SAMSUNG ENGINEERING CO., LTD SAMSUNG SEI TOWER, 467-14 Dogok – 2 Dong, Kangnam-Ku, Seoul, KOREA 135-280
DESIGN MANUAL SEM-9486E PROCESS DESIGN MANUAL
Preparation of Datasheet for Boiler Feed Water Chemical Treatment REV. DATE
:0 : 2006.8.23
SAMSUNG ENGINEERING CO., LTD.
DATE : 2006. 8. 23
DESIGN MANUAL
SEM – 9486E
Preparation of Datasheet
REV. : 0
for Boiler Feed Water Chemical Treatment
PAGE i OF i
CONTENTS Page 1
OBJECTIVES & MAKING..............................................................................1 1.1 1.2 1.3
2
OBJECTIVES.........................................................................................1 COMPLEMENTARY POINT.......................................................................1 MAKING................................................................................................1
COMPONENT OF CHEMICAL INJECTION..................................................1 2.1 2.2
SCALE CONTROL..................................................................................1 CORROSION CONTROL..........................................................................4
2.3 2.4
CONDENSATE RETURN LINE CORROSION CONTROL...............................5 CHEMICAL AGENT INJECTION PLACE.....................................................6
3
SELECTION OF CHEMICALS & INJECTION POINT..................................7
4
INJECTION LIQUID.......................................................................................7 4.1 4.2 4.3
5
INJECTION PUMP.........................................................................................8 5.1 5.2 5.3
6
DILUTION..............................................................................................7 VAPOR PRESS.........................................................................................7 VISCOSITY...............................................................................................7
NO REQ'D...............................................................................................8 CAPACITY (L/HR).....................................................................................8 CAPACITY CONTROL...........................................................................13
SOLUTION TANK........................................................................................13 6.1 6.2 6.3
CAPACITY...........................................................................................13 MATERIAL..............................................................................................13 ACCESSORIES........................................................................................14
7
AGITATOR....................................................................................................15
8
ACCESSORIES............................................................................................15
9
REVISION HISTORY....................................................................................15
DATE : 2006. 8. 23
1
DESIGN MANUAL
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for Boiler Feed Water Chemical Treatment
PAGE 1 OF 15
OBJECTIVES & MAKING 1.1
Objectives This Guide explains technical specification that need in Boiler feed Water Chemical Treatment's Data Sheets creation by Data Sheet Format, and can filled-up correctly through standardization at data sheets and save time.
1.2
Complementary Point This Guide is applied chemical agent to present immediately by producing. But in most cases, chemical agents vendors make complexes of several same kinds of materials according to their light. Therefore, we need preliminary consultations with vendors in choice of final chemical agent. Moreover, because medicines processing is marching by tending to minimize waste water regarding the final pollution problem, it will make up for processing by using newest tendency and Vendor Data.
1.3
Making Write position of Data Sheet Format on left side and find easily explaining on right side. - Example: [1-2]: second row in first data sheet : left side of 12th row in second data sheet - Description: start to right of line no. Data Sheet of Boiler Feed Water's chemical treatment can divide by Scale Control, Corrosion Control, and Condensate Treatment
greatly. 2
COMPONENT OF CHEMICAL INJECTION
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2.1
DESIGN MANUAL
PAGE 2 OF 15
Scale Control 2.1.1 Phosphate Control (Fig. 1.1) Ca, Mg in Boiler evaporation surface is not baking and these salt as insolubility sludge settlement derive, and can remove by Blow-Down keeping in melting state. Because phosphate settlement does not get up well in pH 9.5 low, constant alkalinity is required. Conventional Phosphate Control (Caustic Based Control) By keeping Free Caustic of constant concentration, make sludge, liquefy Silica and protect Carry-Over. PO4's remaining concentration is 10 - 40 mg/ls, alkalinity is 100 350 mg/l NaOH (PH 11.4 - 12). It is applied to Boiler lower than 600 psig, and is used widely because processing is simple. - Coordinated Phosphate-PH Control (Fig. 1.2) Phosphate concentration is keeping 3Na/PO4 ratio by method to control PH with phosphate sodium without using caustic soda. It is applied that operating pressure is 1000 1500 psig low. - Congruent Phosphate Control (Fig. 1.3) Because Hide-Out phenomenon occurs and picks up 'Gouging Attack' of glass caustic soda as for 3Na/PO4 ratio over 1500 psig, PO4 concentration keeps by 2.6 Na/PO4s ratio in 2 - 20 mg/l extent. 2.1.2
Chelating Control Because Chelating Agent (Chelant) occurs soluble reaction product by chemical reaction with metal ion, it be not deposited on the Boiler evaporation surface and increased Boiler efficiency and Reliability. EDTA and NTA are used representatively.
