CN1064677A - Process for preparing aromatic carbonate - Google Patents
Process for preparing aromatic carbonate Download PDFInfo
- Publication number
- CN1064677A CN1064677A CN91101344.XA CN91101344A CN1064677A CN 1064677 A CN1064677 A CN 1064677A CN 91101344 A CN91101344 A CN 91101344A CN 1064677 A CN1064677 A CN 1064677A
- Authority
- CN
- China
- Prior art keywords
- distillation tower
- continuous multi
- stage distillation
- catalyzer
- formula
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Granted
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- BVKZGUZCCUSVTD-UHFFFAOYSA-L Carbonate Chemical compound [O-]C([O-])=O BVKZGUZCCUSVTD-UHFFFAOYSA-L 0.000 title claims abstract description 50
- 125000003118 aryl group Chemical group 0.000 title abstract description 10
- 238000004519 manufacturing process Methods 0.000 title description 19
- 238000004821 distillation Methods 0.000 claims abstract description 293
- -1 aromatic hydroxy compound Chemical class 0.000 claims abstract description 159
- 238000009835 boiling Methods 0.000 claims abstract description 112
- 239000007788 liquid Substances 0.000 claims abstract description 102
- 238000000034 method Methods 0.000 claims abstract description 95
- 239000000203 mixture Substances 0.000 claims abstract description 72
- 239000002994 raw material Substances 0.000 claims abstract description 61
- 239000006227 byproduct Substances 0.000 claims abstract description 48
- 239000000047 product Substances 0.000 claims abstract description 44
- 238000005809 transesterification reaction Methods 0.000 claims abstract description 22
- 239000000463 material Substances 0.000 claims abstract description 15
- 239000007791 liquid phase Substances 0.000 claims description 53
- 239000011541 reaction mixture Substances 0.000 claims description 50
- 239000000376 reactant Substances 0.000 claims description 49
- 229910052799 carbon Inorganic materials 0.000 claims description 32
- 150000001875 compounds Chemical class 0.000 claims description 30
- 239000000945 filler Substances 0.000 claims description 20
- 238000001704 evaporation Methods 0.000 claims description 18
- 230000008676 import Effects 0.000 claims description 17
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 claims description 15
- 150000002191 fatty alcohols Chemical class 0.000 claims description 15
- 238000012856 packing Methods 0.000 claims description 14
- 239000002904 solvent Substances 0.000 claims description 13
- 239000007795 chemical reaction product Substances 0.000 claims description 11
- 239000011949 solid catalyst Substances 0.000 claims description 11
- 239000010949 copper Substances 0.000 claims description 9
- 239000002841 Lewis acid Substances 0.000 claims description 8
- 150000002611 lead compounds Chemical group 0.000 claims description 8
- 150000007517 lewis acids Chemical class 0.000 claims description 7
- 229910052742 iron Inorganic materials 0.000 claims description 6
- 239000006193 liquid solution Substances 0.000 claims description 6
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 claims description 5
- QCWXUUIWCKQGHC-UHFFFAOYSA-N Zirconium Chemical compound [Zr] QCWXUUIWCKQGHC-UHFFFAOYSA-N 0.000 claims description 5
- 229910052802 copper Inorganic materials 0.000 claims description 5
- 229910052809 inorganic oxide Inorganic materials 0.000 claims description 5
- 150000002736 metal compounds Chemical class 0.000 claims description 5
- 229910052726 zirconium Inorganic materials 0.000 claims description 5
- 229910052783 alkali metal Inorganic materials 0.000 claims description 4
- 150000001340 alkali metals Chemical class 0.000 claims description 4
- 229910052793 cadmium Inorganic materials 0.000 claims description 4
- BDOSMKKIYDKNTQ-UHFFFAOYSA-N cadmium atom Chemical compound [Cd] BDOSMKKIYDKNTQ-UHFFFAOYSA-N 0.000 claims description 4
- 229910000765 intermetallic Inorganic materials 0.000 claims description 3
- 238000002156 mixing Methods 0.000 claims description 3
- 238000006243 chemical reaction Methods 0.000 abstract description 131
- 150000002148 esters Chemical class 0.000 abstract description 18
- YGYAWVDWMABLBF-UHFFFAOYSA-N Phosgene Chemical compound ClC(Cl)=O YGYAWVDWMABLBF-UHFFFAOYSA-N 0.000 abstract description 5
- 231100000614 poison Toxicity 0.000 abstract description 5
- 230000007096 poisonous effect Effects 0.000 abstract description 5
- 239000004417 polycarbonate Substances 0.000 abstract description 4
- 229920000515 polycarbonate Polymers 0.000 abstract description 4
- 230000008569 process Effects 0.000 abstract description 4
- 150000007860 aryl ester derivatives Chemical class 0.000 abstract description 3
- ISWSIDIOOBJBQZ-UHFFFAOYSA-N Phenol Chemical compound OC1=CC=CC=C1 ISWSIDIOOBJBQZ-UHFFFAOYSA-N 0.000 description 38
- ROORDVPLFPIABK-UHFFFAOYSA-N diphenyl carbonate Chemical compound C=1C=CC=CC=1OC(=O)OC1=CC=CC=C1 ROORDVPLFPIABK-UHFFFAOYSA-N 0.000 description 38
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 36
- CXHHBNMLPJOKQD-UHFFFAOYSA-M methyl carbonate Chemical compound COC([O-])=O CXHHBNMLPJOKQD-UHFFFAOYSA-M 0.000 description 31
- 239000007789 gas Substances 0.000 description 29
- CQLKDMOFEZPUEJ-UHFFFAOYSA-N aminomethyl phenyl carbonate Chemical compound NCOC(=O)OC1=CC=CC=C1 CQLKDMOFEZPUEJ-UHFFFAOYSA-N 0.000 description 27
- 241000282326 Felis catus Species 0.000 description 26
- 239000003054 catalyst Substances 0.000 description 24
- 238000009833 condensation Methods 0.000 description 19
- 230000005494 condensation Effects 0.000 description 19
- 239000002585 base Substances 0.000 description 18
- 125000000951 phenoxy group Chemical group [H]C1=C([H])C([H])=C(O*)C([H])=C1[H] 0.000 description 18
- 230000004044 response Effects 0.000 description 17
- 238000007600 charging Methods 0.000 description 16
- 238000010438 heat treatment Methods 0.000 description 16
- YEXPOXQUZXUXJW-UHFFFAOYSA-N lead(II) oxide Inorganic materials [Pb]=O YEXPOXQUZXUXJW-UHFFFAOYSA-N 0.000 description 16
- 230000000052 comparative effect Effects 0.000 description 12
- RDOXTESZEPMUJZ-UHFFFAOYSA-N anisole Chemical compound COC1=CC=CC=C1 RDOXTESZEPMUJZ-UHFFFAOYSA-N 0.000 description 11
- HTUMBQDCCIXGCV-UHFFFAOYSA-N lead oxide Chemical compound [O-2].[Pb+2] HTUMBQDCCIXGCV-UHFFFAOYSA-N 0.000 description 11
- 125000000217 alkyl group Chemical group 0.000 description 10
- CUJRVFIICFDLGR-UHFFFAOYSA-N acetylacetonate Chemical compound CC(=O)[CH-]C(C)=O CUJRVFIICFDLGR-UHFFFAOYSA-N 0.000 description 9
- 238000001816 cooling Methods 0.000 description 9
- 125000003545 alkoxy group Chemical group 0.000 description 8
- IWDCLRJOBJJRNH-UHFFFAOYSA-N p-cresol Chemical compound CC1=CC=C(O)C=C1 IWDCLRJOBJJRNH-UHFFFAOYSA-N 0.000 description 8
- 238000010992 reflux Methods 0.000 description 8
- 239000006200 vaporizer Substances 0.000 description 8
- OIFBSDVPJOWBCH-UHFFFAOYSA-N Diethyl carbonate Chemical compound CCOC(=O)OCC OIFBSDVPJOWBCH-UHFFFAOYSA-N 0.000 description 7
- 239000010935 stainless steel Substances 0.000 description 7
- 229910001220 stainless steel Inorganic materials 0.000 description 7
- 239000012808 vapor phase Substances 0.000 description 7
- YCNSGSUGQPDYTK-UHFFFAOYSA-N ethyl phenyl carbonate Chemical compound CCOC(=O)OC1=CC=CC=C1 YCNSGSUGQPDYTK-UHFFFAOYSA-N 0.000 description 6
- 230000035611 feeding Effects 0.000 description 6
- 239000012071 phase Substances 0.000 description 6
- 239000010936 titanium Substances 0.000 description 6
- 229910020282 Pb(OH) Inorganic materials 0.000 description 5
- 239000002253 acid Substances 0.000 description 5
- 230000004087 circulation Effects 0.000 description 5
- 230000006698 induction Effects 0.000 description 5
- 230000013011 mating Effects 0.000 description 5
- 239000012299 nitrogen atmosphere Substances 0.000 description 5
- 238000001637 plasma atomic emission spectroscopy Methods 0.000 description 5
- 230000009257 reactivity Effects 0.000 description 5
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 4
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 4
- BVKZGUZCCUSVTD-UHFFFAOYSA-N carbonic acid Chemical compound OC(O)=O BVKZGUZCCUSVTD-UHFFFAOYSA-N 0.000 description 4
- 239000003153 chemical reaction reagent Substances 0.000 description 4
- JGFBRKRYDCGYKD-UHFFFAOYSA-N dibutyl(oxo)tin Chemical compound CCCC[Sn](=O)CCCC JGFBRKRYDCGYKD-UHFFFAOYSA-N 0.000 description 4
- 238000011049 filling Methods 0.000 description 4
- 125000005843 halogen group Chemical group 0.000 description 4
- UHOVQNZJYSORNB-UHFFFAOYSA-N monobenzene Natural products C1=CC=CC=C1 UHOVQNZJYSORNB-UHFFFAOYSA-N 0.000 description 4
- 125000001624 naphthyl group Chemical group 0.000 description 4
- ISWSIDIOOBJBQZ-UHFFFAOYSA-M phenolate Chemical compound [O-]C1=CC=CC=C1 ISWSIDIOOBJBQZ-UHFFFAOYSA-M 0.000 description 4
- GHMLBKRAJCXXBS-UHFFFAOYSA-N resorcinol Chemical compound OC1=CC=CC(O)=C1 GHMLBKRAJCXXBS-UHFFFAOYSA-N 0.000 description 4
- 238000000926 separation method Methods 0.000 description 4
- 238000007086 side reaction Methods 0.000 description 4
- 150000001447 alkali salts Chemical class 0.000 description 3
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 description 3
- 125000003710 aryl alkyl group Chemical group 0.000 description 3
- 125000004104 aryloxy group Chemical group 0.000 description 3
- 230000008859 change Effects 0.000 description 3
- 235000019628 coolness Nutrition 0.000 description 3
- 125000004093 cyano group Chemical group *C#N 0.000 description 3
- 230000032050 esterification Effects 0.000 description 3
- 238000005886 esterification reaction Methods 0.000 description 3
- 239000012530 fluid Substances 0.000 description 3
- 125000003187 heptyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 description 3
- 125000002887 hydroxy group Chemical group [H]O* 0.000 description 3
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 description 3
- 239000002808 molecular sieve Substances 0.000 description 3
- 150000002894 organic compounds Chemical class 0.000 description 3
- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 description 3
- URGAHOPLAPQHLN-UHFFFAOYSA-N sodium aluminosilicate Chemical compound [Na+].[Al+3].[O-][Si]([O-])=O.[O-][Si]([O-])=O URGAHOPLAPQHLN-UHFFFAOYSA-N 0.000 description 3
- 239000007858 starting material Substances 0.000 description 3
- 238000003756 stirring Methods 0.000 description 3
- 239000000126 substance Substances 0.000 description 3
- 150000003606 tin compounds Chemical class 0.000 description 3
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 3
- MFEVGQHCNVXMER-UHFFFAOYSA-L 1,3,2$l^{2}-dioxaplumbetan-4-one Chemical compound [Pb+2].[O-]C([O-])=O MFEVGQHCNVXMER-UHFFFAOYSA-L 0.000 description 2
- MJKVTPMWOKAVMS-UHFFFAOYSA-N 3-hydroxy-1-benzopyran-2-one Chemical compound C1=CC=C2OC(=O)C(O)=CC2=C1 MJKVTPMWOKAVMS-UHFFFAOYSA-N 0.000 description 2
- QTBSBXVTEAMEQO-UHFFFAOYSA-M Acetate Chemical compound CC([O-])=O QTBSBXVTEAMEQO-UHFFFAOYSA-M 0.000 description 2
- XKRFYHLGVUSROY-UHFFFAOYSA-N Argon Chemical compound [Ar] XKRFYHLGVUSROY-UHFFFAOYSA-N 0.000 description 2
- WJSBIDKGPLWKBH-UHFFFAOYSA-N C1(=CC=CC=C1)O.C(CC)C1=CC=CC=C1 Chemical compound C1(=CC=CC=C1)O.C(CC)C1=CC=CC=C1 WJSBIDKGPLWKBH-UHFFFAOYSA-N 0.000 description 2
- 229910021589 Copper(I) bromide Inorganic materials 0.000 description 2
- 229910021591 Copper(I) chloride Inorganic materials 0.000 description 2
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 description 2
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 2
- YNQLUTRBYVCPMQ-UHFFFAOYSA-N Ethylbenzene Chemical compound CCC1=CC=CC=C1 YNQLUTRBYVCPMQ-UHFFFAOYSA-N 0.000 description 2
- 229910000003 Lead carbonate Inorganic materials 0.000 description 2
- IMNFDUFMRHMDMM-UHFFFAOYSA-N N-Heptane Chemical compound CCCCCCC IMNFDUFMRHMDMM-UHFFFAOYSA-N 0.000 description 2
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 2
- XLOMVQKBTHCTTD-UHFFFAOYSA-N Zinc monoxide Chemical compound [Zn]=O XLOMVQKBTHCTTD-UHFFFAOYSA-N 0.000 description 2
- 125000003158 alcohol group Chemical group 0.000 description 2
- 150000001338 aliphatic hydrocarbons Chemical class 0.000 description 2
- 150000004703 alkoxides Chemical class 0.000 description 2
- 125000001118 alkylidene group Chemical group 0.000 description 2
- 238000004458 analytical method Methods 0.000 description 2
- 230000015572 biosynthetic process Effects 0.000 description 2
- 229910052797 bismuth Inorganic materials 0.000 description 2
- 125000000484 butyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 description 2
- OCKPCBLVNKHBMX-UHFFFAOYSA-N butylbenzene Chemical compound CCCCC1=CC=CC=C1 OCKPCBLVNKHBMX-UHFFFAOYSA-N 0.000 description 2
- OKQPRBCJOFEFQV-UHFFFAOYSA-N butylbenzene phenol Chemical compound C1(=CC=CC=C1)O.C(CCC)C1=CC=CC=C1 OKQPRBCJOFEFQV-UHFFFAOYSA-N 0.000 description 2
- 230000003197 catalytic effect Effects 0.000 description 2
