CN114570178A - Carbon dioxide absorbent and preparation method and application thereof - Google Patents
Carbon dioxide absorbent and preparation method and application thereof Download PDFInfo
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- CN114570178A CN114570178A CN202210318855.3A CN202210318855A CN114570178A CN 114570178 A CN114570178 A CN 114570178A CN 202210318855 A CN202210318855 A CN 202210318855A CN 114570178 A CN114570178 A CN 114570178A
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- carbon dioxide
- absorbent
- amino
- dioxide absorbent
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- CURLTUGMZLYLDI-UHFFFAOYSA-N Carbon dioxide Chemical compound O=C=O CURLTUGMZLYLDI-UHFFFAOYSA-N 0.000 title claims abstract description 100
- 239000002250 absorbent Substances 0.000 title claims abstract description 93
- 230000002745 absorbent Effects 0.000 title claims abstract description 91
- 229910002092 carbon dioxide Inorganic materials 0.000 title claims abstract description 80
- 239000001569 carbon dioxide Substances 0.000 title claims abstract description 50
- 238000002360 preparation method Methods 0.000 title abstract description 7
- 238000010521 absorption reaction Methods 0.000 claims abstract description 48
- 239000003054 catalyst Substances 0.000 claims abstract description 42
- 101000623895 Bos taurus Mucin-15 Proteins 0.000 claims abstract description 28
- 150000003141 primary amines Chemical class 0.000 claims abstract description 18
- -1 amino acid salt Chemical class 0.000 claims abstract description 17
- 150000001412 amines Chemical class 0.000 claims abstract description 14
- 150000003335 secondary amines Chemical class 0.000 claims abstract description 13
- 150000003512 tertiary amines Chemical class 0.000 claims abstract description 13
- BVKZGUZCCUSVTD-UHFFFAOYSA-L Carbonate Chemical compound [O-]C([O-])=O BVKZGUZCCUSVTD-UHFFFAOYSA-L 0.000 claims abstract description 12
- 229910044991 metal oxide Inorganic materials 0.000 claims abstract description 12
- 150000004706 metal oxides Chemical class 0.000 claims abstract description 12
- 239000012621 metal-organic framework Substances 0.000 claims abstract description 12
- 239000002808 molecular sieve Substances 0.000 claims abstract description 12
- URGAHOPLAPQHLN-UHFFFAOYSA-N sodium aluminosilicate Chemical compound [Na+].[Al+3].[O-][Si]([O-])=O.[O-][Si]([O-])=O URGAHOPLAPQHLN-UHFFFAOYSA-N 0.000 claims abstract description 12
- 229920000768 polyamine Polymers 0.000 claims abstract description 11
- 238000000034 method Methods 0.000 claims description 40
- RPNUMPOLZDHAAY-UHFFFAOYSA-N Diethylenetriamine Chemical compound NCCNCCN RPNUMPOLZDHAAY-UHFFFAOYSA-N 0.000 claims description 20
- GLUUGHFHXGJENI-UHFFFAOYSA-N Piperazine Chemical compound C1CNCCN1 GLUUGHFHXGJENI-UHFFFAOYSA-N 0.000 claims description 18
- 238000003795 desorption Methods 0.000 claims description 16
- BWHMMNNQKKPAPP-UHFFFAOYSA-L potassium carbonate Chemical compound [K+].[K+].[O-]C([O-])=O BWHMMNNQKKPAPP-UHFFFAOYSA-L 0.000 claims description 16
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 16
- 239000008367 deionised water Substances 0.000 claims description 14
- 229910021641 deionized water Inorganic materials 0.000 claims description 14
- 239000000203 mixture Substances 0.000 claims description 12
- 229940024606 amino acid Drugs 0.000 claims description 11
- 238000002156 mixing Methods 0.000 claims description 10
- 239000003546 flue gas Substances 0.000 claims description 9
- 229910000027 potassium carbonate Inorganic materials 0.000 claims description 8
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N Titan oxide Chemical compound O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 claims description 6
- MCMNRKCIXSYSNV-UHFFFAOYSA-N Zirconium dioxide Chemical compound O=[Zr]=O MCMNRKCIXSYSNV-UHFFFAOYSA-N 0.000 claims description 6
- VILCJCGEZXAXTO-UHFFFAOYSA-N 2,2,2-tetramine Chemical compound NCCNCCNCCN VILCJCGEZXAXTO-UHFFFAOYSA-N 0.000 claims description 5
- AGPKZVBTJJNPAG-UHFFFAOYSA-N Isoleucine Chemical compound CCC(C)C(N)C(O)=O AGPKZVBTJJNPAG-UHFFFAOYSA-N 0.000 claims description 5
- ROHFNLRQFUQHCH-UHFFFAOYSA-N Leucine Chemical compound CC(C)CC(N)C(O)=O ROHFNLRQFUQHCH-UHFFFAOYSA-N 0.000 claims description 5
- JKQOBWVOAYFWKG-UHFFFAOYSA-N molybdenum trioxide Chemical compound O=[Mo](=O)=O JKQOBWVOAYFWKG-UHFFFAOYSA-N 0.000 claims description 5
- UXFQFBNBSPQBJW-UHFFFAOYSA-N 2-amino-2-methylpropane-1,3-diol Chemical compound OCC(N)(C)CO UXFQFBNBSPQBJW-UHFFFAOYSA-N 0.000 claims description 4
- DHMQDGOQFOQNFH-UHFFFAOYSA-N Glycine Chemical compound NCC(O)=O DHMQDGOQFOQNFH-UHFFFAOYSA-N 0.000 claims description 4
- CDBYLPFSWZWCQE-UHFFFAOYSA-L Sodium Carbonate Chemical compound [Na+].[Na+].[O-]C([O-])=O CDBYLPFSWZWCQE-UHFFFAOYSA-L 0.000 claims description 4
- QDOXWKRWXJOMAK-UHFFFAOYSA-N dichromium trioxide Chemical compound O=[Cr]O[Cr]=O QDOXWKRWXJOMAK-UHFFFAOYSA-N 0.000 claims description 4
- FAGUFWYHJQFNRV-UHFFFAOYSA-N tetraethylenepentamine Chemical compound NCCNCCNCCNCCN FAGUFWYHJQFNRV-UHFFFAOYSA-N 0.000 claims description 4
- CKLJMWTZIZZHCS-REOHCLBHSA-N L-aspartic acid Chemical compound OC(=O)[C@@H](N)CC(O)=O CKLJMWTZIZZHCS-REOHCLBHSA-N 0.000 claims description 3
- WHUUTDBJXJRKMK-VKHMYHEASA-N L-glutamic acid Chemical compound OC(=O)[C@@H](N)CCC(O)=O WHUUTDBJXJRKMK-VKHMYHEASA-N 0.000 claims description 3
- KDXKERNSBIXSRK-YFKPBYRVSA-N L-lysine Chemical compound NCCCC[C@H](N)C(O)=O KDXKERNSBIXSRK-YFKPBYRVSA-N 0.000 claims description 3
- GRLJIIJNZJVMGP-UHFFFAOYSA-N S-Methyl butanethioate Chemical compound CCCC(=O)SC GRLJIIJNZJVMGP-UHFFFAOYSA-N 0.000 claims description 3
- AYFVYJQAPQTCCC-UHFFFAOYSA-N THREONINE Chemical compound CC(O)C(N)C(O)=O AYFVYJQAPQTCCC-UHFFFAOYSA-N 0.000 claims description 3
- 239000013207 UiO-66 Substances 0.000 claims description 3
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 claims description 3
- 229940009098 aspartate Drugs 0.000 claims description 3
- UCMIRNVEIXFBKS-UHFFFAOYSA-N beta-alanine Chemical compound NCCC(O)=O UCMIRNVEIXFBKS-UHFFFAOYSA-N 0.000 claims description 3
- 229910052593 corundum Inorganic materials 0.000 claims description 3
- LVTYICIALWPMFW-UHFFFAOYSA-N diisopropanolamine Chemical compound CC(O)CNCC(C)O LVTYICIALWPMFW-UHFFFAOYSA-N 0.000 claims description 3
- 229940043276 diisopropanolamine Drugs 0.000 claims description 3
