Natural gas processing and purification

o  Why are the acid gases a problem?

o  W h a t a r e t y p i c a l acid gas
concentration in NG?
o  How much purification is needed?
o  What is done with acid gases after
separation from NG?
o  What processes are available for acid
gas removal?
PROBLEMS IN NG & SOLUTIONS
¢  Hydrogen sulfide (H2S) is toxic.
¢  Precursor to carbon disulfide (CS2), mercaptan (RSH),
sulfides (RSR), sulfur (S)
¢  With CO2, carbonyl sulfide (COS) can be formed.
¢  H2S in liquid can be detected using copper strip test
(ASTM D1838-07); in gas using lead acetate coated tape
(ASTM D4084 2007)
¢  Sub-quality gas contains CO2 ≥ 2%, N2 ≥ 4%, H2S ≥
4ppmv.
¢  Purification level: H2S < 6mg/Nm3, CO2 < 50ppmv (to
remove solid in LNG)
¢  Acid gases are disposed through incineration, reaction
with iron (H2S), underground injection. CO2 can be
mineralized.
¢  Sulfur is sequestered into magnesium sulfate brine,
MgSO4 that is benign and thermodynamically stable. 2
NATURAL GAS (NG) PROCESSING

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NG PROCESSING (CONTINUES)
1. Absorption (Sbsorptrion)
- Capturing acid gases (H2S and CO2) from NG by chemical mean (amine
solution)
2. Adsorption
- Capturing acid gases from NG by physical mean (PSA)
3. Membrane
- Capturing acid gases from NG by physical-sieving method
4. Cryogenic recovery and fractionation (train)
- Removing nitrogen from NG
- Extracting ethane, propane, butane from NG into LPG, LNG
5. Distillation
- Removing acid gases from amine solvent
- Removing liquid contaminants from product gas from cryo-separation
6. Desulfurization
- Converting H2S into sulfur
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ABSORPTION
¢  Involves contacting of a gas with a liquid
solvent to remove specific components.
¢  Physical absorption – no chemical reaction;
chemical absorption – involves chemical
reaction
¢  Factor affecting how much gas is absorbed
1.  The gas pressure. Increasing pressure
increases solubility
2.  Solvent temperature. Increasing
temperature decreases solubility
3.  Chemical and physical properties of gas
and solvent
¢  Distillation columns, contactors and
regenerators use internals to provide good
contact between phases needed for separation
1.  Bubble cap trays
2.  Valve trays
3.  Sieve trays 5
4.  Random packing
5.  Structured packing
ABSORPTION (CONTINUES)
¢  Amines are bases, used to remove the acid gases.
¢  With H2S, amine forms amine hydrosulfide, where R is an alkyl or hydrogen
deficient alkane such as methyl (CH3) or ethyl (C2H5)

R1R2R3N + H2S ↔ R1R2R3NH+HS-

¢  With CO2, amine forms amine bicarbonate or amine carbamate

CO2 + H2O + R1R2R3N ↔ R1R2R3NH+HCO3-

CO2 + 2R1R2NH ↔ R1R2NH2+R1R2NCOO-

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ABSORPTION (CONTINUES)
¢  Hot potassium carbonate are also used to remove
the acid gases.

K2CO3 + CO2 + H2O ↔ 2KHCO3

K2CO3 + H2S ↔ KHS + KHCO3

¢  In physical absorption, selexol, a polyethylene

glycol, is used to remove acid gas

CH3-O-CH2-(CH2-O-CH2)n-CH2-O-CH3

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BENFIELD PROCESS
The absorption and regeneration of acid gases in the Benfield
Process are based on the following reactions:
K2CO3 + CO2 + H2O = 2KHCO3 (1)
K2CO3 + H2S = KHS + KHCO3 (2)

In the HiPure Process, the reactions described below are added.

2R2NH + CO2 + H2O = (R2NH2)2CO3 (3)
(R2NH2)2CO3 + CO2 + H2O = 2R2NH2HCO3 (4)
2R2NH + H2S = (R2NH2)2S (5)
(R2NH2)2S + H2S = 2R2NH2HS (6)

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9
ADSORPTION
¢  Molecules adsorbed into adsorbent
and regenerated either by heat or
reduction of pressure. Regeneration of
adsorbent by pressure reduction is
pressure swing adsorption (PSA)
¢  Regeneration of adsorbent by heat is
temperature swing adsorption (TSA).
¢  Adsorption increases with increasing
partial pressure and decreasing
temperature

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PRESSURE SWING ADSORPTION
¢  Pressure Swing Adsorption
(PSA) – Adsorption (1→2),
blow-down (2→3), purge
(3→4), pressurization (4→1).

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Mass adsorbate/mass adsorbent vs. vapor mol fraction
PSA (CONTINUES)
¢  Skarstrom cycle produces waste
from purge step.
¢  Backwashing the waste as feed at
all points in the beds during each
adsorption can improve product
purity.

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MEMBRANES
¢  Membranes utilize solubility and
molecular size differences to
make separation.
¢  They have been used in NG
processing for dehydration, fuel-
gas conditioning, nitrogen and
bulk CO2 removal.
¢  Permeability is the ability of a
gas to diffuse into permeate side
of membrane. Selectivity is the
ratio of two permeabilities.
¢  Membrane process needs pre-
treatment to prevent damage
¢  Typical membrane modules for
NG purification are hollow fiber
and spiral wound.
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CRYOGENIC SEPARATION
¢  CO2, H2S liquefy at different temp-press – Component Boling point
Fractionation train (ºC)
¢  Operates at -100oC, 40 bars using a series of CH4 -161
compressors and heat changers (coolers).
C 2 H6 -89
¢  Crude NG is cooled to -70oC, followed by
compression-cooling until -100oC, 40 bars C 3 H8 -42
before the gas enters distillation column.
C7H16 98
¢  Distillation column separates CH4 from the
other contaminants, mainly H2S and CO2. H2 S -60
¢  The cold product is reintroduced as cooling CO2 -57 @ 5.2 bars
medium.

