07 GasTreating Unsecured

Acid Gas Treating
Chapter 10
Based on presentation by Prof. Art Kidnay
Plant Block Schematic
Adapted from Figure 7.1,

Fundamentals of Natural Gas Processing, 2nd ed.
Kidnay, Parrish, & McCartney
Updated: January 4, 2019

2
Copyright © 2019 John Jechura (jjechura@mines.edu)
Topics
Chemical Absorption Processes
Physical Absorption
Adsorption
Cryogenic Fractionation
Membranes
Nonregenerable H2S Scavengers
Biological Processes
Safety and Environmental Considerations

3
Gas treating
Gas treating involves removing The acid gas problem
contaminants to sufficiently ▪ H2S is highly toxic
low levels to meet ▪ H2S combustion gives SO2 – toxic
specifications & leads to acid rain
▪ Primary focus on removing “acid ▪ CO2 is a diluent in natural gas –
gases” corrosive in presence of H2O
• Carbon dioxide (CO2) Purification levels
• Hydrogen sulfide (H2S) ▪ H2S: Pipeline quality gas requires
• Plus other sulfur species 0.25 grains/100 scf (4 ppmv)
▪ Other contaminants ▪ CO2: pipeline quality gas may
• Mercury allow up to 4 mole%
• Ammonia • Cryogenic applications need
• Elemental sulfur less than 50 ppmv
• Arsenic
4
Two step process
Two steps
▪ Remove the acid gases from natural gas
▪ Dispose of the acid gases
Disposition
▪ CO2
• Vent to atmosphere
• EOR – Enhanced Oil Recovery
• Sequestration
▪ H2S
• Incineration or venting (trace amounts)
• React with scavengers (e.g. iron sponge)
• Convert to elemental sulfur
• Injection into suitable underground formation
5
CO2 Capture and Sequestration
Power Station/Industrial Facility
500
m CO CO
OIL CO 2
CH4 2
2
1000m
IMPERMEABLE
CAP-ROCK
COAL
CO2 Replaces Methane SEAM
IMPERMEABLE Trapped in Coal
CAP-ROCK
1500m
Enhanced Oil
Recovery
SALINE (CO2 Displaces Oil)
RESERVOI CO2 Stored in Saline
RIMPERMEABLE Formation
CAP-ROCK

6
Processes for acid gas removal
Acid Gas Removal Processes
Solvent Absorption
Solid Direct Cryogenic

Chemical Physical Hybrid Membranes
Adsorption Conversion Fractionation
Molecular Cellulose
Selexol Sulfinol sieve acetate Stretford Ryan-Holmes
Amine Alkali Salts

Rectisol Selefining Iron sponge Polyimide Lo Cat
MEA Benfield
Ifpexol Amisol Zinc oxide Polysulfone
DGA Catacarb
Purisol
Giammarco
DEA
Vetrocoke Sepasolv
MPE
DIPA Flexsorb HP
MDEA
Amine
mixtures
Hindered
amines
Figure 10.1, Fundamentals of Natural Gas Processing, 2nd ed., Kidnay, Parrish, & McCartney, 2011

7
Selecting a process
Factors for selecting process
▪ Type & concentration of impurities
▪ Hydrocarbon composition of the gas
▪ Pressure & temperature of the gas
▪ Specifications for outlet gas
▪ Volume of gas to be processed
Four possible scenarios
▪ Only CO2
▪ Only H2S
▪ Both CO2 and H2S
▪ Both CO2 and H2S present but selectively remove H2S
• Allow CO2 slip

8
Selecting a process

9
Chemical Absorption Processes

Physical vs. Chemical Absorption

11
Amine Chemistry
Primary amine (MEA) Gas treating amines are:
A = CH2CH2OH ▪ Weak Lewis Bases
B=H ▪ H+ from weak acids react
AMINE C=H with the electrons on N:
l
l
Secondary amine (DEA)

