CN113477052B - Aminoethylated piperazine, preparation method thereof, carbon dioxide absorbent and application thereof - Google Patents
Aminoethylated piperazine, preparation method thereof, carbon dioxide absorbent and application thereof Download PDFInfo
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- CN113477052B CN113477052B CN202110799940.1A CN202110799940A CN113477052B CN 113477052 B CN113477052 B CN 113477052B CN 202110799940 A CN202110799940 A CN 202110799940A CN 113477052 B CN113477052 B CN 113477052B
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- piperazine
- carbon dioxide
- amine
- methyl
- butyl
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- 238000002360 preparation method Methods 0.000 title claims abstract description 28
- 150000004885 piperazines Chemical class 0.000 title claims abstract description 13
- CURLTUGMZLYLDI-UHFFFAOYSA-N Carbon dioxide Chemical compound O=C=O CURLTUGMZLYLDI-UHFFFAOYSA-N 0.000 title abstract description 112
- 239000001569 carbon dioxide Substances 0.000 title abstract description 56
- 229910002092 carbon dioxide Inorganic materials 0.000 title abstract description 56
- 239000002250 absorbent Substances 0.000 title abstract description 31
- 230000002745 absorbent Effects 0.000 title abstract description 31
- -1 amine ethylated piperazine Chemical class 0.000 claims abstract description 103
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 50
- 238000000034 method Methods 0.000 claims abstract description 21
- GLUUGHFHXGJENI-UHFFFAOYSA-N Piperazine Chemical compound C1CNCCN1 GLUUGHFHXGJENI-UHFFFAOYSA-N 0.000 claims abstract description 18
- 125000000217 alkyl group Chemical group 0.000 claims abstract description 7
- 125000001449 isopropyl group Chemical group [H]C([H])([H])C([H])(*)C([H])([H])[H] 0.000 claims description 58
- 125000004123 n-propyl group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])* 0.000 claims description 58
- 125000004108 n-butyl group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])C([H])([H])* 0.000 claims description 52
- 125000001495 ethyl group Chemical group [H]C([H])([H])C([H])([H])* 0.000 claims description 51
- 125000000959 isobutyl group Chemical group [H]C([H])([H])C([H])(C([H])([H])[H])C([H])([H])* 0.000 claims description 50
- 238000006467 substitution reaction Methods 0.000 claims description 34
- 238000002156 mixing Methods 0.000 claims description 32
- 125000004178 (C1-C4) alkyl group Chemical group 0.000 claims description 23
- BAVYZALUXZFZLV-UHFFFAOYSA-N Methylamine Chemical compound NC BAVYZALUXZFZLV-UHFFFAOYSA-N 0.000 claims description 20
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 claims description 16
- 229940125904 compound 1 Drugs 0.000 claims description 13
- 229940126214 compound 3 Drugs 0.000 claims description 12
- FIIZQHKGJMRJIL-UHFFFAOYSA-N n,3-diphenylprop-2-enamide Chemical compound C=1C=CC=CC=1C=CC(=O)NC1=CC=CC=C1 FIIZQHKGJMRJIL-UHFFFAOYSA-N 0.000 claims description 9
- 229940125782 compound 2 Drugs 0.000 claims description 8
- 150000001875 compounds Chemical class 0.000 claims description 8
- 238000006243 chemical reaction Methods 0.000 abstract description 28
- 238000003795 desorption Methods 0.000 abstract description 19
- 229910052757 nitrogen Inorganic materials 0.000 abstract description 12
- 238000010521 absorption reaction Methods 0.000 abstract description 8
- IMUDHTPIFIBORV-UHFFFAOYSA-N aminoethylpiperazine Chemical compound NCCN1CCNCC1 IMUDHTPIFIBORV-UHFFFAOYSA-N 0.000 abstract description 5
- 125000004122 cyclic group Chemical group 0.000 abstract description 4
- 238000005265 energy consumption Methods 0.000 abstract description 4
- 125000004433 nitrogen atom Chemical group N* 0.000 abstract description 4
- 125000004193 piperazinyl group Chemical group 0.000 abstract description 4
- 230000015556 catabolic process Effects 0.000 abstract description 3
- 238000006731 degradation reaction Methods 0.000 abstract description 3
- 238000010438 heat treatment Methods 0.000 abstract description 3
- 238000007344 nucleophilic reaction Methods 0.000 abstract description 3
- 150000003512 tertiary amines Chemical class 0.000 abstract description 3
- 125000000022 2-aminoethyl group Chemical group [H]C([*])([H])C([H])([H])N([H])[H] 0.000 abstract description 2
- YMWUJEATGCHHMB-UHFFFAOYSA-N Dichloromethane Chemical compound ClCCl YMWUJEATGCHHMB-UHFFFAOYSA-N 0.000 description 114
- HEMHJVSKTPXQMS-UHFFFAOYSA-M sodium hydroxide Inorganic materials [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 42
- 238000003756 stirring Methods 0.000 description 37
- 239000005457 ice water Substances 0.000 description 26
- 239000002904 solvent Substances 0.000 description 26
- 239000003153 chemical reaction reagent Substances 0.000 description 25
- 239000007789 gas Substances 0.000 description 24
- 239000000243 solution Substances 0.000 description 24
- 239000011259 mixed solution Substances 0.000 description 21
- 239000012074 organic phase Substances 0.000 description 20
- 239000012071 phase Substances 0.000 description 20
- 239000003795 chemical substances by application Substances 0.000 description 15
- 238000005660 chlorination reaction Methods 0.000 description 15
- 238000001035 drying Methods 0.000 description 15
- HEDRZPFGACZZDS-MICDWDOJSA-N Trichloro(2H)methane Chemical compound [2H]C(Cl)(Cl)Cl HEDRZPFGACZZDS-MICDWDOJSA-N 0.000 description 14
- FYSNRJHAOHDILO-UHFFFAOYSA-N thionyl chloride Chemical compound ClS(Cl)=O FYSNRJHAOHDILO-UHFFFAOYSA-N 0.000 description 14
- 238000007599 discharging Methods 0.000 description 13
- 238000000605 extraction Methods 0.000 description 13
- 238000001816 cooling Methods 0.000 description 12
- GSEJCLTVZPLZKY-UHFFFAOYSA-N Triethanolamine Chemical compound OCCN(CCO)CCO GSEJCLTVZPLZKY-UHFFFAOYSA-N 0.000 description 10
- 239000007864 aqueous solution Substances 0.000 description 10
- 238000002791 soaking Methods 0.000 description 10
- ZMANZCXQSJIPKH-UHFFFAOYSA-N Triethylamine Chemical compound CCN(CC)CC ZMANZCXQSJIPKH-UHFFFAOYSA-N 0.000 description 9
- 229940125898 compound 5 Drugs 0.000 description 9
- 238000003760 magnetic stirring Methods 0.000 description 8
- 239000000126 substance Substances 0.000 description 8
- 238000005160 1H NMR spectroscopy Methods 0.000 description 7
- 230000015572 biosynthetic process Effects 0.000 description 7
- 238000009835 boiling Methods 0.000 description 7
- 238000012512 characterization method Methods 0.000 description 7
- 230000000052 comparative effect Effects 0.000 description 7
- 239000002994 raw material Substances 0.000 description 7
- 238000003786 synthesis reaction Methods 0.000 description 7
- XIBJAEUNYGEDAU-UHFFFAOYSA-N 1-(2-chloroethyl)piperazine;hydrochloride Chemical compound Cl.ClCCN1CCNCC1 XIBJAEUNYGEDAU-UHFFFAOYSA-N 0.000 description 6
- HEDRZPFGACZZDS-UHFFFAOYSA-N Chloroform Chemical compound ClC(Cl)Cl HEDRZPFGACZZDS-UHFFFAOYSA-N 0.000 description 6
- CDBYLPFSWZWCQE-UHFFFAOYSA-L Sodium Carbonate Chemical compound [Na+].[Na+].[O-]C([O-])=O CDBYLPFSWZWCQE-UHFFFAOYSA-L 0.000 description 6
- 150000001412 amines Chemical class 0.000 description 6
- 239000012320 chlorinating reagent Substances 0.000 description 6
- 239000002274 desiccant Substances 0.000 description 6
- 238000004821 distillation Methods 0.000 description 6
- 238000012360 testing method Methods 0.000 description 6
- 239000007832 Na2SO4 Substances 0.000 description 5
- 239000003960 organic solvent Substances 0.000 description 5
- 229910052938 sodium sulfate Inorganic materials 0.000 description 5
