CN105536438A - Tertiary amine-functionalized protic ionic liquid formulated solution and preparation method and application thereof - Google Patents
Tertiary amine-functionalized protic ionic liquid formulated solution and preparation method and application thereof Download PDFInfo
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- CN105536438A CN105536438A CN201610087309.8A CN201610087309A CN105536438A CN 105536438 A CN105536438 A CN 105536438A CN 201610087309 A CN201610087309 A CN 201610087309A CN 105536438 A CN105536438 A CN 105536438A
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- 239000002608 ionic liquid Substances 0.000 title claims abstract description 80
- 238000002360 preparation method Methods 0.000 title abstract description 4
- 238000010521 absorption reaction Methods 0.000 claims abstract description 26
- 150000003512 tertiary amines Chemical group 0.000 claims abstract description 17
- 150000001768 cations Chemical class 0.000 claims abstract description 10
- 150000001450 anions Chemical class 0.000 claims abstract description 9
- 239000002131 composite material Substances 0.000 claims abstract description 8
- 239000000243 solution Substances 0.000 claims description 35
- QTBSBXVTEAMEQO-UHFFFAOYSA-N Acetic acid Chemical compound CC(O)=O QTBSBXVTEAMEQO-UHFFFAOYSA-N 0.000 claims description 24
- 238000000034 method Methods 0.000 claims description 23
- 238000006243 chemical reaction Methods 0.000 claims description 11
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 9
- 150000007524 organic acids Chemical class 0.000 claims description 8
- 125000001302 tertiary amino group Chemical group 0.000 claims description 8
- 239000007864 aqueous solution Substances 0.000 claims description 7
- 239000000126 substance Substances 0.000 claims description 7
- FERIUCNNQQJTOY-UHFFFAOYSA-N Butyric acid Chemical compound CCCC(O)=O FERIUCNNQQJTOY-UHFFFAOYSA-N 0.000 claims description 6
- IUNMPGNGSSIWFP-UHFFFAOYSA-N dimethylaminopropylamine Chemical class CN(C)CCCN IUNMPGNGSSIWFP-UHFFFAOYSA-N 0.000 claims description 6
- XBDQKXXYIPTUBI-UHFFFAOYSA-N dimethylselenoniopropionate Natural products CCC(O)=O XBDQKXXYIPTUBI-UHFFFAOYSA-N 0.000 claims description 6
- BDAGIHXWWSANSR-UHFFFAOYSA-N methanoic acid Natural products OC=O BDAGIHXWWSANSR-UHFFFAOYSA-N 0.000 claims description 6
- 125000001453 quaternary ammonium group Chemical group 0.000 claims description 6
- DILRJUIACXKSQE-UHFFFAOYSA-N n',n'-dimethylethane-1,2-diamine Chemical compound CN(C)CCN DILRJUIACXKSQE-UHFFFAOYSA-N 0.000 claims description 5
- 238000003756 stirring Methods 0.000 claims description 5
- 125000002091 cationic group Chemical group 0.000 claims description 4
- GTEXIOINCJRBIO-UHFFFAOYSA-N 2-[2-(dimethylamino)ethoxy]-n,n-dimethylethanamine Chemical compound CN(C)CCOCCN(C)C GTEXIOINCJRBIO-UHFFFAOYSA-N 0.000 claims description 3
- 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 3
- KWYHDKDOAIKMQN-UHFFFAOYSA-N N,N,N',N'-tetramethylethylenediamine Chemical compound CN(C)CCN(C)C KWYHDKDOAIKMQN-UHFFFAOYSA-N 0.000 claims description 3
- 235000011054 acetic acid Nutrition 0.000 claims description 3
- 239000002253 acid Substances 0.000 claims description 3
- 235000019253 formic acid Nutrition 0.000 claims description 3
- RMIODHQZRUFFFF-UHFFFAOYSA-N methoxyacetic acid Chemical compound COCC(O)=O RMIODHQZRUFFFF-UHFFFAOYSA-N 0.000 claims description 3
- UKODFQOELJFMII-UHFFFAOYSA-N pentamethyldiethylenetriamine Chemical compound CN(C)CCN(C)CCN(C)C UKODFQOELJFMII-UHFFFAOYSA-N 0.000 claims description 3
- 235000019260 propionic acid Nutrition 0.000 claims description 3
- 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 3
- 230000008929 regeneration Effects 0.000 abstract description 21
- 238000011069 regeneration method Methods 0.000 abstract description 21