N A = CH2CH2OH ABC substituents influence:
B = CH2CH2OH ▪ How fast acids react with N:
C=H ▪ Temperature bulge in
A C absorber
▪ Energy required in
B Tertiary amine (MDEA)
A = CH2CH2OH regenerator
B = CH2CH2OH ▪ Chemical Stability
C = CH3 ▪ Unwanted reactions
Dow Oil & Gas – Gas Treating Technology
Presentation to URS Washington Division, August 2009
Rich Ackman – ackmanrb@dow.com

12
Sterically hindered amines – selective H2S
absorbers
Diisopropanolamine (DIPA) 2-amino,2-methyl,1-propanol (AMP)
CH3
HOCH2 C NH2
CH3

13
Amines
Amines remove H2S and CO2 in two step process:
▪ Gas dissolves in solvent (physical absorption)
▪ Dissolved gas (a weak acid) reacts with weakly basic amines
H2S reaction
R1R2R3N + H2S ↔ R1R2R3NH+HS-
CO2 reacts two ways with amine:
▪ With water
CO2 + H2O + R1R2R3N ↔ R1R2R3NH+ HCO3-
• Much slower than H2S reaction
▪ Without water
CO2 + 2 R1R2NH ↔ R1R2NH2 + R1R2NCOO -
• Faster but requires one H attached to the N
• Use tertiary amines to “slip” CO2

14
Comparison of acid gas removal solvents
Process Capable of Removes Selective Minimum CO2 Solution subject
meeting COS, CS2, & H2S level to degradation?
H2S spec? mercaptans removal obtainable (degrading
species)
Monoethanolamine Yes Partial No 100 ppmv at Yes (COS, CO2,
(MEA) low to CS2, SO2, SO3 and
moderate mercaptans)
pressures
Diethanolamine (DEA) Yes Partial No 50 ppmv in Some (COS, CO2,
SNEA-DEA CS2, HCN and
process mercaptans)
Triethanolamine (TEA) No Slight No Minimum Slight (COS, CS2
partial and mercaptans)
pressure of 0.5
psia (3 kPa)
Methyldiethanolamine Yes Slight Some Bulk removal No
(MDEA) only
Part of Table 10.1, Fundamentals of Natural Gas Processing, 2nd ed., Kidnay, Parrish, & McCartney, 2011

15
Representative operating parameters
MEA DEA DGA MDEA
Weight % amine 15 to 25 30 to 40 50 to 60 40 to 50
Rich amine acid gas loading
0.45 to 0.52 0.21 to 0.81 0.35 to 0.44 0.20 to 0.81
mole acid gas / mole amine
Acid gas pickup
0.33 to 0.40 0.20 to 0.80 0.25 to 0.38 0.20 to 0.80
Lean solution residual acid gas
~0.12 ~0.01 ~0.06 0.005 to 0.01
Table 10.3, Fundamentals of Natural Gas Processing, 2nd ed., Kidnay, Parrish, & McCartney, 2011

16
Gas Treating Amines
Generic Amines
Load Relative
▪ MEA Wt% Mol%
Range Capacity
(monoethanolamine) MEA 18% 6.1% 0.35 1
• 15 – 18% wt. (5 – 6.1% mol) DGA 50% 14.6% 0.45 3.09
▪ DEA (diethanolamine) DEA 28% 6.3% 0.48 1.41
MDEA 50% 13.1% 0.49 3.02
• 25 – 30% wt. (5.4 – 6.8%
mol) CompSol 20 50% 10.4% 0.485 2.37
CR 402 50% 14.7% 0.49 3.38
▪ DIPA AP 814 50% 13.9% 0.485 3.16
(diisopropanolamine)
• 30% - 50% wt. (5.5 – 11.9% Presentation to URS Washington Division, August 2009
mol) Rich Ackman – ackmanrb@dow.com
▪ MDEA
(methyldiethanolamine)
• 35% - 50% wt. (7.5 – 13.1%
mol)

17
Amine Solution Densities
Lean amine composition will
dictate volumetric circulation
rate & pumping power
required
▪ Need to determine
density/volumetric flow at actual
pumping temperature
m ( P ) V ( P ) V gH
WBHP = = =
pump pump pump
GPSA Engineering Data Book, 13th ed.