- OUYCCCASQSFEME-UHFFFAOYSA-N tyrosine Chemical compound OC(=O)C(N)CC1=CC=C(O)C=C1 OUYCCCASQSFEME-UHFFFAOYSA-N 0.000 claims description 3
- 229910001845 yogo sapphire Inorganic materials 0.000 claims description 3
- BSRGOPQVDCJHIW-UHFFFAOYSA-N 2-(2-aminophenyl)propanoic acid Chemical compound OC(=O)C(C)C1=CC=CC=C1N BSRGOPQVDCJHIW-UHFFFAOYSA-N 0.000 claims description 2
- 229940058020 2-amino-2-methyl-1-propanol Drugs 0.000 claims description 2
- KZSNJWFQEVHDMF-BYPYZUCNSA-N L-valine Chemical compound CC(C)[C@H](N)C(O)=O KZSNJWFQEVHDMF-BYPYZUCNSA-N 0.000 claims description 2
- QNAYBMKLOCPYGJ-UHFFFAOYSA-M alaninate Chemical compound CC(N)C([O-])=O QNAYBMKLOCPYGJ-UHFFFAOYSA-M 0.000 claims description 2
- CBTVGIZVANVGBH-UHFFFAOYSA-N aminomethyl propanol Chemical compound CC(C)(N)CO CBTVGIZVANVGBH-UHFFFAOYSA-N 0.000 claims description 2
- 229910052681 coesite Inorganic materials 0.000 claims description 2
- 229910052906 cristobalite Inorganic materials 0.000 claims description 2
- XGZVUEUWXADBQD-UHFFFAOYSA-L lithium carbonate Chemical compound [Li+].[Li+].[O-]C([O-])=O XGZVUEUWXADBQD-UHFFFAOYSA-L 0.000 claims description 2
- 229910052808 lithium carbonate Inorganic materials 0.000 claims description 2
- ZLNQQNXFFQJAID-UHFFFAOYSA-L magnesium carbonate Chemical compound [Mg+2].[O-]C([O-])=O ZLNQQNXFFQJAID-UHFFFAOYSA-L 0.000 claims description 2
- 239000001095 magnesium carbonate Substances 0.000 claims description 2
- 229910000021 magnesium carbonate Inorganic materials 0.000 claims description 2
- 239000000377 silicon dioxide Substances 0.000 claims description 2
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N silicon dioxide Inorganic materials O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 claims description 2
- 229910000108 silver(I,III) oxide Inorganic materials 0.000 claims description 2
- 229910000029 sodium carbonate Inorganic materials 0.000 claims description 2
- 229910052682 stishovite Inorganic materials 0.000 claims description 2
- 229910052905 tridymite Inorganic materials 0.000 claims description 2
- 239000013154 zeolitic imidazolate framework-8 Substances 0.000 claims description 2
- MFLKDEMTKSVIBK-UHFFFAOYSA-N zinc;2-methylimidazol-3-ide Chemical compound [Zn+2].CC1=NC=C[N-]1.CC1=NC=C[N-]1 MFLKDEMTKSVIBK-UHFFFAOYSA-N 0.000 claims description 2
- FUOOLUPWFVMBKG-UHFFFAOYSA-N 2-Aminoisobutyric acid Chemical compound CC(C)(N)C(O)=O FUOOLUPWFVMBKG-UHFFFAOYSA-N 0.000 claims 3
- SNDPXSYFESPGGJ-UHFFFAOYSA-N 2-aminopentanoic acid Chemical compound CCCC(N)C(O)=O SNDPXSYFESPGGJ-UHFFFAOYSA-N 0.000 claims 2
- WRBRCYPPGUCRHW-UHFFFAOYSA-N 2-iminobutanoic acid zwitterion Chemical compound CCC(=N)C(O)=O WRBRCYPPGUCRHW-UHFFFAOYSA-N 0.000 claims 2
- HZIHVNNCKFUSJN-UHFFFAOYSA-N 2,3-diaminopentanoic acid Chemical compound CCC(N)C(N)C(O)=O HZIHVNNCKFUSJN-UHFFFAOYSA-N 0.000 claims 1
- 229960005141 piperazine Drugs 0.000 claims 1
- AGGKEGLBGGJEBZ-UHFFFAOYSA-N tetramethylenedisulfotetramine Chemical compound C1N(S2(=O)=O)CN3S(=O)(=O)N1CN2C3 AGGKEGLBGGJEBZ-UHFFFAOYSA-N 0.000 claims 1
- 229960001124 trientine Drugs 0.000 claims 1
- 238000011069 regeneration method Methods 0.000 abstract description 72
- 230000008929 regeneration Effects 0.000 abstract description 66
- 238000005265 energy consumption Methods 0.000 abstract description 6
- 239000003623 enhancer Substances 0.000 abstract description 4
- 239000000126 substance Substances 0.000 abstract description 4
- 239000000243 solution Substances 0.000 description 85
- 239000003463 adsorbent Substances 0.000 description 20
- OGIDPMRJRNCKJF-UHFFFAOYSA-N titanium oxide Inorganic materials [Ti]=O OGIDPMRJRNCKJF-UHFFFAOYSA-N 0.000 description 14
- KXDHJXZQYSOELW-UHFFFAOYSA-M Carbamate Chemical compound NC([O-])=O KXDHJXZQYSOELW-UHFFFAOYSA-M 0.000 description 12
- 239000007789 gas Substances 0.000 description 11
- 229910052799 carbon Inorganic materials 0.000 description 10
- 238000006243 chemical reaction Methods 0.000 description 10
- UGFAIRIUMAVXCW-UHFFFAOYSA-N Carbon monoxide Chemical compound [O+]#[C-] UGFAIRIUMAVXCW-UHFFFAOYSA-N 0.000 description 8
- 239000002253 acid Substances 0.000 description 8
- BVKZGUZCCUSVTD-UHFFFAOYSA-M Bicarbonate Chemical compound OC([O-])=O BVKZGUZCCUSVTD-UHFFFAOYSA-M 0.000 description 7
- DGAQECJNVWCQMB-PUAWFVPOSA-M Ilexoside XXIX Chemical compound C[C@@H]1CC[C@@]2(CC[C@@]3(C(=CC[C@H]4[C@]3(CC[C@@H]5[C@@]4(CC[C@@H](C5(C)C)OS(=O)(=O)[O-])C)C)[C@@H]2[C@]1(C)O)C)C(=O)O[C@H]6[C@@H]([C@H]([C@@H]([C@H](O6)CO)O)O)O.[Na+] DGAQECJNVWCQMB-PUAWFVPOSA-M 0.000 description 7
- 230000000052 comparative effect Effects 0.000 description 7
- 238000010438 heat treatment Methods 0.000 description 7
- 235000011181 potassium carbonates Nutrition 0.000 description 7
- GZWNUORNEQHOAW-UHFFFAOYSA-M potassium;2-aminoacetate Chemical compound [K+].NCC([O-])=O GZWNUORNEQHOAW-UHFFFAOYSA-M 0.000 description 7
- 230000008569 process Effects 0.000 description 7
- 229910052708 sodium Inorganic materials 0.000 description 7
- 239000011734 sodium Substances 0.000 description 7
- ZLMJMSJWJFRBEC-UHFFFAOYSA-N Potassium Chemical group [K] ZLMJMSJWJFRBEC-UHFFFAOYSA-N 0.000 description 6
- 238000011068 loading method Methods 0.000 description 6
- 239000011259 mixed solution Substances 0.000 description 6
- 229910052757 nitrogen Inorganic materials 0.000 description 6
- 229910052700 potassium Inorganic materials 0.000 description 6
- 229960003975 potassium Drugs 0.000 description 6
- 239000011591 potassium Substances 0.000 description 6
- 238000010223 real-time analysis Methods 0.000 description 6
- 238000003756 stirring Methods 0.000 description 6
- 238000012360 testing method Methods 0.000 description 6
- 238000005303 weighing Methods 0.000 description 6
- 150000003839 salts Chemical class 0.000 description 5
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 4
- QUSNBJAOOMFDIB-UHFFFAOYSA-N Ethylamine Chemical compound CCN QUSNBJAOOMFDIB-UHFFFAOYSA-N 0.000 description 4
- PAFZNILMFXTMIY-UHFFFAOYSA-N cyclohexylamine Chemical compound NC1CCCCC1 PAFZNILMFXTMIY-UHFFFAOYSA-N 0.000 description 4
- 238000010586 diagram Methods 0.000 description 4
- 239000007788 liquid Substances 0.000 description 4
- UJLZCNZPJMYEKF-UHFFFAOYSA-M potassium;2-aminopropanoate Chemical compound [K+].CC(N)C([O-])=O UJLZCNZPJMYEKF-UHFFFAOYSA-M 0.000 description 4
- 230000001172 regenerating effect Effects 0.000 description 4
