CA2664970C - Self-concentrating absorbent for acid gas separation - Google Patents
Self-concentrating absorbent for acid gas separation Download PDFInfo
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- CA2664970C CA2664970C CA2664970A CA2664970A CA2664970C CA 2664970 C CA2664970 C CA 2664970C CA 2664970 A CA2664970 A CA 2664970A CA 2664970 A CA2664970 A CA 2664970A CA 2664970 C CA2664970 C CA 2664970C
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- 239000002253 acid Substances 0.000 title claims abstract description 135
- 239000002250 absorbent Substances 0.000 title claims abstract description 124
- 230000002745 absorbent Effects 0.000 title claims abstract description 124
- 238000000926 separation method Methods 0.000 title claims description 62
- 238000000034 method Methods 0.000 claims abstract description 49
- 239000008246 gaseous mixture Substances 0.000 claims abstract description 36
- 239000007789 gas Substances 0.000 claims description 133
- 238000010521 absorption reaction Methods 0.000 claims description 88
- 150000001412 amines Chemical class 0.000 claims description 64
- 239000003795 chemical substances by application Substances 0.000 claims description 55
- 238000011069 regeneration method Methods 0.000 claims description 46
- 230000008929 regeneration Effects 0.000 claims description 44
- CURLTUGMZLYLDI-UHFFFAOYSA-N Carbon dioxide Chemical compound O=C=O CURLTUGMZLYLDI-UHFFFAOYSA-N 0.000 claims description 40
- 239000002904 solvent Substances 0.000 claims description 28
- 230000005484 gravity Effects 0.000 claims description 23
- -1 glycol ethers Chemical class 0.000 claims description 22
- 239000001569 carbon dioxide Substances 0.000 claims description 20
- 229910002092 carbon dioxide Inorganic materials 0.000 claims description 20
- 238000007385 chemical modification Methods 0.000 claims description 19
- 150000003839 salts Chemical class 0.000 claims description 19
- HZAXFHJVJLSVMW-UHFFFAOYSA-N 2-Aminoethan-1-ol Chemical compound NCCO HZAXFHJVJLSVMW-UHFFFAOYSA-N 0.000 claims description 16
- AQSJGOWTSHOLKH-UHFFFAOYSA-N phosphite(3-) Chemical class [O-]P([O-])[O-] AQSJGOWTSHOLKH-UHFFFAOYSA-N 0.000 claims description 16
- BVKZGUZCCUSVTD-UHFFFAOYSA-M Bicarbonate Chemical class OC([O-])=O BVKZGUZCCUSVTD-UHFFFAOYSA-M 0.000 claims description 12
- QGJOPFRUJISHPQ-UHFFFAOYSA-N Carbon disulfide Chemical compound S=C=S QGJOPFRUJISHPQ-UHFFFAOYSA-N 0.000 claims description 12
- 239000007864 aqueous solution Substances 0.000 claims description 12
- 150000004649 carbonic acid derivatives Chemical class 0.000 claims description 12
- UAOMVDZJSHZZME-UHFFFAOYSA-N diisopropylamine Chemical compound CC(C)NC(C)C UAOMVDZJSHZZME-UHFFFAOYSA-N 0.000 claims description 12
- 229910019142 PO4 Inorganic materials 0.000 claims description 10
- 150000003863 ammonium salts Chemical class 0.000 claims description 10
- 159000000011 group IA salts Chemical class 0.000 claims description 10
- 235000021317 phosphate Nutrition 0.000 claims description 10
- 150000003013 phosphoric acid derivatives Chemical class 0.000 claims description 10
- 150000001642 boronic acid derivatives Chemical class 0.000 claims description 9
- LYCAIKOWRPUZTN-UHFFFAOYSA-N ethylene glycol Natural products OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 claims description 9
- MWUXSHHQAYIFBG-UHFFFAOYSA-N Nitric oxide Chemical compound O=[N] MWUXSHHQAYIFBG-UHFFFAOYSA-N 0.000 claims description 8
- NQRYJNQNLNOLGT-UHFFFAOYSA-N Piperidine Chemical compound C1CCNCC1 NQRYJNQNLNOLGT-UHFFFAOYSA-N 0.000 claims description 8
- RAHZWNYVWXNFOC-UHFFFAOYSA-N Sulphur dioxide Chemical compound O=S=O RAHZWNYVWXNFOC-UHFFFAOYSA-N 0.000 claims description 8
- JJWKPURADFRFRB-UHFFFAOYSA-N carbonyl sulfide Chemical compound O=C=S JJWKPURADFRFRB-UHFFFAOYSA-N 0.000 claims description 8
- 230000001351 cycling effect Effects 0.000 claims description 8
- JQVDAXLFBXTEQA-UHFFFAOYSA-N dibutylamine Chemical compound CCCCNCCCC JQVDAXLFBXTEQA-UHFFFAOYSA-N 0.000 claims description 8
- ACVYVLVWPXVTIT-UHFFFAOYSA-M phosphinate Chemical compound [O-][PH2]=O ACVYVLVWPXVTIT-UHFFFAOYSA-M 0.000 claims description 8
- UEZVMMHDMIWARA-UHFFFAOYSA-M phosphonate Chemical compound [O-]P(=O)=O UEZVMMHDMIWARA-UHFFFAOYSA-M 0.000 claims description 8
- XRBCRPZXSCBRTK-UHFFFAOYSA-N phosphonous acid Chemical compound OPO XRBCRPZXSCBRTK-UHFFFAOYSA-N 0.000 claims description 8
- AKEJUJNQAAGONA-UHFFFAOYSA-N sulfur trioxide Chemical compound O=S(=O)=O AKEJUJNQAAGONA-UHFFFAOYSA-N 0.000 claims description 8
- RWSOTUBLDIXVET-UHFFFAOYSA-N Dihydrogen sulfide Chemical class S RWSOTUBLDIXVET-UHFFFAOYSA-N 0.000 claims description 7
- 239000007788 liquid Substances 0.000 claims description 7
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 7
- 235000013877 carbamide Nutrition 0.000 claims description 6
- ZBCBWPMODOFKDW-UHFFFAOYSA-N diethanolamine Chemical compound OCCNCCO ZBCBWPMODOFKDW-UHFFFAOYSA-N 0.000 claims description 6
- WGCNASOHLSPBMP-UHFFFAOYSA-N hydroxyacetaldehyde Natural products OCC=O WGCNASOHLSPBMP-UHFFFAOYSA-N 0.000 claims description 6
- 229910001463 metal phosphate Inorganic materials 0.000 claims description 6
- CRVGTESFCCXCTH-UHFFFAOYSA-N methyl diethanolamine Chemical compound OCCN(C)CCO CRVGTESFCCXCTH-UHFFFAOYSA-N 0.000 claims description 6
- 150000003672 ureas Chemical class 0.000 claims description 6
- 150000001408 amides Chemical class 0.000 claims description 5
- 150000002169 ethanolamines Chemical class 0.000 claims description 5
- 239000012528 membrane Substances 0.000 claims description 5
- 125000000217 alkyl group Chemical group 0.000 claims description 4
- 229940043279 diisopropylamine Drugs 0.000 claims description 4
- 239000002608 ionic liquid Substances 0.000 claims description 4
- 229920000642 polymer Polymers 0.000 claims description 4
- GSEJCLTVZPLZKY-UHFFFAOYSA-N Triethanolamine Chemical compound OCCN(CCO)CCO GSEJCLTVZPLZKY-UHFFFAOYSA-N 0.000 claims description 3
- 150000001298 alcohols Chemical class 0.000 claims description 3
- 150000001299 aldehydes Chemical class 0.000 claims description 3
- 150000001335 aliphatic alkanes Chemical class 0.000 claims description 3
- MTHSVFCYNBDYFN-UHFFFAOYSA-N diethylene glycol Chemical compound OCCOCCO MTHSVFCYNBDYFN-UHFFFAOYSA-N 0.000 claims description 3
- 150000002148 esters Chemical class 0.000 claims description 3
- 150000002170 ethers Chemical class 0.000 claims description 3
- 150000002334 glycols Chemical class 0.000 claims description 3
- 150000002576 ketones Chemical class 0.000 claims description 3
- HXJUTPCZVOIRIF-UHFFFAOYSA-N sulfolane Chemical compound O=S1(=O)CCCC1 HXJUTPCZVOIRIF-UHFFFAOYSA-N 0.000 claims description 3
- 229930195735 unsaturated hydrocarbon Natural products 0.000 claims description 3
- LQZZUXJYWNFBMV-UHFFFAOYSA-N dodecan-1-ol Chemical compound CCCCCCCCCCCCO LQZZUXJYWNFBMV-UHFFFAOYSA-N 0.000 claims description 2
- 150000004673 fluoride salts Chemical class 0.000 claims description 2
- 239000006096 absorbing agent Substances 0.000 claims 1
- PXQLVRUNWNTZOS-UHFFFAOYSA-N sulfanyl Chemical compound [SH] PXQLVRUNWNTZOS-UHFFFAOYSA-N 0.000 claims 1
- 239000012071 phase Substances 0.000 description 71
- 239000000243 solution Substances 0.000 description 8
- 239000007795 chemical reaction product Substances 0.000 description 6
- BVKZGUZCCUSVTD-UHFFFAOYSA-L Carbonate Chemical compound [O-]C([O-])=O BVKZGUZCCUSVTD-UHFFFAOYSA-L 0.000 description 5
- 239000000203 mixture Substances 0.000 description 5
- VNWKTOKETHGBQD-UHFFFAOYSA-N methane Chemical compound C VNWKTOKETHGBQD-UHFFFAOYSA-N 0.000 description 4
- 239000003960 organic solvent Substances 0.000 description 4
- 238000003756 stirring Methods 0.000 description 4
- 230000015572 biosynthetic process Effects 0.000 description 3
- 239000012535 impurity Substances 0.000 description 3
- BWDBEAQIHAEVLV-UHFFFAOYSA-N 6-methylheptan-1-ol Chemical compound CC(C)CCCCCO BWDBEAQIHAEVLV-UHFFFAOYSA-N 0.000 description 2
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 2
- 238000006243 chemical reaction Methods 0.000 description 2
- 238000010586 diagram Methods 0.000 description 2
- 238000010438 heat treatment Methods 0.000 description 2
- 239000007791 liquid phase Substances 0.000 description 2
- 239000003345 natural gas Substances 0.000 description 2
- 238000005191 phase separation Methods 0.000 description 2
- 238000005086 pumping Methods 0.000 description 2
- 239000007790 solid phase Substances 0.000 description 2
- 238000012546 transfer Methods 0.000 description 2
- GVGLGOZIDCSQPN-PVHGPHFFSA-N Heroin Chemical compound O([C@H]1[C@H](C=C[C@H]23)OC(C)=O)C4=C5[C@@]12CCN(C)[C@@H]3CC5=CC=C4OC(C)=O GVGLGOZIDCSQPN-PVHGPHFFSA-N 0.000 description 1
- 150000001413 amino acids Chemical class 0.000 description 1
- 239000003125 aqueous solvent Substances 0.000 description 1
- 229910052799 carbon Inorganic materials 0.000 description 1
- 238000005119 centrifugation Methods 0.000 description 1