- -1 quaternary ammonium ions Chemical class 0.000 abstract description 20
- 239000007789 gas Substances 0.000 abstract description 16
- 230000000694 effects Effects 0.000 abstract description 12
- 238000005265 energy consumption Methods 0.000 abstract description 8
- 239000002440 industrial waste Substances 0.000 abstract description 5
- 230000005588 protonation Effects 0.000 abstract 2
- 125000002924 primary amino group Chemical class [H]N([H])* 0.000 abstract 1
- 239000006193 liquid solution Substances 0.000 description 13
- 239000002994 raw material Substances 0.000 description 12
- 239000002250 absorbent Substances 0.000 description 7
- 239000007788 liquid Substances 0.000 description 7
- 230000002745 absorbent Effects 0.000 description 6
- 150000001412 amines Chemical class 0.000 description 6
- 230000015572 biosynthetic process Effects 0.000 description 6
- CRVGTESFCCXCTH-UHFFFAOYSA-N methyl diethanolamine Chemical compound OCCN(C)CCO CRVGTESFCCXCTH-UHFFFAOYSA-N 0.000 description 6
- 238000011084 recovery Methods 0.000 description 5
- 238000003786 synthesis reaction Methods 0.000 description 4
- 150000001875 compounds Chemical class 0.000 description 3
- 238000003795 desorption Methods 0.000 description 3
- 150000003141 primary amines Chemical group 0.000 description 3
- 241001044369 Amphion Species 0.000 description 2
- 239000003795 chemical substances by application Substances 0.000 description 2
- 238000005516 engineering process Methods 0.000 description 2
- 125000000524 functional group Chemical group 0.000 description 2
- 150000008040 ionic compounds Chemical class 0.000 description 2
- VNWKTOKETHGBQD-UHFFFAOYSA-N methane Chemical compound C VNWKTOKETHGBQD-UHFFFAOYSA-N 0.000 description 2
- 150000007530 organic bases Chemical class 0.000 description 2
- 230000002441 reversible effect Effects 0.000 description 2
- 229920006395 saturated elastomer Polymers 0.000 description 2
- 238000000926 separation method Methods 0.000 description 2
- 230000005945 translocation Effects 0.000 description 2
- 239000012190 activator Substances 0.000 description 1
- 125000003277 amino group Chemical group 0.000 description 1
- KGBXLFKZBHKPEV-UHFFFAOYSA-N boric acid Chemical compound OB(O)O KGBXLFKZBHKPEV-UHFFFAOYSA-N 0.000 description 1
- 239000004327 boric acid Substances 0.000 description 1
- 230000006837 decompression Effects 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 238000001704 evaporation Methods 0.000 description 1
- 230000008020 evaporation Effects 0.000 description 1
- 238000002474 experimental method Methods 0.000 description 1
- 238000009472 formulation Methods 0.000 description 1
- 230000007062 hydrolysis Effects 0.000 description 1
- 238000006460 hydrolysis reaction Methods 0.000 description 1
- 150000002460 imidazoles Chemical class 0.000 description 1
- 150000002500 ions Chemical class 0.000 description 1
- 238000012423 maintenance Methods 0.000 description 1
- 239000000463 material Substances 0.000 description 1
- 239000000203 mixture Substances 0.000 description 1
- 239000003345 natural gas Substances 0.000 description 1
- 238000006386 neutralization reaction Methods 0.000 description 1
- 239000003960 organic solvent Substances 0.000 description 1
- 150000003233 pyrroles Chemical class 0.000 description 1
- 238000004064 recycling Methods 0.000 description 1
- 230000008439 repair process Effects 0.000 description 1
- PNGLEYLFMHGIQO-UHFFFAOYSA-M sodium;3-(n-ethyl-3-methoxyanilino)-2-hydroxypropane-1-sulfonate;dihydrate Chemical compound O.O.[Na+].[O-]S(=O)(=O)CC(O)CN(CC)C1=CC=CC(OC)=C1 PNGLEYLFMHGIQO-UHFFFAOYSA-M 0.000 description 1
- 239000002904 solvent Substances 0.000 description 1
- 238000010189 synthetic method Methods 0.000 description 1
- 238000012360 testing method Methods 0.000 description 1
- 238000012546 transfer Methods 0.000 description 1
