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1) 2) Introduction on Acid Gases Various Types of Processes :
a.
I.
Chemical Absorption
Amine Solutions
Applications of Amine Solutions Design & Operation of Amine Units Recommendations of Unit Design Other Types of Amines Conventional Potassium Carbonate Process Improved Hot Carbonate Process
II.
b.
I.
Physical Absorption
The IFPEXOL Process
c. d.
Adsorption Permeation
ACID GASES
Definition
Acid Gas
is a gas containing acidic components such as CO2, H2S, COS (carbonyl sulphide), CS2 (carbon sulphide) RSH that can form acidic solutions when mixed with water.
Composition
Target
mainly contains of CO2 and H2S gases. Both gases can cause corrosion. These gases are obtained after a sweetening process applied to a sour gas. accompanied by small quantities of CS2, COS and RSH H2S content 4 ppm H2S content 4 ppm CO2 content 100 ppm; to prevent CO2 fr. Freezing out at low T H2S content can be left as it is CO2 content can be left as it is
i.
Gas transmission:
Have to be extracted first if to be used commercially, removed highly toxic H2S to undergo cryogenic treatment, reduced CO2 and H2S to be piped to a distant treatment plant, left CO2 and H2S during transportation.
CHEMICAL ABSORPTION
Definition:
Chemical absorption is a type of separation process. absorbent solution (solvent) reacts chemically with acid gases presence in natural gas to produce compounds. the compounds can be dissociated by heating or operating at low pressure of stripping. Used solvent is regenerated and re-use again example : gas sweetening process.
Technologies
The carbon dioxide concentration must be removed to less than 2% Carbon dioxide must also be removed prior to low temperature processing for NGL recovery. Current facilities used is amine processing Carbon dioxide is removed through the use of amine based solvents. The challenge faced is from keeping the solvent clean and operating within the process constraints of the system. Membrane systems also have been used for carbon dioxide removal One challenge for membrane systems is reaching the low allowable carbon dioxide levels required by the pipeline system Using adsorbent (molecular sieve system) for carbon dioxide removal can, for certain applications, allow for CO2 removal without the operational challenges of amine based systems or the process limitations faced by the membrane systems.
CO2 is strongly adsorbed, the adsorbent properties can be tailored so that it can also remove H2O vapor. Elimination is for dehydration, as is the case with N2 rejection, providing an operational and cost benefit.
Amine Solutions
For industrial purposes, can use 3 types of amines:
Monoethanolamine (MEA) Diethanolamine (DEA) Methyldiethanolamine (MDEA) Properties
MEA = 15-18 wt% (H2S, CO2) ; <10% of acid gases DEA = 15-20 wt% / 25-40 wt% (H2S, CO2)
Gas
Lean amine
Tray = 4-6 P= change V= change T= 35-50oC Tray = 20 P = Low T = 120-140 C(160- 247-269oC) water
SEPARATOR
CONDENSER
Process Description Acid Gases Removal in NG (Step 1-3) Step 1: i. Removal of loose water, liquid hydrocarbon, solid particles ii. In a separator (change in Pressure and Volume of NG) Step 2: i. Takes place in an absorber ii. 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 amine at T=35-50oC T= lean amine inlet > T=NG to prevent condensation of hydrocarbon Trays have to be kept far apart Step 3: Takes place in a separation drum Control entrainment of amine solution (impingement extractor) Final separation between NG and amine solution
Amine Solutions
(residual)
Process Description Regeneration of Rich Amine- NG+Acid Gases (Step 4-7) Step 4: i. 1st stage separation of rich amine solution and light hydrocarbon ii. Rich amine solution is flashed in a flash drum (change in Pressure and Volume) iii. Re-absorption using 4-6 trays Step 5: i. Takes place in an Regeneration Column ii. Preheated (heat exchanger) and fed to the top of regeneration column (20 trays) at low pressure iii. Absorption of acid gases takes place by contact in absorber trays in the column iv. Reboiling temperature must be carefully monitored to prevent thermal degradation of amine solution. Step 6: i. Takes place in a condenser ii. Acid gases and water vapour leave at the top of the regenerator; and enter a condenser where most of the water is condensed iii. The water is re-routed to the top of the regenerator to provide a reflux for the regeneration column
Amine Solutions
Step 7: i. The hot lean (or regenerated) aminesolution leaves the bottom of the regenerator heats the rich amine ii. Lean amine is then cooled by air/water before being fed into amine surge tank iii. Amine tank has to be inerted (maintain under N2 pressure) to avoid any risk of amine oxidising with air
With respect to CO2: - primary amines behave like MEA. - secondary amines behave like DEA. - rapid reaction. - both later form ethanolamine carbamate. - using hydrolysis of CO2 will form bicarbonate (slow reaction). - reactions occur: 1) 2R2NH + CO2 R2NCOOR2NH2 (carbamate) 2) R2NH + CO2 + H2O R2RNH HCO3 (bicarbonate)
Reactions: - allow determination of minimum flow rate of amine solution. - according to amine solutions concentration. - the circulation flow rates used is higher than stoichiometric flow rate.
