CN108047040A - A kind of method of ethylene carbonate and alcohols one-step synthesis carbonic acid symmetrical ester - Google Patents
A kind of method of ethylene carbonate and alcohols one-step synthesis carbonic acid symmetrical ester Download PDFInfo
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- CN108047040A CN108047040A CN201711380448.0A CN201711380448A CN108047040A CN 108047040 A CN108047040 A CN 108047040A CN 201711380448 A CN201711380448 A CN 201711380448A CN 108047040 A CN108047040 A CN 108047040A
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- Prior art keywords
- catalyst
- reaction
- carbonic acid
- alcohols
- ethylene carbonate
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- 150000001298 alcohols Chemical class 0.000 title claims abstract description 61
- 238000000034 method Methods 0.000 title claims abstract description 60
- 150000002148 esters Chemical class 0.000 title claims abstract description 57
- KMTRUDSVKNLOMY-UHFFFAOYSA-N Ethylene carbonate Chemical compound O=C1OCCO1 KMTRUDSVKNLOMY-UHFFFAOYSA-N 0.000 title claims abstract description 55
- BVKZGUZCCUSVTD-UHFFFAOYSA-N carbonic acid Chemical compound OC(O)=O BVKZGUZCCUSVTD-UHFFFAOYSA-N 0.000 title claims abstract description 51
- 238000003786 synthesis reaction Methods 0.000 title claims abstract description 37
- 230000015572 biosynthetic process Effects 0.000 title claims abstract description 36
- MTHSVFCYNBDYFN-UHFFFAOYSA-N diethylene glycol Chemical compound OCCOCCO MTHSVFCYNBDYFN-UHFFFAOYSA-N 0.000 claims abstract description 214
- LYCAIKOWRPUZTN-UHFFFAOYSA-N Ethylene glycol Chemical compound OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 claims abstract description 132
- 238000006243 chemical reaction Methods 0.000 claims abstract description 132
- 239000003054 catalyst Substances 0.000 claims abstract description 106
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims abstract description 63
- WGCNASOHLSPBMP-UHFFFAOYSA-N hydroxyacetaldehyde Natural products OCC=O WGCNASOHLSPBMP-UHFFFAOYSA-N 0.000 claims abstract description 23
- 239000011148 porous material Substances 0.000 claims abstract description 23
- 150000002989 phenols Chemical class 0.000 claims abstract description 19
- 239000002994 raw material Substances 0.000 claims abstract description 19
- WVDDGKGOMKODPV-UHFFFAOYSA-N Benzyl alcohol Chemical compound OCC1=CC=CC=C1 WVDDGKGOMKODPV-UHFFFAOYSA-N 0.000 claims abstract description 18
- 229920005862 polyol Polymers 0.000 claims abstract description 18
- 150000003077 polyols Chemical class 0.000 claims abstract description 16
- 239000002131 composite material Substances 0.000 claims abstract description 13
- BVKZGUZCCUSVTD-UHFFFAOYSA-L Carbonate Chemical compound [O-]C([O-])=O BVKZGUZCCUSVTD-UHFFFAOYSA-L 0.000 claims abstract description 11
- -1 ethylene carbonate ester Chemical class 0.000 claims abstract description 7
- URGAHOPLAPQHLN-UHFFFAOYSA-N sodium aluminosilicate Chemical compound [Na+].[Al+3].[O-][Si]([O-])=O.[O-][Si]([O-])=O URGAHOPLAPQHLN-UHFFFAOYSA-N 0.000 claims description 46
- 239000002808 molecular sieve Substances 0.000 claims description 44
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 claims description 30
- 239000000969 carrier Substances 0.000 claims description 27
- 239000000243 solution Substances 0.000 claims description 24
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 22
- 239000012670 alkaline solution Substances 0.000 claims description 21
- 238000002360 preparation method Methods 0.000 claims description 20
- 229910001868 water Inorganic materials 0.000 claims description 19
- 150000001875 compounds Chemical class 0.000 claims description 16
- 229910002651 NO3 Inorganic materials 0.000 claims description 15
- NHNBFGGVMKEFGY-UHFFFAOYSA-N Nitrate Chemical compound [O-][N+]([O-])=O NHNBFGGVMKEFGY-UHFFFAOYSA-N 0.000 claims description 15
- 239000007788 liquid Substances 0.000 claims description 13
- TWRXJAOTZQYOKJ-UHFFFAOYSA-L Magnesium chloride Chemical compound [Mg+2].[Cl-].[Cl-] TWRXJAOTZQYOKJ-UHFFFAOYSA-L 0.000 claims description 12
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 claims description 12
- VSCWAEJMTAWNJL-UHFFFAOYSA-K aluminium trichloride Chemical compound Cl[Al](Cl)Cl VSCWAEJMTAWNJL-UHFFFAOYSA-K 0.000 claims description 12
- AIYUHDOJVYHVIT-UHFFFAOYSA-M caesium chloride Chemical compound [Cl-].[Cs+] AIYUHDOJVYHVIT-UHFFFAOYSA-M 0.000 claims description 12
- ZCCIPPOKBCJFDN-UHFFFAOYSA-N calcium nitrate Chemical compound [Ca+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O ZCCIPPOKBCJFDN-UHFFFAOYSA-N 0.000 claims description 12
- 229910052700 potassium Inorganic materials 0.000 claims description 12
- FGIUAXJPYTZDNR-UHFFFAOYSA-N potassium nitrate Chemical compound [K+].[O-][N+]([O-])=O FGIUAXJPYTZDNR-UHFFFAOYSA-N 0.000 claims description 12
- 230000032683 aging Effects 0.000 claims description 11
- 229910052792 caesium Inorganic materials 0.000 claims description 10
- 229910052791 calcium Inorganic materials 0.000 claims description 10
- 229910052744 lithium Inorganic materials 0.000 claims description 10
- 229910052749 magnesium Inorganic materials 0.000 claims description 10
- 229910052701 rubidium Inorganic materials 0.000 claims description 10
- 229910052708 sodium Inorganic materials 0.000 claims description 10
- 239000011734 sodium Substances 0.000 claims description 10
- CDBYLPFSWZWCQE-UHFFFAOYSA-L sodium carbonate Substances [Na+].[Na+].[O-]C([O-])=O CDBYLPFSWZWCQE-UHFFFAOYSA-L 0.000 claims description 10
- 239000002253 acid Substances 0.000 claims description 9
- 238000005406 washing Methods 0.000 claims description 9
- 229910052802 copper Inorganic materials 0.000 claims description 8
- 229910052742 iron Inorganic materials 0.000 claims description 8
- 239000000463 material Substances 0.000 claims description 8
- KWYUFKZDYYNOTN-UHFFFAOYSA-M potassium hydroxide Substances [OH-].[K+] KWYUFKZDYYNOTN-UHFFFAOYSA-M 0.000 claims description 8
- 230000008569 process Effects 0.000 claims description 8
- WMFOQBRAJBCJND-UHFFFAOYSA-M Lithium hydroxide Chemical compound [Li+].[OH-] WMFOQBRAJBCJND-UHFFFAOYSA-M 0.000 claims description 7
- 229910052783 alkali metal Inorganic materials 0.000 claims description 7
- 229910000272 alkali metal oxide Inorganic materials 0.000 claims description 7
- 150000001340 alkali metals Chemical class 0.000 claims description 7
- 238000000975 co-precipitation Methods 0.000 claims description 7
- 238000001035 drying Methods 0.000 claims description 7
- UXVMQQNJUSDDNG-UHFFFAOYSA-L Calcium chloride Chemical compound [Cl-].[Cl-].[Ca+2] UXVMQQNJUSDDNG-UHFFFAOYSA-L 0.000 claims description 6
- 229910021578 Iron(III) chloride Inorganic materials 0.000 claims description 6
- 229910002339 La(NO3)3 Inorganic materials 0.000 claims description 6
- 229910002249 LaCl3 Inorganic materials 0.000 claims description 6
- CPLXHLVBOLITMK-UHFFFAOYSA-N Magnesium oxide Chemical compound [Mg]=O CPLXHLVBOLITMK-UHFFFAOYSA-N 0.000 claims description 6
- CSNNHWWHGAXBCP-UHFFFAOYSA-L Magnesium sulfate Chemical compound [Mg+2].[O-][S+2]([O-])([O-])[O-] CSNNHWWHGAXBCP-UHFFFAOYSA-L 0.000 claims description 6
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 claims description 6
- QAOWNCQODCNURD-UHFFFAOYSA-L Sulfate Chemical compound [O-]S([O-])(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-L 0.000 claims description 6
- MCMNRKCIXSYSNV-UHFFFAOYSA-N Zirconium dioxide Chemical compound O=[Zr]=O MCMNRKCIXSYSNV-UHFFFAOYSA-N 0.000 claims description 6
- 229910001626 barium chloride Inorganic materials 0.000 claims description 6
- WDIHJSXYQDMJHN-UHFFFAOYSA-L barium chloride Chemical compound [Cl-].[Cl-].[Ba+2] WDIHJSXYQDMJHN-UHFFFAOYSA-L 0.000 claims description 6
- IWOUKMZUPDVPGQ-UHFFFAOYSA-N barium nitrate Inorganic materials [Ba+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O IWOUKMZUPDVPGQ-UHFFFAOYSA-N 0.000 claims description 6
- NLSCHDZTHVNDCP-UHFFFAOYSA-N caesium nitrate Inorganic materials [Cs+].[O-][N+]([O-])=O NLSCHDZTHVNDCP-UHFFFAOYSA-N 0.000 claims description 6
- FLJPGEWQYJVDPF-UHFFFAOYSA-L caesium sulfate Chemical compound [Cs+].[Cs+].[O-]S([O-])(=O)=O FLJPGEWQYJVDPF-UHFFFAOYSA-L 0.000 claims description 6
- 238000001354 calcination Methods 0.000 claims description 6
- 239000001110 calcium chloride Substances 0.000 claims description 6
- 229910001628 calcium chloride Inorganic materials 0.000 claims description 6
- 239000000470 constituent Substances 0.000 claims description 6
- 229910052593 corundum Inorganic materials 0.000 claims description 6
- 238000005470 impregnation Methods 0.000 claims description 6
- RBTARNINKXHZNM-UHFFFAOYSA-K iron trichloride Chemical compound Cl[Fe](Cl)Cl RBTARNINKXHZNM-UHFFFAOYSA-K 0.000 claims description 6
- VCJMYUPGQJHHFU-UHFFFAOYSA-N iron(III) nitrate Inorganic materials [Fe+3].[O-][N+]([O-])=O.[O-][N+]([O-])=O.[O-][N+]([O-])=O VCJMYUPGQJHHFU-UHFFFAOYSA-N 0.000 claims description 6
- ICAKDTKJOYSXGC-UHFFFAOYSA-K lanthanum(iii) chloride Chemical compound Cl[La](Cl)Cl ICAKDTKJOYSXGC-UHFFFAOYSA-K 0.000 claims description 6
- 238000011068 loading method Methods 0.000 claims description 6
- 229910001629 magnesium chloride Inorganic materials 0.000 claims description 6
- 229910052751 metal Inorganic materials 0.000 claims description 6
- 239000002184 metal Substances 0.000 claims description 6
- 238000002156 mixing Methods 0.000 claims description 6
- 229910000029 sodium carbonate Inorganic materials 0.000 claims description 6
- 229910001631 strontium chloride Inorganic materials 0.000 claims description 6