- HZAXFHJVJLSVMW-UHFFFAOYSA-N 2-Aminoethan-1-ol Chemical compound NCCO HZAXFHJVJLSVMW-UHFFFAOYSA-N 0.000 description 4
- UGFAIRIUMAVXCW-UHFFFAOYSA-N Carbon monoxide Chemical compound [O+]#[C-] UGFAIRIUMAVXCW-UHFFFAOYSA-N 0.000 description 4
- 239000003546 flue gas Substances 0.000 description 4
- VNWKTOKETHGBQD-UHFFFAOYSA-N methane Chemical compound C VNWKTOKETHGBQD-UHFFFAOYSA-N 0.000 description 4
- 239000000203 mixture Substances 0.000 description 4
- BTLPDHQFRXFTBR-UHFFFAOYSA-N n-ethyl-2-piperazin-1-ylethanamine Chemical compound CCNCCN1CCNCC1 BTLPDHQFRXFTBR-UHFFFAOYSA-N 0.000 description 4
- HDSZRJMNBCRATE-UHFFFAOYSA-N n-methyl-2-piperazin-1-ylethanamine Chemical compound CNCCN1CCNCC1 HDSZRJMNBCRATE-UHFFFAOYSA-N 0.000 description 4
- 238000010992 reflux Methods 0.000 description 4
- 238000007789 sealing Methods 0.000 description 4
- 238000000967 suction filtration Methods 0.000 description 4
- WFCSWCVEJLETKA-UHFFFAOYSA-N 2-piperazin-1-ylethanol Chemical compound OCCN1CCNCC1 WFCSWCVEJLETKA-UHFFFAOYSA-N 0.000 description 3
- BVKZGUZCCUSVTD-UHFFFAOYSA-L Carbonate Chemical compound [O-]C([O-])=O BVKZGUZCCUSVTD-UHFFFAOYSA-L 0.000 description 3
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 3
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 3
- PMZURENOXWZQFD-UHFFFAOYSA-L Sodium Sulfate Chemical group [Na+].[Na+].[O-]S([O-])(=O)=O PMZURENOXWZQFD-UHFFFAOYSA-L 0.000 description 3
- 239000003463 adsorbent Substances 0.000 description 3
- 239000008346 aqueous phase Substances 0.000 description 3
- 230000008901 benefit Effects 0.000 description 3
- 229910052799 carbon Inorganic materials 0.000 description 3
- 230000000694 effects Effects 0.000 description 3
- NNGMSZSNODTRTA-UHFFFAOYSA-N n-ethyl-2-[4-[2-(ethylamino)ethyl]piperazin-1-yl]ethanamine Chemical compound CCNCCN1CCN(CCNCC)CC1 NNGMSZSNODTRTA-UHFFFAOYSA-N 0.000 description 3
- LZEBHQQBLHMJOG-UHFFFAOYSA-N n-methyl-2-(4-methylpiperazin-1-yl)ethanamine Chemical compound CNCCN1CCN(C)CC1 LZEBHQQBLHMJOG-UHFFFAOYSA-N 0.000 description 3
- MJLJCXIJHSVEOY-UHFFFAOYSA-N n-methyl-2-[4-[2-(methylamino)ethyl]piperazin-1-yl]ethanamine Chemical compound CNCCN1CCN(CCNC)CC1 MJLJCXIJHSVEOY-UHFFFAOYSA-N 0.000 description 3
- BWHMMNNQKKPAPP-UHFFFAOYSA-L potassium carbonate Substances [K+].[K+].[O-]C([O-])=O BWHMMNNQKKPAPP-UHFFFAOYSA-L 0.000 description 3
- 229910000027 potassium carbonate Inorganic materials 0.000 description 3
- 239000011734 sodium Substances 0.000 description 3
- 229910000029 sodium carbonate Inorganic materials 0.000 description 3
- 239000002912 waste gas Substances 0.000 description 3
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 2
- IAZDPXIOMUYVGZ-UHFFFAOYSA-N Dimethylsulphoxide Chemical compound CS(C)=O IAZDPXIOMUYVGZ-UHFFFAOYSA-N 0.000 description 2
- QUSNBJAOOMFDIB-UHFFFAOYSA-N Ethylamine Chemical compound CCN QUSNBJAOOMFDIB-UHFFFAOYSA-N 0.000 description 2
- ZHNUHDYFZUAESO-UHFFFAOYSA-N Formamide Chemical compound NC=O ZHNUHDYFZUAESO-UHFFFAOYSA-N 0.000 description 2
- 229910000831 Steel Inorganic materials 0.000 description 2
- 238000003556 assay Methods 0.000 description 2
- 125000000484 butyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 description 2
- 239000004568 cement Substances 0.000 description 2
- 238000000354 decomposition reaction Methods 0.000 description 2
- 238000005034 decoration Methods 0.000 description 2
- 230000007613 environmental effect Effects 0.000 description 2
- 238000009776 industrial production Methods 0.000 description 2
- BDAGIHXWWSANSR-UHFFFAOYSA-N methanoic acid Natural products OC=O BDAGIHXWWSANSR-UHFFFAOYSA-N 0.000 description 2
- 238000012986 modification Methods 0.000 description 2
- 230000004048 modification Effects 0.000 description 2
- 239000003345 natural gas Substances 0.000 description 2
- 238000011056 performance test Methods 0.000 description 2
- XHXFXVLFKHQFAL-UHFFFAOYSA-N phosphoryl trichloride Chemical compound ClP(Cl)(Cl)=O XHXFXVLFKHQFAL-UHFFFAOYSA-N 0.000 description 2
- WGYKZJWCGVVSQN-UHFFFAOYSA-N propylamine Chemical compound CCCN WGYKZJWCGVVSQN-UHFFFAOYSA-N 0.000 description 2
- 230000035484 reaction time Effects 0.000 description 2
- 239000007787 solid Substances 0.000 description 2
- 239000010959 steel 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
- 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
- FGSHJLJPYBUBHO-UHFFFAOYSA-N 2-chloroethyl(methyl)azanium;chloride Chemical compound [Cl-].C[NH2+]CCCl FGSHJLJPYBUBHO-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
- 239000012359 Methanesulfonyl chloride Substances 0.000 description 1
- OPKOKAMJFNKNAS-UHFFFAOYSA-N N-methylethanolamine Chemical compound CNCCO OPKOKAMJFNKNAS-UHFFFAOYSA-N 0.000 description 1
- 238000005481 NMR spectroscopy Methods 0.000 description 1
- XSQUKJJJFZCRTK-UHFFFAOYSA-N Urea Chemical compound NC(N)=O XSQUKJJJFZCRTK-UHFFFAOYSA-N 0.000 description 1
- KPAMAAOTLJSEAR-UHFFFAOYSA-N [N].O=C=O Chemical compound [N].O=C=O KPAMAAOTLJSEAR-UHFFFAOYSA-N 0.000 description 1
- 150000001335 aliphatic alkanes Chemical class 0.000 description 1
- 150000001348 alkyl chlorides Chemical group 0.000 description 1
- 125000003277 amino 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
- BVCZEBOGSOYJJT-UHFFFAOYSA-N ammonium carbamate Chemical compound [NH4+].NC([O-])=O BVCZEBOGSOYJJT-UHFFFAOYSA-N 0.000 description 1
- 239000001099 ammonium carbonate Substances 0.000 description 1
- 239000004202 carbamide Substances 0.000 description 1
- KXDHJXZQYSOELW-UHFFFAOYSA-N carbonic acid monoamide Natural products NC(O)=O KXDHJXZQYSOELW-UHFFFAOYSA-N 0.000 description 1
- 150000001732 carboxylic acid derivatives Chemical class 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
- 238000005516 engineering process Methods 0.000 description 1
- 238000001704 evaporation Methods 0.000 description 1
- 239000012847 fine chemical Substances 0.000 description 1
- 235000019253 formic acid Nutrition 0.000 description 1
- 239000002803 fossil fuel Substances 0.000 description 1
- 238000004817 gas chromatography Methods 0.000 description 1
- 239000005431 greenhouse gas Substances 0.000 description 1
- OAKJQQAXSVQMHS-UHFFFAOYSA-N hydrazine Substances NN OAKJQQAXSVQMHS-UHFFFAOYSA-N 0.000 description 1
- 238000005984 hydrogenation reaction Methods 0.000 description 1
- 230000002779 inactivation Effects 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- 239000000463 material Substances 0.000 description 1
- QARBMVPHQWIHKH-UHFFFAOYSA-N methanesulfonyl chloride Chemical compound CS(Cl)(=O)=O QARBMVPHQWIHKH-UHFFFAOYSA-N 0.000 description 1
- CRVGTESFCCXCTH-UHFFFAOYSA-N methyl diethanolamine Chemical compound OCCN(C)CCO CRVGTESFCCXCTH-UHFFFAOYSA-N 0.000 description 1
- 239000012046 mixed solvent Substances 0.000 description 1
- 239000002052 molecular layer Substances 0.000 description 1
- 231100000252 nontoxic Toxicity 0.000 description 1
- 230000003000 nontoxic effect Effects 0.000 description 1
- AICOOMRHRUFYCM-ZRRPKQBOSA-N oxazine, 1 Chemical compound C([C@@H]1[C@H](C(C[C@]2(C)[C@@H]([C@H](C)N(C)C)[C@H](O)C[C@]21C)=O)CC1=CC2)C[C@H]1[C@@]1(C)[C@H]2N=C(C(C)C)OC1 AICOOMRHRUFYCM-ZRRPKQBOSA-N 0.000 description 1
- 229920000515 polycarbonate Polymers 0.000 description 1
- 239000004417 polycarbonate Substances 0.000 description 1
- 239000011541 reaction mixture Substances 0.000 description 1
- 238000004064 recycling Methods 0.000 description 1
- 238000011160 research Methods 0.000 description 1
- 229920006395 saturated elastomer Polymers 0.000 description 1
- 238000000926 separation method Methods 0.000 description 1
- 238000001179 sorption measurement Methods 0.000 description 1
