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Acid Gas Removal
Acid Gas Removal
CONDENSER
Lean amine
Tray = 4-6
P= change
V= change water
T= 35-50oC Tray = 20
P = high P = Low
Tray = 20-30 T = 120-140 C(160- 247-269oC)
SEPARATOR
water
P = change
V = change
N2
Reactions:
- allow determination of minimum flow rate of amine solution.
- according to amine solution’s concentration.
- the circulation flow rates used is higher than stoichiometric flow rate.
Applications of Amine Solutions
1. MEA
advantages:
• used in solution of 15-18 wt%, to avoid corrosion
• reacts strongly with CO2 and H2S
• easily regenerated
• easily degraded: - by oxidation
- by reaction of COS and CS2
- by overheating the solution
• remove degradation product that can cause corrosion and foaming.
• high vapor pressure causes non negligible losses.
• recommended for treatment of natural gas with low acid gas content
(<10%)
• enables compliance with strict acid gas specifications
disadvantages:
• operation energy consuming.
• required very careful operation of unit.
Applications of Amine Solutions (2)
2. DEA
advantages:
• used in 15-20 wt% solution but upgraded from 25-40 wt% solution
• reduced in solution circulation flow rate and energy consumption
• greater resistance to degradation than MEA
• low in vapor pressure make DEA losses are reduced
• effective in simultaneously remove CO2,H2S
• preferable to replace MEA for treatment of natural gas with low acid gas
content
disadvantages:
• operation energy consuming.
• required very careful operation of unit.
Applications of Amine Solutions (3)
3. MDEA
advantages:
• used in 35 –50 wt% solution
• for extraction of H2S and leaving some CO2 in treated gas
• for production of CO2 with little H2S to enhance oil recovery fluid.
• H2S enrichment of acid gas before treatment in Claus unit
• not behave in the same way as MEA and DEA
• rate of reaction for MDEA-H2S extremely fast
• rate of reaction for MDEA-CO2 involves formation of carbonic acid and
slow
disadvantages:
• difference rates of reaction - possible to simultaneously adsorbs H2S
• contact time is too short for adsorption of all CO2
Design And Operation of Amine Treating Units
(1)
Purposes:
• to minimize investment and operating costs
• to achieve optimum performance (meet specifications or stream factor)
Control Methods:
• optimization of process scheme
– split flow scheme **(figure 2)
– two stage scheme **(figure 3)
– recovery of energy from rich amine expansion
Flash Drum
• to recover light HC dissolved in amine solution.
• light HC contain acid gases reduced during regeneration of solution.
• degassed HC can be used in fuel gas network.
• if HC contain of acid gases, later re-absorbed by washing with lean amine
Recommendations of Unit Design (2)
Absorber
• a place where acid gases were removed by chemical reactions
• minimized the amine circulation flow rate gives reason of economy
• avoid corrosion by following two constraints:
• Maximum amine concentration in the solution
• Maximum acid gas concentration in the amine solution
• advisable to raise tube bundle higher in the shell to facilitate flow of liquid
• saturated low pressure steam is reboiled far to avoid thermal degradation
of amine and limit corrosion of reboiler
• the tube bundle constantly submerged with liquid to prevent tubes drying
out and formation of hot spots
• make sure that the levels of liquid is 15 –20 cm above upper tubes of
bundle
Recommendations of Unit Design (4)
Reclaimer
• used when justified by production of non-regenerable (chemical reaction)
• a systematically in MEA units
• operation is carried out at T= 125oC with reaction of COS and CS2 to form
non-regenerable compounds
• impose purification of MEA solution to avoid accumulation of
contaminants
• a type of kettle placed parallel to regenerator reboiler
• perform batch distillation of small proportion of lean amine (1-3%)
• degradation products, non-volatile salts and solid particles accumulates in
bottom of shell
• focus on sized up the unit with exception of distance between lower part
of bundle and bottom of shell is greater (25-40 cm).
