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Hydrogen

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Contents. 3

Introduction

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Hydrogen

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Production o hydrogen rom light hydrocarbons

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Process eatures

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Process options

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Modular hydrogen plants

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Liquid hydrogen technology

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Contact

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Introduction. Linde - the company´s background in the hydrogen business. Ever since hydrogen was in demand in the chemical and ertilizer industry – and more recently in the petrochemicals ield – Linde was involved with the latest improvements in hydrogen generation. For example, the puriication o various industrial raw gas eedstocks like coke oven and coal gasiication gases, sophisticated and tailor made sourgas steps with chemical and/or physical absorption, and adsorption steps ollowed by low temperature puriication and rectiication processes with “cold box“ units.

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Hydrogen. The demand o hydrogen grew as the world´s consumption o reinery products increased by the ever growing industrialization. The demand or better and more abundant automotive uels called or better yields rom the limited eedstock crude oil. In turn the demand or hydrogen import grew to balance the hydrogen reining catalytic reinery process steps.

Hydrogen plant in Germany

Amongst all hydrogen technology suppliers, Linde is the outstanding contractor or complete hydrogen plants and the only company who owns all technologies inhouse, covering the complete range o petrochemical eedstocks rom natural gas through LPG, reinery o-gases and naphtha up to heavy uel oil, asphalt and coal.

These technologies are basically: – Steam reorming technology or light HC-eedstock combined with Linde´s own PSA systems or hydrogen puriication. – Partial oxidation technology or heavy HCeedstock ollowed by a sequence o various integrated process steps to shit, desulurize and puriy the raw hydrogen. The pure oxygen or the gasiication is produced with a Linde air separation unit.

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Hydrogen plant in Australia

The speciic Linde know-how in all these ields are the essential advantage or a successul integration and complete inhouse optimization o all process sections. The results are highly eicient and reliably operating hydrogen plants. Since the early 70´s Linde avoured and promoted with innovative improvements the now well established steam reorming/pressure swing adsorption technology or the production o pure and ultrapure hydrogen preerably rom light hydrocarbon eedstock.

Proven know-how in design and construction o urnaces, steam reormers and heaters has been completed with the acquisition o Selas o America, which is now Selas Fluid Processing Co. in the USA and SELAS-LINDE GmbH in G ermany. Linde together with Selas have developed their own proprietary top ired reormer design. Combining the know-how o the Engineering Division – and the Gases Divis ion – the company is in the unique position to build, own and operate complete hydrogen plants or continuous supply o hydrogen over the ence to large reineries and chemical companies. The extensive eedback o operating data and inormation on process and equipment perormance in operating plants provides Linde with substantial background or the yet more eicient design o uture plants.

More than 200 new hydrogen plants have been built all over the world, or clients in the reining, chemical and ertilizer industry, with capacities ranging rom below 1,000 Nm 3/h to well above 100,000 Nm3/h, and or processing o all types o eedstock. Most o these plants have been built on a lump-sum turn-key basis.

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Production o hydrogen rom light hydrocarbons. Linde has a well-proven technology for hydrogen manufacture by catalytic steam reforming of light hydrocarbons in combination with Linde´s highly efficient pressure swing adsorption process. A typical lowsheet or a Linde designed large capacity hydrogen plant is shown in igure 1.

The basic process steps 1. Hydrodesulurization o eed stock 2. Steam reorming 3. Heat recovery rom reormed and rom combustion lue gas to produce process and export steam 4. Single stage adiabatic high temperature CO-shit conversion 5. Final hydrogen puriication by pressure swing adsorption

Figure 1

Demin water Export steam    s    s    e    c    o    r     P    m    a    e     t     S

Feed pretreatment

Waste heat recovery

H2-recycle

Steam reorming

CO-shit conversion

Feed

Pressure swing adsorption Hydrogen

Fuel Purgegas

Steam reormer

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Process eatures. Process design and optimization or every process step and in particular the optimized linking o operating parameters between the two essential process steps: reorming urnace and pressure swing adsorption unit are based exclusively on Linde´s own process and operating know-how. Commissioning and start-up o the plants as well as operator training and ater sales service are perormed by experienced specialists. The reormer urnace A compact re box design with vertical hanging catalyst tubes arranged in multiple, parallel rows. Minimized number o orced drat top-ring burners, integrated into the rebox ceiling. Compared to other designs, burner trimming and individual adjustment to achieve a uniorm heat fow pattern throughout the reormer cross section is substantially aciliated.

supported by the fue gas collecting channels arranged at ground level between the hot reormed gas headers. Thermal expansion as well as tube and catalyst weight are compensated by the adjustable spring hanger system arranged inside the penthouse, removing the mechanical stress rom the hot maniold outlet headers at ground level.