- 238000010792 warming Methods 0.000 description 1
- 239000002912 waste gas Substances 0.000 description 1
- 239000002699 waste material Substances 0.000 description 1
Classifications
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D53/00—Separation of gases or vapours; Recovering vapours of volatile solvents from gases; Chemical or biological purification of waste gases, e.g. engine exhaust gases, smoke, fumes, flue gases, aerosols
- B01D53/14—Separation of gases or vapours; Recovering vapours of volatile solvents from gases; Chemical or biological purification of waste gases, e.g. engine exhaust gases, smoke, fumes, flue gases, aerosols by absorption
- B01D53/1456—Removing acid components
- B01D53/1475—Removing carbon dioxide
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D2252/00—Absorbents, i.e. solvents and liquid materials for gas absorption
- B01D2252/30—Ionic liquids and zwitter-ions
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02A—TECHNOLOGIES FOR ADAPTATION TO CLIMATE CHANGE
- Y02A50/00—TECHNOLOGIES FOR ADAPTATION TO CLIMATE CHANGE in human health protection, e.g. against extreme weather
- Y02A50/20—Air quality improvement or preservation, e.g. vehicle emission control or emission reduction by using catalytic converters
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02C—CAPTURE, STORAGE, SEQUESTRATION OR DISPOSAL OF GREENHOUSE GASES [GHG]
- Y02C20/00—Capture or disposal of greenhouse gases
- Y02C20/40—Capture or disposal of greenhouse gases of CO2
Landscapes
- Chemical & Material Sciences (AREA)
- Engineering & Computer Science (AREA)
- Analytical Chemistry (AREA)
- General Chemical & Material Sciences (AREA)
- Oil, Petroleum & Natural Gas (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Gas Separation By Absorption (AREA)
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
Abstract
The invention provides a tertiary amine-functionalized protic ionic liquid formulated solution. The composite protic ionic liquid formulated solution contains two kinds of cations with the different structures, one kind of the cations are quaternary ammonium ions formed by performing single protonation on primary amine with a tertiary amine functional group, and the other kind of the cations are quaternary ammonium ions formed by performing single protonation on one of multiple tertiary amines, and organic acid radicals are adopted as anions. The synthesized ionic liquid formulated solution is easy to synthesize, low in cost, good in CO2 absorption effect, low in regeneration energy consumption, good in regeneration effect and very suitable for capturing CO2 contained in industrial energy resource gas and industrial waste gas. The invention further discloses a preparation method and application of the ionic liquid formulated solution.
Description
Technical field
The present invention relates to a kind of proton type ionic liquid formula solution and synthetic method thereof of tertiary amino functional and catching CO
2the application of aspect.
Background technology
Along with the aggravation gradually of Global Greenhouse Effect, catch CO
2become the significant concern point of scientists.Industrial usual employing tradition By Amine Solutions (such as MEA, DEA) absorbs CO
2.But traditional By Amine Solutions exists a series of shortcoming: volatile, raw material is caused to lose in a large number; Corrosivity is strong, causes loss to a certain degree to equipment; Easily decompose under high temperature, make it in desorption process, easily cause secondary pollution; Due to organic amine and CO
2combination evaporation latent heat that is strong and water large, the energy consumption of its desorption and regeneration is also very large etc.Therefore, researcher starts to turn to employing New Absorbent to catch CO
2.
