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Providing Solutions for Tomorrow’s Environment 1Providing Solutions for Tomorrow’s Environment
Fundamentals ofFundamentals of
Sour Water StrippingSour Water Stripping
Presented at the
Brimstone Sulfur Symposia
V il C l d S t b 2008Vail, Colorado, September 2008
David K. Stevens
President & CEO
Alan Mosher
Director of Engineering
2Providing Solutions for Tomorrow’s Environment
President & CEO Director of Engineering
2
Outline
Sources and Characteristics of Sour Water
Sour Gas Processing
Refining Processes
l lClaus Tail Gas Treating
Gasification and Similar ProcessesGasification and Similar Processes
Processing SWS Offgas in SRU/TGUsProcessing SWS Offgas in SRU/TGUs
Alternatives Strategies for Sour Water andAlternatives Strategies for Sour Water and
Sour Gas
Providing Solutions for Tomorrow’s Environment 3
Sour Gas
Sources and Characteristics of
Sour Water
Sour Gas Processing
Oil Refining
Gasification and Other Thermal Process
Claus Tail Gas Units
Providing Solutions for Tomorrow’s Environment 4
3
Sour Gas Processing
Sources of Sour Water
Wellhead Facilities
Dry or Wet Pipeline
Plants
Inlet Separators
Li id KO DLiquid KO Drums
– Dehydration UnitDehydration Unit
– Claus Plant
– Compressor Aftercoolers
Providing Solutions for Tomorrow’s Environment 5
Sour Gas Processing
Sources of Sour Water (cont.)
Plants (cont.)
Dehydration Processes
– Glycol Regen Condensate
Solid Bed Absorbent Dehydrator Regen– Solid Bed Absorbent Dehydrator Regen
Gas Treating Units – Reflux Purgeg g
Tail Gas Units – Quench Water
Providing Solutions for Tomorrow’s Environment 6
4
Sour Gas Processing Characteristics
Two Types of Sour Water
Produced Water
– Water that originates in the reservoir and flows up the
tubing with the gastubing with the gas
Condensed Water
– “Salt-free Water” that condenses from the gas after the
gas has left the producing reservoirgas has left the producing reservoir
Providing Solutions for Tomorrow’s Environment 7
Produced Water Characteristics
Originates in Reservoir
Generally Removed in Inlet Separator
H2S and CO2
Salt-Bearing
Anions Cations
Chl id P t iChlorides Potassium
Bromides Sodium
Sulfates Magnesium
Providing Solutions for Tomorrow’s Environment 8
5
Produced Water Characteristics (cont.)
Hydrocarbons
Methanol/Hydrate Inhibitors
Corrosion Inhibitors
Hydrocarbons
Providing Solutions for Tomorrow’s Environment 9
Produced Water Processing
Injection Well with Filtration
Local
Remote (Trucked)
Stripping
St I j ti St R b ilSteam Injection or Steam Reboiler
Gas – Avoids Salting Out PotentialGas – Avoids Salting Out Potential
Providing Solutions for Tomorrow’s Environment 10
6
Produced Water Processing (cont.)
Offgas Disposal
Flare
Low Tonnage Sulfur Recovery
lRecompression to Pipeline
Evaporation PondsEvaporation Ponds
Salt PresenceSalt Presence
Providing Solutions for Tomorrow’s Environment 11
Condensed Water Characteristics
Condensed After Gas has Left Reservoir
“Salt Free”
H2S and CO2 GlycolsH2S and CO2
Hydrocarbons
G yco s
Methanol
Iron Sulfides Other Hydrate Inhibitors
Amines Corrosion Inhibitors
Providing Solutions for Tomorrow’s Environment 12
7
Condensed Water Processing
Strippingpp g
Steam Injection or Steam Reboiler
Gas
Disposal of Offgas
FlFlare
Claus PlantClaus Plant
Integrate with Tail Gas Quenchteg ate t a Gas Que c
Providing Solutions for Tomorrow’s Environment 13
Condensed Water Processing (cont.)
Disposal of Stripped Sour Waterp pp
Injection Well
Evaporation Pond
Upgrade to BFW
Providing Solutions for Tomorrow’s Environment 14
8
Some Approaches to Sour Water
Stripping in Sour Gas Processing Plants
Integrate a Sour Water Stripper with a Tail Gasg pp
Quench System
Re-use of Tail Gas Quench Water as Boiler Feed
WWater
Providing Solutions for Tomorrow’s Environment 15
Integrated Sour Water Stripper with Tail Gas Quenchg pp Q
16
9
Reuse of Quench Water for BFWQ
17
Oil Refining – Sources of Sour Water
Desalters
/Crude/Vacuum Units
H dHydrotreaters
FCCFCCs
Thermal CrackingThermal Cracking
HydrocrackingHydrocracking
Amine TreatingAmine Treating
Claus Tail Gas Units
Providing Solutions for Tomorrow’s Environment 18
Claus Tail Gas Units
10
Oil Refining – General Trends
Higher Sulfur and Nitrogen Content Crudes
Deeper Levels of Hydroprocessing
Generate Higher Levels of Sour Water
Providing Solutions for Tomorrow’s Environment 19
General Characteristics of
Refinery Sour Water
“Typical” Concentrations
H2S 300 to 12,000 ppm (wt)
NH 100 8 000 ( )NH3 100 to 8,000 ppm (wt)
Molar Ratio NH :H SMolar Ratio NH3:H2S
Between 1 0 and 2 0Between 1.0 and 2.0
Typical 1.1 to 1.4yp
Typical pH between 8 and 10
Sour Water pH dictates NH3:H2S Ratio
Providing Solutions for Tomorrow’s Environment 20
11
Refinery Sour Water
Range of Potential Contaminates
Phenol Organic Acids Hydrocarbon
Cyanide Caustic Chloride
Selenium Mineral Acids HardnessSelenium Mineral Acids Hardness
Providing Solutions for Tomorrow’s Environment 21
How the Bad Actors Behave
Acidic Anions: Chlorides Sulfates FormatesAcidic Anions: Chlorides, Sulfates, Formates
Depress pHp p
Tie-up Ammonium Ion
Alkali Cations: Sodium, Potassium
Raise pHRaise pH
Tie-up Sulfide Ionp
Phenols – Not readily strippable
Cyanide – Corrosive; use of polysulfides to form
thi tthiocyanate
Naphthenic and Cresylic Acids
Providing Solutions for Tomorrow’s Environment 22
Naphthenic and Cresylic Acids
12
How the Bad Actors Behave (cont.)
Heavier Hydrocarbons Multiple problems;Heavier Hydrocarbons – Multiple problems;
Can polymerizeCan polymerize
Carbon Dioxide – Lower pH and tie-up
Ammonia
C l i C i it t h d iCalcium – Can precipitate as hardness in
stripperstripper
Oxygen – Egress can form acid which fixyg g
Ammonia
Amine – Can tie-up Ammonia
Selenium Can precipitate and foul stripper
Providing Solutions for Tomorrow’s Environment 23
Selenium – Can precipitate and foul stripper
The Problem with Phenols
Phenols are not removed due to solubility
h t i ti t t ffi i icharacteristics – not tray efficiencies
Phenolic Bearing Units (With OtherPhenolic – Bearing Units (With Other
Contaminates such as Cyanides and ColloidalContaminates such as Cyanides and Colloidal
Sulfur)
Cokers
Crude Units
FCCFCCs
ARUs and TGU Purge
Providing Solutions for Tomorrow’s Environment 24
ARUs and TGU Purge
13
The Problem with Phenols (cont.)
