CN113457735A - Preparation of strong alkaline homogeneous phase dihydric alcohol metal salt catalyst and method for synthesizing carbonic ester by using same - Google Patents
Preparation of strong alkaline homogeneous phase dihydric alcohol metal salt catalyst and method for synthesizing carbonic ester by using same Download PDFInfo
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- CN113457735A CN113457735A CN202110830021.6A CN202110830021A CN113457735A CN 113457735 A CN113457735 A CN 113457735A CN 202110830021 A CN202110830021 A CN 202110830021A CN 113457735 A CN113457735 A CN 113457735A
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- ethylene glycol
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- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 title claims abstract description 109
- 239000003054 catalyst Substances 0.000 title claims abstract description 88
- 229910052751 metal Inorganic materials 0.000 title claims abstract description 37
- 239000002184 metal Substances 0.000 title claims abstract description 37
- 238000000034 method Methods 0.000 title claims abstract description 34
- 150000003839 salts Chemical class 0.000 title claims abstract description 34
- 150000002148 esters Chemical class 0.000 title claims abstract description 19
- 230000002194 synthesizing effect Effects 0.000 title claims abstract description 13
- 238000002360 preparation method Methods 0.000 title claims description 15
- LYCAIKOWRPUZTN-UHFFFAOYSA-N Ethylene glycol Chemical class OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 claims abstract description 125
- 238000006243 chemical reaction Methods 0.000 claims abstract description 101
- 239000003513 alkali Substances 0.000 claims abstract description 20
- KMTRUDSVKNLOMY-UHFFFAOYSA-N Ethylene carbonate Chemical compound O=C1OCCO1 KMTRUDSVKNLOMY-UHFFFAOYSA-N 0.000 claims abstract description 9
- 229910052799 carbon Inorganic materials 0.000 claims abstract description 7
- KWYUFKZDYYNOTN-UHFFFAOYSA-M Potassium hydroxide Chemical compound [OH-].[K+] KWYUFKZDYYNOTN-UHFFFAOYSA-M 0.000 claims description 25
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 25
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 claims description 24
- WGCNASOHLSPBMP-UHFFFAOYSA-N hydroxyacetaldehyde Natural products OCC=O WGCNASOHLSPBMP-UHFFFAOYSA-N 0.000 claims description 21
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 claims description 15
- 239000002585 base Substances 0.000 claims description 13
- ZSXFZANQMJQBTQ-UHFFFAOYSA-N ethane-1,2-diol;potassium Chemical compound [K].OCCO ZSXFZANQMJQBTQ-UHFFFAOYSA-N 0.000 claims description 11
- 230000002829 reductive effect Effects 0.000 claims description 11
- 239000002994 raw material Substances 0.000 claims description 10
- 239000002904 solvent Substances 0.000 claims description 9
- 239000012266 salt solution Substances 0.000 claims description 8
- -1 glycol anion Chemical class 0.000 claims description 7
- WEVYAHXRMPXWCK-UHFFFAOYSA-N Acetonitrile Chemical compound CC#N WEVYAHXRMPXWCK-UHFFFAOYSA-N 0.000 claims description 6
- WMFOQBRAJBCJND-UHFFFAOYSA-M Lithium hydroxide Chemical compound [Li+].[OH-] WMFOQBRAJBCJND-UHFFFAOYSA-M 0.000 claims description 6
- DKGAVHZHDRPRBM-UHFFFAOYSA-N Tert-Butanol Chemical compound CC(C)(C)O DKGAVHZHDRPRBM-UHFFFAOYSA-N 0.000 claims description 6
- 239000011259 mixed solution Substances 0.000 claims description 6
- 150000001768 cations Chemical class 0.000 claims description 5
- 239000000243 solution Substances 0.000 claims description 5
- WQDUMFSSJAZKTM-UHFFFAOYSA-N Sodium methoxide Chemical compound [Na+].[O-]C WQDUMFSSJAZKTM-UHFFFAOYSA-N 0.000 claims description 4
- RPDAUEIUDPHABB-UHFFFAOYSA-N potassium ethoxide Chemical compound [K+].CC[O-] RPDAUEIUDPHABB-UHFFFAOYSA-N 0.000 claims description 4
- BDAWXSQJJCIFIK-UHFFFAOYSA-N potassium methoxide Chemical compound [K+].[O-]C BDAWXSQJJCIFIK-UHFFFAOYSA-N 0.000 claims description 4
- 238000004321 preservation Methods 0.000 claims description 4
- 238000002390 rotary evaporation Methods 0.000 claims description 4
- MFRIHAYPQRLWNB-UHFFFAOYSA-N sodium tert-butoxide Chemical compound [Na+].CC(C)(C)[O-] MFRIHAYPQRLWNB-UHFFFAOYSA-N 0.000 claims description 4
- AQVNXGRBASVGRC-UHFFFAOYSA-N [Li].OCCO Chemical compound [Li].OCCO AQVNXGRBASVGRC-UHFFFAOYSA-N 0.000 claims description 3
- NWJKPSLXLQLUTC-UHFFFAOYSA-N ethane-1,2-diol;sodium Chemical compound [Na].OCCO NWJKPSLXLQLUTC-UHFFFAOYSA-N 0.000 claims description 3
- MFGOFGRYDNHJTA-UHFFFAOYSA-N 2-amino-1-(2-fluorophenyl)ethanol Chemical compound NCC(O)C1=CC=CC=C1F MFGOFGRYDNHJTA-UHFFFAOYSA-N 0.000 claims description 2
- 150000004703 alkoxides Chemical class 0.000 claims description 2
- 150000001450 anions Chemical class 0.000 claims description 2
- HUCVOHYBFXVBRW-UHFFFAOYSA-M caesium hydroxide Inorganic materials [OH-].[Cs+] HUCVOHYBFXVBRW-UHFFFAOYSA-M 0.000 claims description 2
- 150000002009 diols Chemical class 0.000 claims description 2
- 238000001704 evaporation Methods 0.000 claims description 2
- 150000007529 inorganic bases Chemical class 0.000 claims description 2
- 239000000203 mixture Substances 0.000 claims description 2
- 150000007530 organic bases Chemical class 0.000 claims description 2
- LPNYRYFBWFDTMA-UHFFFAOYSA-N potassium tert-butoxide Chemical compound [K+].CC(C)(C)[O-] LPNYRYFBWFDTMA-UHFFFAOYSA-N 0.000 claims description 2
- 238000007789 sealing Methods 0.000 claims description 2
- QDRKDTQENPPHOJ-UHFFFAOYSA-N sodium ethoxide Chemical compound [Na+].CC[O-] QDRKDTQENPPHOJ-UHFFFAOYSA-N 0.000 claims description 2
- RPACBEVZENYWOL-XFULWGLBSA-M sodium;(2r)-2-[6-(4-chlorophenoxy)hexyl]oxirane-2-carboxylate Chemical compound [Na+].C=1C=C(Cl)C=CC=1OCCCCCC[C@]1(C(=O)[O-])CO1 RPACBEVZENYWOL-XFULWGLBSA-M 0.000 claims description 2
- OIFBSDVPJOWBCH-UHFFFAOYSA-N Diethyl carbonate Chemical compound CCOC(=O)OCC OIFBSDVPJOWBCH-UHFFFAOYSA-N 0.000 abstract description 66
- 230000015572 biosynthetic process Effects 0.000 abstract description 21
- 230000003197 catalytic effect Effects 0.000 abstract description 21
- 238000003786 synthesis reaction Methods 0.000 abstract description 21
- BVKZGUZCCUSVTD-UHFFFAOYSA-L Carbonate Chemical compound [O-]C([O-])=O BVKZGUZCCUSVTD-UHFFFAOYSA-L 0.000 abstract description 8
- 239000000126 substance Substances 0.000 abstract description 5
- 230000002779 inactivation Effects 0.000 abstract description 4
- 238000004519 manufacturing process Methods 0.000 abstract description 4
