CN108129313A - The method of carbonate synthesis symmetrical ester co-production 1,2- propylene glycol - Google Patents
The method of carbonate synthesis symmetrical ester co-production 1,2- propylene glycol Download PDFInfo
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- CN108129313A CN108129313A CN201711380500.2A CN201711380500A CN108129313A CN 108129313 A CN108129313 A CN 108129313A CN 201711380500 A CN201711380500 A CN 201711380500A CN 108129313 A CN108129313 A CN 108129313A
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- Prior art keywords
- catalyst
- reaction
- carbonate
- ester
- glycol
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- 238000000034 method Methods 0.000 title claims abstract description 59
- 150000002148 esters Chemical class 0.000 title claims abstract description 58
- 238000003786 synthesis reaction Methods 0.000 title claims abstract description 38
- 230000015572 biosynthetic process Effects 0.000 title claims abstract description 37
- BVKZGUZCCUSVTD-UHFFFAOYSA-L Carbonate Chemical compound [O-]C([O-])=O BVKZGUZCCUSVTD-UHFFFAOYSA-L 0.000 title claims abstract description 31
- DNIAPMSPPWPWGF-UHFFFAOYSA-N Propylene glycol Chemical compound CC(O)CO DNIAPMSPPWPWGF-UHFFFAOYSA-N 0.000 title claims abstract description 21
- 238000004519 manufacturing process Methods 0.000 title claims abstract description 21
- 229960004063 propylene glycol Drugs 0.000 title claims abstract description 10
- MTHSVFCYNBDYFN-UHFFFAOYSA-N diethylene glycol Chemical compound OCCOCCO MTHSVFCYNBDYFN-UHFFFAOYSA-N 0.000 claims abstract description 213
- 238000006243 chemical reaction Methods 0.000 claims abstract description 126
- 239000003054 catalyst Substances 0.000 claims abstract description 104
- LYCAIKOWRPUZTN-UHFFFAOYSA-N Ethylene glycol Chemical compound OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 claims abstract description 82
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims abstract description 58
- 150000001298 alcohols Chemical class 0.000 claims abstract description 38
- SIXOAUAWLZKQKX-UHFFFAOYSA-N carbonic acid;prop-1-ene Chemical compound CC=C.OC(O)=O SIXOAUAWLZKQKX-UHFFFAOYSA-N 0.000 claims abstract description 33
- BVKZGUZCCUSVTD-UHFFFAOYSA-N carbonic acid Chemical compound OC(O)=O BVKZGUZCCUSVTD-UHFFFAOYSA-N 0.000 claims abstract description 28
- 239000011148 porous material Substances 0.000 claims abstract description 23
- WGCNASOHLSPBMP-UHFFFAOYSA-N hydroxyacetaldehyde Natural products OCC=O WGCNASOHLSPBMP-UHFFFAOYSA-N 0.000 claims abstract description 20
- WVDDGKGOMKODPV-UHFFFAOYSA-N Benzyl alcohol Chemical compound OCC1=CC=CC=C1 WVDDGKGOMKODPV-UHFFFAOYSA-N 0.000 claims abstract description 18
- 150000002989 phenols Chemical class 0.000 claims abstract description 18
- 229920005862 polyol Polymers 0.000 claims abstract description 18
- 150000003077 polyols Chemical class 0.000 claims abstract description 18
- 239000002994 raw material Substances 0.000 claims abstract description 18
- 239000002131 composite material Substances 0.000 claims abstract description 12
- -1 propylene 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
- 239000000969 carrier Substances 0.000 claims description 27
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 claims description 26
- 239000000243 solution Substances 0.000 claims description 26
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 24
- 239000012670 alkaline solution Substances 0.000 claims description 21
- 229910001868 water Inorganic materials 0.000 claims description 21
- 150000001875 compounds Chemical class 0.000 claims description 19
- 238000002360 preparation method Methods 0.000 claims description 19
- 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
- KWYUFKZDYYNOTN-UHFFFAOYSA-M Potassium hydroxide Chemical compound [OH-].[K+] KWYUFKZDYYNOTN-UHFFFAOYSA-M 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
- FGIUAXJPYTZDNR-UHFFFAOYSA-N potassium nitrate Chemical compound [K+].[O-][N+]([O-])=O FGIUAXJPYTZDNR-UHFFFAOYSA-N 0.000 claims description 12
- 229910002651 NO3 Inorganic materials 0.000 claims description 11
- NHNBFGGVMKEFGY-UHFFFAOYSA-N Nitrate Chemical compound [O-][N+]([O-])=O NHNBFGGVMKEFGY-UHFFFAOYSA-N 0.000 claims description 11
- 239000002253 acid Substances 0.000 claims description 11
- 230000032683 aging Effects 0.000 claims description 11
- 229910052744 lithium Inorganic materials 0.000 claims description 11
- 229910052792 caesium Inorganic materials 0.000 claims description 10
- 229910052791 calcium Inorganic materials 0.000 claims description 10
- 229910052749 magnesium Inorganic materials 0.000 claims description 10
- 229910052700 potassium 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
