seals with FML seal chambers are used. In the more concentrated slurries, dual seals are normally specified. Slurry-type dual seals are used in the tougher slurry services. Dual seals are flushed from an external source or a recirculating flush plan may be used. Some Sealmatic pumps are being used in TiO 2 slurries particularly where is important not to introduce flush liquid into the process fluid. The Sealmatic design is normally supplied with a repeller chamber bypass to avoid packing of the solids in the repeller chamber. 4.3 Other Applications There are many other liquids, some of them very corrosive, that must be pumped during the production of TiO 2. These are divided into five categories below and guidelines for handling these chemicals with Flowserve chemical process pumps are presented: 4.3.1 Process Chemicals and Intermediates These chemicals are used in the actual process stream: Sulfuric acid (H2SO4) – This chemical is used to digest the ore in the sulfate process. Because of the concentrations and temperatures of the acid handled in typical TiO 2 operations, CN-7M (D20) is usually suitable. The Polybase is frequently used with sulfuric acid pumps, but due to the highly oxidizing nature of acid above 70% concentration, the standard black Polybase should be replaced with the special GT45 (red) material. The primary concern in mechanical seal selection is corrosion. Alloy 20 seal parts may not be suitable and Hastelloy C is the normal material selected. Above 70% acid concentration, silicon carbide faces are generally used. The FML seal chamber should be used. If dual seals are specified, care must be used in selecting the flush liquid as neither water nor alcohol is suitable. Because this can be a difficult liquid to seal, this is an application where magnetic drive pumps are widely used. The Guardian and ChemStar MD models with CN-7M/Alloy 20 construction are suitable plus the Polychem M series will also be an acceptable alternative. Sodium hydroxide (NaOH) – This chemical is used for pH control. CF-8M and CD-4MCu are commonly used as materials of construction. Single mechanical seals with FML seal chambers are suitable; however, a steam or water quench must be provided to avoid solids build-up on the seal faces. Because of the difficulties encountered in sealing NaOH, this is a common application for Guardian, Chemstar MD, and PolyChem M magnetic drive pumps. Titanium tetrachoride (TiCl4) - This material, called “tickle”, is an intermediate chemical in the chloride process. In the absence of water, this is not a particularly corrosive liquid; however, it is toxic and hazardous, if released. It is handled with standard pumps and

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Titanium Dioxide (TiO 2) Applications elaborate seal systems, but this is a prime candidate for Guardian and Chemstar M magnetic drive pumps. CF-8M/316 SS units are suitable. 4.3.2 Dispersants These chemicals are added to the TiO 2 slurries during processing to improve slurry stability. Below are the general categories of dispersants with a few examples of each: 1. Phosphates – TSP (trisodium phosphate), TSPP (tetrasodium pyrophosphate), TKPP (tetrapotassium pyrophosphate), STPP (sodium tripolyphosphate) 2. Alkali salts – sodium silicate, sodium borate, sodium aluminate 3. Amines (polyamines) – aminoethane, diethylene triamine 4. Amino alcohols – amino methyl propanol, morpholine 5, Polyorganic acid salts – sodium citrate These chemicals are not very corrosive and are generally handled with CF-8M or CD-4MCu. Single seals with FML seal chambers are suitable. 4.3.3 Flocculents These chemicals are added to the TiO 2 slurries to increase the efficiency of filtration. Below are some common flocculents: 1. 2. 3. 4. 5.

Sodium chloride Sodium sulfate Magnesium sulfate Aluminum sulfate Aluminum chloride

CD-4MCu is commonly used, particularly for the chlorides, along with CF-8M to handle these chemicals. Single seals with FML seal chambers are suitable. 4.3.4 End Treatment Chemicals These chemicals are used to impart specific properties to the end product. These properties include drying time, color stability, chalk resistance, compatibility with vehicle solvents, photochemical sensitivity, gloss, and tinting strength. Below are some common end treatment chemicals: 1. 2. 3. 4. 5. 6. 7.

Zinc sulfate Titanium sulfate Sodium silicate Sodium aluminate Phosphoric acid Sulfuric acid Sodium hydroxide

The first four chemicals are normally handled with CF-8M or CD-4MCu. Single seals with FML seal chambers are suitable. Sulfuric acid and sodium hydroxide are covered above. Phosphoric acid can be handled with CF-8M or CD-4MCu. Single seals with 316 SS metal parts are suitable and FML seal chambers are recommended.

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Titanium Dioxide (TiO 2) Applications 4.3.5 Recycling, By-Products, Wastes, Pollution Abatement Some of the most corrosive services in a TiO 2 plant are found in this area. There is one organic chemical used in the recycling part of a chloride plant that is not corrosive. Trichloroethylene (TCE) is used to absorb chlorine that is not reacted with the ore. The chlorine is stripped from the TCE and returned to the process. TCE is not a corrosive chemical and is normally handled with ductile iron (DCI). A single mechanical seal with the FML seal chamber is also used. Other chemicals found in this category include sodium hydroxide (NaOH), hydrochloric acid (HCl), sodium hypochlorite (NaOCl), and contaminated wastewaters. Sodium hydroxide (NaOH) is used in scrubbing gaseous effluents from the chloride process. It reacts with chlorine (Cl2) and forms sodium hypochlorite (NaOCl). The handling of sodium hydroxide is covered above. Sodium hypochlorite is very corrosive chemical. The common metallic material used is titanium, although high silicon iron (D51M) is also suitable. For non-metallics, the fluoropolymers are used. Again sealing is difficult and the PolyChem M series will find use here. Hydrochloric acid is commonly handled with non-metallics like Durcon 730 FRP (fiber reinforced plastic) and the fluoropolymers (PTFE/PFA). If metallic materials are required, then the Hastelloys are normally used. Sealing of HCl is difficult and costly. Either costly single seals are required or dual seals with the attendant flushing requirements are used. Because of the difficulties encountered in sealing HCl, the PolyChem M series pumps will be ideally suited for this service. The contaminated wastewaters are handled with non-metallics and higher alloy metallics. Where applicable, the FRP self-priming pump has found use. Specific knowledge of the wastewater composition is required to select the proper materials.

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Titanium Dioxide (TiO2) Applications Appendix A TiO2 Producers USA and Canada

COMPANY Dupont

Kemira Kerr-McGee Kronos Louisiana Pigment Millenium Inorganics

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PLANT LOCATION De Lisle, MS Edgemoor, DE Antioch, CA New Johnsonville, TN Savannah, GA Hamilton, MS Varennes, PQ (Canada) Lake Charles, LA Ashtabula, OH Baltimore, MD

A-1

OUTPUT (thousands t) Chloride Sulfate 280 128 38 320 91 54 145 55 20 110 104 86 51 44

Titanium Dioxide (TiO2) Applications Appendix A TiO2 Producers Latin America

COMPANY Dupont Tibras Titanio

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PLANT LOCATION Altamira, Mexico Salvador, Brazil

A-2

OUTPUT (thousands t) Chloride Sulfate 100 55

Titanium Dioxide (TiO2) Applications Appendix A TiO2 Producers Europe, Middle East, and Africa

COMPANY Bayer Kemira Kronos

Millenium Inorganics Sachtleben Saudi Arabia-Other Thann et Mulhouse Tioxide

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PLANT LOCATION Antwerp, Belgium Uerdingen, Germany Pori, Finland Rotterdam, Netherlands Gent, Belgium Leverkusen, Germany Nordenham, Germany Fredrikstad, Norway Stallingborough, UK Duisburg-Hamborn, Ger. Le Havre, France Thann, France Calais, France Scarlino, Italy Huelva, Spain Grimsby, UK Greatham, UK Johannesburg, South Africa

A-3

OUTPUT (thousands t) Chloride Sulfate 24 105 90 56 55 105 35 60 31 109 80 65 110 35 110 81 80 80 80 45

Titanium Dioxide (TiO2) Applications Appendix A TiO2 Producers Asia-Pacific

COMPANY China - Other Dupont Hankook India - Other Ishihara Sangyo

PLANT LOCATION Kuan Yin, Taiwan Inchon, Korea Yokkaichi, Japan Jurong, Singapore

Japan - Other Millenium Inorg. Tioxide Tiwest

Bunbury, Australia Telok Kalung, Malaysia Kwinana, Australia

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OUTPUT (thousands t) Chloride Sulfate 113 88 36 22 55 100 42 166 79 50 80

Titanium Dioxide (TiO 2) Applications Appendix B Other Pump Applications The focus of this manual is on the application of Flowserve chemical process pumps in TiO 2 operations. However, there are potential applications for other types of Flowserve pumps. Many plants have their own power plants so there are boiler feed water applications. There may also be requirements for very large pumps to handle various water applications. In addition, it is not uncommon for the sulfate operations to have a captive sulfuric acid plant. These sorts of applications must be sought out at any TiO 2 facility.

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B-1

Hydrocracking Applications Table of Contents Page Number 1.

Introduction 1.1 Rationale and Methodology 1.2 Hydrocracking Process

2.

1-1 1-1


3.

2-1 2-1

Flowserve Experience 3.1 Flowserve Sales 3.2 Decision Makers 3.3 Competitive Advantages of Flowserve Petroleum Process Pumps 3.4 Guidelines for Mechanical Seals 3.5 Operating Unit and Pump Details

4.

3-1 3-1 3-2 3-3 3-3

Pump Recommendations 4.1 Introduction to Pump Recommendations 4.2 Charge Pump and Hydraulic Turbine 4.3 Other Hydrocracking Unit Pumps

4-2 4-2 4-2

Appendix A Appendix B

A-1 B-1

Appendix C

Hydrocracker Units API Material Designations for Pumps and Mechanical Seals Other Pump Applications

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C-1

Hydrocracking Applications Exhibits Page Number 1. Typical Hydrocracker Unit

1-3

2. World Oil Consumption

2-1

3. Global Distribution of Hydrocracking Capacity

3-1

4. Typical Power Recovery Turbine Arrangements

4-4

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Hydrocracking Applications 1.

Introduction

1.1 Rationale and Methodology The petroleum refining industry consists of approximately 700 facilities located around the world. A petroleum refinery is a factory that takes a raw material—crude oil—and turns it into finished products, most notably gasoline but also hundreds of other useful products including diesel fuel, jet fuel, kerosene, and naphtha. Crude oil is a mixture of many different hydrocarbons and small amounts of impurities. The exact composition of crude oils varies significantly depending on their source. Even though the basics of all refineries are the same, these are complex systems with multiple operations and the specific operations found at any given refinery will depend on the properties of the crude oil being refined and the desired product output. Flowserve petroleum process pumps enjoy widespread use in all phases of refining. Because no two refineries are the same, the application requirements present a broad range of pumping challenges. Through long and close collaboration with the major refiners in the world, Flowserve possesses a wealth of applications and problem solving expertise. This manual will look at one downstream process—hydrocracking—in some detail with the goal of increasing familiarity with this key operation. In addition to discussing hydrocracking technology, the manual will present proven pump configurations that have provided reliable, dependable service. Finally, features unique to Flowserve petroleum process pumps will be highlighted along with the benefits these features provide to end-users. 1.2 Hydrocracking Process There are three basic steps in refining: separation, conversion, and treatment. The separation step is essentially fractional distillation where liquids and vapors are separated into components, or fractions, according to weight and boiling point. Some useable products are realized here, but more commonly, the fractions are sent on to the conversion step. The conversion step, also called downstream processing, converts the fractions into intermediate streams that eventually become finished products. Finally, there is the treatment step where streams are carefully combined through blending, purifying, and fine-tuning to produce finished products that meet market demand, customer specifications and government standards. Refiners have spent much time and effort on the conversion step because this is where the money is made in a refinery through the conversion of low value fractions to high value products, primarily gasoline. Common conversion processes include thermal cracking (visbreaking), coking, catalytic cracking, catalytic hydrocracking, hydrotreating, alkylation, isomerization, polymerization, catalytic reforming, solvent extraction, dewaxing, propane deasphalting, and many others. The most commonly used conversion method is cracking. Cracking means decomposition by heat. Heavy (large) hydrocarbon molecules are decomposed, or “cracked”, into lighter (smaller) molecules. Cracking can be performed by heat alone, but the use of a catalyst has largely replaced pure thermal cracking because this results