- 239000012535 impurity Substances 0.000 abstract description 2
- 125000003158 alcohol group Chemical group 0.000 abstract 1
- 150000002334 glycols Chemical class 0.000 abstract 1
- JOYRKODLDBILNP-UHFFFAOYSA-N Ethyl urethane Chemical compound CCOC(N)=O JOYRKODLDBILNP-UHFFFAOYSA-N 0.000 description 62
- 230000000694 effects Effects 0.000 description 25
- 238000005809 transesterification reaction Methods 0.000 description 23
- 239000000047 product Substances 0.000 description 18
- 230000008569 process Effects 0.000 description 15
- 230000035484 reaction time Effects 0.000 description 8
- 238000010521 absorption reaction Methods 0.000 description 7
- 239000006227 byproduct Substances 0.000 description 7
- 238000001228 spectrum Methods 0.000 description 7
- IEJIGPNLZYLLBP-UHFFFAOYSA-N dimethyl carbonate Chemical compound COC(=O)OC IEJIGPNLZYLLBP-UHFFFAOYSA-N 0.000 description 6
- 230000004580 weight loss Effects 0.000 description 6
- XSQUKJJJFZCRTK-UHFFFAOYSA-N Urea Chemical compound NC(N)=O XSQUKJJJFZCRTK-UHFFFAOYSA-N 0.000 description 5
- 238000004458 analytical method Methods 0.000 description 5
- 239000004202 carbamide Substances 0.000 description 5
- RUOJZAUFBMNUDX-UHFFFAOYSA-N propylene carbonate Chemical compound CC1COC(=O)O1 RUOJZAUFBMNUDX-UHFFFAOYSA-N 0.000 description 5
- IAZDPXIOMUYVGZ-WFGJKAKNSA-N Dimethyl sulfoxide Chemical compound [2H]C([2H])([2H])S(=O)C([2H])([2H])[2H] IAZDPXIOMUYVGZ-WFGJKAKNSA-N 0.000 description 4
- LRHPLDYGYMQRHN-UHFFFAOYSA-N N-Butanol Chemical compound CCCCO LRHPLDYGYMQRHN-UHFFFAOYSA-N 0.000 description 4
- WPYMKLBDIGXBTP-UHFFFAOYSA-N benzoic acid Chemical compound OC(=O)C1=CC=CC=C1 WPYMKLBDIGXBTP-UHFFFAOYSA-N 0.000 description 4
- BDERNNFJNOPAEC-UHFFFAOYSA-N propan-1-ol Chemical compound CCCO BDERNNFJNOPAEC-UHFFFAOYSA-N 0.000 description 4
- 238000006136 alcoholysis reaction Methods 0.000 description 3
- 238000000354 decomposition reaction Methods 0.000 description 3
- MTHSVFCYNBDYFN-UHFFFAOYSA-N diethylene glycol Chemical compound OCCOCCO MTHSVFCYNBDYFN-UHFFFAOYSA-N 0.000 description 3
- 238000005265 energy consumption Methods 0.000 description 3
- 239000002815 homogeneous catalyst Substances 0.000 description 3
- 238000007142 ring opening reaction Methods 0.000 description 3
- 239000007858 starting material Substances 0.000 description 3
- 239000005711 Benzoic acid Substances 0.000 description 2
- 229910014033 C-OH Inorganic materials 0.000 description 2
- CURLTUGMZLYLDI-UHFFFAOYSA-N Carbon dioxide Chemical compound O=C=O CURLTUGMZLYLDI-UHFFFAOYSA-N 0.000 description 2
- 229910014570 C—OH Inorganic materials 0.000 description 2
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 description 2
- 238000001157 Fourier transform infrared spectrum Methods 0.000 description 2
- KFZMGEQAYNKOFK-UHFFFAOYSA-N Isopropanol Chemical compound CC(C)O KFZMGEQAYNKOFK-UHFFFAOYSA-N 0.000 description 2
- BZLVMXJERCGZMT-UHFFFAOYSA-N Methyl tert-butyl ether Chemical compound COC(C)(C)C BZLVMXJERCGZMT-UHFFFAOYSA-N 0.000 description 2
- KFMCTMBLJIQCGV-UHFFFAOYSA-N OC(O)COC(O)=O Chemical compound OC(O)COC(O)=O KFMCTMBLJIQCGV-UHFFFAOYSA-N 0.000 description 2
- YGYAWVDWMABLBF-UHFFFAOYSA-N Phosgene Chemical compound ClC(Cl)=O YGYAWVDWMABLBF-UHFFFAOYSA-N 0.000 description 2
- DNIAPMSPPWPWGF-UHFFFAOYSA-N Propylene glycol Chemical compound CC(O)CO DNIAPMSPPWPWGF-UHFFFAOYSA-N 0.000 description 2
- CDBYLPFSWZWCQE-UHFFFAOYSA-L Sodium Carbonate Chemical group [Na+].[Na+].[O-]C([O-])=O CDBYLPFSWZWCQE-UHFFFAOYSA-L 0.000 description 2
- 238000005452 bending Methods 0.000 description 2
- 235000010233 benzoic acid Nutrition 0.000 description 2
- 230000006315 carbonylation Effects 0.000 description 2
- 238000005810 carbonylation reaction Methods 0.000 description 2
- 238000012512 characterization method Methods 0.000 description 2
- 239000006185 dispersion Substances 0.000 description 2
- 238000004821 distillation Methods 0.000 description 2
- 238000003912 environmental pollution Methods 0.000 description 2
- UOQTVEMFXWKBBS-UHFFFAOYSA-N ethyl 2-hydroxyethyl carbonate Chemical compound CCOC(=O)OCCO UOQTVEMFXWKBBS-UHFFFAOYSA-N 0.000 description 2
- JBTWLSYIZRCDFO-UHFFFAOYSA-N ethyl methyl carbonate Chemical compound CCOC(=O)OC JBTWLSYIZRCDFO-UHFFFAOYSA-N 0.000 description 2
- 230000002401 inhibitory effect Effects 0.000 description 2
- 239000013067 intermediate product Substances 0.000 description 2
- 239000002608 ionic liquid Substances 0.000 description 2
- ZXEKIIBDNHEJCQ-UHFFFAOYSA-N isobutanol Chemical compound CC(C)CO ZXEKIIBDNHEJCQ-UHFFFAOYSA-N 0.000 description 2
- 229910001416 lithium ion Inorganic materials 0.000 description 2
- 231100000053 low toxicity Toxicity 0.000 description 2
- 230000007246 mechanism Effects 0.000 description 2
- BWHMMNNQKKPAPP-UHFFFAOYSA-L potassium carbonate Chemical compound [K+].[K+].[O-]C([O-])=O BWHMMNNQKKPAPP-UHFFFAOYSA-L 0.000 description 2
- 230000002441 reversible effect Effects 0.000 description 2
- 238000005070 sampling Methods 0.000 description 2
- 238000000926 separation method Methods 0.000 description 2
- 239000011734 sodium Substances 0.000 description 2
- 238000010183 spectrum analysis Methods 0.000 description 2
- 238000002411 thermogravimetry Methods 0.000 description 2
- 238000004448 titration Methods 0.000 description 2
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical group [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 1
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 1
- HBBGRARXTFLTSG-UHFFFAOYSA-N Lithium ion Chemical compound [Li+] HBBGRARXTFLTSG-UHFFFAOYSA-N 0.000 description 1
- 230000009471 action Effects 0.000 description 1
- 230000004913 activation Effects 0.000 description 1
- 150000001298 alcohols Chemical class 0.000 description 1
- 230000029936 alkylation Effects 0.000 description 1
- 238000005804 alkylation reaction Methods 0.000 description 1
- 239000003242 anti bacterial agent Substances 0.000 description 1
- 229940088710 antibiotic agent Drugs 0.000 description 1
- 238000013459 approach Methods 0.000 description 1
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 1
- UXXXZMDJQLPQPH-UHFFFAOYSA-N bis(2-methylpropyl) carbonate Chemical compound CC(C)COC(=O)OCC(C)C UXXXZMDJQLPQPH-UHFFFAOYSA-N 0.000 description 1
- 125000004432 carbon atom Chemical group C* 0.000 description 1
- 125000005587 carbonate group Chemical group 0.000 description 1
- BVKZGUZCCUSVTD-UHFFFAOYSA-N carbonic acid Chemical compound OC(O)=O BVKZGUZCCUSVTD-UHFFFAOYSA-N 0.000 description 1
