ACID GAS REMOVAL

PROCESSES AND SELECTION

 CONTENTS

1. Acid Gas Constituents

2. Why Acid Gas Removal
3. Processes
4. Process Selection
 ACID GAS CONSTITUENTS IN
NATURAL GAS

• Hydrogen Sulphide H2S

• Carbon Dioxide CO2
 WHY ACID GAS REMOVAL ?
• Meet Pipeline / Sales gas
specification
• Avoid corrosion
• Environmental issues (Reduce
SOx emission)
• Meeting Heating Value
SALES GAS
SPECIFICATION - Typical
• 5-10 ppmv H2S
• < 5% CO2
 TOXICITY OF H2S

ppmv Period of exposure

10 Threshold Limit value for Prolonged Exposure

10-100 Slight symptoms after several hours
200-300 Maximum concentration for 1 hr.
without serious consequences
500-700 Dangerous after 30 min-1 hr
700-900 Fatal for 30 min or less
>1000 Death in minutes
 ACID GAS REMOVAL
PROCESSES
• Solvent Absorption Processes
• Scavengers and Solid Beds
• Membranes
• Direct Oxidation

Acid Gas Clean Up

• Claus Process
• Liquid Redox Process
SOLVENT ABSORPTION PROCESSES
Amine Based Processes
 AMINE BASED PROCESSES (CONT.)
• Regenerative Process
• Removes H2S, CO2, some COS and Mercaptans
• Includes MEA, DEA, MDEA (ETHANOLAMINES)
• Ethanolamines are clear, colorless, slightly pungent
odor, reactive and available at low cost.
MEA DEA MDEA

Mol. Wt. 61 105 119

Acid gas pickup, 0.33 - 0.35 - 0.2 –

mols/mol amine 0.4 0.65 0.55
Solution Conc. (wt.%) 10-20 25-35 30-50

• MDEA gives selectivity.

• Commercial Amine Processes:
➢ Sulfinol/ADIP (Shell)
➢ Flexsorb (Exxon)
➢ UCAR (Union Carbide)
AMINE BASED PROCESSES - OPERATING
PROBLEMS
• Corrosion
– At higher acid gas concentration
– At higher temperature
• Solution Degradation
– Exposure to air
– Reaction with COS
– High skin temperature.
• Foaming
– Presence of hydrocarbon liquid, solids,
foreign materials
 CARBONATE PROCESSES

• Scheme similar to amine based processes

• Typically uses aqueous solution of potassium carbonate
• High solution temperature
• Requires relatively high pressure of CO2
• Removes H2S, CO2, COS and RSH
• 2-stage / 3-stage processes are used to meet lower outlet
CO2 specification.

OPERATING PROBLEMS
• Corrosion
- Higher at reaction points
- Requires stress relieving

• Flashing and cavitation - Pressure reduction points

• Erosion - Filtration minimizes erosion problem
 COMMERCIAL CARBONATE PROCESSES

• UOP Benfield - Reduces corrosion

• Adventica Technologies - Proprietory
additives
• UOP Hipure - DEA + Hot carbonate (2-
Stage Process)
 PHYSICAL SOLVENT PROCESS
Physical solvent process is considered when:
• The partial pressure of the acid gas in the feed is
greater than 50 psi
• The heavy hydrocarbon concentration in the feed gas
is low
• Bulk removal of acid gas is required
• Selective removal of H2S is required
These processes are attractive because little or no
energy is required for regeneration. The solvents are
regenerated by:
• Multi-stage flashing to low pressures
• Regeneration at low temperatures with an inert
stripping gas
• Heating & stripping of solution with steam/solvent
vapors.
PHYSICAL SOLVENT PROCESS – FLOW
SCHEME
COMMERCIAL PHYSICAL SOLVENT
PROCESSES
SELEXOL (UOP)
• Solvent used is Dimethyl ether of
polyethlylene glycol
• Chemically inert
• Removes COS, H2S, RSH, NH3, HCN and
metal carbonyls.

PURISOL (LURGI)
• Uses N-methyl-2 Pyrrolidone (NMP-Purisol)
• Has high selectivity for H2S
RECTISOL (LURGI)

• Uses refrigerated solution of methanol

• Used mainly for purification of natural gas for LNG
production
SCAVENGER & SOLID BED
• Non-regenerable (for removal of small
amounts of H2S)
➢ Amine based - triazines

➢ Fixed Bed - ZnO, iron oxide, doped

charcoal, doped alumina
➢ Nitrate solutions

➢ Metal oxide slurries (e g. iron oxide, zinc

oxide)
• Contacting between sour gas and
scavenger chemical
➢ Bubble Tower - single or lead/lag

➢ In-line injection

➢ Downhole injection

➢ Fixed beds, single or lead/lag

 CARBON BASED ADSORBENT
• Lurgi oxorbon process - Solid bed iodine doped carbon
• Sulphur impregnated carbon is used for Hg removal.

