®

DELIVERING KNOWLEDGE. DEVELOPING COMPETENCE.

Acid Gas Treating

Section 4
 “Acid Gas” Treatment

Acid Gas: H2S and / or CO2

H2S + Water  Sulfuric Acid
CO2 + Water  Carbonic Acid
– Causes Corrosion, Reduces Heating Value
“Sour Gas” Contains H2S with / without CO2
“Sweet Gas” can Contain CO2 but not H2S

Removal Desired:
– Contract Specifications
– Corrosion Control
– Safety (H2S Kills)
– Pollution Control
– Sulfide Stress Cracking

© 2011 Dr. O. Barkat & PetroSkills, LLC. All rights reserved.

 What is H2S? Hydrogen Sulfide

Colorless Gas

Specific Gravity = 1.18 (Settles in Air)

Smells Like Rotten Eggs at 0.2+ ppm

Deadens Sense of Smell at 100+ ppm

Almost as Lethal as Hydrogen Cyanide

More Lethal than Carbon Monoxide

© 2011 Dr. O. Barkat & PetroSkills, LLC. All rights reserved.

 Toxicity of Various Gases

Immediate Danger
Common Name Chemical Formula Level ppm
Chlorine Cl 30
Hydrogen Cyanide HCN 50
Sulfur Dioxide SO2 100
(formed when H2S is burned or reacts with Oxygen)

Hydrogen Sulfide H2S 300

Carbon Monoxide CO 1,200
Carbon Dioxide CO2 40,000

© 2011 Dr. O. Barkat & PetroSkills, LLC. All rights reserved.

 Physiological Effects of Hydrogen Sulfide

Concentrations in Air Physiological Effects

% by VOL PPM
.00001 .1 Faint / Unpleasant Odor
.0001 1.0 Obvious Moderate Rotten Egg Odor
.001 10 Eye Irritation; PEL (Permissible Exposure Level): 8 hrs OK
.0015 15 STEL (Short-Term Exposure Level): 15 Minutes OK
.003 30 Strong Unpleasant Odor; Not Intolerable
.005 50 Max Peak:10 min Exposure Per 8 hr Shift
.010 100 Cough / Eyes Hurt, Loss of Smell in 2 to 15 min
.020 200 Rapid Loss of Smell; Throat and Eyes Burn
.050 500 Dizziness; Lose Reasoning; Unconscious in Minutes
.070 700 Rapid Unconsciousness; Stop Breathing; Death in 5 Min
.100 + 1000+ Unconscious at Once; Death in 2 Minutes or Less

Note: 1 ppm (H2S at STP) = 6.3 grains / scf = 1.44 milligrams / sm

© 2011 Dr. O. Barkat & PetroSkills, LLC. All rights reserved.

 Where in the Oil Patch is H2S?

Sour Reservoirs

Sweet Reservoirs
– With Bacterial Growth
– From Drilling / Completion / Treating Fluids

Injection Facilities
– With Bacterial Growth
– Waterflooding Sweet Oil Reservoirs
as Hydrocarbons Decompose

© 2011 Dr. O. Barkat & PetroSkills, LLC. All rights reserved.

 H2S Chemical Reactions
Forms SO2 (Sulfur Dioxide)
– If Burned or if Reacts with Oxygen

Forms FeS (Ferrous Sulfide)

– Reaction with Iron and H2O Which When Exposed to Air
– FeS + O2  FeO (Ferrous Oxide)
Which Generates Enough Heat to Ignite Remaining H2S

Forms, with Water:

– H2SO3 (Sulfurous Acid)
– H2SO4 (Sulfuric Acid)

Causes Hydrogen Embrittlement of Iron / Steel

“Sulfide Stress Cracking”
– Hard Steels More Susceptible than Soft Steels

© 2011 Dr. O. Barkat & PetroSkills, LLC. All rights reserved.

 H2S Corrosion Protection

Coatings

Material Selection

Inhibitors

Closed System

© 2011 Dr. O. Barkat & PetroSkills, LLC. All rights reserved.