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical group Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 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
- 230000008569 process Effects 0.000 claims description 8
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims description 7
- 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
- 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
- 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
- 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
- 238000001035 drying Methods 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
- YIXJRHPUWRPCBB-UHFFFAOYSA-N magnesium nitrate Inorganic materials [Mg+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O YIXJRHPUWRPCBB-UHFFFAOYSA-N 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
- BWHMMNNQKKPAPP-UHFFFAOYSA-L potassium carbonate Chemical compound [K+].[K+].[O-]C([O-])=O BWHMMNNQKKPAPP-UHFFFAOYSA-L 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
- 229910052799 carbon Inorganic materials 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
- 229910017604 nitric acid 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
- 239000007848 Bronsted acid Substances 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
- 229910000027 potassium carbonate 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
- 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
- 238000001308 synthesis method Methods 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
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical compound [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 claims description 2
- 239000005864 Sulphur Substances 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
- 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
- QQONPFPTGQHPMA-UHFFFAOYSA-N propylene Natural products CC=C QQONPFPTGQHPMA-UHFFFAOYSA-N 0.000 claims description 2
- 238000005086 pumping Methods 0.000 claims description 2
- 239000006227 byproduct Substances 0.000 abstract description 8
- 239000012043 crude product Substances 0.000 abstract description 2
- 230000002779 inactivation Effects 0.000 abstract description 2
- 238000001577 simple distillation Methods 0.000 abstract description 2
- 238000004140 cleaning Methods 0.000 abstract 1
- 239000002699 waste material Substances 0.000 abstract 1
- 235000019441 ethanol Nutrition 0.000 description 64
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 34
- 239000000047 product Substances 0.000 description 26
- 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 13
- 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
- 239000003795 chemical substances by application Substances 0.000 description 8
- 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
- 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
- 238000005406 washing Methods 0.000 description 5
- YGYAWVDWMABLBF-UHFFFAOYSA-N Phosgene Chemical compound ClC(Cl)=O YGYAWVDWMABLBF-UHFFFAOYSA-N 0.000 description 4
- QAOWNCQODCNURD-UHFFFAOYSA-L Sulfate Chemical compound [O-]S([O-])(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-L 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
- KTUFCUMIWABKDW-UHFFFAOYSA-N oxo(oxolanthaniooxy)lanthanum Chemical compound O=[La]O[La]=O KTUFCUMIWABKDW-UHFFFAOYSA-N 0.000 description 3
- 238000012545 processing Methods 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
- 238000013019 agitation Methods 0.000 description 2
- 229910052804 chromium Inorganic materials 0.000 description 2
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- 238000005260 corrosion Methods 0.000 description 2
- 238000005516 engineering process Methods 0.000 description 2
- 230000007613 environmental effect Effects 0.000 description 2
- 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 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
- 238000001556 precipitation Methods 0.000 description 2
- 230000035484 reaction time Effects 0.000 description 2
- 150000003839 salts Chemical class 0.000 description 2
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- 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
- KMTRUDSVKNLOMY-UHFFFAOYSA-N Ethylene carbonate Chemical compound O=C1OCCO1 KMTRUDSVKNLOMY-UHFFFAOYSA-N 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
- 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
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 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
- 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
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- 125000001495 ethyl group Chemical group [H]C([H])([H])C([H])([H])* 0.000 description 1