Ionic liquid refers to the ionic compound of fusing point below 100 DEG C.What we studied usually is ionic liquid at room temperature, that is: the ionic compound be at room temperature in a liquid state.Ionic liquid at room temperature has the following advantages: vapour pressure is extremely low, not easily decomposes; Can opereating specification wide, there is good heat endurance and chemical stability; With inorganic substances, all there is good solvability to organic; Acid-base value is adjustable.Due to these advantages of ionic liquid, the amine organic solvent adopting ionic liquid to replace traditional industry use absorbs CO
2cause the common concern of scientists.In more than ten years in the past, researcher synthesize a large amount of with imidazoles, pyrroles, quaternary amine etc. for cation, tetrafluoro boric acid, hexafluorophosphoric acid etc. are anion ion liquid.These ionic liquids are to CO
2absorption be only limitted to Physical Absorption, therefore uptake has certain limitation.Scientist starts concern then can to CO
2carry out the functional ionic liquids of chemical absorbing.That is: can with CO
2on functional group's cation of being incorporated into ionic liquid of reaction or anion.Sanchez reports, when 0.1MPa, the functional ionic liquids containing a primary amine group is to CO
2uptake be 13 times of general ionic liquid.The patent CN101486661A of our seminar reports a kind of method for making of tetraalkyl quaternary ammonium type amino acid ion liquid, mentions amino acid ion liquid to CO in this patent
2there is good reversible selective absorption.The patents such as Zhejiang University CN103755639A, Denmark University of Science and Technology CN104470633A all report functional ionic liquids for absorbing CO
2advantage: functional group and CO
2carry out chemical reaction, breach the little and defect that mass transfer is slow of conventional ion liquid physics absorptive capacity.But, although functional ionic liquids is to CO
2assimilation effect excellent, it is still subject to the restriction of series of factors in commercial Application, as: cost of material is high, synthesis technique is complicated, viscosity is large, desorb energy consumption is large.
Proton type ionic liquid is by a certain percentage by acid-base neutralization Reactive Synthesis by bronsted weak acid and bronsted weak base.Because cation is the quaternary ammonium that a weak base is formed after protonated, make the overall basicity of system lower, itself and CO
2interaction force weaken, be conducive to increase its absorb CO
2reversible while also reduce the regeneration energy consumption of system.But due to CO
2sour gas, the too low maintenance that can be unfavorable for again absorptive capacity of system basicity.
Summary of the invention
The present invention makes up uptake by tertiary amine functional group of introducing extra in proton type ionic liquid structure, and this is the main innovation part of the proton type ionic liquid formula solution of the tertiary amino functional that the present invention proposes.This formula solution system directly can be synthesized by one-step method, and technique is simple; Raw materials used low price, cost is low; Itself and CO
2reversible chemical reaction can occur, uptake is high; Energy consumption needed for regenerative process is also little, and therefore it is a kind of Green absorption agent with prospects for commercial application.
The present invention is intended to proton type ionic liquid formula solution and the method for making thereof of explanation tertiary amino functional and is absorbing CO
2in application.
Technical scheme of the present invention is as follows:
A proton type ionic liquid solution for compound tertiary amino functional, it refers to the aqueous solution of the proton type ionic liquid comprising two class tertiary amino functionals, two class ionic liquids respectively: category-A: with
monoprotonated polynary tertiary aminefor cationic proton type ionic liquid; Category-B: with containing tertiary amine functional group
monoprotonated primary aminefor cationic proton type ionic liquid, the anion of two described class proton type ionic liquids is organic acid, the mol ratio of two described class ionic liquids is category-A ionic liquid: category-B ionic liquid=0.1 ~ 0.5, the concentration of the aqueous solution of described ionic liquid is the gross mass mark of contained ionic liquid, is 60 ~ 80%.
Above-mentioned composite proton type ionic liquid solution, the cation of described category-A proton type ionic liquid is tetramethylethylenediamine, 4-methyl-diaminopropane, two dimethylamino ethyl ether or pentamethyl-diethylenetriamine etc.
polynary tertiary aminein a kind of through single protonated after formed quaternary ammonium; The cation of described category-B proton type ionic liquid is that N, N-dimethyl-ethylenediamine, N, N-dimethyl-1,3-diaminopropanes etc. contain tertiary amine functional group
primary aminein a kind of through single protonated after formed quaternary ammonium; The structure of two class proton type ionic liquids is as follows respectively, wherein Y
-for anion:
Category-A proton type ionic liquid:
Category-B proton type ionic liquid:
Above-mentioned composite proton type ionic liquid solution, the organic acid that anion adopts can be the one in the acid group of formic acid, acetic acid, propionic acid, butyric acid or methoxyacetic acid.
