CN101993378B - 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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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 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
2The sour gas such as S, the existence of these sour gas all can exert an adverse impact to following process and the utilization of gas, therefore need to carry out depickling to it and process.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 sealing 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 industrial production.The method as absorption agent, is used for CO with the aqueous solution of organic alcohol amine (such as 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 larger receptivity to sour gas, and under normal temperature and pressure, every mole of hydramine can absorb CO
2, SO
2Or H
2Approximately 0.5 mole of S.The advantages such as the purity of purification is high although the hydramine method has, hydro carbons absorbs less, industry experience is abundant, but hydramine itself has certain volatility, the gas that in use 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, has broad application prospects at aspects such as extracting and separating, catalyzed reaction, gas absorption.Ionic liquid can make up the shortcoming of traditional hydramine volatilization as the absorption agent of sour gas, can not pollute the gas and the environment that need purification, can not cause because of volatilization the absorption agent loss.At present, more existing investigators are carrying out useful exploration aspect ionic liquid absorption sour gas.
US20060251558A1 report butyl methyl tetrafluoroborate ([bmim]
+[BF
4]
-) and butyl methyl imidazoleacetic acid salt ([bmim]
+[CH
3COO]
-) aqueous solution of two kinds of ionic liquids absorbs CO
2, at 24 ℃ of absorption temperature, CO
2When dividing potential drop 0.3MPa, water-content 14%, CO
2Balance Absorption amount 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 Absorption amount 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 at normal temperatures and pressures 3h, 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 the viscosity of this ionic liquid is large, and synthetic cost is high.
CN1709553A has reported take amino acid as anion ion liquid, can be used for CO
2Absorption, CO under 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 is complicated, and cost is high, and viscosity is large, 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; The cost of such ionic liquid is high, has limited its range of application.
(Angew.Chem.Int.Ed., 2004,43:2415-2417) report 1,1,3, the 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 is high.
Zhang Suojiang etc. (J.Chem.Eng.Data, 2007,52:596-599, CN1327934C) have reported with alcoholamine carboxylate ion liquid and have absorbed SO
2Method, in the time of 25 ℃, SO
2Absorbed dose in such ionic liquid is 0.4～1.91mol/mol ionic liquid; The thermostability of such ionic liquid is not good, and the temperature during heating desorption can not be too high.
Can see, the positively charged ion multi-source of the ionic liquid that is used for acid gas absorption of having reported is in imidazoles, pyridine, guanidine, hydramine etc., and the synthesis step of ionic liquid is complicated, and cost is high, 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, developing low-cost ionic liquid, and improve ionic liquid to the receptivity of sour gas, for ionic liquid at the industrial application important in inhibiting aspect acid gas absorption.
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 due to volatilization, and increase substantially the receptivity to sour gas.
For reaching above-mentioned purpose, the invention provides a kind of amino-contained ionic liquid for absorbing sour gas, this ionic liquid contains one or more in primary amine, secondary amine, 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 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 by acid-base neutralisation reaction 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, in 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, 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, in 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, acetic acid, propionic acid, butyric acid, trifluoroacetic acid, phenylformic acid, toluylic acid, cyclopentyl formic acid, 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, acetic acid or phenylformic acid.