DESIGN MANUAL
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1)
PAGE 3 OF 15
Use extent - Low hardness (below 1 ppm) of make-up water applies and high hardness (over 2 ppm) is not economical. - Usually, NTA below 900 psig, EDTA below 1200 psig is applied. (Table 2-1) The following table shows the reaction ratio in parts per million for technical grades of EDTA and NTA.
FOR. 1 PPM IT TAKES METAL ION PPM 100% EDTA 38% EDTA* 100% PPM NTA Total Hardness Calcium Magnesium
(10) 9.5 15.8
(25) (41.6)
2.75 6.9 11.45
Iron
6.8
(17.9)
4.9
Copper
6.0
(15.8)
4.3
Aluminum
14.1
(37.1)
10.0
*Commercial grade EDTA is marketed suppliers may have different strengths. 2.1.3
as
38%
solution,
but
some
Organic Agents If Ca, Mg salts is made sludge by phosphate process, it be can removed by blow-down without sticking on metal surface as keeping by fluid form using organic matter. Organic matter
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PAGE 4 OF 15
is Tannin, Lignin, starch, seaweeds etc. 2.2
Corrosion Control 2.2.1
PH Control Caustic soda (NaOH) and soda ash (NaCO3) are used by counteragent.
2.2.2
Removal of Dissolved Oxygen After it is removed to 0.005 mg/l by De-aerator, remained O2 is removed by chemical agents. 1)
Sodium Sulfite (Na2 SO3) It is used below 900 psig and Hydrazine is used over 900 psig. It is not used in case Sulfur picks up Catalyst fouling. - Reaction 1/2O2 + Na2SO3 -----> Na2SO4. 3Fe2O3 + Na2SO3 -----> 2Fe3O4 + Na2SO4 - Reaction rate It can decreased reaction time using recently developed Cobalt catalyst.
2)
Hydrazine It does not increase Boiler Water's Solid than Sulfite and need not to Boiler Blow-down. - Reaction N2H4 + O2 --------------> 2H2O + N2
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It is very slow reaction than Sulfite. 2.3
Condensate Return Line Corrosion Control Soluble O2, CO2 in steam condensation cause corrosion. Among them, CO2 create carbonate in water and increase corrosion under PH 5.9. 2.3.1
PH Control 1)
Neutralizing Amine As acting directly with coal mine and it is volatility alkali material that raise PH. Morpholine (C4H9NO), Cyclo Hexylamine (C6H13N), DEAE (Di-Ethyl-Amino Ethanol, C6H15NO) etc. are used. - Distribution Ratio (DR) As CO2 is carried with steam, neutralizing amine be must distilled steam. Also, it must be able to neutralize carbonic acid by CO2 of team condensation because is melted at steam condensation. Distilled tendency is described separation ratio when steam is condensed.
Amine concentration in vapor amine concentration in steam DR = ---------------------------------------- = ------------------------------------------Amine concentration in liquid amine concentration in condensate (Table 4-1) 2.3.2
Ammonia
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When there is not damage in ammonia steam process with condensate water polishing unit, it is decreased to use them than to use volatile amine. But it is economical to use condensate water for PH control. 2.3.3
Film Protection 1)
Filming Amine - By chemical agent to keep corrosion prevention over coating, systems to leak amount of air or included much CO2 is used filming amine or inhibitor. - Must not use in system to happen Catalyst Coat. - There are Octadecylamine (C18 H37 NH2), Hexadecylamine (C16 H33 NH2), and Dioctadecylamine (C36 H73 NH2) etc. - Injection agent is injected slowly by small quantity and is not proportional in CO2 concentration. Because it is formed very thin film, it does not disturb electric heat and improve electric heat to cause drop wise condensation.