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- 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
- 239000001301 oxygen Substances 0.000 description 1
- 229910052760 oxygen Inorganic materials 0.000 description 1
- 239000002574 poison Substances 0.000 description 1
- 231100000614 poison Toxicity 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
- 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
- 230000006641 stabilisation Effects 0.000 description 1
- 238000011105 stabilization Methods 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
Classifications
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- 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
- B01J29/00—Catalysts comprising molecular sieves
- B01J29/04—Catalysts comprising molecular sieves having base-exchange properties, e.g. crystalline zeolites
- B01J29/06—Crystalline aluminosilicate zeolites; Isomorphous compounds thereof
- B01J29/65—Crystalline aluminosilicate zeolites; Isomorphous compounds thereof of the ferrierite type, e.g. types ZSM-21, ZSM-35 or ZSM-38, as exemplified by patent documents US4046859, US4016245 and US4046859, respectively
- B01J29/69—Crystalline aluminosilicate zeolites; Isomorphous compounds thereof of the ferrierite type, e.g. types ZSM-21, ZSM-35 or ZSM-38, as exemplified by patent documents US4046859, US4016245 and US4046859, respectively containing arsenic, antimony, bismuth, vanadium, niobium, tantalum, polonium, chromium, molybdenum, tungsten, manganese, technetium or rhenium
-
- 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
- B01J35/00—Catalysts, in general, characterised by their form or physical properties
- B01J35/60—Catalysts, in general, characterised by their form or physical properties characterised by their surface properties or porosity
- B01J35/61—Surface area
-
- 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
- B01J35/00—Catalysts, in general, characterised by their form or physical properties
- B01J35/60—Catalysts, in general, characterised by their form or physical properties characterised by their surface properties or porosity
- B01J35/64—Pore diameter
- B01J35/647—2-50 nm
-
- 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
- C07C29/128—Preparation of compounds having hydroxy or O-metal groups bound to a carbon atom not belonging to a six-membered aromatic ring by alcoholysis
- C07C29/1285—Preparation of compounds having hydroxy or O-metal groups bound to a carbon atom not belonging to a six-membered aromatic ring by alcoholysis of esters of organic acids
-
- 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
- B01J2229/00—Aspects of molecular sieve catalysts not covered by B01J29/00
- B01J2229/10—After treatment, characterised by the effect to be obtained
- B01J2229/18—After treatment, characterised by the effect to be obtained to introduce other elements into or onto the molecular sieve itself
-
- 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)
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- Chemical Kinetics & Catalysis (AREA)
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- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
- Low-Molecular Organic Synthesis Reactions Using Catalysts (AREA)
Abstract
The method of 1,2 propylene glycol of carbonate synthesis symmetrical ester co-production is related to a kind of carbonate synthesis symmetrical ester method, and the present invention has the efficient alkaline catalyst of composite pore structural, for propene 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 1,2 propylene glycol in crude product obtained by the reaction.Wherein, propylene carbonate ester conversion rate can reach 95%.1,2 propylene glycol of by-product is i.e. separable by simple distillation as largeization raw material.Entire reaction process cleaning, efficient, pollution-free, no any waste generation.Work as propene 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 carbonate synthesis symmetrical ester method, more particularly to a kind of carbonate synthesis symmetrical ester co-production 1,
The method of 2- propylene glycol.
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 certain 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 safety of battery
Energy and service life.
Consulting literatures are it is found 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 strong corrosive during simultaneous reactions, it is desirable that equipment has corrosion resistant
Corrosion increases 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 increased.
（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 route 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.