Prepare a method for the proton type ionic liquid solution of above-mentioned compound tertiary amino functional, it can adopt one kettle way to obtain, that is: by described in N mole
polynary tertiary amine, M mole described containing tertiary amine functional group
primary aminethe reactor with stirring is put into together with water, at room temperature while stirring the mode that (N+M) mole organic acid adds with stream is added in reactor in 0.5 ~ 1.0h, continue the proton type ionic liquid solution that reaction 1 ~ 8h just can obtain described compound tertiary amino functional, wherein, M:N=0.1 ~ 0.5, and the mass fraction of water is 20 ~ 40%.After testing, two class organic bases receive organic acid H proton respectively, generate category-A and the category-B proton type ionic liquid containing tertiary amine functional group separately.
The proton type ionic liquid solution of above-mentioned compound tertiary amino functional is mainly used in CO
2absorption and separation, its process mechanism is: the structure of category-B ionic liquid (activator) is through resetting (the H proton translocation on primary amine group is on tertiary amine group) fast, and dissociate primary amine group, it and CO
2there is reversible chemical reaction, generate amphion RNH
2 +cOO
-(R represents the remainder of B), the H proton translocation on this amphion is on the tertiary amine group of category-A ionic liquid (main absorbent), and self is converted into RNHCOO
-, RNHCOO
-again with water generation hydrolysis, generate HCO
3 -and RNH
2, newly-generated RNH
2can fast Acquisition CO again
2, so repeat to absorb.Under the effect of above-mentioned mechanism, the existing good absorption CO of this solion
2capacity also has very high absorption rate, and the energy consumption of regeneration of absorption solution is also low, has a extensive future.
The proton type ionic liquid solution of above-mentioned compound tertiary amino functional can be used for CO in energy gas (as biogas, refinery gas, natural gas) and industrial waste gas
2catch.Containing the CO of 1 ~ 5% in usual energy gas
2, containing the CO of about 10 ~ 15% in industrial waste gas
2.The proton type ionic liquid solution of compound tertiary amino functional of the present invention and energy gas or industrial waste gas realize CO by counter current contacting in absorption tower
2catch.The operating pressure scope on absorption tower is 0.1 ~ 20Mpa, and operating temperature range is 20 ~ 60 DEG C.From the rich CO that tower bottom flow goes out
2absorbent carries out desorption and regeneration by the method for the decompression that heats up.Regeneration pressure scope is 10 ~ 100Kpa, and regeneration temperature range is 80 ~ 100 DEG C.Absorbent after regeneration can reuptake CO
2, realize recycling.Meanwhile, the proton type ionic liquid solution of compound tertiary amino functional of the present invention can either absorb CO as absorbent separately
2, also can further with the composite formation combination solution of the aqueous solution of the methyl diethanolamine (MDEA) of L mole, and N:L=1 ~ 10.MDEA can play the effect of category-A proton type ionic liquid equally, improves combination solution to CO
2uptake.
The proton type ionic liquid solution of the compound tertiary amino functional that the present invention proposes is to CO
2have larger uptake, and solution viscosity is little, absorption rate is large; Regeneration is easy and energy consumption is low, and compared with traditional By Amine Solutions MEA, energy consumption reduces nearly 40%; Raw material is simple and easy to get, low price; Synthesis adopts one-step method, and technique is simple.In a word, the proton type ionic liquid formula solution of this tertiary amino functional is the Green absorption agent that a class has prospects for commercial application.
Specific implementation method
Further illustrate the present invention by the following examples.
Embodiment 1: with N, N-dimethyl-ethylenediamine (Mmol), 4-methyl-diaminopropane (Nmol), acetic acid (M+Nmol), water are raw material, preparation gross mass is 20g, the gross mass mark of ionic liquid is 60% and the compound ion liquid solution of M:N=0.5 and implement its absorb CO
2application.
(i) method for making: take 8g pure water, 0.0227molN, N-dimethyl-ethylenediamine, 0.0454mol 4-methyl-diaminopropane in stirred reactor.Open stirring, 0.0681mol acetic acid is dropwise added dropwise in reactor.After being added dropwise to complete, reaction continues 8h, can obtain target product compound ion liquid solution.
(ii) CO is absorbed
2amount: get the above-mentioned compound ion liquid solution of 4g and be placed in absorption kettle, pass into CO wherein
2.At normal temperature, CO
2equilibrium partial pressure is under the condition of 0.1MPa, and its saturated absorption amount is about 0.09g (CO
2)/g (sol).
