CN101993378A - Amido-containing ionic liquid used for absorbing acidic gases and preparation method and application thereof - Google Patents
Amido-containing ionic liquid used for absorbing acidic gases and preparation method and application thereof Download PDFInfo
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- CN101993378A CN101993378A CN2010102796347A CN201010279634A CN101993378A CN 101993378 A CN101993378 A CN 101993378A CN 2010102796347 A CN2010102796347 A CN 2010102796347A CN 201010279634 A CN201010279634 A CN 201010279634A CN 101993378 A CN101993378 A CN 101993378A
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- 239000002608 ionic liquid Substances 0.000 title claims abstract description 131
- 239000007789 gas Substances 0.000 title claims abstract description 63
- 125000003368 amide group Chemical group 0.000 title claims abstract description 6
- 238000002360 preparation method Methods 0.000 title abstract description 13
- 230000002378 acidificating effect Effects 0.000 title abstract 6
- 238000010521 absorption reaction Methods 0.000 claims abstract description 125
- 150000002500 ions Chemical class 0.000 claims abstract description 45
- 239000002253 acid Substances 0.000 claims abstract description 39
- 229920000768 polyamine Polymers 0.000 claims abstract description 29
- 238000000034 method Methods 0.000 claims abstract description 22
- 150000007524 organic acids Chemical class 0.000 claims abstract description 18
- VNWKTOKETHGBQD-UHFFFAOYSA-N methane Chemical compound C VNWKTOKETHGBQD-UHFFFAOYSA-N 0.000 claims abstract description 12
- 238000006386 neutralization reaction Methods 0.000 claims abstract description 7
- 239000003034 coal gas Substances 0.000 claims abstract description 5
- 239000003345 natural gas Substances 0.000 claims abstract description 5
- 150000003141 primary amines Chemical class 0.000 claims abstract description 3
- 150000003335 secondary amines Chemical class 0.000 claims abstract description 3
- 150000003512 tertiary amines Chemical class 0.000 claims abstract description 3
- 239000007788 liquid Substances 0.000 claims description 63
- RWSOTUBLDIXVET-UHFFFAOYSA-N Dihydrogen sulfide Chemical compound S RWSOTUBLDIXVET-UHFFFAOYSA-N 0.000 claims description 62
- 238000003756 stirring Methods 0.000 claims description 43
- -1 polyethylene Polymers 0.000 claims description 25
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 24
- 150000001412 amines Chemical class 0.000 claims description 24
- 239000000243 solution Substances 0.000 claims description 18
- 239000007864 aqueous solution Substances 0.000 claims description 16
- 229910052500 inorganic mineral Inorganic materials 0.000 claims description 16
- 239000011707 mineral Substances 0.000 claims description 16
- 239000003795 chemical substances by application Substances 0.000 claims description 13
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 claims description 12
- VGGSQFUCUMXWEO-UHFFFAOYSA-N Ethene Chemical compound C=C VGGSQFUCUMXWEO-UHFFFAOYSA-N 0.000 claims description 11
- 238000006243 chemical reaction Methods 0.000 claims description 11
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 claims description 10
- 239000007787 solid Substances 0.000 claims description 9
- VILCJCGEZXAXTO-UHFFFAOYSA-N 2,2,2-tetramine Chemical compound NCCNCCNCCN VILCJCGEZXAXTO-UHFFFAOYSA-N 0.000 claims description 7
- 229960001124 trientine Drugs 0.000 claims description 7
- GRYLNZFGIOXLOG-UHFFFAOYSA-N Nitric acid Chemical compound O[N+]([O-])=O GRYLNZFGIOXLOG-UHFFFAOYSA-N 0.000 claims description 6
- 229910017604 nitric acid Inorganic materials 0.000 claims description 6
- FAGUFWYHJQFNRV-UHFFFAOYSA-N tetraethylenepentamine Chemical compound NCCNCCNCCNCCN FAGUFWYHJQFNRV-UHFFFAOYSA-N 0.000 claims description 6
- QTBSBXVTEAMEQO-UHFFFAOYSA-M Acetate Chemical compound CC([O-])=O QTBSBXVTEAMEQO-UHFFFAOYSA-M 0.000 claims description 5
- 239000004698 Polyethylene Substances 0.000 claims description 5
- WPYMKLBDIGXBTP-UHFFFAOYSA-N benzoic acid Chemical compound OC(=O)C1=CC=CC=C1 WPYMKLBDIGXBTP-UHFFFAOYSA-N 0.000 claims description 5
- 235000010299 hexamethylene tetramine Nutrition 0.000 claims description 5
- 229920000573 polyethylene Polymers 0.000 claims description 5
- JOXIMZWYDAKGHI-UHFFFAOYSA-N toluene-4-sulfonic acid Chemical compound CC1=CC=C(S(O)(=O)=O)C=C1 JOXIMZWYDAKGHI-UHFFFAOYSA-N 0.000 claims description 5
- FERIUCNNQQJTOY-UHFFFAOYSA-N Butyric acid Chemical compound CCCC(O)=O FERIUCNNQQJTOY-UHFFFAOYSA-N 0.000 claims description 4
- UGFAIRIUMAVXCW-UHFFFAOYSA-N Carbon monoxide Chemical compound [O+]#[C-] UGFAIRIUMAVXCW-UHFFFAOYSA-N 0.000 claims description 4
- RPNUMPOLZDHAAY-UHFFFAOYSA-N Diethylenetriamine Chemical compound NCCNCCN RPNUMPOLZDHAAY-UHFFFAOYSA-N 0.000 claims description 4
- CPELXLSAUQHCOX-UHFFFAOYSA-N Hydrogen bromide Chemical compound Br CPELXLSAUQHCOX-UHFFFAOYSA-N 0.000 claims description 4
- NBIIXXVUZAFLBC-UHFFFAOYSA-N Phosphoric acid Chemical compound OP(O)(O)=O NBIIXXVUZAFLBC-UHFFFAOYSA-N 0.000 claims description 4
- DTQVDTLACAAQTR-UHFFFAOYSA-N Trifluoroacetic acid Chemical compound OC(=O)C(F)(F)F DTQVDTLACAAQTR-UHFFFAOYSA-N 0.000 claims description 4
- 235000009508 confectionery Nutrition 0.000 claims description 4
- NZNMSOFKMUBTKW-UHFFFAOYSA-N cyclohexanecarboxylic acid Chemical compound OC(=O)C1CCCCC1 NZNMSOFKMUBTKW-UHFFFAOYSA-N 0.000 claims description 4
- XBDQKXXYIPTUBI-UHFFFAOYSA-N dimethylselenoniopropionate Natural products CCC(O)=O XBDQKXXYIPTUBI-UHFFFAOYSA-N 0.000 claims description 4
- 239000003546 flue gas Substances 0.000 claims description 4
- BDAGIHXWWSANSR-UHFFFAOYSA-N methanoic acid Natural products OC=O BDAGIHXWWSANSR-UHFFFAOYSA-N 0.000 claims description 4
- 230000001476 alcoholic effect Effects 0.000 claims description 3
- 230000001413 cellular effect Effects 0.000 claims description 3