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Hydrocracking Applications in higher yields of gasoline. Catalytic cracking in the presence of hydrogen, or hydrocracking, is used to process the most difficult to crack fractions. Hydrocracking was developed in 1962 by Chevron. Two factors drove the development of this process: heavy demand for gasoline and the availability of large amounts of byproduct hydrogen from catalytic reformer units. It is the most versatile of the conversion operations and can process a wide range of feedstocks. In addition to producing gasoline, hydrocracking has gained worldwide recognition for the high-quality distillates it produces. And, in this environmentally conscious period, hydrocracking is the best source of low-sulfur, low-aromatics diesel fuel as well as high-smoke-point jet fuel. Exhibit 1 is a simplified schematic of a single-stage hydrocracker unit. The unit utilizes a fixed-bed catalytic cracking reactor operating at pressures up to 3000 psig (210 kg/cm2) and temperatures up to 700oF (370oC). The feedstock is often hydrotreated first to remove impurities (hydrogen sulfide and ammonia) that will poison the catalyst. The hydrocracking catalysts are typically regenerated off-site after two to four years of use. Two-stage systems are also very common. Two-stage configurations can handle a wider range of feedstocks and feed rates with nearly complete conversion. With twostage systems, impurities can be removed in the first stage, replacing hydrotreating, while optimizing catalyst performance and prolonging catalyst life. Hydrocracking technology is being continually improved. It offers the capability for upgrading existing facilities to produce lighter products. For grassroots facilities, it is a common process selection because it offers so much operating flexibility.

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EXHIBIT 1 TYPICAL HYDROCRACKER UNIT PROCESS GAS

MAKEUP HYDROGEN

LIGHT NAPTHA

HYDROGEN RECYCLE

R E A C T O R FURNACE

FEED PUMP

MOTOR

HP S E P A R A T O R

SOUR WATER

1-3

HEAVY NAPTHA

KEROSENE JET FUEL

DIESEL

HYD. TURBINE

RECYCLE

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LP S E P A R A T O R

F R A C T I O N A T O R


Market Profile

2.1 Market Drivers Refiners today are finding that increased demand for high-quality transportation fuels is forcing them to convert a higher percentage of crude oil to lighter products. One forecast predicts that gasoline supplies are adequate and demand will grow about 2% per year through 2005. However, demand for other transportation fuels—most notably jet and diesel fuels—will grow much more rapidly through this period at a rate of 5-6% per year. For many refiners, expanding hydrocracking capacity is one way to meet this growing demand. With hydrocracking, refiners can maintain profitability without sacrificing yield or product quality. Obviously, petroleum refining is a global endeavor. Today, much of the hydrocracking capacity is located in the USA. However, future growth will be elsewhere. Exhibit 1 shows crude oil consumption now and the projected consumption in 2005 for four regions of the world. Exhibit 2

Million barrels per day

World Oil Consumption 35 30 25 20 15 10 5 0

1999 2005

USA & Canada

Europe, Middle East, Africa

Asia-Pacific Latin America

Projected growth rates in consumption in these regions between now and 2005 are: USA & Canada Europe, Middle East, Africa Asia-Pacific Latin America

9% 12% 19% 23%

2.2 Competition The primary global competitors in hydrocracker projects are IDP and Sulzer. Regional competitors are Ebara and Shin-Nippon in the Asia-Pacific region and David Brown in Europe, Middle East, Africa region. Flowserve petroleum process pumps have a long history of dependable service in petroleum refineries all over the world. Flowserve’s global presence will allow the

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Hydrocracking Applications company to participate in the refining market as hydrocracker units are de-bottlenecked and added to refineries worldwide. Petroleum refining is a very competitive and costconscience business and the company’s ability to assist refiners in improving pump reliability will be key as this can lead to improved profitability. The features that provide Flowserve petroleum process pumps with competitive advantages will be highlighted in Section 3.3.

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3.1 Flowserve Sales Hydrocracking capacity worldwide is about 3.75 MMbpd (million barrels per day). The global distribution of this capacity is shown in Exhibit 3. In Appendix A, there are tables for the four regions shown in Exhibit 3 listing the locations and capacities of the existing hydrocracking units. Exhibit 3 Global Distribution of Hydrocracking Capacity

Latin America 4%

Asia-Pacific 20%

USA & Canada 43% Europe, Middle East, Africa 33%

As was shown in Exhibit 2, the growth in oil consumption is projected to be greatest in Latin America and the Asia-Pacific regions, locations with the lowest hydrocracking capacity. These two regions of the world will likely see growth in hydrocracking capacity over the next five years. 3.2 Decision Makers The charge pump is a key component in any hydrocracker unit. Even though an engineering firm may handle the design and construction of the unit, the end-user will generally be heavily involved in the selection of the charge pump supplier. Also, if a hydraulic turbine is part of the system, this component will most likely come from the same supplier as the charge pump since they will be operated together. Past experience with hydrocracker applications will weigh favorably for potential charge pump and hydraulic turbine suppliers. The buying decision involving the process pumps is much more subject to competitive pressures, although here again, experience and installed base are important considerations.

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Hydrocracking Applications 3.3 Competitive Advantages of Flowserve Petroleum Process Pumps Flowserve has achieved a reputation for supplying high quality, dependable pumping equipment to the petroleum industry and has gained a wealth of experience through handling the critical services found in refinery applications. The most critical pump service in a hydrocracker unit is the charge feed pump. This pump must be able to handle very high pressures and temperatures, and multistage, double-case pumps are normally used. The Flowserve HDO pump is the ideal selection for this critical service. The HDO design, which is fully compliant with API 610 (8th Edition), offers some unique features that will increase pump performance and reliability. These features include: • • •

Axially split inner casing design Special bearing construction First-stage, double-suction impeller design

The axially split inner casing design offers many operational benefits in hydrocracker units: + the design is inherently safe at any pressure. + there is uniform heat distribution throughout the pump inner case. + all running clearances remain concentric due to special inner casing machining. + the fully assembled rotating element is balanced as a unit. + the axial hydraulic loads are inherently balanced. The special bearing construction consists of double-acting, pivot-shoe thrust bearings and self-aligning, lubricated babbitt-lined radial bearings. The construction offers the benefits of: + maximum reliability. + reduced maintenance costs. + low noise levels. Finally, the optional first-stage, double-suction impeller design gives the user the benefits of: + low NPSH requirements. + elimination of need for a separate booster pump. The other pump applications in hydrocracker units can normally be handled by singlestage, overhung and between bearings API process pumps. The Flowserve overhung designs combine a long history of expertise and experience. The SCE family of pumps, which are fully compliant with API 610 (8th Edition), can handle a very broad range of single stage applications. Also, the very large installed base of these pumps provides a history of successful performance in all types of petroleum services. 3.4 Guidelines for Mechanical Seals There are many challenging mechanical seal applications in a hydrocracker unit. In fact, seal failures were a significant problem with early hydrocracker units, but new seal developments, particularly the introduction of metal bellows designs, have lead to acceptable seal life. High temperature is the major cause of seal problems. Proper seal selection is critical to trouble-free operation and because of the severity of many of the applications, the advice of a Flowserve FSD sealing specialist should be sought.

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3-2

Hydrocracking Applications 3.5 Operating Unit and Pump Details The critical application in a hydrocracker unit is the charge pump. If a hydraulic turbine is used, it will be coupled to the charge pump and it also represents a critical component in the system. However, the process pumps, water handling pumps, and any auxiliary pumps must provide reliable service for the unit to operate dependably and profitably. In section 4, Pump Applications, proven pump configurations (materials, seals, flush plans, etc.) will be presented.

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Hydrocracking Applications 4.1 Introduction to Pump Recommendations The key pump in a hydrocracking unit is the charge pump; however, there are a number of other services requiring Flowserve petroleum process pumps. Below is a discussion of typical Flowserve petroleum process pump applications and representative pump configurations that have proven successful in hydrocracking units. This information should be helpful in understanding Flowserve’s involvement in this critical refinery process. 4.2 Charge Pump and Hydraulic Turbine Typical operating conditions for the reactor charge pump in a hydrocracking unit are 450oF (232oC) liquid temperature and 3,000 psig (207 bar) discharge pressure. Because of the high temperature and pressure encountered in this application, a double case, multistage pump is normally used. The Flowserve petroleum process pump best suited for this service is the Byron Jackson Type HDO. The API 610 material designation normally specified for this service is either C-6 or A-8 (see Appendix B). Mechanical seal selection is key to trouble-free operation of this critical pump. Metal bellows seals are normally used with an API 610 seal code of BSTRN (see Appendix B). An auxiliary sealing device comprised of a close clearance floating carbon throttle bushing is also used. An API Plan 32 seal flushing system and an API Plan 62 auxiliary system with an anti-coking device are included. It is not uncommon practice to utilize a hydraulic turbine (also called a power recovery turbine or PRT) in conjunction with the reactor charge pump. The turbine develops power from the pressure reduction of the liquid leaving the high-pressure separator. The power developed by the turbine is used to operate the reactor charge pump. From onethird to one-half the power required by the reactor charge pump can come from the turbine. Exhibit 4 shows schematics for two typical PRT arrangements. The turbine is essentially the same as the reactor charge feed pump except the liquid enters the discharge and exits the suction. The same pump configuration detailed above for the reactor charge feed application would be used for the hydraulic turbine. 4.3 Other Hydrocracking Unit Pumps There are a number of other applications with the hydrocracking unit and these are listed below with comments relative to typical configurations: 4.3.1 Recycle Pump Operating conditions: 670 oF (354oC), 120 psig discharge pressure. Recommended pump: Byron Jackson Type SCE, API material code – C-6 or A-8. Mechanical seal: Metal bellows, API code – BSTRX, close clearance floating carbon throttle bushing. Auxiliary seal systems: API Plan 32, API Plan 62 with anti-coking device. 4.3.2 Splitter Charge Pump Operating conditions: 450 oF (232oC), 200 psig discharge pressure. Recommended pump: Byron Jackson Type SCE, API material code – S-5 or S-6. Mechanical seal: Metal bellows, API code – BSTRX, close clearance floating carbon throttle bushing. Auxiliary seal systems: API Plan 32, API Plan 62 with anti-coking device.

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4-2

Hydrocracking Applications 4.3.3 Stabilizer Feed Pump Operating conditions: 450 oF (232oC), 200 psig discharge pressure. Recommended pump: Byron Jackson Type TSHO, API material code – S-5. Mechanical seal: Pusher seal, API code – BSTFX, close clearance floating carbon throttle bushing. Auxiliary seal systems: API Plan 11, API Plan 62 with anti-coking device. 4.3.4 Stabilizer Reflux Pump Operating conditions: 100 oF (38oC), 250 psig discharge pressure. Recommended pump: Byron Jackson Type SCE, API material code – S-5. Mechanical seal: Pusher seal, API code – BSTFM, close clearance floating carbon throttle bushing. Auxiliary seal systems: API Plan 11. 4.3.5 Heavy Naphtha Pump Operating conditions: 235 oF (113oC), 140 psig discharge pressure. Recommended pump: Byron Jackson Type SCE, API material code – S-5. Mechanical seal: Pusher seal, API code – BSTFM, close clearance floating carbon throttle bushing. Auxiliary seal systems: API Plan 11, API Plan 62 with anti-coking device. 4.3.6 Kerosene Pump Operating conditions: 390 oF (199oC), 130 psig discharge pressure. Recommended pump: Byron Jackson Type SCE, API material code – S-5. Mechanical seal: Metal bellows, API code – BSTRN, close clearance floating carbon throttle bushing. Auxiliary seal systems: API Plan 11, API Plan 62 with anti-coking device. 4.3.7 Diesel Pump Operating conditions: 500 oF (260oC), 430 psig discharge pressure. Recommended pump: Byron Jackson Type SCE, API material code – S-5. Mechanical seal: Metal bellows, API code – BSTRN, close clearance floating carbon throttle bushing. Auxiliary seal systems: API Plan 11, API Plan 62 with anti-coking device.