- 239000000356 contaminant Substances 0.000 description 1
- 238000007796 conventional method Methods 0.000 description 1
- 238000004821 distillation Methods 0.000 description 1
- 238000001914 filtration Methods 0.000 description 1
- 229910000037 hydrogen sulfide Inorganic materials 0.000 description 1
- 230000035699 permeability Effects 0.000 description 1
- 238000012545 processing Methods 0.000 description 1
- 238000000746 purification Methods 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 238000005979 thermal decomposition reaction Methods 0.000 description 1
- 239000003021 water soluble solvent Substances 0.000 description 1
Landscapes
- Gas Separation By Absorption (AREA)
Abstract
An process for efficiently deacidizing a gaseous mixture is described. The process utilizes a self-concentrating absorbent that absorbs an acid gas at reduced overall energy costs for the deacidizing operation.
Description
TITLE OF THE INVENTION
[0001] Self-Concentrating Absorbent for Acid Gas Separation FIELD OF THE INVENTION
[0004] The present invention relates to a process for deacidizing a gaseous mixture using a self-concentrating absorbent. More particularly, the present invention relates to a method for the separation of an acid gas from a gaseous mixture using a self-concentrating absorbent, which reduces the overall energy costs for such deacidizing operation.
BACKGROUND OF THE INVENTION
[0005] Removal of acid gas from gas mixture is required for many processes, such as, deacidizatiopn of a raw natural gas or any other gaseous mixture that contains significant amounts of an acid gas, e.g., hydrogen sulfide (H2S), carbon dioxide (CO2), or similar contaminants. The deacidization process reduces the acid gas impurity in the gaseous mixture to acceptable levels. This is commonly done with an amine gas treatment process. Amine gas treatment processes are common in various types of industrial settings, such as refineries, natural gas processing plants, and petrochemical plants. Amine gas treatment processes include the processes utilizing aqueous solutions of amines to remove acid gas, such as H2S and CO2.
[0006] A common deacidization process is gas-liquid absorption. Such process typically involves contacting a gaseous mixture containing an acid gas to be removed with an aqueous amine solution, whereby the amine solution is an absorbent that absorbs the acid gas. In industrial settings, the most commonly used amines are alkanolamines, such as monoethanolamine (MEA) and diethanolamine (DEA). The use of the alkanolamine methyldiethanolamine (MDEA) for CO2 separation has recently become notable for use in industrial settings.
Diisopropanolarnine (DIPA) is currently used in the Sultinorproce,ss and in the SCOT*process for Claus plant tail acid gas purification.
[0007] In the typical gas-liquid absorption process, after an acid gas is absorbed into the absorbent in an absorption unit, the gas-rich absorbent is sent to a regeneration unit, where the gas-rich absorbent is treated and separated to regenerate the absorbed gas and the gas-lean absorbent.
The regenerated gas-lean absorbent is then recycled back into the absorption unit and the acid gas is either collected or discharged, depending on the purpose of the user. In this type of gas-liquid absorption, the regeneration process accounts for greater than 80% of the total energy costs because the entire volume of the absorbent effluent must be regenerated in order to be reused in the absorption unit. In addition, the typical gas-liquid absorption process is limited to the use of an absorbent in the form of one liquid phase.
BRIEF SUMMARY OF THE INVENTION
[0008] It is now discovered that a method for deacidizing a gaseous mixture involving a self-concentrating absorbent increases the absorption rate of an acid gas from the gaseous mixture and reduces the overall energy costs for such deacidizing operation.
100091 In one general aspect, embodiments of the present invention relate to a method for deacidizing a gaseous mixture comprising an acid gas. The method comprises:
contacting the gaseous mixture with an absorbent in an absorption unit, wherein the absorbent comprises an amine dissolved in a solvent at a first concentration;
allowing the absorbent to absorb the acid gas to form a concentrated-amine phase, wherein the concentrated-amine phase is mechanically separable from the remaining of the absorbent and comprises a concentrated amine at a concentration higher than the first concentration and an absorbed acid gas, wherein the concentrated amine comprises the amine or the amine having a chemical modification, and the absorbed acid gas comprises the acid gas or the acid gas having a chemical modification;
* Trade-mark
[0001] Self-Concentrating Absorbent for Acid Gas Separation FIELD OF THE INVENTION
[0004] The present invention relates to a process for deacidizing a gaseous mixture using a self-concentrating absorbent. More particularly, the present invention relates to a method for the separation of an acid gas from a gaseous mixture using a self-concentrating absorbent, which reduces the overall energy costs for such deacidizing operation.
BACKGROUND OF THE INVENTION
[0005] Removal of acid gas from gas mixture is required for many processes, such as, deacidizatiopn of a raw natural gas or any other gaseous mixture that contains significant amounts of an acid gas, e.g., hydrogen sulfide (H2S), carbon dioxide (CO2), or similar contaminants. The deacidization process reduces the acid gas impurity in the gaseous mixture to acceptable levels. This is commonly done with an amine gas treatment process. Amine gas treatment processes are common in various types of industrial settings, such as refineries, natural gas processing plants, and petrochemical plants. Amine gas treatment processes include the processes utilizing aqueous solutions of amines to remove acid gas, such as H2S and CO2.
[0006] A common deacidization process is gas-liquid absorption. Such process typically involves contacting a gaseous mixture containing an acid gas to be removed with an aqueous amine solution, whereby the amine solution is an absorbent that absorbs the acid gas. In industrial settings, the most commonly used amines are alkanolamines, such as monoethanolamine (MEA) and diethanolamine (DEA). The use of the alkanolamine methyldiethanolamine (MDEA) for CO2 separation has recently become notable for use in industrial settings.
Diisopropanolarnine (DIPA) is currently used in the Sultinorproce,ss and in the SCOT*process for Claus plant tail acid gas purification.
[0007] In the typical gas-liquid absorption process, after an acid gas is absorbed into the absorbent in an absorption unit, the gas-rich absorbent is sent to a regeneration unit, where the gas-rich absorbent is treated and separated to regenerate the absorbed gas and the gas-lean absorbent.
The regenerated gas-lean absorbent is then recycled back into the absorption unit and the acid gas is either collected or discharged, depending on the purpose of the user. In this type of gas-liquid absorption, the regeneration process accounts for greater than 80% of the total energy costs because the entire volume of the absorbent effluent must be regenerated in order to be reused in the absorption unit. In addition, the typical gas-liquid absorption process is limited to the use of an absorbent in the form of one liquid phase.
BRIEF SUMMARY OF THE INVENTION
[0008] It is now discovered that a method for deacidizing a gaseous mixture involving a self-concentrating absorbent increases the absorption rate of an acid gas from the gaseous mixture and reduces the overall energy costs for such deacidizing operation.
100091 In one general aspect, embodiments of the present invention relate to a method for deacidizing a gaseous mixture comprising an acid gas. The method comprises:
contacting the gaseous mixture with an absorbent in an absorption unit, wherein the absorbent comprises an amine dissolved in a solvent at a first concentration;
allowing the absorbent to absorb the acid gas to form a concentrated-amine phase, wherein the concentrated-amine phase is mechanically separable from the remaining of the absorbent and comprises a concentrated amine at a concentration higher than the first concentration and an absorbed acid gas, wherein the concentrated amine comprises the amine or the amine having a chemical modification, and the absorbed acid gas comprises the acid gas or the acid gas having a chemical modification;
* Trade-mark
2 =
separating the concentrated-amine phase from the remaining of the absorbent;
cycling the remaining of the absorbent back into the absorption unit;
providing the concentrated-amine phase to a regeneration unit, so as to obtain the acid gas and the concentrated amine; and cycling the regenerated concentrated amine back into the absorption unit.