Non-Phenol Bearing Unitsg
Hydrotreaters
Desulfurization Units
Providing Solutions for Tomorrow’s Environment 25
Chemistry of Refinery Sour Water
“Sour Water” forms as Water and Hydrocarbony
are in contact and partition the Hydrogen
Sulfide and Ammonia in accordance with
Henry’s LawHenry s Law
The Ammonia and Hydrogen Sulfide dissolvedThe Ammonia and Hydrogen Sulfide dissolved
in the now “Sour Water” ionize to the
equilibrium extent according the pH and
temperature
Providing Solutions for Tomorrow’s Environment 26
14
Chemistry of Refinery Sour Water (cont.)
Ammonia and Hydrogen Sulfide can only be
stripped if in parent gaseous form i e exertingstripped if in parent gaseous form, i.e. exerting
a partial pressure The iononized componentsa partial pressure. The iononized components
do not strip
Presence of ions which raise the pH tie-up
Sulfides and aid Ammonia stripping
Conversely presence of ions which lower the
pH tie up the Ammonia and aid SulfidepH tie-up the Ammonia and aid Sulfide
stripping
Providing Solutions for Tomorrow’s Environment 27
stripping
Approach to Sour Water Management
in the Oil Refinery
Stripped Sour Water Specifications
Re-use Strategy
Feed Preparation
Sour Water Stripper
Sour Water Offgas Disposal
Providing Solutions for Tomorrow’s Environment 28
15
Stripped Sour Water Specifications
Typical WWTP Influent Requirements
25 ppm Ammonia
10 ppm Hydrogen Sulfide
Lower specs are often observed
W SHA SBenzene Waste NESHAPS
Providing Solutions for Tomorrow’s Environment 29
Sour Water Reuse
Recycle All Stripped Sour Water to Desalter orRecycle All Stripped Sour Water to Desalter or
CokerCoker
Segregate Phenolic and Non-Phenolic Sourg g
Water
Recycle Non-Phenolic to
Hydrotreaters/DesulfurizersHydrotreaters/Desulfurizers
– Hydrotreaters can’t tolerate Phenolsy
– SWS only removes 10 to 50 % of Phenol
Recycle Phenolic Sour Water to Desalter were
Oil t t th Ph li C d
Providing Solutions for Tomorrow’s Environment 30
Oil extracts the Phenolic Compounds
16
Sour Water Feed Preparation
Inlet Feed Separation and Hydrocarbon Flash
and Skimming
Vent to Safe Location
dSour Water Feed Surge
3 D St T t3-Day Storage Target
Oil SkimOil Skim
Design to Prevent Short Circuitg
Providing Solutions for Tomorrow’s Environment 31
Sour Water Stripper Design
Non-Refluxed
Direct Steam Injection or Reboiler
Very High Water Content of Offgas
(70 % l @ 13 i )(70+% vol @ 13 psig)
RefluxedRefluxed
Direct Steam Injection or ReboilerDirect Steam Injection or Reboiler
Overhead Condenser or Pump Aroundp
Conventional Practice (40+% vol @ 13 psig)
Providing Solutions for Tomorrow’s Environment 32
17
Conventional Sour Water Stripper
Practice: Oil Refinery
T M i D i Ch i P /CTwo Main Design Choices – Pros/Cons
Pump Around vs Overhead CondenserPump Around vs. Overhead Condenser
Direct Steam Injection vs. ReboilerDirect Steam Injection vs. Reboiler
General Trends
Steam to Feed Ratio
Feed Tray Location
Feed Concentration
St C t d N b f TSteam Cost and Number of Trays
Caustic Injection and Chlorides
Providing Solutions for Tomorrow’s Environment 33
Caustic Injection and Chlorides
Conventional Overhead Condenser
34
18
Pump Around Condenserp
35
Sour Water Stripper Design Approach
l fMaterials of Construction
CS as predominant choice in the daCS was predominant choice in the day
Overhead Line was most often upgradedpg
Current designs upgrade – especially as function of
f dfeed
Simulation BasisSimulation Basis
Sour – Pro/II
GPA Sour – Pro/II
OLI El t l t P /II ( ti i j ti t di )OLI Electrolyte – Pro/II (caustic injection studies)
Elusive Phenol Removal Process?
Providing Solutions for Tomorrow’s Environment 36
Elusive Phenol Removal Process?
19
Sour Water Stripper Design Approach
(cont.)
Design Basis Issuesg
Don’t Over Estimate Feed Sourness
Tower Stability and Control Problems
MOC Upgrade Creep
Design Margin CreepDesign Margin Creep
Providing Solutions for Tomorrow’s Environment 37
Sour Water Stripper Design Approach
(cont.)
Nice to Haves
Can’t ha e eno gh h drocarbon skimmingCan’t have enough hydrocarbon skimming
capabilityp y
Likewise with surge and storage – but be
reasonable
Dual ReboilersDual Reboilers
Live Steam InjectionLive Steam Injection
Some degree of redundancy/overcapacity for
catch-up and addressing the inevitable fouling
episode(s)
Providing Solutions for Tomorrow’s Environment 38
episode(s)
20
Sour Water Offgas Disposal
Flare - Back-up and Limited
Fired Heaters
Direct Combustion of SWS Offgas
Separate NH3 from H2S and Burn Ammonia in
HeaterHeater
Claus SRUsClaus SRUs
The Most Common Approachpp
And the Most Interesting
Providing Solutions for Tomorrow’s Environment 39
Separate Ammonia from
Hydrogen Sulfide
Most common approach in refinery applicationMost common approach in refinery application
is Chevron WWTis Chevron WWT
Two Column Operationp
Ammonia can be recovered
Aqueous
AnhydrousAnhydrous
Main ConcernsMain Concerns
CAPEX (Due to Equipment Count and MOC)
Complexity
Ammonia Sales
Providing Solutions for Tomorrow’s Environment 40
Ammonia Sales
21
Chevron WWT Process
41
Sour Water From Claus Tail Gas Treating
Sour Water Produced from QuenchSour Water Produced from Quench
Claus / Tail Gas FeedsClaus / Tail Gas Feeds
ComponentsComponents
H2S TOC
NH3 Thiosulfate
CO Sulfide
Production Characteristics
CO2 Sulfide
100 LTPD S Generates 10.5 gpm Sour Water
100 STPD Ammonia Generates 40.5 gpm Sour
Water
Providing Solutions for Tomorrow’s Environment 42
Water
22
Calculated Effect of Sour Water Stripper Offgas in
Claus SRUs on Quench Water Purge
15
16
m
14
15urge,gpm
13
WaterPu
12
uenchW
10
11
uousQu
9
10
Continu
8
0 5 10 15 20 250 5 10 15 20 25
% NH3 (vol) in Total Amine Acid Gas plus SWS Offgas
(Constant 100 ETPD)
43
Calculated Effect of Sour Water Stripper Offgas in
Claus SRUs on Quench Water Purge
60
m
50
ge,gpm
40
aterPurg
30
enchWa
20
ousQue
10
Continuo
0
C
0
0 5 10 15 20 25
% NH3 (vol) in Total Amine Acid Gas plus SWS Offgas
44
3 ( ) p g
(100 LTPD Amine Acid Gas)
23
Gasification and Other Similar Processes
G d i d f C lGases derived from Coal
Producer GasProducer Gas
Water Gases
Coke Oven Gas
By-product of Coal Coking
Coal or Pet Coke Gasification
Syngas for Power
iAmmonia
Synthetic Natural Gas
Providing Solutions for Tomorrow’s Environment 45
Synthetic Natural Gas
Sour Water From Gasification
and Other Similar Processes
Ammonia and Cyanides Produced During the
Thermal Processing are present in the coal-
d dderived gas
U t 1 % l A iUp to 1 % vol Ammonia
0 1 to 0 25% vol Hydrogen Cyanide0.1 to 0.25% vol Hydrogen Cyanide
Processes Available to Remove the AmmoniaProcesses Available to Remove the Ammonia
directly from the Coal-Derived Gas
Providing Solutions for Tomorrow’s Environment 46
24
Sour Water From Gasification
and Other Similar Processes (cont.)