Invention content
The purpose of the present invention is to provide a kind of methods of carbonate synthesis symmetrical ester co-production 1,2-PD, propose a kind of
The response path of one-step synthesis method carbonic acid symmetrical ester, the reaction of the one-step synthesis carbonic acid symmetrical ester is short with synthesis path, technique
The characteristics of flow is simple, selectivity of product and high income, catalyst stabilization non-inactivation.
The purpose of the present invention is what is be achieved through the following technical solutions：
The method of carbonate synthesis symmetrical ester co-production 1,2-PD, the method includes following preparation process：
Specific one-step synthesis method carbonic acid symmetrical ester reaction route equation is as follows：
+2ROH→HOCH2CHOHCH3+ROCOOR…………………………………(1)
Raw material is respectively propene 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；
Product 1,2- propylene glycol and carbonic acid symmetrical ester molar ratio 1：1 generation, using the path can effectively a large amount of coproduction 1,2- third
Glycol；
The catalyst of catalysis single step reaction of the present invention is with mesoporous and microcellular structure compound basic catalyst；
It is X/S with mesoporous and microcellular structure compound basic catalyst general formula, wherein X is includes 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；In Zn, B, Al, Ga it is a kind of or
The oxide of person's multiple element；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 of carriers such as MgO and ZnO oxide；
Its hydrogen type molecular sieve of S molecular sieve carriers first passes around ion exchange, and Bronsted acid by metal ion is poisoned, makes it not
With Bronsted acidity；The ion-exchanger for poisoning molecular sieve is hydrochloride, the sulphur of Li, Na, K, Rb, Cs, Ca, Fe, Mg, Cu
Hydrochlorate 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；
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 alkalinity 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.
The method of the carbonate synthesis symmetrical ester co-production 1,2-PD, gives an account of the preparation of micro porous molecular sieve carrier
Method, the molecular sieve of the different topology structure of carrier include the one or more of EMT, MOR, MWW, FAU, MFI, FER, BEA；
The acid solution includes H4EDTA、HCl、HNO3One or more, preferably H4EDTA；The addition of acid solution at least will
All molecular sieves are flooded, can be 10-20 times, preferably 15 times of molecular sieve volume；The alkaline solution include NaOH,
Na2CO3One or more, preferably NaOH；A concentration of 0.05mol/L-2.0mol/L of alkaline solution；Alkaline solution adds
All molecular sieves will at least be flooded by entering amount, be 5-15 times, preferably 10 times of molecular sieve volume.
The method of the carbonate synthesis symmetrical ester co-production 1,2-PD, gives an account of the preparation of micro porous molecular sieve carrier
Method, the M-meso-S carrier mesoporous pore sizes obtained are distributed as 4-34nm, and specific aperture is related with alkaline solution concentration used.
The method of the carbonate synthesis symmetrical ester co-production 1,2-PD, it is described that there is mesoporous and microcellular structure carrier
Loading type alkali metal oxide catalyst, it is characterised in that using coprecipitation method or infusion process：
1）The coprecipitated hydroxide for including but not limited to alkali metal and ammonium with alkaline solution, such as lithium hydroxide, hydroxide
Sodium, potassium hydroxide and ammonium hydroxide；Carbonate, bicarbonate, formates and the acetate of alkali metal, as lithium carbonate, sodium carbonate,
Two or more mixed liquors of the solution of potassium carbonate etc. or above-mentioned alkaline solution；Liquid used in alkaline substance solution is situated between
Matter is preferably water, but is also not necessarily limited to water；
2）The addition of alkaline solution will at least flood all carriers, be 10-20 times or more of carrier bulk, and preferably 15
Times, it is 10-14 that solution PH value is controlled when coprecipitated, and 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 be -20 days 1 hour, preferably 60 DEG C, ageing time 5 days；Catalyst wash
It is preferably water to wash medium, 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, water
Number is washed depending on efflux pH is washed；Catalyst drying temperature can be -150 DEG C of room temperature, and the time can be -10 days 1 hour, preferably
It is 120 DEG C, 3-5 days dry；Calcination temperature be 150-800 DEG C, the time be 1-50 hours, preferably 500-700 DEG C, 30 hours time；
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 (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；
4）The dipping method can use co-impregnation, the method that can also use step impregnation；Drying temperature can be room temperature~
150 DEG C, the time is 1 hour~20 days；Calcination temperature is 550~650 DEG C, and the time is 1~50 hour；The load of composite pore structural
The content of metal X is the 0.1-50% of vehicle weight in type catalyst Formula；
5）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 method of the carbonate synthesis symmetrical ester co-production 1,2-PD, described its fixed bed of carbonate synthesis symmetrical ester
Successive reaction scheme is：Under normal pressure to 10MPa reaction pressures, liquid charging stock propene 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,
Reaction carbonate synthesis symmetrical ester, air speed are 0.1-100 h to above-mentioned catalyst existence condition in next step-1, reaction temperature 50-250
Under conditions of DEG C, catalyst is compound basic catalyst, and catalyst amount is the 0.1-3wt% of material quality, and product carbonic acid is symmetrical
Ester yield is not less than 60%.