- 229920003086 cellulose ether Polymers 0.000 description 1
- 239000007795 chemical reaction product Substances 0.000 description 1
- 239000003153 chemical reaction reagent Substances 0.000 description 1
- 238000002485 combustion reaction Methods 0.000 description 1
- 150000001875 compounds Chemical class 0.000 description 1
- 238000005336 cracking Methods 0.000 description 1
- 230000003247 decreasing effect Effects 0.000 description 1
- 230000018044 dehydration Effects 0.000 description 1
- 238000006297 dehydration reaction Methods 0.000 description 1
- QLVWOKQMDLQXNN-UHFFFAOYSA-N dibutyl carbonate Chemical compound CCCCOC(=O)OCCCC QLVWOKQMDLQXNN-UHFFFAOYSA-N 0.000 description 1
- 238000004455 differential thermal analysis Methods 0.000 description 1
- JMPVESVJOFYWTB-UHFFFAOYSA-N dipropan-2-yl carbonate Chemical compound CC(C)OC(=O)OC(C)C JMPVESVJOFYWTB-UHFFFAOYSA-N 0.000 description 1
- VUPKGFBOKBGHFZ-UHFFFAOYSA-N dipropyl carbonate Chemical compound CCCOC(=O)OCCC VUPKGFBOKBGHFZ-UHFFFAOYSA-N 0.000 description 1
- 238000009826 distribution Methods 0.000 description 1
- ODCCJTMPMUFERV-UHFFFAOYSA-N ditert-butyl carbonate Chemical compound CC(C)(C)OC(=O)OC(C)(C)C ODCCJTMPMUFERV-UHFFFAOYSA-N 0.000 description 1
- 239000003792 electrolyte Substances 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 239000003344 environmental pollutant Substances 0.000 description 1
- 230000001747 exhibiting effect Effects 0.000 description 1
- 238000002474 experimental method Methods 0.000 description 1
- 230000008014 freezing Effects 0.000 description 1
- 238000007710 freezing Methods 0.000 description 1
- 239000002816 fuel additive Substances 0.000 description 1
- 125000000524 functional group Chemical group 0.000 description 1
- 238000002309 gasification Methods 0.000 description 1
- 239000011521 glass Substances 0.000 description 1
- 229910052736 halogen Inorganic materials 0.000 description 1
- 150000002367 halogens Chemical class 0.000 description 1
- 239000002638 heterogeneous catalyst Substances 0.000 description 1
- 239000001257 hydrogen Substances 0.000 description 1
- 229910052739 hydrogen Inorganic materials 0.000 description 1
- IXCSERBJSXMMFS-UHFFFAOYSA-N hydrogen chloride Substances Cl.Cl IXCSERBJSXMMFS-UHFFFAOYSA-N 0.000 description 1
- 229910000041 hydrogen chloride Inorganic materials 0.000 description 1
- 238000009776 industrial production Methods 0.000 description 1
- 238000012844 infrared spectroscopy analysis Methods 0.000 description 1
- 239000007788 liquid Substances 0.000 description 1
- 239000000463 material Substances 0.000 description 1
- 238000002156 mixing Methods 0.000 description 1
- 239000012299 nitrogen atmosphere Substances 0.000 description 1
- 230000000269 nucleophilic effect Effects 0.000 description 1
- 239000003960 organic solvent Substances 0.000 description 1
- 230000003647 oxidation Effects 0.000 description 1
- 238000007254 oxidation reaction Methods 0.000 description 1
- 238000005832 oxidative carbonylation reaction Methods 0.000 description 1
- 239000001301 oxygen Substances 0.000 description 1
- 229910052760 oxygen Inorganic materials 0.000 description 1
- 239000003973 paint Substances 0.000 description 1
- 230000036961 partial effect Effects 0.000 description 1
- DDBREPKUVSBGFI-UHFFFAOYSA-N phenobarbital Chemical compound C=1C=CC=CC=1C1(CC)C(=O)NC(=O)NC1=O DDBREPKUVSBGFI-UHFFFAOYSA-N 0.000 description 1
- 229960002695 phenobarbital Drugs 0.000 description 1
- 239000004014 plasticizer Substances 0.000 description 1
- 231100000719 pollutant Toxicity 0.000 description 1
- 229910000027 potassium carbonate Inorganic materials 0.000 description 1
- 230000001737 promoting effect Effects 0.000 description 1
- 229960004063 propylene glycol Drugs 0.000 description 1
- 238000000197 pyrolysis Methods 0.000 description 1
- 239000000376 reactant Substances 0.000 description 1
- 230000009257 reactivity Effects 0.000 description 1
- 238000004064 recycling Methods 0.000 description 1
- 230000009467 reduction Effects 0.000 description 1
- 239000013557 residual solvent Substances 0.000 description 1
- 229910000029 sodium carbonate Inorganic materials 0.000 description 1
- 239000002910 solid waste Substances 0.000 description 1
- 235000013599 spices Nutrition 0.000 description 1
- 238000001308 synthesis method Methods 0.000 description 1
- 229920003002 synthetic resin Polymers 0.000 description 1
- 239000000057 synthetic resin Substances 0.000 description 1
- 231100000331 toxic Toxicity 0.000 description 1
- 230000002588 toxic effect Effects 0.000 description 1
- ZIBGPFATKBEMQZ-UHFFFAOYSA-N triethylene glycol Chemical compound OCCOCCOCCO ZIBGPFATKBEMQZ-UHFFFAOYSA-N 0.000 description 1
- 230000003313 weakening effect Effects 0.000 description 1
Images
Classifications
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J31/00—Catalysts comprising hydrides, coordination complexes or organic compounds
- B01J31/02—Catalysts comprising hydrides, coordination complexes or organic compounds containing organic compounds or metal hydrides
- B01J31/0201—Oxygen-containing compounds
- B01J31/0211—Oxygen-containing compounds with a metal-oxygen link
- B01J31/0212—Alkoxylates
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C29/00—Preparation of compounds having hydroxy or O-metal groups bound to a carbon atom not belonging to a six-membered aromatic ring
- C07C29/68—Preparation of metal alcoholates
- C07C29/70—Preparation of metal alcoholates by converting hydroxy groups to O-metal groups
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C68/00—Preparation of esters of carbonic or haloformic acids
- C07C68/06—Preparation of esters of carbonic or haloformic acids from organic carbonates
- C07C68/065—Preparation of esters of carbonic or haloformic acids from organic carbonates from alkylene carbonates
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J2231/00—Catalytic reactions performed with catalysts classified in B01J31/00
- B01J2231/40—Substitution reactions at carbon centres, e.g. C-C or C-X, i.e. carbon-hetero atom, cross-coupling, C-H activation or ring-opening reactions
- B01J2231/49—Esterification or transesterification
-
- 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
- Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
- Y02P20/00—Technologies relating to chemical industry
- Y02P20/50—Improvements relating to the production of bulk chemicals
- Y02P20/52—Improvements relating to the production of bulk chemicals using catalysts, e.g. selective catalysts