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4-3


EXHIBIT 4 TYPICAL POWER RECOVERY TURBINE ARRANGEMENTS

FEED PUMP

ELECTRIC MOTOR

CLUTCH

POWER RECOVERY TURBINE

Arrangement 1

ELECTRIC MOTOR

GEAR

FEED PUMP

CLUTCH

Arrangement 2

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POWER RECOVERY TURBINE

Hydrocracking Applications Appendix A Hydrocracker Units - USA and Canada LOCATION COUNTRY Canada

COMPANY

STATE (PROV.)

CAPACITY, CITY

Mbpd1

Petro-Canada

Alberta

Edmonton

18.7

Irving Oil

New Brunswick

St. John

29.7

North Atlantic Ref.

Newfoundland

Comeby Chance

31.5

Imperial Oil

Ontario

Sarnia

13.0

Petro-Canada

Ontario

Mississauga

10.3

Shell Canada

Ontario

Sarnia

6.8

Sunoco

Ontario

Sarnia

24.1

Consumer Co-op

Saskatchewan

Regina

46.0

Yabucoa

15.6

Alaska

Kenai

12.5

Atlantic Richfield

California

Carson

43.0

Chevron

California

El Segundo

113.0

California

Richmond

109.0

Equilon

California

Wilmington

26.6

California

Bakersfield

18.9

California

Martinez

33.8

Exxon

California

Benicia

34.0

Mobil

California

Torrance

23.9

Tosco

California

Los Angeles

24.8

California

San Francisco

64.0

Motiva

Delaware

Delaware City

17.1

Tesoro

Hawaii

Kapolei

18.0

Clark

Illinois

Blue Island

10.0

Citgo

Louisiana

Lake Charles

36.0

Conoco

Louisiana

Westlake

29.0

Exxon

Louisiana

Baton Rouge

22.5

Mobil

Louisiana

Chalmette

19.6

Motiva

Louisiana

Convent

45.0

Louisiana

Norco

36.0

Chevron

Mississippi

Pascagoula

142.0

Exxon

Montana

Billings

4.5

BP Amoco

Ohio

Toledo

25.2

Clark

Ohio

Lima

24.0

Sun

Ohio

Toledo

28.2

Gary-Williams Eng.

Oklahoma

Wynnwood

4.5

Tosco

Pennsylvania

Trainer

20.0

BP Amoco

Texas

Texas City

114.0

Costal

Texas

Corpus Christi

10.5

Exxon

Texas

Baytown

26.0

Mobil

Texas

Beaumont

53.0

Motiva

Texas

Port Arthur

17.8

Shell Deerpark

Texas

Deerpark

64.0

Ultramar Dia. Sham.

Texas

Three Rivers

23.0

Texas

Sunray

28.0

Valero Energy

Texas

Corpus Christi

32.4

Atlantic Richfield

Washington

Ferndale

50.0

Ergon-West Virginia

West Virginia

Newell

4.8

Puerto Rico

Sun

United States

Tesoro Alaska Petro.

1

Mbpd = 1,000 barrels per day

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A-1

Hydrocracking Applications Appendix A Hydrocracker Units Latin America

COUNTRY Argentina Chile Mexico Trinidad Venezuela 1

COMPANY YPF, S.A. Petrox Ref. De Petro. Concon Pemex Petro. Co. of Trinidad Corpoven


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LOCATION Lujan de Cuyo Talcahuano Concon Salamanca Pointe-a-Pierre Judibana Falcon

CAPACITY, Mbpd1 26.0 9.0 10.0 18.5 47.0 52.1

Hydrocracking Applications Appendix A Hydrocracker Units Europe, Middle East, and Africa CAPACITY, COUNTRY

COMPANY

LOCATION

Mbpd1

Bahrain

Bahrain Petro.

Sitra

Congo

Coraf

Pointe-Noire

2.0

Croatia

Ina Ref.

Rijeka

11.9

Czech Republic

Chemopertrol

Litvinov

25.0

Finland

Neste Oy

Porvoo

16.0

FSU

P.O. Naftan Ref.

Slavneft-Mozyr, Belarus

12.0

Bashneftekhimzavody

Ufaneftekhim, Russia

19.2

Sibneft

Omsk, Russia

19.2

France

Ste. Fran. Des Petroles

Lavera

15.3

Germany

DEA Mineraloel

Wesseling

31.0

Deutsche Shell

Godorf

36.0

Veba Oel/Ruhr Oel

Gelsenkirchen

30.0

Wintershall

Lingen

23.0

Greece

Hellenic Petro.

Aspropyrgos

28.0

Italy

Agip Raffinazione

Sannazzaro

30.0

Tarento

15.5

Isab SpA.

Priolo Gargello

65.0

Raff. Di Milazzo

Milazzo

30.0

Saras

Sarroch

50.0

Ivory Coast

Soc. Ivoirienne de Raff.

Abidjan

14.1

Jordan

Jordan Petro. Ref.

Zerka

4.4

Kuwait

Kuwait Nat'l. Petro.

Mina Abdulia

38.0

Mina Al-Ahmadi

36.0

Shuaiba

87.0

Esso Nederland

Rotterdam

39.3

Shell Nederland

Pemis

22.0

Total

Vissingen

45.7

Poland

Petrochemia

Plock

49.5

Portugal

Petrogal

Sines

9.2

Romania

Arpechim

Petesti

9.2

Saudi Arabia

Petromin Shell

Ras Al Khafji

44.0

Saudi Aramco

Ras Tanura

44.0

Jeddah

10.0

Riyadh

33.8

Netherlands

48.6

Slovakia

Slovnaft

Bratislava

17.0

South Africa

Nat'l. Petro. Refiners

Sasolburg

11.5

Spain

Repsol Petro.

Tarragona

15.0

Sweden

Skandinaviska Raff.

Brofjorden-Lysekil

48.6

Switzerland

Tamoil

Collombey

6.4

Syria

Banias Ref.

Banias

25.0

Turkey

Turkish Petro. Ref.

Izmir

16.4

Izmit

23.0

Kirikkale

14.5

United Arab Emirates

Abu Dhabi Nat'l. Oil Co.

Ruwais

26.7

United Kingdom

Shell U.K.

Shell Haven

24.0

BP

Grangemouth

31.5

1


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Table H-1 – Materials for Pump Parts Material Class and Material Abbreviationsa I-2

S-1

S-3

S-4

S-5

S-6

S-8

S-9

C-6

A-7

A-8

D-1

Part

12% CHR

316 AUS

AUS (1&2)

316 AUS (1 & 2)

DUPLEX

Pressure Casing

Yes

Cast Iron

Cast Iron

Carbon Steel

Carbon Steel

Carbon Steel

Carbon Steel

Carbon Steel

Carbon Steel

Carbon Steel

12% CHR

AUS

316 AUS

Duplex

Inner case parts (bowls, diffusers, diaphragms)

No

Cast Iron

Bronze

Cast Iron

Ni-resist

Cast Iron

Carbon Steel

12% CHR

316 AUS

Monel

12% CHR

AUS

316 AUS

Duplex

CI

CI

CI

STL

BRZ

STL

CI

NI-RESIST

STL

STL

STL

STL 12% CHR

STL

STL

STL

MONEL

12% CHR

12% CHR

AUS

316 AUS

DUPLEX

Impeller

Yes

Cast Iron

Bronze

Cast Iron

Ni-resist

Carbon Steel

Carbon Steel

12% CHR

316 AUS

Monel

12% CHR

AUS

316 AUS

Duplex

Case wear rings

No

Cast Iron

Bronze

Cast Iron

Ni-resist

Cast Iron

12% CHR

12% CHR

Hard Faced 316 AUS (3)

Monel

12% CHR hardened

Hard Faced AUS (3)


Duplex (3)

Impeller wear rings

No

Cast Iron

Bronze

Cast Iron

Ni-resist

Cast Iron

12% CHR Hardened

12% CHR Hardened


Monel

12% CHR hardened

Hard Faced AUS (3)


Duplex (3)

Carbon Steel

Carbon Steel

Carbon Steel

Carbon Steel

Carbon Steel

AISI 4140

AISI 4140 (4)

316 AUS

K-Monel

12% CHR

AUS

316 AUS

Duplex

No

12% CHR hardened

Hard bronze

12% CHR hardened

12% CHR hardened or hard faced





K-Monel, hardened


Hard Faced AUS (3)


Duplex (3)

Shaft sleeves, mechanical seals

No

AUS or 12% CHR

AUS or 12% CHR

AUS or 12% CHR

AUS or 12% CHR

AUS or 12% CHR

AUS or 12% CHR

AUS or 12% CHR

AUS or 12% CHR

K-Monel, hardened

AUS or 12% CHR

AUS

316 AUS

Duplex

Throat bushings

No

Cast Iron

Bronze

Cast Iron

Ni-resist

Cast Iron

12% CHR

12% CHR

316 AUS

Monel

12% CHR hardened

AUS

316 AUS

Duplex

Interstage sleeves

No

Cast Iron

Bronze

Cast Iron

Ni-resist

Cast Iron

12% CHR hardened

12% CHR hardened


K-Monel, hardened

12% CHR hardened

Hard Faced AUS (3)


Duplex (3)

Interstage bushings

No

Cast Iron

Bronze

Cast Iron

Ni-resist

Cast Iron

12% CHR hardened

12% CHR hardened


K-Monel, hardened

12% CHR hardened

Hard Faced AUS (3)


Duplex (3)

Seal gland

Yes

316 AUS (5)

316 AUS (5)

316 AUS (5)

316 AUS (5)

316 AUS (5)

316 AUS (5)

316 AUS (5)

316 AUS (5)

Monel

316 AUS (5)

316 AUS (5)

316 AUS (5)

Duplex (5)

Case and gland studs

Yes

Carbon Steel

Carbon Steel

AISI 4140 Steel

AISI 4140 Steel

AISI 4140 Steel

AISI 4140 Steel

AISI 4140 Steel

AISI 4140 Steel

K-Monel, hardened (8)

AISI 4140 Steel

AISI 4140 Steel

AISI 4140 Steel

Duplex (8)

Case gasket

No

AUS, spiral wound (6)







316 AUS, spiral wound (6)

Monel, spiral wound, PTFE filled (6)



316 AUS spiral wound (6)

Duplex SS spiral wound (6)

Discharge head/ suction can

Yes

Carbon Steel

Carbon Steel

Carbon Steel

Carbon Steel

Carbon Steel

Carbon Steel

Carbon Steel

Carbon Steel

Carbon Steel

AUS

AUS

316 AUS

Duplex

Column/bowl shaft bushings

No

Nitrile (7)

Bronze

Filled carbon

Nitrile (7)

Filled carbon

Filled carbon

Filled carbon

Filled carbon

Filled carbon

Filled carbon

Filled carbon

Filled carbon

Filled carbon

Wetted fasteners (bolts)

Yes

Carbon Steel

Carbon Steel

Carbon Steel

Carbon Steel

Carbon Steel

316 AUS

316 AUS

316 AUS

K-Monel

316 AUS

316 AUS

316 AUS

Duplex

b

The abbreviation above the diagonal line indicates the case material; the abbreviation below the diagonal line indicates trim material. Abbreviations are as follows: BRZ = bronze, STL = steel, 12% CHR = 12% chrome, AUS = austenitic stainless steel, CI = cast iron, 316 AUS = Type 316 austenitic stainless steel See 2.11.1.1