The present invention also provides the preparation method of described amino-contained ionic liquid, is wherein 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 methyl alcohol, be made into certain density solution; In the present invention, usually controlling the organic polyamine strength of solution is 30%～80%;
Step 2: in mineral acid or organic acid is water-soluble, ethanol or methyl alcohol, be made into certain density solution; In the present invention, usually controlling acid solutions is 30%～80%;
Step 3: a certain amount of organic polyamine solution is added in the ionic liquid synthesizer, stir; Take a certain amount of acid solution, slowly join in organic polyamine solution in batches, controlling 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 above-mentioned steps 3 in the organic polyamine in organic polyamine solution and acid solution the 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 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 when using, can be pure liquid state or pure solid-state form, can be also the form in water-soluble solution or alcoholic solution, can be also to load on cellular solid, also can with the composite use of other absorption agent.It can be specifically the enrichment 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 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 amine ionic liquid that contains with the form of pure liquid state, pure solid-state, the aqueous solution, alcoholic solution, or load on cellular solid, or with the composite use of other absorption agent, be used for 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 wish 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 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, controlling absorption temperature is-20 ℃ to 50 ℃, absorption pressure is in 10MPa.As preferred embodiment, controlling 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 in the present invention, every mole of ionic liquid can absorb CO
2, H
2S, SO
2More than 2 moles, have the 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 ionic liquid by the mode of step-down and/or intensification, can recover the receptivity of ionic liquid.Wherein, described step-down be with Pressure Drop to 1kPa to 1MPa, 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, the synthesis material of ionic liquid 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 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 to 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 the receptivity of ionic liquid, it is good that it repeats absorptive character, 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 consist of any restriction to practical range of the present invention.
1. the Preparation Example of ionic liquid
Embodiment 1
The synthesizer of ionic liquid is there-necked flask, and stirring arm, dropping funnel and condensing reflux pipe are housed.There-necked flask is placed in ice-water bath.Take a certain amount of triethylene tetramine (TETA), being diluted with water to concentration is 60m%, adds in there-necked flask and stirs.Take equimolar Tetrafluoroboric acid (HBF
4), being diluted with water to concentration is 60m%, adds in dropping funnel, slowly splashes in there-necked flask.Dropwise rear continuation and stir 3h in ice-water bath.Reacted liquid evaporation is removed most of water, use afterwards 60 ℃ of dry 24h of vacuum drying oven, obtain [TETAH]
+[BF
4]
-Ionic liquid.
Embodiment 2
The synthesizer of ionic liquid is there-necked flask, and stirring arm, dropping funnel and condensing reflux pipe are housed.There-necked flask is placed in ice-water bath.Take a certain amount of triethylene tetramine (TETA), being diluted with water to concentration is 60m%, adds in there-necked flask and stirs.Take the Tetrafluoroboric acid (HBF of twice mole
4), being diluted with water to concentration is 60m%, adds in dropping funnel, slowly splashes in there-necked flask.Dropwise rear continuation and stir 3h in ice-water bath.Reacted liquid evaporation is removed most of water, use afterwards 60 ℃ of dry 24h of vacuum drying oven, 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 records 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
The synthesizer of ionic liquid is the same.There-necked flask is placed in ice-water bath.Take a certain amount of tetraethylene pentamine (TEPA), being diluted with water to concentration is 50m%, adds in there-necked flask and stirs.Take equimolar nitric acid (HNO
3), being diluted with water to concentration is 60m%, adds in dropping funnel, slowly splashes in there-necked flask.Dropwise rear continuation and stir 4h in ice-water bath.Reacted liquid evaporation is removed most of water, use afterwards 60 ℃ of dry 24h of vacuum drying oven, obtain [TEPAH]
+[NO
3]
-Ionic liquid.
Embodiment 4
The synthesizer of ionic liquid is the same.There-necked flask is placed in ice-water bath.Take a certain amount of six ethene seven amine (HEHA), being diluted to concentration with dehydrated alcohol is 40m%, adds in there-necked flask and stirs.Take equimolar tosic acid (PTS), being diluted to concentration with dehydrated alcohol is 40m%, adds in dropping funnel, slowly splashes in there-necked flask.Dropwise rear continuation and stir 2h in ice-water bath.Reacted liquid evaporation is removed most of ethanol, use afterwards 60 ℃ of dry 24h of vacuum drying oven, obtain [HEHAH]
+[PTS]
-Ionic liquid.