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- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Engineering & Computer Science (AREA)
- Materials Engineering (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Low-Molecular Organic Synthesis Reactions Using Catalysts (AREA)
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
Abstract
The invention discloses a method for preparing a strong-basicity homogeneous phase dihydric alcohol metal salt catalyst and synthesizing carbonic ester by using the same, relates to a method for preparing a catalyst and synthesizing carbonic ester by using the same, and discloses a method for synthesizing glycol salt which is self-derived in a system, strong-basicity, high in thermal stability and very easy to dissolve in a reaction system, and a process for preparing diethyl carbonate or other low-carbon symmetrical carbonic esters by efficiently catalyzing ethylene carbonate and low-carbon alcohol to perform ester-alcohol exchange reaction. The synthesized EGK shows excellent catalytic effect, has no obvious inactivation phenomenon after being repeatedly used for 5 times, and shows good stability and reusability. EGK also has better universality for catalyzing alcohol exchange reaction between EC and various low-carbon alcohol esters. The ethylene glycol salt catalyst is simple to prepare, is easy to dissolve in a reaction system, does not introduce other organic impurities, shows higher alkali strength, excellent catalytic activity and good cycle stability in EGK, and has important industrial application value in the field of synthesis of carbonate chemicals.
Description
Technical Field
The invention relates to a preparation method of a catalyst and a method for synthesizing carbonic ester by using the catalyst, in particular to a preparation method of a strong-basicity homogeneous phase dihydric alcohol metal salt catalyst and a method for synthesizing carbonic ester by using the catalyst.
Background
Diethyl carbonate (DEC) is linear carbonate, is colorless liquid with ether taste at normal temperature, is insoluble in water, is miscible in most organic solvents, has little harm to the environment, and is slowly decomposed into ethanol and CO2It is a green chemical. DEC is an important organic synthetic intermediate useful as a carbonylation and alkylation reagent; DEC is also an excellent solvent, and can be used as a solvent for synthetic resins, antibiotics, cellulose ethers, paints, plasticizers, phenobarbital, spices and the like, and also can be used as an electrolyte solvent of a lithium ion battery and the like; DEC is also used as a fuel additive for gasoline and diesel, has the advantages of high oxygen content, low toxicity, low vapor pressure, strong volatility resistance, high oil/water distribution coefficient and the like compared with methyl tert-butyl ether, and can reduce pollutant emission and improve the combustion performance of gasoline by adding the DEC. In conclusion, DEC is a green chemical with low toxicity, degradability and wide application prospect.
The DEC synthesis method mainly comprises phosgene method, ethanol oxidation carbonylation method, urea alcoholysis method and CO2Direct conversion and transesterification processes. Phosgene is extremely toxic and causes serious environmental pollution, and the byproduct hydrogen chloride has strong corrosivity on equipment and environment, so the process is eliminated. If the ethanol is catalyzed by halogen-free compounds to carry out oxidative carbonylation, the conversion rate of EtOH is generally lower than 10%, the product system is relatively complex, and the selectivity of the target product DEC is lower than 70%. Even with halogen-containing catalysts, the DEC single pass yield is still below 30% and the catalyst stability is poor. In the urea alcoholysis process, the ethanol raw material is controlled to be far excessive, the generation of byproducts is inhibited, and the molar content of the byproducts is generally more than 10 times that of urea. Even then, the product system is still relatively complex, the main by-product is the Ethyl Carbamate (EC) produced by the partial alcoholysis of urea, and the sum of the selectivity of DEC and EC is less than 80%. The reaction is limited by a thermodynamic equilibrium, with a conversion of the starting material, calculated as urea, of about 30%, even lower than 3% as EtOH,the industrialization prospect is not optimistic. CO22Direct conversion to DEC as an exothermic reaction (. DELTA.)rHθ298 K = −16.6 kJ/mol <0) And does not spontaneously proceed at room temperature (. DELTA.)rGθ298 K = 35.85 kJ/mol >0). The reaction is limited by thermodynamic equilibrium and can only be increased by increasing the reaction pressure and the concentration of CO2 to increase the conversion of EtOH to yield DEC up to 60% at near or up to the supercritical CO2 conditions. However, the byproduct H2O is difficult to remove from the reaction system effectively, and the reaction is limited to proceed in the forward direction. At present, DEC is industrially synthesized by a transesterification method, dimethyl carbonate (DMC) and ethanol (EtOH) are prepared by a reaction-rectification process intensification technology, and a byproduct, Ethyl Methyl Carbonate (EMC), is produced.
The DMC with high quality produced in more than 80 percent of China is synthesized by Propylene Carbonate (PC)/Ethylene Carbonate (EC) and methanol (MeOH) through an ester exchange process, in the process, the DMC and the MeOH are separated out of a reaction system in the form of azeotrope with the content of about 30 to 70 percent, and then are separated in an extraction-rectification or high-low pressure rectification mode. The azeotrope separation energy consumption is high, accounting for about 50% of the total energy consumption of DMC synthesis. The research proposes that starting from the initial raw material PC/EC for synthesizing DMC, the initial raw material PC/EC and EtOH directly carry out transesterification reaction, the products are only 1, 2-propylene glycol/ethylene glycol and DEC, and the whole system has no azeotrope. Therefore, the synthesis of DEC by taking PC/EC as a reaction raw material not only obviously simplifies/shortens the process flow, but also does not relate to azeotrope separation, and obviously reduces the production energy consumption.