Appendix B

Yes

B-1

Shaft (2) Shaft sleeves, packed pumps

a


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Hydrocracking Applications Appendix B Reference and General Notes for Table H-I: 1. Austenitic stainless steels include ISO Types 683-13-10/19 (AISI Standard Types 302, 303, 304, 316, 321, and 347). If a particular type is desired, the purchaser will so state. 2. For vertically suspended pumps with shafts exposed to liquid and running in bushings, the shaft shall be 12 percent chrome, except for Classes S-9, A7, A-8, and D-1. Cantilever (Type VS5) pumps may utilize AISI 4140 where the service liquid will allow. 3. Unless otherwise specified, the need for hard-facing and the specific hard-facing material for each application shall be determined by the vendor and described in the proposal. Alternatives to hard-facing may include opening running clearances (2.6.4) or the use of non-galling materials, such as Nitronic 60 and Waukesha 88, depending on the corrosiveness of the pumped liquid. 4. For Class S-6, the shaft shall be 12 percent chrome if the temperature exceeds 175°C (350°F) or if used for boiler feed service (see Appendix G. Table G-1). 5. The gland shall be furnished with a non-sparking floating throttle bushing of a material such as carbon graphite or glass-filled PTFE, in accordance with 2.7.3.20. Unless otherwise specified, the throttle bushing shall be premium carbon graphite. 6. If pumps with axially split casings are furnished, a sheet gasket suitable for the service is acceptable. Spiral wound gaskets should contain a filler material suitable for the service. 7. Alternate materials may be substituted for liquid temperatures greater than 45°C (110°F) or for other special services. 8. Unless otherwise specified, AISI 4140 steel may be used for non-wetted case and gland studs.

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Appendix B

API Standard 610 Mechanical Seal Materials and Classification Codes

Table H-4 – Fourth Letter of Mechanical Seal Classification Code Fourth Letter E F G H I R X Z

Mechanical seal materials and construction features shall be coded according to the following classification system: First letter:

Balanced (B) or unbalanced (U)

Second letter:

Single (S), unpressurized dual (T), or pressurized dual (D)

Third letter:

Seal gland type (P = plain, no throttle bushing; T = throttle bushing with quench, leakage and/or drain connections; A = auxiliary sealing device, type to be specified) Note: See 2.7.3.21. Gasket materials (see Table H-4) Face materials (see Table H-5)

Fourth letter: Fifth letter:

Seal Ring to Sleeve Gasket PTFE FKM PTFE Nitrile FFKM elastomer Graphite foil As specified Graphite foil

Table H-5 – Fifth Letter of Mechanical Seal Classification Code Sealing Ring Face Materials Fifth Letter L M N O P X

For example, a seal coded BSTFM would be a balanced single seal with throttle bushing seal gland and would have a fluoroelastomer (FKM) stationary gasket, an FKM seal-ring-tosleeve gasket, and carbon against tungsten carbide 2 faces. Seal materials other than those listed above should be coded X and defined on the data sheets (see Appendix B).

Ring 1 Carbon Carbon Carbon Tungsten carbide 2 Silicon carbide As specified

Ring 2 Tungsten carbide 1 Tungsten carbide 2 Silicon carbide Silicon carbide Silicon carbide As specified

Table H-6 – Temperature Limits on Mechanical Seal Gaskets and Bellows

Mechanical Seal Notes

Gasket Material

1. Unless otherwise specified, the spring materials for multiple spring seals shall be Hastelloy C. The spring material for single spring seals shall be austenitic stainless steel (AISI Standard Type 316 or equal). Other metal parts shall be austenitic stainless steel (AISI Standard Type 316 or equal) or another corrosion resistant material suitable for the service, except that metal bellows, where used, shall be of the material recommended by the seal manufacturer for the service. Metal bellows shall have a corrosion rate of less than 50 ìm (2 mils) per year. 2. Unless otherwise specified, the gland plate to seal chamber seal shall be a fluoroelastomer O-ring for services below 150°C (300°F). For temperatures 150°C (300°F) and above or when specified, graphite-filled austenitic stainless steel spiral wound gaskets shall be used. The gasket shall be capable of withstanding the full (uncooled) temperature of the pumped fluid. 3. A metal seal ring shall not have sprayed overlay in place of a solid face. 4. When the pumping temperature exceeds 175°C (350°F), the vendor and seal manufacturer should be jointly consulted about using a cooled flush to the seal faces or running the seal chamber dead-ended with jacket cooling. 5. The temperature limits on mechanical seal gaskets shall be as specified in Table H-6.

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Stationary Seal Ring Gasket FKM FKM PTFE Nitrile FFKM Graphite foil As specified Spiral wound

PTFE Nitrile Neoprene FKM Metal bellowsa FFKM Graphite foil Glass filled TFE Mica/graphite Ethylene propylene a

Ambient or Pumping Temperature Minimum Maximum (°C) (°F) (°C) (°F) -75 -100 200 400 -40 -40 120 250 -20 0 90 200 -20 0 200 400 -12 -240 -212 -240 -57

10 -400 -350 -400 -70

260 400b 230 700 180

500 750b 450 1300 350

Consult manufacturer for minimum and maximum ambient pumping temperature. b Maximum temperature is 870°C (1600°F) for nonoxidizing atmospheres; consult manufacturer.

B-3

Hydrocracking Applications Appendix C Other Pump Applications The focus of this manual is on the application of Flowserve petroleum process pumps in the actual hydrocracking unit. However, there are potential applications for other types of Flowserve pumps in auxiliary services. Some of the potential applications and applicable pumps would be: •

Water services (drain water, sour water, cooling water) – potential for Durco Mark III ANSI and Chemstar ISO pumps. Also potential for Flowserve Vertical Circulator type pumps.

•

Boiler feedwater pumps – potential for type MX pumps.

•

Fire water pumps – potential for type DVS and Vertical Circulator type pumps.

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Delayed Coker Applications Table of Contents Page Number 1.

Introduction 1.1 1.2

2.

Market Drivers Competition

2-1 2-2


4.

1-1 1-1

Market Profiles 2.1 2.2

3.

Rationale and Methodology Delayed Coking Process

Flowserve Sales Decision Makers Competitive Advantages of Flowserve Petroleum Process Pumps Guidelines for Mechanical Seals Operating Unit and Pump Details

3-1 3-1 3-1 3-2 3-3

Pump Recommendations 4.1 4.2 4.3 4.4

Introduction to Pump Recommendations Coker and Heater Charge Pumps Coke Cutter Water Pump Other Delayed Coker Unit Pumps


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Delayed Coker Units API Material Designations for Pumps and Mechanical Seals Other Pump Applications

i

4-2 4-2 4-2 4-2 A-1 B-1 C-1

Delayed Coker Applications Exhibits Page Number 1. Typical Delayed Coker Unit

1-3

2. World Oil Consumption

2-2

3. Global Distribution of Delayed Coker Capacity

3-1

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Delayed Coker Applications 1.

Introduction

1.1 Rationale and Methodology The petroleum refining industry consists of approximately 700 facilities located around the world. A petroleum refinery takes a raw material—crude oil—and turns it into finished products, most notably gasoline but also hundreds of other useful products. Crude oil is a mixture of many different hydrocarbons and small amounts of impurities. The exact composition of crude oils varies significantly depending on their source. Even though the basics of all refineries are the same, these are complex systems with multiple operations and the specific operations found at any given refinery will depend on the properties of the crude oil being refined and the desired product output. Flowserve petroleum process pumps enjoy widespread use in all phases of refining. Because no two refineries are the same, the application requirements present a broad range of pumping challenges. Through long and close collaboration with the major refiners in the world, the company possesses a wealth of applications and problem solving expertise. This manual will look at one downstream process—delayed coking— in some detail with the goal of increasing familiarity with this key operation. In addition to discussing delayed coking technology, the manual will present proven pump configurations that have provided reliable, dependable service. Finally, features unique to Flowserve petroleum process pumps will be highlighted along with the benefits these features provide to end-users. 1.2 Delayed Coking Process There are three basic steps in refining: separation, conversion, and treatment. The separation step is essentially fractional distillation where liquids and vapors are separated into components, or fractions, according to weight and boiling point. Some useable products are realized here, but more commonly, the fractions are sent on to the conversion step. The conversion step, also called downstream processing, converts the fractions into intermediate streams that eventually become finished products. Finally, there is the treatment step where streams are carefully combined through blending, purifying, and fine-tuning to produce finished products that meet customer specifications and government standards. Refiners have spent much time and effort on the conversion step because this is where the money is made in a refinery through the conversion of low value fractions to high value products, primarily gasoline. Common conversion processes include thermal cracking (visbreaking), coking, catalytic cracking, catalytic hydrocracking, hydrotreating, alkylation, isomerization, polymerization, catalytic reforming, solvent extraction, dewaxing, propane deasphalting, and many others. To meet the formidable processing and economic challenges of producing clean transportation fuels from heavy, high-sulfur crudes, refiners are required to convert as much of the feedstock as possible to useable products. Coking is a conversion process that uses residues to produce distillates and petroleum coke. This operation is sometimes referred to as “bottom-of-the-barrel” processing because its feedstock is the heavy residues from the distillation towers.

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Delayed Coker Applications Coking is a non-catalytic thermal cracking process. Cracking simply means decomposition by heat whereby heavy (large) hydrocarbon molecules are decomposed, or “cracked”, into lighter, smaller molecules. There are a number of different coking operations, but delayed coking, developed at Standard Oil of Indiana in 1929, is the most widely used residue-conversion process. This process involves heating the residue feedstock in a furnace to above the coking point so rapidly that coke does not deposit in the furnace heater tubes. There are insulated surge tanks (coke drums) downstream of the furnace and coke deposits in these tanks after passing through the heater tubes, but before subsequent processing. In other words, the coking reaction is delayed, thus the process name. Exhibit 1 is a simplified schematic of the delayed coking process. To make this a continuous process, at least two coking drums are required. While one drum is receiving the coke heater effluent and converting it to gas and coke, the other drum is being decoked. The output of the delayed coking unit includes: • • • • • •

Gas – C4 and lighter gases are fed to a vapor recovery unit where LPG (liquid petroleum gas) and fuel gas are produced. Gasoline – goes to the gasoline pool. Naphtha – can be hydrotreated and used as catalytic reformer feedstock or can go directly to the gasoline pool. LGO – light gas oil is usually hydrotreated and sent to the distillate pool. HGO – heavy gas oil is used as catalytic cracker or hydrocracker feedstock. Coke – depending on the composition of residue feedstock, the coke can be used for fuel, for the manufacture of electrodes for the aluminum industry, for metallurgical applications in ferrous foundry operations and steelmaking, or, for a new application, as a gasification feed.

Delayed coking will play an increasingly important role in the modern refinery because of its ability to convert heavy residues to useful, profitable products.