- YCIMNLLNPGFGHC-UHFFFAOYSA-N catechol Chemical compound OC1=CC=CC=C1O YCIMNLLNPGFGHC-UHFFFAOYSA-N 0.000 description 2
- 239000000470 constituent Substances 0.000 description 2
- OXBLHERUFWYNTN-UHFFFAOYSA-M copper(I) chloride Chemical compound [Cu]Cl OXBLHERUFWYNTN-UHFFFAOYSA-M 0.000 description 2
- 125000000113 cyclohexyl group Chemical group [H]C1([H])C([H])([H])C([H])([H])C([H])(*)C([H])([H])C1([H])[H] 0.000 description 2
- 230000003247 decreasing effect Effects 0.000 description 2
- 230000000694 effects Effects 0.000 description 2
- 229920006351 engineering plastic Polymers 0.000 description 2
- 238000005516 engineering process Methods 0.000 description 2
- 125000004185 ester group Chemical group 0.000 description 2
- 229910052736 halogen Inorganic materials 0.000 description 2
- 150000002367 halogens Chemical class 0.000 description 2
- 125000004435 hydrogen atom Chemical class [H]* 0.000 description 2
- 229910000464 lead oxide Inorganic materials 0.000 description 2
- 229910021514 lead(II) hydroxide Inorganic materials 0.000 description 2
- 229910052748 manganese Inorganic materials 0.000 description 2
- 239000002184 metal Chemical class 0.000 description 2
- 229910052751 metal Inorganic materials 0.000 description 2
- 150000004780 naphthols Chemical class 0.000 description 2
- YCWSUKQGVSGXJO-NTUHNPAUSA-N nifuroxazide Chemical group C1=CC(O)=CC=C1C(=O)N\N=C\C1=CC=C([N+]([O-])=O)O1 YCWSUKQGVSGXJO-NTUHNPAUSA-N 0.000 description 2
- 125000000449 nitro group Chemical group [O-][N+](*)=O 0.000 description 2
- 229910052757 nitrogen Inorganic materials 0.000 description 2
- IXQGCWUGDFDQMF-UHFFFAOYSA-N o-Hydroxyethylbenzene Natural products CCC1=CC=CC=C1O IXQGCWUGDFDQMF-UHFFFAOYSA-N 0.000 description 2
- NWVVVBRKAWDGAB-UHFFFAOYSA-N p-methoxyphenol Chemical compound COC1=CC=C(O)C=C1 NWVVVBRKAWDGAB-UHFFFAOYSA-N 0.000 description 2
- 150000003839 salts Chemical class 0.000 description 2
- 238000001179 sorption measurement Methods 0.000 description 2
- 241000894007 species Species 0.000 description 2
- 229910052719 titanium Inorganic materials 0.000 description 2
- 239000011800 void material Substances 0.000 description 2
- XISNHLSTXMGPIY-UHFFFAOYSA-N (2-hydroxyphenyl) methyl carbonate Chemical compound COC(=O)OC1=CC=CC=C1O XISNHLSTXMGPIY-UHFFFAOYSA-N 0.000 description 1
- ZGSHFDSKHTZINF-UHFFFAOYSA-N (2-methyl-6-phenylphenyl) hydrogen carbonate Chemical compound CC1=CC=CC(C=2C=CC=CC=2)=C1OC(O)=O ZGSHFDSKHTZINF-UHFFFAOYSA-N 0.000 description 1
- PXSSNPBEHHJLDH-UHFFFAOYSA-N 2,3,4,5-tetramethylphenol Chemical compound CC1=CC(O)=C(C)C(C)=C1C PXSSNPBEHHJLDH-UHFFFAOYSA-N 0.000 description 1
- RLEWTHFVGOXXTN-UHFFFAOYSA-N 2,3-diethylphenol Chemical compound CCC1=CC=CC(O)=C1CC RLEWTHFVGOXXTN-UHFFFAOYSA-N 0.000 description 1
- HRQPPTDGMMGDKC-UHFFFAOYSA-N 2,3-dipropylphenol Chemical compound CCCC1=CC=CC(O)=C1CCC HRQPPTDGMMGDKC-UHFFFAOYSA-N 0.000 description 1
- ONIKNECPXCLUHT-UHFFFAOYSA-N 2-chlorobenzoyl chloride Chemical compound ClC(=O)C1=CC=CC=C1Cl ONIKNECPXCLUHT-UHFFFAOYSA-N 0.000 description 1
- FNRMMDCDHWCQTH-UHFFFAOYSA-N 2-chloropyridine;3-chloropyridine;4-chloropyridine Chemical compound ClC1=CC=NC=C1.ClC1=CC=CN=C1.ClC1=CC=CC=N1 FNRMMDCDHWCQTH-UHFFFAOYSA-N 0.000 description 1
- 125000003903 2-propenyl group Chemical group [H]C([*])([H])C([H])=C([H])[H] 0.000 description 1
- VIIIJFZJKFXOGG-UHFFFAOYSA-N 3-methylchromen-2-one Chemical compound C1=CC=C2OC(=O)C(C)=CC2=C1 VIIIJFZJKFXOGG-UHFFFAOYSA-N 0.000 description 1
- PCFMUWBCZZUMRX-UHFFFAOYSA-N 9,10-Dihydroxyanthracene Chemical compound C1=CC=C2C(O)=C(C=CC=C3)C3=C(O)C2=C1 PCFMUWBCZZUMRX-UHFFFAOYSA-N 0.000 description 1
- 101710134784 Agnoprotein Proteins 0.000 description 1
- GJXJMUKOJVFTBX-UHFFFAOYSA-N C(CCC)C1=CC=CC=C1.C(O)(O)=O Chemical compound C(CCC)C1=CC=CC=C1.C(O)(O)=O GJXJMUKOJVFTBX-UHFFFAOYSA-N 0.000 description 1
- CURLTUGMZLYLDI-UHFFFAOYSA-N Carbon dioxide Chemical compound O=C=O CURLTUGMZLYLDI-UHFFFAOYSA-N 0.000 description 1
- 241000522215 Dipteryx odorata Species 0.000 description 1
- 229910000978 Pb alloy Inorganic materials 0.000 description 1
- 229910020220 Pb—Sn Inorganic materials 0.000 description 1
- UCKMPCXJQFINFW-UHFFFAOYSA-N Sulphide Chemical compound [S-2] UCKMPCXJQFINFW-UHFFFAOYSA-N 0.000 description 1
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N Titan oxide Chemical compound O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 description 1
- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical compound [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 description 1
- 229910021536 Zeolite Inorganic materials 0.000 description 1
- HCHKCACWOHOZIP-UHFFFAOYSA-N Zinc Chemical compound [Zn] HCHKCACWOHOZIP-UHFFFAOYSA-N 0.000 description 1
- MCMNRKCIXSYSNV-UHFFFAOYSA-N Zirconium dioxide Chemical compound O=[Zr]=O MCMNRKCIXSYSNV-UHFFFAOYSA-N 0.000 description 1
- NKYPKBBGEBTDFQ-UHFFFAOYSA-M [N+](=O)([O-])C1=C(C(=C(C=C1)[O-])[N+](=O)[O-])[N+](=O)[O-].[Ag+] Chemical compound [N+](=O)([O-])C1=C(C(=C(C=C1)[O-])[N+](=O)[O-])[N+](=O)[O-].[Ag+] NKYPKBBGEBTDFQ-UHFFFAOYSA-M 0.000 description 1
- 125000002777 acetyl group Chemical group [H]C([H])([H])C(*)=O 0.000 description 1
- 230000002378 acidificating effect Effects 0.000 description 1
- 150000007513 acids Chemical class 0.000 description 1
- 230000002411 adverse Effects 0.000 description 1
- 125000002947 alkylene group Chemical group 0.000 description 1
- 229940024548 aluminum oxide Drugs 0.000 description 1
- NEHMKBQYUWJMIP-UHFFFAOYSA-N anhydrous methyl chloride Natural products ClC NEHMKBQYUWJMIP-UHFFFAOYSA-N 0.000 description 1
- 229910052786 argon Inorganic materials 0.000 description 1
- 150000004945 aromatic hydrocarbons Chemical class 0.000 description 1
- 229910052788 barium Inorganic materials 0.000 description 1
- 229910052728 basic metal Inorganic materials 0.000 description 1
- 150000003818 basic metals Chemical class 0.000 description 1
- 125000001797 benzyl group Chemical group [H]C1=C([H])C([H])=C(C([H])=C1[H])C([H])([H])* 0.000 description 1
- JKJWYKGYGWOAHT-UHFFFAOYSA-N bis(prop-2-enyl) carbonate Chemical group C=CCOC(=O)OCC=C JKJWYKGYGWOAHT-UHFFFAOYSA-N 0.000 description 1
- 125000004799 bromophenyl group Chemical group 0.000 description 1
- 125000004369 butenyl group Chemical group C(=CCC)* 0.000 description 1
- YFNONBGXNFCTMM-UHFFFAOYSA-N butoxybenzene Chemical group CCCCOC1=CC=CC=C1 YFNONBGXNFCTMM-UHFFFAOYSA-N 0.000 description 1
- DFFDSQBEGQFJJU-UHFFFAOYSA-N butyl hydrogen carbonate Chemical compound CCCCOC(O)=O DFFDSQBEGQFJJU-UHFFFAOYSA-N 0.000 description 1
- CMIUEWSUNAYXCG-UHFFFAOYSA-N butyl phenyl carbonate Chemical compound CCCCOC(=O)OC1=CC=CC=C1 CMIUEWSUNAYXCG-UHFFFAOYSA-N 0.000 description 1
- 125000004432 carbon atom Chemical group C* 0.000 description 1
- 235000011089 carbon dioxide Nutrition 0.000 description 1
- 150000004649 carbonic acid derivatives Chemical class 0.000 description 1
- 150000004651 carbonic acid esters Chemical class 0.000 description 1
- AIRSESVNOIUYQR-UHFFFAOYSA-N carbonic acid pentylbenzene Chemical compound C(CCCC)C1=CC=CC=C1.C(O)(O)=O AIRSESVNOIUYQR-UHFFFAOYSA-N 0.000 description 1
- MIURHJCJPVLLHQ-UHFFFAOYSA-N carbonic acid;chloromethane Chemical compound ClC.OC(O)=O MIURHJCJPVLLHQ-UHFFFAOYSA-N 0.000 description 1
- 239000007810 chemical reaction solvent Substances 0.000 description 1
- 239000003795 chemical substances by application Substances 0.000 description 1
- ZKXWKVVCCTZOLD-FDGPNNRMSA-N copper;(z)-4-hydroxypent-3-en-2-one Chemical compound [Cu].C\C(O)=C\C(C)=O.C\C(O)=C\C(C)=O ZKXWKVVCCTZOLD-FDGPNNRMSA-N 0.000 description 1
- SVOAENZIOKPANY-UHFFFAOYSA-L copper;octadec-9-enoate Chemical compound [Cu+2].CCCCCCCCC=CCCCCCCCC([O-])=O.CCCCCCCCC=CCCCCCCCC([O-])=O SVOAENZIOKPANY-UHFFFAOYSA-L 0.000 description 1
- 238000002425 crystallisation Methods 0.000 description 1
- 230000008025 crystallization Effects 0.000 description 1
- 125000000753 cycloalkyl group Chemical group 0.000 description 1
- 125000001995 cyclobutyl group Chemical group [H]C1([H])C([H])([H])C([H])(*)C1([H])[H] 0.000 description 1
- 125000004210 cyclohexylmethyl group Chemical group [H]C([H])(*)C1([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C1([H])[H] 0.000 description 1
- 125000001511 cyclopentyl group Chemical group [H]C1([H])C([H])([H])C([H])([H])C([H])(*)C1([H])[H] 0.000 description 1
- 125000001559 cyclopropyl group Chemical group [H]C1([H])C([H])([H])C1([H])* 0.000 description 1
- 230000006837 decompression Effects 0.000 description 1
- 125000002704 decyl group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])* 0.000 description 1
- 238000003795 desorption Methods 0.000 description 1
- QLVWOKQMDLQXNN-UHFFFAOYSA-N dibutyl carbonate Chemical compound CCCCOC(=O)OCCCC QLVWOKQMDLQXNN-UHFFFAOYSA-N 0.000 description 1
- 125000004188 dichlorophenyl group Chemical group 0.000 description 1
- ZEBJPYUECLCDRQ-UHFFFAOYSA-N didecyl carbonate Chemical compound CCCCCCCCCCOC(=O)OCCCCCCCCCC ZEBJPYUECLCDRQ-UHFFFAOYSA-N 0.000 description 1
- 125000006182 dimethyl benzyl group Chemical group 0.000 description 1
- PKPOVTYZGGYDIJ-UHFFFAOYSA-N dioctyl carbonate Chemical compound CCCCCCCCOC(=O)OCCCCCCCC PKPOVTYZGGYDIJ-UHFFFAOYSA-N 0.000 description 1
- HNPSIPDUKPIQMN-UHFFFAOYSA-N dioxosilane;oxo(oxoalumanyloxy)alumane Chemical compound O=[Si]=O.O=[Al]O[Al]=O HNPSIPDUKPIQMN-UHFFFAOYSA-N 0.000 description 1
- TVUBDAUPRIFHFN-UHFFFAOYSA-N dioxosilane;oxygen(2-);titanium(4+) Chemical compound [O-2].[O-2].[Ti+4].O=[Si]=O TVUBDAUPRIFHFN-UHFFFAOYSA-N 0.000 description 1
- HSNQKJVQUFYBBY-UHFFFAOYSA-N dipentyl carbonate Chemical compound CCCCCOC(=O)OCCCCC HSNQKJVQUFYBBY-UHFFFAOYSA-N 0.000 description 1
- VUPKGFBOKBGHFZ-UHFFFAOYSA-N dipropyl carbonate Chemical compound CCCOC(=O)OCCC VUPKGFBOKBGHFZ-UHFFFAOYSA-N 0.000 description 1
- 238000001035 drying Methods 0.000 description 1
- 125000001495 ethyl group Chemical group [H]C([H])([H])C([H])([H])* 0.000 description 1
- JBTWLSYIZRCDFO-UHFFFAOYSA-N ethyl methyl carbonate Chemical compound CCOC(=O)OC JBTWLSYIZRCDFO-UHFFFAOYSA-N 0.000 description 1
- 230000008020 evaporation Effects 0.000 description 1
- 125000001207 fluorophenyl group Chemical group 0.000 description 1
- 238000004508 fractional distillation Methods 0.000 description 1
- 239000012634 fragment Substances 0.000 description 1
- 238000002309 gasification Methods 0.000 description 1
- 239000011521 glass Substances 0.000 description 1
- JMANVNJQNLATNU-UHFFFAOYSA-N glycolonitrile Natural products N#CC#N JMANVNJQNLATNU-UHFFFAOYSA-N 0.000 description 1
- 239000001307 helium Substances 0.000 description 1
- 229910052734 helium Inorganic materials 0.000 description 1
- SWQJXJOGLNCZEY-UHFFFAOYSA-N helium atom Chemical compound [He] SWQJXJOGLNCZEY-UHFFFAOYSA-N 0.000 description 1
- QEEKDIUXTJLWMX-UHFFFAOYSA-N heptyl phenyl carbonate Chemical compound CCCCCCCOC(=O)OC1=CC=CC=C1 QEEKDIUXTJLWMX-UHFFFAOYSA-N 0.000 description 1
- 125000001072 heteroaryl group Chemical group 0.000 description 1
- 125000004051 hexyl group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])* 0.000 description 1
- LNLXSADGXCRMIV-UHFFFAOYSA-N hexyl phenyl carbonate Chemical compound CCCCCCOC(=O)OC1=CC=CC=C1 LNLXSADGXCRMIV-UHFFFAOYSA-N 0.000 description 1
- 229930195733 hydrocarbon Natural products 0.000 description 1
- 239000001257 hydrogen Substances 0.000 description 1
- 229910052739 hydrogen Inorganic materials 0.000 description 1
- 150000002440 hydroxy compounds Chemical class 0.000 description 1
- 229910052500 inorganic mineral Inorganic materials 0.000 description 1
- 229910052745 lead Inorganic materials 0.000 description 1
- 229910052981 lead sulfide Inorganic materials 0.000 description 1
- 239000003446 ligand Substances 0.000 description 1
- 239000011344 liquid material Substances 0.000 description 1
- 230000014759 maintenance of location Effects 0.000 description 1
- 229960003505 mequinol Drugs 0.000 description 1
- LVWZTYCIRDMTEY-UHFFFAOYSA-N metamizole Chemical class O=C1C(N(CS(O)(=O)=O)C)=C(C)N(C)N1C1=CC=CC=C1 LVWZTYCIRDMTEY-UHFFFAOYSA-N 0.000 description 1
- 125000001160 methoxycarbonyl group Chemical group [H]C([H])([H])OC(*)=O 0.000 description 1
- QJWHNEPTWBAGED-UHFFFAOYSA-N methyl (2-nitrophenyl) carbonate Chemical compound COC(=O)OC1=CC=CC=C1[N+]([O-])=O QJWHNEPTWBAGED-UHFFFAOYSA-N 0.000 description 1
- 125000006178 methyl benzyl group Chemical group 0.000 description 1
- 125000005911 methyl carbonate group Chemical class 0.000 description 1
- YAQMLOLRWFBMJL-UHFFFAOYSA-N methyl naphthalen-1-yl carbonate Chemical compound C1=CC=C2C(OC(=O)OC)=CC=CC2=C1 YAQMLOLRWFBMJL-UHFFFAOYSA-N 0.000 description 1
- 239000011707 mineral Substances 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 229910052750 molybdenum Inorganic materials 0.000 description 1
- CQDGTJPVBWZJAZ-UHFFFAOYSA-N monoethyl carbonate Chemical compound CCOC(O)=O CQDGTJPVBWZJAZ-UHFFFAOYSA-N 0.000 description 1