Typical Thermal Processing involves some form
of Water Quench or Scrubber
The Sour Water contains all the Ammonia and
some of the Hydrogen Sulfide from the coal derivedsome of the Hydrogen Sulfide from the coal-derived
gas
Other water soluble components like organic acids
d h land phenols are present
Providing Solutions for Tomorrow’s Environment 47
Some Interesting Processes from theg
Coal Gas Industry Practices & Experience
Direct Ammonia Removal Processes
React with Strong H2SO4 or H3PO4 to Produce
lf h h dAmmonium Sulfate or Ammonium Phosphate and
Acid GasAcid Gas
Phosam Process to Separate NH3 and Acid Gases3
from the Gas Stream
Providing Solutions for Tomorrow’s Environment 48
25
Some Interesting Processes from theg
Coal Gas Industry Practices & Experience
Ammonia Processing After Water Scrubbing
and Sour Water Stripping
Catalytic Destruction of NH3 in Presence of H2S
O id ti f NH d H S i Cl Pl tOxidation of NH3 and H2S in Claus Plant or
Incinerator
Providing Solutions for Tomorrow’s Environment 49
Ammonium Sulfate or Ammonium Phosphatep
50
26
Phosam Process
51
Catalytie NH3 Destruction and Sulfur Recoveryy 3 y
52
27
Even More Interesting Processes from
the Coke-Oven Gas Processing Industry
Process for Ammonia Removal and Recovery
from Ammonia Bearing Acid Gas
Processes for Ammonia and Hydrogen Sulfide
R l U i A iRemoval Using Ammonia
Providing Solutions for Tomorrow’s Environment 53
Ammonia Removal and Recoveryo a e o a a d eco e y
54
28
Acid Gas and Ammonia Removal with Ammonia Recoveryc d Gas a d o a e o a t o a eco e y
55
Chemistry of Ammonia-Based
Processes for H2S and CO2 Removal
Hydrogen Sulfide
2 NH3 (g) + H2S (g) → (NH4)2 S3 (g) 2 (g) ( 4)2
NH3 (g) + H2S (g) → (NH4) HS (aq)
Carbon Dioxide
2 NH3 (g) + CO2 (g) + H2O (l) → (NH4)2 CO3 (aq)
2 NH3 (g) + CO2 (g) → NH4 CO2 NH2 (aq)
Providing Solutions for Tomorrow’s Environment 56
29
Sour Water Offgas to Claus SRUs
Normally can process up to 2 – 4% (vol)Normally can process up to 2 4% (vol)
ammonia in Claus SRU without modification to
a conventional straight-through design
Above this level need additional design
considerations: preheat two zone thermalconsiderations: preheat, two-zone thermal
reactor etc.reactor etc.
Over 25% (vol) ammonia in total feed gases( ) g
need to address potential NOx formation
Providing Solutions for Tomorrow’s Environment 57
Sour Water Offgas to Claus SRUs (cont.)
Typically like to see Claus thermal reactor
effluent ammonia content less than 100 ppmveffluent ammonia content less than 100 ppmv
Some reports of Claus thermal reactor effluentp
ammonia up to 500 to 600 ppmv without
difficultydifficulty
Overhead Line Temperature MaintenanceOverhead Line Temperature Maintenance
KO DrumKO Drum
Contains No Demister
Multiple Level DevicesMultiple Level Devices
Fully Traced and Insulated
Providing Solutions for Tomorrow’s Environment 58
30
Sour Water Offgas to Claus SRUs (cont.)
Instrument Taps
Large (2” or 3” on Vessel)
All TracedAll Traced
Diaphragm Sealsp g
Steam Outs
O i d V t i TOversized Venturi Taps
High Level TripHigh Level Trip
Isolates Sour Water Offgas Only
Providing Solutions for Tomorrow’s Environment 59
Sour Water Offgas to Claus SRUs (cont.)
Mixing SWS Gas with Amine Acid Gas
l iSalt Formation
Under Deposit CorrosionUnder Deposit Corrosion
All Lines No Pocket and Top Entryp y
Minimum Distance After Mix Point
Providing Solutions for Tomorrow’s Environment 60
31
Sour Water Offgas to Claus SRUs (cont.)
Amine Acid Gas Preheater
Process on Tube Side
BEM Axial Flow Configuration to Eliminate Pockets
Si l P t Eli i t P k tSingle Pass to Eliminate Pockets
Tube Sheet Material – SA-516-70 w/ 0 1875” (min )Tube Sheet Material SA 516 70 w/ 0.1875 (min.)
347 SS Overlay
Tube Material – SA-249-TP 321 SS
All 321 SS M i l S bili d / A l d– All 321 SS Materials are Stabilized / Annealed
Tube to Tubesheet Joint is Rolled and Seal Welded
Providing Solutions for Tomorrow’s Environment 61
Tube to Tubesheet Joint is Rolled and Seal Welded
Ammonia Salts
Solids Deposition Possibilities
Ammonia Forms a Number Salts That Can
Produce Deposits
Ammonium Hydrosulfide
NH H S → NH HSNH3 + H2S → NH4-HS
Ammonium CarbamateAmmonium Carbamate
2NH3 + CO2 → NH4-CO2-NH23 2 → 4 2 2
Ammonium Bicarbonate
NH3 + CO2 + H2O → NH4-HCO3
Providing Solutions for Tomorrow’s Environment 62
32
Ammonia Salts
Solids Deposition Possibilities (cont.)