- 239000002131 composite material Substances 0.000 claims description 3
- GEYOCULIXLDCMW-UHFFFAOYSA-N 1,2-phenylenediamine Chemical compound NC1=CC=CC=C1N GEYOCULIXLDCMW-UHFFFAOYSA-N 0.000 claims description 2
- OSWFIVFLDKOXQC-UHFFFAOYSA-N 4-(3-methoxyphenyl)aniline Chemical compound COC1=CC=CC(C=2C=CC(N)=CC=2)=C1 OSWFIVFLDKOXQC-UHFFFAOYSA-N 0.000 claims description 2
- LSNNMFCWUKXFEE-UHFFFAOYSA-M Bisulfite Chemical compound OS([O-])=O LSNNMFCWUKXFEE-UHFFFAOYSA-M 0.000 claims description 2
- AFVFQIVMOAPDHO-UHFFFAOYSA-N Methanesulfonic acid Chemical compound CS(O)(=O)=O AFVFQIVMOAPDHO-UHFFFAOYSA-N 0.000 claims description 2
- NSOXQYCFHDMMGV-UHFFFAOYSA-N Tetrakis(2-hydroxypropyl)ethylenediamine Chemical compound CC(O)CN(CC(C)O)CCN(CC(C)O)CC(C)O NSOXQYCFHDMMGV-UHFFFAOYSA-N 0.000 claims description 2
- 229910000147 aluminium phosphate Inorganic materials 0.000 claims description 2
- RUOKPLVTMFHRJE-UHFFFAOYSA-N benzene-1,2,3-triamine Chemical compound NC1=CC=CC(N)=C1N RUOKPLVTMFHRJE-UHFFFAOYSA-N 0.000 claims description 2
- KGBXLFKZBHKPEV-UHFFFAOYSA-N boric acid Chemical compound OB(O)O KGBXLFKZBHKPEV-UHFFFAOYSA-N 0.000 claims description 2
- 239000004327 boric acid Substances 0.000 claims description 2
- JBDSSBMEKXHSJF-UHFFFAOYSA-N cyclopentanecarboxylic acid Chemical compound OC(=O)C1CCCC1 JBDSSBMEKXHSJF-UHFFFAOYSA-N 0.000 claims description 2
- 235000019253 formic acid Nutrition 0.000 claims description 2
- SYECJBOWSGTPLU-UHFFFAOYSA-N hexane-1,1-diamine Chemical compound CCCCCC(N)N SYECJBOWSGTPLU-UHFFFAOYSA-N 0.000 claims description 2
- 125000004435 hydrogen atom Chemical group [H]* 0.000 claims description 2
- 229910000042 hydrogen bromide Inorganic materials 0.000 claims description 2
- XMBWDFGMSWQBCA-UHFFFAOYSA-N hydrogen iodide Chemical compound I XMBWDFGMSWQBCA-UHFFFAOYSA-N 0.000 claims description 2
- 229940071870 hydroiodic acid Drugs 0.000 claims description 2
- 239000000203 mixture Substances 0.000 claims description 2
- 235000019260 propionic acid Nutrition 0.000 claims description 2
- AOHJOMMDDJHIJH-UHFFFAOYSA-N propylenediamine Chemical compound CC(N)CN AOHJOMMDDJHIJH-UHFFFAOYSA-N 0.000 claims description 2
- IUVKMZGDUIUOCP-BTNSXGMBSA-N quinbolone Chemical compound O([C@H]1CC[C@H]2[C@H]3[C@@H]([C@]4(C=CC(=O)C=C4CC3)C)CC[C@@]21C)C1=CCCC1 IUVKMZGDUIUOCP-BTNSXGMBSA-N 0.000 claims description 2
- VOZKAJLKRJDJLL-UHFFFAOYSA-N tolylenediamine group Chemical group CC1=C(C=C(C=C1)N)N VOZKAJLKRJDJLL-UHFFFAOYSA-N 0.000 claims description 2
- ITMCEJHCFYSIIV-UHFFFAOYSA-N triflic acid Chemical compound OS(=O)(=O)C(F)(F)F ITMCEJHCFYSIIV-UHFFFAOYSA-N 0.000 claims description 2
- 238000010189 synthetic method Methods 0.000 claims 1
- 230000008901 benefit Effects 0.000 abstract description 9
- 230000015572 biosynthetic process Effects 0.000 abstract description 7
- 238000003786 synthesis reaction Methods 0.000 abstract description 7
- 238000002156 mixing Methods 0.000 abstract description 3
- 238000000746 purification Methods 0.000 abstract description 2
- 150000007522 mineralic acids Chemical class 0.000 abstract 2
- 239000003513 alkali Substances 0.000 abstract 1
- 238000000197 pyrolysis Methods 0.000 abstract 1
- 238000007670 refining Methods 0.000 abstract 1
- 239000000779 smoke Substances 0.000 abstract 1
- 238000005303 weighing Methods 0.000 description 34
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 33
- 239000005457 ice water Substances 0.000 description 18
- 230000006698 induction Effects 0.000 description 17
- 238000001704 evaporation Methods 0.000 description 12
- 238000001291 vacuum drying Methods 0.000 description 12
- 230000008020 evaporation Effects 0.000 description 11
- 238000003795 desorption Methods 0.000 description 9
- ZZVUWRFHKOJYTH-UHFFFAOYSA-N diphenhydramine Chemical compound C=1C=CC=CC=1C(OCCN(C)C)C1=CC=CC=C1 ZZVUWRFHKOJYTH-UHFFFAOYSA-N 0.000 description 9
- JUJWROOIHBZHMG-UHFFFAOYSA-N Pyridine Chemical compound C1=CC=NC=C1 JUJWROOIHBZHMG-UHFFFAOYSA-N 0.000 description 8
- 229960000935 dehydrated alcohol Drugs 0.000 description 8
- 238000001179 sorption measurement Methods 0.000 description 8
- 229960004756 ethanol Drugs 0.000 description 7
- ZRALSGWEFCBTJO-UHFFFAOYSA-N Guanidine Chemical compound NC(N)=N ZRALSGWEFCBTJO-UHFFFAOYSA-N 0.000 description 6
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 6
- 239000003463 adsorbent Substances 0.000 description 6
- 150000002460 imidazoles Chemical class 0.000 description 6
- AGGKEGLBGGJEBZ-UHFFFAOYSA-N tetramethylenedisulfotetramine Chemical compound C1N(S2(=O)=O)CN3S(=O)(=O)N1CN2C3 AGGKEGLBGGJEBZ-UHFFFAOYSA-N 0.000 description 6
- LVTYICIALWPMFW-UHFFFAOYSA-N diisopropanolamine Chemical compound CC(O)CNCC(C)O LVTYICIALWPMFW-UHFFFAOYSA-N 0.000 description 5
- 229940043276 diisopropanolamine Drugs 0.000 description 5
- UMJSCPRVCHMLSP-UHFFFAOYSA-N pyridine Natural products COC1=CC=CN=C1 UMJSCPRVCHMLSP-UHFFFAOYSA-N 0.000 description 4
- CHJJGSNFBQVOTG-UHFFFAOYSA-N N-methyl-guanidine Natural products CNC(N)=N CHJJGSNFBQVOTG-UHFFFAOYSA-N 0.000 description 3
- 230000000274 adsorptive effect Effects 0.000 description 3
- SWSQBOPZIKWTGO-UHFFFAOYSA-N dimethylaminoamidine Natural products CN(C)C(N)=N SWSQBOPZIKWTGO-UHFFFAOYSA-N 0.000 description 3
- 230000000694 effects Effects 0.000 description 3
- 238000003912 environmental pollution Methods 0.000 description 3
- 229910001220 stainless steel Inorganic materials 0.000 description 3
- 239000010935 stainless steel Substances 0.000 description 3
- IQQRAVYLUAZUGX-UHFFFAOYSA-N 1-butyl-3-methylimidazolium Chemical compound CCCCN1C=C[N+](C)=C1 IQQRAVYLUAZUGX-UHFFFAOYSA-N 0.000 description 2
- PISLZQACAJMAIO-UHFFFAOYSA-N 2,4-diethyl-6-methylbenzene-1,3-diamine Chemical compound CCC1=CC(C)=C(N)C(CC)=C1N PISLZQACAJMAIO-UHFFFAOYSA-N 0.000 description 2
- HZAXFHJVJLSVMW-UHFFFAOYSA-N 2-Aminoethan-1-ol Chemical compound NCCO HZAXFHJVJLSVMW-UHFFFAOYSA-N 0.000 description 2
