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Providing Solutions for Tomorrows Environment

Fundamentals of
Sour Water Stripping
Presented at the

Brimstone Sulfur Symposia


V il Colorado,
Vail,
C l d September
S t b 2008
David K. Stevens

Alan Mosher

President & CEO

Director of Engineering
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Outline

Sources and Characteristics of Sour Water


Sour Gas Processing
z Refining Processes
l
z Claus
Taill Gas Treating
z Gasification and Similar Processes
z

Processing SWS Offgas in SRU/TGUs


Alternatives Strategies for Sour Water and
Sour Gas
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Sources and Characteristics of


Sour Water

Sour Gas Processing


Oil Refining
Gasification and Other Thermal Process
Claus Tail Gas Units

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Sour Gas Processing


Sources of Sour Water

Wellhead Facilities
Dry or Wet Pipeline

Plants
Inlet Separators
z Liquid
Li id KO D
Drums
z

Dehydration Unit
Claus Plant
Compressor Aftercoolers
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Sour Gas Processing


Sources of Sour Water (cont.)

Plants (cont.)
z

Dehydration Processes
Glycol Regen Condensate
Solid Bed Absorbent Dehydrator Regen

Gas Treatingg Units Reflux Purge


g
z Tail Gas Units Quench Water
z

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Sour Gas Processing Characteristics

Two Types of Sour Water


z

Produced Water
Water that originates in the reservoir and flows up the
tubing with the gas

Condensed Water
Salt-free Water that condenses from the gas after the
gas has left the producing reservoir

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Produced Water Characteristics

Originates in Reservoir
Generally Removed in Inlet Separator
H2S and CO2
Salt-Bearing
Anions

Cations

Chl id
Chlorides

P t i
Potassium

Bromides

Sodium

Sulfates

Magnesium
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Produced Water Characteristics (cont.)

Hydrocarbons
Methanol/Hydrate Inhibitors
Corrosion Inhibitors
Hydrocarbons

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Produced Water Processing

Injection Well with Filtration


Local
z Remote (Trucked)
z

Stripping
Steam IInjection
St
j ti or St
Steam R
Reboiler
b il
z Gas Avoids Salting Out Potential
z

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Produced Water Processing (cont.)

Offgas Disposal
Flare
z Low Tonnage Sulfur Recovery
l
z Recompression to Pipeline
z

Evaporation Ponds
z

Salt Presence

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Condensed Water Characteristics


Condensed After Gas has Left Reservoir
Salt Free

H2S and CO2


Hydrocarbons
Iron Sulfides
Amines

G yco s
Glycols
Methanol
Other Hydrate Inhibitors
Corrosion Inhibitors

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Condensed Water Processing

Stripping
pp g
Steam Injection or Steam Reboiler
z Gas
z

Disposal of Offgas
Flare
Fl
z Claus Plant
z Integrate
Quench
teg ate with
t Tail
a Gas Que
c
z

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Condensed Water Processing (cont.)


p
pp Sour Water
Disposal
of Stripped
Injection Well
z Evaporation Pond
z Upgrade to BFW
z

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Some Approaches to Sour Water


Stripping in Sour Gas Processing Plants

Integrate
g
a Sour Water Stripper
pp with a Tail Gas
Quench System
Re-use of Tail Gas Quench Water as Boiler Feed
Water

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Integrated
g
Sour Water Stripper
pp with Tail Gas Quench
Q

16

Reuse of Q
Quench Water for BFW

17

Oil Refining Sources of Sour Water

Desalters
Crude/Vacuum
Units
/
Hydrotreaters
H d
FCC
FCCs
Thermal Cracking
Hydrocracking
Amine Treating
Claus Tail Gas Units
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Oil Refining General Trends

Higher Sulfur and Nitrogen Content Crudes


Deeper Levels of Hydroprocessing
Generate Higher Levels of Sour Water

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General Characteristics of
Refinery Sour Water

Typical Concentrations
H2 S
z NH3
z

300 to 12,000 ppm (wt)


100 to 8,000
8 000 ppm (wt)
( )

Molar Ratio NH3:H2S


Between 1.0
1 0 and 2.0
20
z Typical
1.1 to 1.4
yp
z

Typical pH between 8 and 10


Sour Water pH dictates NH3:H2S Ratio
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10