Deposition Temperature Depends on Partial
Pressures of NH3, H2S, CO2 and H2O
Salts Typically Begin Depositing from 70 - 140F
Best Practice is Stay at Least 45F Hotter than
C l l t d D iti T tCalculated Deposition Temperature
Providing Solutions for Tomorrow’s Environment 63
64
33
Theoretical Impact of Processing Sour Waterp g
Stripper Offgas on Claus/Tail Gas Unit Capacity
Claus ReactionClaus Reaction
H2S + 3/2 O2 → SO2 + H2O
2 H2S + SO2 → 3S + H2O
3 H2S + 3/2 O2 → 3S + 2 H2O
Ammonia Combustion
3 H2S 3/2 O2 → 3S 2 H2O
2NH3 + 3/2O2 → 2N2 + 3H2O
Overall
3/2 lb mole O2 2 lb mole NH3 17 lb NH3 1 lb mole S ST NH3 2240 lbs S
3 lb mole S 3/2 lb mole O2 1 lb mole NH3 32 lbs 2000 lb NH3 LT S
65
Calculated Effect of Processing SWSg
Offgas on Claus/Tail Gas Unit Capacity
“100 tpd Claus/Tail Gas Unit”
Acid Gas (vol %) SWS Offgas (vol %)
87.5% H2S
4 5% CO
23.2% H2S
33 1% NH4.5% CO2
1.9% C1
33.1% NH3
41.6% H2O1.9% C1
6.1% H2O
41.6% H2O
2.1% C1
Providing Solutions for Tomorrow’s Environment 66
34
Calculated Effect of Processing SWS Offgas ong g
Claus / Tail Gas Capacity at Constant Air Demand
100100
8080
NH3
ed
6060
plusETPD
urProduc
4040
PDSulfurp
LTPDSulfu
2020
LTP
00
0 5 10 15 20 25
NH3% (vol) in Total Amine Acid Gas plus SWS Offgas
67
NH3% (vol) in Total Amine Acid Gas plus SWS Offgas
Calculated Effect of Processing SWS Offgas onCalculated Effect of Processing SWS Offgas on
Claus / Tail Gas Capacity at Constant Air Demand
50100
40
90
80
30
70
PDNH3
DSulfur
20
60
ETP
LTPD
10
5050
040
0 5 10 15 20 25
% NH3 (vol) in Total Amine Acid Gas plus SWS Offgas
68
% ( ) p g
35
Calculated Impact Analysis Based Only
on Required Air Demand
What About Actual Performance Characteristics?
Providing Solutions for Tomorrow’s Environment 69
Simulated Effect of Processing Sour Waterg
Stripper Offgas in Claus / Tail Gas Units
6 85
6 80
6.85
6.75
6.80
Kinetic - Split Flow Model
6.70
MMSCFD
Kinetic - Straight Thru Model
Models are fromSulsim Version 6.0.
6.65
Demand,M
Note that Air Demand predicted by
variousmodels differs by < 5%.
6.60
Air
Kinetic - NH3 Burn Model
Ki i Th d i M d l
6.55
Kinetic - Thermodynamic Model
6.50
0 5 10 15 20 25
( l) i l i id l ff
70
% NH3 (vol) in Total Amine AcidGas plus SWS Offgas
36
Simulated Effect of Sour Water Stripper Offgaspp g
in Claus SRUs on Pressure Drop
1200
1100
1000
/hr
900
ate,lbmol/
ClausTail Gas velocityincreasesby~12% as NH3
contentisincreasedfrom0 - 25%.
Pressure dropisproportionalto the square of the
l
800
Flowra
velocity.
Pressure dropisincreasedby~25% in SRU. Effectis
lessdramatic downstreamof QuenchTower.
700
600
700
600
0 5 10 15 20 25
% NH3 (vol) in Total Amine AcidGas plus SWS Offgas
(C t t 100 ETPD)
71
(Constant 100 ETPD)
New Plant Construction
400
350
400
300
350
250
200
TPDSulfur
150
ET
100
Amine Acid Gas H2S
50
0
0 5 10 15 20 25
% NH3 (vol) in Total Amine AcidGas plus SWS Offgas
72
% NH3 (vol) in Total Amine AcidGas plus SWS Offgas
37
CAPEX Approximation
Basic “100 tpd” Claus/Tail Gas Unit is
US$25MM
Typical Two-Bed Claus
20 24” M i G Li20 or 24” Main Gas Line
Conventional TGU plus IncineratorConventional TGU plus Incinerator
Providing Solutions for Tomorrow’s Environment 73
CAPEX Approximation (cont.)
Adding Ammonia Processing
5% - 115 ETPD is US$28MM (105 LTPD S & 4 STPD NH3)
10% - 140 ETPD is US$31MM (115 LTPD S & 10 STPD NH3)
15% - 165 ETPD is US$35MM (125 LTPD S & 16 STPD NH3)15% 165 ETPD is US$35MM (125 LTPD S & 16 STPD NH3)
20% - 240 ETPD is US$44MM (145 LTPD S & 38 STPD NH3)
25% - 350 ETPD is US$54MM (180 LTPD S & 68 STPD NH3)
Providing Solutions for Tomorrow’s Environment 74
38
What’s it Worth?
10% Ammonia Feed
Additional US$6MM CAPEX
OPEX?
l $ /Ammonia – Nearly US$3MM/Year
20% Ammonia Feed20% Ammonia Feed
Additional US$19MM CAPEXAdditional US$19MM CAPEX
OPEX?
Ammonia – Nearly Over US$11MM/Year
Providing Solutions for Tomorrow’s Environment 75
Alternative Sour Water Management
Processes
Ammonia Separation from Sour Water
Processes
– Chevron WWT Process
US Steel Phosam Process– US Steel Phosam Process
Uses for Recovered Ammonia
– Recover as Anhydrous Ammonia
– Ammonia Sulfate
– Ammonium Thiosulphate– Ammonium Thiosulphate
– Hydrogen
Providing Solutions for Tomorrow’s Environment 76
39
Alternative Sour Water Stripper Offgas
Processes
Di S W S i Off C b iDirect Sour Water Stripper Offgas Combustion
with SO Scrubbingwith SO2 Scrubbing
NO Production?NOx Production?
– John Zink “Noxidizer”
SCR SNCR?– SCR or SNCR?
SO2 ScrubbingSO2 Scrubbing
– Cansolv (SO2 Recycle)
C ti– Caustic
– Ammonia (Ammonia Sulfate or Ammonia Thiosulphate)
Hydrogen – Can be produced from Ammonia
(No Joke)
Providing Solutions for Tomorrow’s Environment 77
(No Joke)
“Noxidizer” with Caustic ScrubberNoxidi er with Caustic Scrubber
78
40
SCR Combustion with SCR and Cansolv ScrubberSCR Combustion with SCR and Cansolv Scrubber
79
Ammonia Thiosulphate ProductionAmmonia Thiosulphate Production
80
41
Some Reflections on Sour Water
There are many different approaches to
managing sour water – most successful, some
h fnot with a few mysteries remaining
Providing Solutions for Tomorrow’s Environment 81
Some Reflections on Sour Water (cont.)
Wh t i th R fi ’ B k P i t t L k tWhat is the Refiner’s Break Point to Look at
Alternatives?Alternatives?
Removing Load from Claus – Options?Removing Load from Claus Options?