- HXJUTPCZVOIRIF-UHFFFAOYSA-N sulfolane Chemical compound O=S1(=O)CCCC1 HXJUTPCZVOIRIF-UHFFFAOYSA-N 0.000 description 1
- 238000010792 warming Methods 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
- B01D53/34—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
-
- 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
- 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)
- Pharmaceuticals Containing Other Organic And Inorganic Compounds (AREA)
Abstract
The invention provides an amine ethylated piperazine, a preparation method thereof, a carbon dioxide absorbent and application thereof, and relates to the technical field of carbon dioxide capture. The aminoethyl piperazine with the structure shown in the formula I is introduced into piperazine as a framework, and the structural toughness of a piperazine ring is utilized to enhance the stability of the aminoethyl piperazine molecule, so that the thermal degradation of the aminoethyl piperazine in the heating desorption process is inhibited; the nitrogen atom of the piperazine skeleton is bonded with an aminoethyl side chain, so that polar nucleophilic reaction sites are increased, and the fluidity and water solubility of the absorbent are enhanced while the capture capacity of the absorbent carbon dioxide is improved; alkyl is bonded at a nitrogen atom of a side chain to be converted into tertiary amine, and the number of N-H bonds in the structure of the aminoethylated piperazine is controlled to reduce the reaction heat in the carbon dioxide absorption process, so that the desorption efficiency of the carbon dioxide is improved, the desorption energy consumption is reduced, and the cyclic use performance for capturing the carbon dioxide is excellent.
Description
Technical Field
The invention relates to the technical field of carbon dioxide capture, and particularly relates to amine ethylated piperazine and a preparation method thereof, a carbon dioxide absorbent and application thereof.
Background
Industrial production using fossil fuels as a main energy source discharges a large amount of flue waste gas rich in carbon dioxide, which is a main greenhouse gas causing global warming, every year, so how to reduce the emission of carbon dioxide to reduce the atmospheric concentration thereof becomes a common problem facing the human society today. Meanwhile, 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 methods such as hydrogenation reduction and the like. 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 industrial flue waste gas rich in carbon dioxide is a main application scene of a carbon dioxide capture technology, and at present, alcohol amine (such as ethanolamine, diethanolamine, triethanolamine, methylethanolamine, methyldiethanolamine, isobutanolamine and the like) absorption methods are mainly adopted in the industry. The most representative of the method is a 30 wt% ethanolamine aqueous solution, carbon dioxide is captured into ammonium carbamate or ammonium bicarbonate (shown as a reaction formula 1-2), the cyclic capture capacity is 6-10 wt%, and the desorption temperature is above 120 ℃.
Reaction formula 1:
reaction formula 2:
however, the alcohol amine absorbent has poor thermal stability and is easy to degrade and deactivate in the heating desorption process, so that the recycling performance of the alcohol amine absorbent is not ideal.
Disclosure of Invention
In view of the above, the present invention aims to provide an aminoethylated piperazine and a preparation method thereof, a carbon dioxide absorbent and an application thereof.
In order to achieve the above object, the present invention provides the following technical solutions:
the invention provides an amine ethylated piperazine, which has a structure shown in a formula I:
in the formula I, R2Is C1-C4 alkyl or
The R is1、R3And R4Independently a C1-C4 alkyl group.
Preferably, the C1-C4 alkyl group includes methyl, ethyl, n-propyl, isopropyl, n-butyl or isobutyl.
The invention provides a preparation method of amine ethylated piperazine,
(i) when said R is2When the alkyl is C1-C4, the preparation method comprises the following steps:
mixing the compound 1, the compound 2 and water, and carrying out substitution reaction to obtain amine ethylated piperazine;
(ii) when said R is2Is composed of
The preparation method comprises the following steps:
mixing the compound 3, the compound 4 and water, and carrying out substitution reaction to obtain amine ethylated piperazine;
Preferably, in step (i), the molar ratio of compound 1 to compound 2 is 1: 5-30;
the temperature of the substitution reaction is 50-80 ℃, and the time is 8-16 h.
The invention provides a preparation method of amine ethylated piperazine in the technical scheme, when R is1Is methyl, R2When the piperazine is methyl, the preparation method of the amine ethylated piperazine comprises the following steps:
mixing the tris (2-chloroethyl) amine hydrochloride, methylamine and water, and carrying out substitution reaction to obtain the amine ethylated piperazine.
Preferably, in step (ii), the molar ratio of compound 3 to compound 4 is 1: 1 to 1.5;
the temperature of the substitution reaction is 50-80 ℃, and the time is 6-12 h.
The invention provides application of the amine ethylated piperazine or the amine ethylated piperazine obtained by the preparation method in the technical scheme as a carbon dioxide absorbent.
The invention provides a carbon dioxide absorbent, which comprises the amine ethylated piperazine or the amine ethylated piperazine obtained by the preparation method in the technical scheme and a solvent; the mass percentage of the aminoethylated piperazine is 0.1-50%; the solvent comprises water and/or an organic solvent.
The invention provides application of the carbon dioxide absorbent in the technical scheme in capturing carbon dioxide in carbon dioxide-containing gas.
Preferably, the carbon dioxide-containing gas comprises power plant flue gas, refinery off gas, steel plant off gas, cement plant off gas, petrochemical plant off gas, water gas, biogas, natural gas, or carbonate ore decomposition gas.
The invention provides an amine ethylated piperazine, which has a structure shown in a formula I:
formula I; in the formula I, R2Is C1-C4 alkyl or
The R is1、R3And R4Independently a C1-C4 alkyl group. Piperazine is introduced as a framework, the structural toughness of a piperazine ring is utilized to enhance the stability of the piperazine molecule, and the thermal degradation of the piperazine in the heating desorption process is further inhibited; the nitrogen atom of the piperazine skeleton is bonded with an aminoethyl side chain, so that polar nucleophilic reaction sites are increased, and the fluidity and water solubility of the absorbent are enhanced while the capture capacity of carbon dioxide is improved; alkyl is bonded at a nitrogen atom of a side chain to be converted into tertiary amine, and the number of N-H bonds in the structure of the aminoethylated piperazine is controlled to reduce the reaction heat in the carbon dioxide absorption process, so that the desorption efficiency of the carbon dioxide is improved, the desorption energy consumption is reduced, and the cyclic use performance for capturing the carbon dioxide is excellent.
The preparation method of the amine ethylated piperazine provided by the technical scheme is simple to operate, wide in source of reaction raw materials, low in production cost and suitable for industrial production.