Refinery Sour Water

Range of Potential Contaminates


Phenol

Organic Acids

Hydrocarbon

Cyanide
Selenium

Caustic
Mineral Acids

Chloride
Hardness

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How the Bad Actors Behave

Acidic Anions: Chlorides,


Chlorides Sulfates
Sulfates, Formates
p
p
Depress
pH
z Tie-up Ammonium Ion
z

Alkali Cations: Sodium, Potassium


Raise pH
p Sulfide Ion
z Tie-up
z

Phenols Not readily strippable


Cyanide Corrosive; use of polysulfides to form
thiocyanate
thi
t
Naphthenic and Cresylic Acids
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11

How the Bad Actors Behave (cont.)

Heavier Hydrocarbons Multiple problems;

Can polymerize
Carbon Dioxide Lower pH and tie-up
Ammonia
C l i
C precipitate
i it t as h
d
iin
Calcium
Can
hardness
stripper
yg Egress
g
Oxygen
can form acid which fix
Ammonia
Amine Can tie-up Ammonia
Selenium Can precipitate and foul stripper
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The Problem with Phenols

Phenols are not removed due to solubility


characteristics
h
t i ti nott ttray efficiencies
ffi i i
Phenolic Bearing Units (With Other
Contaminates such as Cyanides and Colloidal
Sulfur)
Cokers
z Crude Units
z FCCs
FCC
z ARUs and TGU Purge
z

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12

The Problem with Phenols (cont.)

Non-Phenol Bearingg Units


Hydrotreaters
z Desulfurization Units
z

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Chemistry of Refinery Sour Water


y
Sour Water forms as Water and Hydrocarbon
are in contact and partition the Hydrogen
Sulfide and Ammonia in accordance with
Henryss Law
Henry
The Ammonia and Hydrogen Sulfide dissolved
in the now Sour Water ionize to the
equilibrium extent according the pH and
temperature
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13

Chemistry of Refinery Sour Water (cont.)

Ammonia and Hydrogen Sulfide can only be


stripped if in parent gaseous form
form, ii.e.
e exerting
a partial pressure
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
up the Ammonia and aid Sulfide
pH tie
tie-up
stripping
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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

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14

Stripped Sour Water Specifications

Typical WWTP Influent Requirements


25 ppm Ammonia
z 10 ppm Hydrogen Sulfide
z

Lower specs are often observed


Benzene Waste
W
NESHAPS
SHA S

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Sour Water Reuse

Recycle All Stripped Sour Water to Desalter or


Coker
Segregate
g g
Phenolic and Non-Phenolic Sour
Water
z

Recycle Non-Phenolic to
Hydrotreaters/Desulfurizers
Hydrotreaters
cant tolerate Phenols
y
SWS only removes 10 to 50 % of Phenol

Recycle Phenolic Sour Water to Desalter were


Oil extracts
t t th
the Ph
Phenolic
li C
Compounds
d
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15

Sour Water Feed Preparation

Inlet Feed Separation and Hydrocarbon Flash


and Skimming
z

Vent to Safe Location

Sour Water Feedd Surge


3-Day
3
D St
Storage TTargett
z Oil Skim
z Design
g to Prevent Short Circuit
z

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Sour Water Stripper Design

Non-Refluxed
Direct Steam Injection or Reboiler
z Very High Water Content of Offgas
(70 % voll @ 13 psig)
i )
(70+%
z

Refluxed
Direct Steam Injection or Reboiler
z Overhead Condenser or Pump
p Around
z Conventional Practice (40+% vol @ 13 psig)
z

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16

Conventional Sour Water Stripper


Practice: Oil Refinery

Two
T M
Main
i D
Design
i Ch
Choices
i
Pros/Cons
P /C
Pump Around vs
vs. Overhead Condenser
z Direct Steam Injection vs. Reboiler
z

General Trends
Steam to Feed Ratio
z Feed Tray Location
z Feed Concentration
St
C
dN
b off TTrays
z Steam
Costt and
Number
z Caustic Injection and Chlorides
z

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Conventional Overhead Condenser

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17

Pump
p Around Condenser

35

Sour Water Stripper Design Approach

Materials
l off Construction
CS was
day
as predominant choice in the da
z Overhead Line was most often upgraded
pg
z Current designs upgrade especially as function of
f d
feed
z

Simulation Basis
Sour Pro/II
z GPA Sour Pro/II
z OLI El
Electrolyte
t l t Pro/II
P /II (caustic
(
ti iinjection
j ti studies)
t di )
z

Elusive Phenol Removal Process?