• this to avoid disrupting flow of liquid around tubes
• requires the use of stainless steel for the tubes of bundle
Recommendations of Unit Design (5)
Filtration
• important in amine unit
• perform in two stages 1) Cartridge type filter
-to remove solid particles
2) activated carbon bed
-to remove HC and contaminants in amine solution
• is located at point where lean amine leaves amine surge drum
• solution flow through filtration section about 10-20% of amount solution
• flow comes directly from discharge of main pump sending lean amine to
absorber
Diissopropanolamine (DIPA)
• used in aqueous solution in concentration of 30-50%
• DIPA selectivity absorbs H2S rather than CO2
• performance is similar to DEA
• more expensive than DEA but require less energy for regeneration
• more efficient where COS is concerned
• used in Sulfinol process mixed with physical solvent (sulfolane)
Chemical Absorption
T = high
T = 110-120 oC
T = 110-120 oC
K2CO3 = 30-40 wt%
‘Improved’ Hot Carbonate Process
Processes include:
Benfield Process
-hot carbonate solution is activated by DEA and other additives
Catacarb Process
-incorporates amine borate and other additives into carbonate solution
Giammarco-Vetrocoke Process
-arsenic salts are added to the potassium carbonate solution
Why? To give solution a certain degree of selectivity with respect to H2S and CO2:
• by improving sales gas specifications
• by reducing energy required to regenerate solution
• by choosing and dosage of additives
Process Description
Acid Gases Removal in NG (Step 1-2)
Step 1:
i. Separator Unit
ii. Removal of loose water, liquid hydrocarbon, solid particles
iii. Principle of operation: change in Pressure and Volume of NG
Step 2:
i. Absorber Unit
ii. Lean solvent is fed into the top absorber; contact with feed gas flowing
counter-currently in the column
iii. Absorption of acid gases takes place by contact in absorber trays in
the column (20-30 trays depending on the severity of the treatment)
between ascending NG and descending lean solvent
• Absorption pressure = high; temperature= low
• Example of Solvent = methanol, dimethyl ether, propylene
carbonate, n-methyl pyrrolidine
Process Description (cont’d)
Process Description
Solvent Regeneration (Step 3 - ???)
Step 3:
i. Separator Unit
ii. Removal of loose water, liquid hydrocarbon, solid particles
iii. Principle of operation: change in Pressure and Volume of NG
Step 4:
i. Absorber Unit
ii. Lean solvent is fed into the top absorber; contact with feed gas
flowing counter-currently in the column
iii. Absorption of acid gases takes place by contact in absorber trays
in the column (20-30 trays depending on the severity of the
treatment) between ascending NG and descending lean solvent
• Absorption pressure = high; temperature= low
• Example of Solvent = methanol, dimethyl ether, propylene
carbonate, n-methyl pyrrolidine
PHYSICAL ABSORPTION
PROCESSES (5)
IFPEXOL Process(cold Methanol; IFP )
Selexol Process (DMPEG, dimethylether of polyethylene glycol; )
Rectisol Process (cold methanol)
Purisol Process (NMP, n-methyl pyrrolidone)
Sulfinol Process (DIPA-sulfolane di-isopropanolamine; SHELL)
PHYSICAL ABSORPTION
• Definition:
– Is a physical absorption whereby acid gases present in natural
gas is removed by absorbing the acid gases physically under
prescribed operating conditions (T & P)
• Characteristics:
– Acid gases dissolve in the solution under pressure and
temperature
– Favored by high acid gas partial pressure concentrations
(contributed by both pressure of CO2 and/or H2S) and low
temperature
– Use solvent is an operating parameter that will dictate the
degree of efficiency of absorption
– Solvent is regenerated by low pressure expansion of solution
rich in dissolved acid gases
Description of process
Principle
• Based on the solubility variation of the acid gases in the solvent as a function of the partial
pressure
• The process flow diagram does not change whatever the solvent used, with the exception of the
final solvent regeneration
Process Description
Acid Gases Removal in NG (Step 1-2)
Step 1:
i. Separator Unit
ii. Removal of loose water, liquid hydrocarbon, solid particles
iii. Principle of operation: change in Pressure and Volume of NG
Step 2:
i. Absorber Unit
ii. Lean solvent is fed into the top absorber; contact with feed gas flowing counter-currently in the
column
iii. Absorption of acid gases takes place by contact in absorber trays in the column (20-30 trays
depending on the severity of the treatment) between ascending NG and descending lean solvent
• Absorption pressure = high; temperature= low
• Example of Solvent = methanol, dimethyl ether, propylene carbonate, n-methyl pyrrolidine
Process Description (cont’d)
Process Description
Solvent Regeneration (Step 3-5)
Step 3:
i. First expansion phase
ii. Releases dissolved constituents that not soluble in solvent
iii. Applies to light HC and CH4
iv. Gas routed to fuel gas network
v. Large amount gas released due to high solvent flow rate, then will be compressed
and recycled to absorber
Step 4:
i. Second expansion phase
ii. Released CO2 less strongly absorbed by physical solvent than H2S and RSH
Step 5:
i. Third phase (low pressure expansion)
ii. Solution virtually be bring to atmospheric pressure
Lean solvent
P = high
T = low
1st phase: SOLVENT
Tray = 20-30 REGENERATION
Release light HC
Solvent = CH3OH, DME and CH4 2nd phase:
Release CO2 by
physical solvent
EXPANSION
3rd phase:
P= 1 atm
SEPARATOR
P = change
V = change
• Solubility curves remain the same although used solvent with different gases
• CO2 is less adsorbed than H2S where solubility is 3-9 times higher than CO2
• CH4 has very low solubility in physical solvent due to high concentration in feed gas
and non-negligible quantity may absorbed
• Low Temperature, gives high solubility of acid gas like hydrocarbon and solvent loss
can be reduced at same time
• For absorption capacity limitation, the solubility increase regularly with partial
pressure in physical absorption
Utilization (2)
• Physical absorption effectively for high pressure processing of natural gas
containing large amount of acid gases and traces amount of heavy HC
• Attractive process when acid gas partial pressure is high and large flow of
gas to be processed
Purposes:
• dehydration of natural gas
• removal of heavy hydrocarbons (C2+ cut, NGL)
• acid gas removal with single solvent methanol
Process Characteristics:
• perform several functions with same solvent
• save in capital investment because require less equipment, compactness
of installation and reduced in operating cost.