18
Amine Solution Densities
Figures B.1 & B.2, Fundamentals of Natural Gas Processing, 2nd ed., Kidnay, Parrish, & McCartney, 2011

19
Typical Amine Treating Plant
Typical plant configuration

▪ Broad range of treating applications
▪ Low to intermediate specifications
▪ Selective treating, low H2S
▪ Low installed cost

20
Amine Tower Parameters
Tower Design Considerations
▪ Gas Composition
▪ Trays
• System Factor Bubble Area
o MEA/DEA – 0.75 abs (0.85 reg)
o MDEA & Formulated Solvents – 0.70 abs (0.85 reg)
• System Factor Downcomer
o MEA/DEA – 0.73 abs (0.85 reg)
o MDEA & Formulated Solvents – 0.70 abs (0.85 reg)
o Standard Cross Flow vs. High Capacity
❖ Calming Section, MD Trays
▪ Packings
• Random Packing
• Capacity vs. efficiency, GPDC overlay Presentation to URS Washington Division, August 2009
Rich Ackman – ackmanrb@dow.com
• Structured Packing
21
Amine Tower Parameters
Absorber design considerations Absorber Temperature Profiles
Liquid Phase
▪ Pinch points limit 1

2
• Top of tower lean pinch

3
C-1 Conservative
4
C-2 Controlled Efficient
5
• Temperature bulge maximum 6

7
C-3 Intercooler
• Bottom of tower rich pinch 8

9
• Confidence level in VLE

10
11
Stage
12
▪ Temperature profile indicator 13

14
15
16
17
18
19
20
21
22
23
24
80 100 120 140 160 180 200
Temperature [°F]

22
Amine Approximate Guidelines
MEA DEA DGA MDEA
Acid gas pickup, scf/gal @ 100°F 3.1 – 4.3 6.7 – 7.5 4.7 – 7.3 3 – 7.5
Acid gas pickup, mols/mol amine 0.33 – 0.40 0.20 – 0.80 0.25 – 0.38 0.20 – 0.80
Lean solution residual acid gas, mol/mol amine ~ 0.12 ~ 0.01 ~ 0.06 0.005 – 0.01
Rich solution acid gas loading, mol/mol amine 0.45 – 0.52 0.21 – 0.81 0.35 – 0.44 0.20 – 0.81
Max. solution concentration, wt% 25 40 60 65
Approximate reboiler heat duty, Btu/gal lean 1,000 – 1,200 840 – 1,100 – 1,300 800 – 900
solution 1,000
Steam heated ave. heat flux in reboiler, Btu/hr ft2 9,000 – 6,300 – 9,000 –10,000 6,300 –
10,000 7,400 7,400
Reboiler temperature, °F 225 – 260 230 – 260 250 – 270 230 – 270
Heats of reaction (approximate)

Btu/lb H2S 610 555 674 530
Btu/lb CO2 825 730 850 610
GPSA Engineering Data Book, 14th ed., portion of Figure 21-4

23
Amine System Initial Design
Amine solvent considerations
▪ Lean amine concentration (wt% amine in water)
▪ Rich & lean amine loadings (mole acid gas per mole amine) – difference is the
allowed amine pick-up
Determine amount of acid gas to be absorbed
▪ Difference between what can be contained in the treated gas & what is in the feed
gas
Determine rate of lean amine to the absorber
▪ Molar rate amine based on the allowed pick-up
▪ Total mass rate amine+water based on the allowed lean amine concentration
▪ Total volumetric flowrate (standard conditions) based on lean amine concentration
Determine the reboiler duty for regeneration
▪ Based on heat of regeneration for each amine & acid gas (CO2 & H2S)

24
Operating issues with amine units
Corrosion – caused by:
▪ High amine concentrations
▪ Rich amine loadings
▪ Oxygen
▪ Heat stable salts (HSS)
Foaming – caused by
▪ Suspended solids
▪ Surface active agents
▪ Liquid hydrocarbons
▪ Amine degradation products (heat stable salts)