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18

Sour Water Stripper Design Approach


(cont.)
g Basis Issues
Design
Dont Over Estimate Feed Sourness
z Tower Stability and Control Problems
z MOC Upgrade Creep
z Design Margin Creep
z

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Sour Water Stripper Design Approach


(cont.)

Nice to Haves
Cant ha
have
enough
hydrocarbon
e eno
gh h
drocarbon skimming
capability
p
y
z Likewise with surge and storage but be
reasonable
z Dual Reboilers
z Live Steam Injection
z Some degree of redundancy/overcapacity for
catch-up and addressing the inevitable fouling
episode(s)
z

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19

Sour Water Offgas Disposal

Flare - Back-up and Limited


Fired Heaters
Direct Combustion of SWS Offgas
z Separate NH3 from H2S and Burn Ammonia in
Heater
z

Claus SRUs
The Most Common Approach
pp
z And the Most Interesting
z

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Separate Ammonia from


Hydrogen Sulfide

Most common approach in refinery application


is Chevron WWT
Two Column Operation
p
Ammonia can be recovered
Aqueous
z Anhydrous
z

Main Concerns
CAPEX (Due to Equipment Count and MOC)
z Complexity
z Ammonia Sales
z

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20

Chevron WWT Process

41

Sour Water From Claus Tail Gas Treating

Sour Water Produced from Quench


Claus / Tail Gas Feeds
Components
H2S
NH3
CO2

TOC
Thiosulfate
Sulfide

Production Characteristics

100 LTPD S Generates 10.5 gpm Sour Water


z 100 STPD Ammonia Generates 40.5 gpm Sour
Water
z

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21

Calculated Effect of Sour Water Stripper Offgas in


Claus SRUs on Quench Water Purge
Continu
uous Qu
uench W
Water Pu
urge, gpm
m

16
15
14
13
12
11
10
9
8
0

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
C
Continuo
ous Que
ench Wa
ater Purg
ge, gpm
m

60

50

40

30

20

10

0
0

10

15

20

25

plus SWS Offgas


g
% NH3 ((vol)) in Total Amine Acid Gas p
(100 LTPD Amine Acid Gas)
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Gasification and Other Similar Processes

Gases
G
derived
d i d ffrom C
Coall
Producer Gas
z Water Gases
z

Coke Oven Gas


By-product of Coal Coking

Coal or Pet Coke Gasification


Syngas for Power
i
z Ammonia
z Synthetic Natural Gas
z

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Sour Water From Gasification


and Other Similar Processes

Ammonia and Cyanides Produced During the


Thermal Processing are present in the coald
derived
d gas
U to
t 1 % voll Ammonia
A
i
Up
z 0.1
0 1 to 0.25%
0 25% vol Hydrogen Cyanide
z

Processes Available to Remove the Ammonia


directly from the Coal-Derived Gas
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23

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
derived
some of the Hydrogen Sulfide from the coal
coal-derived
gas
z Other water soluble components like organic acids
and
d phenols
h
l are present
z

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Some Interestingg Processes from the


Coal Gas Industry Practices & Experience

Direct Ammonia Removal Processes


React with Strong H2SO4 or H3PO4 to Produce
Ammonium Sulfate
lf
or Ammonium Phosphate
h h
and
d
Acid Gas
z Phosam Process to Separate NH3 and Acid Gases
from the Gas Stream
z

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24

Some Interestingg Processes from the


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 off NH3 and
d H2S iin Cl
z Oxidation
Claus Pl
Plantt or
Incinerator
z

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Ammonium Sulfate or Ammonium Phosphate


p

50

25

Phosam Process

51

Catalytie
y NH3 Destruction and Sulfur Recoveryy

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26

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
lU
i A
i
Removal
Using
Ammonia

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Ammonia
o a Removal
e o a and
a d Recovery
eco e y

54

27

Acid
c d Gas and
a d Ammonia
o a Removal
e o a with
t Ammonia
o a Recovery
eco e y