To our knowledge, EC directly with EtOH has very few reports on the synthesis of DEC by transesterification. With reference to the EC and MeOH transesterification processes, the catalysts reported are broadly classified into two broad categories, homogeneous and heterogeneous. The heterogeneous catalyst is easy to separate from the reaction system, but has low catalytic efficiency, high activation energy and needs high temperature or long-time reaction. The reported homogeneous catalysts mainly include: CH (CH)3ONa、CH3OK and C2H5Strong alkali containing alkali such as ONa, KOH, NaOH, K2CO3、Na2Inorganic strong base such as CO3, and ionic liquid catalyst. Soluble organic strong bases have excellent reactivity, but they are sensitive to water and are extremely deactivated. Has already been worked beforeStrictly proves the inactivation process and evolution mechanism of the strain, and the inactivation product is Na2CO3. The deactivated alkaline mixed product is difficult to separate in the industrial production process and pollutes the environment. The low solubility of the inorganic strong base in the carbonate starting material results in low dispersion in the homogeneous reaction system and relatively low catalytic efficiency. The ionic liquid generally has poor thermal stability, is easy to decompose at high temperature, has high preparation cost and is easy to cause environmental pollution in the preparation process.
Disclosure of Invention
The invention aims to provide a preparation method of a strong-basicity homogeneous phase dihydric alcohol metal salt catalyst and a method for synthesizing carbonic ester thereof. The developed ethylene glycol salt catalyst is used for synthesizing a diethyl carbonate product through ester exchange reaction, and shows extremely high reaction activity, the reaction balance can be achieved after the reaction is carried out for 30 min at 75-85 ℃, and the catalyst also shows extremely high catalytic activity even under the conditions of room temperature (25 ℃) and 0 ℃.
The purpose of the invention is realized by the following technical scheme:
the preparation method of the strongly basic homogeneous phase dihydric alcohol metal salt catalyst comprises the steps of carrying out ester exchange reaction on ethylene carbonate and low-carbon alcohol by using the catalyst which is homogeneous phase ethylene glycol salt; the metal alkoxide catalyst is ethylene glycol metal salt; the glycol metal salt comprises a glycol anion and a metal cation; the cation being Li+、Na+、K+Or Cs+(ii) a The anion is a structure shown in formula I;
formula I
The preparation method comprises the following preparation steps:
a1) adding inorganic or organic strong base into the glycol solution to react at a certain temperature to obtain a mixed solution of glycol metal salt solution and water;
a2) and (3) removing water from the mixed solution of the glycol metal salt and water through reduced pressure rotary evaporation to obtain the glycol metal salt solution, and adding a solvent for sealing and storing.
The preparation method of the strong-basicity homogeneous phase dihydric alcohol metal salt catalyst,
the molar ratio of the ethylene glycol to the alkali is 1/1-4/1;
the alkali is organic alkali or inorganic alkali;
the organic base comprises sodium methoxide, sodium ethoxide, sodium tert-butoxide, potassium methoxide, potassium ethoxide or potassium tert-butoxide;
the inorganic base includes lithium hydroxide, sodium hydroxide, potassium hydroxide, and cesium hydroxide;
the metal salt comprises at least one of Li salt, Na salt, K salt and Cs salt;
the glycol metal salt solution is a mixed solution of glycol metal salt and glycol;
the certain temperature is 25-120 ℃;
the pressure is 0.001-50 KPa;
the rotary evaporation temperature is 110-140 ℃;
preferably, in step a1), the base is potassium methoxide, potassium ethoxide, tert-butanol or potassium hydroxide;
preferably, in step a1), the reaction conditions are: reacting for 30-60 minutes at 50-80 ℃;
preferably, in step a2), the reaction conditions are: rotary evaporating at 120-130 deg.c for 1-5 hr;
preferably, in step a2), the solvent is selected from at least one of methanol, ethanol, ethylene glycol and acetonitrile;
preferably, in the step a2), the preservation temperature is 0-50 ℃ for sealed preservation;
preferably, in step a2), the ratio of ethylene glycol metal salt solution to solvent is 1/1-1/3.
A method for synthesizing carbonic ester by using strongly basic homogeneous diol metal salt catalyst comprises the following scheme: the reaction raw materials are ethylene carbonate and low-carbon alcohol; the ethylene glycol metal salt catalyst is at least one or a mixture of lithium Ethylene Glycol (EGLi), sodium ethylene glycol (EGNa), potassium Ethylene Glycol (EGK) and cesium Ethylene Glycol (EGCs); the lower alcohol is C1-C4 normal and isomeric alcohol; the reaction temperature is 25-120 deg.C, preferably 65-110 deg.C.
The invention has the advantages and effects that:
1) the ethylene glycol salt catalyst provided by the invention solves the problems of low solubility of inorganic strong base in a carbonate system, influence of impurity water generated by the inorganic strong base and ethanol on catalytic efficiency and product quality and the like.
2) The ethylene glycol salt catalyst provided by the invention solves the problems that the organic strong base can only be used once in a carbonate system and is easy to inactivate, remarkably reduces the production cost of the catalyst and reduces the generation of strong alkaline solid wastes.
3) The ethylene glycol metal salt catalyst provided by the invention is used for synthesizing a diethyl carbonate product through ester exchange reaction, and has extremely high reaction activity and recycling stability.
4) The ethylene glycol metal salt catalyst provided by the invention shows high-efficiency catalytic activity of C1-C4 normal alcohol ester exchange reaction and universality of EC and alcohol ester exchange reaction with different structures.
The synthesized EGK has the strength of 15.0< H- <18.4, is equivalent to KOH, has the alkali amount of 6.18 mmol/g and has the water content of 0.64 percent. As the radius of the cation (Li +, Na +, and K +) increases, its alkali content and catalytic ability gradually increase. The EGK catalyst is reacted for only 5 min at 0 ℃, the conversion rate of EC reaches 33.67%, the selectivity of DEC exceeds 99%, the yield of DEC is 33.34%, the TOF value reaches 456.66 molDEC molcat-1. h-1, and an excellent catalytic effect is shown.
Drawings
FIG. 1 is a photograph of an EGK catalyst synthesized in example 1 of the present invention.
FIG. 2 shows the nuclear magnetic H spectrum of the EGK catalyst synthesized in example 1 of the present invention.
FIG. 3 is a nuclear magnetic C spectrum of EGK catalyst synthesized in example 1 of the present invention.
FIG. 4 is a thermogravimetric analysis of the EGK catalyst synthesized in example 1 of the present invention.
Fig. 5 is an FTIR spectrum of an EGK catalyst synthesized in example 1 of the present invention.
FIG. 6 is a graph showing the effect of reaction temperature on EC and EtOH transesterification reactions according to the present invention.
FIG. 7 is a graph showing the effect of reaction time on EC and EtOH transesterification reactions at different temperatures according to the present invention.
FIG. 8 is a graph showing the effect of feed mole ratio on EC and EtOH transesterification reactions in accordance with the present invention.
FIG. 9 is a graph showing the effect of EGK catalyst content on EC and EtOH transesterification reactions.
FIG. 10 shows the effect of EGK of the present invention on catalyzing the transesterification of EC and C1-C4 alcohol.
FIG. 11 shows the reuse of EGK catalysts according to the invention.
Detailed Description
The present invention will be described in detail with reference to examples, but the present invention is not limited to these examples.
In the present invention, "EGLi" means lithium ethylene glycol.
In the present invention, "EGNa" means sodium ethylene glycol.
In the present invention, "EGK" means potassium ethylene glycol.