The invention provides a carbon dioxide absorbent, which comprises the amine ethylated piperazine or the amine ethylated piperazine obtained by the preparation method in the technical scheme and water. Compared with the traditional alcohol amine absorption method, the method has the advantages that the molecular layer surface is designed for the absorbent structure, and the following excellent performances are achieved: (1) piperazine with structural toughness is introduced to serve as an absorbent molecular skeleton to enhance the stability of the absorbent molecular skeleton, and as shown in the test results of the examples, the absorbent provided by the invention can absorb CO at high temperature and high pressure (150 ℃ C.)22MPa) for more than 100h without degradation and inactivation, the nuclear magnetic resonance and gas chromatography spectrograms of the absorbent are unchanged from the initial state, and the carbon dioxide capture capacity under the standard condition is not reduced; (2) the structure of the absorbent is bonded with a hydrazine ethyl side chain to increase polar nucleophilic reaction sites and improve the capture effect on carbon dioxide, and as shown by the test result of an example, the capture capacity of the carbon dioxide can reach 11.5 wt% within 100min at 40 ℃ under 1 atm; (3) the side chain amino group is converted into tertiary amine through the bonded alkyl group, so that the reaction heat in the carbon dioxide absorption process is reduced, the desorption efficiency is improved, the desorption energy consumption is reduced, and the cyclic utilization rate is improved. The absorbent provided by the invention has the advantages of good thermal stability, high desorption efficiency, low desorption energy consumption and high trapping capacity.
Detailed Description
The invention provides an amine ethylated piperazine, which has a structure shown in a formula I:
in the formula I, R2Is C1-C4 alkyl or
In the present invention, said R1、R3And R4Independently is a C1-C4 alkyl group; the C1-C4 alkyl group preferably includes methyl, ethyl, n-propyl, isopropyl, n-butyl or isobutyl.
In the invention, in the I, when R is1When being methyl, R2Methyl, ethyl, n-propyl, isopropyl, n-butyl or isobutyl; when R is1When being ethyl, R2Methyl, ethyl, n-propyl, isopropyl, n-butyl or isobutyl; when R is1When n-propyl, R2Methyl, ethyl, n-propyl, isopropyl, n-butyl or isobutyl; when R is1When it is isopropyl, R2Methyl, ethyl, n-propyl, isopropyl, n-butyl or isobutyl; when R is1When being n-butyl, R2Methyl, ethyl, n-propyl, isopropyl, n-butyl or isobutyl; when R is1When not being butyl, R2Methyl, ethyl, n-propyl, isopropyl, n-butyl or isobutyl.
In the invention, in the I, when R is1Methyl, R3When being methyl, R4Methyl, ethyl, n-propyl, isopropyl, n-butyl or isobutyl; when R is1Methyl, R3When being ethyl, R4Methyl, ethyl, n-propyl, isopropyl, n-butyl or isobutyl; when R is1Methyl, R3When n-propyl, R4Methyl, ethyl, n-propyl, isopropyl, n-butyl or isobutyl; when R is1Methyl, R3When it is isopropyl, R4Methyl, ethyl, n-propyl, isopropyl, n-butyl or isobutyl; when R is1Methyl, R3When being n-butyl, R4Methyl, ethyl, n-propyl, isopropyl, n-butyl or isobutyl; when R is1Methyl, R3When not being iso-butyl, R4Methyl, ethyl, n-propyl, isopropyl, n-butyl or isobutyl.
In the invention, in the I, when R is1Ethyl, R3When being methyl, R4Methyl, ethyl, n-propyl, isopropyl, n-butyl or isobutyl; when R is1Ethyl, R3When being ethyl, R4Methyl, ethyl, n-propyl, isopropyl, n-butyl or isobutyl; when R is1Ethyl, R3When n-propyl, R4Methyl, ethyl, n-propyl, isopropyl, n-butyl or isobutyl; when R is1Ethyl, R3When it is isopropyl, R4Methyl, ethyl, n-propyl, isopropyl, n-butyl or isobutyl; when R is1Ethyl, R3When being n-butyl, R4Methyl, ethyl, n-propyl, isopropyl, n-butyl or isobutyl; when R is1Ethyl, R3When not being iso-butyl, R4Methyl, ethyl, n-propyl, isopropyl, n-butyl or isobutyl.
In the invention, in the I, when R is1Is n-propyl, R3When being methyl, R4Methyl, ethyl, n-propyl, isopropyl, n-butyl or isobutyl; when R is1Is n-propyl, R3When being ethyl, R4Methyl, ethyl, n-propyl, isopropyl, n-butyl or isobutyl; when R is1Is n-propyl, R3When n-propyl, R4Methyl, ethyl, n-propyl, isopropyl, n-butyl or isobutyl; when R is1Is n-propyl, R3When it is isopropyl, R4Methyl, ethyl, n-propyl, isopropyl, n-butyl or isobutyl; when R is1Is n-propyl, R3When being n-butyl, R4Methyl, ethyl, n-propyl, isopropyl, n-butyl or isobutyl; when R is1Is n-propyl, R3When not being butyl, R4Methyl, ethyl, n-propyl, isopropyl, n-butyl or isobutyl.
In the invention, in the I, when R is1Is isopropyl, R3When being methyl, R4Methyl, ethyl, n-propyl, isopropyl, n-butyl or isobutyl; when R is1Is isopropyl, R3When being ethyl, R4Methyl, ethyl, n-propyl, isopropyl, n-butyl or isobutyl; when R is1Is isopropyl, R3When n-propyl, R4Methyl, ethyl, n-propyl, isopropyl, n-butyl or isobutyl; when R is1Is isopropyl, R3When it is isopropyl, R4Methyl, ethyl, n-propyl, isopropyl, n-butyl or isobutyl; when R is1Is isopropyl, R3When being n-butyl, R4Methyl, ethyl, n-propyl, isopropyl, n-butyl or isobutyl; when R is1Is isopropyl, R3When not being iso-butyl, R4Methyl, ethyl, n-propyl, isopropyl, n-butyl or isobutyl.
In the invention, in the I, when R is1N-butyl, R3When being methyl, R4Methyl, ethyl, n-propyl, isopropyl, n-butyl or isobutyl; when R is1N-butyl, R3When being ethyl, R4Methyl, ethyl, n-propyl, isopropyl, n-butyl or isobutyl; when R is1N-butyl, R3When n-propyl, R4Methyl, ethyl, n-propyl, isopropyl, n-butyl or isobutyl; when R is1N-butyl, R3When it is isopropyl, R4Methyl, ethyl, n-propyl, isopropyl, n-butyl or isobutyl; when R is1N-butyl, R3When being n-butyl, R4Methyl, ethyl, n-propyl, isopropyl, n-butyl or isobutyl; when R is1N-butyl, R3When not being iso-butyl, R4Methyl, ethyl, n-propyl, isopropyl, n-butyl or isobutyl.
In the invention, in the I, when R is1Iso-butyl, R3When being methyl, R4Methyl, ethyl, n-propyl, isopropyl, n-butyl or isobutyl; when R is1Iso-butyl, R3When being ethyl, R4Methyl, ethyl, n-propyl, isopropyl, n-butyl or isobutyl; when R is1Iso-butyl, R3When n-propyl, R4Methyl and ethylAlkyl, n-propyl, isopropyl, n-butyl or isobutyl; when R is1Iso-butyl, R3When it is isopropyl, R4Methyl, ethyl, n-propyl, isopropyl, n-butyl or isobutyl; when R is1Iso-butyl, R3When n-butyl, R4Methyl, ethyl, n-propyl, isopropyl, n-butyl or isobutyl; when R is1Iso-butyl, R3When not being iso-butyl, R4Methyl, ethyl, n-propyl, isopropyl, n-butyl or isobutyl.
The invention provides a preparation method of amine ethylated piperazine in the technical scheme, (i) when R is in the formula2When the alkyl is C1-C4, the preparation method comprises the following steps:
mixing the compound 1, the compound 2 and water, and carrying out substitution reaction to obtain amine ethylated piperazine;
(ii) when said R is2Is composed of
The preparation method comprises the following steps:
mixing the compound 3, the compound 4 and water, and carrying out substitution reaction to obtain amine ethylated piperazine;
In the present invention, all the raw material components are commercially available products well known to those skilled in the art unless otherwise specified.
When said R is2When the alkyl is C1-C4, the preparation method comprises the following steps: mixing the compound 1, the compound 2 and water, and carrying out substitution reaction to obtain amine ethylated piperazine;
In the present invention, the C1-C4 alkyl group is preferably the same as the aforementioned C1-C4 alkyl groups, and thus, the description thereof is omitted.