2.4
Chemical Agent Injection Place Most chemical or organic matter is continuously fed into pump, it does not make a problem, but phosphate processing can make a problem in supply line. - Phosphate Soda: Directly injected boiler drum. Only, Hexametaphosphate can be injected in supply line. - Caustic soda, soda ash: Supply line. Only, injected in Boiler drum if BFW is high hardness, temperature, pH. - Organic sludge controller: Supply line. or Boiler drum - Chelants: Use Sus Quill between BFW Pump and Boiler Drum but
DATE : 2006. 8. 23
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avoid to inject in Boiler Drum - Amine & Ammonia Steam header/BFW Line (Boiler input) 3
SELECTION OF CHEMICALS & INJECTION POINT Record decision in [1 - 12] ∼ [1 - 25] by Item.
4
INJECTION LIQUID 4.1
Dilution Used dilution (Wt %) is as following. Chemical
Injected dilution Agent specification
Phosphate soda 1.0 - 3.0 % Caustic soda
1.0 - 3.0 %
Hydrazine 0.5 - 3.0 % over 99.9% Ammonia 1.0 - 3.0 % over 99.9% Neutralizing Amine Sodium sulfite 4.2
KS KS 35-60% solution, 5-25% solution, 40% solution KS
Vapor Press Usually, because dilution by water is high, steam pressure at operating temperature (10∼30℃) almost ignore. Specially, neutralization amine with low flash point and hydrazine are used solution without Flash Point, (each under 40%, 35%)
5
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4.3
DESIGN MANUAL
PAGE 8 OF 15
Viscosity
INJECTION PUMP 5.1
Required No. Establish supply Unit (tank, pump, connection pipe laying, chief) by each chemical agent, and establish supply pump by each boiler in case of phosphate soda. And establish a Common Stand-By pump per a Unit.
5.2
Capacity (L/hr) The following is Nor. Capacity. Explain and decide to take into account extra margin 200%. 5.2.1
Scale Control 1) Injection of Sodium Phosphate (tri-Phosphate) The injected amount is sum of phosphate soda amount and phosphate amount in Blow. - Molecular formula: Na3 PO4 12H2O [MW=380] 380 - W (g/HR) = ――― × P × B + 2.28 × H × F 95 380 1 PPM req'd = ――― × P × ―― + 2.28 × H 95 N W = Injected amount, P = PO4 concentration in boiler [ppm] B = Blow amount [T/H], N = F/B. Concentration Cycle F = Feed Water [T/H] *1. Actual used amount becomes different according to
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crystal water of phosphate. *2. Form of settlement is Ca3 (PO4) Ca (OH) 2, ratio of phosphate for hardness ingredient 380 × 2 ――――――― × 1.2 = 2.28 100 × (3+1) 2) Injection of Sodium Phosphate (di-Sodium Phosphate) - Molecular formula: Na3 HPO4 12H2O [MW=380] 358 - W (g/HR) = ――― × P × B + 2.15 × H × F 95 3) Injection Phosphate)
of
poly
Sodium
Phosphate
(hexa-meta-
- Molecular formula: (NaPO3)6, MW = 612 612 612 - W (g/HR) = ――― × P × B + ――― × H × F 570 N 1000 612/6 × 2 612 *3. ―――――― × 1.2 = ――― 100 × 4 1000
4)
Chelant -The injection amount is decided concentration, ph, temperature, used Chelant's reactivity. - EDTA of 1mol reacts with metal of 1mol and inject
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PAGE 10 OF 15
to 1 - 2 ppm excess amount to necessary Chelant (table 2 - 1) by Feed Water. Over dosing brings Boiler Metal's loss. 5) 5.2.2
Organic Agents
Corrosion Control 1)
NaOH Because NaOH is not evaporated by Steam, amount which NaOH is lost by Blow-Down.