- 231100000987 absorbed dose Toxicity 0.000 description 2
- 239000002250 absorbent Substances 0.000 description 2
- 230000007613 environmental effect Effects 0.000 description 2
- 238000009776 industrial production Methods 0.000 description 2
- 239000000463 material Substances 0.000 description 2
- 230000004224 protection Effects 0.000 description 2
- 238000010926 purge Methods 0.000 description 2
- 238000010992 reflux Methods 0.000 description 2
- 150000003839 salts Chemical class 0.000 description 2
- 239000002904 solvent Substances 0.000 description 2
- 239000002594 sorbent Substances 0.000 description 2
- PVXVWWANJIWJOO-UHFFFAOYSA-N 1-(1,3-benzodioxol-5-yl)-N-ethylpropan-2-amine Chemical compound CCNC(C)CC1=CC=C2OCOC2=C1 PVXVWWANJIWJOO-UHFFFAOYSA-N 0.000 description 1
- AIOUIOXOYKOMLG-UHFFFAOYSA-N C(CCC)C1=C(N=C(N1)CC(=O)O)C Chemical class C(CCC)C1=C(N=C(N1)CC(=O)O)C AIOUIOXOYKOMLG-UHFFFAOYSA-N 0.000 description 1
- 238000004566 IR spectroscopy Methods 0.000 description 1
- QMMZSJPSPRTHGB-UHFFFAOYSA-N MDEA Natural products CC(C)CCCCC=CCC=CC(O)=O QMMZSJPSPRTHGB-UHFFFAOYSA-N 0.000 description 1
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 1
- CDBYLPFSWZWCQE-UHFFFAOYSA-L Sodium Carbonate Chemical compound [Na+].[Na+].[O-]C([O-])=O CDBYLPFSWZWCQE-UHFFFAOYSA-L 0.000 description 1
- 230000002411 adverse Effects 0.000 description 1
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 description 1
- 150000001413 amino acids Chemical class 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 238000006555 catalytic reaction Methods 0.000 description 1
- 125000002091 cationic group Chemical group 0.000 description 1
- 238000004140 cleaning Methods 0.000 description 1
- 239000000571 coke Substances 0.000 description 1
- 230000008878 coupling Effects 0.000 description 1
- 238000010168 coupling process Methods 0.000 description 1
- 238000005859 coupling reaction Methods 0.000 description 1
- ZBCBWPMODOFKDW-UHFFFAOYSA-N diethanolamine Chemical compound OCCNCCO ZBCBWPMODOFKDW-UHFFFAOYSA-N 0.000 description 1
- 238000007599 discharging Methods 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 150000002357 guanidines Chemical class 0.000 description 1
- 238000010438 heat treatment Methods 0.000 description 1
- 229930195733 hydrocarbon Natural products 0.000 description 1
- 150000002430 hydrocarbons Chemical class 0.000 description 1
- CRVGTESFCCXCTH-UHFFFAOYSA-N methyl diethanolamine Chemical compound OCCN(C)CCO CRVGTESFCCXCTH-UHFFFAOYSA-N 0.000 description 1
- LSHROXHEILXKHM-UHFFFAOYSA-N n'-[2-[2-[2-(2-aminoethylamino)ethylamino]ethylamino]ethyl]ethane-1,2-diamine Chemical compound NCCNCCNCCNCCNCCN LSHROXHEILXKHM-UHFFFAOYSA-N 0.000 description 1
- 230000007935 neutral effect Effects 0.000 description 1
- 238000012797 qualification Methods 0.000 description 1
- 239000002994 raw material Substances 0.000 description 1
- 239000012429 reaction media Substances 0.000 description 1
- 239000000741 silica gel Substances 0.000 description 1
- 229910002027 silica gel Inorganic materials 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- HXJUTPCZVOIRIF-UHFFFAOYSA-N sulfolane Chemical compound O=S1(=O)CCCC1 HXJUTPCZVOIRIF-UHFFFAOYSA-N 0.000 description 1
Landscapes
- Gas Separation By Absorption (AREA)
Abstract
The invention provides an amido-containing ionic liquid used for absorbing acidic gases and a preparation method and application thereof and in particular relates to a method for absorbing acidic gases of CO2, H2S, SO2 and the like by using an amido-containing ionic liquid. The amido-containing ionic liquid comprises one or more of primary amine, secondary amine and tertiary amine, wherein positive ions of the ionic liquid are derived from organic polyamines, negative ions of the ionic liquid are derived from inorganic acid or organic acid, and the ionic liquid is prepared by mixing the organic polyamines with the inorganic acid or organic acid and then carrying out neutralization reaction through acid and alkali. The ionic liquid has the advantages of low cost, simple preparation method, strong absorbing capability and short balance time, can be used for the enriching of acidic gases, the deacidification refining of acid-containing gases of natural gas, refinery gas, methane, coal gas, synthesis gas, coke-oven gas, pyrolysis gas, smoke, motor vehicle tail gas and the like and the purification of gases under a proper space and an operating environment; meanwhile, the ionic liquid absorbing the acidic gases can release the acidic gases through pressure reduction and temperature raise, thus the absorbing capability of the ionic liquid is restored and the multiple absorption property of the ionic liquid is better.
Description
Technical field
The invention relates to the functionalized ion liquid and preparation method thereof and application of a kind of amino-contained in the chemical field, particularly utilize this amino-contained ionic liquid to absorb sour gas or contain the method that the acid gas depickling purifies.
Background technology
Sweet natural gas, refinery gas, associated gas, biogas, coal-seam gas, coal gas, synthetic gas etc. often contain CO
2, H
2Sour gas such as S, the existence of these sour gas all can exert an adverse impact to the following process and the utilization of gas, therefore need carry out depickling to it and handle.In addition, flue gas, motor-vehicle tail-gas etc. generally contain CO
2, SO
2Deng sour gas, these sour gas are known from experience polluted air, and cause Greenhouse effect, therefore need to remove SO before discharging
2, or with CO
2Deng collecting and seal up for safekeeping.The absorption of sour gas and removing at aspects such as industrial production, household utilization, environmental improvement, atmosphere protections all has and important meaning.