MEA
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
advantages:
disadvantages:
operation energy consuming. required very careful operation of unit.
disadvantages:
operation energy consuming. required very careful operation of unit.
disadvantages:
difference rates of reaction - possible to simultaneously adsorbs H2S contact time is too short for adsorption of all CO2
**(figure 2) **(figure 3)
Process Schemes
Split Flow (Fig 2) flow of regenerated amine was split into 2 streams first stream is fed in to the absorber a little less than half way up second stream is fed into the top of the absorber complementary cooling the amine means that a stricter specification can be achieved for gas treated diameter of upper part of absorber will be reduced. Two Stage (Fig 3) two different amine solutions fed into absorber at different levels. semi regenerated solution withdrawn from the middle of regenerator. it is cooled and fed into absorber halfway up regenerated solution from bottom of regenerator is cooled it is fed into top of absorber to meet acid gas specifications more complex Recovery of Energy less capital investment reduces energy consumption in regenerator reboiler from rich amine expansion for absorber operated at high pressure and high amine circulation flow rate rich amine leave absorber in an expansion turbine before fed to flash drum energy thus recovered can supply part of energy required for pumping lean amine that feeds the absorber
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
amine solution enters top of absorber at high temperature gas fed into bottom of the absorber, to avoid risk of heavy HC condensed absorber trays should be spaced sufficiently wide apart. foaming will increase pressure drop hence delta P in column should regularly being monitored droplet separator is placed at top of column to limit entrainment of amine can be reduced by treated gas and by washing the gas with water make up distilled water is injected into washing loop
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
basic material used is carbon steel but some used of stainless steel corrosion much more severe in processing rich CO2 unit used of copper alloy is strictly prohibited in amine units expansion valves on rich amine line and piping immediately sensitive points with respect to erosion corrosion used of stellite expansion valve and large size piping can minimize corrosion caused by flow velocity and degassing of acid gases flow velocity should be limited to around 1m/s and bends with wide radius anneal all the welded areas in order to relieve stresses caused by welding develop several corrosion inhibitors where the effectiveness depends on number of factors
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
-Using Potassium Carbonate
carbonate solution hydrolyses COS and CS2 into CO2 ,and H2S are absorbed by solution RSH are partially removed from feed gas process is well suited to feed gases containing high proportion of CO2 high H2S with little CO2, make solution difficult to regenerate CO2 contributes to extraction of H2S from solution during regeneration involves lower capital investment and operating costs Does not meet severe specifications for the sales gas level of performance can be improved by using split / 2-stage scheme advisable to use stainless steel for the boiler tubes and expansion valves annealing is good to relieve stresses cause by welding.