W [g/H] = 0.91 × [CO2] × F [CO2]: ppm concentration, F: Feed Water [T/H] 2)
PH control agent Can find from NaOH suitableness (Equivalent NaOH Quantity). ( table 3-1 )
amount
Na2 CO3 1/4.5, SO3 1/2.85 Na2 SO3 1/4.5, CO3 1/2.55 Na3PO4 12H2O 1/15, PO4 1/3.75 3)
De-oxidant, Na2 SO3 8 - 10 ppm per oxygen 1 ppm is required and the injection amount originates to Blow-Down by request remaining excess concentration.
W = B × [SO3] × 1.6 W: used Amount (g/H) B: Blow-Down (T/H)
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Boiler pressure concentration limit SO3 ―――――――― ―――――――――― 0-600 psig 30-50 ppm SO32600-900 psig 10-20 900 psig 4-6 4)
De-oxidant, Hydrazine 1ppm per O2 1 ppm requires theoretically but 1.5 - 2 ppm is applied actually. BFW's concentration limit is 0.05- 0.1 ppm.
remaining
50 W = ―― × [O2] × 2 × F (g/H) or 32 50 W = ―― ([O2] + [N2H4] × F 32 Pure material can not use because of low flash point, use 35% solution without flash point. 5)
Neutralizing Amine Volatility amine makes neutralization product by reacting with CO2 and later CO2 is recovered in circulation cycle because drop in Deaerator if is heated, but recovery rate is different by distribution ratio of used amine and operating condition of deaerator. That is, recovery rate of Morpholine (DR = 0.4) is high and that of Cyclohexylamine (DR = 2.0) is low because of loss in apparatus for excluding air.
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The inject amount is decided according to necessity density (picture - reference) and the recovery rate in boiler drum. The inject amount is calculated by amount to neutralize CO2 of condensate water and keep fixed request pH in a boiler drum. - Used concentration Because of danger of fire, used 40 % solution.
pH at 25 ℃
Ami ne : CO2 wei ght r at i o
Fig 5.1 pH vs., Amine/CO2 Concentration Fig 5.2 pH vs., Amine Concentration 6)
Ammonia When reclaim and reuse condensate water, ammonia of about 70% is lost in De-Aerator.
7)
Filming Amine
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Injection is slowly by small amount and is not proportional in CO2 concentration. 5.3
Capacity Control 5.3.1
Stroke Adjustment It is used most usually by method to control flux controlling Stroke's length.
5.3.2
Speed Control It is used when wish to control correct flux in all range(0 ~ 100%) adjusting Motor's rotations by VVVF using Inverter.
120 × F rpm = ――――― , F : frequency (ex : 60HZ) P P: pole (ex: 4 poles) 5.3.3
Capacity Control Range Do 0∼100 % to principle but promise accuracy in 10∼100 % ordinarily in case of Stroke control.
6
SOLUTION TANK 6.1
Capacity Chemical agent tank establishes one by one per chemical kind and makes capacity can possess during about 3 days.
6.2
Material
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Material is Stainless Steel ordinarily. 6.3
Accessories 6.3.1
Level Gauge & Alarm Attach seeing through or reflection surface (Level Gauge) on each tank, and low level alarm must ring to central panel.
6.3.2
Floating Cover Do to minimize evaporation of volatility material with Hydrazine, Ammonia and Amine, and intercept surface with air always as establish to keep away air contact of deoxidizer (hydrazine, Sodium Sulfite).
6.3.3
Steam Heater Establish for keeping proper temperature of chemical agent.
6.3.4
Measuring Cup It is small size tank having making scale that installed on top of main tank and used to add measured amount of chemicals to main tank.
6.3.5
Inner Basket Establish into tank upper part side to elutriate Over-Size's lump when chemical agent is injected on main frame, and attach Opening Cover.
6.3.6
Steam Bubbling Pipe
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Establish Agitator in phosphate and sulfuric acid tank for powder solid to melt easily. 7
AGITATOR It is used to liquefy Phosphates and Na2 SO3.
8
ACCESSORIES
9
REVISION HISTORY Rev
Date
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0
06.08.23
All
Revision Status - Team : Process Eng'g Team - Made by : J.W. Lee - Checked by : J.C. Ro, E.D. Lee, Henry Sung, B.S. Son - Approved by : C.S. Jung
APPENDIX 1 DATA SHEET FORMAT
APPENDIX 2 SIMPLE DATA SHEET