Embodiment 5
The synthesizer of ionic liquid is the same.There-necked flask is placed in ice-water bath.Take a certain amount of five ethene hexamines (PEHA), being diluted with water to concentration is 40m%, adds in there-necked flask and stirs.Take equimolar hydrochloric acid (HCl), being diluted with water to concentration is 50m%, adds in dropping funnel, slowly splashes in there-necked flask.Dropwise rear continuation and stir 2h in ice-water bath.Reacted liquid evaporation is removed most of water, use afterwards 60 ℃ of dry 24h of vacuum drying oven, obtain [PEHAH]
+[Cl]
-Ionic liquid.
Embodiment 6
The synthesizer of ionic liquid is the same.There-necked flask is placed in ice-water bath.Take a certain amount of polyethylene polyamine (PEPA), being diluted to concentration with dehydrated alcohol is 50m%, adds in there-necked flask and stirs.Take equimolar phenylformic acid (BA), being diluted to concentration with dehydrated alcohol is 60m%, adds in dropping funnel, slowly splashes in there-necked flask.Dropwise rear continuation and stir 4h in ice-water bath.Reacted liquid evaporation is removed most of ethanol, use afterwards 60 ℃ of dry 24h of vacuum drying oven, obtain [PEPAH]
+[BA]
-Ionic liquid.
Embodiment 7
The synthesizer of ionic liquid is the same.There-necked flask is placed in ice-water bath.Take a certain amount of triethylene tetramine (TETA), being diluted with water to concentration is 50m%, adds in there-necked flask and stirs.Take the sulfuric acid (H of 1/2nd TETA mole numbers
2SO
4), being diluted with water to concentration is 50m%, adds in dropping funnel, slowly splashes in there-necked flask.Dropwise rear continuation and stir 3h in ice-water bath.Reacted liquid evaporation is removed most of water, use afterwards 60 ℃ of dry 24h of vacuum drying oven, obtain 2[TETAH]
+[SO
4]
2-Ionic liquid.
Embodiment 8
The synthesizer of ionic liquid is the same.There-necked flask is placed in ice-water bath.Take a certain amount of six ethene seven amine (HEHA), being diluted with water to concentration is 40m%, adds in there-necked flask and stirs.Take 2 times of HEHA mole numbers to nitric acid (HNO
3), being diluted with water to concentration is 50m%, adds in dropping funnel, slowly splashes in there-necked flask.Dropwise rear continuation and stir 2h in ice-water bath.Reacted liquid evaporation is removed most of water, use afterwards 60 ℃ of dry 24h of vacuum drying oven, obtain [HEHAH
2]
2+2[NO
3]
-Ionic liquid.
Embodiment 9
The synthesizer of ionic liquid is the same.There-necked flask is placed in ice-water bath.Take a certain amount of diethyl toluene diamine (DETDA), being diluted to concentration with dehydrated alcohol is 60m%, adds in there-necked flask and stirs.Take equimolar acetic acid (HAc), being diluted to concentration with dehydrated alcohol is 70m%, adds in dropping funnel, slowly splashes in there-necked flask.Dropwise rear continuation and stir 5h in ice-water bath.Reacted liquid evaporation is removed most of ethanol, use afterwards 60 ℃ of dry 24h of vacuum drying oven, 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 of ionic liquid absorption sour gas is the stainless steel encloses container with pressure and temperature demonstration and induction stirring.With [TETAH] synthetic in the embodiment 1 of accurate weighing
+[BF
4]
-Ionic liquid adds in absorption unit, is placed in water bath with thermostatic control, opens induction stirring, passes into CO in absorption unit
2Gas absorbs CO under 20 ℃ of absorption temperature, normal pressure
2, approximately 0.5h reaches balance, the CO of absorption
2With the mol ratio of ionic liquid be 1.5.
Embodiment 11
Ionic liquid absorbs the device of sour gas with embodiment 10.With [HEHAH] synthetic in the embodiment 4 of accurate weighing
+[PTS]
-Ionic liquid aqueous solution adds in absorption unit, is placed in water bath with thermostatic control, opens induction stirring, passes into CO in absorption unit
2Gas absorbs CO under 15 ℃ of absorption temperature, absorption pressure 2MPa
2, approximately 1h reaches balance, the CO of absorption
2With the mol ratio of ionic liquid be 3.8.