25
HYSYS Example Simulation

26
Hot potassium carbonate process (Hot Pot)
Major reactions
Acid Gas
K2CO3 + CO2 + H2O ⇄ 2 KHCO3
K2CO3 + H2S ⇄ KHS + KHCO3 Sweet Condenser
Product Gas
Lean
Solution
contactor
Sour
Feed Gas
Steam
Rich
Solution
Absorber Stripper
27
Physical Absorption

Characteristics of physical absorption processes
Most efficient at high partial
pressures
Heavy hydrocarbons strongly
absorbed by solvents used
Solvents can be chosen for
selective removal of sulfur
compounds
Regeneration requirements
low compared to amines &
Hot Pot Figure from UOP SelexolTM Technology for Acid Gas Removal, UOP, 2009
Retrieved March 2016 from
http://www.uop.com/?document=uop-selexol-technology-for-acid-gas-
Can be carried out at near- removal&download=1
ambient temperatures
Partial dehydration occurs along with acid gas removal
29
Comparison of chemical and physical solvents
Advantages Disadvantages
Chemical Solvent Relatively insensitive to H2S High energy requirements for
(e.g., amines, hot and CO2 partial pressure regeneration of solvent
potassium carbonate)
Can reduce H2S and CO2 to Generally not selective
ppm levels between CO2 and H2S
Amines are in a water
solution and thus the treated
gas leaves saturated with
water
Physical solvents Low energy requirements for May be difficult to meet H2S
(e.g., Selexol, regeneration specifications
Rectisol)
Can be selective between H2S Very sensitive to acid gas
and CO2 partial pressure

30
Physical Solvents – Selexol
Characteristics
▪ Poly (Ethylene Glycol) Dimethyl Ether
CH3 - O - (CH2 - CH2 - O)n - CH3 where n is from 3 to 10
▪ Selexol is a mixture of homologues so the physical properties are approximate
▪ Clear fluid that looks like tinted water
Capabilities
▪ H2S selective or non selective removal – very low spec. - 4 ppm
▪ CO2 selective or non selective removal – 2% to 0.1%
▪ Water dew point control
▪ Hydrocarbon dew point control
• See relative solubilities; more efficient to remove hydrocarbon vs. refrigeration
▪ Organic sulfur removal – mercaptans, disulfides, COS

31
Selexol Processes
Physical solvent which favors high pressure & high partial pressure
Configurations
▪ H2S & organic sulfur removal
• Steam stripping for regeneration
▪ CO2 removal
• Flash regeneration
• Chiller for low CO2
Special applications
▪ Siloxanes are removed from landfill gas
▪ Metal carbonyl are removed from gasifier gas

32
Solubility in Selexol at 70oF (21oC)
H 2S
30
Solubility, scf / gal Selexol
20
CH3SH
CO2
10
COS
CH4
0 200 400 600

Gas Partial Pressure, psia

33
Selexol process – CO2 separation
UOP SelexolTM Technology for Acid Gas Removal, UOP, 2009

Retrieved March 2016 from http://www.uop.com/?document=uop-selexol-technology-for-acid-gas-removal&download=1

34
Selexol process – sulfur removal & CO2 capture
UOP SelexolTM Technology for Acid Gas Removal, UOP, 2009

Retrieved March 2016 from http://www.uop.com/?document=uop-selexol-technology-for-acid-gas-removal&download=1

35
Membranes

Membrane systems
Based on Fick’s law of diffusion through the membrane
Si Di ( pi )
Ji =
L
where: Ji is the molar flux of component i through

the membrane
Si is the solubility term
Di is the diffusion coefficient
Δpi is the partial pressure difference across
the membrane
L is the thickness of the membrane
The permeability combines the properties of  P 
solubility & diffusion yi ,permeate   feed  yi ,feed
P 
 permeate 
▪ Differs for each compound
▪ Provides selectivity
37
Module configurations – hollow fiber
Approximately 70% of membrane systems are hollow fiber
Low Pressure, Bore-Side Gas Feed Module
Courtesy MTR

38
Module configurations – spiral wound
Continued Development of Gas Separation Membranes for Highly Sour Service, Cnop, Dormndt, & schott, UOP
Retrieved March 2016 from http://www.uop.com/?document=uop-continued-development-of-gas-separation-membranes-technical-
paper&download=1