Typical Water Cost and Upgrade Complexity to BFW
– City / Potable
– WellWell
– Surface
Sour Water– Sour Water
Is Ammonia Recovery a Better Way – Re-look at
Economics given Energy Costs and Green
Solutions???
Providing Solutions for Tomorrow’s Environment 82
Solutions???

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Fundamentals of sour water stripping

  • 1. 1 Providing Solutions for Tomorrow’s Environment 1Providing Solutions for Tomorrow’s Environment Fundamentals ofFundamentals of Sour Water StrippingSour Water Stripping Presented at the Brimstone Sulfur Symposia V il C l d S t b 2008Vail, Colorado, September 2008 David K. Stevens President & CEO Alan Mosher Director of Engineering 2Providing Solutions for Tomorrow’s Environment President & CEO Director of Engineering
  • 2. 2 Outline Sources and Characteristics of Sour Water Sour Gas Processing Refining Processes l lClaus Tail Gas Treating Gasification and Similar ProcessesGasification and Similar Processes Processing SWS Offgas in SRU/TGUsProcessing SWS Offgas in SRU/TGUs Alternatives Strategies for Sour Water andAlternatives Strategies for Sour Water and Sour Gas Providing Solutions for Tomorrow’s Environment 3 Sour Gas Sources and Characteristics of Sour Water Sour Gas Processing Oil Refining Gasification and Other Thermal Process Claus Tail Gas Units Providing Solutions for Tomorrow’s Environment 4
  • 3. 3 Sour Gas Processing Sources of Sour Water Wellhead Facilities Dry or Wet Pipeline Plants Inlet Separators Li id KO DLiquid KO Drums – Dehydration UnitDehydration Unit – Claus Plant – Compressor Aftercoolers Providing Solutions for Tomorrow’s Environment 5 Sour Gas Processing Sources of Sour Water (cont.) Plants (cont.) Dehydration Processes – Glycol Regen Condensate Solid Bed Absorbent Dehydrator Regen– Solid Bed Absorbent Dehydrator Regen Gas Treating Units – Reflux Purgeg g Tail Gas Units – Quench Water Providing Solutions for Tomorrow’s Environment 6
  • 4. 4 Sour Gas Processing Characteristics Two Types of Sour Water Produced Water – Water that originates in the reservoir and flows up the tubing with the gastubing with the gas Condensed Water – “Salt-free Water” that condenses from the gas after the gas has left the producing reservoirgas has left the producing reservoir Providing Solutions for Tomorrow’s Environment 7 Produced Water Characteristics Originates in Reservoir Generally Removed in Inlet Separator H2S and CO2 Salt-Bearing Anions Cations Chl id P t iChlorides Potassium Bromides Sodium Sulfates Magnesium Providing Solutions for Tomorrow’s Environment 8
  • 5. 5 Produced Water Characteristics (cont.) Hydrocarbons Methanol/Hydrate Inhibitors Corrosion Inhibitors Hydrocarbons Providing Solutions for Tomorrow’s Environment 9 Produced Water Processing Injection Well with Filtration Local Remote (Trucked) Stripping St I j ti St R b ilSteam Injection or Steam Reboiler Gas – Avoids Salting Out PotentialGas – Avoids Salting Out Potential Providing Solutions for Tomorrow’s Environment 10
  • 6. 6 Produced Water Processing (cont.) Offgas Disposal Flare Low Tonnage Sulfur Recovery lRecompression to Pipeline Evaporation PondsEvaporation Ponds Salt PresenceSalt Presence Providing Solutions for Tomorrow’s Environment 11 Condensed Water Characteristics Condensed After Gas has Left Reservoir “Salt Free” H2S and CO2 GlycolsH2S and CO2 Hydrocarbons G yco s Methanol Iron Sulfides Other Hydrate Inhibitors Amines Corrosion Inhibitors Providing Solutions for Tomorrow’s Environment 12
  • 7. 7 Condensed Water Processing Strippingpp g Steam Injection or Steam Reboiler Gas Disposal of Offgas FlFlare Claus PlantClaus Plant Integrate with Tail Gas Quenchteg ate t a Gas Que c Providing Solutions for Tomorrow’s Environment 13 Condensed Water Processing (cont.) Disposal of Stripped Sour Waterp pp Injection Well Evaporation Pond Upgrade to BFW Providing Solutions for Tomorrow’s Environment 14
  • 8. 8 Some Approaches to Sour Water Stripping in Sour Gas Processing Plants Integrate a Sour Water Stripper with a Tail Gasg pp Quench System Re-use of Tail Gas Quench Water as Boiler Feed WWater Providing Solutions for Tomorrow’s Environment 15 Integrated Sour Water Stripper with Tail Gas Quenchg pp Q 16
  • 9. 9 Reuse of Quench Water for BFWQ 17 Oil Refining – Sources of Sour Water Desalters /Crude/Vacuum Units H dHydrotreaters FCCFCCs Thermal CrackingThermal Cracking HydrocrackingHydrocracking Amine TreatingAmine Treating Claus Tail Gas Units Providing Solutions for Tomorrow’s Environment 18 Claus Tail Gas Units
  • 10. 10 Oil Refining – General Trends Higher Sulfur and Nitrogen Content Crudes Deeper Levels of Hydroprocessing Generate Higher Levels of Sour Water Providing Solutions for Tomorrow’s Environment 19 General Characteristics of Refinery Sour Water “Typical” Concentrations H2S 300 to 12,000 ppm (wt) NH 100 8 000 ( )NH3 100 to 8,000 ppm (wt) Molar Ratio NH :H SMolar Ratio NH3:H2S Between 1 0 and 2 0Between 1.0 and 2.0 Typical 1.1 to 1.4yp Typical pH between 8 and 10 Sour Water pH dictates NH3:H2S Ratio Providing Solutions for Tomorrow’s Environment 20
  • 11. 11 Refinery Sour Water Range of Potential Contaminates Phenol Organic Acids Hydrocarbon Cyanide Caustic Chloride Selenium Mineral Acids HardnessSelenium Mineral Acids Hardness Providing Solutions for Tomorrow’s Environment 21 How the Bad Actors Behave Acidic Anions: Chlorides Sulfates FormatesAcidic Anions: Chlorides, Sulfates, Formates Depress pHp p Tie-up Ammonium Ion Alkali Cations: Sodium, Potassium Raise pHRaise pH Tie-up Sulfide Ionp Phenols – Not readily strippable Cyanide – Corrosive; use of polysulfides to form thi tthiocyanate Naphthenic and Cresylic Acids Providing Solutions for Tomorrow’s Environment 22 Naphthenic and Cresylic Acids