- AHBGXTDRMVNFER-UHFFFAOYSA-L strontium dichloride Chemical compound [Cl-].[Cl-].[Sr+2] AHBGXTDRMVNFER-UHFFFAOYSA-L 0.000 claims description 6
- DHEQXMRUPNDRPG-UHFFFAOYSA-N strontium nitrate Inorganic materials [Sr+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O DHEQXMRUPNDRPG-UHFFFAOYSA-N 0.000 claims description 6
- 229910001845 yogo sapphire Inorganic materials 0.000 claims description 6
- 239000007848 Bronsted acid Substances 0.000 claims description 5
- XLOMVQKBTHCTTD-UHFFFAOYSA-N Zinc monoxide Chemical compound [Zn]=O XLOMVQKBTHCTTD-UHFFFAOYSA-N 0.000 claims description 5
- 238000006555 catalytic reaction Methods 0.000 claims description 5
- 238000007600 charging Methods 0.000 claims description 5
- 238000007598 dipping method Methods 0.000 claims description 5
- 238000003756 stirring Methods 0.000 claims description 5
- 238000005342 ion exchange Methods 0.000 claims description 4
- YIXJRHPUWRPCBB-UHFFFAOYSA-N magnesium nitrate Inorganic materials [Mg+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O YIXJRHPUWRPCBB-UHFFFAOYSA-N 0.000 claims description 4
- 229910017604 nitric acid Inorganic materials 0.000 claims description 4
- 239000001301 oxygen Substances 0.000 claims description 4
- 229910052760 oxygen Inorganic materials 0.000 claims description 4
- 239000000126 substance Substances 0.000 claims description 4
- 238000000967 suction filtration Methods 0.000 claims description 4
- QTBSBXVTEAMEQO-UHFFFAOYSA-M Acetate Chemical compound CC([O-])=O QTBSBXVTEAMEQO-UHFFFAOYSA-M 0.000 claims description 3
- QGZKDVFQNNGYKY-UHFFFAOYSA-O Ammonium Chemical compound [NH4+] QGZKDVFQNNGYKY-UHFFFAOYSA-O 0.000 claims description 3
- VHUUQVKOLVNVRT-UHFFFAOYSA-N Ammonium hydroxide Chemical compound [NH4+].[OH-] VHUUQVKOLVNVRT-UHFFFAOYSA-N 0.000 claims description 3
- BVKZGUZCCUSVTD-UHFFFAOYSA-M Bicarbonate Chemical compound OC([O-])=O BVKZGUZCCUSVTD-UHFFFAOYSA-M 0.000 claims description 3
- 229910052684 Cerium Inorganic materials 0.000 claims description 3
- 229910052782 aluminium Inorganic materials 0.000 claims description 3
- 229910000329 aluminium sulfate Inorganic materials 0.000 claims description 3
- DIZPMCHEQGEION-UHFFFAOYSA-H aluminium sulfate (anhydrous) Chemical compound [Al+3].[Al+3].[O-]S([O-])(=O)=O.[O-]S([O-])(=O)=O.[O-]S([O-])(=O)=O DIZPMCHEQGEION-UHFFFAOYSA-H 0.000 claims description 3
- 239000000908 ammonium hydroxide Substances 0.000 claims description 3
- 229910052925 anhydrite Inorganic materials 0.000 claims description 3
- 229910052788 barium Inorganic materials 0.000 claims description 3
- FFBHFFJDDLITSX-UHFFFAOYSA-N benzyl N-[2-hydroxy-4-(3-oxomorpholin-4-yl)phenyl]carbamate Chemical compound OC1=C(NC(=O)OCC2=CC=CC=C2)C=CC(=C1)N1CCOCC1=O FFBHFFJDDLITSX-UHFFFAOYSA-N 0.000 claims description 3
- 229910052796 boron Inorganic materials 0.000 claims description 3
- OSGAYBCDTDRGGQ-UHFFFAOYSA-L calcium sulfate Chemical compound [Ca+2].[O-]S([O-])(=O)=O OSGAYBCDTDRGGQ-UHFFFAOYSA-L 0.000 claims description 3
- 229910052681 coesite Inorganic materials 0.000 claims description 3
- 229910052906 cristobalite Inorganic materials 0.000 claims description 3
- 150000004675 formic acid derivatives Chemical class 0.000 claims description 3
- XLYOFNOQVPJJNP-UHFFFAOYSA-M hydroxide Chemical compound [OH-] XLYOFNOQVPJJNP-UHFFFAOYSA-M 0.000 claims description 3
- 229910052741 iridium Inorganic materials 0.000 claims description 3
- 229910000360 iron(III) sulfate Inorganic materials 0.000 claims description 3
- 229910052943 magnesium sulfate Inorganic materials 0.000 claims description 3
- 229910052748 manganese Inorganic materials 0.000 claims description 3
- 229910021645 metal ion Inorganic materials 0.000 claims description 3
- 229910052697 platinum Inorganic materials 0.000 claims description 3
- OTYBMLCTZGSZBG-UHFFFAOYSA-L potassium sulfate Chemical compound [K+].[K+].[O-]S([O-])(=O)=O OTYBMLCTZGSZBG-UHFFFAOYSA-L 0.000 claims description 3
- 229910052939 potassium sulfate Inorganic materials 0.000 claims description 3
- 229910052703 rhodium Inorganic materials 0.000 claims description 3
- 229910052707 ruthenium Inorganic materials 0.000 claims description 3
- 150000003839 salts Chemical class 0.000 claims description 3
- 239000000377 silicon dioxide Substances 0.000 claims description 3
- 229910052709 silver Inorganic materials 0.000 claims description 3
- 229910052682 stishovite Inorganic materials 0.000 claims description 3
- 229910052712 strontium Inorganic materials 0.000 claims description 3
- 229910052905 tridymite Inorganic materials 0.000 claims description 3
- 229910052721 tungsten Inorganic materials 0.000 claims description 3
- 229910052727 yttrium Inorganic materials 0.000 claims description 3
- 229910052725 zinc Inorganic materials 0.000 claims description 3
- 229910052726 zirconium Inorganic materials 0.000 claims description 3
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 claims description 2
- ZLMJMSJWJFRBEC-UHFFFAOYSA-N Potassium Chemical compound [K] ZLMJMSJWJFRBEC-UHFFFAOYSA-N 0.000 claims description 2
- XTXRWKRVRITETP-UHFFFAOYSA-N Vinyl acetate Chemical compound CC(=O)OC=C XTXRWKRVRITETP-UHFFFAOYSA-N 0.000 claims description 2
- 238000013459 approach Methods 0.000 claims description 2
- 230000008859 change Effects 0.000 claims description 2
- 229910052733 gallium Inorganic materials 0.000 claims description 2
- 239000001257 hydrogen Substances 0.000 claims description 2
- 229910052739 hydrogen Inorganic materials 0.000 claims description 2
- 230000008676 import Effects 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
- 231100000572 poisoning Toxicity 0.000 claims description 2
- 230000000607 poisoning effect Effects 0.000 claims description 2
- TYJJADVDDVDEDZ-UHFFFAOYSA-M potassium hydrogencarbonate Chemical compound [K+].OC([O-])=O TYJJADVDDVDEDZ-UHFFFAOYSA-M 0.000 claims description 2
- 238000005086 pumping Methods 0.000 claims description 2
- 238000001308 synthesis method Methods 0.000 claims description 2
- 239000006227 byproduct Substances 0.000 abstract description 10
- 238000004140 cleaning Methods 0.000 abstract description 3
- 239000012043 crude product Substances 0.000 abstract description 2
- 230000002779 inactivation Effects 0.000 abstract 1
- 238000001577 simple distillation Methods 0.000 abstract 1
- 235000019441 ethanol Nutrition 0.000 description 81
- 239000000047 product Substances 0.000 description 33
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 31
- IEJIGPNLZYLLBP-UHFFFAOYSA-N dimethyl carbonate Chemical group COC(=O)OC IEJIGPNLZYLLBP-UHFFFAOYSA-N 0.000 description 18
- JBTWLSYIZRCDFO-UHFFFAOYSA-N ethyl methyl carbonate Chemical compound CCOC(=O)OC JBTWLSYIZRCDFO-UHFFFAOYSA-N 0.000 description 17
- 230000004044 response Effects 0.000 description 14
- XTEGARKTQYYJKE-UHFFFAOYSA-M Chlorate Chemical compound [O-]Cl(=O)=O XTEGARKTQYYJKE-UHFFFAOYSA-M 0.000 description 10
- MRELNEQAGSRDBK-UHFFFAOYSA-N lanthanum oxide Inorganic materials [O-2].[O-2].[O-2].[La+3].[La+3] MRELNEQAGSRDBK-UHFFFAOYSA-N 0.000 description 9
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 7
- 238000004587 chromatography analysis Methods 0.000 description 7
- 230000000694 effects Effects 0.000 description 7
- XMJHPCRAQCTCFT-UHFFFAOYSA-N methyl chloroformate Chemical compound COC(Cl)=O XMJHPCRAQCTCFT-UHFFFAOYSA-N 0.000 description 7
- 238000005070 sampling Methods 0.000 description 7
- 239000003795 chemical substances by application Substances 0.000 description 6
- OIFBSDVPJOWBCH-UHFFFAOYSA-N Diethyl carbonate Chemical compound CCOC(=O)OCC OIFBSDVPJOWBCH-UHFFFAOYSA-N 0.000 description 5
- IXCSERBJSXMMFS-UHFFFAOYSA-N hydrogen chloride Substances Cl.Cl IXCSERBJSXMMFS-UHFFFAOYSA-N 0.000 description 5
- 229910000041 hydrogen chloride Inorganic materials 0.000 description 5
- 229910001960 metal nitrate Inorganic materials 0.000 description 5
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 4
- YGYAWVDWMABLBF-UHFFFAOYSA-N Phosgene Chemical compound ClC(Cl)=O YGYAWVDWMABLBF-UHFFFAOYSA-N 0.000 description 4
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N Titan oxide Chemical compound O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 description 4
- 239000012018 catalyst precursor Substances 0.000 description 4
- 229910044991 metal oxide Inorganic materials 0.000 description 4
- 150000004706 metal oxides Chemical class 0.000 description 4
- 239000011259 mixed solution Substances 0.000 description 4
- 239000003513 alkali Substances 0.000 description 3
- 239000008367 deionised water Substances 0.000 description 3
- 229910021641 deionized water Inorganic materials 0.000 description 3
- RIFGWPKJUGCATF-UHFFFAOYSA-N ethyl chloroformate Chemical compound CCOC(Cl)=O RIFGWPKJUGCATF-UHFFFAOYSA-N 0.000 description 3
- 238000001802 infusion Methods 0.000 description 3
- OJURWUUOVGOHJZ-UHFFFAOYSA-N methyl 2-[(2-acetyloxyphenyl)methyl-[2-[(2-acetyloxyphenyl)methyl-(2-methoxy-2-oxoethyl)amino]ethyl]amino]acetate Chemical compound C=1C=CC=C(OC(C)=O)C=1CN(CC(=O)OC)CCN(CC(=O)OC)CC1=CC=CC=C1OC(C)=O OJURWUUOVGOHJZ-UHFFFAOYSA-N 0.000 description 3
- KTUFCUMIWABKDW-UHFFFAOYSA-N oxo(oxolanthaniooxy)lanthanum Chemical compound O=[La]O[La]=O KTUFCUMIWABKDW-UHFFFAOYSA-N 0.000 description 3
- 238000005809 transesterification reaction Methods 0.000 description 3
- CURLTUGMZLYLDI-UHFFFAOYSA-N Carbon dioxide Chemical compound O=C=O CURLTUGMZLYLDI-UHFFFAOYSA-N 0.000 description 2
- JUJWROOIHBZHMG-UHFFFAOYSA-N Pyridine Chemical compound C1=CC=NC=C1 JUJWROOIHBZHMG-UHFFFAOYSA-N 0.000 description 2