(iii) absorption rate: get the above-mentioned compound ion liquid solution of 4g, at CO
290% time used of uptake that initial pressure is that under 0.1MPa condition, system reaches capacity (balance) is 1.5min.Apparent reaction rate constant is 0.98min
-1.
(iv) regeneration effect: this composite proton type ionic liquid solution saturated absorption CO
2after, adopt the intermittent method vacuumizing and be warming up to 80 DEG C to regenerate.Recovery time is 20min.Solution after regeneration is absorbed CO again
2, its assimilation effect comparatively fresh solvent only reduces about 4%.This shows this compound ion liquid regeneration of waste liquor excellent effect, and regeneration completeness can reach 96%.Experiment proves, if increase the recovery time, regeneration completeness can reach 100%.
Embodiment 2: the raw material and the method for making that adopt embodiment 1, the gross mass mark that we have prepared ionic liquid is respectively the aqueous solution of 70%, 80%.Under normal temperature, they absorb CO
2effect list in table 1.Compare for convenience, our the results are shown in table also by embodiment 1.Wherein, n (0.1/0.1MPa) refers to that gas stagnation pressure is 0.1Mpa, CO
2when equilibrium partial pressure is 0.1Mpa, compound ion liquid solution is to CO
2saturated absorption amount; T refers to CO
2when initial pressure is 0.1MPa, compound ion liquid solution reaches capacity 90% time used of (balance) uptake; K refers to apparent reaction rate constant; Regeneration efficiency when regeneration completeness refers to that the recovery time is 20min.
Table 1. different formulations concentration is on the impact absorbed
Embodiment 3: the raw material and the method for making that adopt embodiment 1, we have prepared, and gross mass is 1000g, the gross mass mark of ionic liquid is the formula solution of 70%, wherein the ratio of the amount of substance of N, N-dimethyl-ethylenediamine (Mmol) and 4-methyl-diaminopropane (Nmol) is respectively 0.5,0.25,0.1.They are used for industrial waste gas (0.1MPa, the CO of 40 DEG C
2molar concentration is about 10%) middle CO
2absorption and separation, assimilation effect lists in table 2.N (0.01/0.1Mpa) refers to that waste gas stagnation pressure is 0.1Mpa, CO
2equilibrium partial pressure is under 0.01Mpa, and this compound ion liquid solution is to CO
2saturated absorption amount; Time used when t refers to that compound ion liquid solution reaches this Balance Absorption amount 90%; K refers to apparent reaction rate constant; Regeneration efficiency when regeneration completeness refers to that the recovery time is 20min.
The different mol ratio of table 2. two kinds of organic amines is on the impact absorbed
Embodiment 4: with N, N-dimethyl-1,3-diaminopropanes (Mmol), 4-methyl-diaminopropane (Nmol), acetic acid (M+Nmol) are raw material, preparation gross mass is 10kg, the gross mass mark of ionic liquid is 70% and the compound ion liquid solution of M:N=0.25 implement it and absorb high pressure energy gas (10MPa, the CO of 30 DEG C
2molar concentration is about 2%) middle CO
2application.
The method for making of this compound ion liquid solution is consistent with embodiment 1, and it absorbs CO in the high pressure energy gas of 30 DEG C
2effect list in table 3.Compare for convenience, we will absorb high pressure energy gas (10MPa, the CO of 30 DEG C with N, N-dimethyl-ethylenediamine, 4-methyl-diaminopropane, acetic acid is raw material, other ratio is all consistent with embodiment 4 formula solution
2molar concentration is about 2%) middle CO
2effect also list in table 3.Wherein, n (0.2/10Mpa) refers to that gas stagnation pressure is 10Mpa, CO
2when equilibrium partial pressure is 0.2MPa, compound ion liquid solution is to CO
2saturated absorption amount; Time used when t refers to that compound ion liquid solution reaches this Balance Absorption amount 90%; K refers to apparent reaction rate constant; Regeneration efficiency when regeneration completeness refers to that the recovery time is 20min.