 H2S Corrosion Resistant Material

Fiberglass and Plastics: Impervious to

– H2S
– H2SO3
– H2SO4

Soft Metals to Reduce Susceptibility to

H2S Embrittlement
– Limit Steel Hardness to < 22 Rockwell C

Special Alloys
– Stainless Steel
– Monel Steel
– Aluminum Bronze
© 2011 Dr. O. Barkat & PetroSkills, LLC. All rights reserved.
 Closed System
Consider Even When Using:
– Inhibitors
– Coatings
– Special Material

Ferrous Sulfide Still Forms if Iron Present

! ! DANGER: Explosive if Oxygen Present ! !
Solution  Keep Air Out  Closed System
– All Tanks and Vessels Sealed
– All Vents / Hatches Closed
– Recovery System on All Vents

Reservoir Fluid May Contain Oxygen

© 2011 Dr. O. Barkat & PetroSkills, LLC. All rights reserved.

 Hydrogen Embrittlement
Hydrogen Atoms (H+) from H2S Invade Steel’s
Crystaline Structure Wanders Freely

Some H+ Atoms are Trapped at Voids, Impurities, or

Grain Boundaries

Other H+ Atoms Join to Form Molecules too Large

to Move thru Steel

Hydrogen Gas Collects, Builds Pressure and Forms

Bubbles / Cracks

Steel Loses Tensile Strength: Becomes Brittle

– Limit Steel Hardness to < 22 Rockwell C
– Accelerated by Temperatures > 105F (40C)

© 2011 Dr. O. Barkat & PetroSkills, LLC. All rights reserved.

Hydrogen Embrittlement

© 2011 Dr. O. Barkat & PetroSkills, LLC. All rights reserved.

Stress Corrosion Cracking

© 2011 Dr. O. Barkat & PetroSkills, LLC. All rights reserved.

Sulfide Stress Cracking

from
Exposure
to H2S

© 2011 Dr. O. Barkat & PetroSkills, LLC. All rights reserved.

Sulfide Stress Cracking

0.1% 1% 10%

© 2011 Dr. O. Barkat & PetroSkills, LLC. All rights reserved.

H2S Pitting and Embrittlement

© 2011 Dr. O. Barkat & PetroSkills, LLC. All rights reserved.

 Hydrogen Sulfide Treatment

25 to 30% of Worldwide Reserves Contain H2S

Pipeline Specifications Typically Require

< 4 ppm

Gas with H2S Often also Contains CO2

– (Usually Below Pipeline Specification of < 3%)

Presence of CO2 Complicates H2S Removal

© 2011 Dr. O. Barkat & PetroSkills, LLC. All rights reserved.

H2S Removal and Sulfur Recovery Systems
Scavenging Chemicals :
Low Volumes / Concentrations
< 1000 lb / day < 300 ppm
Chemical Solvents :
Medium Volumes / Concentrations
< 60,000 lb / day ( Flare Acid Gases )
 Amine Systems  Potassium Carbonate  Proprietary Systems

Direct Conversion to Elemental Sulfur

Large Volumes / Concentration
> 60,000 lb / day

Sulfur Content (lb / Day ) = . 084 QMMCFD ( PPMH2S )

© 2011 Dr. O. Barkat & PetroSkills, LLC. All rights reserved.
 Gas Sweetening Processes

Scavenging Chemicals: Solid Bed Absorption / Adsorption

Chemical Reaction or Ionic Bonding
▪ Iron Sponge ▪ Zinc Oxide ▪ Proprietary Scavenger Systems
○ Sulfur-Rite ○ SulfaTreat

Chemical Solvents :
Chemical Reaction and / or Absorption
▪ Amines: MEA, DEA, MDEA, DGA, DIPA ▪ Proprietary Products
○ Selexol ○ Ucarsol ○ Sulfinol ○ Flexsorb ○ CrystaSulf ○ Rectisol