[0010] In an embodiment of the present invention, the absorbent and the absorbed acid gas move downward from the absorption unit to the separation unit by gravity, and the separated concentrated-amine phase moves downward from the separation unit to the regeneration unit by gravity.
[0011] In another general aspect, embodiments of the present invention relate to a system for deacidizing a gaseous mixture comprising an acid gas. The system comprises:
an absorption unit adapted to allow contact between the gaseous mixture and an absorbent comprising an amine dissolved in a solvent at a first concentration, wherein the absorbent absorbs the acid gas to form a concentrated-amine phase, wherein the concentrated-amine phase is mechanically separable from the remaining of the absorbent, and the concentrated-amine phase comprises a concentrated amine at a concentration higher than the first concentration and an absorbed acid gas, wherein the concentrated amine comprises the amine or the amine having a chemical modification, and the absorbed acid gas comprises the acid gas or the acid gas having a chemical modification a separation unit adapted to allow separation of the concentrated-amine phase from the remaining of the absorbent; and a regeneration unit adapted to allow regeneration of the concentrated-amine phase, so as to obtain the acid gas and the concentrated amine.
[0012] In an embodiment of the present invention, the absorption unit, the separation unit and the regeneration unit are in a single tower, wherein the separation unit is placed in a position lower than the absorption unit and the regeneration unit is placed in a position lower than the separation unit, so that after the gas absorption, the absorbent and the absorbed acid gas move downward from the absorption unit to the separation unit by gravity, and the concentrated-amine phase moves downward from the separation unit to the regeneration unit by gravity.
[0013] In yet another general aspect, embodiments of the present invention relate to a method for deacidizing a gaseous mixture comprising an acid gas. The method comprises:
contacting the gaseous mixture with an absorbent in an absorption unit, wherein the absorbent comprises an agent dissolved in a solvent at a first concentration, wherein the agent is
separating the concentrated-amine phase from the remaining of the absorbent;
cycling the remaining of the absorbent back into the absorption unit;
providing the concentrated-amine phase to a regeneration unit, so as to obtain the acid gas and the concentrated amine; and cycling the regenerated concentrated amine back into the absorption unit.
[0010] In an embodiment of the present invention, the absorbent and the absorbed acid gas move downward from the absorption unit to the separation unit by gravity, and the separated concentrated-amine phase moves downward from the separation unit to the regeneration unit by gravity.
[0011] In another general aspect, embodiments of the present invention relate to a system for deacidizing a gaseous mixture comprising an acid gas. The system comprises:
an absorption unit adapted to allow contact between the gaseous mixture and an absorbent comprising an amine dissolved in a solvent at a first concentration, wherein the absorbent absorbs the acid gas to form a concentrated-amine phase, wherein the concentrated-amine phase is mechanically separable from the remaining of the absorbent, and the concentrated-amine phase comprises a concentrated amine at a concentration higher than the first concentration and an absorbed acid gas, wherein the concentrated amine comprises the amine or the amine having a chemical modification, and the absorbed acid gas comprises the acid gas or the acid gas having a chemical modification a separation unit adapted to allow separation of the concentrated-amine phase from the remaining of the absorbent; and a regeneration unit adapted to allow regeneration of the concentrated-amine phase, so as to obtain the acid gas and the concentrated amine.
[0012] In an embodiment of the present invention, the absorption unit, the separation unit and the regeneration unit are in a single tower, wherein the separation unit is placed in a position lower than the absorption unit and the regeneration unit is placed in a position lower than the separation unit, so that after the gas absorption, the absorbent and the absorbed acid gas move downward from the absorption unit to the separation unit by gravity, and the concentrated-amine phase moves downward from the separation unit to the regeneration unit by gravity.
[0013] In yet another general aspect, embodiments of the present invention relate to a method for deacidizing a gaseous mixture comprising an acid gas. The method comprises:
contacting the gaseous mixture with an absorbent in an absorption unit, wherein the absorbent comprises an agent dissolved in a solvent at a first concentration, wherein the agent is
3 selected from the group consisting of amino-acid salts, amides, alkaline salts, alkaline-earth salts, ammonium salts, ureas, alkaline metal phosphates, carbonates, borates, acid phosphites, phosphites, phosphonite, phosphinate, phosphonate, acid phosphates, pyrophosphites, bicarbonates, metaborates, diborates, tetraborates, pentaborates, and combinations thereof;
allowing the absorbent to absorb the acid gas to form a concentrated-agent phase, wherein the concentrated-agent phase is mechanically separable from the remaining of the absorbent and comprises a concentrated agent at a concentration higher than the first concentration and an absorbed acid gas, wherein the concentrated agent comprises the agent or the agent having a chemical modification, and the absorbed acid gas comprises the acid gas or the acid gas having a chemical modification;
separating the concentrated-agent phase from the remaining of the absorbent;
cycling the remaining of the absorbent back into the absorption unit;
providing the concentrated-agent phase to a regeneration unit, so as to obtain the acid gas and the concentrated agent; and cycling the regenerated concentrated agent back into the absorption unit.
[0014] In another general aspect, embodiments of the present invention relate to a system for deacidizing a gaseous mixture comprising an acid gas. The system comprises:
an absorption unit adapted to allow contact between the gaseous mixture and an absorbent comprising an agent dissolved in a solvent at a first concentration, wherein the agent is selected from the group consisting of amino-acid salts, amides, alkaline salts, alkaline-earth salts, ammonium salts, ureas, alkaline metal phosphates, carbonates, borates, acid phosphites, phosphites, phosphonite, phosphinate, phosphonate, acid phosphates, pyrophosphites, bicarbonates, metaborates, diborates, tetraborates, pentaborates, and combinations thereof;
wherein the absorbent absorbs the acid gas to form a concentrated-agent phase, the concentrated-agent phase is mechanically separable from the remaining of the absorbent, and the concentrated-agent phase comprises a concentrated agent at a concentration higher than the first concentration and an absorbed acid gas, wherein the concentrated agent comprises the agent or the agent having a chemical modification, and the absorbed acid gas comprises the acid gas or the acid gas having a chemical modification;
allowing the absorbent to absorb the acid gas to form a concentrated-agent phase, wherein the concentrated-agent phase is mechanically separable from the remaining of the absorbent and comprises a concentrated agent at a concentration higher than the first concentration and an absorbed acid gas, wherein the concentrated agent comprises the agent or the agent having a chemical modification, and the absorbed acid gas comprises the acid gas or the acid gas having a chemical modification;
separating the concentrated-agent phase from the remaining of the absorbent;
cycling the remaining of the absorbent back into the absorption unit;
providing the concentrated-agent phase to a regeneration unit, so as to obtain the acid gas and the concentrated agent; and cycling the regenerated concentrated agent back into the absorption unit.
[0014] In another general aspect, embodiments of the present invention relate to a system for deacidizing a gaseous mixture comprising an acid gas. The system comprises:
an absorption unit adapted to allow contact between the gaseous mixture and an absorbent comprising an agent dissolved in a solvent at a first concentration, wherein the agent is selected from the group consisting of amino-acid salts, amides, alkaline salts, alkaline-earth salts, ammonium salts, ureas, alkaline metal phosphates, carbonates, borates, acid phosphites, phosphites, phosphonite, phosphinate, phosphonate, acid phosphates, pyrophosphites, bicarbonates, metaborates, diborates, tetraborates, pentaborates, and combinations thereof;
wherein the absorbent absorbs the acid gas to form a concentrated-agent phase, the concentrated-agent phase is mechanically separable from the remaining of the absorbent, and the concentrated-agent phase comprises a concentrated agent at a concentration higher than the first concentration and an absorbed acid gas, wherein the concentrated agent comprises the agent or the agent having a chemical modification, and the absorbed acid gas comprises the acid gas or the acid gas having a chemical modification;
4 a separation unit adapted to allow separation of the concentrated-agent phase from the remaining of the absorbent; and a regeneration unit adapted to allow regeneration of the concentrated-agent phase, so as to obtain the acid gas and the concentrated agent.
100151 Other aspects, features and advantages of the invention will be apparent from the following disclosure, including the detailed description of the invention and its preferred embodiments and the appended claims.
BRIEF DESCRIPTION OF THE SEVERAL VIEWS OF THE DRAWINGS
100161 The foregoing summary, as well as the following detailed description of the invention, will be better understood when read in conjunction with the appended drawings.
For the purpose of illustrating the invention, there are shown in the drawings embodiments which are presently preferred. It should be understood, however, that the invention is not limited to the precise arrangements and instrumentalities shown.
100171 In the drawings:
100181 Fig. 1 is a flow diagram showing the steps of the deacidization process according to an embodiment of the present invention; and [00191 Fig. 2 is a flow diagram showing the steps of the deacidization process according to another embodiment of the present invention.
DETAILED DESCRIPTION OF THE INVENTION
t00201 Unless defined otherwise, all technical and scientific terms used herein have the same meaning as commonly understood to one of ordinary skill in the art to which this invention pertains.