Embodiment 12
Ionic liquid absorbs the device of sour gas with embodiment 10.With [PEPAH] synthetic in the embodiment 6 of accurate weighing
+[BA]
-Ionic liquid aqueous solution adds in absorption unit, is placed in water bath with thermostatic control, opens induction stirring, passes into CO in absorption unit
2Gas absorbs CO under 30 ℃ of absorption temperature, absorption pressure 5MPa
2, approximately 0.5h reaches balance, the CO of absorption
2With the mol ratio of ionic liquid be 2.5.
Embodiment 13
Ionic liquid absorbs the device of sour gas with embodiment 10.With [PEHAH] synthetic in the embodiment 5 of accurate weighing
+[Cl]
-Ionic liquid aqueous solution adds in absorption unit, is placed in water bath with thermostatic control, opens induction stirring, passes into CO in absorption unit
2Gas absorbs CO under 10 ℃ of absorption temperature, absorption pressure 1MPa
2, approximately 1.5h reaches balance, the CO of absorption
2With the mol ratio of ionic liquid be 2.9.
Embodiment 14
Ionic liquid absorbs the device of sour gas with embodiment 10.With [HEHAH] synthetic in the embodiment 4 of accurate weighing
+[PTS]
-Ionic liquid aqueous solution adds in absorption unit, is placed in water bath with thermostatic control, opens induction stirring, passes into H in absorption unit
2S gas absorbs H under 20 ℃ of absorption temperature, normal pressure
2S, approximately 1h reaches balance, the H of absorption
2The mol ratio of S and ionic liquid is 3.0.
Embodiment 15
Ionic liquid absorbs the device of sour gas with embodiment 10.With [PEPAH] synthetic in the embodiment 6 of accurate weighing
+[BA]
-Ionic liquid aqueous solution adds in absorption unit, is placed in water bath with thermostatic control, opens induction stirring, passes into H in absorption unit
2S gas absorbs H under 30 ℃ of absorption temperature, absorption pressure 1.5MPa
2S, approximately 0.5h reaches balance, the H of absorption
2The mol ratio of S and ionic liquid is 2.3.
Embodiment 16
Ionic liquid absorbs the device of sour gas with embodiment 10.With 2[TETAH synthetic in the embodiment 7 of accurate weighing]
+[SO
4]
2-Ionic liquid aqueous solution adds in absorption unit, is placed in water bath with thermostatic control, opens induction stirring, passes into H in absorption unit
2S gas absorbs H under 10 ℃ of absorption temperature, absorption pressure 1MPa
2S, approximately 1.5h reaches balance, the H of absorption
2The mol ratio of S and ionic liquid is 3.1.
Embodiment 17
Ionic liquid absorbs the device of sour gas with embodiment 10.With [TEPAH] synthetic in the embodiment 3 of accurate weighing
+[NO
3]
-Ionic liquid aqueous solution adds in absorption unit, is placed in water bath with thermostatic control, opens induction stirring, passes into SO in absorption unit
2Gas absorbs SO under 10 ℃ of absorption temperature, absorption pressure 2MPa
2, approximately 1.5h reaches balance, the SO of absorption
2With the mol ratio of ionic liquid be 2.8.
Embodiment 18
Ionic liquid absorbs the device of sour gas with embodiment 10.With [DETDAH] synthetic in the embodiment 9 of accurate weighing
+[Ac]
-Ionic liquid adds in absorption unit, is placed in water bath with thermostatic control, opens induction stirring, passes into SO in absorption unit
2Gas absorbs SO under 30 ℃ of absorption temperature, absorption pressure 3MPa
2, approximately 1h reaches balance, the SO of absorption
2With the mol ratio of ionic liquid be 1.3.