- KRKNYBCHXYNGOX-UHFFFAOYSA-N citric acid Chemical compound OC(=O)CC(O)(C(O)=O)CC(O)=O KRKNYBCHXYNGOX-UHFFFAOYSA-N 0.000 description 3
- 230000007246 mechanism Effects 0.000 description 3
- 238000000926 separation method Methods 0.000 description 3
- MTCFGRXMJLQNBG-UHFFFAOYSA-N serine Chemical compound OCC(N)C(O)=O MTCFGRXMJLQNBG-UHFFFAOYSA-N 0.000 description 3
- MIJDSYMOBYNHOT-UHFFFAOYSA-N 2-(ethylamino)ethanol Chemical compound CCNCCO MIJDSYMOBYNHOT-UHFFFAOYSA-N 0.000 description 2
- YIJFIIXHVSHQEN-UHFFFAOYSA-N 3-Aminocaproic acid Chemical compound CCCC(N)CC(O)=O YIJFIIXHVSHQEN-UHFFFAOYSA-N 0.000 description 2
- PECYZEOJVXMISF-UHFFFAOYSA-N 3-aminoalanine Chemical compound [NH3+]CC(N)C([O-])=O PECYZEOJVXMISF-UHFFFAOYSA-N 0.000 description 2
- WOMTYMDHLQTCHY-UHFFFAOYSA-N 3-methylamino-1,2-propanediol Chemical compound CNCC(O)CO WOMTYMDHLQTCHY-UHFFFAOYSA-N 0.000 description 2
- PIICEJLVQHRZGT-UHFFFAOYSA-N Ethylenediamine Chemical compound NCCN PIICEJLVQHRZGT-UHFFFAOYSA-N 0.000 description 2
- ODKSFYDXXFIFQN-BYPYZUCNSA-N L-arginine Chemical compound OC(=O)[C@@H](N)CCCN=C(N)N ODKSFYDXXFIFQN-BYPYZUCNSA-N 0.000 description 2
- BAVYZALUXZFZLV-UHFFFAOYSA-N Methylamine Chemical compound NC BAVYZALUXZFZLV-UHFFFAOYSA-N 0.000 description 2
- UEEJHVSXFDXPFK-UHFFFAOYSA-N N-dimethylaminoethanol Chemical compound CN(C)CCO UEEJHVSXFDXPFK-UHFFFAOYSA-N 0.000 description 2
- 229940124532 absorption promoter Drugs 0.000 description 2
- 239000012752 auxiliary agent Substances 0.000 description 2
- 239000002131 composite material Substances 0.000 description 2
- 230000000694 effects Effects 0.000 description 2
- 238000005516 engineering process Methods 0.000 description 2
- 238000006317 isomerization reaction Methods 0.000 description 2
- 238000006386 neutralization reaction Methods 0.000 description 2
- 239000002994 raw material Substances 0.000 description 2
- ZEZSZCSSTDPVDM-UHFFFAOYSA-M sodium;2-aminopropanoate Chemical compound [Na+].CC(N)C([O-])=O ZEZSZCSSTDPVDM-UHFFFAOYSA-M 0.000 description 2
- 239000002904 solvent Substances 0.000 description 2
- 238000001179 sorption measurement Methods 0.000 description 2
- 238000005406 washing Methods 0.000 description 2
- HZAXFHJVJLSVMW-UHFFFAOYSA-N 2-Aminoethan-1-ol Chemical compound NCCO HZAXFHJVJLSVMW-UHFFFAOYSA-N 0.000 description 1
- HLSMPONBWJBOKA-UHFFFAOYSA-N 3-(1h-indol-2-yl)propanoic acid Chemical compound C1=CC=C2NC(CCC(=O)O)=CC2=C1 HLSMPONBWJBOKA-UHFFFAOYSA-N 0.000 description 1
- 101001039157 Homo sapiens Leucine-rich repeat-containing protein 25 Proteins 0.000 description 1
- 102100040695 Leucine-rich repeat-containing protein 25 Human genes 0.000 description 1
- OPKOKAMJFNKNAS-UHFFFAOYSA-N N-methylethanolamine Chemical compound CNCCO OPKOKAMJFNKNAS-UHFFFAOYSA-N 0.000 description 1
- KWYUFKZDYYNOTN-UHFFFAOYSA-M Potassium hydroxide Chemical class [OH-].[K+] KWYUFKZDYYNOTN-UHFFFAOYSA-M 0.000 description 1
- 230000009471 action Effects 0.000 description 1
- 229910000288 alkali metal carbonate Inorganic materials 0.000 description 1
- 150000008041 alkali metal carbonates Chemical class 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- BVKZGUZCCUSVTD-UHFFFAOYSA-N carbonic acid Chemical compound OC(O)=O BVKZGUZCCUSVTD-UHFFFAOYSA-N 0.000 description 1
- 239000003153 chemical reaction reagent Substances 0.000 description 1
- 150000001875 compounds Chemical class 0.000 description 1
- 238000011109 contamination Methods 0.000 description 1
- 238000001816 cooling Methods 0.000 description 1
- 238000005261 decarburization Methods 0.000 description 1
- 238000000354 decomposition reaction Methods 0.000 description 1
- 238000011161 development Methods 0.000 description 1
- 230000018109 developmental process Effects 0.000 description 1
- 238000002474 experimental method Methods 0.000 description 1
- 239000000706 filtrate Substances 0.000 description 1
- 238000001914 filtration Methods 0.000 description 1
- 238000006703 hydration reaction Methods 0.000 description 1
- 239000012535 impurity Substances 0.000 description 1
- 230000002401 inhibitory effect Effects 0.000 description 1
- 230000005764 inhibitory process Effects 0.000 description 1
- 239000000463 material Substances 0.000 description 1
- 239000012528 membrane Substances 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- JKKWCLRJAFFWQO-UHFFFAOYSA-M potassium 3-amino-2-methylpropanoate Chemical compound [K+].NCC(C)C([O-])=O JKKWCLRJAFFWQO-UHFFFAOYSA-M 0.000 description 1
- 239000001508 potassium citrate Substances 0.000 description 1
- 229960002635 potassium citrate Drugs 0.000 description 1
- QEEAPRPFLLJWCF-UHFFFAOYSA-K potassium citrate (anhydrous) Chemical compound [K+].[K+].[K+].[O-]C(=O)CC(O)(CC([O-])=O)C([O-])=O QEEAPRPFLLJWCF-UHFFFAOYSA-K 0.000 description 1
- 235000011082 potassium citrates Nutrition 0.000 description 1
- OGPUHVKGUZPMMV-UHFFFAOYSA-M potassium;2-amino-3-methylbutanoate Chemical compound [K+].CC(C)C(N)C([O-])=O OGPUHVKGUZPMMV-UHFFFAOYSA-M 0.000 description 1
- KTGYMVZCDCHOFH-UHFFFAOYSA-M potassium;3-aminopropanoate Chemical compound [K+].NCCC([O-])=O KTGYMVZCDCHOFH-UHFFFAOYSA-M 0.000 description 1
- 239000000047 product Substances 0.000 description 1
- 230000001737 promoting effect Effects 0.000 description 1
- 230000036632 reaction speed Effects 0.000 description 1
- 238000004064 recycling Methods 0.000 description 1
- 230000009467 reduction Effects 0.000 description 1
- 230000009919 sequestration Effects 0.000 description 1
- HRXQJPKAYPDDFU-UHFFFAOYSA-M sodium;2-amino-3-methylbutanoate Chemical compound [Na+].CC(C)C(N)C([O-])=O HRXQJPKAYPDDFU-UHFFFAOYSA-M 0.000 description 1
- QKJPFZCCZMBRFB-UHFFFAOYSA-M sodium;3-aminopropanoate Chemical compound [Na+].NCCC([O-])=O QKJPFZCCZMBRFB-UHFFFAOYSA-M 0.000 description 1
- 230000001988 toxicity Effects 0.000 description 1
- 231100000419 toxicity Toxicity 0.000 description 1
- 238000001926 trapping method Methods 0.000 description 1
Images
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
- B01D53/46—Removing components of defined structure
- B01D53/62—Carbon oxides
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- 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
- B01D53/74—General processes for purification of waste gases; Apparatus or devices specially adapted therefor
- B01D53/86—Catalytic processes
- B01D53/8671—Removing components of defined structure not provided for in B01D53/8603 - B01D53/8668