39
Module configurations – spiral wound

40
Membrane module flow schemes
No moving parts
Allows for greater CO2 removal
Simple, reliable operation
High hydrocarbon recovery
Low hydrocarbon recovery
Requires recycle compressor
Feed with high CO2

Intermediate hydrocarbon recovery
UOP SeparexTM Membrane Technology, UOP, 2009

Reduced compression
Retrieved March 2016 from http://www.slideshare.net/hungtv511/uop-separex-membrane-technology

41
CO2/CH4 Separation Example
Two stage process (non-optimized)

42
CO2/CH4 Separation Example
Retentate (B)
Retentate (B)
Feed (A)
Permeate (C)
Feed (A)
(D)
Permeate (C)
(E)

43
Adsorption

Acid gas removal by adsorption (mole sieves)

45
Nonregenerable H2S Scavengers

Nonregenerable H2S scavengers
Process Phase Process
Solid-based processes Iron oxides
Zinc oxides
Liquid-based processes Amine-aldehyde condensates
Caustic
Aldehydes
Oxidizers
Metal-oxide slurries
Table 10.9, Fundamentals of Natural Gas Processing, 2nd ed., Kidnay, Parrish, & McCartney, 2011

47
Summary

Summary
Appropriate technology based on…
▪ Amount of acid gas to be removed
▪ Concentration of acid gas in feed gas
▪ Pressure of feed gas
Very typical to find an amine treating system to remove H2S
and/or CO2
▪ May be able to “slip” CO2 into treated gas depending on the final specs

49
Supplemental Slides

CO2 Sources &
Disposition Options
“Study places CO2 capture cost between $34 and $61/ton”

Oil & Gas Journal, Oct. 12, 2009

51

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Acid Gas Treating

Adapted from Figure 7.1,

Updated: January 4, 2019

Updated: January 4, 2019

Power Station/Industrial Facility

Updated: January 4, 2019

Solid Direct Cryogenic

Amine Alkali Salts

Updated: January 4, 2019

Updated: January 4, 2019

Updated: January 4, 2019

Updated: January 4, 2019

Updated: January 4, 2019

Secondary amine (DEA)

Updated: January 4, 2019

Diisopropanolamine (DIPA) 2-amino,2-methyl,1-propanol (AMP)

Updated: January 4, 2019

Updated: January 4, 2019

Updated: January 4, 2019

Updated: January 4, 2019

Updated: January 4, 2019

GPSA Engineering Data Book, 13th ed.

Updated: January 4, 2019

Updated: January 4, 2019

Typical plant configuration

Updated: January 4, 2019

▪ Pinch points limit 1

• Top of tower lean pinch

• Temperature bulge maximum 6

• Bottom of tower rich pinch 8

• Confidence level in VLE

▪ Temperature profile indicator 13

Updated: January 4, 2019

Max. solution concentration, wt% 25 40 60 65

Heats of reaction (approximate)

GPSA Engineering Data Book, 14th ed., portion of Figure 21-4

Updated: January 4, 2019

Updated: January 4, 2019

Updated: January 4, 2019

Updated: January 4, 2019

Updated: January 4, 2019

Updated: January 4, 2019

Updated: January 4, 2019

Updated: January 4, 2019

0 200 400 600

Updated: January 4, 2019

UOP SelexolTM Technology for Acid Gas Removal, UOP, 2009

Updated: January 4, 2019

UOP SelexolTM Technology for Acid Gas Removal, UOP, 2009

Updated: January 4, 2019

Updated: January 4, 2019

where: Ji is the molar flux of component i through

Low Pressure, Bore-Side Gas Feed Module

Updated: January 4, 2019

Updated: January 4, 2019

Updated: January 4, 2019

Feed with high CO2

UOP SeparexTM Membrane Technology, UOP, 2009

Updated: January 4, 2019

Updated: January 4, 2019

Updated: January 4, 2019

Updated: January 4, 2019

Updated: January 4, 2019

Updated: January 4, 2019