- 125000000740 n-pentyl group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])* 0.000 description 1
- NXPPAOGUKPJVDI-UHFFFAOYSA-N naphthalene-1,2-diol Chemical compound C1=CC=CC2=C(O)C(O)=CC=C21 NXPPAOGUKPJVDI-UHFFFAOYSA-N 0.000 description 1
- 125000001400 nonyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 description 1
- 125000002347 octyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 description 1
- SISIHJVIARPYCK-UHFFFAOYSA-N octyl phenyl carbonate Chemical compound CCCCCCCCOC(=O)OC1=CC=CC=C1 SISIHJVIARPYCK-UHFFFAOYSA-N 0.000 description 1
- TWNQGVIAIRXVLR-UHFFFAOYSA-N oxo(oxoalumanyloxy)alumane Chemical compound O=[Al]O[Al]=O TWNQGVIAIRXVLR-UHFFFAOYSA-N 0.000 description 1
- TZMFJUDUGYTVRY-UHFFFAOYSA-N pentane-2,3-dione Chemical compound CCC(=O)C(C)=O TZMFJUDUGYTVRY-UHFFFAOYSA-N 0.000 description 1
- JQQSUOJIMKJQHS-UHFFFAOYSA-N pentaphenyl group Chemical group C1=CC=CC2=CC3=CC=C4C=C5C=CC=CC5=CC4=C3C=C12 JQQSUOJIMKJQHS-UHFFFAOYSA-N 0.000 description 1
- 125000001147 pentyl group Chemical group C(CCCC)* 0.000 description 1
- 150000002989 phenols Chemical class 0.000 description 1
- ORUWSEKEVGOAQR-UHFFFAOYSA-N phenyl prop-2-enyl carbonate Chemical compound C=CCOC(=O)OC1=CC=CC=C1 ORUWSEKEVGOAQR-UHFFFAOYSA-N 0.000 description 1
- CHWRSCGUEQEHOH-UHFFFAOYSA-N potassium oxide Chemical compound [O-2].[K+].[K+] CHWRSCGUEQEHOH-UHFFFAOYSA-N 0.000 description 1
- 229910001950 potassium oxide Inorganic materials 0.000 description 1
- 238000012545 processing Methods 0.000 description 1
- 125000001436 propyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])[H] 0.000 description 1
- FOWDZVNRQHPXDO-UHFFFAOYSA-N propyl hydrogen carbonate Chemical compound CCCOC(O)=O FOWDZVNRQHPXDO-UHFFFAOYSA-N 0.000 description 1
- 238000000746 purification Methods 0.000 description 1
- NYNWIVKBKRXPTH-UHFFFAOYSA-N pyridin-2-ylmethyl hydrogen carbonate Chemical compound OC(=O)OCC1=CC=CC=N1 NYNWIVKBKRXPTH-UHFFFAOYSA-N 0.000 description 1
- 125000004076 pyridyl group Chemical group 0.000 description 1
- 238000012797 qualification Methods 0.000 description 1
- 125000005493 quinolyl group Chemical group 0.000 description 1
- 150000003254 radicals Chemical class 0.000 description 1
- 229910001404 rare earth metal oxide Inorganic materials 0.000 description 1
- 230000035484 reaction time Effects 0.000 description 1
- 238000000066 reactive distillation Methods 0.000 description 1
- 230000003134 recirculating effect Effects 0.000 description 1
- 238000011084 recovery Methods 0.000 description 1
- 230000002441 reversible effect Effects 0.000 description 1
- 229960001866 silicon dioxide Drugs 0.000 description 1
- 235000012239 silicon dioxide Nutrition 0.000 description 1
- 239000000377 silicon dioxide Substances 0.000 description 1
- ADZWSOLPGZMUMY-UHFFFAOYSA-M silver bromide Chemical compound [Ag]Br ADZWSOLPGZMUMY-UHFFFAOYSA-M 0.000 description 1
- 229910052708 sodium Inorganic materials 0.000 description 1
- 239000007787 solid Substances 0.000 description 1
- 230000002459 sustained effect Effects 0.000 description 1
- 238000012360 testing method Methods 0.000 description 1
- 229910052718 tin Inorganic materials 0.000 description 1
- 229960005196 titanium dioxide Drugs 0.000 description 1
- OGIDPMRJRNCKJF-UHFFFAOYSA-N titanium oxide Inorganic materials [Ti]=O OGIDPMRJRNCKJF-UHFFFAOYSA-N 0.000 description 1
- 125000003944 tolyl group Chemical group 0.000 description 1
- 238000012546 transfer Methods 0.000 description 1
- 229910052723 transition metal Inorganic materials 0.000 description 1
- 150000003624 transition metals Chemical class 0.000 description 1
- 150000003739 xylenols Chemical class 0.000 description 1
- 125000005023 xylyl group Chemical group 0.000 description 1
- 239000010457 zeolite Substances 0.000 description 1
- 239000011701 zinc Substances 0.000 description 1
- 239000011787 zinc oxide Substances 0.000 description 1
- 150000003755 zirconium compounds Chemical class 0.000 description 1
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Abstract
Dialkyl carbonate in aromatic carbonate of the present invention or its mixture process for continuously producing, carbonate alkyl aryl ester or its mixture material and aromatic hydroxy compound, carbonate alkyl aryl ester or its mixture reaction thing are sent into continuously in the continuous multi-stage distillation tower and carry out transesterification under catalyzer are existed, take out liquid high boiling point continuously from the tower bottom simultaneously, aryl carbonates or its mixture product are taken out low-boiling by-products from the continuous still battery of tower top.The inventive method can be high-speed, and highly selective and high yield are made continuously and need not be made poly carbonate aryl ester or the required aryl carbonates raw material of various isocyanic ester etc. by poisonous phosgene.
Description
The present invention relates to process for preparing aromatic carbonate.More particularly, the present invention relates to the continuous high-efficient manufacture method of aryl carbonates or its mixture, wherein with formula
Dialkyl carbonate, formula
Carbonate alkyl aryl ester or its mixture material and formula Ar
1The aromatic hydroxy compound of OH
Carbonate alkyl aryl ester or its mixture reaction thing carry out transesterification and make with raw material and reactant corresponding
(R and Ar are selected from the R corresponding to raw material and reactant respectively for aryl carbonates or its mixture
1, R
2, R
3And Ar
1, Ar
2, Ar
3), the present invention sends into raw material and reactant in the continuous multi-stage distillation tower continuously, in this distillation tower, in the presence of catalyzer, carry out transesterification, take out liquid aryl carbonates or its mixture high boiling point product simultaneously from this distillation tower bottom continuously and take out the gaseous state low-boiling by-products from this distillation tower top continuous still battery.
Aryl carbonates in recent years as need not be poisonous phosgene make purposes very widely the poly carbonate aryl ester engineering plastics raw material or need not poisonous phosgene make the raw material of various isocyanic ester.Known available dialkyl carbonate, carbonate alkyl aryl ester or its mixture material and aromatic hydroxy compound, carbonate alkyl aryl ester or its mixture reaction thing carry out transesterification and get the corresponding aryl carbonates or the aryl carbonates manufacture method of its mixture.
But these transesterifications are balanced reaction, and this balance is partial to feed system one side again, so be difficult to become industrially preparing process because of speed of response makes this aryl carbonates manufacture method slowly.
For improving this method, many schemes have been proposed, wherein major part is related to the catalyzer that improves speed of response and develop.Dialkyl carbonate and aromatic hydroxy compound are being reacted and make carbonate alkyl aryl ester, in the method for diaryl carbonate or its mixture, catalyzer for example Louis such as available transition metal halide maybe can form lewis acidic compound (spy of Japan opens clear 51-105032 communique, the spy opens clear 56-123948 communique, the spy opens clear 56-123949 communique (No. the 2528412nd, the open communique of Deutsches Reichs-Patent application, No. 1499530 specification sheets of English Patent, No. 4182726 specification sheets of United States Patent (USP))), (spy of Japan opens clear 54-48733 communique (No. the 2736062nd, the open communique of Deutsches Reichs-Patent application) to tin compounds such as organotin alkoxide and organotin oxides, the spy opens clear 54-63023 communique, the spy opens clear 60-169444 communique (No. 4554110 specification sheets of United States Patent (USP)), the spy of Japan opens clear 60-169445 communique (No. 4552704 specification sheets of United States Patent (USP)), the spy of Japan opens clear 62-277345 communique, Te Kaiping 1-265063 communique), basic metal or alkaline earth salt and alkoxide (spy of Japan opens clear 56-25138 communique), lead compound (spy of Japan opens clear 57-176932 communique), copper, iron, metal complexes such as zirconium (spy of Japan opens clear 57-183745 communique), titanic acid ester (spy of Japan opens clear 58-185536 communique (No. 4410464 specification sheets of United States Patent (USP))), the mixture of Lewis acid and protonic acid (spy of Japan opens clear 60-173016 communique (seeing No. 4609501 specification sheets of United States Patent (USP))), Sc, Mo, Mn, Bi, the compound of Te etc. (spy of Japan opens flat 1-265064 communique) and ironic acetate (spy of Japan opens clear 61-172852 communique) etc.
In addition, in that intermolecular transesterification of the same race is made in the method for diaryl carbonate diaryl carbonate and the non-homogenizing of dialkyl carbonate by carbonate alkyl aryl ester, (spy of Japan opens clear 51-75044 communique (No. the 2552907th, the open communique of Deutsches Reichs-Patent application to for example available Lewis acid of catalyzer with producing lewis acidic transistion metal compound, United States Patent (USP) the 4045464th specification sheets)), polymerizability tin compound (spy of Japan opens clear 60-169444 communique (No. 4554110 specification sheets of United States Patent (USP))), OH(X is selected from Sn and Ti likes R-X(=O), R is selected from 1 valency alkyl) compound (spy of Japan opens clear 60-169445 communique (No. 4552704 specification sheets of United States Patent (USP))), the mixture of Lewis acid and protonic acid (spy of Japan opens clear 60-173016 communique (No. 4609501 specification sheetss of United States Patent (USP))), plumbous catalyzer (spy of Japan opens flat 1-93560 communique), titanium and zirconium compounds (spy of Japan opens flat 1-265062 communique), (spy of Japan opens flat 1-265063 communique, Sc to tin compound, Mo, Mn, Bi, the compound of Te etc. (spy of Japan opens flat 1-265064 communique) etc.
But, in the method for the catalyzer that uses these kinds, can not improve speed of response effectively, therefore can not be and highly selective and make aryl carbonates with high yield through the reaction of short period of time.
For the yield of the aryl carbonates that makes these reactions improves, also carried out other test, balance is moved to the product direction as far as possible.This method is when making aryl carbonates with dialkyl carbonate and aromatic hydroxy compound, (spy of Japan opens clear 54-48732 communique (No. the 2736063rd, the open communique of Deutsches Reichs-Patent application) when for example having been proposed in methylcarbonate with phenol reactant by-product methanol and azeotropic to be formed the method that the agent component distillation removes, the spy of Japan opens clear 61-291545 communique), the method (spy of Japan opens clear 58-185536 communique (No. 410464 specification sheets of United States Patent (USP))) of removing with the molecular sieve adsorption by-product methanol.
But, in the method for Japanese kokai publication sho 54-48732 communique, must carry out the complex operations of Separation and Recovery from azeotropic mixture as a large amount of heptane that use of entrainer.In addition, in this method, be as the criterion with the phenol of sending into, after long-time reaction in 45 hours, the aryl carbonates yield only is 3.5%.
In addition, open in the described method of clear 58-185536 communique the spy of Japan, except that must in the 1g by-product methanol, adding a large amount of molecular sieve of 8-10g, the complicated technology of the methyl alcohol desorption of the molecular sieve adsorption of making also must be arranged.
Therefore, these methods are difficult in industrial enforcement.
And, up to the present in the foregoing invention of Ti Chuing, reactive mode is preferably, for separating to distill from the solvent of raw material or product or coexistence, removes the pure by product in will reacting, knownly can be provided with distillation or the device of fractional distillation functions tower on reactor top (spy of Japan opens clear 56-123948 communique (No. 4182726 specification sheets of United States Patent (USP)), the spy opens clear 56-25138 communique, the spy opens clear 60-169444 communique (No. 4554110 specification sheets of United States Patent (USP)), the spy opens clear 60-169445 communique (No. 4552704 specification sheets of United States Patent (USP)), the spy opens clear 60-173016 communique (No. 4609501 specification sheets of United States Patent (USP)), the spy opens clear 61-172852 communique, the spy opens clear 61-291545 communique, and the spy opens clear 62-277345 communique).