Embodiment 19
Ionic liquid absorbs the device of sour gas with embodiment 10.With [HEHAH] synthetic in the embodiment 4 of accurate weighing
+[PTS]
-Ionic liquid aqueous solution adds in absorption unit, is placed in water bath with thermostatic control, opens induction stirring, passes into SO in absorption unit
2Gas absorbs SO under 20 ℃ of absorption temperature, absorption pressure 4MPa
2, approximately 1h reaches balance, the SO of absorption
2With the mol ratio of ionic liquid be 4.2.
Embodiment 20
Ionic liquid absorbs the device of sour gas with embodiment 10.With [HEHAH synthetic in the embodiment 8 of accurate weighing
2]
2+2[NO
3]
-Ionic liquid aqueous solution adds in absorption unit, is placed in water bath with thermostatic control, opens induction stirring, passes into SO in absorption unit
2Gas absorbs SO under 30 ℃ of absorption temperature, absorption pressure 2MPa
2, approximately 1h reaches balance, the SO of absorption
2With the mol ratio of ionic liquid be 2.9.
Embodiment 21
Ionic liquid absorbs the device of sour gas with embodiment 10.With [TETAH synthetic in the embodiment 2 of accurate weighing
2]
2+2[BF
4]
-Ionic liquid aqueous solution adds in absorption unit, is placed in water bath with thermostatic control, opens induction stirring, passes into SO in absorption unit
2Gas absorbs SO under 25 ℃ of absorption temperature, absorption pressure 3MPa
2, approximately 1.5h reaches balance, the SO of absorption
2With the mol ratio of ionic liquid be 1.5.
Embodiment 22
Ionic liquid absorbs the device of sour gas with embodiment 10.At first with [TETAH] synthetic in 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 absorption unit, be placed in water bath with thermostatic control, open induction stirring, pass into CO in absorption unit
2Gas absorbs CO under 25 ℃ of absorption temperature, absorption pressure 5MPa
2, approximately 0.5h reaches balance, the CO of absorption
2With the mol ratio of ionic liquid be 2.6.
Embodiment 23
With [HEHAH] synthetic in the embodiment 4 of accurate weighing
+[PTS]
-Ion liquid dissolving is in a small amount of dehydrated alcohol, and with porous silica gel mix and blend 1h, most of ethanol is removed in evaporation afterwards, then uses 80 ℃ of dry 24h of vacuum drying oven, obtains load [HEHAH]
+[PTS]
-The solid adsorbent of ionic liquid.The device of solid adsorbent absorbing acid gases is the stainless steel encloses container that shows with pressure and temperature.Sorbent material is packed in adsorption unit, be placed in water bath with thermostatic control, pass into CO in adsorption unit
2Gas, CO absorption under 20 ℃ of adsorption temps, adsorptive pressure 1MPa
2, approximately 1h reaches balance, the CO of absorption
2With the mol ratio of ionic liquid be 3.2.
Embodiment 24
With [PEPAH] synthetic in the embodiment 6 of accurate weighing
+[BA]
-Ion liquid dissolving is in a small amount of dehydrated alcohol, and with neutral alumina mix and blend 1h, most of ethanol is removed in evaporation afterwards, then uses 80 ℃ of dry 24h of vacuum drying oven, obtains load [PEPAH]
+[BA]
-The solid adsorbent of ionic liquid.The device of solid adsorbent absorbing acid gases is the stainless steel encloses container that shows with pressure and temperature.Sorbent material is packed in adsorption unit, be placed in water bath with thermostatic control, pass into H in adsorption unit
2S gas adsorbs H under 25 ℃ of adsorption temps, adsorptive pressure 1MPa
2S, approximately 1h reaches balance, the H of absorption
2The mol ratio of S and ionic liquid is 2.2.