Otherwise, certain terms used herein have the meanings as set in the specification, it must be noted that as used herein and in the appended claims, the singular forms "a", "an" and "the"
include plural references unless the context clearly indicates otherwise.
[00211 In one general aspect, the present invention relates to a process of deacidizing a gaseous mixture using a self-concentrating amine absorption, while minimizing energy costs and maximizing absorption rates.
[0022J According to an embodiment of the present invention, an absorbent and a gaseous mixture containing an acid gas to be removed are contacted in an absorption unit. The absorbent
100151 Other aspects, features and advantages of the invention will be apparent from the following disclosure, including the detailed description of the invention and its preferred embodiments and the appended claims.
BRIEF DESCRIPTION OF THE SEVERAL VIEWS OF THE DRAWINGS
100161 The foregoing summary, as well as the following detailed description of the invention, will be better understood when read in conjunction with the appended drawings.
For the purpose of illustrating the invention, there are shown in the drawings embodiments which are presently preferred. It should be understood, however, that the invention is not limited to the precise arrangements and instrumentalities shown.
100171 In the drawings:
100181 Fig. 1 is a flow diagram showing the steps of the deacidization process according to an embodiment of the present invention; and [00191 Fig. 2 is a flow diagram showing the steps of the deacidization process according to another embodiment of the present invention.
DETAILED DESCRIPTION OF THE INVENTION
t00201 Unless defined otherwise, all technical and scientific terms used herein have the same meaning as commonly understood to one of ordinary skill in the art to which this invention pertains.
Otherwise, certain terms used herein have the meanings as set in the specification, it must be noted that as used herein and in the appended claims, the singular forms "a", "an" and "the"
include plural references unless the context clearly indicates otherwise.
[00211 In one general aspect, the present invention relates to a process of deacidizing a gaseous mixture using a self-concentrating amine absorption, while minimizing energy costs and maximizing absorption rates.
[0022J According to an embodiment of the present invention, an absorbent and a gaseous mixture containing an acid gas to be removed are contacted in an absorption unit. The absorbent
5 comprises an amine or an agent dissolved in a solution at a first concentration. During the absorption, amine or the agent in the absorbent is spontaneously concentrated into a concentrated-amine or concentrated-agent phase. After the absorption is complete, the concentrated-amine or concentrated-agent phase is mechanically separable from the remaining of the absorbent, i.e., the concentrated-amine or concentrated-agent phase does not form a solution with the remaining of the absorbent.
[0023] The acid gas to be removed can be, for example, one or more acid gases selected from the group consisting of carbon dioxide (CO2), sulfur dioxide (SO2), sulfur trioxide (SO3), hydrogen sulfide (H2S), carbon oxysulfide (COS), carbon disulfide (CS2), mercaptans (RSH), nitric oxide (NO), nitric dioxide (NO2), fluorides, HC1, and a combination thereof.
[0024] The absorption unit according to embodiments of the present invention can be, for example, an absorption column or a membrane contractor, or any other gas-liquid contacting units that are known to those skilled in the art.
[0025] It is readily appreciated by those skilled in the art that the absorbent can comprise one or more amines dissolved in a solvent. Examples of the amines include, but are not limited to monoethanolamine, diethanolamine, triethanolamine, ethanolamines, isopropanolamines, ethyleneamines, alkyl alkanolamines, methyldiethanolamine, piperidine, dibutylamine, diisopropylamine, derivatives thereof, or mixtures thereof.
[0026] The solvent can be aqueous or organic. For example, the aqueous solvent can be water, an aqueous solution of one or more salts, including, but not limited to, alkaline salts, ammonium salts, alkanolamine salts, alkaline-earth salts, or derivatives thereof. The organic solvent can comprise one or more components, including, but not limited to, alcohols, glycols, alkanes, unsaturated hydrocarbon, ethers, esters, aldehyde, ketones, glycol ethers, alkylene carbonates, dialkyl carbonates, sulfolane, and derivatives thereof, such as ionic liquids, polymers. The solvent can further be a combination of an aqueous solution and an organic solvent.
[0027] In a preferred embodiment, the organic solvent comprises a C8 to C12 alcohol.
[0028] The solvent can also be water insoluble or slightly water soluble solvent, such as water insoluble alcohol, glycol, or glycol ether. The solvent can further be ionic liquids or polymers.
10029] In an embodiment of the present invention, the absorbent comprises an amine solution, including, but not limited to an alcohol, glycol or glycol ether solution of monoethanolamine, diethanolamine, triethanolamine, ethanolamines, isopropanolamines, ethyleneamines, alkyl alkanolamines, methyldiethanolamine, piperidine, dibutylamine, diisopropylamine, derivatives thereof, or mixtures thereof.
[0023] The acid gas to be removed can be, for example, one or more acid gases selected from the group consisting of carbon dioxide (CO2), sulfur dioxide (SO2), sulfur trioxide (SO3), hydrogen sulfide (H2S), carbon oxysulfide (COS), carbon disulfide (CS2), mercaptans (RSH), nitric oxide (NO), nitric dioxide (NO2), fluorides, HC1, and a combination thereof.
[0024] The absorption unit according to embodiments of the present invention can be, for example, an absorption column or a membrane contractor, or any other gas-liquid contacting units that are known to those skilled in the art.
[0025] It is readily appreciated by those skilled in the art that the absorbent can comprise one or more amines dissolved in a solvent. Examples of the amines include, but are not limited to monoethanolamine, diethanolamine, triethanolamine, ethanolamines, isopropanolamines, ethyleneamines, alkyl alkanolamines, methyldiethanolamine, piperidine, dibutylamine, diisopropylamine, derivatives thereof, or mixtures thereof.
[0026] The solvent can be aqueous or organic. For example, the aqueous solvent can be water, an aqueous solution of one or more salts, including, but not limited to, alkaline salts, ammonium salts, alkanolamine salts, alkaline-earth salts, or derivatives thereof. The organic solvent can comprise one or more components, including, but not limited to, alcohols, glycols, alkanes, unsaturated hydrocarbon, ethers, esters, aldehyde, ketones, glycol ethers, alkylene carbonates, dialkyl carbonates, sulfolane, and derivatives thereof, such as ionic liquids, polymers. The solvent can further be a combination of an aqueous solution and an organic solvent.
[0027] In a preferred embodiment, the organic solvent comprises a C8 to C12 alcohol.
[0028] The solvent can also be water insoluble or slightly water soluble solvent, such as water insoluble alcohol, glycol, or glycol ether. The solvent can further be ionic liquids or polymers.
10029] In an embodiment of the present invention, the absorbent comprises an amine solution, including, but not limited to an alcohol, glycol or glycol ether solution of monoethanolamine, diethanolamine, triethanolamine, ethanolamines, isopropanolamines, ethyleneamines, alkyl alkanolamines, methyldiethanolamine, piperidine, dibutylamine, diisopropylamine, derivatives thereof, or mixtures thereof.
6 [0030] In an embodiment of the present invention, the amine can be another agent instead, the other agent can be amino-acids, amino-acid salts, amides, alkaline salts, ammonium salts, ureas, alkaline metal phosphates, carbonates, borates, acid phosphites, phosphites, phosphonite, phosphinate, phosphonate, acid phosphates, pyrophosphites, bicarbonates, metaborates, diborates, tetraborates, pentaborates, derivatives thereof, or combinations thereof. The solvent can be water, an aqueous solution of one or more salts, including, but not limited to, alkaline salts, ammonium salts, alkanolarnine salts, alkaline-earth salts, ureas, alkaline metal phosphates, acid phosphites, phosphites, phosphonite, phosphinate, phosphonate, acid phosphates, pyrophosphites, carbonates, bicarbonates, borates, metaborates, diborates, tetraborates, pentaborates, or derivatives thereof. The organic solvent can comprise one or more components, including, but not limited to, alcohols, glycols, alkanes, unsaturated hydrocarbon, ethers, esters, aldehyde, ketones, glycol ethers, alkylene carbonates, dialkyl carbonates, sulfolane, and derivatives thereof, such as ionic liquids, polymers, such as, the absorbent comprises a carbonates or borates aqueous solution.
[0031] In an embodiment of the present application, the absorbent comprises a solution of an amine at a concentration selected from the group consisting of 0.1%, 1%, 5%, 10%, 15%, 20%, 25%, 30%, 35%, 40%, 45%, 50%, 55%, 60%, 65%, 70%, 75%, 80 %, 85%, 90%, etc.
[0032] According to embodiments of the present invention, when the acid gas contacts with the absorbent, the acid gas can be absorbed physically, chemically, or both physically and chemically.
After physical absorption, the acid gas is absorbed in the absorbent, mainly in the concentrated-amine phase, without being chemically modified. After chemical absorption, however, the acid gas is absorbed in the absorbent, mainly in the concentrated-amine phase, after being chemically modified, e.g., in a reaction product of the amine and the acid gas.
[0033] In one embodiment of the present invention, the reaction product of the amine with the acid gas is substantially insoluble in the solvent.