55

Chemistry of Ammonia-Based
Processes for H2S and CO2 Removal

Hydrogen Sulfide
2 NH3 (g) + H2S (g) ((NH4)2 S
NH3 (g) + H2S (g)
(NH4) HS (aq)

Carbon Dioxide
2 NH3 (g) + CO2 (g) + H2O (l)
2 NH3 (g) + CO2 (g)

(NH4)2 CO3 (aq)


NH4 CO2 NH2 (aq)

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28

Sour Water Offgas to Claus SRUs

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
preheat, two
two-zone
zone thermal
reactor etc.
Over 25% ((vol)) ammonia in total feed ggases
need to address potential NOx formation
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Sour Water Offgas to Claus SRUs (cont.)

Typically like to see Claus thermal reactor


effluent ammonia content less than 100 ppmv
Some reports
p
of Claus thermal reactor effluent
ammonia up to 500 to 600 ppmv without
difficulty
Overhead Line Temperature Maintenance
KO Drum
z
z
z

Contains No Demister
Multiple Level Devices
Fully Traced and Insulated
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29

Sour Water Offgas to Claus SRUs (cont.)

Instrument Taps
Large (2 or 3 on Vessel)
z All Traced
z Diaphragm
p g Seals
z Steam Outs
z Oversized
O
i dV
Venturi
t i TTaps
z

High Level Trip


z

Isolates Sour Water Offgas Only

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Sour Water Offgas to Claus SRUs (cont.)

Mixing SWS Gas with Amine Acid Gas


Salt
l Formation
i
z Under Deposit Corrosion
z All Lines No Pocket and Top
p Entryy
z Minimum Distance After Mix Point
z

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30

Sour Water Offgas to Claus SRUs (cont.)

Amine Acid Gas Preheater


Process on Tube Side
z BEM Axial Flow Configuration to Eliminate Pockets
Si l P
i t P
k t
z Single
Pass tto Eli
Eliminate
Pockets
z Tube Sheet Material SA
SA-516-70
516 70 w/ 0.1875
0 1875 (min.)
(min )
347 SS Overlay
z Tube Material SA-249-TP 321 SS
z

i l are SStabilized
bili d / A
l d
All 321 SS M
Materials
Annealed

Tube to Tubesheet Joint is Rolled and Seal Welded

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Ammonia Salts
Solids Deposition Possibilities

Ammonia Forms a Number Salts That Can


Produce Deposits
Ammonium Hydrosulfide
HS
NH3 + H2S NH4-HS
z Ammonium Carbamate
2NH3 + CO2 NH4-CO2-NH2
z Ammonium Bicarbonate
NH3 + CO2 + H2O NH4-HCO3
z

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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 dD
Calculated
Deposition
iti TTemperature
t

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Theoretical Impact
p of Processingg Sour Water
Stripper Offgas on Claus/Tail Gas Unit Capacity

Claus Reaction
H2S + 3/2 O2

SO2 + H2O

2 H2S + SO2

3S + H2O

3 H2S + 3/2 O2

3S + 2 H2O

Ammonia Combustion
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

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Calculated Effect of Processingg SWS


Offgas on Claus/Tail Gas Unit Capacity

100 tpd Claus/Tail Gas Unit


Acid Gas (vol %)
SWS Offgas (vol %)
87.5% H2S
z 4.5%
4 5% CO2
z 1.9% C1
z 6.1% H2O
z

23.2% H2S
z 33.1%
33 1% NH3
z 41.6% H2O
z 2.1% C1
z

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33

100

100

80

80

60

60

40

40

20

20

LTP
PD Sulfur p
plus ETPD NH3

LTPD Sulfu
ur Produced

Calculated Effect of Processingg SWS Offgas


g on
Claus / Tail Gas Capacity at Constant Air Demand

0
0

10

15

20

25

NH3% (vol) in Total Amine Acid Gas plus SWS Offgas


67

Calculated Effect of Processing SWS Offgas on


Claus / Tail Gas Capacity at Constant Air Demand
100

50

90

40

30

ETP
PD NH3

LTPD
D Sulfur

80

70
20
60

10

50

40

0
0

10

15

20

25

% NH3 ((vol)) in Total Amine Acid Gas plus


p SWS Offgas
g
68

34

Calculated Impact Analysis Based Only


on Required Air Demand

What About Actual Performance Characteristics?