But in these methods, reaction all needs to carry out in the reactor that has catalyzer to exist.Therefore, the distillation tower part that reactor top is provided with only is used for other component separating of existing in the alcohol that will generate in the reactor and the reactor, this can open the content that clear 61-291545 communique describes in detail from the spy of Japan and be clear that, for example this communique is pointed out, " in the reaction of this class; adopt the reaction distillation method usually; wherein in the reactor; react in the tower bottom reactor of reaction distillation distillation tower being set and taking on one side, in top of tower from the carbonic ether that generate distillation remove lower boiling methyl alcohol on one side " (right hurdle 12-17 is capable for this communique page 1).
That is to say that the device that the reaction distillation of these existing methods adopts reactive moieties and distillation fraction to exist respectively only distills in the distillation tower part, does not react.Therefore, in the existing method, be reflected in the liquid phase in the reactor and carry out, only make the low-boiling point alcohol by product then enter gas phase through liquid-gas interface from liquid phase, the balance of reaction could be to the product side shifting, and reaction also just can go on.The reactor that these methods are used is grooved, amass for reactor section because liquid-gas interface is long-pending, smaller, well imagine that reaction is very slow, for example open the embodiment and special the opening among the embodiment of clear 54-48732 communique and the clear 54-48733 communique of Te Kai of clear 61-291545 communique the spy of Japan, intermittent reaction want sustained reaction 8-45 hour long-time like this.In so long reaction method, not only easily cause the side reaction of raw material and intermediate, but also easily make aryl carbonates generation side reaction that in addition, selectivity is low.The result is that so long reaction method yields poorly, and is difficult in industrial enforcement.
And, be referred to as in the method for reaction distillation up to the present using existence respectively part of reacting and the device that carries out the distillatory part, the spy of Japan opens clear 61-291545 communique and (points out during page 3 lower-left hurdle 4-9 is capable, " reaction distillation operation can intermittently or be carried out continuously; when methylcarbonate and phenol are carried out transesterification; need main equipment because of its speed of response is slow when carrying out continuously, so preferably take the mode of intermittently carrying out." in fact; in the described whole embodiment of aforementioned various communiques that up to the present propose; dialkyl carbonate and aromatic hydroxy compound two reaction reagents react with the catalyzer reactor of packing into simultaneously; perhaps its a kind of reaction reagent (being generally the high boiling point aromatic hydroxy compound) is sent into reactor simultaneously with catalyzer; and infeed the method that another kind of reaction reagent reacts simultaneously, all are intermittent modes in a word.Therefore, up to the present, just do not propose two reaction reagents are sent into continuously at all, take out the successive reaction mode of product simultaneously continuously.
In this case, the inventor furthers investigate, the result shockingly finds to develop the shortcoming of the above-mentioned the whole bag of tricks that does not up to the present propose, and can high speed of response, highly selective is made the method for aryl carbonates continuously, wherein raw material and reactant are sent in the continuous multi-stage distillation tower continuously, in this distillation tower in the transesterification that carries out in the presence of the catalyzer between two materials, take out liquid aryl carbonates or its mixture high boiling point product simultaneously continuously from this distillation tower bottom, and take out low-boiling by-products from this distillation tower top continuous still battery simultaneously, but therefore can high speed of response highly selective and continuous high-efficient rate ground manufacturing aryl carbonates or its mixture.But also find, many continuous multi-stage distillation towers can be made up and made high boiling point product and/or low-boiling products recirculation dexterously, but the therefore efficient highland desired aryl carbonates that obtains of manufacturing or its mixture continuously more.
The present invention promptly is found to be the basis with these and finishes.
Therefore, the present invention seeks to propose can high speed of response, but the method for aryl carbonates is made on highly selective and continuous high-efficient rate ground, wherein uses the continuous multi-stage distillation tower as reaction tower.
Another purpose of the present invention is propose to use many continuous multi-stage distillation towers and efficient is more made the method for the desired aryl carbonates that obtains in the highland.
That is to say, according to basic embodiment of the present invention, be the method that proposes to make continuously aryl carbonates or its mixture, wherein will be selected from formula
Dialkyl carbonate, formula
Carbonate alkyl aryl ester and composition thereof raw material and be selected from formula Ar
1The aromatic hydroxy compound of OH, formula
The reactant (R wherein of carbonate alkyl aryl ester and composition thereof
1, R
2And R
3Be respectively 1-10 carbon alkyl, 3-10 carbon alicyclic radical or 6-10 carbon aralkyl, Ar
1, Ar
2And Ar
3Be respectively 5-30 carbon aryl) carry out transesterification, make the formula corresponding with raw material and reactant
Aryl carbonates or its mixture (wherein R and Ar are selected from the R corresponding with raw material and reactant respectively
1, R
2, R
3And Ar
1, Ar
2, Ar
3), obtain simultaneously the formula ROH corresponding with raw material and reactant and/or
The Fatty Alcohol(C12-C14 and C12-C18) of (R is above-mentioned definition), dialkyl carbonate or its mixture by product, it is characterized in that in this distillation tower in making liquid phase or solution-air carry out transesterification between two materials mutually in the presence of the catalyzer, take out the liquid high boiling point reaction mixture that contains aryl carbonates or its mixture simultaneously from this distillation tower bottom continuously, and take out the gaseous low boiling point reaction mixture that contains by product from this distillation tower top continuous still battery simultaneously.
The reaction that comprises in the inventive method is as follows:
(R
1, R
2, R
3And Ar
1, Ar
2, Ar
3Be above-mentioned definition.Each Ar is respectively Ar in the formula (4)
2Or Ar
3, each R is respectively R
2Or R
3In the formula (4), if R
2=R
3, Ar
2=Ar
3, then reaction is intermolecular transesterification of the same race, is referred to as non-homogenizing reaction usually).
When the inventive method is characterised in that and carries out these reactions in the presence of catalyzer in the continuous multi-stage distillation tower, the low-boiling products that reaction generates is separated from reaction system through distillation, but uses this method highly selective, make aryl carbonates continuously expeditiously.
According to the method, balance extremely is partial to the present invention reaction of material system (for example, formula (1) equilibrium constant of reaction is 10
-3-10
-4About) can high speed of response carry out, therefore can be continuously and highly selective is made aryl carbonates expeditiously, this is beat all fully.
Compare with existing method, speed of response is fast in the inventive method, and selectivity and yield (or output) can improve again greatly, and this is beat all fully, and reason is also not too bright accurately for it, and result of implementation that can the inventive method is made following deduction for the basis.
That is to say that aforementioned formula (1)-(4) are balanced reaction, and its balance is partial to material system terrifically.Therefore, no matter in which reaction, improve reactivity, just the low-boiling by-products that reaction must be generated (being generally the Fatty Alcohol(C12-C14 and C12-C18) in the reaction of formula (1) and (2), the dialkyl carbonate of formula (3) and (4) reaction) is removed from the liquid phase of reaction system as quickly as possible.
But, as described in above-mentioned various communiques of the prior art, can not improve speed of response in the reactive mode that the reactor that application distillation tower top is provided with carries out.Wherein, not only reaction zone only limits to the reactor part that catalyzer exists, and will react the low-boiling by-products that generates is distilled into gas phase from the liquid of reactor part liquid-gas interface and amass also very little.
On the contrary, make catalyzer be present in the interior vast scope of continuous multi-stage distillation tower in the inventive method, therefore can make its liquid-gas interface long-pending very big, reaction just can be carried out in vast zone.In these zones, the steam of sending to the fluent meterial of reaction and the ascension that makes progress from the below carries out gas-to-liquid contact repeatedly, is carrying out distillatory simultaneously, and the limit coronite flows downward.At this moment, low-boiling products is evaporated from liquid phase and is entered gas phase.The result makes inner each composition of continuous multi-stage distillation tower reach finite concentration to distribute.For example, when the reaction of formula (1) and (2) is carried out, from the high-order bit that has that catalyzer exists to the tower bottom, high boiling point product carbonate alkyl aryl ester and/or the diaryl carbonate concentration distribution in liquid increases progressively usually successively, and from tower top to the tower bottom, the concentration distribution of low-boiling products Fatty Alcohol(C12-C14 and C12-C18) in liquid then successively decreased usually successively, and concentration may be very low in this liquid near the tower bottom.On the other hand, to tower top, the concentration distribution of Fatty Alcohol(C12-C14 and C12-C18) in vapor phase then increases progressively successively from the tower bottom.
In addition, when for example the reaction of formula (3) and (4) is carried out, from the high-order bit that has that catalyzer exists to the tower bottom, the concentration distribution of high boiling point product diaryl carbonate in liquid increases progressively usually successively, and from tower top to the tower bottom, the concentration distribution of low-boiling products dialkyl carbonate in liquid then successively decreased usually successively, and concentration may be very low in this liquid near the tower bottom.On the other hand, to tower top, the concentration distribution of dialkyl carbonate in vapor phase then increases progressively successively from the tower bottom.
In the inventive method, these are reflected in this continuous multi-stage distillation tower and carry out, consider with the optional position in its conversion zone, as the liquid phase in the reaction system, the result of reaction is under the state that is close to equilibrium composition it, can think that it consists of the composition under the vapor liquid equilibrium state of vapor phase and liquid phase correspondence.Therefore, liquid phase is at this position stopped reaction, more than this, do not react, and in fact, liquid phase is constantly to dirty, the low vapor phase of lower boiling reaction product concentration is reacted when carrying out gas-to-liquid contact again, and the concentration of high boiling point product aryl carbonates can further improve again in the liquid phase simultaneously.
And in the existing method of in the reactor that distillation tower top is provided with, reacting, reaction is only carried out in reactor, distillation tower will separate with lower boiling starting compound steam from the low-boiling products steam that enters gas phase after liquid-gas interface comes out in the reactor simply, and make the lower boiling starting compound with liquid state to dirty, be nothing but to play the effect of returning reactor.
Therefore, compare with existing method, the inventive method is that excellent effect is arranged, can think its major cause have following some.
(1) compares with the reaction formation of application response still, can make that liquid-gas interface is long-pending to reach very big, low-boiling by-products is moved to the mass transfer of vapor phase become easily.
(2) liquid phase of continuous multi-stage distillation tower internal reaction system is carried out gas-to-liquid contact repeatedly with the steam of the ascension that makes progress from the below, and the limit coronite is to dirty.Therefore, not only can carry out continuously, and can improve reactivity between raw material and the reactant (and among the existing method of application response still, when carrying out operate continuously if take out aryl carbonates purpose compound continuously, just be difficult to improve the reactivity of starting compound, in fact, the up to the present basic method that does not just have to propose continuous enforcement.In this method, improve reactivity, just must react for a long time with intermittent mode.）
(3) steam that rises in the continuous multi-stage distillation tower, with dropping liq repeatedly carry out gas-to-liquid contact on one side, rise on one side.Therefore, the heat energy that steam is possessed is effectively used.
Among the present invention, can use general expression as the dialkyl carbonate of raw material
Expression, wherein R
1Be 1-10 carbon alkyl, 3-10 carbon alicyclic radical, 6-10 carbon aralkyl, for example can enumerate methyl, ethyl, propyl group (each isomer), allyl group, butyl (each isomer), butenyl (each isomer), amyl group (each isomer), hexyl (each isomer), heptyl (each isomer), octyl group (each isomer), nonyl (each isomer), decyl (each isomer), alkyl such as cyclohexyl methyl; Cyclopropyl, cyclobutyl, cyclopentyl, cyclohexyl, alicyclic radicals such as suberyl; Benzyl, styroyl (each isomer), methyl-benzyl (each isomer), hydrocinnamyl, aralkyl such as benzene butyl.
And, at these alkyl, alicyclic radical, carbonatoms is no more than 10 in the aralkyl, and available other substituting group, low alkyl group for example, lower alkoxy, lower alkoxy, cyano group, halogen atom replaces, and can contain unsaturated link(age) in addition.
As containing this R
1Dialkyl carbonate, for example can enumerate methylcarbonate, diethyl carbonate, dipropyl carbonate (each isomer), carbonic acid diallyl, carbonic acid dibutene ester (each isomer), dibutyl carbonate (each isomer), diamyl carbonate (each isomer), carbonic acid dihexyl (each isomer), carbonic acid two heptyl esters (each isomer), carbonic acid dioctyl ester (each isomer), carbonic acid ester in two ninth of the ten Heavenly Stems (each isomer), carbonic acid didecyl ester (each isomer), carbonic acid two ring pentyl esters, carbonic acid two cyclohexyls, carbonic acid two ring heptyl esters, dipheryl carbonate ethyl ester (each isomer), dipheryl carbonate propyl ester (each isomer), dipheryl carbonate butyl ester (each isomer), carbonic acid benzyl dichloride ester (each isomer), carbonic acid dimethoxy benzyl ester (each isomer), carbonic acid dimethoxy methyl esters, carbonic acid dimethoxy ethyl ester (each isomer), carbonic acid dichloro ethyl ester (each isomer), carbonic acid dicyan ethyl ester (each isomer), dimethyl benzyl etc.
In these dialkyl carbonates, R preferably
1Be selected from the dialkyl carbonate of the following low alkyl group of 4 carbon, be more preferably methylcarbonate.
In addition, among the present invention, can use general expression Ar as the aromatic hydroxy compound of reactant
1OH represents (Ar
1Be 5-30 carbon aryl), if directly connect hydroxyl on the aryl, then no matter which kind of all can.As this Ar
1, for example can enumerate phenyl, tolyl (each isomer), xylyl (each isomer), trimethylphenyl (each isomer), tetramethylphenyl (each isomer), ethylbenzene base (each isomer), propyl phenyl (each isomer), butylbenzene base (each isomer), diethyl phenyl (each isomer), methylethyl phenyl (each isomer), penta phenyl (each isomer), own phenyl (each isomer), hexamethylene phenyl phenyl and various alkane phenyl such as (each isomer); Methoxyphenyl (each isomer), phenelyl (each isomer), butoxyphenyl various alkoxyphenyl radicals such as (each isomer); Fluorophenyl (each isomer), chloro-phenyl-(each isomer), bromophenyl (each isomer), chloromethane phenyl (each isomer), dichlorophenyl various halogenophenyls such as (each isomer); Various substituted-phenyls shown in the following formula:
(wherein the direct chain of A or-O-,-S-,-CO-,-SO
2-wait divalent radical or formula
Deng alkylidene group or substituted alkylene (R wherein
4, R
5, R
6, R
7Be respectively hydrogen, low alkyl group, cycloalkyl, aryl or aralkyl, also available in case of necessity halogen atom, alkoxyl group replaces) or following formula shown in encircle alkylidene group:
(wherein K is the integer of 3-11, and hydrogen atom can be used replacements such as low alkyl group, aryl, halogen atom), and the available low alkyl group of aromatic ring, lower alkoxy, ester group, hydroxyl, nitro, halogen, substituting groups such as cyano group replace); Naphthyl (each isomer), first naphthyl (each isomer), diformazan naphthyl (each isomer), chloronaphthyl, methylnaphthyl (each isomer), methoxy-naphthyl (each isomer), cyanogen naphthyl naphthyl and various substituted naphthyls such as (each isomer); Pyridyl (each isomer), tonka-bean base (each isomer), quinolyl (each isomer), picolyl (each isomer), chloropyridine base (each isomer), methylcoumarin base (each isomer), the various replacements such as (each isomer) of toluquinoline base and substituted heteroaryl etc. not.