In the present invention, the preparation method of the compound 1 preferably comprises the following steps: mixing the compound 5, thionyl chloride which is a chlorination reagent and a soluble compound 5 solvent, and carrying out chlorination reaction to obtain a compound 1;
in the present invention, the chlorinating agent preferably comprises one or more of thionyl chloride, phosphorus oxychloride and methanesulfonyl chloride. In the present invention, the molar ratio of the compound 5 to the chlorinating agent is preferably 1: 1.5-5, more preferably 1: 2 to 3. In the present invention, the soluble compound 5 solvent is preferably a chloroalkane-based solvent, more preferably including dichloromethane; the amount of the solvent of the soluble compound 5 is not particularly limited, and the raw materials can be dissolved; in the embodiment of the present invention, the ratio of the amount of the substance of the compound 5 to the volume of the solvent for the soluble compound 5 is preferably 24 mmol: 35 mL. In the present invention, the mixing is performed by dissolving the compound 5 in a solvent that is soluble to the compound 5, and then dropping a chlorinating agent; the stirring speed is preferably 400-700 r/min, and more preferably 500-600 r/min; the dropping speed is not specially limited, and the dropping can be carried out at a constant speed; in the embodiment of the invention, the dripping speed is preferably 13-14 mmol/min; the dropwise addition is preferably carried out using a constant pressure dropping funnel. In the invention, the temperature of the chlorination reaction is preferably 25-80 ℃, and more preferably 35-65 ℃; the chlorination reaction time is preferably 4-24 hours, and more preferably 8-12 hours; the chlorination reaction is preferably carried out under oil bath conditions; the reactions that occur during the chlorination reaction are as follows:
after the chlorination reaction, the method preferably further comprises cooling a system of the chlorination reaction to room temperature and then performing suction filtration to obtain the compound 1. The cooling method of the present invention is not particularly limited, and a cooling method known to those skilled in the art may be used. In the present invention, the suction filtration is preferably performed by a water pump.
In the present invention, the molar ratio of the compound 1 to the compound 2 is preferably 1: 5-30, more preferably 1: 10-25, most preferably 1: 15 to 20. In the present invention, the order of mixing is preferably such that the compound 2 is dissolved in water to give an amine solution; mixing the obtained amine solution with compound 3; the concentration of the amine solution is preferably 20-45 wt%, and more preferably 30-40 wt%. In the present invention, the mixing method is preferably stirring mixing, and the speed and time of stirring mixing are not particularly limited in the present invention, and the raw materials may be uniformly mixed.
In the invention, the temperature of the substitution reaction is preferably 50-80 ℃, and more preferably 60-70 ℃; the time of the substitution reaction is preferably 8-16 h, and more preferably 10-12 h; the substitution reaction is preferably carried out in an autoclave. In the present invention, the reactions occurring during the substitution reaction are as follows:
after the substitution reaction, the method preferably further comprises the steps of cooling the system of the substitution reaction to room temperature, adding a first alkaline reagent under the stirring condition, mixing for 20-60 min, then carrying out first standing and layering, adding a second alkaline reagent into the obtained aqueous organic phase (upper layer) under the stirring condition, mixing for 0.5-2 h, then carrying out second standing and layering, extracting the obtained aqueous organic phase (upper layer), drying the obtained organic phase, and concentrating to constant weight to obtain the aminoethyl piperazine. In the present invention, the cooling is preferably performed by using ice waterAnd (5) soaking in a bath. In the invention, the stirring speed is preferably 800-1200 r/min, and more preferably 1000-1100 r/min. In the present invention, the first and second alkaline agents independently preferably include Na2CO3、K2CO3NaOH or KOH; the first alkaline reagent and the second alkaline reagent are used in the form of alkaline reagent solid or alkaline reagent aqueous solution, and the concentration of the alkaline reagent aqueous solution is preferably 40-60 wt%; the first alkaline reagent is used for removing HCl generated in the reaction; the first alkaline agent is preferably added in 4-5 times, and the molar ratio of the compound 1 to the first alkaline agent is preferably 1: 5-15, more preferably 1: 10-12; the second alkaline reagent is preferably added in 3-4 times, and the molar ratio of the compound 1 to the second alkaline reagent is preferably 1: 4-10, more preferably 1: 5-8; the first alkaline agent and the second alkaline agent are added in portions in order to prevent the alkaline agent from dissolving a large amount of heat to cause bumping of the solution. In the present invention, the first standing layer and the second standing layer are preferably carried out in a separatory funnel. In the present invention, the extractant for extraction preferably includes dichloromethane or chloroform; the amount of the extractant used in the present invention is not particularly limited, and the amount of the extractant known to those skilled in the art can be used; in the present example, the ratio of the amount of substance of compound 1 to the volume of the extractant is preferably 24 mmol: 15mL, and the number of times of extraction is preferably 3-4. In the present invention, the drying means is preferably drying with a drying agent, and the drying agent is preferably anhydrous sodium sulfate. In the present invention, the concentration is preferably performed by distillation under reduced pressure; the reduced pressure distillation is preferably carried out using a rotary evaporator.
When said R is2Is composed of
The preparation method comprises the following steps: mixing the compound 3, the compound 4 and water, and carrying out substitution reaction to obtain amine ethylated piperazine;
In the present invention, the C1-C4 alkyl group is preferably the same as the aforementioned C1-C4 alkyl groups, and thus, the description thereof is omitted.
In the present invention, the molar ratio of the compound 3 to the compound 4 is preferably 1: 1 to 1.5, more preferably 1: 1.1 to 1.4, most preferably 1: 1.2 to 1.3. In the invention, the temperature of the substitution reaction is preferably 50-80 ℃ and the time is 6-12 h. In the present invention, the order of mixing is preferably such that the compound 4 is dissolved in water to give an amine solution; mixing the obtained amine solution with compound 3; the concentration of the amine solution is preferably 20-45 wt%, and more preferably 30-40 wt%. In the present invention, the ratio of the amount of the substance of the compound 3 to the volume of water is preferably 12 mmol: 10-15 mL, more preferably 12 mmol: 12-13 mL.
In the invention, the temperature of the substitution reaction is preferably 50-80 ℃, and more preferably 60-70 ℃; the time of the substitution reaction is preferably 6-12 h, and more preferably 8-10 h; the substitution reaction is preferably carried out in an oil bath with stirring; the stirring speed is preferably 800-1200 r/min, and more preferably 900-1000 r/min. In the present invention, the reactions occurring during the substitution reaction are as follows:
after the substitution reaction, the method preferably further comprises the steps of cooling the system of the substitution reaction to room temperature, adding a third alkaline reagent under the stirring condition, mixing for 20-60 min, standing for layering, adding a fourth alkaline reagent into the obtained aqueous organic phase (upper layer) under the stirring condition, mixing for 0.5-2 h, standing for layering, extracting the obtained aqueous organic phase (upper layer), drying the obtained organic phase, and concentrating to constant weight to obtain the aminoethyl piperazine. In the present invention, the cooling is preferably performed by soaking in an ice-water bath. In the invention, the stirring speed is preferably 800-1200 r/min, and more preferably 10001100 r/min. In the present invention, the third and fourth alkaline agents independently preferably comprise Na2CO3、K2CO3NaOH or KOH; the third alkaline reagent and the fourth alkaline reagent are used in the form of alkaline reagent solid or alkaline reagent aqueous solution, and the concentration of the alkaline reagent aqueous solution is preferably 40-60 wt%, and the third alkaline reagent is used for removing HCl generated in the reaction; the third alkaline reagent is preferably added in 3-4 times, and the molar ratio of the compound 3 to the third alkaline reagent is preferably 1: 4-10, more preferably 1: 10-12; the fourth alkalinity is preferably added in 3-4 times, and the molar ratio of the compound 3 to the fourth alkalinity agent is preferably 1: 2-6, more preferably 1: 3-5; the third alkaline agent and the fourth alkaline agent are added in portions in order to prevent the alkaline agent from dissolving a large amount of heat to cause bumping of the solution. In the present invention, the third standing layer and the fourth standing layer are preferably performed in a separatory funnel. In the present invention, the extractant for extraction preferably includes dichloromethane or chloroform; the amount of the extractant used in the present invention is not particularly limited, and the amount of the extractant known to those skilled in the art can be used; in the present example, the ratio of the amount of substance of compound 1 to the volume of the extractant is preferably 24 mmol: 15mL, and the number of times of extraction is preferably 3-4. In the present invention, the drying means is preferably drying with a drying agent, and the drying agent preferably includes anhydrous sodium sulfate. In the present invention, the concentration is preferably performed by distillation under reduced pressure; the reduced pressure distillation is preferably carried out using a rotary evaporator.
In the present invention, when R is1Is methyl, R2When the piperazine is methyl, the preparation method of the amine ethylated piperazine comprises the following steps:
mixing the tris (2-chloroethyl) amine hydrochloride, methylamine and water, and carrying out substitution reaction to obtain the amine ethylated piperazine.