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Simulated Effect of Processingg Sour Water


Stripper Offgas in Claus / Tail Gas Units
6 85
6.85

6 80
6.80
Kinetic - Split Flow Model

Air Demand, M
MMSCFD

6.75
Kinetic - Straight Thru Model
6.70

Models are from Sulsim Version 6.0.

6.65

Note that Air Demand predicted by


various models differs by < 5%.
Kinetic - NH3 Burn Model

6.60

Ki i - Thermodynamic
Kinetic
Th
d
i M
Model
d l
6.55

6.50
0

10

15

20

25

% NH3 (vol)
( l) in
i Totall Amine
i Acid
id Gas plus
l SWS Offgas
ff
70

35

Simulated Effect of Sour Water Stripper


pp Offgas
g
in Claus SRUs on Pressure Drop
1200

1100

Flowraate, lbmol//hr

1000
Claus Tail Gas velocity increases by ~12% as NH3
content is increased from 0 - 25%.

900

Pressure drop is proportional to the square of the


velocity.
l
Pressure drop is increased by ~25% in SRU. Effect is
less dramatic downstream of Quench Tower.

800

700

600
0

10

15

20

25

% NH3 (vol) in Total Amine Acid Gas plus SWS Offgas


(C t t 100 ETPD)
(Constant
71

New Plant Construction


400

350

300

ETTPD Sulfur

250

200

150
Amine Acid Gas H2S

100

50

0
0

10

15

20

25

% NH3 (vol) in Total Amine Acid Gas plus SWS Offgas


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36

CAPEX Approximation

Basic 100 tpd Claus/Tail Gas Unit is


US$25MM
Typical Two-Bed Claus
M i G
z 20 or 24 Main
Gas Li
Line
z Conventional TGU plus Incinerator
z

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CAPEX Approximation (cont.)

Adding Ammonia Processing


z
z
z
z
z

5% - 115 ETPD is US$28MM


10% - 140 ETPD is US$31MM
15% - 165 ETPD is US$35MM
20% - 240 ETPD is US$44MM
25% - 350 ETPD is US$54MM

(105 LTPD S & 4 STPD NH3)


(115 LTPD S & 10 STPD NH3)
(125 LTPD S & 16 STPD NH3)
(145 LTPD S & 38 STPD NH3)
(180 LTPD S & 68 STPD NH3)

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Whats it Worth?

10% Ammonia Feed


Additional US$6MM CAPEX
z OPEX?
l US$3MM/Year
$
/
z Ammonia Nearly
z

20% Ammonia Feed


Additional US$19MM CAPEX
z OPEX?
z Ammonia Nearly Over US$11MM/Year
z

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Alternative Sour Water Management


Processes

Ammonia Separation from Sour Water


z

Processes
Chevron WWT Process
US Steel Phosam Process

Uses for Recovered Ammonia


Recover as Anhydrous Ammonia
Ammonia Sulfate
Ammonium Thiosulphate
Hydrogen
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38

Alternative Sour Water Stripper Offgas


Processes

Direct
Di
SSour W
Water SStripper
i
Off
Offgas C
Combustion
b i
with SO2 Scrubbing
z

NOx Production?

John Zink Noxidizer


SCR or SNCR?

SO2 Scrubbing

Cansolv (SO2 Recycle)


Caustic
C ti
Ammonia (Ammonia Sulfate or Ammonia Thiosulphate)

Hydrogen Can be produced from Ammonia


(No Joke)
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Noxidizer
Noxidi er with Caustic Scrubber

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39

SCR Combustion with SCR and Cansolv Scrubber

79

Ammonia Thiosulphate Production

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40

Some Reflections on Sour Water

There are many different approaches to


managing sour water most successful, some
not with
h a ffew mysteries remaining

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Some Reflections on Sour Water (cont.)

What
Wh t is
i th
the R
Refiners
fi B
Breakk P
Point
i t tto LLookk att
Alternatives?
Removing Load from Claus Options?
z Typical Water Cost and Upgrade Complexity to BFW
z

City / Potable
Well
Surface
Sour Water
z

Is Ammonia Recovery a Better Way Re-look at


Economics given Energy Costs and Green
Solutions???
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