As having this Ar
1Aromatic hydroxy compound, for example available phenol; Cresylol (each isomer), xylenol (each isomer), front three phenol (each isomer), tetramethyl phenol (each isomer), ethylphenol (each isomer), propyl benzene phenol (each isomer); butylbenzene phenol (each isomer), diethyl phenol (each isomer), first and second phenol (each isomer); first propyl benzene phenol (each isomer); dipropyl phenol (each isomer), first butylbenzene phenol (each isomer), penta phenol (each isomer); own phenol (each isomer), hexamethylene phenol various alkylphenols such as (each isomer); Mequinol (each isomer), guoethol various alcoxyl phenol such as (each isomer); Various fortified phenols shown in the following formula:
(A is with aforementioned); Naphthols (each isomer) and various substituted naphthol; Pyridone (each isomer), Hydroxycoumarin (each isomer), hydroxyquinoline heteroaromatic oxy-compound such as (each isomer) etc.In addition, the also available aromatic hydroxy compound that 2 hydroxyls are arranged, Resorcinol for example, Resorcinol, pyrocatechol, naphthalenediol, oxanthranol and alkyl thereof replace dihydroxy compound; Aromatic dihydroxy compound shown in the following formula:
(wherein A is with aforementioned, and aromatic ring can be used low alkyl group, lower alkoxy, and ester group, nitro, cyano group, substituting groups such as halogen atom replace) etc.
In these aromatic hydroxy compounds, the present invention is Ar preferably
1Be selected from the compound of 6-10 carbon aromatics monohydroxy, more preferably use phenol.
In addition, the carbonate alkyl aryl ester that can be used as raw material of the present invention can be used general expression
Expression, wherein R
2Can with R
1Identical or different, can be 1-10 carbon alkyl, 3-10 carbon alicyclic radical, 6-10 carbon aralkyl, Ar
2Can with Ar
1Identical or different, can be 5-30 carbon aryl.As this R
2, can enumerate and aforementioned R
1Identical base, and Ar
2Also can enumerate and aforementioned Ar
1Identical base.
As having this R
2And Ar
2Carbonate alkyl aryl ester, for example can enumerate carbonic acid aminomethyl phenyl ester, the carbonic acid ethyl phenyl ester, carbonic acid propyl group phenylester (each isomer), carbonic acid allyl phenyl ester, carbonic acid butyl phenyl ester (each isomer), carbonic acid amyl group phenylester (each isomer), carbonic acid hexyl phenylester (each isomer), carbonic acid heptyl phenylester (each isomer), carbonic acid octyl phenyl ester (each isomer), carbonic acid nonyl second phenylester (each isomer), carbonic acid decyl fourth phenylester (each isomer), carbonic acid methyl tolyl ester (each isomer), carbonic acid ethyl tolyl ester (each isomer), carbonic acid propyltoluene base ester (each isomer), carbonic acid butyl toluene base ester (each isomer), carbonic acid allyl group tolyl ester (each isomer), carbonic acid methyl dimethoxy phenylester (each isomer), carbonic acid methyl trimethoxy base base ester (each isomer), carbonic acid methyl chloride phenylester (each isomer), carbonic acid methyl nitrophenyl ester (each isomer), carbonic acid methyl methoxy phenylester (each isomer), carbonic acid methyl isopropyl phenyl ester (each isomer), carbonic acid methyl naphthyl ester (each isomer), carbonic acid picolyl ester (each isomer), carbonic acid ethyl cumyl ester (each isomer), carbonic acid toluyl phenylester (each isomer), carbonic acid ethyl xylyl ester (each isomer), carbonic acid benzyl xylyl ester, carbonic acid methyl hydroxyphenyl ester (each isomer), ethylene oxyphenyl ester (each isomer), methoxycarbonyl xenol (each isomer), carbonic acid methyl Hydroxybiphenyl ester (each isomer), carbonic acid methyl 2-hydroxyphenyl propyl phenyl ester (each isomer), carbonic acid ethyl 2-hydroxyphenyl propyl phenyl ester (each isomer) etc.In these carbonate alkyl aryl esters, preferred R
2Be 1-4 carbon alkyl, Ar
2Be the compound of 6-10 carbon aryl, more preferably adopt carbonic acid aminomethyl phenyl ester.
And can use general expression as reactant carbonate alkyl aryl ester of the present invention
Expression, R
3With R
1, R
2Identical or different, can be 1-10 carbon alkyl, 3-10 carbon alicyclic radical, 6-10 carbon aralkyl, Ar
3With Ar
1, Ar
2Identical or different, can be 5-30 carbon aryl.As this R
3, can enumerate and aforementioned R
1Identical base, and as Ar
3, also can enumerate and aforementioned Ar
1Identical base.
As having this R
3And Ar
3Carbonate alkyl aryl ester, can enumerate with aforementioned
Identical example.
In these carbonate alkyl aryl esters, preferably use R
3Be 1-4 carbon alkyl, Ar
3Be the compound of 6-10 carbon aryl, more preferably adopt carbonic acid aminomethyl phenyl ester.
In the inventive method, carry out formula (1), (2), (3) and (4) are when respectively reacting, dialkyl carbonate and carbonate alkyl aryl ester raw material all available a kind or 2 kinds or multiple using with, and aromatic hydroxy compound and carbonate alkyl aryl ester reactant also available a kind or 2 kinds or multiple using with.
And, shown in the formula (4) in the transesterification, R
2=R
3=R, Ar
2=Ar
3Therefore during=Ar, just becoming between the carbonate alkyl aryl ester molecule of the same race and carry out transesterification, thereby obtain diaryl carbonate and dialkyl carbonate, is method preferably.
In addition, in formula (1)-(4), R
1=R
2=R
3=R and Ar
1=Ar
2=Ar
3During=Ar, the reaction of formula (1)-(4) can be combined, thereby can be that raw material obtains diaryl carbonate through carbonate alkyl aryl ester with dialkyl carbonate and aromatic hydroxy compound by formula (5) and (6), this be the good especially embodiment of the present invention.
If formula (6) reaction gained dialkyl carbonate by product is as the raw material of formula (5) reaction and recirculation, the result is available 1mol dialkyl carbonate and 2mol aromatic hydroxy compound and obtain 1mol diaryl carbonate and 2mol Fatty Alcohol(C12-C14 and C12-C18).
In aforementioned formula (5) and (6), R=CH
3, Ar=C
6H
5The time, with regard to the simplest available dialkyl carbonate, promptly methylcarbonate makes the important diphenyl carbonate that can be used as polycarbonate and isocyanic ester raw material, this point particularly important at an easy rate.
As catalyst for application of the present invention, for example can use:
(lead compound)
PbO, PbO
2, PbO
4In plumbous oxide; PbS, Pb
2Lead sulfide such as S; Pb(OH)
2, Pb
2O
2(OH)
2Deng lead hydroxide; Na
2PbO
2, K
2PbO
2, NaHPbO
2, KHPbO
2, wait plumbite; Na
2PbO
3, Na
2H
2PbO
4, K
2PbO
3, K
2(Pb(OH)
6), K
4PbO
4, Ca
2PbO
4, CaPbO
3Deng plumbite; PbCO
3, 2PbCO
3, Pb(OH)
2Deng lead carbonate and basic salt thereof; Pb(OCOCH
3)
2, Pb(OCOCH
3)
4, Pb(OCOCH
3)
2.PbO.3H
2Organic acid lead salt and carbonate and basic salts such as O; Bu
4Pb, Ph
4Pb, Bu
3PbCl, Ph
3PbBr, Ph
3Pb(or Ph
6Pb
2), Bu
3PbOH, Ph
3Organo-lead compounds such as PbO (Bu is a butyl, and Ph is a phenyl); Pb(OCH
3)
2, (CH
3O) Pb(OPh), Pb(OPh)
2In alkoxyl group lead, aryloxy lead; Pb-Na, Pb-Ca, Pb-Ba, Pb-Sn, lead alloys such as Pb-Sb; Lead glance, the hydrate of lead minerals such as zink sulphide and these lead compounds;
(copper family metallic compound)
CuCl, CuCl
2, CuBr, CuBr
2, CuI, CuI
2, Cu(OAc)
2, Cu(acac)
2, cupric oleate, Bu
2Cu, (CH
3O)
2Cu, AgNO
3, AgBr, silver trinitrophenolate, AgC
6H
6CIO
4, Ag(Block Le バ レ Application)
3NO
3, (AuC ≡ C-C(CH
3)
3) n, (Cu(C
7H
8) Cl)
4Deng copper family metal-salt and ligand (OAc is an ethanoyl, and acac is the methyl ethyl diketone dentate); (alkali metal coordination compound)
Li(acac), LiN(C
4H
9)
2Deng alkali metal coordination compound ((acac) with above-mentioned definition);
(zine coordination compound)
Zn(acac)
2Deng zine coordination compound ((acac) with above-mentioned definition);
(cadmium coordination compound)
Cd(acac)
2Deng cadmium coordination compound ((acac) with above-mentioned definition);
(iron family metal compound)
Fe(C
10H
8) (CO)
5, Fe(CO)
5, Fe(C
3H
6) (CO)
3, Co(
)
2(PEt
2Ph)
2, CoC
5F
5(CO)
2, Ni-π-C
5H
5NO, the two luxuriant iron family metal coordination compoundes such as iron that close;
(zirconium coordination compound)
Zr(acac)
4(, wait the zirconium coordination compound (acac) with above-mentioned definition;
(Lewis acid or Lewis acid form compound)
AlX
3, TiX
3, TiX
4, VOX
3, VX
5, ZnX
2, FeX
3, SnX
4Lewis acids such as (wherein X are a halogen, acetoxyl group, alkoxyl group, aryloxy) and formation Lewis acid transistion metal compound;
(organo-tin compound)
(CH
3)
3SnOCOCH
3, (C
2H
5)
3SnOCOC
6H
5, Bu
3SnOCOCH
3, Ph
3SnOCOCH
3, Bu
2Sn(OCOCH
3)
2, Bu
2Sn(OCOC
11H
23)
2, Ph
3SnOCH
3, (C
2H
5)
3SnOPh, Bu
2Sn(OCH
3)
2, Bu
2Sn(OC
2H
5)
2, Bu
2Sn(OPh)
2, Ph
2Sn(OCH
3)
2, (C
2H
5)
3SnOH, Ph
3SnOH, Bu
2SnO, (C
8H
17)
2SnO, Bu
2SnCl
2, BuSnO(OH) wait organo-tin compound;
(inorganic oxide)
Silicon-dioxide, aluminum oxide, titanium oxide, silicon-dioxide titanium oxide, zinc oxide, zirconium white, potassium oxide, zeolite, inorganic oxides such as rare earth oxide; These inorganic oxides can be through the in addition modification of method such as surperficial silylanizing;
And other.
These catalyzer can dissolve in reaction system, also can not dissolve.And, these catalyzer can with reaction in be the inert compound or carrier mixes, or thereon by carrier band.
Certainly, these catalyzer can be with reaction system in the organic compound that exists, Fatty Alcohol(C12-C14 and C12-C18) for example, aromatic hydroxy compound, carbonate alkyl aryl ester, the material that diaryl carbonate, dialkyl carbonate etc. react, and available raw material and the reactant of sending into reaction in advance, or product is heat-treated.
In these catalyzer, especially preferably use PbO, PbO
2, Pb
3O
4In plumbous oxide; Pb(OH)
2, Pb
2O
2(OH)
2Deng lead hydroxide; PbCO
3, 2PbCO
3Pb(OH)
2Deng lead carbonate and basic salt thereof; Pb(OCH
3)
2, (CH
3O) Pb(OPh), Pb(OPh)
2In alkoxyl group lead, lead compounds such as aryloxy lead are more preferably the organic compound that exists in these lead compounds and the reaction system to react, or these lead compounds raw material and reactant of sending into reaction in advance, or product is heat-treated.
It is 2 or above distillation tower that the used continuous multi-stage distillation tower of the present invention can be theoretical distillation hop count, in fact can be any distillation tower that carries out continuous still battery.As this continuous multi-stage distillation tower, for example can use bubble-plate column, adopt porous plate, valve tray, the tray column of adverse current column plate etc. has Raschig ring, Lessing ring, bohr ring, saddle type filler, square saddle type filler, Rod Dixon filler, MeMahon packing, ヘ リ パ Star Network, ス Le ザ-filler, the packing tower of various fillers such as メ ラ パ Star Network etc. can use any operate continuously multistage distillation tower usually.(hop count of alleged distillation tower among the present invention, at its plate number of tray column middle finger, and packed tower and other distillation tower middle finger number of theoretical plates).More particularly, can preferably use column plate-filler mixing column with column plate part and the merging of filler filling part.And in the liquid phase in being used in distillation tower during insoluble solid catalyst, this solid catalyst preferably can be used to instead of part or all filler and the tower distillation tower of filler of filling.
According to the present invention, must there be catalyzer in the continuous multi-stage distillation tower, preferably make in the continuous multi-stage distillation tower to have catalyzer in the tower section more than 2 sections or 2 sections.
Make the method that has catalyzer in this continuous multi-stage distillation tower can be with any suitable method, for example, in that use can be in distillation tower in the liquid phase during soluble even catalyzer, can send into catalyzer continuously in distillation tower can make and have catalyzer in the reaction system, or when adopting in distillation tower in the liquid phase insoluble non-homogeneous catalyzer (solid catalyst), solid catalyst can be distributed in this distillation tower and make and have catalyzer in the reaction system, also can and use these methods.
When even catalyzer is sent into this distillation tower continuously, can send into separately or in two kinds of parallel feedings at raw material and reactant, also can send in the tower section different with the raw material supplying position.And, at the bottom of tower, count, when the tower fragment position more than at least 1 section is arranged, then can send into catalyzer in any position.But, be actually in this distillation tower at catalyst supply and react in lower area for the position, so preferably sending into catalyzer to the zone the raw material supplying position from cat head.And when using the NON-UNIFORM SOLID catalyzer, then can fill this catalyzer of necessary amount in the position of this distillation tower necessity, and there is the theoretical tower hop count of this catalyst layer to can be more than at least 1 section, be preferably more than at least 2 sections.This solid catalyst also can be simultaneously as the filler of distillation tower.
In addition, there is not the zone of catalyzer in this distillation tower, the common distillation tower function as the concentration response product then can be arranged.