In the present invention, the tris (2-chloroethyl) amine hydrochloride is preferably obtained by mixing triethanolamine, a chlorinating agent and a soluble triethanolamine solvent and carrying out a chlorination reaction. In the present invention, the soluble triethanolamine solvent preferably includes a chlorinated alkane solvent, more preferably includes dichloromethane; the dosage of the soluble triethanolamine solvent is not specially limited, and the raw materials can be dissolved; in the embodiment of the present invention, the ratio of the amount of the triethanolamine substance to the volume of the soluble triethanolamine solvent is preferably 24 mmol: 35 mL. In the invention, the mixing mode is that triethanolamine is dissolved in a soluble triethanolamine solvent, and then a chlorinating agent is dripped; the stirring speed is preferably 400-700 r/min, and more preferably 500-600 r/min; the stirring time is preferably 5-15 min, and more preferably 10 min; the dropping speed is not specially limited, and the dropping can be carried out at a constant speed; in the embodiment of the invention, the dripping speed is preferably 13-14 mmol/min; the dropwise addition is preferably carried out using a constant pressure dropping funnel. In the invention, the temperature of the chlorination reaction is preferably 25-80 ℃, and more preferably 35-65 ℃; the chlorination reaction time is preferably 4-24 hours, and more preferably 8-12 hours; the chlorination reaction is preferably carried out under oil bath conditions; the reactions that occur during the chlorination reaction are as follows:
after the chlorination, the present invention preferably further comprises evaporating the system of the chlorination to remove soluble triethylamine solvent and excess chlorinating agent to obtain tris (2-chloroethyl) amine hydrochloride.
In the present invention, the molar ratio of tris (2-chloroethyl) amine hydrochloride to methylamine is preferably 1: 5 to 30, more preferably 1: 10-25, most preferably 1: 15 to 20. In the present invention, the order of mixing is preferably dissolving methylamine in water to obtain a methylamine solution; mixing the obtained methylamine solution with tris (2-chloroethyl) amine hydrochloride; the concentration of the methylamine solution is preferably 20-45 wt%, and more preferably 30-40 wt%. In the present invention, the mixing method is preferably stirring mixing, and the speed and time of stirring mixing are not particularly limited in the present invention, and the raw materials may be uniformly mixed.
In the invention, the temperature of the substitution reaction is preferably 50-80 ℃, and more preferably 60-70 ℃; the time of the substitution reaction is preferably 8-16 h, and more preferably 10-12 h; the substitution reaction is preferably carried out in an autoclave. In the present invention, the reactions occurring during the substitution reaction are as follows:
after the substitution reaction, the method preferably further comprises the steps of cooling a system of the substitution reaction to room temperature, adding an alkaline reagent under the stirring condition, mixing for 20-60 min, standing for layering, extracting and drying the obtained organic phase, and concentrating to constant weight to obtain the amine ethylated piperazine. In the present invention, the cooling is preferably performed by soaking in an ice-water bath. In the invention, the stirring speed is preferably 800-1200 r/min, and more preferably 1000-1100 r/min. In the present invention, the alkaline agent preferably includes Na2CO3、K2CO3NaOH or KOH; the function of the alkaline reagent is to remove HCl generated in the reaction; the alkaline reagent is preferably added in 4-5 times, and the molar ratio of the triethylamine to the alkaline reagent is preferably 1: 5-15, more preferably 1: 10-12; the alkaline agent is added in portions in order to prevent the alkaline agent from dissolving a large amount of heat to cause bumping of the solution. In the present invention, the standing separation is preferably performed in a separatory funnel. In the present invention, the extractant for extraction preferably includes dichloromethane or chloroform; the amount of the extractant used in the present invention is not particularly limited, and the amount of the extractant known to those skilled in the art can be used; in the embodiment of the invention, the ratio of the amount of the triethylamine substance to the volume of the extracting agent is preferably 6 mmol: 5mL, and the extraction frequency is preferably 3-4. In the present invention, the drying means is preferably drying with a drying agent, and the drying agent is preferably anhydrous sodium sulfate. In the present invention, the concentration is preferably performed by distillation under reduced pressure; the reduced pressure distillation is preferably carried out using a rotary evaporator.
The invention provides application of the amine ethylated piperazine or the amine ethylated piperazine obtained by the preparation method in the technical scheme as a carbon dioxide absorbent.
The invention provides a carbon dioxide absorbent, which comprises the amine ethylated piperazine or the amine ethylated piperazine obtained by the preparation method in the technical scheme and a solvent.
In the invention, the mass percentage content of the aminoethylated piperazine in the carbon dioxide absorbent is preferably 10-50%, more preferably 20-40%, and most preferably 30-35%.
In the present invention, the solvent includes water and/or an organic solvent; the organic solvent preferably comprises sulfolane and/or dimethyl sulfoxide; when the solvent is a mixed solvent of water and an organic solvent, the volume ratio of the water to the organic solvent is not particularly limited in the present invention, and any ratio may be used.
The invention provides application of the carbon dioxide absorbent in the technical scheme in capturing carbon dioxide in carbon dioxide-containing gas. In the present invention, the carbon dioxide-containing gas includes power plant flue gas, refinery tail gas, steel plant tail gas, cement plant tail gas, petrochemical plant tail gas, water gas, biogas, natural gas, or carbonate ore decomposition gas. In the present invention, the conditions under which the carbon dioxide absorbent traps carbon dioxide in flue gas of a power plant preferably include: the preferable flue gas pressure is 0.01-0.05 MPa, more preferable is 0.02-0.04 MPa, and most preferable is 0.03 MPa; the absorption temperature is preferably 40-60 ℃, more preferably 45-55 ℃, and most preferably 50 ℃; the absorption time is preferably 0.1 to 1 hour, and more preferably 0.5 to 0.8 hour.
In the invention, the carbon dioxide absorbent after absorbing carbon dioxide is preferably desorbed and recycled. In the invention, the desorption temperature is preferably 80-130 ℃, more preferably 90-120 ℃, and most preferably 100-110 ℃; the desorption time is preferably 0.1 to 1 hour, and more preferably 0.5 to 0.8 hour.
The technical solution of the present invention will be clearly and completely described below with reference to the embodiments of the present invention. It is to be understood that the described embodiments are merely exemplary of the invention, and not restrictive of the full scope of the invention. All other embodiments, which can be derived by a person skilled in the art from the embodiments given herein without making any creative effort, shall fall within the protection scope of the present invention.
Example 1
Synthesis of N- (2-methylaminoethyl) -N' -methyl-piperazine
Step 1: in a 500mL single-neck flask, 240mmol of triethanolamine was dissolved in 350mL of dichloromethane and stirred at 600r/min at room temperature for 10 min. 1200mmol of thionyl chloride is dropwise added into the solution at a constant speed by a constant-pressure dropping funnel under the cooling of an ice water bath, and the dropwise addition is finished within 30 min. The vial was then transferred to a 40 ℃ oil bath and reacted at reflux for 12 h. The solvent dichloromethane and excess thionyl chloride were then removed on a rotary evaporator to give the intermediate tris (2-chloroethyl) amine hydrochloride.
And 2, step: transferring all the tris (2-chloroethyl) amine hydrochloride obtained in the step 1 into a 500mL high-pressure reaction kettle, adding 260mL of 40 wt% methylamine aqueous solution, sealing, and reacting for 12h under the conditions of 60 ℃ oil bath and 800r/min stirring speed; soaking the autoclave in ice-water bath for 1h, transferring the reaction mixture into a 1L beaker cooled by the ice-water bath, adding 120g NaOH in 4 batches under the magnetic stirring condition of 1000r/min, stirring for 30min, transferring all the mixture into a 500mL separating funnel, standing for layering, discharging the milky white water phase, extracting the dark yellow water-containing organic phase for 3 times by using dichloromethane, wherein the using amount of the dichloromethane for single extraction is 200mL, combining the dichloromethane phases, and then using anhydrous Na2SO4The mixture was dried overnight, then the solvent dichloromethane was removed by a rotary evaporator and distilled under reduced pressure to constant weight to give N- (2-methylaminoethyl) -N' -methyl-piperazine (boiling point 88-95 ℃ at 1mm Hg pressure, total molar yield of two steps 30%, purity 99%). Nuclear magnetic characterization data:1HNMR(400MHz,CDCl3)δ＝2.27(s,3H),2.42-2.49(m,13H),2.65(t,J＝6.0Hz,2H)。
comparative example 1
Synthesis of N- (2-methylaminoethyl) -piperazine
Step 1: dissolving 240mmol of 2-hydroxyethyl piperazine in 350mL of dichloromethane in a 500mL single-neck bottle, stirring for 10min at room temperature under 600r/min, dropwise adding 400mmol of thionyl chloride into the solution at a constant speed by using a constant-pressure dropping funnel under an ice water bath, after dropwise adding within 30min, transferring the single-neck bottle to a 40 ℃ oil bath for reflux reaction for 12h, then removing the single-neck bottle from the oil bath, cooling to room temperature, and performing suction filtration to constant weight by using a water pump to obtain an intermediate 2-chloroethyl piperazine hydrochloride.