  • 12. 12 How the Bad Actors Behave (cont.) Heavier Hydrocarbons Multiple problems;Heavier Hydrocarbons – Multiple problems; Can polymerizeCan polymerize Carbon Dioxide – Lower pH and tie-up Ammonia C l i C i it t h d iCalcium – Can precipitate as hardness in stripperstripper Oxygen – Egress can form acid which fixyg g Ammonia Amine – Can tie-up Ammonia Selenium Can precipitate and foul stripper Providing Solutions for Tomorrow’s Environment 23 Selenium – Can precipitate and foul stripper The Problem with Phenols Phenols are not removed due to solubility h t i ti t t ffi i icharacteristics – not tray efficiencies Phenolic Bearing Units (With OtherPhenolic – Bearing Units (With Other Contaminates such as Cyanides and ColloidalContaminates such as Cyanides and Colloidal Sulfur) Cokers Crude Units FCCFCCs ARUs and TGU Purge Providing Solutions for Tomorrow’s Environment 24 ARUs and TGU Purge
  • 13. 13 The Problem with Phenols (cont.) Non-Phenol Bearing Unitsg Hydrotreaters Desulfurization Units Providing Solutions for Tomorrow’s Environment 25 Chemistry of Refinery Sour Water “Sour Water” forms as Water and Hydrocarbony are in contact and partition the Hydrogen Sulfide and Ammonia in accordance with Henry’s LawHenry s Law The Ammonia and Hydrogen Sulfide dissolvedThe Ammonia and Hydrogen Sulfide dissolved in the now “Sour Water” ionize to the equilibrium extent according the pH and temperature Providing Solutions for Tomorrow’s Environment 26
  • 14. 14 Chemistry of Refinery Sour Water (cont.) Ammonia and Hydrogen Sulfide can only be stripped if in parent gaseous form i e exertingstripped if in parent gaseous form, i.e. exerting a partial pressure The iononized componentsa partial pressure. The iononized components do not strip Presence of ions which raise the pH tie-up Sulfides and aid Ammonia stripping Conversely presence of ions which lower the pH tie up the Ammonia and aid SulfidepH tie-up the Ammonia and aid Sulfide stripping Providing Solutions for Tomorrow’s Environment 27 stripping Approach to Sour Water Management in the Oil Refinery Stripped Sour Water Specifications Re-use Strategy Feed Preparation Sour Water Stripper Sour Water Offgas Disposal Providing Solutions for Tomorrow’s Environment 28
  • 15. 15 Stripped Sour Water Specifications Typical WWTP Influent Requirements 25 ppm Ammonia 10 ppm Hydrogen Sulfide Lower specs are often observed W SHA SBenzene Waste NESHAPS Providing Solutions for Tomorrow’s Environment 29 Sour Water Reuse Recycle All Stripped Sour Water to Desalter orRecycle All Stripped Sour Water to Desalter or CokerCoker Segregate Phenolic and Non-Phenolic Sourg g Water Recycle Non-Phenolic to Hydrotreaters/DesulfurizersHydrotreaters/Desulfurizers – Hydrotreaters can’t tolerate Phenolsy – SWS only removes 10 to 50 % of Phenol Recycle Phenolic Sour Water to Desalter were Oil t t th Ph li C d Providing Solutions for Tomorrow’s Environment 30 Oil extracts the Phenolic Compounds
  • 16. 16 Sour Water Feed Preparation Inlet Feed Separation and Hydrocarbon Flash and Skimming Vent to Safe Location dSour Water Feed Surge 3 D St T t3-Day Storage Target Oil SkimOil Skim Design to Prevent Short Circuitg Providing Solutions for Tomorrow’s Environment 31 Sour Water Stripper Design Non-Refluxed Direct Steam Injection or Reboiler Very High Water Content of Offgas (70 % l @ 13 i )(70+% vol @ 13 psig) RefluxedRefluxed Direct Steam Injection or ReboilerDirect Steam Injection or Reboiler Overhead Condenser or Pump Aroundp Conventional Practice (40+% vol @ 13 psig) Providing Solutions for Tomorrow’s Environment 32
  • 17. 17 Conventional Sour Water Stripper Practice: Oil Refinery T M i D i Ch i P /CTwo Main Design Choices – Pros/Cons Pump Around vs Overhead CondenserPump Around vs. Overhead Condenser Direct Steam Injection vs. ReboilerDirect Steam Injection vs. Reboiler General Trends Steam to Feed Ratio Feed Tray Location Feed Concentration St C t d N b f TSteam Cost and Number of Trays Caustic Injection and Chlorides Providing Solutions for Tomorrow’s Environment 33 Caustic Injection and Chlorides Conventional Overhead Condenser 34
  • 18. 18 Pump Around Condenserp 35 Sour Water Stripper Design Approach l fMaterials of Construction CS as predominant choice in the daCS was predominant choice in the day Overhead Line was most often upgradedpg Current designs upgrade – especially as function of f dfeed Simulation BasisSimulation Basis Sour – Pro/II GPA Sour – Pro/II OLI El t l t P /II ( ti i j ti t di )OLI Electrolyte – Pro/II (caustic injection studies) Elusive Phenol Removal Process? Providing Solutions for Tomorrow’s Environment 36 Elusive Phenol Removal Process?
  • 19. 19 Sour Water Stripper Design Approach (cont.) Design Basis Issuesg Don’t Over Estimate Feed Sourness Tower Stability and Control Problems MOC Upgrade Creep Design Margin CreepDesign Margin Creep Providing Solutions for Tomorrow’s Environment 37 Sour Water Stripper Design Approach (cont.) Nice to Haves Can’t ha e eno gh h drocarbon skimmingCan’t have enough hydrocarbon skimming capabilityp y Likewise with surge and storage – but be reasonable Dual ReboilersDual Reboilers Live Steam InjectionLive Steam Injection Some degree of redundancy/overcapacity for catch-up and addressing the inevitable fouling episode(s) Providing Solutions for Tomorrow’s Environment 38 episode(s)
  • 20. 20 Sour Water Offgas Disposal Flare - Back-up and Limited Fired Heaters Direct Combustion of SWS Offgas Separate NH3 from H2S and Burn Ammonia in HeaterHeater Claus SRUsClaus SRUs The Most Common Approachpp And the Most Interesting Providing Solutions for Tomorrow’s Environment 39 Separate Ammonia from Hydrogen Sulfide Most common approach in refinery applicationMost common approach in refinery application is Chevron WWTis Chevron WWT Two Column Operationp Ammonia can be recovered Aqueous AnhydrousAnhydrous Main ConcernsMain Concerns CAPEX (Due to Equipment Count and MOC) Complexity Ammonia Sales Providing Solutions for Tomorrow’s Environment 40 Ammonia Sales