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 description 2
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 2
- 229910052799 carbon Inorganic materials 0.000 description 2
- SIXOAUAWLZKQKX-UHFFFAOYSA-N carbonic acid;prop-1-ene Chemical compound CC=C.OC(O)=O SIXOAUAWLZKQKX-UHFFFAOYSA-N 0.000 description 2
- 229910052804 chromium Inorganic materials 0.000 description 2
- 230000007797 corrosion Effects 0.000 description 2
- 238000005260 corrosion Methods 0.000 description 2
- 238000005516 engineering process Methods 0.000 description 2
- 230000007613 environmental effect Effects 0.000 description 2
- 238000004519 manufacturing process Methods 0.000 description 2
- JKQOBWVOAYFWKG-UHFFFAOYSA-N molybdenum trioxide Chemical compound O=[Mo](=O)=O JKQOBWVOAYFWKG-UHFFFAOYSA-N 0.000 description 2
- 238000005832 oxidative carbonylation reaction Methods 0.000 description 2
- BWHMMNNQKKPAPP-UHFFFAOYSA-L potassium carbonate Chemical compound [K+].[K+].[O-]C([O-])=O BWHMMNNQKKPAPP-UHFFFAOYSA-L 0.000 description 2
- 238000001556 precipitation Methods 0.000 description 2
- 238000012545 processing Methods 0.000 description 2
- 230000035484 reaction time Effects 0.000 description 2
- 239000002904 solvent Substances 0.000 description 2
- 229910052596 spinel Inorganic materials 0.000 description 2
- 239000011029 spinel Substances 0.000 description 2
- 238000010189 synthetic method Methods 0.000 description 2
- UGFAIRIUMAVXCW-UHFFFAOYSA-N Carbon monoxide Chemical compound [O+]#[C-] UGFAIRIUMAVXCW-UHFFFAOYSA-N 0.000 description 1
- 206010013786 Dry skin Diseases 0.000 description 1
- IAYPIBMASNFSPL-UHFFFAOYSA-N Ethylene oxide Chemical compound C1CO1 IAYPIBMASNFSPL-UHFFFAOYSA-N 0.000 description 1
- WHXSMMKQMYFTQS-UHFFFAOYSA-N Lithium Chemical compound [Li] WHXSMMKQMYFTQS-UHFFFAOYSA-N 0.000 description 1
- HBBGRARXTFLTSG-UHFFFAOYSA-N Lithium ion Chemical compound [Li+] HBBGRARXTFLTSG-UHFFFAOYSA-N 0.000 description 1
- GRYLNZFGIOXLOG-UHFFFAOYSA-N Nitric acid Chemical compound O[N+]([O-])=O GRYLNZFGIOXLOG-UHFFFAOYSA-N 0.000 description 1
- GOOHAUXETOMSMM-UHFFFAOYSA-N Propylene oxide Chemical compound CC1CO1 GOOHAUXETOMSMM-UHFFFAOYSA-N 0.000 description 1
- WQDUMFSSJAZKTM-UHFFFAOYSA-N Sodium methoxide Chemical compound [Na+].[O-]C WQDUMFSSJAZKTM-UHFFFAOYSA-N 0.000 description 1
- 238000010306 acid treatment Methods 0.000 description 1
- 238000013019 agitation Methods 0.000 description 1
- 229910001413 alkali metal ion Inorganic materials 0.000 description 1
- 229910052784 alkaline earth metal Inorganic materials 0.000 description 1
- 229910000287 alkaline earth metal oxide Inorganic materials 0.000 description 1
- 150000001342 alkaline earth metals Chemical class 0.000 description 1
- 229930013930 alkaloid Natural products 0.000 description 1
- 150000001412 amines Chemical class 0.000 description 1
- 238000009835 boiling Methods 0.000 description 1
- 239000001569 carbon dioxide Substances 0.000 description 1
- 229910002092 carbon dioxide Inorganic materials 0.000 description 1
- 229910002091 carbon monoxide Inorganic materials 0.000 description 1
- UFLFSNVZQRNKOX-UHFFFAOYSA-N carbonic acid;ethenyl acetate Chemical compound OC(O)=O.CC(=O)OC=C UFLFSNVZQRNKOX-UHFFFAOYSA-N 0.000 description 1
- 230000003197 catalytic effect Effects 0.000 description 1
- 239000007795 chemical reaction product Substances 0.000 description 1
- 239000003153 chemical reaction reagent Substances 0.000 description 1
- 230000007423 decrease Effects 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 238000002242 deionisation method Methods 0.000 description 1
- 239000003599 detergent Substances 0.000 description 1
- 239000006185 dispersion Substances 0.000 description 1
- 239000003792 electrolyte Substances 0.000 description 1
- 238000004134 energy conservation Methods 0.000 description 1
- 238000005265 energy consumption Methods 0.000 description 1
- 238000003912 environmental pollution Methods 0.000 description 1
- 125000001495 ethyl group Chemical group [H]C([H])([H])C([H])([H])* 0.000 description 1
- 239000012065 filter cake Substances 0.000 description 1
- 239000003205 fragrance Substances 0.000 description 1
- 239000007789 gas Substances 0.000 description 1
- 230000036541 health Effects 0.000 description 1
- 239000002815 homogeneous catalyst Substances 0.000 description 1
- 238000001027 hydrothermal synthesis Methods 0.000 description 1
- 150000002460 imidazoles Chemical class 0.000 description 1
- 239000002608 ionic liquid Substances 0.000 description 1
- 150000002500 ions Chemical class 0.000 description 1
- 150000002576 ketones Chemical class 0.000 description 1
- 229910001416 lithium ion Inorganic materials 0.000 description 1
- 229910003002 lithium salt Inorganic materials 0.000 description 1
- 159000000002 lithium salts Chemical class 0.000 description 1
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 229910052759 nickel Inorganic materials 0.000 description 1
- 231100000252 nontoxic Toxicity 0.000 description 1
- 230000003000 nontoxic effect Effects 0.000 description 1
- 239000003960 organic solvent Substances 0.000 description 1
- 239000002574 poison Substances 0.000 description 1
- 231100000614 poison Toxicity 0.000 description 1
- 229910000027 potassium carbonate Inorganic materials 0.000 description 1
- 239000002243 precursor Substances 0.000 description 1
- 238000000746 purification Methods 0.000 description 1
- UMJSCPRVCHMLSP-UHFFFAOYSA-N pyridine Natural products COC1=CC=CN=C1 UMJSCPRVCHMLSP-UHFFFAOYSA-N 0.000 description 1
- 229910001404 rare earth metal oxide Inorganic materials 0.000 description 1
- 239000000376 reactant Substances 0.000 description 1
- 238000004064 recycling Methods 0.000 description 1
- 238000010992 reflux Methods 0.000 description 1
- 238000000926 separation method Methods 0.000 description 1
- 239000002002 slurry Substances 0.000 description 1
- 239000000725 suspension Substances 0.000 description 1
- 239000004408 titanium dioxide Substances 0.000 description 1
- 238000012546 transfer Methods 0.000 description 1
- 238000002604 ultrasonography Methods 0.000 description 1
- 238000010792 warming Methods 0.000 description 1
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- 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
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- B01J29/00—Catalysts comprising molecular sieves
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- B01J29/0308—Mesoporous materials not having base exchange properties, e.g. Si-MCM-41
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- B01J29/00—Catalysts comprising molecular sieves
- B01J29/04—Catalysts comprising molecular sieves having base-exchange properties, e.g. crystalline zeolites
- B01J29/041—Mesoporous materials having base exchange properties, e.g. Si/Al-MCM-41
- B01J29/045—Mesoporous materials having base exchange properties, e.g. Si/Al-MCM-41 containing arsenic, antimony, bismuth, vanadium, niobium, tantalum, polonium, chromium, molybdenum, tungsten, manganese, technetium or rhenium
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- B01J29/00—Catalysts comprising molecular sieves
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- B01J29/06—Crystalline aluminosilicate zeolites; Isomorphous compounds thereof
- B01J29/08—Crystalline aluminosilicate zeolites; Isomorphous compounds thereof of the faujasite type, e.g. type X or Y
- B01J29/084—Y-type faujasite
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- B01J29/06—Crystalline aluminosilicate zeolites; Isomorphous compounds thereof
- B01J29/40—Crystalline aluminosilicate zeolites; Isomorphous compounds thereof of the pentasil type, e.g. types ZSM-5, ZSM-8 or ZSM-11, as exemplified by patent documents US3702886, GB1334243 and US3709979, respectively
- B01J29/405—Crystalline aluminosilicate zeolites; Isomorphous compounds thereof of the pentasil type, e.g. types ZSM-5, ZSM-8 or ZSM-11, as exemplified by patent documents US3702886, GB1334243 and US3709979, respectively containing rare earth elements, titanium, zirconium, hafnium, zinc, cadmium, mercury, gallium, indium, thallium, tin or lead
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- B01J29/70—Crystalline aluminosilicate zeolites; Isomorphous compounds thereof of types characterised by their specific structure not provided for in groups B01J29/08 - B01J29/65
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Abstract
A kind of method of ethylene carbonate and alcohols one-step synthesis carbonic acid symmetrical ester is related to a kind of method of carbonate synthesis symmetrical ester, and the present invention has the efficient alkaline catalyst of composite pore structural, for ethylene carbonate and various alcohols（ROH, R can be straight chain alcohol, isomery alcohol, aromatic alcohol, phenols, the glycol such as various alcohols such as ethylene glycol, diethylene glycol (DEG) and polyol）One-step synthesis carbonic acid symmetrical ester.Only contain carbonic acid symmetrical ester and ethylene glycol in crude product obtained by the reaction.Wherein, ethylene carbonate ester conversion rate can reach 95%.By-product ethylene glycol is i.e. separable by simple distillation as largeization raw material.Entire reaction process cleaning, efficient, pollution-free, no any discarded object generation.Work as ethylene carbonate：Various alcohols molar ratios 1:3,5 MPa of reaction pressure, 100 DEG C of reaction temperature, 5 h of air speed‑1, catalyst uses 5000h non-inactivations, and stability is preferable.