Step 2: transferring all the 2-chloroethyl piperazine hydrochloride obtained in the step 1 into a 500mL high-pressure reaction kettle, adding 260mL of 40 wt% methylamine aqueous solution, sealing, and reacting for 12h under the conditions of 60 ℃ oil bath and 800r/min stirring speed; soaking the autoclave in an ice-water bath for 1h, transferring the reaction mixed solution into a 1L beaker cooled by the ice-water bath, adding 80g of NaOH in 4 batches under the magnetic stirring condition of 1000r/min, stirring for 20min, transferring the mixed solution into a 500mL separating funnel for standing, discharging the milky water phase at the lower layer, pouring the light yellow aqueous organic phase at the upper layer into 200mL NaOH solution with the concentration of 50 wt% cooled by the ice-water bath, stirring for 20min at room temperature, transferring into the 500mL separating funnel for standing and layering again, discharging the water phase at the lower layer, extracting the dark yellow aqueous organic phase at the upper layer for 2 times by using dichloromethane, wherein the volume of dichloromethane used for single extraction is 200mL, and after the dichloromethane phases are combined, anhydrous Na is used for anhydrous Na2SO4Drying overnight, removing solvent dichloromethane by using a rotary evaporator, and then distilling under reduced pressure by using an oil pump until the weight is constant to obtain the N- (2-methylaminoethyl) -piperazine (the boiling point of which under the pressure of 1mm Hg is 82-86 ℃, the total molar yield of the two steps is 45%, and the purity is 99%). Nuclear magnetic characterization data:1H NMR(400MHz,CDCl3)δ＝2.39-2.45(m,9H),2.64(t,J＝4.0Hz,2H),2.85(t,J＝3.2Hz,4H)。
comparative example 2
Synthesis of N- (2-ethylamino ethyl) -piperazine
Step 1: in a 500mL single-neck bottle, 240mmol of 2-hydroxyethyl piperazine is dissolved in 350mL of dichloromethane, the mixture is stirred for 10min at room temperature under the condition of 600r/min, 400mmol of thionyl chloride is uniformly dripped into the solution by a constant-pressure dropping funnel in an ice water bath, after dripping is completed within 30min, the single-neck bottle is immediately transferred into an oil bath at 40 ℃ for reflux reaction for 12h, the single-neck bottle is removed from the oil bath and cooled to room temperature, and the mixture is suction-filtered by a water pump to constant weight, so that the intermediate 2-chloroethyl piperazine hydrochloride is obtained.
Step 2: transferring all the 2-chloroethylpiperazine hydrochloride obtained in the step 1 into a 500mL high-pressure reaction kettle, adding 260mL of 30 wt% ethylamine aqueous solution, sealing, reacting for 12h under the conditions of 60 ℃ oil bath and 800r/min stirring speed, soaking the high-pressure kettle for 1h in an ice water bath, transferring the reaction mixed solution into a 1L beaker cooled by the ice water bath, adding 80g of NaOH in 4 batches under the condition of 1000r/min magnetic stirring, stirring for 20min, transferring all the mixed solution into a 500mL separating funnel for standing, discharging the lower milky aqueous phase, pouring the upper pale yellow aqueous organic phase into 200mL of 50 wt% NaOH solution cooled by the ice water bath, stirring the mixed solution at the room temperature for 20min, transferring into the 500mL separating funnel for standing and layering again, discharging the lower aqueous phase, extracting the upper deep yellow aqueous organic phase with dichloromethane for 2 times, the volume of dichloromethane used for single extraction is 200mL, and anhydrous Na is used after dichloromethane phases are combined2SO4Drying overnight, removing solvent dichloromethane by using a rotary evaporator, and then distilling under reduced pressure by using an oil pump until the weight is constant to obtain the N- (2-ethylamino ethyl) -piperazine (the boiling point is 91-94 ℃ under the pressure of 1mm Hg, the total molar yield of the two steps is 51%, and the purity is 99%). Nuclear magnetic characterization data:1H NMR(400MHz,CDCl3)δ＝2.86(t,J＝5.2Hz,4H),2.61-2.70(m,4H),2.40-2.47(m,6H),1.10(t,J＝7.2Hz,3H)。
comparative example 3
Synthesis of N- (2-N-propylaminoethyl) -piperazine
Step 1: in a 500mL single-neck flask, 240mmol of 2-hydroxyethylpiperazine was dissolved in 350mL of dichloromethane and stirred at 600r/min at room temperature for 10 min. 400mmol of thionyl chloride is dropwise added into the solution at a constant speed by a constant-pressure dropping funnel in an ice water bath, and the dropwise addition is finished within 30 min. And then transferring the single-neck bottle to an oil bath at 40 ℃ for reflux reaction for 12 hours, removing the single-neck bottle from the oil bath, cooling to room temperature, and performing suction filtration by using a water pump until the weight is constant to obtain the intermediate 2-chloroethyl piperazine hydrochloride.
Step 2: transferring all the chloroethyl piperazine hydrochloride obtained in the step 1 into a 500mL high-pressure reaction kettle, then adding 260mL of a 30 wt% n-propylamine aqueous solution, sealing, reacting for 12h under the conditions of 60 ℃ oil bath and 800r/min stirring speed, soaking the high-pressure kettle for 1h in an ice water bath, transferring the reaction mixed solution into a 1L beaker cooled by the ice water bath, adding 80g of NaOH in 4 batches under the condition of 1000r/min magnetic stirring, stirring for 20min, transferring all the mixed solution into a 500mL separating funnel for standing, discharging the milky water phase at the lower layer, pouring the light yellow water-containing organic phase at the upper layer into 200mL of a 50 wt% NaOH solution cooled by the ice water bath, stirring for 20min at the temperature of the mixed solution, transferring into the 500mL separating funnel for standing and separating the layers again, discharging the water phase at the lower layer, extracting the deep yellow water-containing organic phase at the upper layer for 2 times by using dichloromethane, the volume of dichloromethane used for single extraction is 200mL, and anhydrous Na is used after dichloromethane phases are combined2SO4Drying overnight, removing solvent dichloromethane by using a rotary evaporator, and then distilling under reduced pressure by using an oil pump until the weight is constant to obtain the N- (2-N-propylaminoethyl) -piperazine (the boiling point is 99-105 ℃ under the pressure of 1mm Hg, the total molar yield of the two steps is 61%, and the purity is 99%). Nuclear magnetic characterization data:1H NMR(400MHz,CDCl3)δ＝2.86(t,J＝3.2Hz,4H),2.69(t,J＝4.4Hz,2H),2.56(t,J＝4.8Hz,2H),2.40-2.47(m,6H),2.86(sextet,J＝4.8Hz,2H),0.90(t,J＝5.2Hz,3H)。
comparative example 4
Synthesis of N, N' -di (2-methylaminoethyl) -piperazine
In a 500mL single neck flask, 240mmol of N- (2-methylaminoethyl) -piperazine was dissolved in 250mL of water, magnetically stirred at 800r/min in an oil bath at 60 ℃ for 10min, followed by the addition of 290mmol of N-methyl-2-chloroethylamine hydrochloride in 120mL of water. Carrying out oil bath at 60 ℃ and stirring speed of 800r/min for 12h, soaking a single-mouth bottle in ice-water bath for 1h, transferring the reaction mixed solution into a 1L beaker cooled by the ice-water bath, adding 80g of NaOH in 4 batches under magnetic stirring at 1000r/min, stirring for 20min, transferring the mixed solution into a 500mL separating funnel for standing, discharging a lower milky water phase, pouring an upper light yellow aqueous organic phase into 200mL of 50 wt% NaOH solution cooled by the ice-water bath, stirring the mixed solution at room temperature for 20min, transferring the mixed solution into the 500mL separating funnel for standing and layering, discharging a lower water phase, extracting the upper dark yellow aqueous organic phase for 2 times by using dichloromethane, wherein the volume of dichloromethane for single extraction is 200mL, combining dichloromethane phases, and then using anhydrous Na2SO4Drying overnight, removing solvent dichloromethane by using a rotary evaporator, and then distilling under reduced pressure to constant weight to obtain N, N' -bis (2-methylaminoethyl) -piperazine (the boiling point of which is 102-108 ℃ under the pressure of 1mm Hg, the total molar yield of the two steps is 37%, and the purity is 99%). Nuclear magnetic characterization data:1HNMR(400MHz,CDCl3)δ＝2.42-2.48(m,20H),2.64(t,J＝6.0Hz,4H)。