As previously mentioned, basic embodiment of the present invention is to make aryl carbonates or its mixture continuously, wherein will be selected from formula
Dialkyl carbonate, formula
Carbonate alkyl aryl ester and composition thereof raw material and be selected from formula Ar
1The aromatic hydroxy compound of OH, formula
The reactant (R wherein of carbonate alkyl aryl ester and composition thereof
1, R
2And R
3Be respectively 1-10 carbon alkyl, 3-10 carbon alicyclic radical or 6-10 carbon aralkyl, and Ar
1, Ar
2And Ar
3Be respectively 5-30 carbon aryl) carry out transesterification, make the formula corresponding with raw material and reactant
And/or
Aryl carbonates or its mixture product (wherein R and Ar are selected from the R corresponding with raw material and reactant respectively
1, R
2, R
3And Ar
1, Ar
2, Ar
3), obtain simultaneously the formula ROH corresponding with raw material and reactant and/or
The Fatty Alcohol(C12-C14 and C12-C18) of (R is with above-mentioned definition), dialkyl carbonate or its mixture by product, it is characterized in that raw material and reactant are sent in the continuous multi-stage distillation tower continuously, in this distillation tower in carrying out transesterification mutually with liquid phase or solution-air between two materials in the presence of the catalyzer, take out the liquid high boiling point reaction mixture that contains aryl carbonates or its mixture product simultaneously from this distillation tower bottom continuously, and take out the gaseous low boiling point reaction mixture that contains by product from this distillation tower top continuous still battery simultaneously.For the method for this raw material and this reactant being sent into continuously in the continuous multi-stage distillation tower, do not do special qualification, so long as it more than 1 section, is contacted with catalyzer in the preferred zone more than 2 sections in this distillation tower at least at least, then any method all can.For example, can be in effective section introducing port be sent into raw material and reactant the continuous multi-stage distillation tower effective section continuously, and also raw material and reactant can also can import from different sections respectively from same section importing of this distillation tower.
In addition, raw material and reactant all can be liquid, and gaseous state or liquid-gas mixed state is sent into continuously.
Except like this raw material and reactant being sent into the continuous multi-stage distillation tower, in addition also can be preferably from interrupted or continuous charging feed in this distillation tower bottom and/or reactant.
In the charging that raw material and reactant constitute, preferred method of feeding is, the charging of higher is sent into this distillation tower from the tower section more than the tower section that the catalyzer existence is arranged continuously with liquid state or solution-air mixed state, and more lower boiling charging is then sent into gaseous state continuously from this distillation tower bottom.Under this situation, from the high boiling point charging that top is sent into, it is also harmless to contain the lower boiling charging.
Among these chargings, can contain Fatty Alcohol(C12-C14 and C12-C18) and carbonate alkyl aryl ester or diaryl carbonate (reactions of formula (1) or (2)) as product, or dialkyl carbonate and carbonate alkyl aryl ester (reactions of formula (3) or (4)) etc., because the reaction of formula (1)-(4) that the present invention relates to is reversible reaction, so if these production concentrations are too high, charging reactivity so will reduce, and this does not wish to occur.
The ratio that infeeds raw material in the continuous multi-stage distillation tower and reaction volume will change according to the kind of catalyzer and amount and reaction conditions, usually, counts 0.01-1000 times of scope with respect to the reactant amount ratio of raw material with the mol ratio.
According to the present invention, exist following raw material and reactant to react in catalyzer in the continuous multi-stage distillation tower, corresponding generation aryl carbonates purpose product, Fatty Alcohol(C12-C14 and C12-C18) [reactions of formula (1) and (2)], or dialkyl carbonate [reactions of formula (3) and (4)] by product, in these purpose products or the by product, low-boiling products is taken out from this distillation tower continuously with gaseous state.When carrying out the present invention and reacting, this Fatty Alcohol(C12-C14 and C12-C18) or dialkyl carbonate by product are compared with aryl carbonates purpose product, are able to because of boiling point is low usually it is taken out from distillation tower continuously with gaseous state.At this moment, what take out with gaseous state can only be low-boiling by-products, also can be the mixture with raw material and/or reactant, and also may contain a small amount of aryl carbonates high boiling point product in case of necessity.
In this continuous multi-stage distillation tower, the appropriate location beyond the outlet of taking out the gaseous substance contain low-boiling by-products can be located at the bottom of the tower, low-boiling by-products concentration normally up increases along tower in the vapor phase.Therefore, gaseous substance outlet preferably is located at the top that raw material and reaction-ure feeding are supplied with the position, can be located at these feed positions between the cat head or top of tower, more preferably is located at top of tower.
The gaseous state composition of Qu Chuing is by way liquefies such as coolings like this, and its part can be sent this distillation tower top back to, promptly carries out so-called reflux operation.If improve the reflux ratio of this reflux operation,, can make therefore that low-boiling by-products concentration improves in the gaseous state composition of taking-up then because low-boiling by-products becomes the distillation efficiency of vapor phase can improve.But, cross the highland and improve reflux ratio, because of meeting increases necessary heat energy greatly, so also be not preferred.Therefore, reflux ratio is generally 0-20, is preferably 0-10.
According to the inventive method, the aryl carbonates high boiling point product of generation takes out with liquid state continuously from continuous multi-stage distillation tower bottom.In this case, the material that takes out with liquid state can only be an aryl carbonates, also can be the mixture with raw material and/or reactant, but also can contain a small amount of low-boiling products.When employing can be dissolved the high boiling point catalyst that forms in liquid phase, then take out in material and can contain this catalyzer in this liquid state.The fluent meterial that contains aryl carbonates purpose product can be located at the tower bottom, the particularly preferred tower bottom that is provided in a side of from the outlet that the continuous multi-stage distillation tower takes out.The liquid material of Qu Chuing like this, its part can be gone into this distillation tower bottom with gaseous state or gas-liquid mixed attitude foldback after the reboiler heating.
Catalyst system therefor amount of the present invention is because of using the kind of catalyzer, the kind of continuous multi-stage distillation tower, raw material and reactant and amount ratio thereof, temperature of reaction is with the different of reaction conditionss such as reaction pressure and change, catalyzer is being sent into continuously under the situation of continuous multi-stage distillation tower, in the total weight of raw material and reaction-ure feeding, adopt 0.0001-50 weight % usually.And when adopting solid catalyst and being arranged in the continuous multi-stage distillation tower,, preferably adopt the catalytic amount of 0.01-75 volume % with the void tower volumometer of this distillation tower.
According to the present invention, owing to just induce reaction in the continuous multi-stage distillation tower that has catalyzer to exist, the reaction product amount depends on the delay liquid measure in this distillation tower usually.That is to say, adopt identical tower height, during the distillation tower of tower warp, being detained the big distillation tower of liquid measure can prolong the liquid phase residual time relatively, i.e. in the reaction times, this also is preferred.But, when being detained hypervolia,, easily cause the liquid flooding phenomenon because of side reaction may take place in the residence time prolongation.Therefore, the delay liquid measure of the used distillation tower of the present invention becomes with the kind of distillation condition and distillation tower, and the volume ratio that the delay liquid measure accounts for continuous multi-stage distillation tower void tower volume is generally 0.005-0.75.
In addition, according to the present invention, the average retention time of liquid phase in the continuous multi-stage distillation tower is also with reaction conditions and continuous multi-stage distillation tower kind and internal structure (for example kind of tray column or packing tower) variation, be generally 0.001-50 hour, be preferably 0.01-10 hour, more preferably 0.05-2 hour.
Temperature of reaction, promptly the temperature in the continuous multi-stage distillation tower also becomes with raw material and reactant species, is generally 50-350 ℃, is preferably 100-280 ℃ of scope.And reaction pressure becomes with raw materials used and factors such as reactant species and temperature of reaction, can be decompression, normal pressure, and pressurization is generally 0.1mmHg-200kg/cm
2Scope.
Among the present invention, there is no need to use solvent, but, also can use suitable non-active solvent in order more easily to carry out operation, ether for example, aliphatic hydrocarbon, aromatic hydrocarbons, halogenated aliphatic hydrocarbon, halogenated aryl hydrocarbons etc. are as reaction solvent.
And, as the nitrogen of inert substance in the reaction, helium, indifferent gas such as argon gas can coexist in reaction system, remove low-boiling by-products in order to quicken distillation, then can be import aforementioned indifferent gas or the reaction and be inert lower boiling organic compound with gaseous state from continuous multi-stage distillation tower bottom.
For the inventive method more specifically is described, below illustrates the technology that adopts 1 continuous multi-stage distillation tower, but it can not be interpreted as it is any restriction the inventive method.
For example, shown in the 1st figure, incoming mixture that is made of raw material and reactant and catalyzer be from ingress pipe 2, imports continuously through preheater 5 to be provided with in the continuous multi-stage distillation tower 1 of reboiler 10 and condenser 13, and tower bottom is further heating in reboiler 10.In this manner, can react and distill.The catalyzer of continuous multi-stage distillation tower inside exist the liquid component that contains aryl carbonates high boiling point product that generates down from the tower bottom as tower at the bottom of liquid 19 take out continuously.The gas phase composition that contains the lower boiling byproduct of reaction then takes out continuously as overhead gas 12, after the condensation, takes out continuously as liquid of top of the tower 16 again in condenser 13.The part of liquid of top of the tower can pass back into continuous multi-stage distillation tower top from 15.
In addition, shown in the 2nd figure, incoming mixture that raw material and reactant constitute and catalyzer are from managing 2, footpath preheater 5 imports in the continuous multi-stage distillation tower 1 continuously, simultaneously with one of raw material or reactant, promptly than low-boiling compound from ingress pipe 8 ' importing, after vaporizer 10 ' gasification, import continuous multi-stage distillation tower 1 bottom more continuously.Trans like this, can react and distill.Continuous multi-stage distillation tower inside the liquid parts that contains aryl carbonates that generates in the presence of the catalyzer from the tower bottom as tower at the bottom of liquid 19 take out continuously.The gas phase composition that contains low-boiling by-products then takes out continuously as overhead gas 12, after the condensation, takes out continuously as liquid of top of the tower 16 again in condenser 13.
According to the inventive method, can adopt many, particularly 2 continuous multi-stage distillation towers and be raw material and make diaryl carbonate more expeditiously with dialkyl carbonate and aromatic hydroxy compound.
That is to say, according to the present invention's the 2nd embodiment, the inventive method also is included in the above-mentioned basic implementation method, with above-mentioned continuous multi-stage distillation tower as the 1st continuous multi-stage distillation tower, on this basis again in conjunction with adopting the 2nd continuous multi-stage distillation tower, the raw material of sending into continuously in the 1st distillation tower is a formula
Dialkyl carbonate, reactant is formula Ar
1The aromatic hydroxy compound of OH, the aryl carbonates or its mixture product that contain from the high boiling reaction mixture that take out continuously the 1st distillation tower bottom are formula
(R
1And Ar
1With above-mentioned definition) carbonate alkyl aryl ester, the by product that contains from the low-boiling reaction mixture that take out continuously on the 1st distillation tower top is formula R
1The Fatty Alcohol(C12-C14 and C12-C18) of OH contains formula
(R wherein
1And Ar
1With above-mentioned definition) carbonate alkyl aryl ester and the above-mentioned high boiling reaction mixture and the formula of taking out continuously from the 1st distillation tower bottom
(R
3With R
1Identical or different, Ar
3With Ar
1Identical or different, but R
3And Ar
3Can not distinguish and be R simultaneously
1And Ar
1) the carbonate alkyl aryl ester reactant send into continuously in the 2nd the continuous multi-stage distillation tower, in the 2nd distillation tower,, make and contain in carrying out the mutually transesterification between two materials of liquid phase or solution-air in the presence of the catalyzer
And/or
(Ar
1And Ar
3With above-mentioned definition) diaryl carbonate or the high boiling reaction mixture of its mixture product, take out this liquid high boiling point reaction mixture continuously from the 2nd continuous multi-stage distillation tower bottom simultaneously, and contain formula from the 2nd continuous multi-stage distillation tower top continuous still battery taking-up simultaneously
And/or
(R
1And R
3With above-mentioned definition) dialkyl carbonate or the gaseous low boiling point reaction mixture of its mixture by product.
According to the 2nd implementation method, the catalyzer that this catalyzer obtains for dissolving in this liquid phase, exist with solubilised state in this liquid phase in the 1st continuous multi-stage distillation tower and the 2nd continuous multi-stage distillation tower at least one distillation tower, and/or this catalyzer is an insoluble solid catalyst basically in this liquid phase, do not dissolve in the liquid phase at least one distillation tower of the 1st continuous multi-stage distillation tower and the 2nd continuous multi-stage distillation tower, and exist with the decentralized configuration attitude, this also is a preferred embodiment.
R
3With R
1Identical, and Ar
3With Ar
1Not simultaneously, do not contain the formula of taking out from the 2nd continuous multi-stage distillation tower top
The low-boiling reaction mixture of dialkyl carbonate preferably be recycled among the 1st the continuous multi-stage distillation tower.
In addition, according to the 3rd embodiment of the present invention, the inventive method also is included in the above-mentioned basic embodiment, with above-mentioned continuous multi-stage distillation tower as the 1st continuous multi-stage distillation tower, be used in combination the 2nd continuous multi-stage distillation tower on this basis again, the raw material of sending into continuously in the 1st distillation tower is a formula
Dialkyl carbonate, reactant is formula Ar
1The aromatic hydroxy compound of OH, the aryl carbonates or its mixture product that contain from the high boiling reaction mixture that take out continuously the 1st distillation tower bottom are formula
Carbonate alkyl aryl ester, the by product formula R that from the low-boiling reaction mixture that take out continuously on the 1st distillation tower top, contains
1The Fatty Alcohol(C12-C14 and C12-C18) of OH contains formula
Carbonate alkyl aryl ester and the above-mentioned high boiling reaction mixture that takes out continuously from the 1st distillation tower bottom is sent in the 2nd the continuous multi-stage distillation tower continuously, in the 2nd distillation tower, in the presence of catalyzer, carry out liquid phase or solution-air intermolecular transesterification mutually of the same race, make and contain formula
(Ar
1With above-mentioned definition) the high boiling reaction mixture of diaryl carbonate, take out this liquid high boiling point reaction mixture continuously from the 2nd continuous multi-stage distillation tower bottom simultaneously, and take out from the 2nd continuous multi-stage distillation tower top continuous still battery simultaneously and contain formula
The gaseous low boiling point reaction mixture of dialkyl carbonate by product.
According to the 3rd embodiment, contain formula from the 2nd continuous multi-stage distillation tower top taking-up
The lower boiling reaction product of dialkyl carbonate preferably be recycled to the 1st continuous multi-stage distillation tower.
And according to the 3rd implementation method, the catalyzer that this catalyzer obtains for dissolving in this liquid phase, in at least one distillation tower of the 1st continuous multi-stage distillation tower and the 2nd continuous multi-stage distillation tower, exist with solubilised state in this liquid phase, and/or this catalyzer is an insoluble solid catalyst basically in this liquid phase, do not dissolve in the liquid phase at least one distillation tower of the 1st continuous multi-stage distillation tower and the 2nd continuous multi-stage distillation tower, and exist with the decentralized configuration attitude, this also is a preferred embodiment.