Description
Technical field
The present invention relates to a kind of method of carbonate synthesis symmetrical ester, more particularly to one step of a kind of ethylene carbonate and alcohols
The method of carbonate synthesis symmetrical ester.
Background technology
Methyl ethyl carbonate（Methyl Ethyl Carbonate, abbreviation MEC）, molecular formula：C4H8O3, colourless transparent liquid,
1.01 g/mL of density, -55 DEG C of fusing point, 107 DEG C of boiling point is flammable, can be mixed with arbitrary proportion with organic solvent such as alcohol, ketone, ester,
It is a kind of excellent solvent, methyl ethyl carbonate due to having methyl and ethyl simultaneously in its molecular structure, so it has carbonic acid concurrently
The characteristic of dimethyl ester, diethyl carbonate, can be as some special organic synthesis reagents, while it is also the molten of extraordinary fragrance
Agent.
Since the viscosity of methyl ethyl carbonate is small, dielectric constant is big, strong to the dissolubility of lithium salts, therefore it is a kind of excellent
Lithium ion battery electrolyte solvent can improve the energy density and discharge capacity of battery, can more improve the security of battery
Energy and service life.
Consulting literatures understand that methyl ethyl carbonate is mainly the following synthetic method at present：
（One）Phosgenation
Phosgenation is the process using phosgene and methanol/ethanol as Material synthesis methyl ethyl carbonate, and reaction equation is as follows：
COCl2 + CH3OH→CH3OCOCl...................................................
.......................(1)
CH3OCOCl + C2H5OH→CH3OCOOC2H5.............................................
............(2)
COCl2 +C2H5OH→C2H5OCOCl...................................................
......................(3)
C2H5OCOCl + CH3OH→CH3OCOOC2H5.............................................
............(4)
The method Catalysts of Preparing Methyl Ethyl Carbonate byproduct of reaction is more（Main By product is dimethyl carbonate, diethyl carbonate, chloro-carbonic acid
Methyl esters, ethyl chloroformate）, operating difficulties generates the hydrogen chloride of severe corrosive during simultaneous reactions, it is desirable that equipment has corrosion resistant
Corrosion adds equipment investment.Phosgene has hypertoxicity, and great risk, and the method are caused to the health of operating personnel
Methyl ethyl carbonate yield is relatively low, therefore is gradually eliminated.
（Two）Oxidative carbonylation
Oxidative carbonylation is using carbon monoxide, oxygen, methanol and ethyl alcohol as raw material, in certain temperature and pressure and in catalyst
Under existence condition, Catalysts of Preparing Methyl Ethyl Carbonate, reaction equation is as follows：
CH3OH + C2H5OH + CO + O2→CH3OCOOC2H5 +
H2O..................................(5)
The method major defect is that byproduct of reaction is more（Main By product has dimethyl carbonate, diethyl carbonate, water）, follow-up point
From purification difficult, production cost is added.
（Three）Ester-interchange method
1st, methylchloroformate and ethyl alcohol ester-interchange method
Edmund PWoo and Ichiro Minami etc. is reported using methylchloroformate and ethyl alcohol as raw material, passes through ester-interchange method
Catalysts of Preparing Methyl Ethyl Carbonate, reaction equation are as follows：
C2H5OH + CH3OCOCl→CH3OCOOC2H5 +
HCl.......................................................(6)
The catalysts are alkali（Such as pyridine, organic amine）, purer methyl ethyl carbonate can be obtained, but shortcoming is to have used poison
Property higher methylchloroformate, simultaneous reactions generate corrosive hydrogen chloride gas, higher to equipment requirement.
2nd, dimethyl carbonate and diethyl carbonate ester-interchange method
Load metal oxide such as SnO of the Shen Zhen lands et al. using load on alumina2/Al2O3、MoO3/Al2O3、TiO2/
Al2O3Deng as catalyst, using dimethyl carbonate and diethyl carbonate as raw material, by Synthesis of Ethyl Methyl Carbonate by Transesterification,
The mass percent of the catalyst metal oxide of preparation is 2%-30%, remaining is aluminium oxide, and the amount of metal oxide accounts for raw material
The 0.1%-10% of total amount, 50-100 DEG C of reaction temperature carry out 2-48 h under normal pressure, and methyl ethyl carbonate yield is 43.6%.The route
The advantages of be that reaction process is simple, non-environmental-pollution, but shortcoming is that the reaction time is long, the catalyst activity reported at this stage compared with
It is low.
3rd, dimethyl carbonate and ethyl alcohol ester-interchange method
Using dimethyl carbonate and ethyl alcohol as raw material, by Synthesis of Ethyl Methyl Carbonate by Transesterification, raw material used in the route is all
It is non-toxic, reaction condition is mild, environmentally safe, therefore has very by the report of this route Catalysts of Preparing Methyl Ethyl Carbonate
More, the reaction equation involved by the route is as follows：
CH3OCOOCH3 + CH3CH2OH→CH3OCOOCH2CH3 + CH3OH...............................(7)
CN1900047 A are using aluminium oxide, activated carbon, molecular sieve as carrier, carrying alkali metal oxide, alkaline-earth metal oxide
One kind of object and rare-earth oxide, although separation problem is not present in catalyst, activity is not so good as homogeneous catalyst.
CN101289395 A are with NaOH, KOH, CH3ONa、CH3The strong alkaloids such as OK are as catalyst, and the catalyst is in reaction solution
Solubility is bad, and easily precipitation, easy fouling.CN103483200 A are using modified molecular sieve as catalyst, wherein modified member
Element is one or more of alkali metal, alkaline-earth metal, Fe, Zn, Ni, Cu, although catalyst preparation process is simple, reacts institute
The temperature needed is high.CN102850223 A, CN102863339 A and CN102850224 A are using the ionic liquid of imidazoles as catalysis
Agent, recoverable, long lifespan, but catalyst recycling is needed by specially treated.US5962720 is with SmL2、Li、CH3OLi
And CaH2Deng for catalyst, but reaction reaches balance needs three days.
At present, mainly using ester-interchange method as mainstream synthetic route in all of above methyl ethyl carbonate synthetic method, but ester is handed over
Changing the oxide spinel dimethyl ester of method need to be synthesized by ethylene carbonate or propene carbonate by methanol transesterification, and carbonic acid second
Enester needs to prepare by ethylene oxide and titanium dioxide reaction again, and propene carbonate needs propylene oxide and carbon dioxide reaction
It prepares, above-mentioned reaction scheme need to be segmented progress, each elementary reaction object conversion ratio and selectivity of product are low, industrial processes
Energy consumption is big, and operating cost increases.
The content of the invention
It is an object of the invention to provide a kind of ethylene carbonate and the method for alcohols one-step synthesis carbonic acid symmetrical ester, the party
Method is by ethylene carbonate and alcohols（ROH can be straight chain alcohol, isomery alcohol, aromatic alcohol, phenols, glycol such as ethylene glycol, diethylene glycol (DEG) and more
The various alcohols such as alcohol）The method of one-step synthesis carbonic acid symmetrical ester, by-product ethylene glycol are steamed as largeization raw material by simple
It evaporates i.e. separable.Entire reaction process cleaning, efficient, pollution-free, the by-product generation of no any low value.