T = high
T = 110-120 oC
PHYSICAL ABSORPTION
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 Favoured 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 Involves no chemical reaction between acid gases and the solvent
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
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
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 Tray = 20-30 Solvent = CH3OH, DME 1st phase: Release light HC and CH4 SOLVENT REGENERATION 2nd phase: Release CO2 by physical solvent EXPANSION
3rd phase:
SEPARATOR P = change V = change
P= 1 atm
Utilization
Solubility of acid gases in physical solvent is proportional to partial pressure of acid gas 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 Physical solvents easily absorb heavy hydrocarbon (aromatics) Low Temperature, gives high solubility of acid gas like hydrocarbon and solvent loss can be reduced at same time Solubility of CO2 and H2S in CH3OH is high at -30oC to -10oC 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 Adsorbent solution is regenerated by successive phases of expansion without supply of any heat In the last phase, energy consumption of processes is much lower than chemical absorption processes Higher solubility of H2S in physical solvent compared to CO2 allow selective removal of H2S with respect to CO2 For economic analysis, more advantageous if process run at acid gas partial pressure exceeding 4-5 bar
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
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
4.
Sulfinol Process
was developed by Shell a solution contains sulfolane (physical solvent) and di-isopropanolamine (chemical solvent) proportions of sulfolane, DIPA and water are adjusted in case depend on treatment to be performed use of this solvent is to remove small quantities of degradation products from DIPA has lesser tendency to form and remove RSH and COS effectively in presence of physical solvent, means significant absorption of heavy HC (aromatics) acid gas specifications required for natural gas liquefaction plant feeds can easily be met.
ADSORPTION PROCESS
Dehydration by Adsorption
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:
capacity of adsorbents depends on their nature low value of relative humidity gives high capacity of molecular sieve (ex: adsorbent) low dew point is required for cryogenic treatment of natural gas ability to adsorb heavy HC can show the selectivity of adsorbent
DEHYDRATION UNITS
ADSORPTION PHASE: Gas Flow: From top to bottom Adsorbent : Saturated with H2O Polarity of H2O: Stronger HC Molecule: Less Stronger
REGENERATION PHASE: T: 200-300oC P: Low Adsorbent : Activated Al, Si Gel, Mol Sieves Stages of Regeneration: Heating Phase Cooling Phase
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= 720820 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
capacity of adsorbents depends on their nature low value of relative humidity gives high capacity of molecular sieve (ex: adsorbent) low dew point is required for cryogenic treatment of natural gas ability to adsorb heavy HC can show the selectivity of adsorbent
ADSORPTION
Description of Process:
process flow scheme is identical to dehydration, with exception of regeneration gas circuit gas is contain of acid gases and mercaptans cannot be recycled back in regeneration phase of dehydration, water desorbed from molecular sieves by hot regeneration gas can condensed and removed in acid gas removal, acid gas more difficult to extract from regeneration gas regeneration gas contain CO2, can be injected into fuel gas network regeneration gas contain sulfur, can be incinerated or routed to treatment unit
ADSORPTION (2)
Utilization:
Molecular sieves have strong affinity for polar compounds Polar compounds such as water,H2S, mercaptans and CO2 Feed gas contain of water adsorb
PERMEATION PROCESS
PERMEATION
Definition:
Permeation is a technique that used in separating He and H2 from other gases develop extensively for natural gas treatment based on difference in permeation rate that characterizes the speed of diffusion of various constituents through membrane separation takes place through very fine hollow fibers of micro porous membrane. fast gases like H2, He and less content of CO2 and H2S are diffused through membrane slow gases cannot pass through membrane, only constitute residual gas
PERMEATION (1)
a gas in permeator composed of fine hollow fibers 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 at bottom, tube sheet is contained of ends of fibers through which permeate gases passes process is developed for H2 recovery applied in natural gas treatment is limited at present concern re-treatment for CO2 re-injection of gas from oil reservoir
PERMEATION (1)
advantages:
in treating NG very rich in CO2 (over 20%) contains little or no H2S use lower CO2 content to around 2%
disadvantage:
cannot be widely used until improve in permeability and selectivity of membrane and resistance to deterioration