At present, the hydramine method is the gaseous deacidification method of widespread use in the industrial production.This method as absorption agent, is used for CO with the aqueous solution of organic alcohol amine (for example Monoethanolamine MEA BASF MEA, diethanolamine DEA, diisopropanolamine (DIPA) DIPA, N methyldiethanol amine MDEA etc.)
2, H
2S, SO
2Absorption Deng sour gas.Alkanolamine solution has bigger receptivity to sour gas, and every mole of hydramine can absorb CO under the normal temperature and pressure
2, SO
2Or H
2About 0.5 mole of S.Although having, the hydramine method purifies advantages such as purity height, hydro carbons absorb less, industry experience is abundant, but hydramine itself has certain volatility, in use the gas that can purify needs because of volatilization causes secondary pollution, and causes environmental pollution and absorption agent loss.
Ionic liquid is near the salt that is made of zwitterion and be in a liquid state normal temperature, is a kind of emerging solvent, reaction medium and catalyzer.That ionic liquid has is non-volatile, ionic structure can design, liquid state exists that temperature range is wide, good stability, advantages of environment protection, at aspects such as extracting and separating, catalyzed reaction, gas absorption wide application prospect is arranged.Ionic liquid can remedy traditional hydramine evaporable shortcoming as the absorption agent of sour gas, can not pollute the gas and the environment that need purification, can not cause the absorption agent loss because of volatilization.At present, more existing investigators are carrying out useful exploration aspect the ionic liquid absorption sour gas.
US20060251558A1 report butyl methyl tetrafluoroborate ([bmim]
+[BF
4]
-) and butyl methyl imidazoleacetic acid salt ([bmim]
+[CH
3COO]
-) two kinds of ion liquid aqueous solution absorb CO
2, at 24 ℃ of absorption temperature, CO
2When dividing potential drop 0.3MPa, water-content 14%, CO
2Balance absorbed dose in butyl methyl imidazoleacetic acid salt ion liquid is near the 0.25mol/mol ionic liquid; At 24 ℃ of absorption temperature, CO
2When dividing potential drop 0.7MPa, water-content 0.2%, CO
2Balance absorbed dose in butyl methyl tetrafluoroborate ionic liquid is near the 0.10mol/mol ionic liquid; Such ionic liquid is to CO
2Receptivity much smaller than traditional hydramine absorption agent.
(J.Am.Chem.Soc., 2002,124 (6): 926-927) report absorbs CO with [1-butyl-3-(1-aminocarbonyl propyl) imidazoles] tetrafluoroborate ion liquid to Eleanor D.Bates etc.
2, absorb 3h at normal temperatures and pressures, CO
2Absorbed dose in ionic liquid is near the 0.5mol/mol ionic liquid, and the receptivity of traditional absorption agents such as its receptivity and traditional Monoethanolamine MEA BASF, diisopropanolamine (DIPA) is suitable, but this ion liquid viscosity is big, synthesizes the cost height.
CN1709553A has reported with amino acid to be anion ion liquid, can be used for CO
2Absorption, CO under the normal temperature and pressure
2Absorbed dose in ionic liquid can reach the 0.5mol/mol ionic liquid.
WO2008/123651A1 discloses with alkyl imidazole salt, alkyl pyrroles salt, Alkylpiperidine salt, Fixanol, alkyl morpholine salt ion liquid-absorbent SO
2, find that the assimilation effect of alkyl imidazole salt is much better than other four classes ionic liquid.Near 30 ℃, SO
2Optimal absorption amount in the imidazole salts ionic liquid is near the 1.7mol/mol ionic liquid; Such ionic liquid synthesis step complexity, the cost height, viscosity is big, has limited its application.
Jun Huang etc. (Chem.Commun., 2006,4027-4029) report is with 1,1,3, and the 3-tetramethyl guanidine is that cationic ionic liquid absorbs SO
2, SO in the time of 20 ℃
2Absorbed dose in ionic liquid reaches the 1.6mol/mol ionic liquid; Such ion liquid cost height has limited its range of application.
(Angew.Chem.Int.Ed., 2004,43:2415-2417) report 1,1,3,3-tetramethyl guanidine lactate ions liquid-absorbent SO such as Weize Wu
2, 40 ℃, SO during 0.12MPa
2Absorbed dose in ionic liquid reaches the 1.7mol/mol ionic liquid, but such ionic liquid is to CO
2Assimilation effect bad, and cost height.
Zhang Suojiang etc. (J.Chem.Eng.Data, 2007,52:596-599 CN1327934C) has reported with alcoholamine carboxylate ion liquid and has absorbed SO
2Method, in the time of 25 ℃, SO
2Absorbed dose in such ionic liquid is 0.4～1.91mol/mol ionic liquid; Such ion liquid thermostability is not good, and the temperature during heating desorption can not be too high.
Can see that the ion liquid positively charged ion multi-source of having reported that is used for acid gas absorption is in imidazoles, pyridine, guanidine, hydramine etc., ion liquid synthesis step complexity, the cost height, and every mole of ionic liquid absorbs CO
2Generally be no more than 0.5 mole, absorb SO
2Generally be no more than 2.0 moles.
Therefore, the developing low-cost ionic liquid, and improve the receptivity of ionic liquid to sour gas, in the industrial application aspect the acid gas absorption significance is arranged for ionic liquid.
Summary of the invention
The object of the present invention is to provide a kind of amino-contained ionic liquid of cheapness, absorb CO with it
2, H
2S, SO
2Deng sour gas, solve the problems such as Purge gas secondary pollution, environmental pollution and absorption agent loss that traditional organic alcohol amine absorption agent causes owing to volatilization, and increase substantially receptivity sour gas.
For reaching above-mentioned purpose, the invention provides a kind of amino-contained ionic liquid that is used to absorb sour gas, this ionic liquid contains one or more in primary amine, secondary amine, the tertiary amine, be different from traditional positively charged ion multi-source in the ionic liquid of imidazoles, pyridine, guanidine, hydramine etc., the positively charged ion in the ionic liquid of the present invention is to derive from organic polyamine class material.Specifically, amino-contained ionic liquid of the present invention mixes organic polyamine after acid-base neutralisation reacts and makes with mineral acid or organic acid.Have that cost is low, the simple advantage of preparation method.
According to specific embodiments of the present invention, among the present invention, described organic polyamine is selected from one or more in quadrol, propylene diamine, diethylenetriamine, triethylene tetramine, tetraethylene pentamine, five ethene hexamines, six ethene, seven amine, polyethylene polyamine, hexanediamine, phenylenediamine, tolylene diamine, alkyl toluene diamines, the benzene triamine; Preferably, described organic polyamine is diethylenetriamine, triethylene tetramine, tetraethylene pentamine, five ethene hexamines, six ethene, seven amine, polyethylene polyamine or alkyl toluene diamines.
