Fundamentals of Sour Water Stripping

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
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
Sources and Characteristics of

Sour Water
Sour Gas Processing

Oil Refining
Gasification and Other Thermal Process
Claus Tail Gas Units
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
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
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
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
Produced Water Characteristics (cont.)
Hydrocarbons
Methanol/Hydrate Inhibitors
Corrosion Inhibitors
Hydrocarbons
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
10
Produced Water Processing (cont.)
Offgas Disposal
Flare
z Low Tonnage Sulfur Recovery
l
z Recompression to Pipeline
z
Evaporation Ponds
z
Salt Presence
11
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
12
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
13
Condensed Water Processing (cont.)

p
pp Sour Water
Disposal
of Stripped
Injection Well
z Evaporation Pond
z Upgrade to BFW
z
14
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
15
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
18
Oil Refining General Trends
Higher Sulfur and Nitrogen Content Crudes

Deeper Levels of Hydroprocessing
Generate Higher Levels of Sour Water
19
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
20
10
Refinery Sour Water
Range of Potential Contaminates

Phenol
Organic Acids
Hydrocarbon
Cyanide
Selenium
Caustic
Mineral Acids
Chloride
Hardness
21
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
22
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
23
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
24
12
The Problem with Phenols (cont.)
Non-Phenol Bearingg Units

Hydrotreaters
z Desulfurization Units
z
25
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
26
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
27
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
28
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
29
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
30
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
31
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
32
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
33
Conventional Overhead Condenser
34
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?

36
18

(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
37

(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
38
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
39
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
40
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
42
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)
44
22
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
45
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
46
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
47
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
48
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
49
Ammonium Sulfate or Ammonium Phosphate

p
50
25
Phosam Process
51
Catalytie
y NH3 Destruction and Sulfur Recoveryy
52
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
53
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)
56
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
57
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
58
29
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
59
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
60
30
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
61
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
62
31
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
63
64
32
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
65
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
66
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?
69
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

(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

72
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
73
CAPEX Approximation (cont.)
Adding Ammonia Processing

z
z
z
z
z
5% - 115 ETPD is US$28MM

(105 LTPD S & 4 STPD NH3)

74
37
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
75
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
76
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)
77
Noxidizer
Noxidi er with Caustic Scrubber
78
39
SCR Combustion with SCR and Cansolv Scrubber
79
Ammonia Thiosulphate Production
80
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
81
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???
82
41

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Providing Solutions for Tomorrows Environment

Brimstone Sulfur Symposia

President & CEO

Sources and Characteristics of Sour Water

Processing SWS Offgas in SRU/TGUs

Sources and Characteristics of

Sour Gas Processing

Providing Solutions for Tomorrows Environment

Sour Gas Processing

Sour Gas Processing

Gas Treatingg Units Reflux Purge

Providing Solutions for Tomorrows Environment

Sour Gas Processing Characteristics

Two Types of Sour Water

Providing Solutions for Tomorrows Environment

Produced Water Characteristics

Produced Water Characteristics (cont.)

Providing Solutions for Tomorrows Environment

Produced Water Processing

Injection Well with Filtration

Providing Solutions for Tomorrows Environment

Produced Water Processing (cont.)

Providing Solutions for Tomorrows Environment

Condensed Water Characteristics

H2S and CO2

Providing Solutions for Tomorrows Environment

Condensed Water Processing

Providing Solutions for Tomorrows Environment

Condensed Water Processing (cont.)

Providing Solutions for Tomorrows Environment

Some Approaches to Sour Water

Providing Solutions for Tomorrows Environment

Oil Refining Sources of Sour Water

Oil Refining General Trends

Higher Sulfur and Nitrogen Content Crudes

Providing Solutions for Tomorrows Environment

300 to 12,000 ppm (wt)

Molar Ratio NH3:H2S

Typical pH between 8 and 10

Refinery Sour Water

Range of Potential Contaminates

Providing Solutions for Tomorrows Environment

How the Bad Actors Behave

Acidic Anions: Chlorides,

Alkali Cations: Sodium, Potassium

Phenols Not readily strippable

How the Bad Actors Behave (cont.)

Heavier Hydrocarbons Multiple problems;

The Problem with Phenols

Phenols are not removed due to solubility

Providing Solutions for Tomorrows Environment

The Problem with Phenols (cont.)

Non-Phenol Bearingg Units

Providing Solutions for Tomorrows Environment

Chemistry of Refinery Sour Water

Chemistry of Refinery Sour Water (cont.)

Ammonia and Hydrogen Sulfide can only be

Approach to Sour Water Management

Stripped Sour Water Specifications

Providing Solutions for Tomorrows Environment

Stripped Sour Water Specifications

Typical WWTP Influent Requirements

Lower specs are often observed

Providing Solutions for Tomorrows Environment