CN112957896B - Novel aliphatic polyamine solution for capturing carbon dioxide in mixed gas and application thereof - Google Patents
Novel aliphatic polyamine solution for capturing carbon dioxide in mixed gas and application thereof Download PDFInfo
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- CURLTUGMZLYLDI-UHFFFAOYSA-N Carbon dioxide Chemical compound O=C=O CURLTUGMZLYLDI-UHFFFAOYSA-N 0.000 title claims abstract description 88
- 239000001569 carbon dioxide Substances 0.000 title claims abstract description 44
- 229910002092 carbon dioxide Inorganic materials 0.000 title claims abstract description 44
- 229920000768 polyamine Polymers 0.000 title claims abstract description 15
- 125000001931 aliphatic group Chemical group 0.000 title claims abstract description 14
- 238000003795 desorption Methods 0.000 claims abstract description 31
- 239000002250 absorbent Substances 0.000 claims abstract description 29
- 230000002745 absorbent Effects 0.000 claims abstract description 29
- 238000006243 chemical reaction Methods 0.000 claims abstract description 18
- 238000010521 absorption reaction Methods 0.000 claims abstract description 16
- RPNUMPOLZDHAAY-UHFFFAOYSA-N Diethylenetriamine Chemical compound NCCNCCN RPNUMPOLZDHAAY-UHFFFAOYSA-N 0.000 claims abstract description 12
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 11
- YMWUJEATGCHHMB-UHFFFAOYSA-N Dichloromethane Chemical compound ClCCl YMWUJEATGCHHMB-UHFFFAOYSA-N 0.000 claims description 51
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 claims description 51
- 239000000243 solution Substances 0.000 claims description 48
- 239000007789 gas Substances 0.000 claims description 30
- 125000000954 2-hydroxyethyl group Chemical group [H]C([*])([H])C([H])([H])O[H] 0.000 claims description 18
- 125000000959 isobutyl group Chemical group [H]C([H])([H])C([H])(C([H])([H])[H])C([H])([H])* 0.000 claims description 18
- 125000001449 isopropyl group Chemical group [H]C([H])([H])C([H])(*)C([H])([H])[H] 0.000 claims description 18
- 125000004108 n-butyl group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])C([H])([H])* 0.000 claims description 18
- 125000004123 n-propyl group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])* 0.000 claims description 18
- 125000001495 ethyl group Chemical group [H]C([H])([H])C([H])([H])* 0.000 claims description 17
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 claims description 17
- 150000001412 amines Chemical class 0.000 claims description 16
- 239000012074 organic phase Substances 0.000 claims description 14
- -1 biogas Substances 0.000 claims description 12
- 239000012071 phase Substances 0.000 claims description 11
- 239000005457 ice water Substances 0.000 claims description 9
- 238000003756 stirring Methods 0.000 claims description 9
- 239000008346 aqueous phase Substances 0.000 claims description 7
- 239000002904 solvent Substances 0.000 claims description 7
- 239000012047 saturated solution Substances 0.000 claims description 6
- 239000011734 sodium Substances 0.000 claims description 5
- YMDZDFSUDFLGMX-UHFFFAOYSA-N 2-chloro-n-(2-chloroethyl)ethanamine;hydron;chloride Chemical compound [Cl-].ClCC[NH2+]CCCl YMDZDFSUDFLGMX-UHFFFAOYSA-N 0.000 claims description 4
- 150000001875 compounds Chemical class 0.000 claims description 4
- VNWKTOKETHGBQD-UHFFFAOYSA-N methane Chemical compound C VNWKTOKETHGBQD-UHFFFAOYSA-N 0.000 claims description 4
- 239000000203 mixture Substances 0.000 claims description 4
- 239000000126 substance Substances 0.000 claims description 4
- UGFAIRIUMAVXCW-UHFFFAOYSA-N Carbon monoxide Chemical compound [O+]#[C-] UGFAIRIUMAVXCW-UHFFFAOYSA-N 0.000 claims description 3
- BVKZGUZCCUSVTD-UHFFFAOYSA-L Carbonate Chemical compound [O-]C([O-])=O BVKZGUZCCUSVTD-UHFFFAOYSA-L 0.000 claims description 3
- 238000005261 decarburization Methods 0.000 claims description 3
- 239000003546 flue gas Substances 0.000 claims description 3
- 239000002440 industrial waste Substances 0.000 claims description 3
- 229910000831 Steel Inorganic materials 0.000 claims description 2
- 239000004568 cement Substances 0.000 claims description 2
- 238000000354 decomposition reaction Methods 0.000 claims description 2