[0034] The concentrated-amine phase comprises a concentrated amine at a concentration higher than the first concentration and an absorbed acid gas. The concentrated amine can be the amine or the amine having a chemical modification, for example, a reaction product resulting from a chemical reaction between the amine and the acid gas. The absorbed acid gas can be the acid gas or the acid gas having a chemical modification, for example, a reaction product resulting from a chemical reaction between the amine and the acid gas. The concentrated-amine phase can exist as a single phase, e.g., a solution of amine. The concentrated-amine phase can also contain multiple phases.
[0031] In an embodiment of the present application, the absorbent comprises a solution of an amine at a concentration selected from the group consisting of 0.1%, 1%, 5%, 10%, 15%, 20%, 25%, 30%, 35%, 40%, 45%, 50%, 55%, 60%, 65%, 70%, 75%, 80 %, 85%, 90%, etc.
[0032] According to embodiments of the present invention, when the acid gas contacts with the absorbent, the acid gas can be absorbed physically, chemically, or both physically and chemically.
After physical absorption, the acid gas is absorbed in the absorbent, mainly in the concentrated-amine phase, without being chemically modified. After chemical absorption, however, the acid gas is absorbed in the absorbent, mainly in the concentrated-amine phase, after being chemically modified, e.g., in a reaction product of the amine and the acid gas.
[0033] In one embodiment of the present invention, the reaction product of the amine with the acid gas is substantially insoluble in the solvent.
[0034] The concentrated-amine phase comprises a concentrated amine at a concentration higher than the first concentration and an absorbed acid gas. The concentrated amine can be the amine or the amine having a chemical modification, for example, a reaction product resulting from a chemical reaction between the amine and the acid gas. The absorbed acid gas can be the acid gas or the acid gas having a chemical modification, for example, a reaction product resulting from a chemical reaction between the amine and the acid gas. The concentrated-amine phase can exist as a single phase, e.g., a solution of amine. The concentrated-amine phase can also contain multiple phases.
7 =
[0035] Because the absorbent forms the concentrated-amine phase spontaneously upon absorption of the acid gas, the absorbent is also referred to as the self-concentrating amine absorbent.
[0036] The absorbed acid gas accumulates in the concentrated-amine phase.
[0037] After the absorbent absorbs the acid gas, the purified gaseous mixture, with the acid gas being removed or significantly reduced, is released from the absorption unit.
The released purified gaseous mixture can be collected or disposed of, depending on the user's purpose.
[0038] After the absorbent absorbs the acid gas, the contents of the absorption unit are provided to a separation unit to separate the concentrated-amine phase from the remaining of the absorbent.
The formation of the concentrated-amine phase can proceed before, simultaneously, or after the contents of the absorption unit are provided to the separation unit.
[0039] In one embodiment of the present invention, the contents of the absorption unit are provided to the separation unit after the complete formation of the concentrated-amine phase.
[0040] In another embodiment of the present invention, the contents of the absorption unit are provided to the separation unit before the complete formation of the concentrated-amine phase.
[0041] The separation can be achieved using phase separation methods known to those skilled in the art in view of the present disclosure. For example, the concentrated-amine phase can be separated based on the density of the phase, e.g., by a separating drum. The concentrated-amine phase can also be separated based on other properties of the phase, e.g., by a membrane that has different permeability to the concentrated-amine phase and the remaining of the absorbent.
[0042] The separating step of the present invention can be accomplished utilizing one or more types of phase settlers or phase separation units known in the art as suited for separation of bulk liquid phases. Some examples include simple settlers, filtration, centrifugation, membrane, etc.
[0043] After the separation, the remaining of the absorbent contains mostly the solvent. It can also contain the amine at a concentration much lower than the first concentration. The remaining of the absorbent can further contain a small amount of the absorbed acid gas.
After the separation, the remaining of the absorbent is cycled back into the absorption unit for reuse.
[0044] The separated concentrated-amine phase is routed to a regeneration unit, where the concentrated-amine phase is treated to produce or regenerate the amine and the acid gas. The regeneration process according to embodiments of the present invention can be accomplished by regeneration methods known to those skilled in the art in view of the present disclosure. Exemplary regeneration methods include, but are not limited to, thermal decomposition, gas stripping, steam
[0035] Because the absorbent forms the concentrated-amine phase spontaneously upon absorption of the acid gas, the absorbent is also referred to as the self-concentrating amine absorbent.
[0036] The absorbed acid gas accumulates in the concentrated-amine phase.
[0037] After the absorbent absorbs the acid gas, the purified gaseous mixture, with the acid gas being removed or significantly reduced, is released from the absorption unit.
The released purified gaseous mixture can be collected or disposed of, depending on the user's purpose.
[0038] After the absorbent absorbs the acid gas, the contents of the absorption unit are provided to a separation unit to separate the concentrated-amine phase from the remaining of the absorbent.
The formation of the concentrated-amine phase can proceed before, simultaneously, or after the contents of the absorption unit are provided to the separation unit.
[0039] In one embodiment of the present invention, the contents of the absorption unit are provided to the separation unit after the complete formation of the concentrated-amine phase.
[0040] In another embodiment of the present invention, the contents of the absorption unit are provided to the separation unit before the complete formation of the concentrated-amine phase.
[0041] The separation can be achieved using phase separation methods known to those skilled in the art in view of the present disclosure. For example, the concentrated-amine phase can be separated based on the density of the phase, e.g., by a separating drum. The concentrated-amine phase can also be separated based on other properties of the phase, e.g., by a membrane that has different permeability to the concentrated-amine phase and the remaining of the absorbent.
[0042] The separating step of the present invention can be accomplished utilizing one or more types of phase settlers or phase separation units known in the art as suited for separation of bulk liquid phases. Some examples include simple settlers, filtration, centrifugation, membrane, etc.
[0043] After the separation, the remaining of the absorbent contains mostly the solvent. It can also contain the amine at a concentration much lower than the first concentration. The remaining of the absorbent can further contain a small amount of the absorbed acid gas.
After the separation, the remaining of the absorbent is cycled back into the absorption unit for reuse.
[0044] The separated concentrated-amine phase is routed to a regeneration unit, where the concentrated-amine phase is treated to produce or regenerate the amine and the acid gas. The regeneration process according to embodiments of the present invention can be accomplished by regeneration methods known to those skilled in the art in view of the present disclosure. Exemplary regeneration methods include, but are not limited to, thermal decomposition, gas stripping, steam
8 stripping, distillation, treatment through a membrane contractor, pervaporization, pressure differential treatment, and a combination thereof.
[0045] The regenerated acid gas is collected or disposed of depending on the purpose of the user. The regenerated amine is cycled back into the absorption unit for reuse.
[0046] In an embodiment of the present invention, the contents of the absorbent are transferred from one unit to another unit by a pump. In other embodiments of the present invention, the contents of the absorbent are transferred between at least some of the units by gravity.
[0047] In an embodiment of the present invention, the contents of the absorbent move downward from the absorption unit to the separation unit by gravity.
[0048] In another embodiment of the present invention, the separated concentrated-amine phase moves downward from the separation unit to the regeneration unit by gravity.
[0049] In still another embodiment of the present invention, the contents of the absorbent move downward from the absorption unit to the separation unit, and the separated concentrated-amine phase moves downward from the separation unit to the regeneration unit, all by gravity.
[0050] In another general aspect, the present invention relates to a system for deacidizing a gaseous mixture comprising an acid gas. The system comprises an absorption unit, a separation unit and a regeneration unit as those described herein.
[0051] In an embodiment of the present invention, the separation unit is placed in a position lower than the absorption unit, so that the contents of the absorbent move downward from the absorption unit to the separation unit by gravity.
[0052] In another embodiment of the present invention, the regeneration unit is placed in a position lower than the separation unit, so that the separated concentrated-amine phase moves downward from the separation unit to the regeneration unit by gravity.
[0053] In still another embodiment of the present invention, the absorption unit, the separation unit and the regeneration unit are placed in a single tower, wherein the separation unit is placed in a position lower than the absorption unit and the regeneration unit is placed in a position lower than the separation unit, so that the gas-rich absorbent moves downward from the absorption unit to the separation unit by gravity, and the separated concentrated-amine phase moves downward from the separation unit to the regeneration unit by gravity.
[0054] The deacidization process according to embodiments of the present invention can be used to remove an impurity acid gas from a gaseous mixture, in which case the impurity acid gas can be disposed of, with improved efficiency. Alternatively, the deacidization process according to
[0045] The regenerated acid gas is collected or disposed of depending on the purpose of the user. The regenerated amine is cycled back into the absorption unit for reuse.
[0046] In an embodiment of the present invention, the contents of the absorbent are transferred from one unit to another unit by a pump. In other embodiments of the present invention, the contents of the absorbent are transferred between at least some of the units by gravity.
[0047] In an embodiment of the present invention, the contents of the absorbent move downward from the absorption unit to the separation unit by gravity.
[0048] In another embodiment of the present invention, the separated concentrated-amine phase moves downward from the separation unit to the regeneration unit by gravity.
[0049] In still another embodiment of the present invention, the contents of the absorbent move downward from the absorption unit to the separation unit, and the separated concentrated-amine phase moves downward from the separation unit to the regeneration unit, all by gravity.
[0050] In another general aspect, the present invention relates to a system for deacidizing a gaseous mixture comprising an acid gas. The system comprises an absorption unit, a separation unit and a regeneration unit as those described herein.