The purpose of the present invention is what is be achieved through the following technical solutions：
A kind of method of ethylene carbonate and alcohols one-step synthesis carbonic acid symmetrical ester, the described method includes following preparation process：
Specific one-step synthesis method carbonic acid symmetrical ester reaction scheme equation is as follows：
+ 2ROH→HOCH2CH2OH+ROCOOR………………………………………(1)
Raw material is respectively ethylene carbonate and ROH, and wherein ROH can be straight chain alcohol, isomery alcohol, aromatic alcohol, phenols, glycol such as second two
The various alcohols such as alcohol, diethylene glycol (DEG) and polyol；
Glycol product and carbonic acid symmetrical ester molar ratio 1：1 generation, ethylene glycol is largeization that a kind of China largely relies on import
Product, can effectively a large amount of coproduction ethylene glycol using the path；
The catalyst of catalysis single step reaction of the present invention is with mesoporous and microcellular structure compound basic catalyst；Catalyst Formula
For X/S, wherein X is to include Li, Na, K, Rb, Cs；Be、Mg、Ca、Sr、Ba；La、Ce、Y、Zr；Cr、W、Mn；Fe、Ru；Co、Rh、
Ir；Pd、Pt；Cu、Ag；The oxide of one or more kinds of elements in Zn, B, Al, Ga；S is the carrier of different topology structure, is wrapped
Topological structure is included as EMT, MOR, MWW, FAU, MFI, FER, BEA molecular sieve and routine SiO2、Al2O3、ZrO2, MgO and ZnO
Wait one or more kinds of oxides in carriers；
With mesoporous and microcellular structure carrier loading type alkali metal oxide catalyst, the preparation of Jie's micro porous molecular sieve carrier
Method：
1）Dealuminzation：Certain mass M-S carriers are added separately to the molten stirring of acidity of certain temperature, volume, concentration, using pumping
Filter is washed, dry, obtains the M-S-DAl carriers after dealuminzation；
2）Desiliconization：M-S-DAl carriers made from certain mass process 1 are added to certain temperature, concentration, the alkalescence of certain volume
It stirs in solution, using suction filtration, washs, it is dry, obtain multi-stage porous M-S-DAl-DSi carriers；
3）M-S-DAl-DSi carriers made from process 2 are finally put into Muffle furnace roasting, obtaining carrier indicium is：M-meso-S；
Carbonic acid symmetrical ester is prepared through continuous fixed bed reaction or continuous.
A kind of ethylene carbonate and the method for alcohols one-step synthesis carbonic acid symmetrical ester, the S molecular sieve carriers,
Hydrogen type molecular sieve first passes around ion exchange, and Bronsted acid is poisoned by metal ion, it is made not have Bronsted acid；
The ion-exchanger for poisoning molecular sieve is hydrochloride, sulfate or the nitrate of Li, Na, K, Rb, Cs, Ca, Fe, Mg, Cu；Other
Molecular sieve and support preparation method are similar, are designated generally as M-S, and wherein M includes Li, Na, K, Rb, Cs, Ca, Fe, Mg, Cu.
A kind of ethylene carbonate and the method for alcohols one-step synthesis carbonic acid symmetrical ester give an account of micro porous molecular sieve load
The preparation method of body, the molecular sieve of different topology structure include one kind or more of EMT, MOR, MWW, FAU, MFI, FER, BEA
Kind；The acid solution includes H4EDTA、HCl、HNO3One or more, preferably H4EDTA；The addition of acid solution is minimum
All molecular sieves are flooded, are 10-20 times of molecular sieve volume, preferably 15 times；The alkaline solution include NaOH,
Na2CO3One or more, preferably NaOH；The alkaline solution concentration is 0.05mol/L-2.0mol/L；Alkaline solution adds
All molecular sieves will at least be flooded by entering amount, be 5-15 times of molecular sieve volume, preferably 10 times.
A kind of ethylene carbonate and the method for alcohols one-step synthesis carbonic acid symmetrical ester give an account of micro porous molecular sieve load
The preparation of body, the M-meso-S carrier mesoporous pore sizes obtained are distributed as 4-34nm, specific aperture and alkaline solution concentration used
It is related.
A kind of ethylene carbonate and the method for alcohols one-step synthesis carbonic acid symmetrical ester, it is described that there is mesoporous and micropore
The loading type alkali metal oxide catalyst of structure carrier, using coprecipitation method or infusion process：
1）Coprecipitated alkaline solution includes but not limited to the hydroxide of alkali metal and ammonium, such as lithium hydroxide, sodium hydroxide, hydrogen-oxygen
Change potassium and ammonium hydroxide；Carbonate, bicarbonate, formates and the acetate of alkali metal, such as lithium carbonate, sodium carbonate, potassium carbonate
Solution or above-mentioned alkaline solution two or more mixed liquors；Liquid medium used in alkaline substance solution is preferably
Water, but it is also not necessarily limited to water；
2）The addition of alkaline solution will at least flood all carriers, can be 10-20 times or more of carrier bulk, preferably 15
Times, solution PH value is controlled when coprecipitated as 10-14, preferably PH is 11；Coprecipitation method bath temperature can be -99 DEG C of room temperature, preferably 70
℃；Aging temperature can be -80 DEG C of room temperature, ageing time can be 1 it is small when -20 days, preferably 60 DEG C, ageing time 5 days；Catalyst
Washing medium is preferably water, but is also not necessarily limited to water, liquid medium can be 2-10 times of catalyst volume and more than, preferably 2-5 times,
Washing times are depending on efflux pH is washed；Catalyst drying temperature is -150 DEG C of room temperature, -10 days when the time can be 1 small, preferably
It is 120 DEG C, 3-5 days dry；Calcination temperature is 150-800 DEG C, when the time is 1-50 small, preferably 500-700 DEG C, and when the time 30 is small；
The content of metal X is the 0.1-50% of vehicle weight in the loaded catalyst general formula of composite pore structural；
3）The active constituent presoma of the loaded catalyst of compound pore passage structure is preferably Al (NO3)3、KNO3、CsNO3、Mg
(NO3)2、Ca(NO3)2、Ba(NO3)2、Sr(NO3)2、La(NO3)3、Fe(NO3)3、Mn(NO3)3、AlCl3、KCl、CsCl、MgCl2、
CaCl2、BaCl2、SrCl2、LaCl3、FeCl3、MnCl3、Al2(SO4)3、K2SO4、Cs2SO4、MgSO4、CaSO4、La2(SO4)3、
Fe2(SO4)3、Mn2(SO4)3One or more of mixing.
4）Dipping method can use co-impregnation, with the method for step impregnation；Drying temperature can be room temperature~150 DEG C, when
Between for 1 it is small when~20 days；Calcination temperature is 550~650 DEG C, when the time is 1~50 small.The loaded catalyst of composite pore structural
The content of metal X is the 0.1-50% of vehicle weight in general formula；
5）In a preferred approach, the active constituent presoma of the loaded catalyst of compound pore passage structure is preferably Al (NO3)3、
KNO3、CsNO3、Mg(NO3)2、Ca(NO3)2、Ba(NO3)2、Sr(NO3)2、La(NO3)3、Fe(NO3)3、Mn(NO3)3And AlCl3、
KCl、CsCl、MgCl2、CaCl2、BaCl2、SrCl2、LaCl3、FeCl3、MnCl3Middle one or more of mixing.
A kind of ethylene carbonate and the method for alcohols one-step synthesis carbonic acid symmetrical ester, the continuous fixed bed reaction or continuous
Concrete scheme is：Under normal pressure to 10MPa reaction pressures, liquid charging stock ethylene carbonate and various alcohols are beaten with pump（ROH can be
Straight chain alcohol, isomery alcohol, aromatic alcohol, phenols, the glycol such as various alcohols such as ethylene glycol, diethylene glycol (DEG) and polyol）1:3 chargings, above-mentioned
Reaction carbonate synthesis symmetrical ester, air speed are 0.1-100 h to catalyst existence condition in next step-1, 50-250 DEG C of reaction temperature
Under the conditions of, catalyst is compound basic catalyst, and catalyst amount is the 0.1-3wt% of material quality, and product carbonic acid symmetrical ester is received
Rate is not less than 60%.
A kind of ethylene carbonate and the method for alcohols one-step synthesis carbonic acid symmetrical ester, the continuous fixed bed reaction or continuous
During preparing carbonic acid symmetrical ester, optimum condition is ethylene carbonate：Alcohols（ROH is straight chain alcohol, isomery alcohol, aromatic alcohol, phenol
Class, the glycol such as various alcohols such as ethylene glycol, diethylene glycol (DEG) and polyol）Molar ratio 1:3, air speed 0.5-5 h-1, reaction temperature 78-130
℃。
A kind of ethylene carbonate and the method for alcohols one-step synthesis carbonic acid symmetrical ester, the still reaction pressure
0.1-10MPa, (ROH, R are straight chain alcohol to ethylene carbonate, isomery alcohol, aromatic alcohol, phenols, glycol such as second two with various alcohols
Alcohol, diethylene glycol (DEG) and polyol alcohols）Molar ratio 0.1:1 -10:1, under catalyst existence condition reaction prepare carbonic acid symmetrical ester, instead
Closed 25-150 DEG C of reaction 0.5-10 h in kettle are answered, catalyst is basic catalyst, and catalyst amount is the 0.1- of material quality
10 wt %。
Advantages of the present invention is with effect：
1. the present invention is by ethylene carbonate and alcohols（ROH can be straight chain alcohol, isomery alcohol, aromatic alcohol, phenols, glycol such as ethylene glycol,
The various alcohols such as diethylene glycol (DEG) and polyol）The method of one-step synthesis carbonic acid symmetrical ester, a kind of efficient alkaline with composite pore structural
Catalyst；Synthetic route is short, and a step directly obtains target product.Only contain carbonic acid symmetrical ester and second in crude product obtained by the reaction
Glycol, wherein, carbonic acid symmetrical ester yield can reach 94%.By-product ethylene glycol is steamed as largeization raw material by simple
It evaporates i.e. separable.Entire reaction process cleaning, efficient, pollution-free, the by-product generation of no any low value.
Description of the drawings
Fig. 1 is with 15%CaO-5% Cr2O3-3%La2O3/ Zn-meso-Y turns reactant for catalyst differential responses temperature
The influence of rate and dimethyl carbonate yield.
Specific embodiment
With reference to embodiment, the present invention is described in detail.
The present invention is by ethylene carbonate and various alcohols（ROH can be for straight chain alcohol, isomery alcohol, aromatic alcohol, phenols, glycol such as
The various alcohols such as ethylene glycol, diethylene glycol (DEG) and polyol）The response path and the response path of one-step synthesis carbonic acid symmetrical ester are used
Catalyst, the response path is as follows：
Wherein ROH can be straight chain alcohol, isomery alcohol, aromatic alcohol, phenols, the glycol such as various alcohols such as ethylene glycol, diethylene glycol (DEG) and polyol.