comparative example 5
Synthesis of N, N' -di (2-ethylamino ethyl) -piperazine
In a 500mL single neck flask, 240mmol of N- (2-ethylamino-ethyl) -piperazine was dissolved in 250mL of water, magnetically stirred at 800r/min in an oil bath at 60 ℃ for 10min, followed by the addition of 290mmol of N-ethyl-2-chloroethyl120mL of an aqueous solution of amine hydrochloride. Carrying out oil bath at 60 ℃ and stirring speed of 800r/min for 12h, soaking a single-mouth bottle in ice-water bath for 1h, transferring the reaction mixed solution into a 1L beaker cooled by the ice-water bath, adding 80g of NaOH in 4 batches under magnetic stirring at 1000r/min, stirring for 20min, transferring the mixed solution into a 500mL separating funnel for standing, discharging a lower milky water phase, pouring an upper light yellow aqueous organic phase into 200mL of 50 wt% NaOH solution cooled by the ice-water bath, stirring the mixed solution at room temperature for 20min, transferring the mixed solution into the 500mL separating funnel for standing and layering, discharging a lower water phase, extracting the upper dark yellow aqueous organic phase for 2 times by using dichloromethane, wherein the volume of dichloromethane for single extraction is 200mL, combining dichloromethane phases, and then using anhydrous Na2SO4Drying overnight, removing solvent dichloromethane by using a rotary evaporator, and then distilling under reduced pressure to constant weight to obtain the N, N' -bis (2-ethylamino ethyl) -piperazine (the boiling point of which is 122-125 ℃ under the pressure of 1mm Hg, the total molar yield of the two steps is 41%, and the purity is 99%). Nuclear magnetic characterization data:1HNMR(400MHz,CDCl3)δ＝2.63-2.70(m,8H),2.46-2.48(m,10H),1.09(t,J＝4.8Hz,6H)。
comparative example 6
Synthesis of N, N' -di (2-N-propylaminoethyl) -piperazine
In a 500mL single neck flask, 240mmol of N- (2-N-propylaminoethyl) -piperazine was dissolved in 250mL of water, magnetically stirred at 800r/min in an oil bath at 60 ℃ for 10min, followed by addition of 290mmol of N-N-propyl-2-chloroethylamine hydrochloride in 120mL of water. Reacting for 12h under the conditions of oil bath at 60 ℃ and stirring speed of 800r/min, soaking a single-mouth bottle for 1h in ice-water bath, transferring the reaction mixed solution into a 1L beaker cooled by the ice-water bath, adding 80g of NaOH in 4 batches under the magnetic stirring condition of 1000r/min, stirring for 20min, transferring the mixed solution into a 500mL separating funnel for standing, discharging a milky water phase at the lower layer, pouring a light yellow water-containing organic phase at the upper layer into 200mL of 50 wt% N cooled by the ice-water bathStirring the mixed solution in the aOH solution at room temperature for 20min, transferring the mixed solution into a 500mL separating funnel again, standing the mixed solution for layering, discharging a lower aqueous phase, extracting an upper deep yellow aqueous organic phase for 2 times by using dichloromethane, wherein the volume of the dichloromethane for single extraction is 200mL, combining dichloromethane phases, and then using anhydrous Na2SO4Drying overnight, removing solvent dichloromethane by using a rotary evaporator, and then distilling under reduced pressure to constant weight to obtain N, N' -bis (2-N-propylaminoethyl) -piperazine (the boiling point of which under the pressure of 1mm Hg is 145-149 ℃, the total molar yield of the two steps is 43%, and the purity is 99%). Nuclear magnetic characterization data:1H NMR(400MHz,CDCl3)δ＝2.68(t,J＝6.4Hz,4H),2.55(t,J＝7.2Hz,4H),2.45-2.48(m,10H),2.86(sextet,J＝7.6Hz,4H),0.90(t,J＝7.2Hz,6H)。
test example 1
Adsorption Performance test
25g of the aminoethylated piperazine prepared in example 1 and the piperazine prepared in comparative examples 1 to 6 and 75g of deionized water were stirred and mixed uniformly to obtain 7 carbon dioxide water phase adsorbents.
Introducing carbon dioxide-nitrogen mixed gas with the volume content of 15% of carbon dioxide into the carbon dioxide water-phase adsorbent, wherein the flow rate of the mixed gas is 100mL/min, the pressure is 0.1MPa, the oil bath temperature is 40 ℃, the gas flow meter is used for recording the flow rates of inlet gas and outlet gas in real time, and the test results of the trapping performance of the carbon dioxide water-phase adsorbent on the carbon dioxide are shown in Table 1:
TABLE 1 mass percent carbon dioxide capture of absorbent
As is clear from table 1, the aminoethylated piperazine produced by the present invention is excellent in the effect of capturing carbon dioxide.
Test example 2
Desorption Performance test
Under magnetic stirring, 100g of the carbon dioxide absorbent saturated in carbon dioxide absorption in test example 1 was placed in an oil bath, the temperature of the oil bath was raised to 130 ℃, the flow rates of inlet gas and outlet gas were recorded in real time by a gas flow meter, and the results of the desorption percentage of the carbon dioxide absorbent are shown in table 2:
table 2 desorption percentage results for carbon dioxide absorbent
| Aminoethylated piperazines | 100min desorption/assay% | 30min desorption/assay% |
| N- (2-methylaminoethyl) -N' -methyl-piperazine | 100 | 98 |
| N- (2-methylaminoethyl) -piperazine | 100 | 68 |
| N- (2-ethylamino-ethyl) -piperazine | 100 | 77 |
| N- (2-N-propylaminoethyl) -piperazine | 100 | 88 |
| N, N' -bis (2-methylaminoethyl) -piperazine | 100 | 67 |
| N, N' -bis (2-ethylamino-ethyl) -piperazine | 100 | 81 |
| N, N' -bis (2-N-propylaminoethyl) -piperazine | 100 | 89 |
As is clear from table 2, the carbon dioxide-absorbed aminoethylated piperazine prepared by the present invention is excellent in carbon dioxide removal effect.
The foregoing is only a preferred embodiment of the present invention, and it should be noted that, for those skilled in the art, various modifications and decorations can be made without departing from the principle of the present invention, and these modifications and decorations should also be regarded as the protection scope of the present invention.
Claims (5)
1. A preparation method of amine ethylated piperazine is characterized in that,
the aminoethylated piperazine has a structure shown in formula I:
in the formula I, R2Is C1-C4 alkyl or
Said R is1、R3And R4Independently is a C1-C4 alkyl group;
(i) when said R is2When the alkyl is C1-C4, the preparation method comprises the following steps:
mixing the compound 1, the compound 2 and water, and carrying out substitution reaction to obtain amine ethylated piperazine;
(ii) when said R is2Is composed of
The preparation method comprises the following steps:
mixing the compound 3, the compound 4 and water, and carrying out substitution reaction to obtain amine ethylated piperazine;
2. A preparation method of the amine ethylated piperazine is characterized in that,
the aminoethylated piperazine has a structure shown in formula I:
when R is1Is methyl, R2When the piperazine is methyl, the preparation method of the amine ethylated piperazine comprises the following steps:
mixing the tris (2-chloroethyl) amine hydrochloride, methylamine and water for substitution reaction to obtain the amine ethylated piperazine.
3. The method of claim 1, wherein the C1-C4 alkyl group comprises a methyl group, an ethyl group, a n-propyl group, an isopropyl group, a n-butyl group, or an isobutyl group.
4. The method according to claim 1, wherein in step (i), the molar ratio of compound 1 to compound 2 is 1: 5-30;
the temperature of the substitution reaction is 50-80 ℃, and the time is 8-16 h.
5. The method according to claim 1, wherein in step (ii), the molar ratio of compound 3 to compound 4 is 1: 1 to 1.5;
the temperature of the substitution reaction is 50-80 ℃, and the time is 6-12 h.
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