- 238000001035 drying Methods 0.000 claims description 2
- 239000011259 mixed solution Substances 0.000 claims description 2
- 239000003345 natural gas Substances 0.000 claims description 2
- 238000002360 preparation method Methods 0.000 claims description 2
- 238000002791 soaking Methods 0.000 claims description 2
- 239000010959 steel Substances 0.000 claims description 2
- 239000003973 paint Substances 0.000 claims 1
- 238000000034 method Methods 0.000 abstract description 12
- 125000000524 functional group Chemical group 0.000 abstract description 10
- 125000002924 primary amino group Chemical group [H]N([H])* 0.000 abstract description 8
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 abstract description 6
- 238000005265 energy consumption Methods 0.000 abstract description 6
- 125000003277 amino group Chemical group 0.000 abstract description 5
- 229910052799 carbon Inorganic materials 0.000 abstract description 5
- 125000000217 alkyl group Chemical group 0.000 abstract description 4
- 125000001570 methylene group Chemical group [H]C([H])([*:1])[*:2] 0.000 abstract description 3
- 238000006386 neutralization reaction Methods 0.000 abstract description 3
- 239000002052 molecular layer Substances 0.000 abstract description 2
- 229910052757 nitrogen Inorganic materials 0.000 description 15
- RWRDLPDLKQPQOW-UHFFFAOYSA-N Pyrrolidine Chemical compound C1CCNC1 RWRDLPDLKQPQOW-UHFFFAOYSA-N 0.000 description 6
- HEDRZPFGACZZDS-MICDWDOJSA-N Trichloro(2H)methane Chemical compound [2H]C(Cl)(Cl)Cl HEDRZPFGACZZDS-MICDWDOJSA-N 0.000 description 6
- 238000003760 magnetic stirring Methods 0.000 description 6
- 150000003335 secondary amines Chemical class 0.000 description 6
- HZAXFHJVJLSVMW-UHFFFAOYSA-N 2-Aminoethan-1-ol Chemical compound NCCO HZAXFHJVJLSVMW-UHFFFAOYSA-N 0.000 description 4
- KXDHJXZQYSOELW-UHFFFAOYSA-N carbonic acid monoamide Natural products NC(O)=O KXDHJXZQYSOELW-UHFFFAOYSA-N 0.000 description 4
- 150000003512 tertiary amines Chemical class 0.000 description 4
- 238000005160 1H NMR spectroscopy Methods 0.000 description 3
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 3
- BVCZEBOGSOYJJT-UHFFFAOYSA-N ammonium carbamate Chemical compound [NH4+].NC([O-])=O BVCZEBOGSOYJJT-UHFFFAOYSA-N 0.000 description 3
- 238000012512 characterization method Methods 0.000 description 3
- 238000005516 engineering process Methods 0.000 description 3
- ROSDSFDQCJNGOL-UHFFFAOYSA-N Dimethylamine Chemical compound CNC ROSDSFDQCJNGOL-UHFFFAOYSA-N 0.000 description 2
- ZHNUHDYFZUAESO-UHFFFAOYSA-N Formamide Chemical compound NC=O ZHNUHDYFZUAESO-UHFFFAOYSA-N 0.000 description 2
- BAVYZALUXZFZLV-UHFFFAOYSA-N Methylamine Chemical compound NC BAVYZALUXZFZLV-UHFFFAOYSA-N 0.000 description 2
- KPAMAAOTLJSEAR-UHFFFAOYSA-N [N].O=C=O Chemical compound [N].O=C=O KPAMAAOTLJSEAR-UHFFFAOYSA-N 0.000 description 2
- 239000007864 aqueous solution Substances 0.000 description 2
- 230000008901 benefit Effects 0.000 description 2
- 238000004821 distillation Methods 0.000 description 2
- 230000007613 environmental effect Effects 0.000 description 2
- 230000002779 inactivation Effects 0.000 description 2
- 239000000463 material Substances 0.000 description 2
- BDAGIHXWWSANSR-UHFFFAOYSA-N methanoic acid Natural products OC=O BDAGIHXWWSANSR-UHFFFAOYSA-N 0.000 description 2
- BYWDOHJOAPKMOF-UHFFFAOYSA-N n'-methyl-n'-[2-(methylamino)ethyl]ethane-1,2-diamine Chemical compound CNCCN(C)CCN BYWDOHJOAPKMOF-UHFFFAOYSA-N 0.000 description 2
- 238000007789 sealing Methods 0.000 description 2
- 238000000926 separation method Methods 0.000 description 2
- IMNIMPAHZVJRPE-UHFFFAOYSA-N triethylenediamine Chemical compound C1CN2CCN1CC2 IMNIMPAHZVJRPE-UHFFFAOYSA-N 0.000 description 2
- 239000002912 waste gas Substances 0.000 description 2
- KCOPAESEGCGTKM-UHFFFAOYSA-N 1,3-oxazol-4-one Chemical compound O=C1COC=N1 KCOPAESEGCGTKM-UHFFFAOYSA-N 0.000 description 1
- QBPISWMTLKTKMK-UHFFFAOYSA-N 1-[(4-aminophenyl)methyl]pyridin-2-one Chemical compound C1=CC(N)=CC=C1CN1C(=O)C=CC=C1 QBPISWMTLKTKMK-UHFFFAOYSA-N 0.000 description 1
- SDQJTWBNWQABLE-UHFFFAOYSA-N 1h-quinazoline-2,4-dione Chemical compound C1=CC=C2C(=O)NC(=O)NC2=C1 SDQJTWBNWQABLE-UHFFFAOYSA-N 0.000 description 1