The path is using multi-functional compound basic matterial as catalyst, by ethylene carbonate and various alcohols（ROH can be straight chain
Alcohol, isomery alcohol, aromatic alcohol, phenols, the glycol such as various alcohols such as ethylene glycol, diethylene glycol (DEG) and polyol）For one step Gao Xuan of reaction raw materials
Selecting property carbonate synthesis symmetrical ester, basic catalyst are completely insoluble in reaction raw materials and product, and any pollution is not present in reaction process
Object, the glycol product incidentally generated are a kind of bulk chemicals, have a vast market application prospect.Therefore in reaction process
It is entire response path green, energy-saving and environmental protection, efficient it may be said that generated almost without any by-product.
The present invention protects the multi-functional compound basic catalyst of one-step synthesis methyl ethyl carbonate simultaneously.
Such catalyst is specially the loading type alkali metal oxide catalyst with mesoporous and microcellular structure carrier.It is described
Be X/S with the mesoporous and loading type alkali metal oxide catalyst of microcellular structure carrier its general formula, wherein X be comprising Li, Na,
K、Rb、Cs；Be、Mg、Ca、Sr、Ba；La、Ce、Y、Zr；Cr、W、Mn；Fe、Ru；Co、Rh、Ir；Pd、Pt；Cu、Ag；Zn、B、Al、
The oxide of one or more kinds of elements in Ga；S be different topology structure carrier, including topological structure for EMT, MOR, MWW,
FAU, MFI, FER, BEA molecular sieve and routine SiO2、Al2O3、ZrO2, one or more kinds of oxygen in the carriers such as MgO and ZnO
Compound.Wherein molecular sieve first passes around ion exchange, and Bronsted acid is poisoned by metal ion, it is made not have Bronsted
It is acid.The EMT molecular sieve carriers poisoned with alkali metal ion（M-EMT, M can be Li, Na, K, Rb, Cs, Ca, Fe, Mg, Cu）For
Example, preparation method are as follows：The H-EMT molecular sieves that 20g is prepared by hydrothermal synthesis method, be placed in 90 DEG C of 90 mL go from
In sub- water, meanwhile, add in the hydrochloride, sulfate or nitric acid of Li, Na, K, Rb, Cs, Ca, Fe, Mg, Cu of 2 M thereto respectively
Salt, the ion exchange when 90 DEG C small to EMT progress 2.After exchange, obtained molecular sieve precursor is carried out with deionized water
Washing, until no longer containing ion in eluate.It will wash to filter obtained filter cake and be placed in 120 DEG C of baking ovens and be dried, done
Presoma after dry is put into Muffle furnace and carries out 600 DEG C of 6 h of roasting, and Li-EMT, Na-EMT, K-EMT, Rb- are can obtain after roasting
EMT, Ca-EMT, Fe-EMT, Mg-EMT, Cu-EMT and Cs-EMT.Other molecular sieves and support preparation method are similar, unified to mark
For M-S, wherein M is including Li, Na, K, Rb, Cs, Ca, Fe, Mg, Cu etc..
1. the preparation method of Jie's micro porous molecular sieve carrier：
The present invention is handled by carrying out orderly soda acid to different carriers, and final high temperature roasting is made compound with mesoporous and micropore
The molecular sieve carrier of pore structure.The purpose of acid treatment is the Al removed in framework of molecular sieve, so as to fulfill pore-creating, alkali process it is main
Effect makes molecular sieve form meso-hole structure in the Si in framework of molecular sieve is removed, and preparation process comprises the following steps：
1）Dealuminzation：By certain mass M-S carriers be added separately to certain volume, concentration be 0.11 mol/L acid solution in,
Then in oil bath 100 DEG C be stirred at reflux 6 h, using suction filtration, washing, 120 DEG C of dry 8h obtain the M-S-DAl after dealuminzation and carry
Body.
2）Desiliconization：M-S-DAl carriers made from certain mass process 1 are added to the alkalescence of a certain concentration, certain volume
In solution, then 65 DEG C of 30 min of water bath processing, using suction filtration, are washed, 120 DEG C of dry 8h obtain multi-stage porous M-S-DAl-
DSi carriers.
3）Finally M-S-DAl-DSi carriers made from process 2 are put into Muffle furnace, 550 DEG C of guarantors are warming up to 1 DEG C/min
6h is held, obtaining carrier indicium is：M-meso-S.
The molecular sieve of heretofore described different topology structure includes one kind of EMT, MOR, MWW, FAU, MFI, FER, BEA
It is or a variety of；The acid solution includes H4EDTA、HCl、HNO3Deng one or more, preferably H4EDTA；The addition of acid solution
Amount will at least flood all molecular sieves, can be 10-20 times of molecular sieve volume, preferably 15 times；The alkaline solution includes
NaOH、Na2CO3Deng one or more, preferably NaOH；The alkaline solution concentration is 0.05mol/L-2.0mol/L；Alkalescence is molten
The addition of liquid will at least flood all molecular sieves, can be 5-15 times of molecular sieve volume, preferably 10 times.
The M-meso-S carrier mesoporous pore sizes obtained in the present invention are distributed as 4-34nm, specific aperture and alkaline solution used
Concentration is related.
2. the preparation method of composite catalyst：
The preparation of the loaded catalyst X/M-meso-S with composite pore structural uses coprecipitation method or infusion process in the present invention,
Comprise the following steps：
2.1 wherein coprecipitation methods include：
1）The carrier with composite pore structural being prepared be put into Muffle furnace 500 DEG C of roastings 4 it is small when to remove M-meso-
The water adsorbed in S；
2）X metal nitrates, chlorate and the sulfate of M-meso-S mass 0.1-50% is taken, is dissolved in the deionization of certain volume
In water, the mixed solution of certain density X metal nitrates, chlorate and sulfate is made into, it is molten to prepare certain density alkalescence
The M-meso-S carriers for the certain mass being prepared with the deionized water of 10-20 times of volume are mixed, stirred evenly by liquid, and
Afterwards under certain bath temperature and intense agitation, X metal nitrates, chlorate, sulfuric acid is added dropwise simultaneously into mixed liquor
The mixed solution and alkaline solution of salt, control solution pH value during being added dropwise.
3）After the mixed solution of X metal nitrates, chlorate and sulfate is added dropwise, will be coprecipitated after suspension continue
Stir certain time, then aging at room temperature.
4）The solution that aging is finished filters, and the precipitation then washed with the deionized water of certain volume is until washing
Liquid PH is 7.
5）Washing dry certain time at 110-120 DEG C to the catalyst precursor after neutrality.
6）Dried catalyst precursor in Muffle furnace at 550-650 DEG C is roasted to 3-5 h, obtains having compound
The loaded catalyst X/M-meso-S of pore structure.
Coprecipitated alkaline solution of the present invention includes but not limited to the hydroxide of alkali metal and ammonium, such as hydroxide
Lithium, sodium hydroxide, potassium hydroxide and ammonium hydroxide etc.；Carbonate, bicarbonate, formates and the acetate of alkali metal, such as carbon
Two or more mixed liquors of the solution of sour lithium, sodium carbonate, potassium carbonate etc. or above-mentioned alkaline solution.Alkaline substance solution
Liquid medium used is preferably water, but is also not necessarily limited to water.The addition of alkaline solution will at least flood all carriers, can be
10-20 times or more of carrier bulk, preferably 15 times control solution PH value as 10-14 when coprecipitated, preferably PH is 11.
Above-mentioned coprecipitation method bath temperature can be -99 DEG C of room temperature, preferably 70 DEG C；Aging temperature can be -80 DEG C of room temperature, aging
- 20 days, preferably 60 DEG C when time can be 1 small, ageing time 5 days；Catalyst detergent medium is preferably water, but is also not necessarily limited to water,
Liquid medium can be 2-10 times of catalyst volume and more than, preferably 2-5 times, washing times are depending on efflux pH is washed.
Catalyst drying temperature can be -150 DEG C of room temperature, and -10 days, preferably 120 DEG C when the time can be 1 small are 3-5 days dry；
Calcination temperature can be 150-800 DEG C, when the time can be 1-50 small, preferably 500-700 DEG C, and when the time 30 is small.
The content of metal X is the 0.1-50% of vehicle weight in the loaded catalyst general formula of composite pore structural in the present invention.
The active constituent presoma of the loaded catalyst of compound pore passage structure is preferably Al (NO in the present invention3)3、KNO3、
CsNO3、Mg(NO3)2、Ca(NO3)2、Ba(NO3)2、Sr(NO3)2、La(NO3)3、Fe(NO3)3、Mn(NO3)3、AlCl3、KCl、
CsCl、MgCl2、CaCl2、BaCl2、SrCl2、LaCl3、FeCl3、MnCl3、Al2(SO4)3、K2SO4、Cs2SO4、MgSO4、CaSO4、
La2(SO4)3、Fe2(SO4)3、Mn2(SO4)3One or more of mixing.
2.2 infusion processes include：
1）First the M-meso-S carriers with composite pore structural being prepared be put into Muffle furnace 500 DEG C of roastings 4 it is small when,
Remove the water adsorbed in M-meso-S.
2）Metal X mass is taken as the X metal nitrates of M-meso-S mass 0.1-50% and the mixed solution of chlorate,
It is impregnated into several times in ultrasound environments in the M-meso-S carriers duct after roasting；
3）Catalyst precursor after dipping is when 110 DEG C of dryings 10 are small in an oven.
4）Dried catalyst precursor is roasted into 3h for 550 DEG C in Muffle furnace, obtains that there is urging for composite pore structural
Agent X/M-meso-S.
Dipping method described in the present invention can use co-impregnation, the method that can also use step impregnation；Drying temperature can
For room temperature~150 DEG C, when the time can be 1 small~20 days；Calcination temperature can be 550~650 DEG C, when the time can be 1~50 small.
The content of metal X is the 0.1-50% of vehicle weight in the loaded catalyst general formula of composite pore structural.
In preferred embodiments, the active constituent presoma of the loaded catalyst of compound pore passage structure is preferably Al
(NO3)3、KNO3、CsNO3、Mg(NO3)2、Ca(NO3)2、Ba(NO3)2、Sr(NO3)2、La(NO3)3、Fe(NO3)3、Mn(NO3)3With
AlCl3、KCl、CsCl、MgCl2、CaCl2、BaCl2、SrCl2、LaCl3、FeCl3、MnCl3Middle one or more of mixing.