According to specific embodiments of the present invention, among the present invention, described mineral acid or organic acid are selected from one in hydrochloric acid, sulfuric acid, nitric acid, Hydrogen bromide, hydroiodic acid HI, phosphoric acid, boric acid, sulfonic acid, tosic acid, methylsulphonic acid, trifluoromethanesulfonic acid, Tetrafluoroboric acid, phosphofluoric acid, formic acid, acetate, propionic acid, butyric acid, trifluoroacetic acid, phenylformic acid, toluylic acid, cyclopentyl formic acid, the hexahydrobenzoic acid or are multiple; Preferably, described mineral acid or organic acid are hydrochloric acid, sulfuric acid, nitric acid, tosic acid, Tetrafluoroboric acid, phosphofluoric acid, acetate or phenylformic acid.
The present invention also provides described amino-contained preparation method of ionic liquid, wherein is described organic polyamine is mixed with mineral acid or organic acid, through the acid-base neutralisation reaction, makes described amino-contained ionic liquid.Concrete, can be that organic polyamine is mixed, carries out the acid-base neutralisation reaction with mineral acid or organic acid in the aqueous solution or small molecular alcohol solution, temperature of reaction be-50 ℃ to 100 ℃, and reaction pressure is not higher than 1MPa, stirring reaction 0.5h to 10h, synthetic ionic liquid.
According to specific embodiments of the present invention, the described method that contains amine ionic liquid absorption sour gas of preparation of the present invention comprises step:
Step 1: in organic polyamine is water-soluble, ethanol or the methyl alcohol, be made into certain density solution; Among the present invention, controlling the organic polyamine strength of solution usually is 30%～80%;
Step 2: in mineral acid or organic acid is water-soluble, ethanol or the methyl alcohol, be made into certain density solution; Among the present invention, controlling acid solutions usually is 30%～80%;
Step 3: a certain amount of organic polyamine solution is added in the ionic liquid synthesizer, stir; Take by weighing a certain amount of acid solution, slowly join in the organic polyamine solution in batches, the control synthesis temperature is-50 ℃ to 100 ℃, and preferred synthesis temperature is-10 ℃ to 50 ℃, stirs 0.5h to 10h, preferred 1h to 5h;
Step 4: stopped reaction, evaporating solvent, vacuum-drying obtain the ionic liquid of amino-contained.
According to specific embodiments of the present invention, the present invention is when the described ionic liquid of preparation, the ratio of the mole number of described organic polyamine and mineral acid or organic acid mole number (be in the above-mentioned steps 3 in the organic polyamine in the organic polyamine solution and the acid solution ratio of acid) is not more than n: 1 and be not less than 1: m, wherein n is the number of hydrogen proton in mineral acid or the organic acid molecule, and m is the number of amido in the organic polyamine molecule.According to preferred specific embodiments of the present invention, the mole number of described organic polyamine is 1: 2～n with the ratio of mineral acid or organic acid mole number: 1.
The present invention also provides the described amine ionic liquid that contains in the application that is used for absorbing sour gas.Ionic liquid of the present invention can be pure liquid state or pure solid-state form when using, and also can be the form in water-soluble solution or the alcoholic solution, also can be to load on the cellular solid, also can with the composite use of other absorption agent.It specifically can be the enrichment that is used for sour gas, Sweet natural gas, refinery gas, biogas, coal gas, synthetic gas, coke(oven)gas, splitting gas, flue gas, motor-vehicle tail-gas etc. contain the depickling of acid gas and make with extra care, and gas cleaning under suitable space and the operating environment, have the potentiality that substitute traditional organic alcohol amine, have a wide range of applications.
The present invention also provides a kind of described method that the amine ionic liquid absorbs sour gas that contains of utilizing, the method comprising the steps of: with the described form that contains the amine ionic liquid with pure liquid state, pure solid-state, the aqueous solution, alcoholic solution, or load on the cellular solid, or with the composite use of other absorption agent, be used to absorb sour gas.
According to specific embodiments of the present invention, of the present inventionly utilize described containing in the method that the amine ionic liquid absorbs sour gas, the absorbed sour gas of described desire is: CO
2, H
2S, SO
2Scrubbed gas or with the mixture of other gas, or the sour gas that contains of Sweet natural gas, refinery gas, associated gas, biogas, coal-seam gas, coal gas, synthetic gas, flue gas or motor-vehicle tail-gas, or the sour gas under a certain space or the operating environment.
According to specific embodiments of the present invention, of the present inventionly utilize described containing in the method that the amine ionic liquid absorbs sour gas, the control absorption temperature is-20 ℃ to 50 ℃, absorption pressure is in the 10MPa.As embodiment preferred, the control absorption temperature is 0 ℃ to 40 ℃, and absorption pressure is 0.1MPa to 5MPa.
Utilize the described amine ionic liquid that contains to absorb sour gas among the present invention, every mole of ionic liquid can absorb CO
2, H
2S, SO
2More than 2 moles, have advantages such as receptivity is strong, starting time is short Deng sour gas.
According to specific embodiments of the present invention, of the present inventionly utilize the described method that the amine ionic liquid absorbs sour gas that contains, also comprise: after described ionic liquid absorbs sour gas, remove the step of the sour gas in the ionic liquid by the mode of step-down and/or intensification, can recover ion liquid receptivity.Wherein, described step-down is that pressure is reduced to 1kPa to 1MPa, and described intensification is that temperature is risen to 60 ℃ to 150 ℃.
In sum, technical scheme of the present invention has following beneficial effect:
(1) compare with imidazoles of the prior art, pyridine, guanidine class ionic liquid, ion liquid synthesis material provided by the invention is cheap and easy to get, and raw materials cost is low; Ionic liquid is by the neutralization reaction preparation of one step of soda acid, and synthesis process is simple; The preparation process no coupling product belongs to atomic economy reaction, and the preparation process greenization is fit to scale operation;
(2) ionic liquid of the present invention is compared with the traditional hydramine absorption agent and imidazoles, pyridine, guanidine, the alcamines ionic liquid of report, and strong to the receptivity of sour gas, every mole of ionic liquid can absorb CO
2, H
2S, SO
2Surpass 2 moles Deng sour gas, and can not cause secondary pollution Purge gas, have non-environmental-pollution, absorption agent can volatilization loss etc. advantage.
(3) ionic liquid of the present invention can discharge sour gas by step-down and intensification after having absorbed sour gas, recover ion liquid receptivity, its multiple absorption is functional, reusable edible, non-secondary pollution, applied range has good economic benefit, environmental benefit and social benefit.
Embodiment
The present invention is described in detail below by specific embodiment, but can not constitute any qualification to practical range of the present invention.
1. ion liquid preparation embodiment
Embodiment 1
Ion liquid synthesizer is a there-necked flask, and stirring arm, dropping funnel and condensing reflux pipe are housed.There-necked flask is placed ice-water bath.Take by weighing a certain amount of triethylene tetramine (TETA), being diluted with water to concentration is 60m%, adds in the there-necked flask and stirring.Take by weighing equimolar Tetrafluoroboric acid (HBF
4), being diluted with water to concentration is 60m%, adds in the dropping funnel, slowly splashes in the there-necked flask.Dropwise the back and continue in ice-water bath, to stir 3h.Reacted liquid evaporation is removed most of water, use 60 ℃ of dry 24h of vacuum drying oven afterwards, obtain [TETAH]
+[BF
4]
-Ionic liquid.