- OSWFIVFLDKOXQC-UHFFFAOYSA-N 4-(3-methoxyphenyl)aniline Chemical compound COC1=CC=CC(C=2C=CC(N)=CC=2)=C1 OSWFIVFLDKOXQC-UHFFFAOYSA-N 0.000 description 1
- ATRRKUHOCOJYRX-UHFFFAOYSA-N Ammonium bicarbonate Chemical compound [NH4+].OC([O-])=O ATRRKUHOCOJYRX-UHFFFAOYSA-N 0.000 description 1
- 229910000013 Ammonium bicarbonate Inorganic materials 0.000 description 1
- KXDHJXZQYSOELW-UHFFFAOYSA-M Carbamate Chemical compound NC([O-])=O KXDHJXZQYSOELW-UHFFFAOYSA-M 0.000 description 1
- OPKOKAMJFNKNAS-UHFFFAOYSA-N N-methylethanolamine Chemical compound CNCCO OPKOKAMJFNKNAS-UHFFFAOYSA-N 0.000 description 1
- GSEJCLTVZPLZKY-UHFFFAOYSA-N Triethanolamine Chemical compound OCCN(CCO)CCO GSEJCLTVZPLZKY-UHFFFAOYSA-N 0.000 description 1
- XSQUKJJJFZCRTK-UHFFFAOYSA-N Urea Chemical compound NC(N)=O XSQUKJJJFZCRTK-UHFFFAOYSA-N 0.000 description 1
- 125000003368 amide group Chemical group 0.000 description 1
- CBTVGIZVANVGBH-UHFFFAOYSA-N aminomethyl propanol Chemical compound CC(C)(N)CO CBTVGIZVANVGBH-UHFFFAOYSA-N 0.000 description 1
- 235000012538 ammonium bicarbonate Nutrition 0.000 description 1
- 239000001099 ammonium carbonate Substances 0.000 description 1
- 239000003963 antioxidant agent Substances 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 239000004202 carbamide Substances 0.000 description 1
- 239000003575 carbonaceous material Substances 0.000 description 1
- 150000001732 carboxylic acid derivatives Chemical class 0.000 description 1
- 230000015556 catabolic process Effects 0.000 description 1
- 239000003795 chemical substances by application Substances 0.000 description 1
- 230000000052 comparative effect Effects 0.000 description 1
- 238000009833 condensation Methods 0.000 description 1
- 230000005494 condensation Effects 0.000 description 1
- 238000010276 construction Methods 0.000 description 1
- 238000005260 corrosion Methods 0.000 description 1
- 238000006731 degradation reaction Methods 0.000 description 1
- 239000008367 deionised water Substances 0.000 description 1
- 229910021641 deionized water Inorganic materials 0.000 description 1
- ZBCBWPMODOFKDW-UHFFFAOYSA-N diethanolamine Chemical compound OCCNCCO ZBCBWPMODOFKDW-UHFFFAOYSA-N 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 239000012847 fine chemical Substances 0.000 description 1
- 235000019253 formic acid Nutrition 0.000 description 1
- 238000009472 formulation Methods 0.000 description 1
- 239000002803 fossil fuel Substances 0.000 description 1
- 239000005431 greenhouse gas Substances 0.000 description 1
- 238000010438 heat treatment Methods 0.000 description 1
- 238000005984 hydrogenation reaction Methods 0.000 description 1
- 238000011065 in-situ storage Methods 0.000 description 1
- 238000009776 industrial production Methods 0.000 description 1
- 239000002608 ionic liquid Substances 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- 239000012621 metal-organic framework Substances 0.000 description 1
- CRVGTESFCCXCTH-UHFFFAOYSA-N methyl diethanolamine Chemical compound OCCN(C)CCO CRVGTESFCCXCTH-UHFFFAOYSA-N 0.000 description 1
- 230000005012 migration Effects 0.000 description 1
- 238000013508 migration Methods 0.000 description 1
- 230000003472 neutralizing effect Effects 0.000 description 1
- 125000004433 nitrogen atom Chemical group N* 0.000 description 1
- 231100000252 nontoxic Toxicity 0.000 description 1
- 230000003000 nontoxic effect Effects 0.000 description 1
- 229920000515 polycarbonate Polymers 0.000 description 1
- 239000004417 polycarbonate Substances 0.000 description 1
- 239000002994 raw material Substances 0.000 description 1
- 238000004064 recycling Methods 0.000 description 1
- 238000010992 reflux Methods 0.000 description 1
- 239000007787 solid Substances 0.000 description 1
- 238000001179 sorption measurement Methods 0.000 description 1
- 125000001424 substituent group Chemical group 0.000 description 1
- 238000003786 synthesis reaction Methods 0.000 description 1
- 238000005979 thermal decomposition reaction Methods 0.000 description 1
- KJAMZCVTJDTESW-UHFFFAOYSA-N tiracizine Chemical compound C1CC2=CC=CC=C2N(C(=O)CN(C)C)C2=CC(NC(=O)OCC)=CC=C21 KJAMZCVTJDTESW-UHFFFAOYSA-N 0.000 description 1
- 238000010792 warming Methods 0.000 description 1