The present invention is with ethylene carbonate and various alcohols（ROH, R can be straight chain alcohol, isomery alcohol, aromatic alcohol, phenols, glycol
Such as ethylene glycol, diethylene glycol (DEG) and the various alcohols of polyol）For raw material, carbon is synthesized in next step in the catalyst existence condition of above-mentioned preparation
Sour symmetrical ester, reactive mode are two kinds of continuous fixed bed reaction or continuous and slurry bed system still reaction.
Continuous fixed bed reaction or continuous specific embodiment of the present invention is：Under normal pressure to 10MPa reaction pressures, liquid is beaten with pump
Oxide spinel vinyl acetate and various alcohols（ROH can be straight chain alcohol, isomery alcohol, aromatic alcohol, phenols, glycol such as ethylene glycol, diethylene glycol (DEG)
And the various alcohols such as polyol）1:3 chargings react carbonate synthesis symmetrical ester, air speed in next step in above-mentioned catalyst existence condition
For 0.1-100 h-1, under conditions of 50-250 DEG C of reaction temperature, catalyst is the various multi-functional compound alkali protected in the present invention
Property catalyst, catalyst amount be material quality 0.1-3wt%, product carbonic acid symmetrical ester yield be not less than 60%.
During carbonic acid symmetrical ester is prepared with fixed bed reaction, optimum condition is ethylene carbonate：Various alcohols
（ROH can be straight chain alcohol, isomery alcohol, aromatic alcohol, phenols, the glycol such as various alcohols such as ethylene glycol, diethylene glycol (DEG) and polyol）Molar ratio
1:3, air speed 0.5-5 h-1, 78-130 DEG C of reaction temperature.
Still reaction specific embodiment of the present invention is：Reaction pressure 0.1-10MPa, ethylene carbonate and various alcohols (
ROH, R can be straight chain alcohol, isomery alcohol, aromatic alcohol, phenols, the glycol such as various alcohols such as ethylene glycol, diethylene glycol (DEG) and polyol）Molar ratio
0.1:1-10:1, under catalyst existence condition reaction prepare carbonic acid symmetrical ester, closed 25-150 DEG C of reaction 0.5- in reaction kettle
10 h, catalyst are the various basic catalysts protected in the present invention, and catalyst amount is the 0.1-10 wt % of material quality.
During carbonic acid symmetrical ester is prepared with still reaction, preferred ethylene carbonate：Various alcohols（ROH can be straight
Chain alcohol, isomery alcohol, aromatic alcohol, phenols, the glycol such as various alcohols such as ethylene glycol, diethylene glycol (DEG) and polyol）Molar ratio 1:3, reaction temperature
90-140 DEG C of degree.
The catalyst that the present invention is protected is multi-functional compound basic catalyst, it is advantageous that mesoporous significantly improve mass transfer
Effect, and micropore significantly improves carrier specific surface area, improves the dispersion degree in activated centre.In continuous fixed bed reaction or continuous, catalysis
Non-inactivation is reacted in agent for a long time, even if feed space velocity is 100h-1When, product carbonic acid symmetrical ester remains to keep higher yield, urges
Agent is prepared simply, and environmentally safe, energy conservation and environmental protection.In still reaction, post catalyst reaction is by simple processing
Can reuse again, and catalyst be reused many times after remain to keep higher activity.
Embodiment
Embodiment 1
In 50L paste state bed reactor kettles, reaction pressure 2MPa, reaction raw materials ethylene carbonate:Methanol=1:3, it puts into respectively
Each 1.2 kg of basic catalyst that above-mentioned preparation method obtains, reaction solution total volume are 40 L.Mechanic whirl-nett reaction, reaction temperature
100 DEG C, sampling progress chromatography calculating after 10h is reacted, feed stock conversion, product yield are as shown in table 1.
Influence of the 1 variety classes catalyst of table to feed stock conversion, product yield
The reaction is catalyzed with basic catalyst, reaction product is single dimethyl carbonate and ethylene glycol.Except having carbonic acid in upper table
Dimethyl ester（DMC）Generation is outer, has a large amount of ethylene glycol to generate, since ethylene glycol derives from ethylene carbonate（EC）If from carbonic acid
Vinyl acetate calculates selectivity of product, and the selectivity of ethylene glycol is approximately 100% under all reaction conditions.Other specific examples
Using same data expression method.As can be seen from Table 1, if only using molecular sieve carrier as catalyst, reaction result is very poor,
Reaction hardly occurs.When alkaline metal oxide is carried on molecular sieve carrier, catalyst effect has very big promotion, special
It is not when containing La elements in catalyst, the catalytic effect of reaction is optimal.With 15%CaO-5% Cr2O3-3%La2O3/Zn-meso-
Y is catalyst, and EC conversion ratios are up to 83%, and product DMC yields are up to 82%.
Embodiment 2
In 50L paste state bed reactor kettles, reaction pressure 2MPa, reaction raw materials ethylene carbonate：Various alcohols=1:3, input
15%CaO-5% Cr2O3-3%La2O3/ Zn-meso-Y catalyst 1.2kg, reaction solution total volume are 40 L.Mechanic whirl-nett reaction,
100 DEG C of reaction temperature reacts sampling progress chromatography calculating after 10h, feed stock conversion, product carbonic acid symmetrical ester yield such as table
Shown in 2.
Influence of the different alcohols of table 2 to feed stock conversion, product yield
As can be seen from Table 2, using different alcohols as reaction raw materials carbonate synthesis symmetrical ester, reaction result difference is larger, with R
Group becomes complicated, and the conversion ratio of ROH is gradually reduced, and the yield of carbonic acid symmetrical ester is gradually lowered.The reason is that as R group becomes
Complexity, the steric hindrance of ROH become larger, and R group is difficult to close to ethylene carbonate and is substituted.
Embodiment 3
In fixed bed reactors, influence of the differential responses pressure to feed stock conversion and product yield is probed into.In fixed bed
It is packed into 15%CaO-5% Cr2O3-3%La2O350 g of/Zn-meso-Y catalyst, using constant flow pump by ethylene carbonate and various alcohol
Class is with molar ratio 1:3 ratio is pumped into reactor, and air speed is 5 h-1, it is as shown in the table for reaction pressure, 100 DEG C of reaction temperature,
And stablize 500 h, sampling progress chromatography calculating after stablizing, feed stock conversion, product yield are as shown in table 3.
Influence of the 3 differential responses pressure of table to feed stock conversion, product yield
As can be seen from Table 3, with 15%CaO-5% Cr2O3-3%La2O3When/Zn-meso-Y is catalyst, with reaction pressure
Rise reaction-ure conversion-age and DMC yields all increase.When reaction pressure reach 5MPa and more than when, reaction-ure conversion-age and
DMC yields nearly all reach maximum, it is seen that 5MPa is the optimal reaction pressure of the reaction.
Embodiment 4
In fixed bed reactors, influence of the differential responses temperature to feed stock conversion and product yield is probed into.In fixed bed
It is packed into 15%CaO-5% Cr2O3-3%La2O350 g of/Zn-meso-Y catalyst, using constant flow pump by ethylene carbonate and various alcohol
Class is with molar ratio 1:3 ratio is pumped into reactor, and air speed is 5 h-1, reaction pressure 5Mpa, it is as shown in the table for reaction temperature, and
Stablize 500 h, sampling progress chromatography calculating after stablizing, feed stock conversion, product yield are as shown in table 4.
Influence of the 4 differential responses temperature of table to feed stock conversion, product yield
From table 4, it can be seen that increased with the rise reaction-ure conversion-age and DMC yields of reaction temperature, but when temperature is high
After 100 DEG C, continue to raise temperature, reaction-ure conversion-age and product yield are almost unchanged, therefore the proper temperature of the reaction
Control is near 100 DEG C.
Embodiment 5
In fixed bed reactors, influence of the differential responses object molar ratio to feed stock conversion and product yield is probed into.In fixation
15%CaO-5% Cr are packed into bed2O3-3%La2O350 g of/Zn-meso-Y catalyst, using constant flow pump by ethylene carbonate and first
Alcohol is pumped into reactor, and air speed is 5 h-1, ethylene carbonate and methanol specifically reacts molar ratio it is as shown in the table, reaction pressure
5MPa, 100 DEG C of reaction temperature, and stablize 500 h, sampling progress chromatography calculating, feed stock conversion, product yield after stablizing
As shown in table 5.
The different ethylene carbonates of table 5 compare the influence of feed stock conversion, product yield with Methanol Molar
As can be seen from Table 5, ethylene carbonate and Methanol Molar compare reaction result influence it is very big, when ethylene carbonate and methanol
During low mole prop0rtion, ethylene carbonate is largely consumed, DMC high incomes；When ethylene carbonate and methanol high molar ratio, carbonic acid second
Enester conversion ratio declines, and DMC yields also decline.But consider with reference to cost of material and product yield, optimal ethylene carbonate and first
Alcohol molar ratio should be 1:3.
Embodiment 6
In fixed bed reactors, influence of the differential responses air speed to feed stock conversion and product yield is probed into.In fixed bed
It is packed into 15%CaO-5% Cr2O3-3%La2O350 g of/Zn-meso-Y catalyst, using constant flow pump by ethylene carbonate and various alcohol
Class is with molar ratio 1:3 ratio is pumped into reactor, and it is as shown in the table for differential responses air speed, reaction pressure 5MPa, reaction temperature
100 DEG C, and stablize 500 h, sampling progress chromatography calculating after stablizing, feed stock conversion, product yield are as shown in table 6.
Influence of the 6 differential responses air speed of table to feed stock conversion, selectivity of product
As can be seen from Table 6, it is constant at the beginning with the increase reaction-ure conversion-age and dimethyl carbonate yield of air speed, work as air speed
More than 5h-1When, the two declines apparent.The reason is that since air speed is excessive, reaction raw materials have little time to react.Therefore air speed 5h-1For most
Good reaction velocity.
Embodiment 7
In fixed bed reactors, influence of the differential responses duration to feed stock conversion and selectivity of product is probed into, investigates catalysis
The stability of agent.15%CaO-5% Cr are packed into fixed bed2O3-3%La2O350 g of/Zn-meso-Y catalyst, utilizes constant current
Pump is by ethylene carbonate and various alcohols with molar ratio 1:3 ratio is pumped into reactor, and air speed is 5 h-1, reaction pressure
5MPa, 100 DEG C of reaction temperature, and stablize in table the reaction time respectively, and sampling progress chromatography calculating after stablizing, raw material conversion
Rate, product yield are as shown in table 7.