Direct Conversion to Elemental Sulfur

▪ Claus ▪ Modified Claus ▪ Proprietary Products
○ LOCAT ○ Stretford ○ Sulfa-check

Gas Permeation through Membranes

Molecular Sieves / " Molecular Gate " Technology

© 2011 Dr. O. Barkat & PetroSkills, LLC. All rights reserved.
 Scavenging Chemicals
Low Volume / Concentrations < 1000 lb / day < 300 ppm

Iron Sponge Proprietary Scavenger Systems

Sulfur-Rite SulfaTreat
Safer / More Efficient / Expensive

© 2011 Dr. O. Barkat & PetroSkills, LLC. All rights reserved.

 Iron Sponge Unit
IRON OXIDE
GAS TREATING UNIT

SOUR GAS INLET

H2S + FERRIC OXIDE  FERRIC SULFIDE

+ WATER

TREATED GAS OUTLET

© 2011 Dr. O. Barkat & PetroSkills, LLC. All rights reserved.

 Zinc Oxide: Solid Bed Absorption

Solid Granular Bed of Zinc Oxide

Reacts to Form Zinc Sulfide + Water
Sulfide Ion Must Diffuse to Surface of
Zinc Oxide
More Efficient at Temperatures > 250F (120C)
Spent Catalyst Contains  20% Sulfur
by Weight
Disposing Catalyst a Problem:
Heavy Metal Salt
© 2011 Dr. O. Barkat & PetroSkills, LLC. All rights reserved.
 Special Scavenger Systems
Solid, Disposable, Proprietary
Chemically Changes H2S into Iron Pyrite
Handles < 500 # / Day
Non-Toxic, Environmentally Safe
Spent Media OK To Landfill
5 X Effectiveness of Iron Sponge
Handles Heads of Gas

© 2011 Dr. O. Barkat & PetroSkills, LLC. All rights reserved.

 SulfaTreat H2S Removal
Black Pea Sized Solid Scavenger 2 - 3 Times as Effective as Iron Sponge
Chemically Changes H2S into Iron Pyrite Selective to H2S
No Undesirable Off Gases Treatment Gas: Water Saturated 32F < T < 180F

© 2011 Dr. O. Barkat & PetroSkills, LLC. All rights reserved.

 H2S Removal by Chemical Solvents
Almost Complete Removal of H2S (Medium to High Concentration )
Low Operating Cost High Capital Investment
Acid Gas Flows thru Lean Aqueous Solution of Weak Base
Reacts with and Absorbed by Solvent
Rich Solution Regenerated at Lower Temp and Pressure
 REMOVES BOTH CO2 and H2S 
Solvents
DEA Di Ethanol Amine Most Common / Cheapest / Fouled w / CO2
MEA Mono Ethanol Amine Foam / Corrosive / Inert Blanket Gas
DGA Di Glycol Amine Less Corrosive / More Efficient
DIPA Di Iso Propanol Amine Non-Corrosive / Less Heat / Select / Foam
MDEA MethyDiEthanol Amine Non-Corrosive / Less Heat / Select
Potassium Carbonate Requires Heat / Extremely Corrosive
 Selexol  Sulfinol  Flexsorb  Ucarsol
 CrystaSulf  Rectisol  Purisol
© 2011 Dr. O. Barkat & PetroSkills, LLC. All rights reserved.
Chemical Solvent Process for Treating Acid Gas

Liquid Amine Solvent

or Proprietary

© 2011 Dr. O. Barkat & PetroSkills, LLC. All rights reserved.

Flexsorb Regenerator Installation

© 2011 Dr. O. Barkat & PetroSkills, LLC. All rights reserved.

 CrystaSulf Non Aqueous Process
High Pressure High CO2 Content
Amine Unit Output  Dissolved SO2 No Solids Until Crystallizer / Filter

Sulfur
© 2010 PetroSkills, LLC. All rights reserved. 33
Direct Conversion of H2S to Elemental Sulfur

© 2011 Dr. O. Barkat & PetroSkills, LLC. All rights reserved.