Concurrent ring ensures a uniorm temperature prole throughout the reormer tube length. Flame and stable combustion fow pattern is

The radiant reormer box is insulated with multiple layers o ceramic bre blanket insulation, mechanically stable and resistant to thermal stress.

Convection section Depending on the hydrogen product capacity, the convection section - a series o serial heat exchanger coils - is arranged either vertically with ID-fuegas an and stack at reormer burner level or - specically or the higher capacity units - horizontally at ground level or ease o access and reduced structural requirements.

Fuel HP steam

Hydrogen

Combustion air

Feed LP steam Demin water

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Pressure swing adsorption The particular eatures o Linde´s PSA technology are high product recovery rates, low operating costs and operational simplicity. Excellent availability and easy monitoring are ensured by advanced computer control. Extensive know-how and engineering expertise assisted by highly sophisticated computer programs guarantee the design and construction o tailormade and economical plants o the highest quality. Modular skid design o the PSA plants reduces erection time and costs at site. The ully preabricated skids are thoroughly tested beore they leave the workshop. Smooth operation to protect catalysts and reorming tubes require a thorough eed back rom the internal PSA computer system regarding purgegas fow and heating value. This enables the control system to control the urnace´s total uel management in dependence on the nal hydrogen product fow.

Saety philosophy Saety (Hazop-) studies and ESD-system design philosophy are based not only on more than 30 years o steam reorming plant experience but on the cumulative know-how, which the Linde saety experts gained with numerous turn-key lump-sum contracts, especially or large-scale synthesis gas plants as well as or complex olen production units. Environmental protection For steam reorming based hydrogen plants, special care is taken regarding gaseous emission o NOx and CO, calculation o outdoor sound propagation and measurement o noise emission design, design o blow-down and fare system, considering permissible levels or heat radiation and air pollution etc.

Hydrogen plant in China

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Mixed eed gas and steam

Mixed eed pre-heat

Primary reormer

Pre-reormer re-heat

Pre-reormer Reormed gas

Process options. Pre-reorming Pre-reorming is the term applied to the low temperature steam reorming o hydrocarbons in a simple adiabatic reactor using highly active, nickel based catalyst, which promotes the steam reorming reaction at low temperatures. This process was developed in the 1960´s or town gas and synthetic natural gas (SNG) production. Feedstock - ranging rom natural gas to naphtha is converted by the steam reorming reaction to give an equilibrium mixture containing hydrogen, carbon oxides, methane and steam. Depending on the eedstock, the temperature prole can be either endothermic or exothermic.

The advantages provided through the inclusion o a pre-reorming unit may oten be plant specic. Some or all o t he ollowing advantages may apply to a specic case – Fuel savings over stand alone primary reormer – Reduced capital cost o reormer – Higher primary reormer preheat temperatures – Increased eedstock fexibility – Lower involuntary steam production – Lower overall steam/carbon ratios – Provides protection or the main reormer

In its most common application today the main benet comes rom the ability to eectively transer reorming heat load rom the radiant section o a reormer to its convection section.

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MT-shit Apart rom the conventional adiabatic MT-shit, Linde developed and successully installed the isothermal Medium Temperature shit reactor, a xed bed reactor suitable or exothermic and endothermic catalyst reactions, with an integrated helically coiled tube heat exchanger or cooling or heating o the catalyst.

Steam

Circulating water Boiler eed water Gas entry

In the case o isothermal MTS the exothermic catalytic reaction heat is removed by producing steam, with only a ew degrees o temperature dierence throughout the reactor. This isothermal reactor type is successully applied in the chemical industry or the methanol synthesis, or methanation, hydrogenation and or the ® Linde CLINSULF sulur recovery. Gas heated reorming (GHR) The GHR unit is a combination o a gas heated reormer and an oxygen-red autothermal reormer, where the heat o reaction is supplied by the hot gas exiting the autothermal reormer. The main advantages o the GHR process: – Lower energy consumption – Lower investment costs – Primary reormer with fue gas waste heat recovery system is eliminated – No steam production in the reormed gas cooling section, thus eliminating the waste heat boiler – As steam/power generation and oxygen production are conned to independent units, opportunities exist or “over the ence supply“ – Optimum consideration o environmental aspects with regard to zero fue gas rom the core unit and relevant minimum charges originating rom the potential power/steam generation unit The convective as well as the autothermal step can be individually integrated in fow schemes or revamping and capacity increase o existing conventional hydrogen plants.