The method of the carbonate synthesis symmetrical ester co-production 1,2-PD, the continuous fixed bed reaction or continuous prepare carbon
During sour symmetrical ester, optimum condition is propene carbonate：Various 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
℃。
The method of the carbonate synthesis symmetrical ester co-production 1,2-PD, the still reaction scheme are：Reaction pressure
Power 0.1-10MPa, (ROH, R can be straight chain alcohol, isomery alcohol, aromatic alcohol, phenols, glycol such as second to propene carbonate with various alcohols
Glycol, diethylene glycol (DEG) and polyol）Molar ratio 0.1:1 -10:1, under catalyst existence condition reaction prepare carbonic acid symmetrical ester, react
Closed 25-150 DEG C of reaction 0.5-10 h in kettle, catalyst are basic catalyst, and catalyst amount is the 0.1-10 of material quality
wt %。
Advantages of the present invention is with effect：
The present invention is by propene carbonate and various alcohols（ROH can be straight chain alcohol, isomery alcohol, aromatic alcohol, phenols, glycol such as 1,2-
The various alcohols such as propylene glycol, diethylene glycol (DEG) and polyol）The method of one-step synthesis carbonic acid symmetrical ester, it is characterised in that one kind has compound
The efficient alkaline catalyst of pore structure；Synthetic route is short, and a step directly obtains target product.It is contained only in crude product obtained by the reaction
There are carbonic acid symmetrical ester and 1,2-PD, wherein, carbonic acid symmetrical ester yield can reach 94%.By-product 1,2- propylene glycol is made
It is i.e. separable by simple distillation for largeization raw material.Entire reaction process cleans, is efficient, pollution-free, without any low value
By-product generate.
Description of the drawings
Fig. 1 is with 15%BaO-5% Cr2O3-3%La2O3/ Zr-meso- ZSM-35 are catalyst differential responses temperature to anti-
Answer the influence of object conversion ratio and dimethyl carbonate yield.
Specific embodiment
The following describes the present invention in detail with reference to examples.
The present invention is by propene carbonate and various alcohols（ROH can be straight chain alcohol, isomery alcohol, aromatic alcohol, phenols, two
The alcohol such as various alcohols such as ethylene glycol, diethylene glycol (DEG) and polyol）The response path of one-step synthesis carbonic acid symmetrical ester and the response path institute
The catalyst used, the response path are as follows：
+ 2ROH→HOCH2CHOHCH3+ROCOOR……………………………………(8)
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 propene 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 product 1,2-PD incidentally generated is a kind of bulk chemical, has a vast market application prospect.Therefore it reacted
It is entire response path green, energy-saving and environmental protection, efficient it may be said that being generated almost without any by-product in journey.