Chemical / Physical Solvent Process for Treating Acid Gas

CLAUS
PROCESS
CONVERTS
H2S to SULFUR

© 2011 Dr. O. Barkat & PetroSkills, LLC. All rights reserved.

Aqueous Amine – Claus – Tail Gas Treatment

Reboiler

© 2011 Dr. O. Barkat & PetroSkills, LLC. All rights reserved.

LO-CAT® H2S Removal Process (Suncor)

Autocirculation

© 2011 Dr. O. Barkat & PetroSkills, LLC. All rights reserved.

 Gas Permeation Treatment

Gas Diffusion Through Permeable Membranes

P  85% of Flowing Pressure

CO2 Diffuses Quickly

H2S - Diffuses More Slowly

Not Reduced to Pipeline Specifications
Follow-Up Treatment Needed
for Remaining H2S

© 2011 Dr. O. Barkat & PetroSkills, LLC. All rights reserved.

 Molecular Sieves: “Molecular Gate”
< 100 lb / day Sulfur < 300 ppm
Dry Bed of Synthetic Crystalline Solids (Zeolite)
Solid Porous Bed: Controlled Pore Sizes
H2S Enters Pores and Forms Weak Ionic Bonds
Dehydrates Gas as well as Sweetens Gas
Some CO2 Enters Pores: doesn’t bond but blocks
Moderate Pressures:  450 psig Optimum (3100 kPa)
Bed Regenerated with Hot Sweet Gas
(300 – 400F)  175C
Sour Vent Gas is Flared

● Low Flow Rates ● Low Concentrations of H2S

© 2011 Dr. O. Barkat & PetroSkills, LLC. All rights reserved.

 Molecular Gate CO2 Removal Facility

Molecular Gate
Technology
Removes CO2
– 1.5 M Mscf / D
– 30 + % CO2
Sized – Some N2
Zeolite – 20 psig

CO2 = 3.3 Å
H2S = 3.6 Å
N2 = 3.6 Å
Tidelands Oil C1 = 3.8 Å
Longbeach, CA
© 2011 Dr. O. Barkat & PetroSkills, LLC. All rights reserved.
 Selection of Treatment Type

Acid Gas Type and Removal Requirements

– Remove CO2 No H2S in Flowstream
– Remove H2S No CO2 in Flowstream
– Remove Both
– Remove H2S Selectively CO2 in Flowstream

Concentration of Contaminants / Specifications

Daily Volume / Temperature / Pressure / Total Life

Can / Must Sulfur be Recovered?

Richness of Heavy Hydrocarbons (C3+)

© 2011 Dr. O. Barkat & PetroSkills, LLC. All rights reserved.

 H2S Hazards

Enclosed Spaces
– Drains
– Vents (Heavier than Air)
– Opening any Pipe / Valve / Equipment
  Test  
 Retest Before Entry 
Winter Climate Hazards
- Protective Enclosures - Heating Equipment
○ Explosion
○ Ignition Source

MONITOR MONITOR MONITOR

© 2011 Dr. O. Barkat & PetroSkills, LLC. All rights reserved.

 H2S Safety / Rescue

Run Run Run Upwind or Crosswind

Do Not Attempt Rescue Until Adequately Protected

In Hazardous Locations: Always Use Buddy System

Test Atmosphere – Retest Atmosphere

Know and Give Cardiopulmonary Resuscitation

If Buddy Appears Dead: Give CPR anyway

Treat for Shock (Quiet and Warm)

– H2S is Not Cumulative
– Leaves Body Quickly if Breathing

© 2011 Dr. O. Barkat & PetroSkills, LLC. All rights reserved.

Continuous, Portable H2S Monitor

© 2011 Dr. O. Barkat & PetroSkills, LLC. All rights reserved.

 ®

DELIVERING KNOWLEDGE. DEVELOPING COMPETENCE.

Appendix 4A

Iron Sponge Unit Sizing

EXERCISE