AMINE BASED SCAVENGERS

• Triazines, glyoxyls and amines

• There are oil and water soluble versions

• Inline injection and bubble-towers

SULFATREAT
• Uses iron oxide on a ceramic support

• Acid gases adsorb on the surface of solid or

reacts with some components on the surface
 MOLECULAR SIEVES
• Crystalline sodium-calcium alumina silicate for
selective removal of H2S
• If CO2 and H2S are both present on the molecular
sieve, they can form COS
• Adsorption in order of retention is :
water → methanol → RSH → H2S → CO2→
COS
Regeneration gas to flare
Sour Gas
Tower 2
Tower 1

Sweet Gas

Regeneration Gas
 COMMERCIAL SOLID BED
PROCESSES

• UOP, Zeochem, Union Carbide

• Axens Multibed Technology
- Removes Hg, As, H2O, CO2, NH3
and sulfur species.
- Uses special aluminas and zeolite
molecular sieve adsorbent
installed in same or separate
vessels.
IRON OXIDE (SPONGE) PROCESS
• Removes H2S and RSH suing iron oxide
impregnated on wood chips
Packed
Tower

Sweet Gas
Sour Gas K.O. Drum

• Iron Sulfide stays in the packed tower.

• Limited for use with low inlet H2S
concentrations at pressures between 25-
1200 psig
PURASPEC

• Removes H2S, COS, Hg from gas or liquid

• Uses fixed bed of chemical adsorbents
 MEMBRANES
• Do not produce sharp separation
Fast Slow
H2O H2S CO2 O2 CH2
H2 N2
He
• No moving parts
• Low operational personnel requirements
• Small unit capacity
• Temperature alters permeability
– Qi = PiA (PPi,HP - PPi,LP)
– Pi = Permeation coefficient of (P, T, Polymer
type, gas comp.)
ACID GAS CLEANUP / SULFUR PRODUCTION
• Gas phase processes
• Liquid phase processes
GAS PHASE PROCESSES - CLAUS

Step 1 -Oxidation of 1/3 of H2S to SO2 in a

reaction furnace
Step 2 - SO2 and remaining H2S form S
Licensors:Jacobs, AMOCO, SIIRTEC NIGI,
Parsons/BOC, Lurgi, UOP Selectox, Shell
SRU
CLAUS PROCESS (SCHEME)
 LIQUID REDOX PROCESSES
• Removal of H2S from a gas stream by absorption
into an alkaline soln. to form S -- & 2H+
• Conversion of S–- to elemental sulfur by the action of
redox reagent (typically iron attached to a legend).
• Separation & recovery of solid sulfur
• Regeneration of spent redox reagent by reacting it
with oxygen dissolved in the solution
LO-CAT (US filter, Gas Technology Products)
Vent
Sweet Gas Regen Air

Sour Gas

Separator
Sulfur
Oxidiser Filter
Oil / Water Absorber
Dense Slurry

LO-CAT Solution
 PROCESS SELECTION CRITERIA
• Type of impurities to be • Product value and
removed purity requirements
• Degree of removal • Energy costs
• Concentration of acid • Solvent availability
gases • Local environment
• tons/day Sulfur regulations
• Feed Pressure or • Pressure Drop
Temperature allowable
• Presence of heavier • Familiarity and
hydrocarbon resistance to new
• Feed Rate technology
• Relative Economics • H2S/CO2 ratio
• Weight / Size (for
offshore)
 TYPICAL ECONOMIC RANGES
ACID GAS CONTENT (H2S + CO2) Vol%
Low High
<1 <15% 5-70% 10- 15-70% 40-90%
% 50%
Solid Prim & Tertiary Potass. Physical Membra
bed & Tertiary Amine Carb. Solvent nes
Scaveng amine
er
REMOVAL PROCESSES
CO2 H2 S CO2 + H2S SELECTIVE H2S
ONLY ONLY
Amine Amine Amine ADIP/MDEA
Carbonate Sulfinol Sulfinol Rectisol
Physical Selexol Potassium Selexol
Physical Physical Direct Sulfur
Solvent Conversion
Selexol
 PROCESS SELECTION OVERVIEW
100%

Amine + Claus
( + SCOT)
10%
H2S
Conc.
ppm
1%
LO CAT
and Sulferox

1000 ppm

100 ppm Disposable

Solids and
Liquids
10 ppm 1
0.01 0.1 10
Gas Flow, 106 Nm3/d
 Is H2S Present
No (Only High CO2)
Yes
No
Must H2S be removed from CO2 Alkanolamine
Membrane
Yes Potash
Combination

Is there enough H2S for

Claus
Yes No

Selective Amine LO-CAT

Selective Physical Sulferox
Solution Scavengers
Selexol
Combination Process
THANK YOU