In the present invention, "EGCs" refers to cesium ethylene glycol.
In the present invention, "EtOH" refers to ethanol.
In the present invention, "EC" means ethylene carbonate.
In the present invention, "DEC" means diethyl carbonate.
The raw materials in the examples of the present invention were all purchased from commercial sources unless otherwise specified.
In the embodiment of the invention, density analysis, alkali strength analysis and alkali mass analysis, thermogravimetric-differential thermal (TG-DTA) characterization analysis, infrared spectroscopy analysis, nuclear magnetic H spectrum analysis and nuclear magnetic C spectrum analysis are all conventional operations, and a person skilled in the art can operate the analysis according to the instruction of an instrument.
The conversion, selectivity and yield in the examples of the invention were calculated as follows:
X/%= 100×(na + nb+ nc)/( na+ nb + nc + nd)
Sa/%= 100×na/(na + nb+ nc)
Sb/%= 100×nb/(na + nb+ nc
Sc/%= 100×nc/(na + nb+ nc
Y/%= 100×X×Sa
TOF = n target/(nCat × t) = nEC × XEC × S target/(nCat × t)
In the formula: x is the conversion rate of the ethylene carbonate,%; sa is diethyl carbonate selectivity,%; sb is the selectivity of 2-hydroxyethyl ethyl carbonate percent; sc is selectivity of dihydroxyethyl carbonate,%; y is the yield of diethyl carbonate,%; na is the amount of diethyl carbonate material, mol; nb is the amount of 2-hydroxyethyl ethyl carbonate species, mol; nc is the amount of dihydroxyethyl carbonate substance, mol; and nd is the amount of unreacted ethylene carbonate substance, mol. n is the molar mass, mol, of the target product; nCat is the molar weight of the active site of the catalyst, mol; s target is the selectivity,%, of the target product.
Example 1
Fig. 1 is a photograph of a synthesized EGK catalyst.
Synthesis of ethylene glycol potassium catalyst: 2 mol of Ethylene Glycol (EG) solution was added to a 500 mL beaker, 1 mol of potassium hydroxide (KOH) was added to the ethylene glycol solution, it was stirred using a glass rod until it was completely dissolved, and it was rotary evaporated using a rotary evaporator at 100, 120, 130, 135 and 140 ℃ for 3 h after being transferred to a 500 mL eggplant-type bottle. The process is to separate the byproduct water generated by the reaction of potassium hydroxide and ethylene glycol from a reaction system to obtain the catalyst of ethylene glycol and ethylene glycol potassium salt (EGK) with the approximate molar ratio of 1:1, and as shown in figure 1, additionally adding anhydrous ethanol solution with the mass of 4 times of that of the catalyst, uniformly mixing and storing at room temperature. The nuclear magnetic spectrum is shown in figure 2 and figure 3. FIG. 2 Nuclear magnetic H Spectrum of synthesized Potassium ethylene glycol:1h NMR (500 MHz, DMSO-d6) delta 5.58 (s, 1H), 3.37 (s, 17H), 2.50-2.47 (m, 14H); FIG. 3 Nuclear magnetic C Spectrum of synthesized Potassium ethylene glycol:13c NMR (126 MHz, DMSO-d6) delta 64.47, 40.97-37.16 (m). Other methods of synthesis of the ethanediol salts are similar to those of EGK synthesis.
Fig. 2 is a nuclear magnetic H spectrum of the synthesized EGK catalyst.
FIG. 3 is a nuclear magnetic C spectrum of a synthesized EGK catalyst.
Example 2
The physicochemical properties of the synthesized potassium Ethylene Glycol (EGK) catalyst are measured, the density is about 1.3 g/mL, and the freezing point is about-20 ℃. The alkali strength range of the sodium hydroxide is 15.0< H- <18.4 measured by a Hammett indicator method, the sodium hydroxide is equivalent to the alkali strength of potassium hydroxide, and the alkali amount is 6.18 mmol/g measured by a benzoic acid titration method.
Example 3
The effects of EGK synthesis temperatures of 100, 120, 130, 135 and 140 ℃ on catalyst base content, water content and catalytic activity were investigated and the results are shown in table 1. The alkali content of the synthesized EGK salt at different temperatures measured by adopting a benzoic acid titration method is respectively 5.68, 6.02, 6.16, 6.18 and 6.31 mmol/g, which shows that the alkali content of the prepared EGK catalyst is gradually increased along with the increase of the synthesis temperature. The water content of the EGK catalyst is respectively 3.37 percent, 1.44 percent, 1.22 percent, 0.64 percent and 0.69 percent measured by a Karl Fischer trace water analyzer, which indicates that a large amount of water remains in the reaction system at 100 ℃, and the strong hydrogen bond action of water and EG can not separate the generated water out of the reaction system at the temperature; the water content in the system is gradually and obviously reduced by gradually increasing the synthesis temperature, but the water content in the system is basically kept unchanged after the synthesis temperature exceeds 135 ℃, so the synthesis temperature of the subsequent EGK catalyst is preferably 135 ℃. At the synthesis temperature of 100 ℃, the EGK catalyst content is only 1% of EC mass, and the EC conversion rate, DEC molar selectivity and DEC yield are respectively 38.78%, 88.57% and 34.35% at the reaction time of 5 min, when the TOF of the catalyst is as high as 511.54 mol DEC mol lcat-1· h-1The method shows that even if the prepared EGK catalyst contains a large amount of water, the catalyst still shows higher catalytic efficiency, but the water has an influence on the selectivity of a target product and mainly influences the further transesterification efficiency of an intermediate product. As the synthesis temperature increases, the EC conversion rate, the DEC molar selectivity, the DEC yield and the TOF are obviously improved, and the catalyst indexes of the 135 ℃ synthesis reach the highest, namely 76.58%, 99.65%, 76.32% and 1045.13 molDEC molcat-1· h-1. Is continuously liftedThe DEC selectivity, yield and TOF were rather slightly reduced by the synthesis temperature up to 140 ℃, which probably was that the EGK produced promoted the continued dehydration of EG to dimeric or trimeric EGK catalyst, as we detected the production of very small amounts of diethylene glycol as well as triethylene glycol in the high temperature synthesized EGK catalyst. The dipolypotassium salt or tripolypotassium salt has poor dispersion effect in a carbonate reaction system, so that the catalytic efficiency is reduced. In summary, moderate synthesis temperatures allow EGK homogeneous catalysts with higher base content, lower water residue, and no dimerized or highly polymerized ethylene glycol.
TABLE 1 influence of Potassium ethylene glycol catalyst Synthesis temperature on the amount of base, Water content and transesterification Effect
Reaction conditions are as follows: the EC/EtOH molar ratio is 1/10, the addition amount of the homogeneous catalyst is about 1 percent of the EC mass, the reaction temperature is 82 ℃, and the reaction time is 5 min
Example 4
The thermogravimetric-differential thermal analysis of the EGK catalyst under the nitrogen atmosphere is shown in figure 4, and has a three-stage weight loss process, wherein the first stage is that 3.6 percent weight loss is generated in the range from room temperature to 132 ℃ and continuous trace heat absorption is accompanied, and the weight loss is the residual solvent (EtOH) and a small amount of adsorbed water in the catalyst preparation process; significant weight loss of 88.81% was observed in the second stage 132-273 deg.C range. The weight loss slope is approximately kept unchanged and the more close to a high-temperature area, the more obvious the heat absorption is, the process is mainly the gasification of Ethylene Glycol (EG) and the slow decomposition of ethylene glycol potassium, and the higher the temperature is, the faster the decomposition rate of the ethylene glycol potassium is; the third stage 273- & gt 474 ℃ has 5.24% weight loss, the temperature is continuously increased to 500 ℃, the remaining 2.35% of the mass is kept unchanged, and the process is supposed to be the pyrolysis/cracking of the EGK decomposition product.