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FRACTIONATION TRAIN

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 Capacity
Startup
(MTPA)
Bintulu
MLNG 1 1983
7.6

Bintulu
1994 7.8
MLNG 2

Bintulu
2003 3.4
MLNG 3

FRIDAY, AUGUST 31, 2012

MLNG Train 9 Project at Bintulu, Sarawak

Petronas is embarking on a new production

train project at LNG Complex in Bintulu, known
as Petronas LNG Train 9. Train 9 of the
PETRONAS LNG Complex will utilize APCI
Split MRTM liquefaction process technology. GE
is providing a fully integrated solution for Train
9, including GE Oil & Gas turbocompression
equipment and variable speed drive systems.
The scope of GE’s supply includes a low/
medium-pressure mixed refrigerant package
and a propane and high pressure-mixed
refrigerant package, each driven by a Frame
7EA gas turbine with a 13-megawatt induction
motor running at 3,600 rpm and VSI technology
variable speed drive systems. The compression
trains are vital elements of the liquefaction
process, which cools natural gas to a liquid
state
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DISTILLATIONWhere is it needed?
Heat of vaporization (kJ/kg.mol)C
27ºC 97ºC
Water 43870 40750
Propane 14600 0
n-Butane 22090 16160

F=N-ϕ+2 Critical point

F= degree of freedom Liquid

Pressure
N= number of components Solid
ϕ= number of phases
Ex. A pure gas, 1phase, F=2 (variables)
A fluid, 2phases, F=1 Vapor
Triple point

Temperature
Variables (Pv=nzRT): 17
temperature, pressure, concentration
In distiller, pressure is constant, a plot shows temperature (T) vs. concentration (x, y)
DISTILLATION (CONTINUE)

¢  Dew point is a
pressure / temperature
when the liquid first
forms from the vapor,
by increasing pressure
(cryo).
¢  Flash point is a
pressure / temperature
when vapor first forms
from the liquid, by
lowering pressure.
¢  Example of single and
two-stage flash and
liquid vapor envelope.

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DISTILLATION (CONTINUE)
¢  Three-stage flash.
¢  Distillation requires large density
difference between vapor and liquid.

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DESULFURIZATION - CLAUSS PROCESS
¢  Catalytic reaction to convert H2S into sulfur.
¢  It consists of two step reactions: thermal oxidation and catalytic
reaction: 
Step I. 2H2S + 3O2 → 2SO2 + 2H2O
(thermal oxidation in furnace at 1000-1400 °C. Sulfur is formed, but
some H2S remains unreacted, and some SO2 is made)
Step II. 2H2S + SO2 ↔ 3/nSn + 2H2O
(catalytic reaction at 200-350 °C over Al2O3 catalyst )
Sulfur melting point/boiling point
115.2°C/444.6°C

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MODOP & SUPERCLAUSS
¢  Thermodynamic limitations cause 3-5% of H2S not
converted to sulfur and release as tail gas.
¢  Tail gas are treated using titanium-based catalysts
in MODOP (Mobil Oil Direct Oxidation) process, H2S + 1/2O2 → 1/nSn + H2O ..(1)
and iron-based catalysts (or CoMo/Al2O3 catalyst) 1/nSn + O2 →SO2 ..(2)
in SuperClauss process. H2S + 3/2O2 → SO2 + H2O ..(3)
¢  In both processes, removal of water vapor is 2H2S + SO2 ↔ 3/nSn + 2H2O ..(4)
important to prevent catalyst poisoning.
¢  In SuperClauss, excess oxygen is needed.
 

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BIOLOGICAL PROCESS
¢  The Shell-Paques process, or Tiopaq
process, is technology for the
conversion of hydrogen sulfide from
natural, refinery, synthesis and
biogas. It is based on the
biocatalytical conversion of sulfide
into elemental sulfur.
¢  It is an alternative to the Claus
process.
¢  It operates at near-ambient
conditions of temperature, about
30-40 °C, using micro-organisms.
¢  Phototrophic bacteria, Cholorobium
limicola can oxidize sulfide to
elemental sulfur, requiring only light,
CO2, and inorganic nutrients for
growth and is strictly anaerobic.
¢  Other microbs such as Chemotrophs,
Thiobacillus, Thermothrix, Thiothrix, 22
Beggiato may also be used.
FORMATIVE DISCUSSION & EXERCISE
¢  Explain the NG processing.
¢  What is Clauss process?
¢  What are the differences between PSA &
TSA?
¢  Why is pretreatment important in
membrane?
¢  Where are distillation required?
¢  Separation requires work (heat or pressure
difference). Which process use only heat, only
differential pressure or combination of both?
¢  What are the 2 physical properties that
dictate selectivity in membrane?

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FORMATIVE TASK
¢  Present a layout of a NG processing plant
together with contaminants removal
processes and the reactions involved.
¢  Describe the reasons for your option in
process selection.
¢  List down the limitations of the processes.
¢  Explain why different process is needed to
remove different compounds.
¢  Is it possible to remove all the undesired
compounds from 1 process?
¢  Conduct well-organized, logical argument in
the form of oral presentation to colleagues in
a group of 5 to discuss the above issues.
¢  Send in the report and video

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