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 of carriers such as MgO and ZnO oxygen
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 carries out EMT at 90 DEG C the ion exchange of 2 hours.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.Sour processing intent is the Al removed in framework of molecular sieve, so as to fulfill pore-creating, alkali process it is main
The Si that effect is to remove in framework of molecular sieve makes molecular sieve form meso-hole structure, and preparation process includes the following steps：
1）Dealuminzation：Certain mass M-S carriers are added separately in the acid solution of certain volume, a concentration of 0.11 mol/L,
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 alkalinity 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, preferably 15 times of molecular sieve volume；The alkaline solution includes
NaOH、Na2CO3Deng one or more, preferably NaOH；A concentration of 0.05mol/L-2.0mol/L of alkaline solution；Alkalinity is molten
The addition of liquid will at least flood all molecular sieves, can be 5-15 times, preferably 10 times of molecular sieve volume.
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,
Include the following steps：
2.1 wherein coprecipitation methods include：
1）The carrier with composite pore structural being prepared is put into Muffle furnace 500 DEG C of roastings 4 hours 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 alkalinity
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, it is 10-14 that solution PH value is controlled when coprecipitated, and 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
Time can be -20 days 1 hour, preferably 60 DEG C, 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 the time can be -10 days 1 hour, preferably 120 DEG C, 3-5 days dry；
Calcination temperature can be 150-800 DEG C, the time can be 1-50 hours, preferably 500-700 DEG C, 30 hours time.
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）The M-meso-S carriers with composite pore structural being prepared are put into Muffle furnace first and are roasted 4 hours for 500 DEG C,
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 110 DEG C of dryings 10 hours 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；It is dry
Temperature can be room temperature~150 DEG C, and the time can be 1 hour~20 days；Calcination temperature can be 550~650 DEG C, and the time can be 1~50
Hour.
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 propene 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 acrylic ester 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 propene 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, propene 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 propene 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 propene 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.
The reaction is catalyzed with basic catalyst, reaction product is single dimethyl carbonate and 1,2-PD.Except upper table
In have dimethyl carbonate（DMC）Generation is outer, has a large amount of 1,2-PDs to generate, since 1,2-PD derives from propene carbonate
（PC）If calculating selectivity of product from propene carbonate, the selectivity of 1,2-PD is approximate under all reaction conditions
It is 100%.Other specific examples use same data expression method.As can be seen from Table 1, if only using molecular sieve carrier as
Catalyst, reaction result is very poor, and reaction hardly occurs.When alkaline metal oxide is carried on molecular sieve carrier, urge
Agent effect has very big promotion, and when containing La elements particularly in catalyst, the catalytic effect of reaction is best.With 15%BaO-5%
Cr2O3-3%La2O3/ Zr-meso- ZSM-35 are catalyst, and PC conversion ratios are up to 88%, and product DMC yields are up to 88%.
Embodiment 2
In 50L paste state bed reactor kettles, reaction pressure 2MPa, reaction raw materials propene carbonate：Various alcohols=1:3, input
15%BaO-5% Cr2O3-3%La2O3/ Zr-meso- ZSM-35 catalyst 1.2kg, reaction solution total volume are 40 L.Mechanical agitation
Reaction, 100 DEG C of reaction temperature react sampling progress chromatography calculating after 10h, and feed stock conversion, product carbonic acid symmetrical ester are received
Rate is as shown in table 2.
As can be seen from Table 2, using different alcohols as reaction raw materials carbonate synthesis symmetrical ester, reaction result difference is larger,
As R group becomes complicated, the conversion ratio of ROH is gradually reduced, and the yield of carbonic acid symmetrical ester is gradually lowered.The reason is that with R
Group complicates, and the steric hindrance of ROH becomes larger, and R group is difficult to close to propene carbonate and is replaced.
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%BaO-5% Cr2O3-3%La2O350 g of/Zr-meso- ZSM-35 catalyst, using constant flow pump by propene carbonate with
Various alcohols are 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, 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 3.