Embodiment 2
Ion liquid synthesizer is a there-necked flask, and stirring arm, dropping funnel and condensing reflux pipe are housed.There-necked flask is placed ice-water bath.Take by weighing a certain amount of triethylene tetramine (TETA), being diluted with water to concentration is 60m%, adds in the there-necked flask and stirring.Take by weighing the Tetrafluoroboric acid (HBF of twice mole
4), being diluted with water to concentration is 60m%, adds in the dropping funnel, slowly splashes in the there-necked flask.Dropwise the back and continue in ice-water bath, to stir 3h.Reacted liquid evaporation is removed most of water, use 60 ℃ of dry 24h of vacuum drying oven afterwards, obtain [TETAH
2]
2+2[BF
4]
-Ionic liquid.
Ionic liquid to embodiment 1, embodiment 2 carries out Infrared spectroscopy, compares with TETA standard spectrogram, and analytical data writes down as following table.
| Ionic liquid | v H-O | v as(-NH2) | ?v s(N-H) | ?v s(C-H) | δ s(N-H) | δ s(-CH2) | δ C-H | v s(C-N) | γ β |
| TETA | - | 3371 | ?3278 | ?2931 | 1600 | 1457 | 1352 | 1076 | - |
| [TETAH] +[BF 4] - | 3600 | 3363 | ?3269 | ?2922 | 1609 | 1461 | 1364 | 1063 | 765 |
| [TETAH 2] 2+2[BF 4] - | 3616 | - | ?3275 | ?2867 | 1608 | 1467 | 1353 | 1066 | 766 |
Embodiment 3
Ion liquid synthesizer is the same.There-necked flask is placed ice-water bath.Take by weighing a certain amount of tetraethylene pentamine (TEPA), being diluted with water to concentration is 50m%, adds in the there-necked flask and stirring.Take by weighing equimolar nitric acid (HNO
3), being diluted with water to concentration is 60m%, adds in the dropping funnel, slowly splashes in the there-necked flask.Dropwise the back and continue in ice-water bath, to stir 4h.Reacted liquid evaporation is removed most of water, use 60 ℃ of dry 24h of vacuum drying oven afterwards, obtain [TEPAH]
+[NO
3]
-Ionic liquid.
Embodiment 4
Ion liquid synthesizer is the same.There-necked flask is placed ice-water bath.Take by weighing a certain amount of six ethene, seven amine (HEHA), being diluted to concentration with dehydrated alcohol is 40m%, adds in the there-necked flask and stirring.Take by weighing equimolar tosic acid (PTS), being diluted to concentration with dehydrated alcohol is 40m%, adds in the dropping funnel, slowly splashes in the there-necked flask.Dropwise the back and continue in ice-water bath, to stir 2h.Reacted liquid evaporation is removed most of ethanol, use 60 ℃ of dry 24h of vacuum drying oven afterwards, obtain [HEHAH]
+[PTS]
-Ionic liquid.
Embodiment 5
Ion liquid synthesizer is the same.There-necked flask is placed ice-water bath.Take by weighing a certain amount of five ethene hexamines (PEHA), being diluted with water to concentration is 40m%, adds in the there-necked flask and stirring.Take by weighing equimolar hydrochloric acid (HCl), being diluted with water to concentration is 50m%, adds in the dropping funnel, slowly splashes in the there-necked flask.Dropwise the back and continue in ice-water bath, to stir 2h.Reacted liquid evaporation is removed most of water, use 60 ℃ of dry 24h of vacuum drying oven afterwards, obtain [PEHAH]
+[Cl]
-Ionic liquid.
Embodiment 6
Ion liquid synthesizer is the same.There-necked flask is placed ice-water bath.Take by weighing a certain amount of polyethylene polyamine (PEPA), being diluted to concentration with dehydrated alcohol is 50m%, adds in the there-necked flask and stirring.Take by weighing equimolar phenylformic acid (BA), being diluted to concentration with dehydrated alcohol is 60m%, adds in the dropping funnel, slowly splashes in the there-necked flask.Dropwise the back and continue in ice-water bath, to stir 4h.Reacted liquid evaporation is removed most of ethanol, use 60 ℃ of dry 24h of vacuum drying oven afterwards, obtain [PEPAH]
+[BA]
-Ionic liquid.
Embodiment 7
Ion liquid synthesizer is the same.There-necked flask is placed ice-water bath.Take by weighing a certain amount of triethylene tetramine (TETA), being diluted with water to concentration is 50m%, adds in the there-necked flask and stirring.Take by weighing the sulfuric acid (H of 1/2nd TETA mole numbers
2SO
4), being diluted with water to concentration is 50m%, adds in the dropping funnel, slowly splashes in the there-necked flask.Dropwise the back and continue in ice-water bath, to stir 3h.Reacted liquid evaporation is removed most of water, use 60 ℃ of dry 24h of vacuum drying oven afterwards, obtain 2[TETAH]
+[SO
4]
2-Ionic liquid.
Embodiment 8
Ion liquid synthesizer is the same.There-necked flask is placed ice-water bath.Take by weighing a certain amount of six ethene, seven amine (HEHA), being diluted with water to concentration is 40m%, adds in the there-necked flask and stirring.Take by weighing 2 times of HEHA mole numbers to nitric acid (HNO
3), being diluted with water to concentration is 50m%, adds in the dropping funnel, slowly splashes in the there-necked flask.Dropwise the back and continue in ice-water bath, to stir 2h.Reacted liquid evaporation is removed most of water, use 60 ℃ of dry 24h of vacuum drying oven afterwards, obtain [HEHAH
2]
2+2[NO
3]
-Ionic liquid.
Embodiment 9
Ion liquid synthesizer is the same.There-necked flask is placed ice-water bath.Take by weighing a certain amount of diethyl toluene diamine (DETDA), being diluted to concentration with dehydrated alcohol is 60m%, adds in the there-necked flask and stirring.Take by weighing equimolar acetate (HAc), being diluted to concentration with dehydrated alcohol is 70m%, adds in the dropping funnel, slowly splashes in the there-necked flask.Dropwise the back and continue in ice-water bath, to stir 5h.Reacted liquid evaporation is removed most of ethanol, use 60 ℃ of dry 24h of vacuum drying oven afterwards, obtain [DETDAH]
+[Ac]
-Ionic liquid.
2. the embodiment that utilizes ionic liquid of the present invention that sour gas is absorbed
Embodiment 10
The device that ionic liquid absorbs sour gas is the stainless steel encloses container that has pressure and temperature demonstration and induction stirring.With synthetic [TETAH] among the embodiment 1 of accurate weighing
+[BF
4]
-Ionic liquid adds in the absorption unit, places water bath with thermostatic control, opens induction stirring, feeds CO in absorption unit
2Gas absorbs CO under 20 ℃ of absorption temperature, normal pressure
2, about 0.5h reaches balance, the CO of absorption
2With ion liquid mol ratio be 1.5.
Embodiment 11
Ionic liquid absorbs the device of sour gas with embodiment 10.With synthetic [HEHAH] among the embodiment 4 of accurate weighing
+[PTS]
-Ionic liquid aqueous solution adds in the absorption unit, places water bath with thermostatic control, opens induction stirring, feeds CO in absorption unit
2Gas absorbs CO under 15 ℃ of absorption temperature, absorption pressure 2MPa
2, about 1h reaches balance, the CO of absorption
2With ion liquid mol ratio be 3.8.