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- 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
- B01D53/34—Chemical or biological purification of waste gases
- B01D53/74—General processes for purification of waste gases; Apparatus or devices specially adapted therefor
- B01D53/77—Liquid phase processes
- B01D53/78—Liquid phase processes with gas-liquid contact
-
- 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
- B01D53/34—Chemical or biological purification of waste gases
- B01D53/46—Removing components of defined structure
- B01D53/62—Carbon oxides
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D2257/00—Components to be removed
- B01D2257/50—Carbon oxides
- B01D2257/504—Carbon dioxide
-
- 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
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- 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
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- Engineering & Computer Science (AREA)
- Chemical & Material Sciences (AREA)
- Environmental & Geological Engineering (AREA)
- Health & Medical Sciences (AREA)
- Biomedical Technology (AREA)
- Analytical Chemistry (AREA)
- General Chemical & Material Sciences (AREA)
- Oil, Petroleum & Natural Gas (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Gas Separation By Absorption (AREA)
- Treating Waste Gases (AREA)
Abstract
The invention discloses a novel aliphatic polyamine solution for capturing carbon dioxide in mixed gas and application thereof, belonging to the technical field of carbon neutralization. The novel aliphatic polyamine solution comprises, by weight, 20-40 parts of a functionalized diethylenetriamine absorbent and 60-80 parts of water. According to the invention, a plurality of amino functional groups are introduced into the molecular structure of the absorbent, so that the carbon dioxide capture capacity of the absorbent is enhanced; simultaneously, the distance between every two amino functional groups is two methylene groups, so that the proton transfer efficiency between the amino groups in the absorption and desorption processes is enhanced, and the trapping capacity and the reaction rate are further improved; the number of protons contained in the amino groups is controlled by the bonded alkyl groups, so that the reaction heat of the absorbent and carbon dioxide is reduced, the desorption efficiency is improved, and the desorption energy consumption is reduced. According to the invention, through the targeted structure design of the molecular layer, on the basis of increasing the capture capacity of carbon dioxide, the desorption efficiency of the absorbent is improved and the desorption energy consumption is reduced.
Description
Technical Field
The invention belongs to the technical field of carbon neutralization, and relates to a novel aliphatic polyamine solution for capturing carbon dioxide in mixed gas and application thereof.
Background
Industrial production using fossil fuel as a main energy source emits a large amount of flue waste gas rich in carbon dioxide each year, and carbon dioxide is a main greenhouse gas causing global warming, so how to reduce carbon dioxide emission to reduce atmospheric concentration becomes a common problem facing human society at present, and governments all over the world are all dedicated to completing emission reduction tasks stipulated by paris agreement. On the other hand, carbon dioxide is a cheap, easily-obtained, non-combustible, non-toxic, harmless and renewable carbon resource, and can be catalytically converted into chemical raw materials and fine chemicals comprising carboxylic acid, urea, carbonate/polycarbonate, carbamate, oxazolinone, quinazolinedione, methanol, formic acid, formamide and the like by constructing chemical bonds such as C-C, C-N, C-O and hydrogenation reduction and other methods. Therefore, from the perspective of environmental protection and resource utilization, the method has very important research value and ecological benefit for capturing and separating carbon dioxide from flue waste gas discharged from industry, is an effective way for solving relevant environmental problems, and can provide material basis for resource utilization.