As can be seen from Table 3, with 15%BaO-5% Cr2O3-3%La2O3When/Zr-meso- ZSM-35 are catalyst, with
The raising reaction-ure conversion-age and DMC yields of reaction pressure all increase.When reaction pressure reach 5MPa and more than when, reaction
Object conversion ratio and DMC yields nearly all reach maximum value, 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%BaO-5% Cr2O3-3%La2O350 g of/Zr-meso- ZSM-35 catalyst, using constant flow pump by propene carbonate with
Various alcohols are with molar ratio 1:3 ratio is pumped into reactor, and air speed is 5 h-1, reaction pressure 5Mpa, reaction temperature such as table
It is shown, and stablize 500 h, sampling progress chromatography calculating after stablizing, feed stock conversion, product yield are as shown in table 4
From table 4, it can be seen that the raising reaction-ure conversion-age and DMC yields with reaction temperature increase, but when temperature is high
After 100 DEG C, continue to increase 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%BaO-5% Cr are packed into bed2O3-3%La2O350 g of/Zr-meso- ZSM-35 catalyst, using constant flow pump by propylene carbonate
Ester is pumped into methanol in reactor, and air speed is 5 h-1, propene carbonate with methanol specifically reacts molar ratio, and 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 after stablizing
Yield is as shown in table 5.
As can be seen from Table 5, propene carbonate and Methanol Molar compare reaction result influence it is very big, when propene carbonate with
During methanol low mole prop0rtion, propene carbonate is largely consumed, DMC high incomes；When propene carbonate and methanol high molar ratio, carbon
Acid propylene ester conversion rate declines, and DMC yields also decline.But consider with reference to cost of material and product yield, best propene carbonate
1 is should be with methanol molar ratio: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%BaO-5% Cr2O3-3%La2O350 g of/Zr-meso- ZSM-35 catalyst, using constant flow pump by propene carbonate with
Various alcohols are 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, instead
100 DEG C of temperature is answered, and stablizes 500 h, sampling progress chromatography calculating, feed stock conversion, product yield such as 6 institute of table after stablizing
Show.
As can be seen from Table 6, as the increase reaction-ure conversion-age of air speed and dimethyl carbonate yield are constant at the beginning, when
Air speed is 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-1
For optimum response air speed.
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%BaO-5% Cr are packed into fixed bed2O3-3%La2O350 g of/Zr-meso- ZSM-35 catalyst, profit
With constant flow pump by propene 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, sampling progress chromatography calculating, raw material after stablizing
Conversion ratio, product yield are as shown in table 7.
As can be seen from Table 7,5000 h feed stock conversions of reaction experience, product dimethyl carbonate yield are basically unchanged, and are urged
Agent does not inactivate substantially, and catalyst has fabulous stability.The above is only several embodiments of the application, not
Any type of limitation is done to the application, is not to limit this Shen although the application is disclosed as above with preferred embodiment
Please, any person skilled in the art in the range of technical scheme is not departed from, utilizes the technology of the disclosure above
Content makes a little variation or modification is equal to equivalence enforcement case, belongs in the range of technical solution.
Claims (7)
1. the method for carbonate synthesis symmetrical ester co-production 1,2-PD, which is characterized in that prepared the method includes following
Journey：
Specific one-step synthesis method carbonic acid symmetrical ester reaction route equation is as follows：
+2ROH→HOCH2CHOHCH3+ROCOOR…………………………………(1)
Raw material is respectively propene 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；
Product 1,2- propylene glycol and carbonic acid symmetrical ester molar ratio 1：1 generation, using the path can effectively a large amount of coproduction 1,2- third
Glycol；
The catalyst of catalysis single step reaction of the present invention is with mesoporous and microcellular structure compound basic catalyst；
It is X/S with mesoporous and microcellular structure compound basic catalyst general formula, wherein X is includes 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；In Zn, B, Al, Ga it is a kind of or
The oxide of person's multiple element；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 of carriers such as MgO and ZnO oxide；
Its hydrogen type molecular sieve of S molecular sieve carriers first passes around ion exchange, and Bronsted acid by metal ion is poisoned, makes it not
With Bronsted acidity；The ion-exchanger for poisoning molecular sieve is hydrochloride, the sulphur of Li, Na, K, Rb, Cs, Ca, Fe, Mg, Cu
Hydrochlorate 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；
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 alkalinity 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 carbonate synthesis symmetrical ester co-production 1,2-PD according to claim 1, which is characterized in that described
The preparation method of Jie's micro porous molecular sieve carrier, the molecular sieve of the different topology structure of carrier include EMT, MOR, MWW, FAU,
MFI, FER, BEA's is one or more；The acid solution includes H4EDTA、HCl、HNO3It is one or more, preferably
H4EDTA；The addition of acid solution will at least flood all molecular sieves, can be 10-20 times of molecular sieve volume, preferably
15 times；The alkaline solution includes NaOH, Na2CO3One or more, preferably NaOH；The alkaline solution is a concentration of
0.05mol/L-2.0mol/L；The addition of alkaline solution will at least flood all molecular sieves, be the 5-15 of molecular sieve volume
Times, preferably 10 times.