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D2251/00—Reactants
- B01D2251/80—Organic bases or salts
-
- 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
- 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
Abstract
The invention mainly relates to a carbon dioxide absorbent, a preparation method and application thereof. The invention relates to a chemical absorbent mainly used for absorbing carbon dioxide in a power plant, which comprises a main absorbent of a component I: optionally one or more of organic primary amine, secondary amine, tertiary amine or polyamine, wherein the proportion of the components is not more than 30%; component II absorption enhancer: carbonate, amino acid salt and steric hindrance amine, and the proportion of the components is not more than 20%. Component III regeneration promoter: one or more of metal oxide catalyst, metal organic framework catalyst or mesoporous molecular sieve catalyst, and the component proportion does not exceed that of the absorbent absorbing CO2And then, the component III is added, so that the regeneration rate of the absorbent can be remarkably promoted, the regeneration temperature of the absorbent is reduced, and the regeneration energy consumption is reduced.
Description
Technical Field
The invention belongs to the field of gas separation, particularly relates to a carbon dioxide absorbent, and a preparation method and application thereof, and particularly relates to a method for preparing a low-concentration carbon dioxide absorbent and absorbing and regenerating the low-concentration carbon dioxide absorbent.
Background
According to the requirement of 'double carbon' plan in China, the 'carbon peak reaching' is realized in 2030, the 'carbon neutralization' is realized in 2060, and the 'carbon neutralization' technology is required to be researched and developed and promoted. CO conventional at present2The emission reduction scheme is that CO2Capture and sequestration combined use technology (CCUS), i.e. CO2Capture, CO2Utilization of and CO2Sequestration, generally, is a separate technique and a combined technique of the three techniques.
CO according to different application situations and the pressure of the raw material gas2The trapping method can be generally classified into a dry absorption method and a wet absorption method. Dry absorption processes generally include adsorption and membrane processes and are generally applicable to feed gas CO2A lower concentration scenario; the wet absorption method can be divided into chemical absorption method and physical absorption method, and the chemical absorption method is mostly used for raw material gas CO2Higher concentration and lower pressure or atmospheric pressure.
In the prior patent with application number CN104275072B, the conventional chemical method is that the flue gas is contacted with an absorbent under normal pressure to carry out chemical reaction, and CO2Is absorbed into solution, and the absorbing rich solution is heated to CO2Desorbing, and regenerating and recycling the solution. However, the main problem of the prior art is that organic alcohol amine solvent with certain toxicity is generally adopted, so that the process is environment-friendlySecondary contamination may occur.
The prior patent with the application number of CN201210159454.4 introduces a composite activated potash solution, and although the patent adopts an environment-friendly solvent, the regeneration temperature of the solution is higher, the regeneration speed is slower, and further development is needed to reduce the regeneration energy consumption of the absorbent.
The prior patent with application number 202010023368.5 discloses a carbon dioxide adsorbent, a preparation method and application thereof, wherein the preparation method of the adsorbent is that a component a: an alkali metal carbonate and optionally one or more of an organic secondary, tertiary or polyamine; and (b) component b: one or more of a basic amino acid salt and optionally an organic primary amine; and a component c: the weak acid and the weak acid salt are prepared according to a certain preferable proportion. The weak acid and weak acid salt regeneration promoter are added into the absorbent, so that the regeneration rate of the absorbent is improved, the regeneration temperature is further reduced, and the regeneration energy consumption is reduced. However, in the absorbent described in the prior patent application No. 202010023368.5, a weak acid and a weak acid salt regeneration promoter are used as regeneration promoters to be mixed with the component a and the component b in one step, and although the component c has a regeneration promoting effect, the absorption performance of the component a and the component b is inhibited to a certain extent only by one-step mixing, and the performance of the absorbent mixed with the component a and the component b cannot be fully exerted, and in addition, it is noted that the absorbent described in the prior patent application No. 202010023368.5 has an absorption temperature of 50 ℃ and a desorption temperature of 90 ℃, while the weak acid and the weak acid salt are easily oxidized and decomposed at a temperature above 50 ℃, and have no good stability, and the operating cost of the absorbent is increased.
For this reason, in order to solve the inhibition effect of the regeneration promoter on the absorbent, the main absorbent of the component I is limited to one or more of organic primary amine, secondary amine, tertiary amine and polyamine, the absorption promoter of the component II is limited to one or more of optional carbonate, basic amino acid salt and steric hindrance amine, and the absorbent only relates to the component I and the component II in the absorption process. The method solves the problem of inhibiting the absorbent by the regeneration promoter in the absorption process, and can reduce the operation temperature of the absorbent to 40 ℃. The component III regeneration promoter is limited to one or more of metal oxide catalyst, metal organic framework catalyst or mesoporous molecular sieve catalyst with higher stability. The step of adding the component III is optimized, the regeneration operation temperature and the regeneration energy consumption are further reduced, and the overall operation cost is finally reduced.