The emission of industrial waste gas rich in carbon dioxide is a main application scene of a carbon dioxide capture technology, and at present, an alcohol amine (ethanolamine, diethanolamine, triethanolamine, methylethanolamine, methyldiethanolamine, isobutanolamine and the like) solution absorption method is mainly adopted in the industry. The alcohol amine solution collects carbon dioxide into ammonium carbamate or ammonium bicarbonate, the circulating collection capacity is 6-10 wt%, and the desorption temperature is above 120 ℃ (reaction formula 1 and reaction formula 2). Although the method is mature in technology and has a certain application scale, the molecular weight of the alcohol amine absorbent is limited by low amino content, and the mass trapping capacity cannot be further improved; meanwhile, the reaction heat of the alcohol amine and the carbon dioxide is large, so that the heat release in the absorption process is severe, and the problems of high desorption temperature, thermal decomposition inactivation and the like are caused. The ethanolamine absorbent formulation for industrial use also requires the addition of certain amounts of antioxidants, anti-corrosion agents and solubilizers, and is complex in composition.
Due to the structural limitation of the traditional alcohol amine absorbent, the trapping capacity cannot be further improved, and the desorption temperature is high and is easy to thermally degrade and deactivate. Therefore, a great deal of resources are invested in the academia and industry to develop and develop a targeted novel carbon dioxide capture system, such as non-aqueous phase absorbents represented by ionic liquids, organic amines and organic solutions thereof, and solid adsorption materials represented by porous carbon materials and metal organic frameworks. However, in consideration of the current practical production situation, the water phase absorbent which is low in price and can utilize the existing carbon dioxide capture equipment is still the first choice of the industrial decarburization technology. Therefore, in order to achieve the national goal of "striving for carbon neutralization before 2060 years", it is still an urgent task to develop an aqueous phase absorbent having a higher capture capacity and lower desorption energy consumption.
Disclosure of Invention
The invention aims to provide a novel high-capacity and low-energy-consumption aliphatic polyamine solution for capturing carbon dioxide in mixed gas and application thereof, so as to solve the problems of insufficient capturing capacity, high desorption energy consumption, easy thermal degradation and inactivation and the like of the existing alcohol amine solution absorption system.
The technical scheme of the invention is as follows:
a novel efficient and energy-saving aliphatic polyamine solution for capturing carbon dioxide in mixed gas comprises, by weight, 20-40 parts of a functionalized diethylenetriamine absorbent and 60-80 parts of water, wherein diethylenetriamine in the absorbent is bonded with alkyl groups, and all amino groups contained in the absorbent are functionalized into secondary amines and tertiary amines which are alternately arranged.
The invention designs the absorbent structure on the molecular layer surface: 1) the absorbent structure contains three amino functional groups, one part of the amino functional groups directly react with carbon dioxide, the other part of the amino functional groups is used for neutralizing the carbamic acid generated in situ, and the carbon dioxide trapping capacity of the absorbent is enhanced by forming intramolecular ammonium carbamate; 2) the length of a fatty carbon chain between every two amino functional groups is controlled to be two methylene groups, so that the proton migration between adjacent amino functional groups in the carbon dioxide absorption and desorption processes is promoted, and the capture capacity and the reaction rate are further improved; 3) the amido contained in the absorbent is functionalized into alternately arranged secondary amine and tertiary amine by bonding alkyl, so that the number of protons on the nitrogen atom of the absorbent is reduced, the reaction heat of the absorbent and carbon dioxide is reduced, the desorption efficiency is improved, and the desorption energy consumption is reduced.
Further, the functionalized diethylenetriamine is one or more of compounds shown in formula (I), formula (II), formula (III), (IV) and formula (V);
wherein R is1Is methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl or 2-hydroxyethyl;
R2is methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl or 2-hydroxyethyl;
R3is methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl or 2-hydroxyethyl;
R4is methylEthyl, n-propyl, isopropyl, n-butyl, isobutyl or 2-hydroxyethyl;
R5is methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl or 2-hydroxyethyl;
R6is methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl or 2-hydroxyethyl;
R7is methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl or 2-hydroxyethyl;
R8is methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl, 2-hydroxyethyl or a proton;
R9is methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl, 2-hydroxyethyl or a proton.
The preparation method of the functionalized diethylenetriamine absorbent comprises the following steps:
s1, adding the bis (2-chloroethyl) amine hydrochloride (component 1) containing the corresponding functional group and the amine or amine solution (component 2) containing the corresponding functional group into a high-pressure reaction kettle in sequence, and reacting for 12 hours at the temperature of 80-90 ℃; the molar ratio of the component 1 to the component 2 is 1: 5-30;
s2, soaking the autoclave in an ice-water bath for 1h, transferring the reaction mixed solution to a beaker cooled in the ice-water bath, adding NaOH in batches under stirring, wherein the molar ratio of the added NaOH to the component 1 is 10.4; stirring the solution for 30min, transferring the solution into a separating funnel, and standing, wherein a milky NaOH saturated solution phase (lower layer) and a light yellow aqueous organic phase (upper layer) are gradually clear;
s3, collecting a light yellow water-containing organic phase, adding a sodium hydroxide solution, stirring at room temperature for 1h, and then transferring to a separating funnel to stand for layering; the lower aqueous phase was discharged, the upper, pale yellow aqueous organic phase was extracted with dichloromethane, the dichloromethane phases were combined and anhydrous Na was used2SO4Drying overnight, removing the solvent dichloromethane by using a rotary evaporator, and then carrying out reduced pressure distillation to obtain one of the compounds shown in the formula (I), the formula (II), the formula (III), (IV) and the formula (V), wherein the yield is 40-80%.