3. the method for carbonate synthesis symmetrical ester co-production 1,2-PD according to claim 1, which is characterized in that described
The preparation method of Jie's micro porous molecular sieve carrier, the M-meso-S carrier mesoporous pore sizes obtained are distributed as 4-34nm, specific aperture
It is related with alkaline solution concentration used.
4. the method for carbonate synthesis symmetrical ester co-production 1,2-PD according to claim 1, which is characterized in that described
With mesoporous and microcellular structure carrier loading type alkali metal oxide catalyst, it is characterised in that using coprecipitation method or dipping
Method：
1）The coprecipitated hydroxide for including but not limited to alkali metal and ammonium with alkaline solution, such as lithium hydroxide, hydroxide
Sodium, potassium hydroxide and ammonium hydroxide；Carbonate, bicarbonate, formates and the acetate of alkali metal, as lithium carbonate, sodium carbonate,
Two or more mixed liquors of the solution of potassium carbonate etc. or above-mentioned alkaline solution；Liquid used in alkaline substance solution is situated between
Matter is preferably water, but is also not necessarily limited to water；
2）The addition of alkaline solution will at least flood all carriers, be 10-20 times or more of carrier bulk, and preferably 15
Times, it is 10-14 that solution PH value is controlled when coprecipitated, and 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 be -20 days 1 hour, preferably 60 DEG C, ageing time 5 days；Catalyst wash
It is preferably water to wash medium, 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, water
Number is washed depending on efflux pH is washed；Catalyst drying temperature can be -150 DEG C of room temperature, and the time can be -10 days 1 hour, preferably
It is 120 DEG C, 3-5 days dry；Calcination temperature be 150-800 DEG C, the time be 1-50 hours, preferably 500-700 DEG C, 30 hours time；
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 (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；
4）The dipping method can use co-impregnation, the method that can also use step impregnation；Drying temperature can be room temperature~
150 DEG C, the time is 1 hour~20 days；Calcination temperature is 550~650 DEG C, and the time is 1~50 hour；The load of composite pore structural
The content of metal X is the 0.1-50% of vehicle weight in type catalyst Formula；
5）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.
5. the method for carbonate synthesis symmetrical ester co-production 1,2-PD according to claim 1, which is characterized in that described
Its continuous fixed bed reaction or continuous scheme of carbonate synthesis symmetrical ester is：Under normal pressure to 10MPa reaction pressures, liquid charging stock carbon is beaten with pump
Acid propylene ester 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- in next step in above-mentioned catalyst existence condition
100 h-1, under conditions of 50-250 DEG C of reaction temperature, catalyst is compound basic catalyst, and catalyst amount is material quality
0.1-3wt%, product carbonic acid symmetrical ester yield are not less than 60%.
6. the method for carbonate synthesis symmetrical ester co-production 1,2-PD according to claim 5, which is characterized in that described
Continuous fixed bed reaction or continuous, during preparing carbonic acid symmetrical ester, optimum condition is propene carbonate：Various 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.
7. the method for carbonate synthesis symmetrical ester co-production 1,2-PD according to claim 6, which is characterized in that described
Still reaction scheme is：Reaction pressure 0.1-10MPa, (ROH, R can be straight chain alcohol, isomery to propene carbonate with various alcohols
Alcohol, aromatic alcohol, phenols, glycol such as ethylene glycol, diethylene glycol (DEG) and polyol）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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