[0051] In an embodiment of the present invention, the separation unit is placed in a position lower than the absorption unit, so that the contents of the absorbent move downward from the absorption unit to the separation unit by gravity.
[0052] In another embodiment of the present invention, the regeneration unit is placed in a position lower than the separation unit, so that the separated concentrated-amine phase moves downward from the separation unit to the regeneration unit by gravity.
[0053] In still another embodiment of the present invention, the absorption unit, the separation unit and the regeneration unit are placed in a single tower, wherein the separation unit is placed in a position lower than the absorption unit and the regeneration unit is placed in a position lower than the separation unit, so that the gas-rich absorbent moves downward from the absorption unit to the separation unit by gravity, and the separated concentrated-amine phase moves downward from the separation unit to the regeneration unit by gravity.
[0054] The deacidization process according to embodiments of the present invention can be used to remove an impurity acid gas from a gaseous mixture, in which case the impurity acid gas can be disposed of, with improved efficiency. Alternatively, the deacidization process according to
9 embodiments of the present invention can be used to collect an acid gas of interest from a gaseous mixture, with improved efficiency.
[0055] In one embodiment of the present invention, the solvent in an absorbent according to an embodiment of the present invention serves to increase the absorption rate of the acid gas. The acid gas is absorbed into the absorbent at a rate greater than that if it were directly absorbed by the amine.
[0056] In an aspect of the present invention, the energy to be expended for the regeneration process is reduced because only part of the absorbent, the concentrated-amine phase, needs to be regenerated, while the remaining of the absorbent can immediately be recycled for reuse in the absorption unit.
[0057] In yet another aspect of the present invention, the energy to be expended for the deacidization process is further reduced by incorporating two or more of the units used in the process in a single tower, so that the various components can be transferred between some of the units by gravity, instead of pumping. The use of multiple units in a single tower is enabled and becomes practical, because of the relatively smaller size of the concentrated-amine phase that needs to be regenerated. In a conventional liquid-gas separation process, the volume of the gas-rich absorbent that needs to be regenerated is significantly larger than that of the concentrated-amine phase according to embodiments of the present invention. Thus, in the conventional methods, a single tower containing the absorption unit and the regeneration unit would be too tall to be practical.
[0058] Fig. 1 illustrates a particular embodiment of the present invention. A gaseous mixture 1 containing an acid gas to be removed and an absorbent 3 are provided into an absorption unit 10.
The gaseous mixture 1 and the absorbent 3 contact with each other in the absorption unit 10. After the acid gas is absorbed in the absorbent 3 in the absorption unit 10, the purified gaseous mixture 2 is released from the absorption unit 10. The gas-rich absorbent 5 is sent to a separation unit 20, such as a gravity settler tank, for separating the concentrated-amine phase 6 from the remaining of the absorbent 4. After the separation, the remaining of the absorbent 4, comprising most or all components of the solvent and little or none of the amine and little or none of the absorbed acid gas, is cycled back into the absorption unit 10 for reuse, with or without further treatment. The separated concentrated-amine phase 6, containing most or all of the amine and the absorbed acid gas, both with or without chemical modification, optionally one or more components of the solvent, is provided for regeneration.
[0059] Referring to Fig. 1, the separated concentrated-amine phase 6 is routed to a regeneration unit 30, where the concentrated-amine phase 6 is treated to separate the absorbed acid gas 12 from the rest of the concentrated-amine phase, which is the gas-lean phase 14. The absorbed acid gas 12 is further treated to separate the acid gas 18 from the rest 16, which may contain the amine and one or more components of the solvent that react with the acid gas during the absorption of the acid gas and/or the transfer of the absorbed acid gas. The separated acid gas 18 can be disposed of or collected, depending on the user's purpose. The rest 16 is regenerated as part of the gas-lean phase 14. The gas-lean phase 14, which contains the regenerated amine and optionally one or more components of the solvent, is cycled back into the absorption unit 10 for reuse, with or without further treatment.
[0060] As shown in Fig. 1, the remaining of the absorbent 4 from the separation unit 20 and the gas-lean phase 14 from the regeneration unit 30 are mixed together in a mixer 40. The resulting absorbent 3 is then cycled back into the absorption unit 10 for reuse.
According to other embodiments of the present invention, the remaining of the absorbent 4 and the gas-lean phase 14 can each be cycled back into the absorption unit 10 for reuse without being first mixed together.
[0061] Although not shown in Fig. 1, in view of the present disclosure, it is readily appreciated by those skilled in the art that, in addition to the cycled back components of the absorbent 3, additional one or more components of the absorbent 3 can be added to compensate for the loss of the one or more components during the deacidizing process.
[0062] Fig. 2 illustrates another particular embodiment of the present invention. In this process, the absorption unit 10, separation unit 20 and regeneration unit 30 are grouped inside a single tower 100. The gas-rich absorbent from the absorption unit 10 flows downward into the separation unit 20 by gravity, so as to separate the concentrated-amine phase and the remaining of the absorbent 4.
After separation, the concentrated-amine phase flows downward into the regeneration unit 30, by gravity, where the regenerated acid gas 18 and the gas-lean phase 14 are obtained. The remaining of the absorbent 4 and the gas-lean phase 14 further flow downward into the mixer 40, and are mixed in the mixer 40 to obtain the absorbent 3. The absorbent 3 is pumped back into the absorption unit
[0055] In one embodiment of the present invention, the solvent in an absorbent according to an embodiment of the present invention serves to increase the absorption rate of the acid gas. The acid gas is absorbed into the absorbent at a rate greater than that if it were directly absorbed by the amine.
[0056] In an aspect of the present invention, the energy to be expended for the regeneration process is reduced because only part of the absorbent, the concentrated-amine phase, needs to be regenerated, while the remaining of the absorbent can immediately be recycled for reuse in the absorption unit.
[0057] In yet another aspect of the present invention, the energy to be expended for the deacidization process is further reduced by incorporating two or more of the units used in the process in a single tower, so that the various components can be transferred between some of the units by gravity, instead of pumping. The use of multiple units in a single tower is enabled and becomes practical, because of the relatively smaller size of the concentrated-amine phase that needs to be regenerated. In a conventional liquid-gas separation process, the volume of the gas-rich absorbent that needs to be regenerated is significantly larger than that of the concentrated-amine phase according to embodiments of the present invention. Thus, in the conventional methods, a single tower containing the absorption unit and the regeneration unit would be too tall to be practical.
[0058] Fig. 1 illustrates a particular embodiment of the present invention. A gaseous mixture 1 containing an acid gas to be removed and an absorbent 3 are provided into an absorption unit 10.
The gaseous mixture 1 and the absorbent 3 contact with each other in the absorption unit 10. After the acid gas is absorbed in the absorbent 3 in the absorption unit 10, the purified gaseous mixture 2 is released from the absorption unit 10. The gas-rich absorbent 5 is sent to a separation unit 20, such as a gravity settler tank, for separating the concentrated-amine phase 6 from the remaining of the absorbent 4. After the separation, the remaining of the absorbent 4, comprising most or all components of the solvent and little or none of the amine and little or none of the absorbed acid gas, is cycled back into the absorption unit 10 for reuse, with or without further treatment. The separated concentrated-amine phase 6, containing most or all of the amine and the absorbed acid gas, both with or without chemical modification, optionally one or more components of the solvent, is provided for regeneration.
[0059] Referring to Fig. 1, the separated concentrated-amine phase 6 is routed to a regeneration unit 30, where the concentrated-amine phase 6 is treated to separate the absorbed acid gas 12 from the rest of the concentrated-amine phase, which is the gas-lean phase 14. The absorbed acid gas 12 is further treated to separate the acid gas 18 from the rest 16, which may contain the amine and one or more components of the solvent that react with the acid gas during the absorption of the acid gas and/or the transfer of the absorbed acid gas. The separated acid gas 18 can be disposed of or collected, depending on the user's purpose. The rest 16 is regenerated as part of the gas-lean phase 14. The gas-lean phase 14, which contains the regenerated amine and optionally one or more components of the solvent, is cycled back into the absorption unit 10 for reuse, with or without further treatment.
[0060] As shown in Fig. 1, the remaining of the absorbent 4 from the separation unit 20 and the gas-lean phase 14 from the regeneration unit 30 are mixed together in a mixer 40. The resulting absorbent 3 is then cycled back into the absorption unit 10 for reuse.
According to other embodiments of the present invention, the remaining of the absorbent 4 and the gas-lean phase 14 can each be cycled back into the absorption unit 10 for reuse without being first mixed together.
[0061] Although not shown in Fig. 1, in view of the present disclosure, it is readily appreciated by those skilled in the art that, in addition to the cycled back components of the absorbent 3, additional one or more components of the absorbent 3 can be added to compensate for the loss of the one or more components during the deacidizing process.
[0062] Fig. 2 illustrates another particular embodiment of the present invention. In this process, the absorption unit 10, separation unit 20 and regeneration unit 30 are grouped inside a single tower 100. The gas-rich absorbent from the absorption unit 10 flows downward into the separation unit 20 by gravity, so as to separate the concentrated-amine phase and the remaining of the absorbent 4.