Disclosure of Invention
The invention aims to solve the existing technical problems and provides a carbon dioxide absorbent, and a preparation method and application thereof. The carbon dioxide absorbent of the invention can further improve the regeneration rate of the absorbent and reduce the regeneration temperature and the regeneration energy consumption by adding the metal oxide catalyst, the metal organic framework catalyst or the mesoporous molecular sieve catalyst regeneration promoter after absorption and adjusting the adding step of the regeneration promoter, thereby realizing the purpose of reducing the whole operation cost.
The object of the invention can be achieved by the following scheme:
in a first aspect, the present invention provides a carbon dioxide absorbent, which comprises the following components in parts by mass, based on the total mass of the absorbent: not more than 30% of component I; not more than 20% of component II; not more than 10% of component III, the balance being component IV;
the component I comprises one or more of organic primary amine, organic secondary amine, organic tertiary amine and polyamine;
the component II comprises one or more of carbonate, basic amino acid salt and steric hindrance amine;
the component III comprises one or more of a metal oxide catalyst, a metal organic framework catalyst and a mesoporous molecular sieve catalyst;
the component IV comprises deionized water.
According to some embodiments of the invention, the mass fraction of the component I is 10-15% based on the total weight of the absorbent; the mass fraction of the component II is 5-20%; the mass fraction of the component III is 2.5-4.3%. Wherein, the total mass fraction of the component I, the component II and the component III is preferably not more than 30 percent. The component III has less usage amount and can effectively control the operation cost under the condition of higher stability. The adsorbent can better control the absorption capacity and the regeneration rate by controlling the proportional relation between the component I and the regeneration auxiliary agent component III. The absorbent can better control the absorption speed, the regeneration temperature and the regeneration rate by controlling the proportional relation between the component II and the regeneration auxiliary agent component III.
As an embodiment of the invention, in the component I, the organic primary amine comprises one or more of C2-C10 organic primary amines. The organic primary amine is preferably selected from one or more of Monomethylamine (MAPA), Ethylamine (EA), Ethylenediamine (EDA) and Cyclohexylamine (CHA).
As an embodiment of the invention, in the component I, the organic secondary amine comprises one or more of C2-C10 organic secondary amines. The organic secondary amine is preferably one or more of methyl mono-2-hydroxyethylamine (MMEA), N-ethyl-2-hydroxyethylamine (EAE), N-Diethylaniline (DEA) and 3-methylamino-1, 2-propanediol (MAPD).
As an embodiment of the invention, in component I, the organic tertiary amine is selected from one or more of the organic tertiary amines of C2-C10. The organic tertiary amine is preferably selected from one or more of N, N-dimethyl-2-hydroxyethylamine (DMEA), tri-2-hydroxyethylamine (TEA) and Diethylenetriamine (DETA).
As an embodiment of the present invention, in component I, the polyamine is selected from one or more of Diethylenetriamine (DETA), triethylenetetramine (TETA), and Tetraethylenepentamine (TEPA).
As one embodiment of the invention, the main absorbent component I comprises any two of organic primary amine, organic secondary amine, organic tertiary amine and polyamine. Optionally, the mass ratio of the two is 0.01-10: 1. Mass is, for example, 0.01:1, 0.5:1, 1.0:1, 1.5:1, 2.0:1, 2.5:1, 3.0:1, 3.5:1, 4.0:1, 4.5:1, 5.0:1, 5.5:1, 6.0:1, 6.5:1, 7.0:1, 7.5:1, 8.0:1, 8.5:1, 9.0:1, 9.5:1, 10:1, and any value therebetween. Optionally, the mass ratio of the two is preferably 0.5-5: 1.
The main function of the component I is to provide enough absorption capacity, and the invention limits the main absorbent of the component I to one or more of organic primary amine, secondary amine, tertiary amine and polyamine, so that the absorption capacity of the absorbent can be effectively improved, and the cost of the whole absorbent can be reduced.
As an embodiment of the present invention, in the component II, the carbonate includes one or more of potassium carbonate, sodium carbonate, lithium carbonate, and magnesium carbonate.
As an embodiment of the invention, in component II the basic amino acid salt is selected from the group consisting of alpha-aminoacetate, 2-aminopropionate, 3-aminopropionate, 2-amino-3-methylbutyrate, alpha-aminoisohexanate, alpha-amino-beta-methylvalerate, 2-aminophenylpropionate, alpha-iminoate, beta-indolylpropanate, L-2-amino-3-hydroxypropionate, 2-amino-3-p-hydroxyphenylpropionate, L-2-amino-3-mercaptopropionate, methylthiobutyrate, beta-hydroxy-alpha-aminobutyrate, aspartate, alpha-aminoglutarate, 2, 6-diaminohexanoate, beta-aminohexanoate, beta-hydroxy-alpha-aminopropionate, beta-hydroxy-aminopropionate, beta-aminohexanoate, beta-hydroxy-aminopropionate, beta-amino-aminopropionate, beta-aminopropionate, or the salt of the compound of the formula (I, the formula (I), or the formula (I) in which is shown in (I) in which is shown in (I) and (I) in (I) and (I) in which is shown in (I) and (I) in (, One or more of 2-amino-5-guanidino valerate, alpha-amino beta-imidazolyl propionate. The basic amino acid salt is preferably potassium α -aminoacetate, sodium α -aminoacetate, potassium 2-aminopropionate, potassium 3-aminopropionate, sodium 2-aminopropionate, sodium 3-aminopropionate, potassium 2-amino-3-methylbutyrate, sodium 2-amino-3-methylbutyrate, potassium α -aminoisohexate, sodium α -aminoisohexate, potassium α -amino- β -methylpentanoate, sodium α -amino- β -methylpentanoate, potassium 2-aminopropionate, sodium 2-aminopropionate, α -iminosalt, β -indolylacylate, L-2-amino-3-hydroxypropionate, 2-amino-3-p-hydroxyphenylpropionate, L-2-amino-3-mercaptopropionate, potassium 2-aminopropionate, potassium 3-aminoisobutyrate, potassium α -aminoisohexanoate, sodium α -aminoisohexanate, sodium α -aminoisohexanoate, potassium α -amino- β -methylpentanoate, potassium α -amino- β -aminopropionate, potassium 2-aminopropionate, sodium L-2-amino-3-mercaptopropionate, sodium, One or more of methylthio butyrate, beta-hydroxy-alpha-aminobutyrate, aspartate, alpha-aminoglutarate, 2, 6-diaminohexanoate, 2-amino-5-guanidino valerate, and alpha-amino beta-imidazolyl propionate.
As an embodiment of the present invention, in component II, the sterically hindered amine comprises one or more of 2-amino-2-methyl-1, 3 propanediol (AMP), 2-amino-2-methyl-1-propanol (AMPD), Diisopropanolamine (DIPA), Piperazine (PZ).
According to some embodiments of the invention, component II is preferably a combination of said carbonate, amino acid salt and sterically hindered amine. The mass ratio of the carbonate, the amino acid salt and the steric hindrance amine is (0.01-8) to 1 (0.01-8). The mass ratio is, for example, 0.01:1:0.01, 0.5:1:0.5, 1.0:1:1.0, 1.5:1:1.5, 2.0:1:2.0, 2.5:1:2.5, 3.0:1:3.0, 3.5:1:3.5, 4.0:1:4.0, 4.5:1:4.5, 5.0:1:5.0, 5.5:1:5.5, 6.0:1:6.0, 6.5:1:6.5, 7.0:1:7.0, 7.5:1:7.5, 8.0:1:8.0 and any value therebetween. In the experiment, the three absorption promoters can fully exert the efficacy, so the combination of the three is better.
According to some embodiments of the invention, the component II mainly has the effect of improving the absorption speed of the main absorbent of the component I, and the reaction speed of the main absorbent of the component I can be better improved and the operation cost can be reduced by adjusting the proper proportion of the carbonate, the amino acid salt and the sterically hindered amine in the component II.