3. ionic liquid of the present invention absorbs the desorb after sour gas and repeats to absorb embodiment
Embodiment 25
The absorption that embodiment 11 is obtained CO
2[HEHAH]
+[PTS]
-Ionic liquid continues to be stored in absorption unit, is placed in constant temperature oil bath, opens induction stirring, the air outlet valve of opening unit, desorb CO under 80 ℃, normal pressure
2, during 15min, desorption efficiency reaches 90%, 45min desorption efficiency and reaches 98%.With desorb CO
2Ionic liquid continue to absorb CO under 15 ℃ of absorption temperature, absorption pressure 2MPa
2, desorb 45min under 80 ℃, normal pressure more afterwards.So repeat, when the 5th absorbs, the CO of absorption
2With the mol ratio of ionic liquid 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 absorption unit, is placed in 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
2The mol ratio of S and ionic liquid is 2.0.
Embodiment 27
The absorption that embodiment 17 is obtained SO
2[TEPAH]
+[NO
3]
-Ionic liquid continues to be stored in absorption unit, is placed in 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 to absorb SO under 10 ℃ of absorption temperature, absorption pressure 2MPa
2, desorb 30min under 85 ℃, normal pressure more afterwards.So repeat, when the 5th absorbs, the SO of absorption
2With the mol ratio of ionic liquid be 2.5.
Embodiment 28
The absorption that embodiment 23 is obtained CO
2Load [HEHAH]
+[PTS]
-The solid adsorbent of ionic liquid continues to be stored in adsorption unit, is placed in constant temperature oil bath, the air outlet valve of opening unit, desorption CO under 120 ℃, 30kPa
2, during 10min, desorption rate reaches 98%.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 the mol ratio of ionic liquid be 2.9.
Claims (8)
1. amino-contained ionic liquid that be used for to absorb sour gas, this ionic liquid contains one or more in primary amine, secondary amine, and this amino-contained ionic liquid mixes organic polyamine by acid-base neutralisation reacts and makes with mineral acid or organic acid;
Wherein, described organic polyamine is selected from one or more in triethylene tetramine, tetraethylene pentamine, five ethene hexamines, six ethene seven amine, polyethylene polyamine;
Described mineral acid or organic acid are selected from one in hydrochloric acid, sulfuric acid, nitric acid, tosic acid, Tetrafluoroboric acid, phenylformic acid or are multiple;
And the mole number of described organic polyamine is 1: 1～n with the ratio of mineral acid or organic acid mole number: 1, and wherein n is the number of hydrogen proton in mineral acid or organic acid molecule.
2. the synthetic method of amino-contained ionic liquid claimed in claim 1, the 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-50 ℃ to 100 ℃, and reaction pressure is not higher than 1MPa, and stirring reaction 0.5h to 10h synthesizes ionic liquid.
3. amino-contained ionic liquid claimed in claim 1 is in the application that is used for absorbing sour gas.
4. method of utilizing amino-contained ionic liquid claimed in claim 1 to absorb sour gas, the method comprising the steps of:
With the form of described amino-contained ionic liquid with pure liquid state, the aqueous solution, alcoholic solution, or load on cellular solid, or with the composite use of other absorption agent, be used for to absorb sour gas.
5. the method for utilizing amino-contained ionic liquid claimed in claim 1 to absorb sour gas according to claim 4, wherein, the absorbed sour gas of described wish 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 operating environment.
6. the method for utilizing amino-contained ionic liquid claimed in claim 1 to absorb sour gas according to claim 4, wherein, controlling absorption temperature is-20 ℃ to 50 ℃; Absorption pressure is in 10MPa.
7. the method for utilizing amino-contained ionic liquid claimed in claim 1 to absorb sour gas according to claim 6, wherein, controlling absorption temperature is 0 ℃ to 40 ℃, absorption pressure is 0.1MPa to 5MPa.
8. the described method of utilizing amino-contained ionic liquid claimed in claim 1 to absorb sour gas of according to claim 4～7 any one, the method also comprises:
After described ionic liquid absorbs sour gas, remove the step of the sour gas in ionic liquid by the mode of step-down and/or intensification; Wherein, described step-down be with Pressure Drop to 1kPa to 1MPa, described intensification is that temperature is risen to 60 ℃ to 150 ℃.
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