And, when this catalyzer is the catalyzer that dissolving obtains in this liquid phase, preferably all exist with solubilised state in each liquid phase in the 1st continuous multi-stage distillation tower and the 2nd continuous multi-stage distillation tower two distillation tower, this moment the 1st can be identical with each catalyzer in the 2nd distillation tower, also can be different.
Adopt can liquid phase in this reaction system in dissolved obtain catalyzer the time, also comprise in the preferred method catalyst separating, and the processing step that its recirculation is used.That is to say, the catalyzer that exists in the 1st continuous multi-stage distillation tower 1 partly or entirely dissolving be present in this liquid phase, when the high boiling reaction mixture that the 1st distillation tower bottom taken out with liquid state is sent into the 2nd continuous multi-stage distillation tower, the liquid high boiling point reaction mixture of this taking-up is imported the 1st evaporating pot, be separated into and contain formula
Carbonate alkyl aryl ester evaporant and contain after the debris of this catalyst-solvent, part or all of this evaporant sent in the 2nd the continuous multi-stage distillation tower continuously, but and part or all recirculation that contains the debris of this catalyst-solvent send in the 1st the continuous multi-stage distillation tower.
In the isolated debris of the 1st evaporating pot, except this catalyst component, also may contain a spot of feed compound (dialkyl carbonate and/or aromatic hydroxy compound), aryl carbonates (carbonate alkyl aryl ester and/or diaryl carbonate) and other are high boiling point by-products produced.
According to the 3rd implementation method of the present invention, when 1 of the catalyzer that exists in the 2nd continuous multi-stage distillation tower partly or entirely exists with solubilised state in this liquid phase, then the liquid high boiling point reaction mixture of this 2 distillation tower bottom taking-up imports in the 2nd evaporating pot, is separated into and contains formula
Diaryl carbonate evaporant and contain the debris of this catalyst-solvent after, part or all the preferred recirculation that will contain the debris of this catalyst-solvent is sent in the 2nd the continuous multi-stage distillation tower.
In the debris of separating in the 2nd evaporating pot, except this catalyst component, also may contain a small amount of aromatic hydroxy compound and carbonate alkyl aryl ester, diaryl carbonate and other are high boiling point by-products produced.
Such catalyst separating, carry out one of the liquid high boiling point reaction mixture that recirculating process can take out with the liquid high boiling point reaction mixture that takes out from the 1st continuous multi-stage distillation tower bottom and the 2nd continuous multi-stage distillation tower bottom, also available two kinds are carried out.
And contain in these debris of this catalyzer, when containing high boiling point by-products produced except that the purpose product, before these debris recirculation, can be with its part or all taking-up, separate remove high boiling point by-products produced.
In addition, according to the inventive method, contain the high boiling reaction mixture of the desired aryl carbonates that obtains that takes out from continuous multi-stage distillation tower bottom, can distill, the separation and purification method that partial crystallization etc. are common, thus isolate the desired aryl carbonates that obtains separately.
Below the preferred embodiments of the invention are implemented in explanation.
Following embodiment specifies the present invention, but these embodiment are interpreted as it is any limitation of the invention till the ass ascends the ladder.
Embodiment 1
Shown in the 1st figure, the continuous multi-stage distillation tower is a packing tower, by the stainless steel manufacturing, tower height 4m fills out 3 inches in footpath, wherein is filled with Rod Dixon filler (the about 6mm of diameter), cat head down the 1m position from ingress pipe 2, footpath preheater 5, conduit 6 is sent into methylcarbonate continuously, the liquid form mixt that phenol and catalyzer constitute.The heat that reaction distillation is necessary, circulates through conduit 11 through reboiler 10 heating with tower bottom liquid again.Reaction conditions is shown in the 1st table.18 take out the liquid that contain catalyst component and carbonic acid aminomethyl phenyl ester and diphenyl carbonate continuously through conduit 8 and 19 at the bottom of this distillation Tata.Reaction result is shown in the 1st table.And, contain the phenylmethylether that generates with carbonic acid aminomethyl phenyl ester side reaction (decarbonate reaction) of 0.02 weight % in this reaction solution (reaction mixture).Its result shows, is benchmark with phenol, phenylmethylether selectivity 0.8%.And gas condensation in condenser 13 that the conduit 12 that is provided with in cat head 17 distills out.The part of phlegma passes back in this distillation tower 1 through conduit 15, and residue takes out continuously from conduit 16.From this phlegma, can obtain methyl alcohol lower boiling reaction product.
Comparative example 1
Shown in the 6th figure, distillation tower 63 tower height 1m, 1 inch of tower diameter [filling with the Rod Dixon filler (the about 6mm of diameter) that stainless steel is made] is equipped with stirrer 71, and diametered duct 61 is delivered to the 12.6kg liquid of embodiment 1 used same composition in the high-pressure type reactor 62 of 15 liters of capacity.With electric furnace 70 heating, fluid temperature is stabilized in 204 ℃ and reacts reactor 62 while stirring.Distillation tower 63 cats head 69 distillate gas diametered ducts 64 are sent into condensation in the condenser 65.Part phlegma refluxes through conduit 66 and conduit 67, and remainder takes out through conduit 68 continuously with the speed of 2.1kg/hr.Reflux ratio 0.8.When phlegma takes out 4.2kg, reactor 62 coolings, reaction solution takes out from conduit 72, and its weight is 8.4kg.Residue liquid measure and send into the ratio of liquid measure in the still in this comparative example, the ratio of the amount of sending into liquid measure at the bottom of the tower that takes out from conduit 19 among the embodiment 1 with from conduit 6 is identical.And the speed that distillates of distillate is also identical after the gaseous constituent condensation.Analytical results shows, contains 1.8 weight % carbonic acid aminomethyl phenyl esters in the reaction solution, 0.01 weight % diphenyl carbonate, 0.07 weight % phenylmethylether.Every 1kg reaction solution hourly output is the carbonic acid aminomethyl phenyl ester of 9g/kghr, the diphenyl carbonate of 0.05g/kghr.The aryl carbonates selectivity that with phenol is benchmark is that carbonic acid aminomethyl phenyl ester 94%, diphenyl carbonate are 1%.And the selectivity of phenylmethylether by product is 5%.Same reaction carries out that the result is after 4 hours, and phenylmethylether by product selectivity is 7%.
The result of embodiment 1 is, carbonic acid aminomethyl phenyl ester output 34g/kghr(selectivity 97%), diphenyl carbonate output is 0.5g/kghr(selectivity 2%), phenylmethylether by product selectivity 0.8%(is a determined value, does not change in time), compare with the method (comparative example 1) of the batch reactor that is applied in the setting of distillation tower top simply, the inventive method is the high speed of response of aryl carbonates, high yield (yield in unit time height), highly selective, and successive manufacture method.
Embodiment 2-4
Adopt the device identical with embodiment 1, experimentize by reaction conditions shown in the table 1, the results are shown in Table 1.
Shown in the 2nd figure, continuous multi-stage distillation tower 1 is a packing tower, tower height 4m, 3 inches of tower diameters, wherein fill the Rod Dixon filler (the about 6mm of diameter) that stainless steel is made, down to distillation tower 1, send into methylcarbonate continuously, the liquid form mixt that phenol and catalyzer constitute with ingress pipe 2 footpath preheaters 5 to the position of 1m from cat head, wherein methylcarbonate (can contain small amount of phenol) is through ingress pipe 8 ' importing, through vaporizer 10 ' after send into the tower bottom of this distillation tower 1 continuously with gaseous state.Reaction conditions is as shown in table 2.Take out the high boiling point reaction product that contains carbonic acid aminomethyl phenyl ester and diphenyl carbonate from this base product continuously through conduit 19.Simultaneously, the cat head distillate gas is sent into condensation in the condenser 13 through conduit 12, obtains the methyl alcohol low-boiling products then from the liquid that takes out continuously through conduit 16.Reaction result is as shown in table 2.
Embodiment 6-9
Adopt the device identical with embodiment 5 to react by condition shown in the table 2, the result is as shown in table 2.
As shown in Figure 2, the continuous multi-stage distillation tower is a tray column, in order to replace packing tower, establishes 20 sections sieve plates, tower height 6m, and 10 inches of tower diameters under reaction conditions shown in the table 2, are same as embodiment 5 and react.And, be down to send into continuously in the tower position of 0.5m by ingress pipe 2 through incoming mixture and the catalyzer that preheater 5 imports from cat head, the result is as shown in table 2.
Embodiment 11
React continuously with method similarly to Example 1, just send into the mixture that carbonic acid aminomethyl phenyl phenol and catalyzer constitute continuously, in order to the replacement methylcarbonate, the mixture that phenol and catalyzer constitute, reaction conditions is as shown in table 3.Reaction result is, at the bottom of the continuous multi-stage distillation Tata 18 at the bottom of conduit 19 takes out the tower that contains catalyst component and diphenyl carbonate purpose product continuously liquid.Simultaneously, the condensed phlegma of overhead gas composition takes out continuously from conduit 16.This phlegma contains a small amount of phenylmethylether, in addition, is the methylcarbonate low-boiling products, wherein, is that the phenylmethylether by product selectivity of benchmark is 0.7% with carbonic acid aminomethyl phenyl ester, and reaction result is as shown in table 3.
Comparative example 2
Adopt the device identical, wherein from the mixture of conduit 61 introducing 12.6kg and embodiment 11 same compositions with comparative example 1.Use electric furnace 70 reacting by heating stills 62 while stirring, fluid temperature reacts when being stabilized in 195 ℃, and the condensed phlegma of overhead gas composition takes out from conduit 68 continuously with the speed of 1.0kg/hr, reflux ratio 2.1, and other and comparative example 1 react equally.After beginning to take out material, reaction was carried out 3 hours, took out the 3.0kg phlegma.After reactor 62 coolings, reaction solution takes out from conduit 72, and weight is 9.6kg.In this comparative example, the amount of liquid that takes out from reactor and the ratio of phlegma taking-up amount and the embodiment 11 at the bottom of the tower ratio of liquid taking-up amount and overhead condensation liquid taking-up amount be identical.Analytical results shows, generates the diphenyl carbonate of 67.3 weight % in the reaction solution.The diphenyl carbonate output of per hour every kg reaction solution is 224g/kghr.With carbonic acid aminomethyl phenyl ester is that the diphenyl carbonate selectivity of benchmark is 95%.And overhead condensation liquid analysis revealed has the phenylmethylether byproduct of reaction to detect.With carbonic acid aminomethyl phenyl ester is that the phenylmethylether selectivity of benchmark is 5%.This result shows, compares with embodiment 11, and diphenyl carbonate can reach high yield and selectivity in the inventive method.
Embodiment 12-17
Adopt the device identical with embodiment 11, experimentize under condition shown in the table 3, the result is as shown in table 3.
Adopt the device identical with embodiment 5, the mixture that carbonic acid aminomethyl phenyl ester and catalyzer constitute is sent into through preheater 5 continuously from ingress pipe 2, in addition, carbonic acid aminomethyl phenyl ester is from ingress pipe 8 ' importing, through vaporizer 10 ', conduit 11 and send into the tower bottom of distillation tower 1 continuously with gaseous state, reaction is carried out with the method identical with embodiment 5.Reaction conditions is listed in table 4.The liquid that contains diphenyl carbonate reaction product takes out at the bottom of continuous multi-stage distillation Tata continuously.Simultaneously, after condenser 13 condensations, in the liquid that conduit 16 takes out continuously, can obtain methylcarbonate lower boiling reaction product from cat head distilled gas, reaction result is as shown in table 4.
Embodiment 19-20
Adopt the device identical with embodiment 18, react by reaction conditions shown in the table 4, the result is as shown in table 4.
Wherein, embodiment 19 after reacting, contains methyl alcohol and methylcarbonate from ingress pipe 8 ' importing phenol in overhead condensation liquid.
Adopt the tray column identical with embodiment 10 as the continuous multi-stage distillation tower, from the cat head position of 0.5m down, send into charging and catalyzer continuously, press reaction conditions shown in the table 4, and other is same as embodiment 18 and reacts, the result is as shown in table 4.
(modulation of catalyzer)
4kg yellow lead oxide and 20kg diphenyl carbonate one are arised from 180 ℃ of heating 5 hours, produce carbonic acid gas therebetween.Distill down in 10mmHg pressure afterwards and remove most of remaining diphenyl carbonate, be modulated into catalyzer (catalyst A) after the placement cooling in the nitrogen atmosphere.
(manufacturing of diphenyl carbonate)
Shown in the 3rd figure, adopt the device that comprises 2 continuous multi-stage distillation towers.Wherein by being filled with the Rod Dixon filler (the about 6mm of diameter) that stainless steel is made, tower height 4m, the packing tower that tower diameter is 3 inches constitute the 1st continuous multi-stage distillation tower 1 ', from cat head 17 down the position of 1m with methylcarbonate, the liquid form mixt that phenol and catalyst A constitute is from charging ingress pipe 2, through conduit 4, preheater 5 and conduit 6 are sent into continuously, and react toward current downflow in the 1st continuous multi-stage distillation tower.Reaction and distillation institute heat requirement are to send into reboiler 10 heating by tower bottom liquid through conduit 8 and 9, provide through conduit 11 circulations again.Send into condensation the condenser 13 from cat head 17 continuous distilled gases through conduit 12.A part phlegma through conduit 14 and 15 pass back into the 1st continuous multi-stage distillation tower 1 ' among, remainder then takes out continuously through conduit 16.From this phlegma, can obtain containing the low boiling point component of methyl alcohol lower boiling reaction product.And the high boiling point composition that contains catalyst component and carbonic acid aminomethyl phenyl ester 18 takes out through conduit 8 and 19 at the bottom of the tower continuously.
Secondly, by filling the Rod Dixon filler (the about 6mm of diameter) that stainless steel is made, tower height 4m, the packing tower that tower diameter is 3 inches constitutes the 2nd continuous multi-stage distillation tower 20, from the cat head position of 1m down, send into the liquid that takes out at the bottom of the 1st the reaction distillation Tata continuously through conduit 19, in the 2nd continuous multi-stage distillation tower toward dirty and react, distillation institute heat requirement is sent into reboiler 30 heating by the tower lower liquid through conduit 28 and 29, after conduit 31 circulates and provides.And as diaryl carbonates esterification catalyzer in the 2nd the continuous multi-stage distillation tower, usefulness be carbonate alkyl aryl ester catalyzer in the 1st the continuous multi-stage distillation tower, former state is used without separation.The gas that contains methylcarbonate from cat head 26 continuous distilled is sent into condenser 22 condensations through conduit 21.1 partial condensation liquid is among conduit 23 and 24 passes back into the 2nd continuous multi-stage distillation tower 20.The residue phlegma takes out continuously from conduit 23 and 25, after conduit 4, preheater 5 and conduit 6 and recirculation send into the 1st continuous multi-stage distillation tower 1 ' among.And at the bottom of the tower of the 2nd continuous multi-stage distillation tower 27, take out the high boiling point compositions that contain catalyzer and diphenyl carbonate continuously through conduit 28 and 32.Reaction conditions and reach the results are shown among the table 5 after the standard state.