Influence of the reaction experience duration of table 7 to feed stock conversion, product yield
As can be seen from Table 7,5000 h feed stock conversions of reaction experience, product dimethyl carbonate yield are basically unchanged, catalyst
Substantially do not inactivate, catalyst has fabulous stability.
The above is only several embodiments of the application, any type of limitation is not done to the application, although this Shen
Please disclosed as above with preferred embodiment, however not to limit the application, any person skilled in the art is not taking off
In the range of technical scheme, make a little variation using the technology contents of the disclosure above or modification is equal to
Case study on implementation is imitated, is belonged in the range of technical solution.
Claims (8)
1. a kind of method of ethylene carbonate and alcohols one-step synthesis carbonic acid symmetrical ester, which is characterized in that the described method includes with
Lower preparation process：
Specific one-step synthesis method carbonic acid symmetrical ester reaction scheme equation is as follows：
+2ROH→HOCH2CH2OH+ROCOOR………………………………………(1)
Raw material is respectively ethylene carbonate and ROH, and wherein ROH can be straight chain alcohol, isomery alcohol, aromatic alcohol, phenols, glycol such as second two
The various alcohols such as alcohol, diethylene glycol (DEG) and polyol；
Glycol product and carbonic acid symmetrical ester molar ratio 1：1 generation, ethylene glycol is largeization that a kind of China largely relies on import
Product, can effectively a large amount of coproduction ethylene glycol using the path；
The catalyst of catalysis single step reaction of the present invention is with mesoporous and microcellular structure compound basic catalyst；Catalyst Formula
For X/S, wherein X is to include Li, Na, K, Rb, Cs；Be、Mg、Ca、Sr、Ba；La、Ce、Y、Zr；Cr、W、Mn；Fe、Ru；Co、Rh、
Ir；Pd、Pt；Cu、Ag；The oxide of one or more kinds of elements in Zn, B, Al, Ga；S is the carrier of different topology structure, is wrapped
Topological structure is included as EMT, MOR, MWW, FAU, MFI, FER, BEA molecular sieve and routine SiO2、Al2O3、ZrO2, MgO and ZnO
Wait one or more kinds of oxides in carriers；
With mesoporous and microcellular structure carrier loading type alkali metal oxide catalyst, the preparation of Jie's micro porous molecular sieve carrier
Method：
1）Dealuminzation：Certain mass M-S carriers are added separately to the molten stirring of acidity of certain temperature, volume, concentration, using pumping
Filter is washed, dry, obtains the M-S-DAl carriers after dealuminzation；
2）Desiliconization：M-S-DAl carriers made from certain mass process 1 are added to certain temperature, concentration, the alkalescence of certain volume
It stirs in solution, using suction filtration, washs, it is dry, obtain multi-stage porous M-S-DAl-DSi carriers；
3）M-S-DAl-DSi carriers made from process 2 are finally put into Muffle furnace roasting, obtaining carrier indicium is：M-meso-S；
Carbonic acid symmetrical ester is prepared through continuous fixed bed reaction or continuous.
2. the method for a kind of ethylene carbonate according to claim 1 and alcohols one-step synthesis carbonic acid symmetrical ester, feature
It is, the S molecular sieve carriers, hydrogen type molecular sieve first passes around ion exchange, and Bronsted acid is poisoned by metal ion,
It is made not have Bronsted acid；The ion-exchanger for poisoning molecular sieve is the salt of Li, Na, K, Rb, Cs, Ca, Fe, Mg, Cu
Hydrochlorate, sulfate or nitrate；Other molecular sieves and support preparation method are similar, are designated generally as M-S, wherein M include Li,
Na、K、Rb、Cs、Ca、Fe、Mg、Cu。
3. the method for a kind of ethylene carbonate according to claim 1 and alcohols one-step synthesis carbonic acid symmetrical ester, feature
Be, give an account of the preparation method of micro porous molecular sieve carrier, the molecular sieve of different topology structure include EMT, MOR, MWW,
The one or more of FAU, MFI, FER, BEA；The acid solution includes H4EDTA、HCl、HNO3One or more, preferably
H4EDTA；The addition of acid solution will at least flood all molecular sieves, be 10-20 times of molecular sieve volume, and preferably 15
Times；The alkaline solution includes NaOH, Na2CO3One or more, preferably NaOH；The alkaline solution concentration is 0.05mol/
L-2.0mol/L；The addition of alkaline solution will at least flood all molecular sieves, be 5-15 times of molecular sieve volume, preferably
10 times.
4. the method for a kind of ethylene carbonate according to claim 1 and alcohols one-step synthesis carbonic acid symmetrical ester, feature
It is, give an account of the preparation of micro porous molecular sieve carrier, the M-meso-S carrier mesoporous pore sizes obtained are distributed as 4-34nm, specifically
Aperture is related with alkaline solution concentration used.
5. the method for a kind of ethylene carbonate according to claim 1 and alcohols one-step synthesis carbonic acid symmetrical ester, feature
It is, it is described with mesoporous and microcellular structure carrier loading type alkali metal oxide catalyst, using coprecipitation method or dipping
Method：
1）Coprecipitated alkaline solution includes but not limited to the hydroxide of alkali metal and ammonium, such as lithium hydroxide, sodium hydroxide, hydrogen-oxygen
Change potassium and ammonium hydroxide；Carbonate, bicarbonate, formates and the acetate of alkali metal, such as lithium carbonate, sodium carbonate, potassium carbonate
Solution or above-mentioned alkaline solution two or more mixed liquors；Liquid medium used in alkaline substance solution is preferably
Water, but it is also not necessarily limited to water；
2）The addition of alkaline solution will at least flood all carriers, can be 10-20 times or more of carrier bulk, preferably 15
Times, solution PH value is controlled when coprecipitated as 10-14, preferably PH is 11；Coprecipitation method bath temperature can be -99 DEG C of room temperature, preferably 70
℃；Aging temperature can be -80 DEG C of room temperature, ageing time can be 1 it is small when -20 days, preferably 60 DEG C, ageing time 5 days；Catalyst
Washing medium is preferably water, but is also not necessarily limited to water, liquid medium can be 2-10 times of catalyst volume and more than, preferably 2-5 times,
Washing times are depending on efflux pH is washed；Catalyst drying temperature is -150 DEG C of room temperature, -10 days when the time can be 1 small, preferably
It is 120 DEG C, 3-5 days dry；Calcination temperature is 150-800 DEG C, when the time is 1-50 small, preferably 500-700 DEG C, and when the time 30 is small；
The content of metal X is the 0.1-50% of vehicle weight in the loaded catalyst general formula of composite pore structural；
3）The active constituent presoma of the loaded catalyst of compound pore passage structure is preferably Al (NO3)3、KNO3、CsNO3、Mg
(NO3)2、Ca(NO3)2、Ba(NO3)2、Sr(NO3)2、La(NO3)3、Fe(NO3)3、Mn(NO3)3、AlCl3、KCl、CsCl、MgCl2、
CaCl2、BaCl2、SrCl2、LaCl3、FeCl3、MnCl3、Al2(SO4)3、K2SO4、Cs2SO4、MgSO4、CaSO4、La2(SO4)3、
Fe2(SO4)3、Mn2(SO4)3One or more of mixing；
4）Dipping method can use co-impregnation, with the method for step impregnation；Drying temperature can be room temperature~150 DEG C, the time 1
Hour~20 days；Calcination temperature is 550~650 DEG C, when the time is 1~50 small；
The content of metal X is the 0.1-50% of vehicle weight in the loaded catalyst general formula of composite pore structural；
5）In a preferred approach, the active constituent presoma of the loaded catalyst of compound pore passage structure is preferably Al (NO3)3、
KNO3、CsNO3、Mg(NO3)2、Ca(NO3)2、Ba(NO3)2、Sr(NO3)2、La(NO3)3、Fe(NO3)3、Mn(NO3)3And AlCl3、
KCl、CsCl、MgCl2、CaCl2、BaCl2、SrCl2、LaCl3、FeCl3、MnCl3Middle one or more of mixing.
6. the method for a kind of ethylene carbonate according to claim 1 and alcohols one-step synthesis carbonic acid symmetrical ester, feature
It is, the continuous fixed bed reaction or continuous concrete scheme is：Under normal pressure to 10MPa reaction pressures, liquid charging stock carbonic acid is beaten with pump
Vinyl acetate and various alcohols（ROH can be straight chain alcohol, isomery alcohol, aromatic alcohol, phenols, glycol such as ethylene glycol, diethylene glycol (DEG) and polyol etc.
Various alcohols）1:3 chargings react carbonate synthesis symmetrical ester, air speed 0.1-100 in next step in above-mentioned catalyst existence condition
h-1, under conditions of 50-250 DEG C of reaction temperature, catalyst is compound basic catalyst, and catalyst amount is the 0.1- of material quality
3wt%, product carbonic acid symmetrical ester yield are not less than 60%.
7. the method for a kind of ethylene carbonate according to claim 6 and alcohols one-step synthesis carbonic acid symmetrical ester, feature
It is, during the continuous fixed bed reaction or continuous prepares carbonic acid symmetrical ester, optimum condition is ethylene carbonate：Alcohols（ROH is
Straight chain alcohol, isomery alcohol, aromatic alcohol, phenols, the glycol such as various alcohols such as ethylene glycol, diethylene glycol (DEG) and polyol）Molar ratio 1:3, air speed
0.5-5 h-1, 78-130 DEG C of reaction temperature.
8. the method for a kind of ethylene carbonate according to claim 7 and alcohols one-step synthesis carbonic acid symmetrical ester, feature
It is, the still reaction pressure 0.1-10MPa, (ROH, R are straight chain alcohol to ethylene carbonate, isomery alcohol, virtue with various alcohols
Aromatic, phenols, glycol such as ethylene glycol, diethylene glycol (DEG) and polyol alcohols）Molar ratio 0.1:1 -10:1, under catalyst existence condition
Reaction prepares carbonic acid symmetrical ester, closed 25-150 DEG C of reaction 0.5-10 h in reaction kettle, and catalyst is basic catalyst, catalyst
Dosage is the 0.1-10 wt % of material quality.
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