In the step S3, the volume of the added sodium hydroxide solution is 200mL, and the mass fraction is 30-50 wt%; the amount of dichloromethane used was 150 mL. times.3.
The novel aliphatic polyamine solution is applied to decarburization treatment of carbon dioxide-containing industrial waste gas such as power plant flue gas, refinery tail gas, steel plant tail gas, cement plant tail gas, chemical plant tail gas, water gas, biogas, natural gas and carbonate ore decomposition gas;
further, the use conditions of the novel aliphatic polyamine solution are as follows: the pressure of flue gas is 0.01-0.05 MPa, the absorption temperature is 30.0-60.0 ℃, the absorption time is 0.1-0.8 h, the desorption temperature is 80-130 ℃, and the desorption time is 0.1-0.8 h.
The invention has the beneficial effects that:
compared with the traditional alcohol amine solution absorption method, the invention adopts a brand-new absorbent structure design concept and has the following excellent performance; 1) secondary amine functional groups and tertiary functional groups are alternately introduced at the molecular level to serve as reaction sites for trapping carbon dioxide, the carbon dioxide is trapped in the form of intramolecular ammonium carbamate, the capacity is greatly improved, and the maximum content can reach 14.1 wt% within 100 min; 2) the amino groups contained in the absorbent are all functionalized into secondary amine and tertiary amine which are alternately arranged by bonding alkyl substituent groups so as to reduce the number of N-H bonds and control the length of a fatty carbon chain between the amino groups to be two methylene groups, so that the temperature rise of the solution in the absorption process is controlled to be below 8 ℃, the desorption efficiency of carbon dioxide is obviously improved, and the absorbent with each structure can desorb and release more than 80 percent of captured carbon dioxide within 30min under the condition that the heating temperature is 130 ℃.
Taking 100g of bis (2-N, N-dimethylaminoethyl) amine solution with the mass fraction of 25% as an example, the advantages of the solution comprise:
(1) the absorption mass percentage of carbon dioxide of the bis (2-N, N-dimethylaminoethyl) amine solution at 40 ℃ and 0.1atm for 100min is 14.1 percent, the absorption mass percentage at 30min is 11.8 percent, and the maximum temperature rise of the solution in the absorption process is only 5 ℃.
(2) The bis (2-N, N-dimethylaminoethyl) amine solution can realize complete desorption of carbon dioxide within 100min at 130 ℃, and the desorption percentage of the solution in 30min is up to 84%.
(3) While 100g of triethylene diamine solution with the mass fraction of 25% has great heat release in the absorption process under the same condition, and the maximum temperature rise of the solution reaches 15 ℃; and the complete desorption of carbon dioxide can not be realized within 100min under the condition of 130 ℃ (the desorption percentage is 68 percent), and the desorption percentage at 30min is only 46 percent.
Detailed Description
The present invention will be described in further detail with reference to the attached tables and specific examples.
Example 1
Synthesis of N, N' -trimethyldiethylenetriamine
Bis (2-chloroethyl) methylamine hydrochloride (240mmol, 46.21g) and methylamine aqueous solution (40 wt%, 280mL) are sequentially added into a 500mL autoclave, and after sealing, the mixture is reacted in an oil bath (80 ℃) for 12 hours, and the magnetic stirring speed is 800 r/min. After the reaction, the autoclave was immersed in an ice-water bath for 1 hour, and then the reaction solution was transferred to a 1L beaker cooled in an ice-water bath, and NaOH (100g) was added in portions under magnetic stirring (1000 r/min). After the solution is stirred for 30min, the solution is completely transferred into a 500mL separating funnel and stands still, and a milky white NaOH saturated solution phase (lower layer) and a light yellow aqueous organic phase (upper layer) are gradually clear. The light yellow aqueous organic phase was collected in a 500mL beaker, 200mL of sodium hydroxide solution (30 wt%) was added, stirred at room temperature for 1h and then transferred to a 500mL separatory funnel and allowed to stand for separation. After the lower aqueous phase was discharged, the upper pale yellow aqueous organic phase was extracted with dichloromethane (150 mL. times.3), and the dichloromethane phases were combined and anhydrous Na was used2SO4Dry overnight. The solvent dichloromethane is cleaned by a rotary evaporator, and then is distilled under reduced pressure to obtain N, N' -trimethyl diethylenetriamine (101-105 ℃, 20mm Hg), wherein the yield is 43%. Nuclear magnetic characterization data:1H NMR(400MHz,CDCl3)δ＝2.21(s,3H),2.43(s,6H),2.48(t,J＝5.6Hz,4H),2.64(t,J＝6.0Hz,4H)。