Circulating water

Oxygen / steam

Gas exit Isothermal reactor

Natural gas / steam

Syngas

Gas heated reorming

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Reormer urnace

Typical Perormance Figures o a Steam Reorming based Hydrogen Plant

low rate

Product hydrogen

pressure purity low rate temperature pressure

Export steam

Nm³/h MMSCFD bara mol-% T/hr °C bara

Feed and uel consumption

Gcal/hr GJ/hr

Energy consumption (incl. steam credit)

Gcal/1,000 Nm³ H2 GJ/1,000 Nm³ H2

Utilities

Design lexibility

demin. water cooling water electrical energy export steam production uel consumption

T/hr T/hr kW T/1,000 Nm³ H2 GJ/1,000 Nm³ H2

Natural gas

LPG

Naphtha

Reinery gas

50,000 44.8 25.0 99.9

50,000 44.8 25.0 99.9

50,000 44.8 25.0 99.9

50,000 44.8 25.0 99.9

31 390 40

28.9 390 40

28.6 390 40

29.2 390 40

177.8 744.4

181.8 761.2

182.9 765.8

175.8 736.0

3.070 12.853

3.210 13.440

3.222 13.490

3.072 12.862

55.6 160 850

57.5 165 920

60.6 168 945

53.2 157 780

0.5 - 1.2 0.9 - 3.5

0.4 - 1.2 1.8 - 4.3

0.4 - 1.2 1.9 - 4.4

0.4 - 1.1 0.7 - 2.9

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Modular hydrogen plants. With it´s subsidiary Hydro-Chem Linde has a leading position in prefabricated and skidmounted steam reforming hydrogen plants including methanol cracking. Markets served Modular hydrogen plants with typical capacities rom 150 to 12,000 Nm3/h are designed with the ollowing industries in mind: – – – – – – –

Food industry Steel industry Glass industry Polysilicon (electronics and solar panel) Hydrogen peroxide production Hydrogenation processes/oil reneries Oleochemicals

Technology These modular hydrogen plants are based on inhouse steam reorming technology employing a round up-red can reormer type design. Followed by a purication step using in-housestandard 4 or 5-bed PSA technology.

Design The modular plant is designed to meet exact customer needs. The pre-assembled modular designs satisy the most demanding product requirements. The layout is optimized to minimize space and to ease maintenance. Automation The modular designed hydrogen plant can be supplied with ully automatic remote control or unmanned operation including sae start-up and shut-down, supervised by common service centers.

Modular Fabrication Modular abrication o hydrogen acilities is done in own and/or selected external workshops, where or example heat exchangers, vessels, boilers and piping assemblies are abricated. All o the components are assembled in the workshops into compact, l ow-cost and easy to install modular units. The pre-assembled units oer the most economical layout wi thout sacricing access or operation and maintenance.

Modular hydrogen plant

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Liquid hydrogen technology. Liquid hydrogen technology Hydrogen is the vehicle uel or the uture - a sae and pollution ree, environmentally riendly alternative to gasoline and kerosene. Linde is ully prepared to meet this challenge and is already cooperating with companies such as BMW, Daimler, GM and Shell on the development o ueling and storage technologies. Today o course there are already many applications or liquid hydrogen, e.g. in rocket propulsion and semi-conductor manuacture, where high purity blanketing gas is required. Typical industrial plants supplied by Linde or these applications are: – The BOC – AIRCO acility in MAGOG – Canada with a capacity o 13,600 kg/d.

Additionally plants with smaller capacities, down to 500 kg/d, have been s upplied to various countries. Again Linde´s involvement in hydrogen technology covers not only liqueaction but also purication, distribution and storage as well as all aspects o s ae handling. A reerence or this are the cryogenic propellant storage and handling system or the ARIANE 5 rocket propusion test acilities SEP, France and DLR, Germany. To promote the development o the necessary hydrogen inrastructure or vehicles, Linde is engaged in easibility studies with AIRBUS Industries and the European Quebec Hydrogen Project (EQHHPP).