After separation, the concentrated-amine phase flows downward into the regeneration unit 30, by gravity, where the regenerated acid gas 18 and the gas-lean phase 14 are obtained. The remaining of the absorbent 4 and the gas-lean phase 14 further flow downward into the mixer 40, and are mixed in the mixer 40 to obtain the absorbent 3. The absorbent 3 is pumped back into the absorption unit
10, where it forms contact with the gaseous mixture 1, to start another cycle.
[0063] According to other embodiments of the present invention, the remaining of the absorbent 4 and the gas-lean phase 14 can each be pumped back into the absorption unit 10 for reuse without being first mixed together.
100641 Again, in addition to the cycled back components of the absorbent 3, additional one or more components of the absorbent 3 can be added to compensate for the loss of the one or more components during the deacidizing process.
100651 In this embodiment, no pumping energy is required for liquid transfer from the absorption unit 10 to the regeneration unit 30, thus achieves further energy saving.
[0063] According to other embodiments of the present invention, the remaining of the absorbent 4 and the gas-lean phase 14 can each be pumped back into the absorption unit 10 for reuse without being first mixed together.
100641 Again, in addition to the cycled back components of the absorbent 3, additional one or more components of the absorbent 3 can be added to compensate for the loss of the one or more components during the deacidizing process.
100651 In this embodiment, no pumping energy is required for liquid transfer from the absorption unit 10 to the regeneration unit 30, thus achieves further energy saving.
11 [00661 The following examples illustrate the invention but are in no way intended to limit the scope of the present invention.
Example 1 [00671 The absorbent was made of 20% by volume of the amine, monoethanolamine(MEA), and 80% by volume of the solvent, iso-octanol. The absorbent was contacted with a gaseous mixture containing an acid gas, carbon dioxide (CO2), in a stirring cell absorption unit at about 25-45 C, I
atm. MEA in the absorbent was concentrated spontaneously into a concentrated-amine phase, which contained MEA and the reaction product of MEA and CO2.
[00681 After the absorption, the absorbent was settled to separate by gravity the concentrated-amine phase from the remaining of the absorbent. After the separation, the remaining of the absorbent, which contains most of the iso-octanol and optionally some MEA and absorbed CO2, was cycled back into the absorption unit for reuse. In the concentrated-amine phase, the concentration of the total MEA, which includes the chemically unmodified MEA and the reaction product of MEA
and CO2, was about 70 % by volume.
[0069j The separated concentrated-amine phase was forwarded to a regenerator and was treated to obtain the regenerated MEA and CO2 by the method of heating the concentrated-amine phase.
The regenerated MEA was mixed with the remaining of the absorbent. The mixture was cycled back to the stirring cell absorption unit to complete the cycle.
[0070) The CO2 released from the regeneration process was collected.
Example 2 [00711 This example illustrates the absorption of CO2 by a carbonate aqueous solution.
[00721 An absorbent is made of carbonate aqueous solution. The absorbent is contacted with a gas mixture containing acid gas, carbon dioxide (CO2), in a stirring cell absorption unit at 50 C, 1 atm.
100731 During the absorption, carbonate in aqueous solution reacts with CO2 to form bicarbonate. After absorption, the absorbent is cooled to 25 C and the bicarbonate is crystalized.
The bicarbonate solid phase is separated from the absorbent. It is then forwarded to a regeneration section and is treated to obtain the regenerated carbonate and CO2 by the method of heating the solid phase of bicarbonate. The regenerated carbonate is dissolved in aqueous solution and cycled back to the stirring cell absorption unit to complete the cycle.
100741 It will be appreciated by those skilled in the art that changes could be made to the embodiments described above without departing from the broad inventive concept thereof.
Example 1 [00671 The absorbent was made of 20% by volume of the amine, monoethanolamine(MEA), and 80% by volume of the solvent, iso-octanol. The absorbent was contacted with a gaseous mixture containing an acid gas, carbon dioxide (CO2), in a stirring cell absorption unit at about 25-45 C, I
atm. MEA in the absorbent was concentrated spontaneously into a concentrated-amine phase, which contained MEA and the reaction product of MEA and CO2.
[00681 After the absorption, the absorbent was settled to separate by gravity the concentrated-amine phase from the remaining of the absorbent. After the separation, the remaining of the absorbent, which contains most of the iso-octanol and optionally some MEA and absorbed CO2, was cycled back into the absorption unit for reuse. In the concentrated-amine phase, the concentration of the total MEA, which includes the chemically unmodified MEA and the reaction product of MEA
and CO2, was about 70 % by volume.
[0069j The separated concentrated-amine phase was forwarded to a regenerator and was treated to obtain the regenerated MEA and CO2 by the method of heating the concentrated-amine phase.
The regenerated MEA was mixed with the remaining of the absorbent. The mixture was cycled back to the stirring cell absorption unit to complete the cycle.
[0070) The CO2 released from the regeneration process was collected.
Example 2 [00711 This example illustrates the absorption of CO2 by a carbonate aqueous solution.
[00721 An absorbent is made of carbonate aqueous solution. The absorbent is contacted with a gas mixture containing acid gas, carbon dioxide (CO2), in a stirring cell absorption unit at 50 C, 1 atm.
100731 During the absorption, carbonate in aqueous solution reacts with CO2 to form bicarbonate. After absorption, the absorbent is cooled to 25 C and the bicarbonate is crystalized.
The bicarbonate solid phase is separated from the absorbent. It is then forwarded to a regeneration section and is treated to obtain the regenerated carbonate and CO2 by the method of heating the solid phase of bicarbonate. The regenerated carbonate is dissolved in aqueous solution and cycled back to the stirring cell absorption unit to complete the cycle.
100741 It will be appreciated by those skilled in the art that changes could be made to the embodiments described above without departing from the broad inventive concept thereof.
12 The scope of the claims should not be limited by the preferred embodiments and the examples, but should be given the broadest interpretation consistent with the description as a whole.
13
Claims (18)
1. A method for deacidizing a gaseous mixture comprising an acid gas, comprising:
- contacting the gaseous mixture with an absorbent in an absorption unit, wherein the absorbent comprises an amine dissolved in a solvent at a first concentration;
- allowing the absorbent to absorb the acid gas to form a concentrated-amine phase, wherein the concentrated-amine phase is mechanically separable from the remaining of the absorbent and comprises a concentrated amine at a concentration higher than the first concentration and an absorbed acid gas, wherein the concentrated amine comprises the amine or the amine having a chemical modification, and the absorbed acid gas comprises the acid gas or the acid gas having a chemical modification;
- separating the concentrated-amine phase from the remaining of the absorbent;
- cycling the remaining of the absorbent back into the absorption unit;
- providing the concentrated-amine phase to a regeneration unit, so as to obtain the acid gas and the concentrated amine; and - cycling the regenerated concentrated amine back into the absorption unit.
- contacting the gaseous mixture with an absorbent in an absorption unit, wherein the absorbent comprises an amine dissolved in a solvent at a first concentration;
- allowing the absorbent to absorb the acid gas to form a concentrated-amine phase, wherein the concentrated-amine phase is mechanically separable from the remaining of the absorbent and comprises a concentrated amine at a concentration higher than the first concentration and an absorbed acid gas, wherein the concentrated amine comprises the amine or the amine having a chemical modification, and the absorbed acid gas comprises the acid gas or the acid gas having a chemical modification;
- separating the concentrated-amine phase from the remaining of the absorbent;
- cycling the remaining of the absorbent back into the absorption unit;
- providing the concentrated-amine phase to a regeneration unit, so as to obtain the acid gas and the concentrated amine; and - cycling the regenerated concentrated amine back into the absorption unit.
2. The method of claim 1, wherein the acid gas is selected from the group consisting of carbon dioxide (CO2), sulfur dioxide (SO2), sulfur trioxide (SO3), hydrogen sulfide (HS), carbon oxysulfide (COS), carbon disulfide (CS2), mercaptans (RSH), nitric oxide (NO), nitric dioxide (NO2), fluorides, HCl, HF and a combination thereof.
3. The method of claim 1, wherein the amine is selected from the group consisting of monoethanolamine, diethanolamine, triethanolamine, ethanolamines, isopropanolamines, ethyleneamines, alkyl alkanolamines, methyldiethanolamine, piperidine, dibutylamine, diisopropylamine, and a combination thereof.
4. The method of claim 1, wherein the solvent comprises one or more components selected from the group consisting of alcohols, glycols, alkanes, unsaturated hydrocarbon, ethers, esters, aldehydes, ketones, glycol ethers, alkylene carbonates, dialkyl carbonates, sulfolane, ionic liquids, polymers, water, an aqueous solution containing one or more salts selected from alkaline salts, ammonium salts, alkanolamine salts, or alkaline-earth salts, and derivatives thereof.
5. The method of claim 4, wherein the solvent comprises a C8 to C12 alcohol.
6. The method of claim 1, wherein the absorbent comprises at least one amine selected from the group consisting of monoethanolamine, diethanolamine, piperidine, dibutylamine, or diisopropylamine, triethanolanline, ethanolamines, isopropanolamines, ethyleneamines, alkyl alkanolamines and methyldiethanolamine, and the amine is dissolved in a solvent comprising at least one of a C8 - C12 alcohol, glycol and glycol ether.
7. The method of claim 1, wherein the absorption unit is an absorber, a membrane contactor, or any equipment that provides gas liquid contact.