  • 21. 21 Chevron WWT Process 41 Sour Water From Claus Tail Gas Treating Sour Water Produced from QuenchSour Water Produced from Quench Claus / Tail Gas FeedsClaus / Tail Gas Feeds ComponentsComponents H2S TOC NH3 Thiosulfate CO Sulfide Production Characteristics CO2 Sulfide 100 LTPD S Generates 10.5 gpm Sour Water 100 STPD Ammonia Generates 40.5 gpm Sour Water Providing Solutions for Tomorrow’s Environment 42 Water
  • 22. 22 Calculated Effect of Sour Water Stripper Offgas in Claus SRUs on Quench Water Purge 15 16 m 14 15urge,gpm 13 WaterPu 12 uenchW 10 11 uousQu 9 10 Continu 8 0 5 10 15 20 250 5 10 15 20 25 % NH3 (vol) in Total Amine Acid Gas plus SWS Offgas (Constant 100 ETPD) 43 Calculated Effect of Sour Water Stripper Offgas in Claus SRUs on Quench Water Purge 60 m 50 ge,gpm 40 aterPurg 30 enchWa 20 ousQue 10 Continuo 0 C 0 0 5 10 15 20 25 % NH3 (vol) in Total Amine Acid Gas plus SWS Offgas 44 3 ( ) p g (100 LTPD Amine Acid Gas)
  • 23. 23 Gasification and Other Similar Processes G d i d f C lGases derived from Coal Producer GasProducer Gas Water Gases Coke Oven Gas By-product of Coal Coking Coal or Pet Coke Gasification Syngas for Power iAmmonia Synthetic Natural Gas Providing Solutions for Tomorrow’s Environment 45 Synthetic Natural Gas Sour Water From Gasification and Other Similar Processes Ammonia and Cyanides Produced During the Thermal Processing are present in the coal- d dderived gas U t 1 % l A iUp to 1 % vol Ammonia 0 1 to 0 25% vol Hydrogen Cyanide0.1 to 0.25% vol Hydrogen Cyanide Processes Available to Remove the AmmoniaProcesses Available to Remove the Ammonia directly from the Coal-Derived Gas Providing Solutions for Tomorrow’s Environment 46
  • 24. 24 Sour Water From Gasification and Other Similar Processes (cont.) Typical Thermal Processing involves some form of Water Quench or Scrubber The Sour Water contains all the Ammonia and some of the Hydrogen Sulfide from the coal derivedsome of the Hydrogen Sulfide from the coal-derived gas Other water soluble components like organic acids d h land phenols are present Providing Solutions for Tomorrow’s Environment 47 Some Interesting Processes from theg Coal Gas Industry Practices & Experience Direct Ammonia Removal Processes React with Strong H2SO4 or H3PO4 to Produce lf h h dAmmonium Sulfate or Ammonium Phosphate and Acid GasAcid Gas Phosam Process to Separate NH3 and Acid Gases3 from the Gas Stream Providing Solutions for Tomorrow’s Environment 48
  • 25. 25 Some Interesting Processes from theg Coal Gas Industry Practices & Experience Ammonia Processing After Water Scrubbing and Sour Water Stripping Catalytic Destruction of NH3 in Presence of H2S O id ti f NH d H S i Cl Pl tOxidation of NH3 and H2S in Claus Plant or Incinerator Providing Solutions for Tomorrow’s Environment 49 Ammonium Sulfate or Ammonium Phosphatep 50
  • 26. 26 Phosam Process 51 Catalytie NH3 Destruction and Sulfur Recoveryy 3 y 52
  • 27. 27 Even More Interesting Processes from the Coke-Oven Gas Processing Industry Process for Ammonia Removal and Recovery from Ammonia Bearing Acid Gas Processes for Ammonia and Hydrogen Sulfide R l U i A iRemoval Using Ammonia Providing Solutions for Tomorrow’s Environment 53 Ammonia Removal and Recoveryo a e o a a d eco e y 54
  • 28. 28 Acid Gas and Ammonia Removal with Ammonia Recoveryc d Gas a d o a e o a t o a eco e y 55 Chemistry of Ammonia-Based Processes for H2S and CO2 Removal Hydrogen Sulfide 2 NH3 (g) + H2S (g) → (NH4)2 S3 (g) 2 (g) ( 4)2 NH3 (g) + H2S (g) → (NH4) HS (aq) Carbon Dioxide 2 NH3 (g) + CO2 (g) + H2O (l) → (NH4)2 CO3 (aq) 2 NH3 (g) + CO2 (g) → NH4 CO2 NH2 (aq) Providing Solutions for Tomorrow’s Environment 56
  • 29. 29 Sour Water Offgas to Claus SRUs Normally can process up to 2 – 4% (vol)Normally can process up to 2 4% (vol) ammonia in Claus SRU without modification to a conventional straight-through design Above this level need additional design considerations: preheat two zone thermalconsiderations: preheat, two-zone thermal reactor etc.reactor etc. Over 25% (vol) ammonia in total feed gases( ) g need to address potential NOx formation Providing Solutions for Tomorrow’s Environment 57 Sour Water Offgas to Claus SRUs (cont.) Typically like to see Claus thermal reactor effluent ammonia content less than 100 ppmveffluent ammonia content less than 100 ppmv Some reports of Claus thermal reactor effluentp ammonia up to 500 to 600 ppmv without difficultydifficulty Overhead Line Temperature MaintenanceOverhead Line Temperature Maintenance KO DrumKO Drum Contains No Demister Multiple Level DevicesMultiple Level Devices Fully Traced and Insulated Providing Solutions for Tomorrow’s Environment 58
  • 30. 30 Sour Water Offgas to Claus SRUs (cont.) Instrument Taps Large (2” or 3” on Vessel) All TracedAll Traced Diaphragm Sealsp g Steam Outs O i d V t i TOversized Venturi Taps High Level TripHigh Level Trip Isolates Sour Water Offgas Only Providing Solutions for Tomorrow’s Environment 59 Sour Water Offgas to Claus SRUs (cont.) Mixing SWS Gas with Amine Acid Gas l iSalt Formation Under Deposit CorrosionUnder Deposit Corrosion All Lines No Pocket and Top Entryp y Minimum Distance After Mix Point Providing Solutions for Tomorrow’s Environment 60
  • 31. 31 Sour Water Offgas to Claus SRUs (cont.) Amine Acid Gas Preheater Process on Tube Side BEM Axial Flow Configuration to Eliminate Pockets Si l P t Eli i t P k tSingle Pass to Eliminate Pockets Tube Sheet Material – SA-516-70 w/ 0 1875” (min )Tube Sheet Material SA 516 70 w/ 0.1875 (min.) 347 SS Overlay Tube Material – SA-249-TP 321 SS All 321 SS M i l S bili d / A l d– All 321 SS Materials are Stabilized / Annealed Tube to Tubesheet Joint is Rolled and Seal Welded Providing Solutions for Tomorrow’s Environment 61 Tube to Tubesheet Joint is Rolled and Seal Welded Ammonia Salts Solids Deposition Possibilities Ammonia Forms a Number Salts That Can Produce Deposits Ammonium Hydrosulfide NH H S → NH HSNH3 + H2S → NH4-HS Ammonium CarbamateAmmonium Carbamate 2NH3 + CO2 → NH4-CO2-NH23 2 → 4 2 2 Ammonium Bicarbonate NH3 + CO2 + H2O → NH4-HCO3 Providing Solutions for Tomorrow’s Environment 62