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Market Profile

2.1 Market Drivers Petroleum refining is a very competitive endeavor and refiners work very hard to obtain as much saleable product as possible from each barrel of crude oil. Delayed coking permits refiners to process very heavy, high sulfur residues. These residues result from processing crude oils that, because of their high sulfur content, are frequently purchased at a discount. By being able to economically convert these residues into light distillates, the refiners can increase profitability. The petroleum coke produced by the delayed coking process is not an insignificant byproduct. The primary use for petroleum coke is as a fuel although it also finds use in metallurgical applications and as a gasification feed stock. The use of petroleum coke in solid fuel power stations has been growing recently because it provides an inexpensive way to displace coal. On a cost-per-heat unit basis, petroleum coke is about 30% lower than that of bituminous coal. The marketability of petroleum coke is a plus in favor of the delayed coking process. Of all the coking processes, delayed coking is preferred. In fact, in the U.S., 48 out of 54 existing coking units are of the delayed coking type, and up to about 300,000 barrels per day delayed coking capacity will be added in the U.S. over the next 10 years. This represents an increase of about 18%. Below is a list of some planned, near term, delayed coker units: Company Reliance Ind. PEMEX PEMEX PEMEX BP Amoco Clark Oil Petrolera Ameriven Petrozuata Sincor

Location Jamnagar, India Cuidad Madero, Mexico Minatitlan, Mexico Salina Cruz, Mexico Toledo, Ohio Port Arthur, Texas Jose, Venezuela Jose, Venezuela Jose, Venezuela

Capacity, Mbpd1 122 ------28 --90 120 140

Planned Completion 1999 2001 2001 2001 1999 2000 2003 2000 2001

Even though the U.S. leads the world in installed and operating delayed coker capacity, it seems logical that, in the future, units will be built where crude oil consumption growth will be the greatest. Exhibit 2 below shows crude oil consumption now and the projected consumption in 2005 for four regions of the world.

1

1,000 barrels per day

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Delayed Coker Applications Exhibit 2

Million barrels per day

World Oil Consumption 35 30 25 20 15 10 5 0

1999 2005

USA & Canada

Europe, Middle East, Africa

Asia-Pacific Latin America

Projected growth rates in consumption in these regions between now and 2005 are: USA & Canada Europe, Middle East, Africa Asia-Pacific Latin America

9% 12% 19% 23%

2.2 Competition The primary global competitors in delayed coker projects are IDP and Sulzer. Regional competitors are Ebara and Shin-Nippon in the Asia-Pacific region and David Brown in Europe, Middle East, Africa region. Flowserve petroleum process pumps have a long history of dependable service in petroleum refineries all over the world. Flowserve’s global presence will allow the company to participate in the refining market as delayed coker units are added to refineries worldwide. Petroleum refining is a very competitive and cost-conscience business and Flowserve’s ability to assist refiners in improving pump reliability will be key as this can lead to improved profitability. The features that provide Flowserve petroleum process pumps with competitive advantages will be highlighted in Section 3.3.

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3.


3.1 Flowserve Sales Delayed coker capacity worldwide is about 2.95 MMbpd (million barrels per day). The global distribution of this capacity is shown in Exhibit 3. In Appendix A, there are tables for the four regions shown in Exhibit 3 listing the locations and capacities of the existing delayed coker units. Exhibit 3 Global Distribution of Delayed Coker Capacity

Asia-Pacific 11%

Latin America 9%

USA & Canada 58%


As was shown in Exhibit 2, the growth in oil consumption is projected to be greatest in the Asia-Pacific and Latin American regions, locations with the lowest delayed coker capacity. These two regions of the world will likely see growth in delayed coker capacity over the next five to ten years. 3.2 Decision Makers The delayed coker charge and the heater charge pumps are key components in a delayed coker unit. Even though an engineering firm may handle the design and construction of the unit, the end-user will generally be heavily involved in the selection of the supplier of the charge pumps. Past experience with delayed coker applications will weigh favorably for potential charge pump suppliers. The buying decision involving the process pumps is much more subject to competitive pressures, although here again, experience and installed base are important considerations. 3.3 Competitive Advantages of Flowserve Petroleum Process Pumps Flowserve has achieved a reputation for supplying high quality, dependable pumping equipment to the petroleum industry and has gained a wealth of experience through handling the critical services found in refining applications. The critical pumps in a Flowserve RED 1/00

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Delayed Coker Applications delayed coker unit are the delayed coker charge pump and the heater charge pump, and, to a somewhat lesser degree, the coke cutter water pump. The coker and heater charge pumps must handle very high temperatures at high pressures. The Flowserve models DSTHF and DSTHO horizontal, between bearings pump with a double suction first stage is ideally suited for these services. For the coke cutter water application, the pump must achieve a very high discharge pressure. The Flowserve model HDO multistage, double-case design is used. The DSTHF, DSTHO, and HDO designs are fully compliant with API 610 (8th Edition). The DSTHF and DSTHO designs offer maximum reliability for the two charge services because of the following features and benefits: Feature Between bearing design Impellers Circular bearing housing and adapter

Benefit Minimizes deflection at mechanical seal thus increasing seal life. Double suction impellers minimize NPSHR over a wide range of flows. Gives maximum bearing support. Provides better stiffness and lower vibration.

The HDO design offers the following features and benefits to enhance overall performance and reliability: Feature Radially split outer casing Axially split inner casing Special bearing construction First stage double suction impeller design

Benefit Inherently safe at all pressures. Rotating element balanced as a unit. Axial hydraulic loads are balanced. Maximum reliability. Reduced maintenance costs. Low noise levels. Low NPSHR.

The other pump applications in delayed coker units can normally be handled by singlestage, overhung API process pumps. The Flowserve SCE family of process pumps are fully compliant with API 610 (8th Edition) and can handle a very broad range of single stage applications. Also, a very large installed base of these pumps provides a history of successful performance in all types of petroleum services. 3.4 Guidelines for Mechanical Seals There are many challenging mechanical seal applications in a delayed coker unit. The very high temperatures endured by seals in the charge pumps can cause severe problems. The introduction of high temperature, metal bellows designs have helped reduce the problems in these critical pumps. Also, some users are specifying tandem seals for the hydrocarbon services to help meet permitting requirements. Proper seal selection is critical to trouble-free operation and because of the severity of many of the applications, the advice of a Flowserve FSD sealing specialist should be sought.

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3.5 Operating Unit and Pump Details The critical applications in a delayed coker are the charge pumps, and to a somewhat lesser degree, the coke cutter water pump. However, the process pumps, water handling pumps, and any auxiliary pumps must provide reliable service for the unit to operate dependably and profitably. In Section 4, Pump Applications, proven pump configurations (materials, seals, flush plans, etc.) will be presented.

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Delayed Coker Applications 4.1 Introduction to Pump Recommendations The key pumps in a delayed coker unit are the coker charge pump, the heater charge pump, and the coke cutter water pump; however, there are a number of other services requiring Flowserve petroleum process pumps. Below is a discussion of typical Flowserve petroleum process pump applications and representative pump configurations that have proven successful in delayed coker units. This information should be helpful in understanding Flowserve’s involvement in this critical refinery process. 4.2 Coker and Heater Charge Pumps Typical operating conditions for the coker charge pump are 700oF (371oC) liquid temperature and relatively low discharge pressures. For the heater charge pump, the conditions are 660oF (349oC) liquid temperature and 600 psig (42 bar) discharge pressure. The Flowserve petroleum process pump best suited for these services is the Byron Jackson Type DSTHF and DSTHO between bearing radially split designs with a double suction first stage. The API 610 material designation for the coker charge pump is normally specified as S-6 (see Appendix B). For the heater charge pump, both S-5 and C-6 material designations are specified. Mechanical seal selection is key to troublefree operation of these critical pumps. Metal bellows seals are normally used with an API 610 seal code of BSTRX (see Appendix B). An auxiliary sealing device comprised of a close clearance floating carbon throttle bushing is also used. An API Plan 11 seal flushing system and an API Plan 62 auxiliary system with an anti-coking device are included. Dual seals with an API Plan 32 may be required if the service is particularly dirty or if the pump meets the definition of “critical service.” 4.3 Coke Cutter Water Pump This pump application deserves some brief discussion. As shown in Exhibit 1, a typical delayed coker unit has two coke drums. This enables the unit to operate on a continuous basis. As one drum is filling with coke, the other is emptied. High-pressure water is used to “cut” the coke out of the drum and this water is provided by the coke cutter water pump. Typical operating conditions for this pump are 900 gpm (204 m 3/hr) at a discharge pressure of 3500 psig (241 bar). The temperature is less than 150oF (66oC). Because of the high pressure, the Flowserve petroleum process pump best suited for this service is the Byron Jackson Type HDO double case, multi-stage unit. The API 610 material code normally specified is S-6. The API 610 seal code normally used is BSTFM. An auxiliary sealing device comprised of a close clearance floating carbon throttle bushing is also used, and an API Plan 11 flushing system is normally provided. 4.4 Other Delayed Coker Unit Pumps There are a number of other applications with the delayed coker unit and these are listed below with comments relative to typical configurations:

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4.4.1 Condensate Transfer Operating conditions: 300 oF (149oC), 100 psig (6.9 bar). Recommended pump: Byron Jackson Type SCE, API material code – C-6. Mechanical seal: Pusher type, API code – BSTFM. Auxiliary seal system: API Plan 23. 4.4.2 Fractionator Overhead Reflux Operating conditions: 350 oF (177oC), 100 psig (6.9 bar). Recommended pump: Byron Jackson Type SCE, API material code – S-5. Mechanical seal: Metal bellows, API code – BSTRX, close clearance floating carbon throttle bushing. Auxiliary seal system: API Plan 11, API Plan 62 with anti-coking device. 4.4.3 Fractionator Overhead Sour Water Operating conditions: 350 oF (177oC), 75 psig (5.2 bar). Recommended pump: Byron Jackson Type SCE, API material code – A-8. Mechanical seal: Metal bellows, API code – BSTFM, close clearance floating carbon throttle bushing. Auxiliary seal system: API Plan 23. 4.4.4 Light Distillate Sidestream Operating conditions: 500 oF (260oC), 200 psig (13.8 bar). Recommended pump: Byron Jackson Type SCE, API material code – S-5. Mechanical seal: Metal bellows, API code – BSTRN, close clearance floating carbon throttle bushing. Auxiliary seal system: API Plan 11, API Plan 62 with anti-coking device. 4.4.5 Gas Oil Sidestream Operating conditions: 650 oF (343oC), 200 psig (13.8 bar). Recommended pump: Byron Jackson Type SCE, API material code – S-5. Mechanical seal: Metal bellows, API code – BSTRN, close clearance floating carbon throttle bushing. Auxiliary seal system: API Plan 11, API Plan 62 with anti-coking device. 4.4.6 Fractionator Overhead Product Operating conditions: 350 oF (177oC), 250 psig (17.2 bar). Recommended pump: Byron Jackson Type SCE, API material code – S-5. Mechanical seal: Metal bellows, API code – BSTRN, close clearance floating carbon throttle bushing. Auxiliary seal system: API Plan 11, API Plan 62 with anti-coking device. 4.4.7 Dilute Tower Feed Operating conditions: 300 oF (149oC), 175 psig (12.1 bar). Recommended pump: Byron Jackson Type SCE, API material code – S-6. Mechanical seal: Metal bellows, API code – BSTRN, close clearance floating carbon throttle bushing. Auxiliary seal system: API Plan 11, API Plan 62 with anti-coking device.

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Delayed Coker Applications 4.4.8 Preheat Condensate Steam Removal Operating conditions: 250 oF (121oC), 100 psig (6.9 bar). Recommended pump: Byron Jackson Type SCE, API material code – C-6. Mechanical seal: Pusher type, API code – BSTFM. Auxiliary seal system: API Plan 23. 4.4.9 Diluent Pump Operating conditions: 225 oF (107oC), 200 psig (13.8 bar). Recommended pump: Byron Jackson Type SCE, API material code – S-6. Mechanical seal: Pusher type, API code – BSTFM, close clearance floating carbon throttle bushing. Auxiliary seal system: API Plan 11, API Plan 62 with anti-coking device. 4.4.10 Diluent Surge Drum Sour Water Removal Operating conditions: 225 oF (107oC), 100 psig (6.9 bar). Recommended pump: Byron Jackson Type SCE, API material code – A-8. Mechanical seal: Metal bellows, API code – BSTFM, close clearance floating carbon throttle bushing. Auxiliary seal system: API Plan 23. 4.4.11 Quench Water Operating conditions: 200 oF (93oC), 100 psig (6.9 bar). Recommended pump: Byron Jackson Type SCE, API material code – S-6. Mechanical seal: Metal bellows, API code – BSTFM, close clearance floating carbon throttle bushing. Auxiliary seal system: API Plan 23. 4.4.12 Wash Oil Operating conditions: 400 oF (204oC), 150 psig (10.3 bar). Recommended pump: Byron Jackson Type SCE, API material code – S-5. Mechanical seal: Metal bellows, API code – BSTRX, close clearance floating carbon throttle bushing. Auxiliary seal system: API Plan 11, API Plan 62 with anti-coking device. 4.4.13 Coker Recovery Oil Operating conditions: 150 oF (66oC), 200 psig (13.8 bar). Recommended pump: Byron Jackson Type SCE, API material code – S-6. Mechanical seal: Pusher type, API code – BSTFM, close clearance floating carbon throttle bushing. Auxiliary seal system: API Plan 11. 4.4.14 Steamout Sour Water Operating conditions: 150 oF (66oC), 75 psig (5.2 bar). Recommended pump: Byron Jackson Type SCE, API material code – A-8. Mechanical seal: Pusher type, API code – BSTFM, close clearance floating carbon throttle bushing. Auxiliary seal system: API Plan 11.