Embodiment 12
Ionic liquid absorbs the device of sour gas with embodiment 10.With synthetic [PEPAH] among the embodiment 6 of accurate weighing
+[BA]
-Ionic liquid aqueous solution adds in the absorption unit, places water bath with thermostatic control, opens induction stirring, feeds CO in absorption unit
2Gas absorbs CO under 30 ℃ of absorption temperature, absorption pressure 5MPa
2, about 0.5h reaches balance, the CO of absorption
2With ion liquid mol ratio be 2.5.
Embodiment 13
Ionic liquid absorbs the device of sour gas with embodiment 10.With synthetic [PEHAH] among the embodiment 5 of accurate weighing
+[Cl]
-Ionic liquid aqueous solution adds in the absorption unit, places water bath with thermostatic control, opens induction stirring, feeds CO in absorption unit
2Gas absorbs CO under 10 ℃ of absorption temperature, absorption pressure 1MPa
2, about 1.5h reaches balance, the CO of absorption
2With ion liquid mol ratio be 2.9.
Embodiment 14
Ionic liquid absorbs the device of sour gas with embodiment 10.With synthetic [HEHAH] among the embodiment 4 of accurate weighing
+[PTS]
-Ionic liquid aqueous solution adds in the absorption unit, places water bath with thermostatic control, opens induction stirring, feeds H in absorption unit
2S gas absorbs H under 20 ℃ of absorption temperature, normal pressure
2S, about 1h reaches balance, the H of absorption
2S and ion liquid mol ratio are 3.0.
Embodiment 15
Ionic liquid absorbs the device of sour gas with embodiment 10.With synthetic [PEPAH] among the embodiment 6 of accurate weighing
+[BA]
-Ionic liquid aqueous solution adds in the absorption unit, places water bath with thermostatic control, opens induction stirring, feeds H in absorption unit
2S gas absorbs H under 30 ℃ of absorption temperature, absorption pressure 1.5MPa
2S, about 0.5h reaches balance, the H of absorption
2S and ion liquid mol ratio are 2.3.
Embodiment 16
Ionic liquid absorbs the device of sour gas with embodiment 10.With synthetic 2[TETAH among the embodiment 7 of accurate weighing]
+[SO
4]
2-Ionic liquid aqueous solution adds in the absorption unit, places water bath with thermostatic control, opens induction stirring, feeds H in absorption unit
2S gas absorbs H under 10 ℃ of absorption temperature, absorption pressure 1MPa
2S, about 1.5h reaches balance, the H of absorption
2S and ion liquid mol ratio are 3.1.
Embodiment 17
Ionic liquid absorbs the device of sour gas with embodiment 10.With synthetic [TEPAH] among the embodiment 3 of accurate weighing
+[NO
3]
-Ionic liquid aqueous solution adds in the absorption unit, places water bath with thermostatic control, opens induction stirring, feeds SO in absorption unit
2Gas absorbs SO under 10 ℃ of absorption temperature, absorption pressure 2MPa
2, about 1.5h reaches balance, the SO of absorption
2With ion liquid mol ratio be 2.8.
Embodiment 18
Ionic liquid absorbs the device of sour gas with embodiment 10.With synthetic [DETDAH] among the embodiment 9 of accurate weighing
+[Ac]
-Ionic liquid adds in the absorption unit, places water bath with thermostatic control, opens induction stirring, feeds SO in absorption unit
2Gas absorbs SO under 30 ℃ of absorption temperature, absorption pressure 3MPa
2, about 1h reaches balance, the SO of absorption
2With ion liquid mol ratio be 1.3.
Embodiment 19
Ionic liquid absorbs the device of sour gas with embodiment 10.With synthetic [HEHAH] among the embodiment 4 of accurate weighing
+[PTS]
-Ionic liquid aqueous solution adds in the absorption unit, places water bath with thermostatic control, opens induction stirring, feeds SO in absorption unit
2Gas absorbs SO under 20 ℃ of absorption temperature, absorption pressure 4MPa
2, about 1h reaches balance, the SO of absorption
2With ion liquid mol ratio be 4.2.
Embodiment 20
Ionic liquid absorbs the device of sour gas with embodiment 10.With synthetic [HEHAH among the embodiment 8 of accurate weighing
2]
2+2[NO
3]
-Ionic liquid aqueous solution adds in the absorption unit, places water bath with thermostatic control, opens induction stirring, feeds SO in absorption unit
2Gas absorbs SO under 30 ℃ of absorption temperature, absorption pressure 2MPa
2, about 1h reaches balance, the SO of absorption
2With ion liquid mol ratio be 2.9.
Embodiment 21
Ionic liquid absorbs the device of sour gas with embodiment 10.With synthetic [TETAH among the embodiment 2 of accurate weighing
2]
2+2[BF
4]
-Ionic liquid aqueous solution adds in the absorption unit, places water bath with thermostatic control, opens induction stirring, feeds SO in absorption unit
2Gas absorbs SO under 25 ℃ of absorption temperature, absorption pressure 3MPa
2, about 1.5h reaches balance, the SO of absorption
2With ion liquid mol ratio be 1.5.
Embodiment 22
Ionic liquid absorbs the device of sour gas with embodiment 10.At first with synthetic [TETAH] among the embodiment 1
+[BF
4]
-Ionic liquid with etc. the tetramethylene sulfone of quality be made into mixing solutions, the mixing solutions of accurate weighing is added in the absorption unit, place water bath with thermostatic control, open induction stirring, in absorption unit, feed CO
2Gas absorbs CO under 25 ℃ of absorption temperature, absorption pressure 5MPa
2, about 0.5h reaches balance, the CO of absorption
2With ion liquid mol ratio be 2.6.
Embodiment 23
With synthetic [HEHAH] among the embodiment 4 of accurate weighing
+[PTS]
-Ion liquid dissolving mixes stirring 1h in a small amount of dehydrated alcohol with porous silica gel, most of ethanol is removed in evaporation afterwards, uses 80 ℃ of dry 24h of vacuum drying oven again, obtains load [HEHAH]
+[PTS]
-Ion liquid solid adsorbent.The device of solid adsorbent absorption sour gas is to have the stainless steel encloses container that pressure and temperature shows.Sorbent material is packed in the adsorption unit, place water bath with thermostatic control, in adsorption unit, feed CO
2Gas, CO absorption under 20 ℃ of adsorption temps, adsorptive pressure 1MPa
2, about 1h reaches balance, the CO of absorption
2With ion liquid mol ratio be 3.2.
Embodiment 24
With synthetic [PEPAH] among the embodiment 6 of accurate weighing
+[BA]
-Ion liquid dissolving mixes stirring 1h in a small amount of dehydrated alcohol with neutral alumina, most of ethanol is removed in evaporation afterwards, uses 80 ℃ of dry 24h of vacuum drying oven again, obtains load [PEPAH]
+[BA]
-Ion liquid solid adsorbent.The device of solid adsorbent absorption sour gas is to have the stainless steel encloses container that pressure and temperature shows.Sorbent material is packed in the adsorption unit, place water bath with thermostatic control, in adsorption unit, feed H
2S gas adsorbs H under 25 ℃ of adsorption temps, adsorptive pressure 1MPa
2S, about 1h reaches balance, the H of absorption
2S and ion liquid mol ratio are 2.2.