  • 32. 32 Ammonia Salts Solids Deposition Possibilities (cont.) Deposition Temperature Depends on Partial Pressures of NH3, H2S, CO2 and H2O Salts Typically Begin Depositing from 70 - 140F Best Practice is Stay at Least 45F Hotter than C l l t d D iti T tCalculated Deposition Temperature Providing Solutions for Tomorrow’s Environment 63 64
  • 33. 33 Theoretical Impact of Processing Sour Waterp g Stripper Offgas on Claus/Tail Gas Unit Capacity Claus ReactionClaus Reaction H2S + 3/2 O2 → SO2 + H2O 2 H2S + SO2 → 3S + H2O 3 H2S + 3/2 O2 → 3S + 2 H2O Ammonia Combustion 3 H2S 3/2 O2 → 3S 2 H2O 2NH3 + 3/2O2 → 2N2 + 3H2O Overall 3/2 lb mole O2 2 lb mole NH3 17 lb NH3 1 lb mole S ST NH3 2240 lbs S 3 lb mole S 3/2 lb mole O2 1 lb mole NH3 32 lbs 2000 lb NH3 LT S 65 Calculated Effect of Processing SWSg Offgas on Claus/Tail Gas Unit Capacity “100 tpd Claus/Tail Gas Unit” Acid Gas (vol %) SWS Offgas (vol %) 87.5% H2S 4 5% CO 23.2% H2S 33 1% NH4.5% CO2 1.9% C1 33.1% NH3 41.6% H2O1.9% C1 6.1% H2O 41.6% H2O 2.1% C1 Providing Solutions for Tomorrow’s Environment 66
  • 34. 34 Calculated Effect of Processing SWS Offgas ong g Claus / Tail Gas Capacity at Constant Air Demand 100100 8080 NH3 ed 6060 plusETPD urProduc 4040 PDSulfurp LTPDSulfu 2020 LTP 00 0 5 10 15 20 25 NH3% (vol) in Total Amine Acid Gas plus SWS Offgas 67 NH3% (vol) in Total Amine Acid Gas plus SWS Offgas Calculated Effect of Processing SWS Offgas onCalculated Effect of Processing SWS Offgas on Claus / Tail Gas Capacity at Constant Air Demand 50100 40 90 80 30 70 PDNH3 DSulfur 20 60 ETP LTPD 10 5050 040 0 5 10 15 20 25 % NH3 (vol) in Total Amine Acid Gas plus SWS Offgas 68 % ( ) p g
  • 35. 35 Calculated Impact Analysis Based Only on Required Air Demand What About Actual Performance Characteristics? Providing Solutions for Tomorrow’s Environment 69 Simulated Effect of Processing Sour Waterg Stripper Offgas in Claus / Tail Gas Units 6 85 6 80 6.85 6.75 6.80 Kinetic - Split Flow Model 6.70 MMSCFD Kinetic - Straight Thru Model Models are fromSulsim Version 6.0. 6.65 Demand,M Note that Air Demand predicted by variousmodels differs by < 5%. 6.60 Air Kinetic - NH3 Burn Model Ki i Th d i M d l 6.55 Kinetic - Thermodynamic Model 6.50 0 5 10 15 20 25 ( l) i l i id l ff 70 % NH3 (vol) in Total Amine AcidGas plus SWS Offgas
  • 36. 36 Simulated Effect of Sour Water Stripper Offgaspp g in Claus SRUs on Pressure Drop 1200 1100 1000 /hr 900 ate,lbmol/ ClausTail Gas velocityincreasesby~12% as NH3 contentisincreasedfrom0 - 25%. Pressure dropisproportionalto the square of the l 800 Flowra velocity. Pressure dropisincreasedby~25% in SRU. Effectis lessdramatic downstreamof QuenchTower. 700 600 700 600 0 5 10 15 20 25 % NH3 (vol) in Total Amine AcidGas plus SWS Offgas (C t t 100 ETPD) 71 (Constant 100 ETPD) New Plant Construction 400 350 400 300 350 250 200 TPDSulfur 150 ET 100 Amine Acid Gas H2S 50 0 0 5 10 15 20 25 % NH3 (vol) in Total Amine AcidGas plus SWS Offgas 72 % NH3 (vol) in Total Amine AcidGas plus SWS Offgas
  • 37. 37 CAPEX Approximation Basic “100 tpd” Claus/Tail Gas Unit is US$25MM Typical Two-Bed Claus 20 24” M i G Li20 or 24” Main Gas Line Conventional TGU plus IncineratorConventional TGU plus Incinerator Providing Solutions for Tomorrow’s Environment 73 CAPEX Approximation (cont.) Adding Ammonia Processing 5% - 115 ETPD is US$28MM (105 LTPD S & 4 STPD NH3) 10% - 140 ETPD is US$31MM (115 LTPD S & 10 STPD NH3) 15% - 165 ETPD is US$35MM (125 LTPD S & 16 STPD NH3)15% 165 ETPD is US$35MM (125 LTPD S & 16 STPD NH3) 20% - 240 ETPD is US$44MM (145 LTPD S & 38 STPD NH3) 25% - 350 ETPD is US$54MM (180 LTPD S & 68 STPD NH3) Providing Solutions for Tomorrow’s Environment 74
  • 38. 38 What’s it Worth? 10% Ammonia Feed Additional US$6MM CAPEX OPEX? l $ /Ammonia – Nearly US$3MM/Year 20% Ammonia Feed20% Ammonia Feed Additional US$19MM CAPEXAdditional US$19MM CAPEX OPEX? Ammonia – Nearly Over US$11MM/Year Providing Solutions for Tomorrow’s Environment 75 Alternative Sour Water Management Processes Ammonia Separation from Sour Water Processes – Chevron WWT Process US Steel Phosam Process– US Steel Phosam Process Uses for Recovered Ammonia – Recover as Anhydrous Ammonia – Ammonia Sulfate – Ammonium Thiosulphate– Ammonium Thiosulphate – Hydrogen Providing Solutions for Tomorrow’s Environment 76
  • 39. 39 Alternative Sour Water Stripper Offgas Processes Di S W S i Off C b iDirect Sour Water Stripper Offgas Combustion with SO Scrubbingwith SO2 Scrubbing NO Production?NOx Production? – John Zink “Noxidizer” SCR SNCR?– SCR or SNCR? SO2 ScrubbingSO2 Scrubbing – Cansolv (SO2 Recycle) C ti– Caustic – Ammonia (Ammonia Sulfate or Ammonia Thiosulphate) Hydrogen – Can be produced from Ammonia (No Joke) Providing Solutions for Tomorrow’s Environment 77 (No Joke) “Noxidizer” with Caustic ScrubberNoxidi er with Caustic Scrubber 78
  • 40. 40 SCR Combustion with SCR and Cansolv ScrubberSCR Combustion with SCR and Cansolv Scrubber 79 Ammonia Thiosulphate ProductionAmmonia Thiosulphate Production 80
  • 41. 41 Some Reflections on Sour Water There are many different approaches to managing sour water – most successful, some h fnot with a few mysteries remaining Providing Solutions for Tomorrow’s Environment 81 Some Reflections on Sour Water (cont.) Wh t i th R fi ’ B k P i t t L k tWhat is the Refiner’s Break Point to Look at Alternatives?Alternatives? Removing Load from Claus – Options?Removing Load from Claus Options? Typical Water Cost and Upgrade Complexity to BFW – City / Potable – WellWell – Surface Sour Water– Sour Water Is Ammonia Recovery a Better Way – Re-look at Economics given Energy Costs and Green Solutions??? Providing Solutions for Tomorrow’s Environment 82 Solutions???