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Delayed Coker Applications Appendix A Delayed Coker Units USA and Canada COUNTRY

COMPANY

Canada

Petro-Canada Imperial Oil Consumer Co-op United States Hunt Refining Atlantic Richfield Chevron Equilon

Exxon Mobil Tosco Ultramar Citgo Clark Amoco El Dorado Framland Ind. Nat'l. Co-op Refinery BP Amoco Citgo Conoco Exxon Mobil Motiva Transamerica Koch Refinery Chevron Conoco Valero Energy BP Amoco Clark Conoco Sun Amoco Citgo

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LOCATION STATE (PROV.) Alberta Ontario Saskatchewan Alabama California California California California California California California California California Illinois Illinois Indiana Kansas Kansas Kansas Louisiana Louisiana Louisiana Louisiana Louisiana Louisiana Louisiana Minnesota Mississippi Montana New Jersey Ohio Ohio Oklahoma Oklahoma Texas Texas

A-1

CITY

Edmonton Sarnia Regina Tuscaloosa Carson El Segundo Wilmington Bakersfield Martinez Benicia Torrance San Francisco Wilmington Lemont Hartford Whiting El Dorado Coffeyville McPherson Belle Chasse Lake Charles Westlake Baton Rouge Chalmette Norco Norco Rosemount Pascagoula Billings Paulsboro Toledo Lima Ponca City Tulsa Texas City Corpus Christi

CAPACITY Mbpd1 7.5 23.3 8.8 10.8 57.0 64.0 37.8 19.4 23.2 25.5 50.2 42.2 22.0 25.1 15.0 34.2 18.0 16.5 20.8 22.5 84.6 64.1 102.0 33.8 25.5 75.0 70.0 71.0 16.0 23.2 28.0 22.5 21.8 8.5 40.4 36.0

Delayed Coker Applications Appendix A (Continued) Delayed Coker Units USA and Canada Clark Costal Crown Central Koch Refinery LaGloria Oil & Gas Lyondell-Citgo Mobil Motiva Shell Deerpark Chevron BP Amoco Atlantic Richfield Equilon Frontier Oil & Gas

Texas Port Arthur Texas Corpus Christi Texas Pasadena Texas Corpus Christi Texas Tyler Texas Houston Texas Beaumont Texas Port Arthur Texas Deer Park Utah Salt Lake City Virginia Yorktown Washington Ferndale Washington Anacortes Wyoming Cheyenne TOTAL - USA and CANADA

1


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37.5 17.0 12.5 15.0 6.0 87.3 41.6 49.5 59.1 7.2 19.5 51.0 24.1 9.0 1702.5

Delayed Coker Applications Appendix A Delayed Coker Units Latin America

COUNTRY Argentina

Aruba Brazil

Venezuela 1

COMPANY ESSO SAPA YPF, S.A.

LOCATION Campana La Plata Lujan de Cuyo Costal Aruba San Nicolas Petrobras Betim Cubatao Paulina Corpoven Judibana Falcon TOTAL - LATIN AMERICA


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CAPACITY, Mbpd1 25.0 39.0 40.0 31.0 19.0 30.4 29.3 52.1 265.8

Delayed Coker Applications Appendix A Delayed Coker Units Europe, Middle East, and Africa

COUNTRY Albania Croatia Egypt FSU

Germany

Italy Kuwait Myanmar Norway Romania

Spain Syria United Kingdom 1

COMPANY Albpetrol Ina Ind. Nafte Suez Petro.

LOCATION

Ballshi Sisnk El-Suez Baku, Azerbaijan Atyrau, Kazakhstan Pavlodar, Kazakhstan Bashneftekhimzavody, Russia Perm, Russia Volgogard, Russia Sibneft-Omsk, Russia Sidanco-Angarsk, Russia Turkmenbashi, Turkmenistan Kherson, Ukraine Nadvornaja, Ukraine Fergena, Uzbekistan Min. Oberrhein Karlsruhe OMV, A.G. Burghasen Veba Oel/Ruhr Oel Gelsenkirchen Wintershall Lingen Praoil Gela, Ragusa Kuwait Nat'l . Petro. Mina Abdlia Muanma Petro. Thanlyin Statoil Mongstad Mongstad Astra Ploiesti Petrobrasi Ploiesti Petromedia Midia Petrotel Ploiesti Refinaria Darmanesti Darmanesti Rafo Onesti Repsol Petro. La Coruna Puertollano Homs Refinery Homs Conoco South Killingholme TOTAL - EUROPE, MIDDLE EAST, & AFRICA


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CAPACITY, Mbpd1 12.0 5.9 16.5 38.5 13.7 11.3 7.1 13.5 24.8 13.9 11.2 28.6 12.0 7.0 17.7 26.0 27.5 28.0 23.4 45.0 60.0 5.2 25.0 8.6 12.7 22.0 11.5 9.5 4.5 13.5 16.0 18.2 68.0 658.3

Delayed Coker Applications Appendix A Delayed Coker Units Asia-Pacific

COUNTRY China

India

Indonesia Japan Malaysia South Korea Taiwan 1

COMPANY China Nat'l. Petro.

LOCATION

Daquint Fushun Dashanzi Jinzhou Urumqi Sinopec Anquig Baling Jingmen Jinling Maoming Qilu Zhenhai Bangaigon Ref. & Petro. Bangaigon, Assam Indian Oil Barauni, Bihar Gawahati, Assam Pertamina Damai, Central Samatra Japan Energy Mizushima, Okayama Kao Oil Yamaguchi, Osaka Petronas Melaka II Hyundai Daesan Chinese Petro. Kaohsiung TOTAL - ASIA-PACIFIC


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CAPACITY, Mbpd1 13.0 35.0 8.0 20.0 8.0 8.0 12.0 8.0 12.0 12.0 16.0 8.0 10.0 20.0 6.0 32.6 23.4 17.1 21.0 19.0 15.0 324.1

Table H-1 – Materials for Pump Parts Material Class and Material Abbreviationsa I-2

S-1

S-3

S-4

S-5

S-6

S-8

S-9

C-6

A-7

A-8

D-1

Part

12% CHR

316 AUS

AUS (1&2)

316 AUS (1 & 2)

DUPLEX

Pressure Casing

Yes

Cast Iron

Cast Iron

Carbon Steel

Carbon Steel

Carbon Steel

Carbon Steel

Carbon Steel

Carbon Steel

Carbon Steel

12% CHR

AUS

316 AUS

Duplex

Inner case parts (bowls, diffusers, diaphragms)

No

Cast Iron

Bronze

Cast Iron

Ni-resist

Cast Iron

Carbon Steel

12% CHR

316 AUS

Monel

12% CHR

AUS

316 AUS

Duplex

CI

CI

CI

STL

BRZ

STL

CI

NI-RESIST

STL

STL

STL

STL 12% CHR

STL

STL

STL

MONEL

12% CHR

12% CHR

AUS

316 AUS

DUPLEX

Impeller

Yes

Cast Iron

Bronze

Cast Iron

Ni-resist

Carbon Steel

Carbon Steel

12% CHR

316 AUS

Monel

12% CHR

AUS

316 AUS

Duplex

Case wear rings

No

Cast Iron

Bronze

Cast Iron

Ni-resist

Cast Iron

12% CHR

12% CHR


Monel

12% CHR hardened

Hard Faced AUS (3)


Duplex (3)

Impeller wear rings

No

Cast Iron

Bronze

Cast Iron

Ni-resist

Cast Iron

12% CHR Hardened

12% CHR Hardened


Monel

12% CHR hardened

Hard Faced AUS (3)


Duplex (3)

Carbon Steel

Carbon Steel

Carbon Steel

Carbon Steel

Carbon Steel

AISI 4140

AISI 4140 (4)

316 AUS

K-Monel

12% CHR

AUS

316 AUS

Duplex

No

12% CHR hardened

Hard bronze

12% CHR hardened






K-Monel, hardened


Hard Faced AUS (3)


Duplex (3)

Shaft sleeves, mechanical seals

No

AUS or 12% CHR

AUS or 12% CHR

AUS or 12% CHR

AUS or 12% CHR

AUS or 12% CHR

AUS or 12% CHR

AUS or 12% CHR

AUS or 12% CHR

K-Monel, hardened

AUS or 12% CHR

AUS

316 AUS

Duplex

Throat bushings

No

Cast Iron

Bronze

Cast Iron

Ni-resist

Cast Iron

12% CHR

12% CHR

316 AUS

Monel

12% CHR hardened

AUS

316 AUS

Duplex

Interstage sleeves

No

Cast Iron

Bronze

Cast Iron

Ni-resist

Cast Iron

12% CHR hardened

12% CHR hardened


K-Monel, hardened

12% CHR hardened

Hard Faced AUS (3)


Duplex (3)

Interstage bushings

No

Cast Iron

Bronze

Cast Iron

Ni-resist

Cast Iron

12% CHR hardened

12% CHR hardened


K-Monel, hardened

12% CHR hardened

Hard Faced AUS (3)


Duplex (3)

Seal gland

Yes

316 AUS (5)

316 AUS (5)

316 AUS (5)

316 AUS (5)

316 AUS (5)

316 AUS (5)

316 AUS (5)

316 AUS (5)

Monel

316 AUS (5)

316 AUS (5)

316 AUS (5)

Duplex (5)

Case and gland studs

Yes

Carbon Steel

Carbon Steel

AISI 4140 Steel

AISI 4140 Steel

AISI 4140 Steel

AISI 4140 Steel

AISI 4140 Steel

AISI 4140 Steel

K-Monel, hardened (8)

AISI 4140 Steel

AISI 4140 Steel

AISI 4140 Steel

Duplex (8)

Case gasket

No








316 AUS, spiral wound (6)

Monel, spiral wound, PTFE filled (6)



316 AUS spiral wound (6)

Duplex SS spiral wound (6)

Discharge head/ suction can

Yes

Carbon Steel

Carbon Steel

Carbon Steel

Carbon Steel

Carbon Steel

Carbon Steel

Carbon Steel

Carbon Steel

Carbon Steel

AUS

AUS

316 AUS

Duplex

Column/bowl shaft bushings

No

Nitrile (7)

Bronze

Filled carbon

Nitrile (7)

Filled carbon

Filled carbon

Filled carbon

Filled carbon

Filled carbon

Filled carbon

Filled carbon

Filled carbon

Filled carbon

Wetted fasteners (bolts)

Yes

Carbon Steel

Carbon Steel

Carbon Steel

Carbon Steel

Carbon Steel

316 AUS

316 AUS

316 AUS

K-Monel

316 AUS

316 AUS

316 AUS

Duplex

b

The abbreviation above the diagonal line indicates the case material; the abbreviation below the diagonal line indicates trim material. Abbreviations are as follows: BRZ = bronze, STL = steel, 12% CHR = 12% chrome, AUS = austenitic stainless steel, CI = cast iron, 316 AUS = Type 316 austenitic stainless steel See 2.11.1.1

Appendix B

Yes

B-1

Shaft (2) Shaft sleeves, packed pumps

a


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I-1 Fullb Compliance Material?