Fig. 4 is a thermogravimetric analysis of the synthesized EGK catalyst.
Example 5
The functional group characterization of the EGK catalyst is shown in FIG. 5, 3356 cm-1The absorption peak at the wave number is classified as an ethylene glycol O-H stretching vibration peak; 2939 and 2873 cm-1The absorption peak at the wave number is attributed to the CH2 stretching vibration peak; 1654 cm-1The absorption peak at the wave number is the stretching vibration of O-H; 1450. 1380 and 1296 cm-1Absorption peaks at wave numbers are respectively assigned to CH2 bending vibration peak and C-OH in-plane bending vibration; 1089. 1056 and 885 cm-1The absorption peaks at wavenumbers are respectively attributed to C-OH stretching vibration and CH2 in-plane rocking vibration.
Fig. 5 is an FTIR spectrum of the synthesized EGK catalyst.
Example 6
The results of the effect of different reaction temperatures on the synthesis of DEC by transesterification with EGK as catalyst are shown in FIG. 6. At an extremely low temperature of 0 ℃, the reaction is carried out for only 5 min, the conversion rate of EC reaches 33.67 percent, the selectivity of DEC exceeds 99 percent, the yield of DEC reaches 33.34 percent, and the TOF value is 456.66 molDEC molcat-1· h-1The EGK catalyst still shows higher capability of promoting EC ring opening and ester exchange of linear carbonate and EtOH at low temperature of 0 ℃; when the reaction temperature was increased to 25 ℃, the conversion of EC increased to 51.62%, the DEC selectivity and yield were 99.50% and 51.36%, respectively, and the TOF value increased to 703.43 molDEC molcat-1· h-1(ii) a The reaction temperature was further raised to 50, 70 and 82 ℃, EC conversion and DEC yield continued to increase, DEC selectivity was maintained above 99% at all times, and TOF values increased to 790.44, 986.33 and 1045.13 molDEC molcat, respectively-1· h-1It is very interesting that the slope of the DEC yield with temperature is approximately uniform, with an inherent relationship worth deep consideration. The results fully show that the synthesized EGK catalyst has excellent capacity of catalyzing EC ring opening and EtOH ester exchange, and the catalytic efficiency is obviously improved along with the increase of the reaction temperature.
FIG. 6 Effect of reaction temperature on EC and EtOH transesterification reactions.
Example 7
EGK is used as a catalyst, reaction products are collected and analyzed within the time range of 1-300 min at fixed sampling intervals under the conditions of room temperature and azeotropic reaction temperature, and the influence of different reaction times on the synthesis of DEC by ester exchange is shown in figure 7. Because of the extremely high EGK catalytic transesterification efficiency, the DEC selectivity reaches over 99 percent under all temperature conditions, and basically has no intermediate productThe product is produced, so the DEC yield is basically consistent with the EC conversion rate. At 25 ℃, the yield of DEC is gradually increased along with the gradual extension of 5, 15, 30, 60, 120 and 180 to 300 min of reaction time, and the reaction equilibrium is reached at 180 min; at 82 ℃, the reaction equilibrium is reached within 30 min, at this time, the EC conversion rate is close to 92%, the DEC selectivity reaches more than 99%, and the DEC yield is about 92%. TOF calculated by two temperatures is the maximum value of initial reaction and reaches 703.43 and 1045.13 molDEC molcat-1· h-1Then, the TOF value is gradually reduced under the equilibrium limit of the concentration of the product glycol in the reaction system; TOF values at reaction equilibrium were 34.99 and 209.56 molDEC molcat, respectively-1· h-1. As the reaction time was extended, the DEC yield was gradually increased until reaction equilibrium was reached. For the synthesized EGK catalyst, the influence of the temperature on the EGK catalytic efficiency is not obvious in the early reaction stage, but the inhibiting effect of the glycol concentration on the EGK catalyst is more obvious at low temperature and the inhibiting effect is weakened at high temperature along with the generation of products.
FIG. 7 effect of reaction time on EC and EtOH transesterification reactions at different temperatures.
Example 8
The results of the molar ratio of the different starting materials on the activity of the transesterification synthesis of DEC with EGK as catalyst and maintaining its mass at 1% of the EC mass are shown in fig. 8. The DEC selectivity reaches over 99 percent under different raw material moles, and no intermediate product is generated basically. The yield of DEC was 50.71% at an EC/EtOH molar ratio of 1/3, and TOF was 694.41 molDEC molcat-1· h-1(ii) a Increasing the EC/EtOH molar ratio to 1/6 increased the yield of DEC to 64.35% and TOF to 881.28 molDEC molcat-1· h-1(ii) a The yield of DEC continued to increase as the EC/EtOH molar ratio continued to increase at 1/9, 1/10, and 1/12, with yield of DEC reaching 83.17% at a molar ratio of 1/12 and a TOF of 1139.13 molDEC molcat-1· h-1. Because EC and EtOH are subjected to transesterification in a reversible way, the reaction is promoted to be carried out in a positive direction by increasing the proportion of the reaction raw material EtOH, the EC conversion is promoted, the yield of DEC is further improved, and the conversion times of the EGK active center in unit time are gradually improved along with the increase of the proportion of EC/EtOH. Even though the EC/EtOH molar ratio is 1/3, the product still has the advantages of better performanceThe high DEC yield indicates that EGK has good transesterification effect and directional catalytic capability.
FIG. 8 effect of feed mole ratio on EC and EtOH transesterification.
Example 9
FIG. 9 Effect of EGK catalyst content on EC and EtOH transesterification.
FIG. 9 examines the effect of EGK catalyst content on the reaction activity at 5 min of reaction. When the catalyst content was 0.2% by mass EC, the DEC yield was only 10.39%, exhibiting poor catalytic activity, TOF of 711.12 molDEC molcat-1· h-1But at this time, the DEC selectivity is still higher than 90%; the DEC yield increased gradually with increasing catalyst content, increasing to 91.98% with increasing catalyst content to 2% and 629.84 molDEC molcat for TOF-1· h-1(ii) a The DEC yield was no longer significantly increased by continuing to increase the amount of catalyst to 3%. This is because the catalyst content is increased, the number of active centers is increased, the contact efficiency of the active centers with the reactants is improved, and the reaction is promoted to proceed in the positive direction. However, when the reaction approaches the equilibrium conversion rate, more catalyst content has little influence on the reaction, and the catalyst simultaneously increases the forward and reverse reaction rates, and the difference can be compared only by reducing the reaction time or lowering the reaction temperature and other weakening experimental conditions.