8. The method of claim 1, wherein the solvent increases the absorption of the acid gas into the absorbent as compared to the absorption of the acid gas by the amine alone.
9. The method of claim 1, wherein the concentrated-amine phase moves downward by gravity from the absorption unit to a separation unit for separating the concentrated-amine phase from the remaining of the absorbent.
10. The method of claim 1, wherein after the step of separation, the concentrated-amine phase moves downward by gravity from a separation unit, for separating the concentrated-amine phase from the remaining of the absorbent, to the regeneration unit.
11. A system for deacidizing a gaseous mixture comprising an acid gas, comprising:
-an absorption unit adapted to allow contact between the gaseous mixture and an absorbent comprising an amine dissolved in a solvent at a first concentration, wherein the absorbent absorbs the acid gas to form a concentrated-amine phase, wherein the concentrated-amine phase is mechanically separable from the remaining of the absorbent, and the concentrated-amine phase comprises a concentrated amine at a concentration higher than the first concentration and an absorbed acid gas, wherein the concentrated amine comprises the amine or the amine having a chemical modification, and the absorbed acid gas comprises the acid gas or the acid gas having a chemical modification - a separation unit adapted to allow separation of the concentrated-amine phase from the remaining of the absorbent; and - a regeneration unit adapted to allow regeneration of the concentrated-amine phase, so as to obtain the acid gas and the concentrated amine.
-an absorption unit adapted to allow contact between the gaseous mixture and an absorbent comprising an amine dissolved in a solvent at a first concentration, wherein the absorbent absorbs the acid gas to form a concentrated-amine phase, wherein the concentrated-amine phase is mechanically separable from the remaining of the absorbent, and the concentrated-amine phase comprises a concentrated amine at a concentration higher than the first concentration and an absorbed acid gas, wherein the concentrated amine comprises the amine or the amine having a chemical modification, and the absorbed acid gas comprises the acid gas or the acid gas having a chemical modification - a separation unit adapted to allow separation of the concentrated-amine phase from the remaining of the absorbent; and - a regeneration unit adapted to allow regeneration of the concentrated-amine phase, so as to obtain the acid gas and the concentrated amine.
12. The system of claim 11, wherein the concentrated-amine phase moves downward from the absorption unit to the separation unit by gravity.
13. The system of claim 12, wherein the absorption unit, the separation unit and the regeneration unit are placed in a single tower, wherein the separation unit is placed in a position lower than the absorption unit and the regeneration unit is placed in a position lower than the separation unit, so that after the absorbent absorbs the acid gas, the concentrated-amine phase moves downward from the absorption unit to the separation unit by gravity, and after the step of separation, the concentrated- amine phase moves downward from the separation unit to the regeneration unit by gravity.
14. The system of claim 11, wherein the regeneration unit is placed in a position lower than the separation unit, so that after the step of separation, the concentrated-amine phase moves downward from the separation unit to the regeneration unit by gravity.
15. A method for deacidizing a gaseous mixture comprising an acid gas, comprising:
- contacting the gaseous mixture with an absorbent in an absorption unit, wherein the absorbent comprises an agent dissolved in a solvent at a first concentration, wherein the agent is selected from the group consisting of amino-acid salts, amides, alkaline salts, alkaline-earth salts, ammonium salts, ureas, alkaline metal phosphates, carbonates, borates, acid phosphites, phosphites, phosphonite, phosphinate, phosphonate, acid phosphates, pyrophosphites, bicarbonates, metaborates, diborates, tetraborates, pentaborates, and combinations thereof;
- allowing the absorbent to absorb the acid gas to form a concentrated-agent phase, wherein the concentrated-agent phase is mechanically separable from the remaining of the absorbent and comprises a concentrated agent at a concentration higher than the first concentration and an absorbed acid gas, wherein the concentrated agent comprises the agent or the agent having a chemical modification, and the absorbed acid gas comprises the acid gas or the acid gas having a chemical modification;
- separating the concentrated-agent phase from the remaining of the absorbent;
- cycling the remaining of the absorbent back into the absorption unit;
- providing the concentrated-agent phase to a regeneration unit, so as to obtain the acid gas and the concentrated agent; and - cycling the regenerated concentrated agent back into the absorption unit. 16
- contacting the gaseous mixture with an absorbent in an absorption unit, wherein the absorbent comprises an agent dissolved in a solvent at a first concentration, wherein the agent is selected from the group consisting of amino-acid salts, amides, alkaline salts, alkaline-earth salts, ammonium salts, ureas, alkaline metal phosphates, carbonates, borates, acid phosphites, phosphites, phosphonite, phosphinate, phosphonate, acid phosphates, pyrophosphites, bicarbonates, metaborates, diborates, tetraborates, pentaborates, and combinations thereof;
- allowing the absorbent to absorb the acid gas to form a concentrated-agent phase, wherein the concentrated-agent phase is mechanically separable from the remaining of the absorbent and comprises a concentrated agent at a concentration higher than the first concentration and an absorbed acid gas, wherein the concentrated agent comprises the agent or the agent having a chemical modification, and the absorbed acid gas comprises the acid gas or the acid gas having a chemical modification;
- separating the concentrated-agent phase from the remaining of the absorbent;
- cycling the remaining of the absorbent back into the absorption unit;
- providing the concentrated-agent phase to a regeneration unit, so as to obtain the acid gas and the concentrated agent; and - cycling the regenerated concentrated agent back into the absorption unit. 16
16. The method of claim 15, wherein the solvent comprises water, an aqueous solution containing one or more salts selected from alkaline salts, ammonium salts, alkanolamine salts, alkaline-earth salts, phosphates, acid phosphites, phosphites, phosphonite, phosphinate, phosphonate, acid phosphates, pyrophosphites, carbonates, bicarbonates, borates, metaborates, diborates, tetraborates, or pentaborates.
17. A system for deacidizing a gaseous mixture comprising an acid gas, comprising:
- an absorption unit adapted to allow contact between the gaseous mixture and an absorbent comprising an agent dissolved in a solvent at a first concentration, wherein the agent is selected from the group consisting of amino-acid salts, amides, alkaline salts, alkaline-earth salts, ammonium salts, ureas, alkaline metal phosphates, carbonates, borates, acid phosphites, phosphites, phosphonite, phosphinate, phosphonate, acid phosphates, pyrophosphites, bicarbonates, metaborates, diborates, tetraborates, pentaborates, and combinations thereof;
- wherein the absorbent absorbs the acid gas to form a concentrated-agent phase, the concentrated-agent phase is mechanically separable from the remaining of the absorbent, and the concentrated-agent phase comprises a concentrated agent at a concentration higher than the first concentration and an absorbed acid gas, wherein the concentrated agent comprises the agent or the agent having a chemical modification, and the absorbed acid gas comprises the acid gas or the acid gas having a chemical modification;
- a separation unit adapted to allow separation of the concentrated-agent phase from the remaining of the absorbent; and - a regeneration unit adapted to allow regeneration of the concentrated-agent phase, so as to obtain the acid gas and the concentrated agent.
- an absorption unit adapted to allow contact between the gaseous mixture and an absorbent comprising an agent dissolved in a solvent at a first concentration, wherein the agent is selected from the group consisting of amino-acid salts, amides, alkaline salts, alkaline-earth salts, ammonium salts, ureas, alkaline metal phosphates, carbonates, borates, acid phosphites, phosphites, phosphonite, phosphinate, phosphonate, acid phosphates, pyrophosphites, bicarbonates, metaborates, diborates, tetraborates, pentaborates, and combinations thereof;
- wherein the absorbent absorbs the acid gas to form a concentrated-agent phase, the concentrated-agent phase is mechanically separable from the remaining of the absorbent, and the concentrated-agent phase comprises a concentrated agent at a concentration higher than the first concentration and an absorbed acid gas, wherein the concentrated agent comprises the agent or the agent having a chemical modification, and the absorbed acid gas comprises the acid gas or the acid gas having a chemical modification;
- a separation unit adapted to allow separation of the concentrated-agent phase from the remaining of the absorbent; and - a regeneration unit adapted to allow regeneration of the concentrated-agent phase, so as to obtain the acid gas and the concentrated agent.
18. The system of claim 17, wherein the solvent comprises water, an aqueous solution containing one or more salts selected from alkaline salts, ammonium salts, alkanolamine salts, alkaline-earth salts, phosphates, acid phosphites, phosphites, phosphonite, phosphinate, phosphonate, acid phosphates, pyrophosphites, carbonates, bicarbonates, borates, metaborates, diborates, tetraborates, or pentaborates.
Applications Claiming Priority (4)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| US12/250,257 | 2008-10-13 | ||
| US12/250,257 US7718151B1 (en) | 2006-04-07 | 2008-10-13 | Methods and systems for deacidizing gaseous mixtures |
| US12/430,998 US7846407B2 (en) | 2006-04-07 | 2009-04-28 | Self-concentrating absorbent for acid gas separation |
| US12/430,998 | 2009-04-28 |
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| Publication Number | Publication Date |
|---|---|
| CA2664970A1 CA2664970A1 (en) | 2010-04-13 |
| CA2664970C true CA2664970C (en) | 2016-03-01 |
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| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CA2664970A Active CA2664970C (en) | 2008-10-13 | 2009-04-30 | Self-concentrating absorbent for acid gas separation |
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