As an embodiment of the invention, in component III, the metal oxide catalyst is selected from ZnO, TiO2、ZrO2、Al2O3、Ag2O、Cr2O3、V2O5、MoO3、WO3One or more of (a). The metal oxide catalyst is preferably ZnO or TiO2、ZrO2、Al2O3、MoO3One or more of (a). (ii) a
As an embodiment of the invention, in component III, the metal organic framework catalyst is selected from one or more of ZIF-8, ZIF-67 and UiO-66. The metal organic framework catalyst is preferably UiO-66.
As an embodiment of the invention, in the component III, the mesoporous molecular sieve catalyst is selected from HZSM-5, SAPO-34 and CMK-3-SiO2One or more of CMK-3-MCM-41 and CMK-3-SBA-15. The mesoporous molecular sieve catalyst is preferably one or more of HZSM-5, CMK-3-MCM-41 and CMK-3-SBA-15.
In one embodiment of the present invention, the component III is two of a metal oxide catalyst, a metal organic framework catalyst, and a mesoporous molecular sieve catalyst. Optionally, the mass ratio of the two components is 1-10: 1. The mass ratio is preferably 2-6:1, more preferably 2.5-4.5: 1. Optionally two are better than one, three are less good than two.
The invention absorbs CO in the absorbent2And a metal oxide catalyst, a metal organic framework catalyst or a mesoporous molecular sieve catalyst is added into the reaction kettle, so that the regeneration rate can be effectively improved, and the reaction regeneration temperature can be further reduced.
In a second aspect, the present invention provides a method for preparing a carbon dioxide absorbent, the method comprising the steps of:
s1, mixing the component I and part of the component IV to completely dissolve the component I, and adding the mixture of the component II and the rest of the component IV to obtain an absorption part mixture of the low-concentration carbon dioxide absorbent;
s2, absorbing CO at S12Thereafter, component III is fed to step S1 for absorbing CO2And obtaining a desorption part mixture of the carbon dioxide absorbent, namely the carbon dioxide absorbent, in the obtained mixture.
The invention also provides a method for absorbing carbon dioxide by using the carbon dioxide absorbent, which comprises the following steps: mixing a component I and a component IV to completely dissolve the component I, and then adding a component II to obtain an absorption part mixture of the low-concentration carbon dioxide absorbent; absorbing CO from the mixture of step S12Then adding the component III to obtain the carbon dioxide absorbent; subsequently heating and passing N2Regenerating, reacting, and filtering to obtain component III, wherein the filtrate is the absorption part mixture of the carbon dioxide absorbent.
In a third aspect, the invention provides an application of the carbon dioxide absorbent, wherein the application is the application in the capture of carbon dioxide in flue gas discharged from a power plant flue gas. Application of method for preparing low-concentration carbon dioxide absorbent and absorbing and regenerating low-concentration carbon dioxide absorbent in capturing carbon dioxide in flue gas discharged by power plant flue gas containing CO2High concentration of CO is required2The absorbent has absorption capacity and can stably use the regenerated catalyst.
Compared with the prior art, the invention has the following beneficial effects:
(1) the whole absorption efficiency of the composite absorbent can be improved by 10-15% compared with the prior art by adjusting the main absorbent of the component I and the absorption enhancer of the component II in a proper proportion.
(2) The efficiency of the absorption part and the desorption part of the low-concentration carbon dioxide absorbent can be maximized by adjusting the composition of the component III and the step of adding the component III.
(3) The overall mass proportion of the component I, the component I and the component III is controlled within 30 percent, so that the working temperature of the absorbent can be reduced by 20 percent, the working temperature in the desorption process is reduced by 30 percent, and the cost is reduced by 70 percent.
Drawings
Other features, objects and advantages of the invention will become more apparent upon reading of the detailed description of non-limiting embodiments with reference to the following drawings:
FIG. 1 CO of the present invention2A flow diagram of an absorption process;
FIG. 2 is a graph of the absorption curves of the examples;
FIG. 3 is a graph comparing the regeneration rates of examples;
FIG. 4 is a diagram of a bulk absorbent reaction process;
FIG. 5 is a diagram of an absorption enhancer reaction process;
FIG. 6 is a diagram for explaining the reaction process of the accelerator.
Detailed Description
The invention is described in detail below with reference to the figures and specific embodiments. The following examples, which are set forth to provide a detailed description of the invention and a detailed description of the operation, will help those skilled in the art to further understand the present invention. It should be noted that the scope of the present invention is not limited to the following embodiments, and that several modifications and improvements made on the premise of the idea of the present invention belong to the scope of the present invention.
The invention provides a carbon dioxide absorbent, as shown in figure 1, flue gas discharged by a power plant firstly enters a flue gas washing tower to elute non-gas impurities, and then enters an absorption tower through a decarburization induced draft fan to carry out CO absorption2Capture and absorption of CO2The purified flue gas is washed by water in a water washing tower and then discharged; the absorbent in the absorption tower absorbs CO2Then forming a rich solution and a lean solution which enter a lean and rich solution heat exchanger through a rich solution pump; the lean solution is cooled by a lean solution pump through a cooler and then returns to the absorption tower, and the rich solution is heated by a rich solution pump through a heater and enters a desorption tower for CO2Desorbing, cooling by a cooler after gas-liquid separation, introducing into a gas-liquid separator, and introducing CO2The absorption liquid after desorption is returned to the desorption tower through a pump and then returned to the lean-rich liquid exchanger; the desorber temperature is provided by the vapor via the reboiler.
FIG. 4 shows CO absorption by the main absorbent2In the primary amine solution, carbon dioxide reacts with primary amine to form carbamate, and the carbamate exists in the primary amine solution, but a certain amount of carbonate ions and bicarbonate ions also exist in the solution due to decomposition of the carbamate or direct hydration reaction of the carbon dioxide. The reaction mechanism of the secondary amine solution for absorbing carbon dioxide is similar to that of the primary amine, and carbon dioxide also exists in the form of carbamate, carbonate and bicarbonate in the solution at the same time. The carbon dioxide exists in the tertiary amine solution only in the form of carbonate and bicarbonate ions which are easy to decompose, the carbon dioxide in the solution is released, and the energy consumption for regenerating the absorbent is lower. The polyamine contains three kinds of amines, i.e., primary amine, secondary amine, and tertiary amine, and generally contains many primary and secondary amines, so that the form of carbon dioxide existing in the polyamine is mainly carbamate.
FIG. 5 shows the main absorption enhancer CO2Reaction process of (A), CO2Reacting with carbonate to form bicarbonate; CO 22The reaction with the amino acid salt is similar to the reaction process of the main absorbent, and the carbamate is generated; the sterically hindered amine takes secondary amine and tertiary amine as main components and reacts to generate carbamate and bicarbonate ions.
FIG. 6 shows desorption promoters, both of which are catalysts, wherein the catalysts of the metal oxide and the mesoporous molecular sieve are used for catalyzing CO2The desorption mechanism is basically similar, all by absorbing CO2The carbamate formed later is protonated and adsorbed on the surface of the catalyst,then, molecular isomerization is carried out under the action of a catalyst, so that carbon-nitrogen bonds in the carbamate are lengthened and then broken, and then CO is removed2Separation from carbamate, and finally CO2Desorbing from the surface of the catalyst to complete the regeneration. And metal organic framework catalyst for catalyzing CO2The desorption mechanism is that the carbamate molecules are isomerized firstly, so that the carbon-nitrogen bonds in the carbamate are lengthened and then broken, and CO is obtained2In the form of bicarbonate, with subsequent further isomerization of CO2Adsorption on the catalyst surface, and finally CO2Desorbing from the surface of the catalyst to complete the regeneration. If the amount is too large, the amine structure is destroyed, bicarbonate is formed, and carbon dioxide is not formed.