Liquid hydrogen production acility at refnery in Leuna, Germany

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LH2- ueling station in USA

Δ CGH2- ueling station in Tokio

Mobile CGH2 and LH2- ueling station

CGH2 and LH2- ueling station in Germany

Δ

Designing processes – constructing plants. Linde´s Engineering Division continuously develops extensive process engineering know-how in the planning, project management and construction o turnkey industrial plants. The range o products comprises: − Petrochemical plants − LNG and natural gas processing plants − Synthesis gas plants − Hydrogen plants − Gas processing plants − Adsorption plants − Air separation plants − Cryogenic plants − Biotechnological plants − Furnaces or petrochemical plants and reneries

Linde and its subsidiaries manuacture: − Packaged units, cold boxes − Coil-wound heat exchangers − Plate-n heat exchangers − Cryogenic standard tanks − Air heated vaporizers − Spiral-welded aluminium pipes

More than 3,800 plants worldwide document the leading position of the Engineering Division in international plant construction.

Engineering Division Schalchen Plant Tacherting, Germany Phone +49.8621.85-0 Fax +49.8621.85-6620 [email protected] Linde-KCA-Dresden GmbH Dresden, Germany Phone +49.351.250-30 Fax +49.351.250-4800 [email protected] Selas-Linde GmbH Pullach, Germany Phone +49.89.7447-470 Fax +49.89.7447-4717 [email protected] Cryostar SAS Hésingue, France Phone +33.389.70-2727 Fax +33.389.70-2777 in[email protected] Linde CryoPlants Ltd. Aldershot, Great Britain Phone +44.1.252.3313-51 Fax +44.1.252.3430-62 in[email protected]

Linde Impianti Italia S.p.A. Rome, Italy Phone +39.066.5613-1 Fax +39.066.5613-200 [email protected]

Linde Engenharia do Brasil Ltda. Rio de Janeiro, Brazil Phone +55.21.3545-2255 Fax +55.21.3545-2257  [email protected]

Linde Engineering India Pvt. Ltd. Vadodara, Gujarat, India Phone +91.265.3056-789 Fax +91.265.2335-213 [email protected]

Linde Kryotechnik AG Pungen, Switzerland Phone +41.52.3040-555 Fax +41.52.3040-550 in[email protected]

Linde Process Plants (Pty.) Ltd.  Johannesburg, South Arica Phone +27.11.490-0513 Fax +27.11.490-0412 [email protected]

Linde Engineerig Far East, Ltd. Seoul, South Korea Phone +82.2789-6697 Fax +82.2789-6698 [email protected]

Cryo AB Göteborg, Sweden Phone +46.3164-6800 Fax +46.3164-2220 [email protected]

Linde-KCA Russia Branch Moscow, Russia Phone +7.495.646-5242 Fax +7.795.646-5243 [email protected]

Linde Engineering Division Bangkok, Thailand Phone +66.2636-1998 Fax +66.2636-1999 [email protected]

Linde Process Plants, Inc. Tulsa, OK, U.S.A. Phone +1.918.4771-200 Fax +1.918.4771-100 [email protected]

Linde Arabian Contracting Co. Ltd. Riyadh, Kingdom o Saudi Arabia Phone +966.1.419-1193 Fax +966.1.419-1384 [email protected]

Linde Engineering Co. Ltd. Dalian, P.R. o China Phone +86.411.39538-800 Fax +86.411.39538-855  [email protected]

Selas Fluid Processing Corp. Blue Bell, PA, U.S.A. Phone +1.610.834-0300 Fax +1.610.834-0473  john.mcdermott@selasluid.com

Linde Engineering Middle East LLC Abu Dhabi, United Arab Emirates Phone +971.2.4477-631 Fax +971.2.4475-953 [email protected]

Linde Engineering Co. Ltd. Hangzhou, P.R. o China Phone +86.571.87858-222 Fax +86.571.87858-200 [email protected]

Linde AG Engineering Division, Head oice, Dr.-Carl-von-Linde-Str. 6-14, 82049 Pullach, Germany Phone +49.89.7445-0, Fax +49.89.7445-4908, E-Mail: in[email protected], www.linde.com

Linde Engineering Division Beijing Representative Oice Beijing, P.R. o China Phone +86.10.6437-7014 Fax +86.10.6437-6718 [email protected] Linde AG Taiwan Branch Engineering Division Taipei, Taiwan Phone +886.2.2786-3131 Fax +886.2.2652-5871 [email protected] Linde Australia Pty. Ltd. Chatswood N.S.W., Australia Phone +61.29411-4111 Fax +61.29411-1470 [email protected]

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