3. ionic liquid of the present invention absorbs desorb and the multiple absorption embodiment behind the sour gas
Embodiment 25
The absorption that embodiment 11 is obtained CO
2[HEHAH]
+[PTS]
-Ionic liquid continues to be stored in the absorption unit, places constant temperature oil bath, opens induction stirring, the air outlet valve of opening unit, desorb CO under 80 ℃, normal pressure
2, desorption efficiency reaches 90% during 15min, and the 45min desorption efficiency reaches 98%.With desorb CO
2Ionic liquid continue under 15 ℃ of absorption temperature, absorption pressure 2MPa, to absorb CO
2, desorb 45min under 80 ℃, normal pressure more afterwards.So repeat, when the 5th absorbs, the CO of absorption
2With ion liquid mol ratio be 3.4.
Embodiment 26
The absorption that embodiment 15 is obtained H
2[PEPAH] of S
+[BA]
-Ionic liquid continues to be stored in the absorption unit, places constant temperature oil bath, opens induction stirring, the air outlet valve of opening unit, desorb H under 85 ℃, normal pressure
2S, the 20min desorption efficiency reaches 96%.With desorb H
2The ionic liquid of S continues to absorb H under 30 ℃ of absorption temperature, absorption pressure 1.5MPa
2S, desorb 20min under 85 ℃, normal pressure more afterwards.So repeat, when the 5th absorbs, the H of absorption
2S and ion liquid mol ratio are 2.0.
Embodiment 27
The absorption that embodiment 17 is obtained SO
2[TEPAH]
+[NO
3]
-Ionic liquid continues to be stored in the absorption unit, places constant temperature oil bath, opens induction stirring, the air outlet valve of opening unit, desorb SO under 85 ℃, normal pressure
2, the 30min desorption efficiency reaches 97%.With desorb SO
2Ionic liquid continue under 10 ℃ of absorption temperature, absorption pressure 2MPa, to absorb SO
2, desorb 30min under 85 ℃, normal pressure more afterwards.So repeat, when the 5th absorbs, the SO of absorption
2With ion liquid mol ratio be 2.5.
Embodiment 28
The absorption that embodiment 23 is obtained CO
2Load [HEHAH]
+[PTS]
-Ion liquid solid adsorbent continues to be stored in the adsorption unit, places constant temperature oil bath, the air outlet valve of opening unit, desorption CO under 120 ℃, 30kPa
2, desorption rate reaches 98% during 10min.With desorption CO
2Solid adsorbent continue CO absorption under 20 ℃ of adsorption temps, adsorptive pressure 1MPa
2, desorption 10min under 120 ℃, 30kPa more afterwards.So repeat, when the 5th is adsorbed, the CO of absorption
2With ion liquid mol ratio be 2.9.
Claims (10)
1. amino-contained ionic liquid that is used to absorb sour gas, this ionic liquid contains one or more in primary amine, secondary amine, the tertiary amine, and this amino-contained ionic liquid mixes organic polyamine after acid-base neutralisation reacts and makes with mineral acid or organic acid.
2. the amine ionic liquid that contains according to claim 1, wherein, described organic polyamine is selected from one or more in quadrol, propylene diamine, diethylenetriamine, triethylene tetramine, tetraethylene pentamine, five ethene hexamines, six ethene, seven amine, polyethylene polyamine, hexanediamine, phenylenediamine, tolylene diamine, alkyl toluene diamines, the benzene triamine; Preferably, described organic polyamine is diethylenetriamine, triethylene tetramine, tetraethylene pentamine, five ethene hexamines, six ethene, seven amine, polyethylene polyamine or alkyl toluene diamines.
3. according to claim 1 or the 2 described amine ionic liquids that contain, wherein, described mineral acid or organic acid are selected from one in hydrochloric acid, sulfuric acid, nitric acid, Hydrogen bromide, hydroiodic acid HI, phosphoric acid, boric acid, sulfonic acid, tosic acid, methylsulphonic acid, trifluoromethanesulfonic acid, Tetrafluoroboric acid, phosphofluoric acid, formic acid, acetate, propionic acid, butyric acid, trifluoroacetic acid, phenylformic acid, toluylic acid, cyclopentyl formic acid, the hexahydrobenzoic acid or are multiple; Preferably, described mineral acid or organic acid are hydrochloric acid, sulfuric acid, nitric acid, tosic acid, Tetrafluoroboric acid, phosphofluoric acid, acetate or phenylformic acid.
4. the amine ionic liquid that contains according to claim 1, wherein, the mole number of described organic polyamine is not more than n with the ratio of mineral acid or organic acid mole number: 1 and be not less than 1: m, and wherein n is the number of hydrogen proton in mineral acid or the organic acid molecule, m is the number of amido in the organic polyamine molecule; The mole number of preferred described organic polyamine is 1: 2～n with the ratio of mineral acid or organic acid mole number: 1.
5. each described ion liquid synthetic method of amine that contains of claim 1～4, this method comprises:
Organic polyamine is mixed, carries out the acid-base neutralisation reaction in the aqueous solution or small molecular alcohol solution with mineral acid or organic acid, temperature of reaction is preferably-10 ℃ to 50 ℃ for-50 ℃ to 100 ℃, reaction pressure is not higher than 1MPa, the preferred 1h to 5h of stirring reaction 0.5h to 10h, synthetic ionic liquid.
6. each described amine ionic liquid that contains of claim 1～4 is in the application that is used for absorbing sour gas.
7. one kind is utilized each described method that contains amine ionic liquid absorption sour gas of claim 1～4, and the method comprising the steps of:
With the described form that contains the amine ionic liquid with pure liquid state, pure solid-state, the aqueous solution, alcoholic solution, or load on the cellular solid, or with the composite use of other absorption agent, be used to absorb sour gas.
8. each the described method that contains amine ionic liquid absorption sour gas of claim 1～4 of utilizing according to claim 7, wherein, the absorbed sour gas of described desire is: CO
2, H
2S, SO
2Scrubbed gas or with the mixture of other gas, or the sour gas that contains of Sweet natural gas, refinery gas, associated gas, biogas, coal-seam gas, coal gas, synthetic gas, flue gas or motor-vehicle tail-gas, or the sour gas under a certain space or the operating environment.
9. each the described method that contains amine ionic liquid absorption sour gas of claim 1～4 of utilizing according to claim 7, wherein, the control absorption temperature is-20 ℃ to 50 ℃, preferred absorption temperature is 0 ℃ to 40 ℃; Absorption pressure is in the 10MPa, and preferred absorption pressure is 0.1MPa to 5MPa.
10. according to claim 7 or 8 or 9 described each described methods that contain amine ionic liquid absorption sour gas of claim 1～4 of utilizing, this method also comprises:
After described ionic liquid absorbs sour gas, remove the step of the sour gas in the ionic liquid by the mode of step-down and/or intensification; Wherein, described step-down is that pressure is reduced to 1kPa to 1MPa, and described intensification is that temperature is risen to 60 ℃ to 150 ℃.
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