The present invention is further described below with reference to examples, which are intended to be illustrative only, and are not intended to limit the scope of the present invention in any way.
The examples, in which specific conditions are not specified, were carried out according to conventional conditions or conditions recommended by the manufacturer. The reagents or instruments used are not indicated by the manufacturer, and are all conventional products commercially available.
Example 1
Dissolving 7.5g of Diethylenetriamine (DETA) in the component I in 30ml of deionized water to form a solution A;
dissolving 1.0g of potassium carbonate, 4.0g of potassium aminoacetate and 1.0g of piperazine in the component II in 20ml of deionized water to form a mixed solution B, namely an absorbent absorption part;
mixing the above absorbent solutions, placing into a three-neck flask with condenser and thermometer, maintaining the temperature of the solution in the flask at 40 deg.C under heating of oil bath, and adding 15% CO at flow rate of 120ml/min2Introducing the mixed gas into the bottom of the solution, absorbing for 2h, and measuring CO in the solution by using a real-time analysis method2And (4) content.
In absorbing CO2Then 1.25g of TiO were added2And 1.25g of HZSM-5 (in which TiO)2The mass ratio of the adsorbent to the HZSM-5 is 1:1), and then the adsorbent is uniformly mixed to form an adsorbent desorption part;
the oil bath was then tempered to 65 ℃ and N was passed through at a flow rate of 20ml/min2Carrying out regeneration test, stirring at 100rpm for 1h, and measuring CO in the solution by real-time weighing method2Content, from which the regeneration rate of the absorbing solution was calculated.
Wherein the regeneration rate of the absorption solution (CO in the solution before regeneration)2Loading of-CO in solution after regeneration2The supported amount of (d)/regeneration time (3.31-1.05)/60 (0.0377 mol/(L · min), the results are shown in table 1.
Example 2
Dissolving 7.5g of Diethylenetriamine (DETA) in the component I in 30ml of deionized water to form a solution A;
dissolving 1.25g of potassium carbonate, 4.5g of potassium aminoacetate and 1.25g of piperazine in 20ml of deionized water to form a mixed solution B, namely an absorbent part;
mixing the above absorbent solutions, placing into a three-neck flask with condenser and thermometer, maintaining the temperature of the solution in the flask at 40 deg.C under heating of oil bath, and adding 15% CO at flow rate of 120ml/min2Introducing the mixed gas into the bottom of the solution, absorbing for 2h, and measuring CO in the solution by using a real-time analysis method2And (4) content.
In absorbing CO2Then 1.30g of TiO were added2And 1.30g of HZSM-5 (in which TiO)2The mass ratio of the adsorbent to the HZSM-5 is 1:1), and then the adsorbent is uniformly mixed to form an adsorbent desorption part;
the oil bath was then tempered to 65 ℃ and N was passed through at a flow rate of 20ml/min2Carrying out regeneration test, stirring at 100rpm for 1h, and measuring CO in the solution by real-time weighing method2Content, from which the regeneration rate of the absorbing solution was calculated.
Wherein the regeneration rate of the absorption solution (CO in the solution before regeneration)2Loading of-CO in solution after regeneration2The supported amount of (d)/regeneration time (3.61-1.98)/60 (0.0272 mol/(L · min), the results are shown in table 1.
Example 3
Dissolving 7.5g of Diethylenetriamine (DETA) in the component I in 30ml of deionized water to form a solution A;
dissolving 1.5g of potassium carbonate, 5.0g of potassium aminoacetate and 1.5g of piperazine in the component II in 20ml of deionized water to form a mixed solution B, namely an absorbent absorption part;
mixing the above absorbent solutions, placing into a three-neck flask with condenser and thermometer, maintaining the temperature of the solution in the flask at 40 deg.C under heating of oil bath, and adding 15% CO at flow rate of 120ml/min2Introducing the mixed gas into the bottom of the solution, absorbing for 2h, and measuring CO in the solution by using a real-time analysis method2And (4) content.
In absorbing CO2Then 1.35g of TiO were added2And 1.35g of HZSM-5 (in which TiO)2The mass ratio of the adsorbent to the HZSM-5 is 1:1), and then the adsorbent is uniformly mixed to form an adsorbent desorption part;
the oil bath was then tempered to 65 ℃ and N was passed through at a flow rate of 20ml/min2Carrying out regeneration test, stirring at 100rpm for 1h, and measuring CO in the solution by real-time weighing method2Content, from which the regeneration rate of the absorbing solution was calculated.
Wherein the regeneration rate of the absorption solution (CO in the solution before regeneration)2Loading of-CO in solution after regeneration2The supported amount of (c)/regeneration time (3.7-1.98)/60 (0.0447 mol/(L · min) were as shown in table 1.
Example 4
Dissolving 7.5g of Diethylenetriamine (DETA) in the component I in 30ml of deionized water to form a solution A;
taking 1.75g of potassium carbonate, 5.5g of potassium aminoacetate and 1.75g of piperazine in the component II, and dissolving the components in 20ml of deionized water to form a mixed solution B, namely an absorbent part;
mixing the above absorbent solutions, placing into a three-neck flask with condenser and thermometer, maintaining the temperature of the solution in the flask at 40 deg.C under heating of oil bath, and adding 15% CO at flow rate of 120ml/min2Introducing the mixed gas into the bottom of the solution, absorbing for 2h, and measuring CO in the solution by using a real-time analysis method2And (4) content.
In the absorption of CO2Then 1.40g of TiO were added2And 1.40g of HZSM-5 (which isMedium TiO 22The mass ratio of the adsorbent to the HZSM-5 is 1:1), and then the adsorbent is uniformly mixed to form an adsorbent desorption part;
the oil bath was then tempered to 65 ℃ and N was passed through at a flow rate of 20ml/min2Carrying out regeneration test, stirring at 100rpm for 1h, and measuring CO in the solution by real-time weighing method2Content, from which the regeneration rate of the absorbing solution was calculated.
Wherein the regeneration rate of the absorption solution (CO in the solution before regeneration)2Loading of-CO in solution after regeneration2The supported amount of (c)/regeneration time (4.05-2.26)/60 (0.0298 mol/(L · min) were as shown in table 1.
Example 5
Dissolving 7.5g of Diethylenetriamine (DETA) in the component I in 30ml of deionized water to form a solution A;
2.00g of potassium carbonate, 6.0g of potassium aminoacetate and 2.00g of piperazine in the component II are dissolved in 20ml of deionized water to form a mixed solution B, namely an absorbent absorption part;
mixing the above absorbent solutions, placing into a three-neck flask with condenser and thermometer, maintaining the temperature of the solution in the flask at 40 deg.C under heating of oil bath, and adding 15% CO at flow rate of 120ml/min2Introducing the mixed gas into the bottom of the solution, absorbing for 2h, and measuring CO in the solution by using a real-time analysis method2And (4) content.
In absorbing CO2Then 1.45g of TiO were added2And 1.45g of HZSM-5 (in which TiO was present)2The mass ratio of the adsorbent to the HZSM-5 is 1:1), and then the adsorbent is uniformly mixed to form an adsorbent desorption part;
the oil bath was then tempered to 65 ℃ and N was passed through at a flow rate of 20ml/min2Carrying out regeneration test, stirring at 100rpm for 1h, and measuring CO in the solution by real-time weighing method2Content, from which the regeneration rate of the absorbing solution was calculated.