Hydrocracking Applications Appendix B Reference and General Notes for Table H-I: 1. Austenitic stainless steels include ISO Types 683-13-10/19 (AISI Standard Types 302, 303, 304, 316, 321, and 347). If a particular type is desired, the purchase will so state. 2. For vertically suspended pumps with shafts exposed to liquid and running in bushings, the shaft shall be 12 percent chrome, except for Classes S-9, A7, A-8, and D-1. Cantilever (Type VS5) pumps may utilize AISI 4140 where the service liquid will allow. 3. Unless otherwise specified, the need for hard-facing and the specific hard-facing material for each application shall be determined by the vendor and described in the proposal. Alternatives to hard-facing may include opening running clearances (2.6.4) or the use of non-galling materials, such as Nitronic 60 and Waukesha 88, depending on the corrosiveness of the pumped liquid. 4. For Class S-6, the shaft shall be 12 percent chrome if the temperature exceeds 175°C (350°F) or if used for boiler feed service (see Appendix G. Table G-1). 5. The gland shall be furnished with a non-sparking floating throttle bushing of a material such as carbon graphite or glass-filled PTFE, in accordance with 2.7.3.20. Unless otherwise specified, the throttle bushing shall be premium carbon graphite. 6. If pumps with axially split casings are furnished, a sheet gasket suitable for the service is acceptable. Spiral would gaskets should contain a filler material suitable for the service. 7. Alternate materials may be substituted for liquid temperatures greater than 45°C (110°F) or for other special services. 8. Unless otherwise specified, AISI 4140 steel may be used for non-wetted case and gland studs.

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Appendix B Table H-4 – Fourth Letter of Mechanical Seal Classification Code Fourth Stationary Seal Seal Ring to Letter Ring Gasket Sleeve Gasket E FKM PTFE F FKM FKM G PTFE PTFE H Nitrile Nitrile I FFKM FFKM elastomer R Graphite foil Graphite foil X As specified As specified Z Spiral wound Graphite foile

API Standard 610 Mechanical Seal Materials and Classification Codes Mechanical seal materials and construction features shall be coded according to the following classification system: First letter:

Balanced (B) or unbalanced (U)

Second letter:

Single (S), unpressurized dual (T), or pressurized dual (D)

Third letter:

Seal gland type (P = plain, no throttle bushing; T = throttle bushing with quench, leakage and/or drain connections; A = auxiliary sealing device, type to be specified) Note: See 2.7.3.21. Gasket materials (see Table H-4) Face materials (see Table H-5)

Fourth letter: Fifth letter:

Table H-5 – Fifth Letter of Mechanical Seal Classification Code Sealing Ring Face Materials Fifth Letter L M N O P X

For example, a seal coded BSTFM would be a balanced single seal with throttle bushing seal gland and would have a fluoroelastomer (FKM) stationary gasket, an FKM seal-ring-tosleeve gasket, and carbon against tungsten carbide 2 faces. Seal materials other than those listed above should be coded X and defined on the state sheets (see Appendix B).

Ring 2 Tungsten carbide 1 Tungsten carbide 2 Silicon carbide Silicon carbide Silicon carbide As specified

Table H-6 – Temperature Limits on Mechanical Seal Gaskets and Bellows Ambient or Pumping Temperature Gasket Material Minimum Maximum

Mechanical Seal Notes 1. Unless otherwise specified, the spring materials for multiple spring seals shall be Hastelloy C. The spring materials for single spring seals shall be austenitic stainless steel (AISI Standard Type 316 or equal). Other metal parts shall be austenitic stainless steel (AISI Standard Type 316 or equal) or another corrosion resistant material suitable for the service, except that metal bellows, where used, shall be of the material recommended by the seal manufacturer for the service. Metal bellows shall have a corrosion rate of less than 50 ìm (2 mils) per year. 2. Unless otherwise specified, the gland plate to seal chamber seal shall be a fluoroelastomer O-ring for services below 150°C (300°F) and above or when specified, graphitefilled austenitic stainless steel spiral wound gaskets shall be used. The gasket shall be capable of withstanding the full (uncooled) temperature of the pumped fluid. 3. A metal seal ring shall not have sprayed overlay in place of a solid face. 4. When the pumping temperature exceeds 175°C (350°F), the vendor and seal manufacturer should be jointly consulted about using a cooled flush to the seal faces or running the seal chamber dead-ended with jacket cooling. 5. The temperature limits on mechanical seal gaskets shall be as specified in Table H-6.

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Ring 1 Carbon Carbon Carbon Tungsten carbide 2 Silicon carbide As specified

PTFE Nitrile Neoprene FKM Metal bellows a FFKM Graphite foil Glass filled TFE Mica/graphite Ethylene propylene a

(°C) -75 -40 -20 -20

(°F) -100 -40 0 0

(°C) 200 120 90 200

(°F) 400 250 200 400

-12 -240 -212 -240 -57

10 -400 -350 -400 -70

260 400b 230 700 180

500 750b 450 1300 350

Consult manufacturer for minimum and maximum ambient pumping temperature. b Maximum temperature is 870°C (1600°F for nonoxidizing atmospheres; consult manufacturer.

B-3

Delayed Coker Applications Appendix C Other Pump Applications The focus of this manual is on the application of Flowserve petroleum process pumps in the actual delayed coker unit. However, there are potential applications for other types of Flowserve pumps in auxiliary services. Some of the potential applications and applicable pumps would be: •

Water services (drain water, sour water, cooling water) – potential for Durco Mark III ANSI and Chemstar ISO pumps. Also potential for Flowserve Vertical Circulator type pumps.

•

Boiler feedwater pumps – potential for type MX pumps.

•

Fire water pumps – potential for type DVS and Vertical Circulator type pumps.

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Combined Cycle Unit Applications Table of Contents Page Number 1.

Introduction 1.1 1.2

2.

Market Drivers Competition

2-1 2-4


4.

1-1 1-1

Market Profiles 2.1 2.2

3.

Rationale and Methodology Combined Cycle Process

Flowserve Sales Decision Makers Competitive Advantages of Flowserve Pumps Guidelines for Mechanical Seals Operating Unit and Pump Details

3-1 3-1 3-1 3-2 3-2

Pump Recommendations 4.1 4.2 4.3 4.4 4.5

Introduction to Pump Recommendations HRSG Feedwater Pumps Auxiliary Steam Boiler Feedwater Pump Condensate Pumps Circulating Pumps

Appendix A Auxiliary Pumps for Combined Cycle Units

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4-2 4-2 4-2 4-2 4-2 A-1

Combined Cycle Unit Applications Exhibits Page Number 1-3

1. Simple Cycle Unit Schematic 2. Combined Cycle Unit Schematic

1-4

3. Global Power Production by Fuel Source

2-2

4. Global Distribution of Projected New Generating Capacity

2-3

5. Two-Turbine Combined Cycle Unit

4-3

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Combined Cycle Unit Applications 1.

Introduction

1.1 Rationale and Methodology The electric power generation industry is truly global. Electricity is generated everywhere. The industry takes an energy source and converts that energy into electricity. The type of generating plant is usually defined by the energy source. The typical and traditional energy sources are coal, gas (usually natural gas), nuclear, petroleum, and other (e.g., hydro, wind, solar). The energy is typically used to generate steam, which in turn drives a turbine that drives the electric generator. However, some systems by-pass the steam cycle and directly drive the generator. The energy source is the most critical variable in these complex systems. The choice of the energy source depends on many factors including cost, availability, handling characteristics, and environmental concerns. In today’s energy marketplace, natural gas has emerged as the preferred energy source. There are many potential applications for Flowserve pumps in electric power generating operations. Because of the wealth of applications and problem solving expertise the company has accumulated over many years, there is much that Flowserve can offer to this market. Since natural gas has become the preferred energy source for new electric power projects, this manual will focus on a relatively new technology – combined cycle – that promises to offer rapid and continual growth. In addition to discussing combined cycle technology, the manual will present pump configurations that will provide reliable, dependable service in these generating units. Finally, features of Flowserve pumps will be highlighted along with the benefits these features provide to combined cycle operators. 1.2

Combined Cycle Process

Gas turbines have been used for some time to generate electricity. A gas turbine typically consists of an axial-flow compressor and one or more combustion chambers. The compressor pressurizes air that is mixed with the fuel, usually natural gas, and the fuel and air mixture is burned in the combustion chamber. The hot gases formed during combustion drive the turbine and run the compressor. If the turbine is attached to an electric generator and the hot exhaust gases from the turbine are allowed to escape to the atmosphere, this forms a simple cycle generating unit with an efficiency of about 30%. Exhibit 1 is a schematic of a simple cycle unit. A combined cycle generating unit makes use of the hot exhaust gases from the gas turbine. These gases are routed through a heat recovery steam generator (HRSG) and the steam produced is used to drive a steam turbine that in turn drives an electric generator. This combination increases thermal efficiency and reduces fuel consumption. In fact, combined cycle units are approaching 60% efficiency. Exhibit 2 is a schematic of a combined cycle unit. Combined cycle units can also operate as cogenerators. A cogenerator is a facility that produces electricity and another form of useful thermal energy, usually steam. Steam is removed from the unit either before or after it passes through the steam turbine and is routed to other processes generally for heating purposes.

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1-1

Combined Cycle Unit Applications The electric power generating industry is changing rapidly with the major trend being from regulation toward competition. To remain competitive and to meet the challenges of this rapidly changing market, electricity producers must strive for maximum efficiency. Combined cycle technology is proving to be one of the key tools that permits producers to meet these challenges.

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EXHIBIT 1 SIMPLE CYCLE UNIT SCHEMATIC

Fuel

Compressor

Turbine

Air Exhaust

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Generator

Electricity


EXHIBIT 2 COMBINED CYCLE UNIT SCHEMATIC

Fuel

Gas Turbine

Compressor

Generator

Electricity

Air Exhaust

Steam Heat Recovery Steam Generator

Steam Turbine

Generator

Condenser

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Electricity


Market Profile

2.1 Market Drivers There are two major segments of the electric power generation industry and the market drivers are very different in these segments. The segments are the developed world economies (primarily North America and Western Europe) and the emerging world economies. The future growth of electric power generation in these two segments will be influenced by different factors. In the developed economies, the growth will not be closely related to GDP growth because GDP growth will be in low energy usage industries and energy conservation efforts are prevalent and effective. Rather, growth will be driven by the aging of the existing power infrastructure and the required upgrading and replacement of this infrastructure. In the emerging economies, growth will be driven by surging demand for electricity. Even though there will be strong demand for more generating capacity, the growth rate will be limited by financing constraints and political uncertainties. Growth worldwide should average slightly over 3% for the foreseeable future with 30% of the growth occurring in the developed economies and 70% in the emerging economies. The electric power generation industry is in the midst of profound change and is being buffeted by many forces. One example of profound change is shown in growth forecasts for the major electric power providers. There are four major providers in the electric power generation industry; namely, utilities, industrial (captive), independent power producers (IPP), and merchant producers. Table 1 below shows the percentage of new projects either completed in 1997, or planned for 1999 and 2001. Table 1 Percentage of New Project by Type Provider

Utilities Industrial IPP Merchant

1997 38% 12% 50% 0%

1999 25% 10% 55% 10%

2001 20% 12% 50% 18%

As this table shows, most of the growth in the electric power generation industry is in IPP’s and merchant producers and not in the traditional utility and industrial segments. Another industry trend that is causing profound change is the shift from regulation to competition. In fact, this trend has been the major contributor to growth of IPP’s and merchant producers. In addition to competitive pressures, there is the pressure to grow to meet increased demand, particularly in the emerging economies. It is estimated that the current global generating capacity is about 3,000 gigawatts (GW)1. Exhibit 2 below shows the distribution of this global capacity by the primary energy sources.