example 2
Bis (2-N, N-dimethylaminoethyl) amine
Adding bis (2-chloroethyl) amine hydrochloride (240mmol, 42.84g) and dimethylamine aqueous solution (33 wt%, 280mL) into a 500mL high-pressure reaction kettle in sequence, sealing, and reacting in an oil bath (80 ℃) for 12h (the pressure is about 2-3 atm in the process), wherein the magnetic stirring speed is 800 r/min. After the reaction, the autoclave was immersed in an ice-water bath for 1 hour, and then the reaction solution was transferred to a 1L beaker cooled in an ice-water bath, and NaOH (100g) was added in portions under magnetic stirring (1000 r/min). After the solution is stirred for 30min, the solution is completely transferred into a 500mL separating funnel and stands still, and a milky white NaOH saturated solution phase (lower layer) and a light yellow aqueous organic phase (upper layer) are gradually clear. The light yellow aqueous organic phase was collected in a 500mL beaker, 200mL of sodium hydroxide solution (30 wt%) was added, stirred at room temperature for 1h and then transferred to a 500mL separatory funnel and allowed to stand for separation. After the lower aqueous phase was discharged, the upper pale yellow aqueous organic phase was extracted with dichloromethane (150 mL. times.3), and the dichloromethane phases were combined and anhydrous Na was used2SO4Dry overnight. After a rotary evaporator is used for removing the solvent dichloromethane, the solvent dichloromethane is distilled under reduced pressure to obtain bis (2-N, N-dimethylaminoethyl) amine (108-111 ℃ and 20mm Hg), and the yield is 48%. Nuclear magnetic characterization data:1H NMR(400MHz,CDCl3)δ＝2.19(s,12H),2.39(t,J＝6.0Hz,4H),2.67(t,J＝6.4Hz,4H).
example 3
Bis (2- (1-tetrahydropyrrolyl) ethyl) amine
Bis (2-chloroethyl) amine hydrochloride (240mmol, 42.84g), tetrahydropyrrole (1200mmol, 85.35g) and water (150mL) were added in this order to a 500mL single-neck flask and reacted for 12h in an oil bath (90 ℃) with magnetic stirring at 800r/min under reflux condensation. After the reaction was complete, the solution was transferred to a 1L beaker cooled in an ice-water bath and NaOH (100g) was added in portions under magnetic stirring (1000 r/min). Stirring for 30min, transferring toAfter standing in a 500mL separating funnel, the milky white NaOH saturated solution phase (lower layer) and the pale yellow aqueous organic phase (upper layer) became gradually clear. After the lower aqueous phase was discharged, the upper pale yellow aqueous organic phase was extracted with dichloromethane (150 mL. times.3), and the dichloromethane phases were combined and anhydrous Na was used2SO4Dry overnight. And (3) removing the solvent dichloromethane and redundant pyrrolidine by using a rotary evaporator, and then carrying out reduced pressure distillation to obtain the product bis (2- (1-pyrrolyl) ethyl) amine (114-118 ℃ and 2mm Hg), wherein the yield is 64%. Nuclear magnetic characterization data:1H NMR(400MHz,CDCl3)δ＝1.74-1.76(m,8H),2.48-2.50(m,8H),2.59(t,J＝4.4Hz,4H),2.75(t,J＝4.0Hz,4H).
example 4
Adding 25g of bis (2-N, N-dimethylaminoethyl) amine and 75g of deionized water into a 250mL round-bottom flask in sequence, stirring uniformly, then slowly introducing carbon dioxide-nitrogen mixed gas with the carbon dioxide content of 15%, wherein the flow is 100mL/min, the pressure is 0.1MPa, the oil bath temperature is controlled to be 40 ℃, and the gas inlet flow and the gas outlet flow are recorded in real time by using a gas flowmeter. The absorption mass percentage of carbon dioxide of the bis (2-N, N-dimethylaminoethyl) amine solution is 14.1 percent at 100min and 11.8 percent at 30 min.
Example 5
In a similar manner to example 4, the structure of the functionalized diethylenetriamine was changed while controlling the flow rate of the carbon dioxide-nitrogen mixed gas to 100mL/min, the pressure to 0.1MPa, and the oil bath temperature to 40 ℃, and the carbon dioxide capturing performance at 40 ℃ for 100min and 30min was obtained as shown in the following Table (Table 1).