The different promoter of table 3. (M) is on the impact absorbed
Embodiment 5: the raw material with 4-methyl-diaminopropane, two dimethylamino ethyl ether, pentamethyl-diethylenetriamine, tetramethylethylenediamine being polynary tertiary amine respectively, with N, N-dimethyl-1,3-diaminopropanes, acetic acid are together with the raw materials such as water, and the gross mass mark through Reactive Synthesis ionic liquid is the formula solution of 70%.Wherein, N, N-dimethyl-1,3-diaminopropanes is 0.25 with the ratio of the amount of substance of polynary tertiary amine.Method for making with implement it and absorb high pressure energy gas (10MPa, the CO of 30 DEG C
2molar concentration is about 2%) middle CO
2application the same manner as in Example 4.Assimilation effect lists in table 4.
The different main absorbent of table 4. is on the impact absorbed
Embodiment 5: with 4-methyl-diaminopropane (Nmol) and N, N-dimethyl-1,3-diaminopropanes (Mmol) is organic base raw material, respectively with formic acid, acetic acid, propionic acid, butyric acid and methoxyacetic acid for organic acid (N+Mmol) raw material, through reacting the aqueous solution that the gross mass mark preparing compound ion liquid is 70% and M:N=0.25, and implement its absorption normal temperature CO
2application.Method for making and absorption CO
2method is the same manner as in Example 1.Absorb CO
2effect lists in table 5.
Table 5. different anions is on the impact absorbed
Embodiment 6: by the compound ion liquid solution in embodiment 1 with the composite formation compound system of MDEA, makes main absorbent (Nmol) be respectively 10,5,1 with the ratio of the amount of substance of MDEA (Lmol).Implement this compound system and absorb normal temperature CO
2application process the same manner as in Example 1.Assimilation effect lists in table 6.
Table 6. formula solution forms compound system application with MDEA and absorbs CO
2effect
Claims (5)
1. a proton type ionic liquid solution for compound tertiary amino functional, is characterized in that: it refers to the aqueous solution of the proton type ionic liquid comprising two class tertiary amino functionals, two class ionic liquids respectively: category-A: with
simple substance the polynary tertiary amine of sonizationfor cationic proton type ionic liquid; Category-B: with containing tertiary amine functional group
monoprotonated primary aminefor cationic proton type ionic liquid, the anion of two described class proton type ionic liquids is organic acid.The mol ratio of two described class ionic liquids is category-A ionic liquid: category-B ionic liquid=0.1 ~ 0.5, and the concentration of the aqueous solution of described ionic liquid is the gross mass mark of contained ionic liquid, is 60 ~ 80%.
2. composite proton type ionic liquid solution according to claim 1, is characterized in that: the cation of described category-A proton type ionic liquid is tetramethylethylenediamine, 4-methyl-diaminopropane, two dimethylamino ethyl ether or pentamethyl-diethylenetriamine etc.
polynary tertiary aminein a kind of through single protonated after formed quaternary ammonium; The cation of described category-B proton type ionic liquid is that N, N-dimethyl-ethylenediamine, N, N-dimethyl-1,3-diaminopropanes etc. contain tertiary amine functional group
primary aminein a kind of through single protonated after formed quaternary ammonium; The structure of two class proton type ionic liquids is as follows respectively, wherein Y
-for anion:
Category-A proton type ionic liquid:
Category-B proton type ionic liquid:
3. composite proton type ionic liquid solution according to claim 1, is characterized in that: the organic acid that anion adopts is the one in the acid group of formic acid, acetic acid, propionic acid, butyric acid or methoxyacetic acid.
4. prepare a method for the proton type ionic liquid solution of compound tertiary amino functional according to claim 1, it is characterized in that: it can adopt one kettle way to obtain, that is: by described in N mole
polynary tertiary amine, M mole described containing tertiary amine functional group
primary aminethe reactor with stirring is put into together with water, at room temperature while stirring the mode that (N+M) mole organic acid adds with stream is added in reactor in 0.5 ~ 1.0h, continue the proton type ionic liquid solution that reaction 1 ~ 8h obtains described tertiary amino functional, wherein, M:N=0.1 ~ 0.5, and the mass fraction of water is 20 ~ 40%.
5. the proton type ionic liquid solution of compound tertiary amino functional according to claim 1 is at CO
2absorption, be separated in application.
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