1

One gigawatt = one billion watts

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Exhibit 3

Global Power Production by Fuel Source Other 16% Coal 44%

Petroleum 10%

Nuclear 18% Gas 12%

The growth rate in generating capacity over the next 10 years is forecast to be about 3.2%; however, the growth rates of each of the input energy sources are quite different as is shown in Table 2 below. Table 2 Global Growth Rates by Input Energy Source Input Energy Source Gas Coal Petroleum Nuclear

Projected Annual Growth Rate 6.4% 3.7% 2.2% 0.5%

As this table shows, the projected growth in generating capacity fueled by gas is twice the overall growth rate and 73% greater than coal, the number two fuel. As further proof that gas will be the predominant fuel, it is estimated that over the next 5-7 years over 85% of the new capacity added to the U.S. electric power generation industry will be gas turbine based. Even though gas fired units will not be dominate globally, they will be major factors particularly in regions where natural gas is readily available. One recent forecast has projected the growth of new electric generating capacity over the next 10 years. This forecast estimates 695 GW of new capacity with a global distribution as shown in Exhibit 3. This forecast further estimates that gas will fuel at least 40% of the new capacity. It should be noted that natural gas will not fuel only combined cycle or even gas turbine units. Natural gas is used to fuel many traditional steam turbine units. However, because of the advantages of combined cycle technology, much of the natural gas will go toward fueling these types of units.

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Combined Cycle Unit Applications Exhibit 4

Global Distribution of Projected New Generating Capacity USA & Canada 12% Latin America 11% Asia-Pacific 52% Europe, Middle East, Africa 25%

All the above indicates that gas fired turbines will be a major factor in the growth of the electric power generation industry, and with increased emphasis on competition and profitability, combined cycle units should be the preferred technology. There are other factors that also favor combined cycle technology. Below is a summary of the factors that make combined cycle technology attractive: • • • • • • • •

Lower initial investment cost Smaller land parcels needed Higher efficiency Lower operating and maintenance costs Faster return on investment Environmental factors (very low pollution potential because most units fired with natural gas) Versatility Ease of obtaining permits

As a more definitive comparison of combined cycle technology versus the other types of generating units, Table 3 below is presented.

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TABLE 3 COMPARISON OF GENERATING UNITS

INVESTMENT GENERATING METHOD COSTS – US$/kW Nuclear >$5,000/kW Nuclear (incl. waste disposal) Conventional coal $750/kW w/ FGD 1 Conventional coal $700/kW Combined cycle $600/kW 1 – flue gas desulfurization

OPERATING EFFICIENCY 32%

OPERATINGCOSTS US$/kWh $0.023-0.040/kWh $0.040-0.057/kWh

38 – 42% 39 – 43% 57%

$0.030/kWh

There are some regional comments worth considering. Combined cycle units will be favored in North America because of competitive factors, environmental issues, and short construction cycles. Combined cycle units will be built in parts of Latin America because of the availability of natural gas. Europe will favor combined cycle units because of environmental concerns. China, which has huge potential, will likely stress traditional coal fired units short term, but as natural gas becomes more available, combined cycle will receive increased emphasis. Natural gas is currently a preferred fuel for electricity generation because it is readily available at attractive prices and it is environmentally friendly. However, coal is still a very abundant fuel and will continue to be a factor particularly as coal gasification technology advances. In the U.S., the Department of Energy is assisting in the development of integrated gasification combined cycle (IGCC). These plants will use gasified coal as fuel to operate a standard combined cycle unit. Three operating demonstration projects are up and running. One of these projects, located in Tampa, Florida, has Flowserve pumps installed for the boiler feedwater and water circulating applications so the company is gaining valuable experience in this emerging technology. Active research projects are underway in advanced gasification systems, hot gas desulfurization, hot gas particulate removal, and advanced turbine systems. Fully developed and proven IGCC technology could lead to coal being the most economical, long-term fuel of choice for electricity production. In fact, the Department of Energy estimates that successful development of IGCC technology could lead to it providing about 30% (approximately 450 GW) of the U.S. electricity by the year 2050. 2.2 Competition The primary global competitors in the electric power generation industry are IDP, KSB, Weir, and Sulzer. One major regional competitor is Ebara in the Asia-Pacific. Flowserve pumps have performed well in many power industry applications for many years. The global presence of the Flowserve organization will allow the company to participate in

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Combined Cycle Unit Applications the power industry worldwide. The electric power generation industry is becoming more competitive and cost-conscience and Flowserve can assist power companies in improving pump reliability that leads to improved profitability. The features that provide Flowserve pumps with competitive advantages will be highlighted in Section 3.3.

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3.1 Flowserve Sales There will be global demand for new electric power generating capacity for the foreseeable future. Demand for new capacity will be strongest in the Asia-Pacific and Europe-Middle East-Africa regions, but the USA-Canada and Latin America regions will see significant growth also. At least 40% of the new demand will be supplied by gas turbine facilities and most of these will use combined cycle technology. The global presence of Flowserve should allow the company to be an active participant in this growth. 3.2 Decision Makers Engineering firms are the key players in determining the equipment supplier(s) for new electric power generating facilities. These firms generally have a rotating equipment specialist assigned to each project and this individual will be the key decision maker regarding pump selection frequently with input from the end-user’s rotating equipment specialist. Price is important along with the past experience and reputation of the pump supplier. 3.3 Competitive Advantages of Flowserve Pumps Flowserve has achieved a reputation for supplying high quality, dependable pumping equipment to the electric power generation industry and has gained a wealth of experience through handling many of the critical services found in central power generating units. Most of the critical applications in combined cycle units involve water handling; namely, boiler feedwater services, condensate services, and water circulating services. The boiler feedwater pumps must handle high pressures and fairly high flow rates and for these services between bearing multistage pumps are commonly used. For very high pressures, double case pumps are sometimes required. The condensate services typically have very low values for NPSH available and vertically suspended double case pumps are used. The water circulating services characteristically have very high flow rates at low pressures and vertically suspended mixed flow and axial flow pumps are used. For the boiler feedwater services, Flowserve models MX, MSN, DVMX, HDB, and HDBI are commonly used. These between bearing single and double casing multistage pumps offer the following features and benefits: Feature Axially split case Double suction first stage impeller (option) Finned bearing housing Dynamic balancing of fully assembled rotating unit

Benefit Ease of maintenance Minimizes NPSHR Maximum heat dissipation Minimize vibration

Another type of pump used for boiler feedwater services in combined cycle units is the ringsection (also called segmental ring, diffuser, or “pancake”) design. Flowserve competes against this type of pump by promoting the lines, and the features and benefits, listed above.

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Combined Cycle Unit Applications For the condensate water services, Flowserve model VLT pumps are commonly used. These vertically suspended double case pumps offer the following features and benefits for these difficult services: Feature Standard large eye first stage impeller Integral wear rings Registered motor fit Four piece rigid adjustable coupling

Benefit Very low NPSH required Lower initial cost Better alignment, reduced vibration Superior alignment, eases seal replacement

For the circulating water services, Flowserve vertically suspended axial and mixed flow pumps are commonly used. Typical models include the HQ, HXH, and RXL. Features and benefits of these pumps include: Feature Open, semi-open, and closed impellers available Integral bearing retainer Engineered to customer specifications Split-ring, keyed impeller

Benefit Optimum hydraulic coverage Positive alignment, reduced maintenance Maximize efficiency Reliable, safe operation

Depending on the combined cycle unit design, there can be applications for other types of Flowserve pumps. Appendix A lists some of the possible auxiliary applications. 3.4 Guidelines for Mechanical Seals Water, particularly hot water, is difficult to seal. As the temperature increases, the viscosity, and therefore the lubricity, of water drops dramatically. For this reason, proper seal design and materials of construction are critical to providing long and dependable life. To insure proper seal selection for the critical water handling pumps in a combined cycle unit, the advice of a Flowserve FSD sealing specialist should be sought. 3.5 Operating Unit and Pump Details The critical pump applications in a combined cycle unit are the water handling pumps. In Section 4, Pump Applications, proven pump configurations (models, materials, seals, etc.) will be presented.

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Combined Cycle Unit Applications 4.1 Introduction to Pump Recommendations Regardless of the size of a combined cycle unit, the water handling pumps are critical elements in the performance of the unit. To give a sense of the types of pumps typically used and the configuration of these pumps, below is presented the water handling pumps (HRSG feedwater, auxiliary steam boiler feedwater, condensate, and circulating water) for a 500 MW 2 combined cycle unit. This is a two-turbine unit and Exhibit 4 is a schematic of this unit showing the placement of the pumps. 4.2 HRSG Feedwater Pumps Total dynamic head (TDH) @ rated capacity – 5800 ft (1768 m) Capacity @ rated TDH – 950 gpm (216 m 3/hr) Temperature – 300oF (149 oC) Pump Model – MSN (6X6X11MM, 12 stage) Material of construction – Case and impeller (ASTM A743, Grade CA-6NM) Mechanical seal – Flowserve Type QB (Material Code – 5N4A, API Code – BSTFM) 4.3 Auxiliary Steam Boiler Feedwater Pumps (These pumps are not shown in Exhibit 4. These are used as start-up pumps or as fill pumps for the system and their location will depend on the individual system design.) Total dynamic head (TDH) @ rated capacity – 760 ft (232 m) Capacity @ rated TDH – 550 gpm (125 m 3/hr) Temperature – 220oF (104 oC) Pump Model – SCE (3X6X15M) Material of construction – Case (Carbon steel), impeller (ASTM A743, Grade CA-6NM) Mechanical seal – Flowserve Type QB (Material Code – 5N4A, API Code – BSTFM) 4.4 Condensate Pumps Total dynamic head (TDH) @ rated capacity – 575 ft (175 m) Capacity @ rated TDH – 1475 gpm (335 m 3/hr) Temperature – 100oF (38oC) Pump Model – VLT (1300) Material of construction – Case and impeller (Cast iron) Mechanical seal – Flowserve Type QB (Material Code – 5N4A, API Code – BSTFM) 4.5 Circulating Water Pumps Total dynamic head (TDH) @ rated capacity – 80 ft (24 m) Capacity @ rated TDH – 55,300 gpm (12,560 m 3/hr) Temperature – 80oF (27oC) Pump Model – 48 HXH (1 stage VCT) Material of construction – Case (Cast iron), impeller (316L SS)

2

MW = megawatt = one million watts

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Compressor

Gas Turbine

Generator

Electricity

Gas Turbine

Generator

Electricity

Generator

Electricity

Fuel

Air Compressor

Exhaust

Steam Heat Recovery Steam Generator

Steam Turbine

Condenser

HRSG Feedwater Pump

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Condensate Pump

Condenser Hot Well

4-3

Cooling Water Circulating Pump

Combined Cycle Unit Applications Appendix A Auxiliary Pumps for Combined Cycle Units There are a number of potential applications for other types of Flowserve pumps in combined cycle units. These may not be part of the specification for the actual unit but rather these may be found in specifications for auxiliary services. Some common descriptions for auxiliary pumps include: • • • • • • • • • • • •

Service water Chlorine booster Evaporator coil feed Filter backwash Gland water circulation Auxiliary cooling water Glycol solution recirculation Evaporator feed Service water jockey Glycol heater drain Turbine oil transfer Chemical feed

An integrated gasification combined cycle unit (IGCC) will include a coal handling system and there will probably be need for the following pumps: • • • • •

Dust suppression spray Dump building sump Coal pile runoff pond Treatment pond discharge Floor drain sump

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Flowserve Pump Application Manual

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