TABLE 1 carbon dioxide Capture Performance of functionalized diethylenetriamine solutions
Example 6
100g of a carbon dioxide absorbing saturated solution of bis (2-N, N-dimethylaminoethyl) amine from example 4 was charged into a 250mL round bottom flask, and the temperature of the oil bath was raised to 130 ℃ with stirring, and the flow of inlet and outlet gases was recorded in real time with a gas flow meter. The desorption percentage of carbon dioxide of the solution of bis (2-N, N-dimethylaminoethyl) amine at 100min is 100%, and the desorption percentage at 30min is 84%.
Example 7
Similarly to example 6, the oil bath temperature was controlled to 130 ℃, the structure of the functionalized diethylenetriamine was changed, and the desorption performance of carbon dioxide at 100min and 30min under 130 conditions was obtained as shown in the following table (table 2). Wherein, the structure (N, N' -dimethyldiethylenetriamine) shown in the sequence number 6 is not in the structure range described in the patent and is only shown as a comparative desorption effect. Experimental results show that the absorbent structure construction strategy of secondary amine and tertiary amine alternate configuration that this patent provided can effectively promote absorbent desorption efficiency: all the absorbents (taking serial numbers 1-5 as examples) can realize complete desorption within 100min, and the desorption percentage at 30min can also reach more than 80%; the N, N' -dimethyldiethylenetriamine (serial number 6) with the inverse secondary amine series structure can not be completely desorbed, and the recycling performance is poor.
Table 2 carbon dioxide desorption performance of functionalized diethylenetriamine solution
The above examples are only some of the specific embodiments of the present invention. Obviously, there are many variations to the described embodiments of the present invention, and therefore all variations which may be derived directly or indirectly from the disclosure herein by a person skilled in the art are to be considered within the scope of the present invention.
Claims (4)
1. A novel aliphatic polyamine solution for capturing carbon dioxide in mixed gas is characterized in that: the water-based paint comprises, by weight, 20-40 parts of a functionalized diethylenetriamine absorbent and 60-80 parts of water; the functionalized diethylenetriamine is one or more of compounds shown in formula (I), formula (II), formula (III), (IV) and formula (V);
wherein R is1Is methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl or 2-hydroxyethyl;
R2is methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl or 2-hydroxyethyl;
R3is methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl or 2-hydroxyethyl;
R4is methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl or 2-hydroxyethyl;
R5is methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl or 2-hydroxyethyl;
R6is methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl or 2-hydroxyethyl;
R7is methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl or 2-hydroxyethyl;
R8is methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl, 2-hydroxyethyl or a proton;
R9is methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl, 2-hydroxyethyl or a proton.
2. The novel fatty polyamine solution of claim 1, wherein: the preparation method of the functionalized diethylenetriamine absorbent comprises the following steps:
s1, adding the bis (2-chloroethyl) amine hydrochloride containing the corresponding function as a component 1 and the amine or amine solution containing the corresponding function as a component 2 into a high-pressure reaction kettle in sequence, and reacting for 12 hours at the temperature of 80-90 ℃; the molar ratio of the component 1 to the component 2 is 1: 5-30;
s2, soaking the autoclave in an ice-water bath for 1h, transferring the reaction mixed solution to a beaker cooled in the ice-water bath, adding NaOH in batches under stirring, wherein the molar ratio of the added NaOH to the component 1 is 10.4; stirring the solution for 30min, then transferring the solution into a separating funnel, and standing, wherein a milky NaOH saturated solution phase and a light yellow aqueous organic phase are gradually clear;
s3, collecting a light yellow water-containing organic phase, adding a sodium hydroxide solution, stirring at room temperature for 1h, and then transferring to a separating funnel to stand for layering; the lower aqueous phase was discharged, the upper, pale yellow aqueous organic phase was extracted with dichloromethane, the dichloromethane phases were combined and anhydrous Na was used2SO4Drying overnight, removing solvent dichloromethane with rotary evaporator, and distilling under reduced pressure to obtain one of compounds shown in formula (I), formula (II), formula (III), (IV) and formula (V).
3. Use of a novel aliphatic polyamine solution according to claim 1 or 2 for capturing carbon dioxide in a gas mixture, characterized in that: the novel aliphatic polyamine solution is applied to decarburization treatment of industrial waste gas containing carbon dioxide in power plant flue gas, refinery tail gas, steel plant tail gas, cement plant tail gas, chemical plant tail gas, water gas, biogas, natural gas and carbonate ore decomposition gas.
4. Use of the novel aliphatic polyamine solution according to claim 3 for capturing carbon dioxide in mixed gases, characterized in that: the novel aliphatic polyamine solution is used under the following conditions: the pressure of the mixed gas is 0.01-0.05 MPa, the absorption temperature is 30.0-60.0 ℃, the absorption time is 0.1-0.8 h, the desorption temperature is 80-130 ℃, and the desorption time is 0.1-0.8 h.
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