• perform selective purification treatment since H2S more soluble in CH3OH
than CO2
THE IFPEXOL PROCESS (2)
Process Description:
• raw NG mixed with CH3OH from top of stripping column to inlet of separator
• feed gas enters the bottom column recovers CH3OH from aqueous solution
• cold CH3OH solution flows counter-currently to gas and absorbs acid gases
and S
2. Cold Methanol
• can be called as IFPEXOL & Rectisol Process
• CH3OH used in absorber at temperature below 0oC in range of –30oC
• minimizes loss CH3OH of through vaporization in treated gas
• promote solution of acid gases in solvent
• cold CH3OH used for processing natural gas rich in acid gases and
synthesis gas
• uses of CH3OH are such as:
• dehydration
• acid gas removal
• natural gas liquid recovery
Types of Industrial Solvent (3)
3. n- Methyl Pyrrolidone (NMP)
• can be called as Purisol Process
• has property in common with polyethylene glycol dimethylether
• high selectivity of H2S with respect to CO2
Principle:
• A physical process whereby a suitable porous solid with
specific property is able to fix water molecules on the
surface of pores where water vapor condensed
• Characteristic of Adsorbents
– have very large internal contact, 250-850 m2/g
– Possess a strong affinity for water vapour and a high capacity for
adsorption
– Be easily and economically regenerable
– Undergo slight pressure drop under flow of gas
– Possess good mechanical strength
DEHYDRATION
Dehydration by Adsorption
1. Adsorption Phase
• gas flow through drier from top to bottom
• adsorbent saturated with water
• halted phase first before reach breakthrough point
• polarity of water much stronger attraction on adsorbent
• ejects hydrocarbon molecules that less stronger
2. Regeneration Phase
• regenerate bed of adsorbent
• performed operation by increase temperature or lower the pressure
• can be performed by heating bed of adsorbent
• 2 stage of regeneration of drier: heating phase & cooling phase
DEHYDRATION
Dehydration by Adsorption
Adsorbent:
• should posses strong affinity for water vapor
• high capacity for adsorption process
• easily and economically re-generable
• undergo little drop in pressure
• posses good mechanical strength
Types of Adsorbent:
• activated alumina
• silica gel
• molecular sieves
• activated carbon
DEHYDRATION
Dehydration by Adsorption
Adsorbent Characteristics:
REGENERATION PHASE:
ADSORPTION PHASE:
T: 200-300oC Adsorbent : Activated Al, Si Gel, Mol Sieves
Gas Flow: From top to bottom Stages of Regeneration: Heating Phase
P: Low Cooling Phase
Adsorbent : Saturated with H2O
Polarity of H2O: Stronger
HC Molecule: Less Stronger
Dehydration by Adsorption
Process Description:
• using 2 columns called dryers packed with solid adsorbent
• involve 2 phase: adsorption phase & regeneration phase
1. Adsorption Phase
• gas flow through drier from top to bottom
• adsorbent saturated with water
• halted phase first before reach breakthrough point
• polarity of water much stronger attraction on adsorbent
• ejects hydrocarbon molecules that is less stronger
2. Regeneration Phase
• regenerate bed of adsorbent
• performed operation by increasing in T (200-300 oC) or lowering the P,
or by a combination of both
• can be performed by heating bed of adsorbent
• 2 stage of regeneration of drier: heating phase & cooling phase
– Heating Phase: Hot air desorb the water from the adsorbent
– Cooling Phase: Drier is cooled at the end of the heating phase to the
initial condition
Types of Adsorbent
• activated alumina
– SA=280 m2/g; pore volume=0.4 m3/g; pore diameter=2-4 nm; density= 720-
820 kg/m3)
– Reduce content by 1 ppmv
– Regeneration T= 150-220 oC
• silica gel
– SA=550-800 m2/g; pore volume=0.35-0.5 m3/g; pore diameter=2.5 nm;
density= 720-800 kg/m3)
– Reduce content by 10 ppmv
– Regeneration T= 150-250 oC
• activated carbon
Design of Adsorption Dehydration Units
Choice of Adsorbent
Dryer Arrangement
• located in shell
• one end fiber closed off by epoxy resin plug and the other end enables
recovery the gas that passes through membrane
• on top, tube sheet close off the hollow fibers while at same time allow
evacuation of residual gas
disadvantage:
• cannot be widely used until improve in permeability and selectivity
of membrane and resistance to deterioration