Example 10
Fig. 10 shows the results of synthetic EGK catalysts used in EC and various alcohol transesterification reactions, with selected alcohols including linear methanol, ethanol, n-propanol and n-butanol, and isopropanol, isobutanol and t-butanol with branched structures. The molar ratio of EC to the alcohol with different structures is 1/10, the EGK content is 1 percent of the mass of EC, and the reaction lasts for 30 min. The EC conversion, selectivity and yield of dimethyl carbonate when the methanol is subjected to ester exchange at 68 ℃ are respectively 86.96 percent, 99.57 percent and 86.59 percent; when the catalyst reacts with ethanol at 82 ℃, the effects are respectively 91.92%, 99.88% and 91.80%; results were 74.99%, 99.85% and 74.88% respectively at 82 ℃ with n-propanol; the results of the reaction with n-butanol at 82 ℃ were 72.51%, 99.41% and 72.14%, respectively. The results show that EGK catalyzes EC to exchange with C1-C4 normal-alcohol ester to have good reaction effect, the selectivity of the generated carbonate exceeds 99 percent, but the EC conversion rate and the yield of the target carbonic acid are gradually reduced along with the increase of carbon chains. Meanwhile, the influence of C3 and C4 isomeric alcohol is considered in FIG. 10, the yield of diisopropyl carbonate is only 4.29%, and the yield is reduced by 70.59% compared with that of dipropyl carbonate under the same reaction conditions; the yield of diisobutyl carbonate and di-tert-butyl carbonate is 27.01 percent and 1.85 percent respectively, which is reduced by 45.13 percent and 70.29 percent compared with the yield of dibutyl carbonate. The above experimental results show that the catalytic activity of the alcohol is remarkably reduced with the increase of the number of branched chains of the alcohol with the same number of carbon atoms. In combination with the knowledge of the carbonate exchange reaction mechanism, we believe that the primary reason is that the isomeric alcohol is difficult to activate by ethylene glycol oxyanions, and the activated isomeric alcohol oxyanions are more hydrophilic than ethoxy anions, resulting in less activated isomeric alcohol oxyanions in the reaction system; the second reason is that isomeric alcohol oxyanion steric hindrance effect causes that nucleophilic attack on EC is relatively difficult and promotes reduction of EC ring-opening capability. In conclusion, EGK shows high catalytic activity for the normal alcohol ester exchange reaction of C1-C4 and universality for the alcohol ester exchange reaction of EC and different structures.
FIG. 10 EGK catalyzes the effect of EC and C1-C4 alcohol transesterification.
Example 11
EGK with the EC mass content of 3% is used as a catalyst, the EGK is sampled and analyzed after reacting for 5 min at 82 ℃, then EtOH with the EC molar weight being 20 times of that of the EC is additionally added for reacting for 20 min, then reduced pressure distillation is carried out, after products EG and DEC and unreacted raw material EC are separated out, the residual catalyst in a distillation flask is repeated for the next cycle, the catalytic stability of the EGK is inspected, and the relationship between the EC conversion rate, the DEC selectivity and the yield and the repeated use frequency of the EGK is shown in figure 11. The EC conversion, DEC selectivity and yield were 91.87%, 99.95% and 91.83% respectively when EGK was first used. In the second cycle experiment, the EC conversion, DEC selectivity and yield were slightly decreased, 86.71%, 99.03% and 85.86%, respectively, with a 5.16% decrease in EC conversion and a 5.97% decrease in DEC yield compared to the first. The fifth cycle used, EC conversion, DEC selectivity and yield were 82.96%, 98.43% and 81.66%, respectively. One of the reasons for the slight decrease in catalytic activity of EGK during the recycle process may be the loss of catalyst during the recycle process due to multiple sampling. In conclusion, the EGK is repeatedly used for five times, each time, the reaction is only carried out for 5 min, the excellent reaction activity is still realized, the yield and the selectivity of the DEC are always kept to be more than 80 percent and 98 percent, no obvious inactivation phenomenon occurs, and the EGK is proved to have better stability and reusability in the ester exchange reaction of EC and EtOH.
Fig. 11 reuse of EGK catalyst.
The above description is only for the purpose of illustrating the present invention and is not intended to limit the present invention in any way, and the present invention is not limited to the above description, but rather should be construed as being limited to the scope of the present invention.
Claims (3)
1. The preparation method of the strongly alkaline homogeneous phase dihydric alcohol metal salt catalyst is characterized by comprising the following steps: the catalyst is homogeneous phase ethylene glycol salt, and the reaction is ester exchange reaction of ethylene carbonate and low-carbon alcohol; the metal alkoxide catalyst is ethylene glycol metal salt; the glycol metal salt comprises a glycol anion and a metal cation; the cation being Li+、Na+、K+Or Cs+(ii) a The anion is a structure shown in formula I;
formula I
The preparation method comprises the following preparation steps:
a1) adding inorganic or organic strong base into the glycol solution to react at a certain temperature to obtain a mixed solution of glycol metal salt solution and water;
a2) and (3) removing water from the mixed solution of the glycol metal salt and water through reduced pressure rotary evaporation to obtain the glycol metal salt solution, and adding a solvent for sealing and storing.
2. The method for preparing a strongly basic homogeneous glycol metal salt catalyst according to claim 1, wherein:
the molar ratio of the ethylene glycol to the alkali is 1/1-4/1;
the alkali is organic alkali or inorganic alkali;
the organic base comprises sodium methoxide, sodium ethoxide, sodium tert-butoxide, potassium methoxide, potassium ethoxide or potassium tert-butoxide;
the inorganic base includes lithium hydroxide, sodium hydroxide, potassium hydroxide, and cesium hydroxide;
the metal salt comprises at least one of Li salt, Na salt, K salt and Cs salt;
the glycol metal salt solution is a mixed solution of glycol metal salt and glycol;
the certain temperature is 25-120 ℃;
the pressure is 0.001-50 KPa;
the rotary evaporation temperature is 110-140 ℃;
preferably, in step a1), the base is potassium methoxide, potassium ethoxide, tert-butanol or potassium hydroxide;
preferably, in step a1), the reaction conditions are: reacting for 30-60 minutes at 50-80 ℃;
preferably, in step a2), the reaction conditions are: rotary evaporating at 120-130 deg.c for 1-5 hr;
preferably, in step a2), the solvent is selected from at least one of methanol, ethanol, ethylene glycol and acetonitrile;
preferably, in the step a2), the preservation temperature is 0-50 ℃ for sealed preservation;
preferably, in step a2), the ratio of ethylene glycol metal salt solution to solvent is 1/1-1/3.
3. The method for synthesizing carbonic ester by using strongly basic homogeneous diol metal salt catalyst is characterized by comprising the following steps: the method comprises the following scheme: the reaction raw materials are ethylene carbonate and low-carbon alcohol; the ethylene glycol metal salt catalyst is at least one or a mixture of lithium Ethylene Glycol (EGLi), sodium ethylene glycol (EGNa), potassium Ethylene Glycol (EGK) and cesium Ethylene Glycol (EGCs); the lower alcohol is C1-C4 normal and isomeric alcohol; the reaction temperature is 25-120 deg.C, preferably 65-110 deg.C.
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| CN115108912A (en) * | 2022-06-02 | 2022-09-27 | 沈阳化工大学 | Strongly alkaline ionic liquid catalyzed CO 2 Method for synthesizing dimethyl carbonate catalyst |
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