Wherein the regeneration rate of the absorption solution (CO in the solution before regeneration)2Loading of-CO in solution after regeneration2The supported amount of (c)/regeneration time (4.17-2.46)/60 (0.0285 mol/(L · min), the results are shown in table 1.
Example 6
Dissolving 7.5g of Diethylenetriamine (DETA) in the component I in 30ml of deionized water to form a solution A;
2.25g of potassium carbonate, 6.5g of potassium aminoacetate and 2.25g of piperazine in the component II are dissolved in 20ml of deionized water to form a mixed solution B, namely an absorbent part;
mixing the above absorbent solutions, placing into a three-neck flask with condenser and thermometer, maintaining the temperature of the solution in the flask at 40 deg.C under heating of oil bath, and adding 15% CO at flow rate of 120ml/min2Introducing the mixed gas into the bottom of the solution, absorbing for 2h, and measuring CO in the solution by using a real-time analysis method2And (4) content.
In absorbing CO2Then 1.35g of TiO were added2And 1.35g of HZSM-5 (in which TiO)2The mass ratio of the adsorbent to HZSM-5 is 1:1), and then the adsorbent is desorbed after being uniformly mixed;
the oil bath was then tempered to 65 ℃ and N was passed through at a flow rate of 20ml/min2Carrying out regeneration test, stirring at 100rpm for 1h, and measuring CO in the solution by real-time weighing method2Content, from which the regeneration rate of the absorbing solution was calculated.
Wherein the regeneration rate of the absorption solution (CO in the solution before regeneration)2Loading of-CO in solution after regeneration2The supported amount of (c)/regeneration time (4.43 to 0.78)/60 (0.0608 mol/(L · min) were as shown in table 1.
Comparative example 1:
the absorbent solution component I was composed of 3.25g Diethylenetriamine (DETA) and 3.25g triethylenetetramine (TETA) monopetamine, and the other specific procedures were the same as in example 3. The results are shown in Table 1.
Comparative example 2:
in comparison with example 3, 0.5g of TiO was added in an amount greater than that of component III in the absorbent solution2Other specific operation steps are the same as those in example 3. The results are shown in Table 1.
Comparative example 3:
in comparison with example 3, 1.0g of TiO was added in more amount as component III in the absorbent solution2Other toolsThe procedure was the same as in example 2. The results are shown in Table 1.
Comparative example 4
Compared with the example 3, the absorbent solution is added with only the components I and II, and other specific operation steps are the same as the example 2. The results are shown in Table 1.
Comparative example 5
Compared with example 3, the difference is only that: component II was 2g of potassium glycinate and 6g of monoethanolamine and the results are given in Table 1.
Comparative example 6
Compared with example 3, the difference is only that: component III was 1.35g of citric acid and 1.35g of potassium citrate and the results are given in Table 1.
The carbon dioxide absorption curves of the absorbent solutions prepared in the respective examples and comparative examples are shown in fig. 2, and the regeneration rates versus the ratios are shown in fig. 3; the regeneration rate of the absorbent is shown in Table 1.
TABLE 1
It should be noted that the above-mentioned embodiments are only for explaining the present invention, and do not set any limit to the present invention. The present invention has been described with reference to exemplary embodiments, but the words which have been used herein are words of description and illustration, rather than words of limitation. The invention can be modified, as prescribed, within the scope of the claims and without departing from the scope and spirit of the invention. Although the invention has been described herein with reference to particular means, materials and embodiments, the invention is not intended to be limited to the particulars disclosed herein, but rather extends to all other methods and applications having the same functionality.
Claims (10)
1. The carbon dioxide absorbent is characterized by comprising the following components in percentage by mass based on the total mass of the absorbent:
not more than 30% of component I; not more than 20% of component II; no more than 10% of component III; the balance being component IV;
the component I comprises one or more of organic primary amine, organic secondary amine, organic tertiary amine and polyamine;
the component II comprises one or more of carbonate, basic amino acid salt and steric hindrance amine;
the component III comprises one or more of a metal oxide catalyst, a metal organic framework catalyst and a mesoporous molecular sieve catalyst;
the component IV comprises deionized water.
2. The carbon dioxide absorbent according to claim 1, wherein the mass fraction of the component I is 10-15% of the total weight of the absorbent; the mass fraction of the component II is 5-20%; the mass fraction of the component III is 2.5-4.3%.
3. The carbon dioxide absorbent according to claim 1, wherein in component I, the organic primary amine comprises one or more of C2-C10 organic primary amines; the secondary organic amine comprises one or more of secondary organic amines of C2-C10; the organic tertiary amine is selected from one or more of C2-C10; the polyamine is selected from one or more of Diethylenetriamine (DETA), triethylene tetramine (TETA) and Tetraethylenepentamine (TEPA).
4. The carbon dioxide absorbent according to claim 1, wherein in component II, the carbonate comprises one or more of potassium carbonate, sodium carbonate, lithium carbonate, magnesium carbonate; the basic amino acid salt is selected from the group consisting of alpha-aminoacetate, 2-aminopropionate, 3-aminopropionate, 2-amino-3-methylbutyrate, alpha-aminoiso-hexanoate, alpha-amino-beta-methylvalerate, 2-aminophenylpropionate, alpha-imidoate, beta-indolylproate, L-2-amino-3-hydroxypropionate, 2-amino-3-p-hydroxyphenylpropionate, L-2-amino-3-mercaptopropionate, methylthiobutyrate, beta-hydroxy-alpha-aminobutyrate, aspartate, alpha-aminoglutarate, 2, 6-diaminohexanoate, 2-amino-5-guanidinopropionate, 2-amino-3-aminovalerate, 2-aminoisobutyrate, 2-aminovalerate, 2-aminoisobutyrate, 2-aminovalerate, 2-aminoisobutyrate, 2-iminobutyrate, and 2-iminobutyrate, One or more of alpha-amino beta-imidazolyl propionate; the sterically hindered amine comprises one or more of 2-amino-2-methyl-1, 3-propanediol, 2-amino-2-methyl-1-propanol, diisopropanolamine and piperazine.
5. The carbon dioxide absorbent according to claim 1, wherein in component III, the metal oxide catalyst is selected from ZnO, TiO2、ZrO2、Al2O3、Ag2O、Cr2O3、V2O5、MoO3、WO3One or more of (a).
6. The carbon dioxide absorbent according to claim 1, wherein in component III, the metal organic framework catalyst is selected from one or more of ZIF-8, ZIF-67, UiO-66.
7. The carbon dioxide absorbent according to claim 1, wherein in component III, the mesoporous molecular sieve catalyst is selected from the group consisting of HZSM-5, SAPO-34, CMK-3-SiO2One or more of CMK-3-MCM-41 and CMK-3-SBA-15.
8. The carbon dioxide absorbent according to claim 1, wherein component III is two of a metal oxide catalyst, a metal organic framework catalyst, and a mesoporous molecular sieve catalyst.
9. A method for preparing a carbon dioxide absorbent according to claim 1, characterized in that the method comprises the steps of:
s1, mixing the component I and part of the component IV to completely dissolve the component I, and adding the mixture of the component II and the rest of the component IV to obtain an absorption part mixture of the low-concentration carbon dioxide absorbent;
s2, absorbing CO at S12Thereafter, component III is fed to step S1 for absorbing CO2And obtaining a desorption part mixture of the carbon dioxide absorbent, namely the carbon dioxide absorbent, in the obtained mixture.
10. Use of a carbon dioxide absorbent according to claim 1 for the capture of carbon dioxide from flue gases emitted from power plants.
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| CN116550118A (en) * | 2023-07-09 | 2023-08-08 | 浙江百能科技有限公司 | Integrated separation device and method for activating absorption crystallization |
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