(modulation of catalyzer)
4kg dibutyl tin oxide and 20kg phenol one are arised from 180 ℃ of heating 10 hours, and the water of generation distills with phenol to be removed.Afterwards, normal pressure down distillation is removed most of remaining phenol, places cooling in the nitrogen atmosphere and is modulated into catalyzer (catalyst B).
(manufacturing of diphenyl carbonate)
Use the device identical,, operate equally by embodiment 22 except that with the catalyst B replacement catalyst A with embodiment 22.Reaction conditions and reach standard state after the results are shown in table 5.
(modulation of catalyzer)
Inferior lead of 4kg acetate and 20kg carbonic acid aminomethyl phenyl ester one are arised from 180 ℃ of heating 10 hours.Then, in 100mmHg down distillation remove most of remaining carbonic acid aminomethyl phenyl ester etc., place cooling in the nitrogen atmosphere and be modulated into catalyzer (catalyzer C).
(manufacturing of diphenyl carbonate)
Adopt the 4th figure shown device.By being filled with the Rod Dixon filler (the about 6mm of diameter) that stainless steel is made, tower height 4m, the packing tower that tower diameter is 3 inches constitute the 1st continuous multi-stage distillation tower 1 ', from its cat head 17 position of 1m down, from charging ingress pipe 2, send into continuously by methylcarbonate through preheater 5 and conduit 6, the liquid form mixt that phenol and catalyzer C constitute, at the 1st continuous multi-stage distillation tower 1 ' interior to dirty and react.Reaction and distillation institute heat requirement are by containing from the part of the low boiling point component of conduit 8 ' new methylcarbonate that imports and the follow-up methylcarbonate of sending into from the 2nd continuous multi-stage distillation tower 20 recirculation through conduit 9 ' send into vaporizer 10 ' heating, after conduit 11 is sent into and provided.And send into condenser 13 and condensation is taken out continuously from conduit 16 again through conduit 12 from cat head 17 distilled gases.Can obtain containing the low-boiling reaction mixture of methyl alcohol reaction product from this phlegma.And the high boiling reaction mixture that contains carbonic acid aminomethyl phenyl ester and catalyst component 18 takes out through conduit 19 at the bottom of the tower continuously.
Secondly, by being filled with the Rod Dixon filler (the about 6mm of diameter) that stainless steel is made, tower height 4m, the packing tower that tower diameter is 3 inches constitutes the 2nd continuous multi-stage distillation tower 20, down send into the liquid that takes out at the bottom of the 1st continuous multi-stage distillation tower 1 ' tower continuously through conduit 19 in the position of 1m from cat head, toward dirty and react, distillation institute heat requirement is sent into reboiler 30 heating by tower bottom liquid through conduit 28 and 29 in the 2nd continuous multi-stage distillation tower 20, again through conduit 31 circulations and provide.Wherein, as the diaryl carbonates esterification catalyzer in the 2nd the continuous multi-stage distillation tower 20, usefulness be the 1st continuous multi-stage distillation tower 1 ' in used carbonate alkyl aryl ester catalyzer, former state is used without separation.Distillate the gas that contains methylcarbonate that comes continuously from cat head 26 and send into condensation the phlegma 22 through conduit 21.1 partial condensation liquid passes back in the 2nd reactive distillation column 20 through conduit 23 and 24.Remaining phlegma takes out continuously from conduit 23 and 25, again through conduit 3 and 4,6 circulations of preheater 5 and conduit send into the 1st continuous multi-stage distillation tower 1 ' in.And the phlegma that a part is taken out from conduit 25 through conduit 7 and vaporizer 10 ' circulation deliver to the 1st continuous multi-stage distillation tower 1 ' the bottom.And 27 take out the high boiling reaction mixtures that contain catalyzer and diphenyl carbonate continuously at the bottom of the tower of the 2nd continuous multi-stage distillation tower 20 through conduit 28 and 32.Reaction conditions and reach the table 5 that the results are shown in after the standard state.
Use the device identical with embodiment 24, except that with the p-cresol replacement phenol, other is operated equally by embodiment 24.Reaction conditions and reach the table 5 that the results are shown in after the standard state.
Use the device identical with embodiment 24, except that with the diethyl carbonate replacement methylcarbonate, other is operated equally by embodiment 24.Reaction conditions and reach the table 5 that the results are shown in after the standard state.
(modulation of catalyzer)
With 15kg phenol, 5kg carbonic acid aminomethyl phenyl ester and 4kg dibutyl tin oxide one arise from 180 ℃ of heating 10 hours, and the water of generation distills with phenol to be removed.Then, in normal pressure down distillation remove most of remaining phenol and carbonic acid aminomethyl phenyl ester, place cooling in the nitrogen atmosphere and modulate catalyzer (catalyzer D).
(manufacturing of diphenyl carbonate)
Use the device identical with embodiment 24, remove the usefulness catalyzer D replacement catalyzer C, other is pressed embodiment 24 and operates equally.Reaction conditions and reach the table 5 that the results are shown in after the standard state.
Use the device identical with embodiment 24, except that with the four phenoxide titaniums replacement catalyzer C, other is operated equally by embodiment 24.Reaction conditions and reach the results are shown among the table 5 after the standard state.
(modulation of catalyzer)
4kg yellow lead oxide and 20kg phenol one are arised from 180 ℃ of heating 10 hours, and the water of generation and phenol distill together to be removed, thereby is modulated into catalyzer (catalyzer E).
(manufacturing of diphenyl carbonate)
Adopt device as shown in Figure 5.By 20 sections sieve plates are housed, tower height 6m, the tray column that tower diameter is 10 inches constitute the 1st continuous multi-stage distillation tower 1 ', from its cat head 17 toward the position of 0.5m, charging ingress pipe 2, through conduit 4 and 39, preheater 5 and conduit 6 are sent into methylcarbonate continuously with liquid state, the mixture that phenol and catalyzer E constitute, in the 1st continuous multi-stage distillation 1 ' interior toward dirty and react.React and distill necessary heat, by contain from conduit 8 ' and 9 ' the new methylcarbonate that imports and from the 2nd follow-up continuous multi-stage distillation tower 20 through conduit 24, the part of the low-boiling reaction mixture of 25 and 7 round-robin methylcarbonates, after vaporizer 10 ' middle heating, send into and provide through conduit 11 again.Take out continuously from conduit 16 after conduit 12 is sent into condenser 13 condensations from cat head distilled gas.From this phlegma, can obtain to contain the low-boiling reaction mixture of methyl alcohol lower boiling reaction product.And 18 reaction solutions that take out continuously import the 1st evaporating pot 33 through conduit 19 at the bottom of the tower.The debris that contains carbonic acid aminomethyl phenyl esterifying catalyst from the bottom of evaporating pot 33 through conduit 34,38,39, preheater 5 and conduit 6 and recirculation send into the 1st continuous multi-stage distillation tower 1 ' among.Wherein, the catalyzer of recirculation reaches normality during the stage, then stops to import catalyzer E from conduit 2.
Flow through 1 part of debris of conduit 34 again through conduit 35 from evaporating pot 33, reboiler 36 and conduit 37 are recycled among the evaporating pot 33, the evaporant of the carbon containing acid methyl phenylester that is evaporated from evaporating pot 33, through conduit 40 from being located at the ingress pipe 41 of cat head 26 following 1.5m positions, infeed continuously by 20 sections sieve plates are housed, tower height 6m is among the 2nd the continuous multi-stage distillation tower 20 that the tray column that tower diameter is 10 inches constitutes.Diaryl carbonates catalyzer (catalyzer E) is through conduit 51, from cat head down the ingress pipe 48 that is provided with of the position of 1.5m send into the 2nd continuous multi-stage distillation tower 20 continuously with liquid state.The major part of the gaseous carbon acid methyl phenylester of sending in the 2nd continuous multi-stage distillation tower 20 becomes liquid in tower, again with catalyzer in the tower toward dirty, thereby react.Reaction and distillation institute heat requirement are tower bottom liquid to be sent into reboiler 30 through conduit 28 and 29 heat, and send into distillation tower and provide through conduit 31 again.The low-boiling reaction mixture that contains methylcarbonate from cat head 26 continuous distilled is sent into condenser 22 condensations through conduit 21.1 partial condensation liquid is among conduit 23 and 24 is sent into the 2nd continuous multi-stage distillation tower 20.Remaining phlegma takes out continuously from conduit 23 and 25, again through conduit 3,4 and 39, preheater 5 and conduit 6 recirculation send into the 1st continuous multi-stage distillation tower 1 ' within.And the part of the phlegmas that take out continuously from conduit 25 through conduit 7 and 9 ', vaporizer 10 ' with conduit 11 and from the 1st continuous multi-stage distillation tower 1 ' under recirculation.27 high boiling reaction mixtures that contain catalyzer and diphenyl carbonate that take out continuously import the 2nd evaporating pot 42 from conduit 28 and 32 at the bottom of the tower of the 2nd continuous multi-stage distillation tower 20.Flow through 1 part of debris of conduit 43 through conduit 44 from evaporating pot 42, and evaporating pot 42 is sent in reboiler 45 and conduit 46 circulations, takes out continuously with liquid state through conduit 52 and condenser 49 and conduit 50 from the evaporant of evaporating pot 42 evaporations.This evaporant is for being the material of main component with the diphenyl carbonate.And the debris that contains diaryl carbonates esterification catalyzer from the bottom of evaporating pot 42 through conduit 43,47, the 2nd continuous multi-stage distillation tower 20 sent in 48 recirculation.Wherein, the round-robin catalyzer stops to import catalyzer E from conduit 51 when reaching normality.The flow and the composition of each several part are listed in table 6.Reaction conditions and reach the table 7 that the results are shown in after the standard state.
(modulation of catalyzer)
After gama-alumina (Japan waves society day and makes, merchant's name N611 N) 5kg fills the garden tube (long 100cm, diameter 10cm) of quartzy glass one-tenth, the garden tube is put into pipe furnace.Behind nitrogen replacement, 200 ℃ were heated 5 hours, and made the gama-alumina drying.Then, be heated to 200 ℃ the interior benzole soln (20wt%) that adds tetramethoxy-silicane of garden tube, flow velocity 50ml/hr lasts 10 hours, to handle gama-alumina.Place cooling in the nitrogen atmosphere and be modulated into catalyzer (catalyzer F).
(manufacturing of diphenyl carbonate)
The 1st continuous multi-stage distillation tower and the 2nd continuous multi-stage distillation tower are used 1.5 inches of diameters respectively, the packing tower of high 2m, and filler is wherein then used catalyzer E, in addition, operates according to embodiment 24.Reaction conditions and reach the table 5 that the results are shown in after the standard state.
Comparative example 3
Adopt the 6th figure shown device identical, introduce and the mixture 12.8kg of embodiment 23 same compositions from conduit 61 with comparative example 1.Use electric furnace 70 reacting by heating stills 62 while stirring, fluid temperature reacts when being stabilized in 202 ℃, takes out phlegma continuously from conduit 68, speed 1.0kg/hr, and other is then operated equally with comparative example 1, thus realization response.When taking out the 12.1kg phlegma, the cooling reactor takes out reaction solution from conduit 72, and its weight is 0.7kg.In this comparative example 3, in the reactor among remaining liquid measure and the ratio of sending into liquid measure and the embodiment 23, liquid measure is identical with the ratio of the amount of sending into from conduit 6 at the bottom of the tower that takes out from conduit 28.Analytical results shows that the diphenyl carbonate growing amount is 14.0 weight % in the reaction solution.The diphenyl carbonate growing amount of per hour every kg reaction solution is 12g/kghr.The diphenyl carbonate selectivity that with phenol is benchmark is 83%.And the liquid of top of the tower analysis revealed is that the phenylmethylether by product selectivity of benchmark is 8% with phenol.
With result's (diphenyl carbonate growing amount 524g/kghr, selectivity 95%) of this result and embodiment 23 relatively, as can be seen, the inventive method is can high speed of response, highly selective, and high yield, and make the superior method of diphenyl carbonate continuously.
The explanation of the 1st table
(mark explanation)
DMC: methylcarbonate
DEC: diethyl carbonate
PhOH: phenol
Pb(Oph)
2: two phenoxy group lead
Ti(OPh)
4: four phenoxide titaniums
MPC: carbonic acid aminomethyl phenyl ester
MTC: carbonic acid methyl tolyl ester
EPC: carbonic acid ethyl phenyl ester
DPC: diphenyl carbonate
DTC: carboxylol ester
Wt%: weight %
(notes) are catalyst concn ICP(high-frequency induction mating type plasma emission spectrometry instrument 1.) analyze.
2. aryl carbonates output is shown with the g numerical table in the liquid at the bottom of every kg tower per hour.
3. the aryl carbonates selectivity is a benchmark with the aromatic hydroxy compound in the charging.
(mark explanation)
DMC: methylcarbonate
DEC: diethyl carbonate
PhOH: phenol
Pb(OPh)
2: two phenoxy group lead
Ti(OPh)
4: four phenoxide titaniums
MPC: carbonic acid aminomethyl phenyl ester
MTC: carbonic acid methyl tolyl ester
EPC: carbonic acid ethyl phenyl ester
DPC: diphenyl carbonate
DTC: carboxylol ester
Wt%: weight %
(notes) are catalyst concn ICP(high-frequency induction mating type plasma emission spectrometry instrument 1.) analyze.
2. aryl carbonates output is shown with the g numerical table in the liquid at the bottom of every kg tower per hour.
3. the aryl carbonates selectivity is a benchmark with the aromatic hydroxy compound in the charging.
The explanation of the 3rd table
(mark explanation)
Pb(OPh)
2: two phenoxy group lead
Bu
2SnO: dibutyl tin oxide
Ti(OPh)
4: four phenoxide titaniums
MPC: carbonic acid aminomethyl phenyl ester
MTC: carbonic acid methyl tolyl ester
EPC: carbonic acid ethyl phenyl ester
DPC: diphenyl carbonate
DTC: carboxylol ester
Wt%: weight %
(notes) are catalyst concn ICP(high-frequency induction mating type plasma emission spectrometry instrument 1.) analyze.
2. diaryl carbonate output is shown with the g numerical table in the liquid at the bottom of every kg tower per hour.
3. the diaryl carbonate selectivity is a benchmark with the carbonate alkyl aryl ester in the charging.
The explanation of the 4th table
(mark explanation)
PhOH: phenol
Pb(OPh)
2: two phenoxy group lead
Bu
2SnO: dibutyl tin oxide
MPC: carbonic acid aminomethyl phenyl ester
DPC: diphenyl carbonate
Wt%: weight %
(notes) are catalyst concn ICP(high-frequency induction mating type plasma emission spectrometry instrument 1.) analyze.
2. diaryl carbonate output is shown with the g numerical table in the liquid at the bottom of every kg tower per hour.
3. the diaryl carbonate selectivity is a benchmark with the carbonate alkyl aryl ester in the charging.
The notes of the 5th table)
(notes) are catalyst concn ICP(high-frequency induction mating type plasma emission spectrometry instrument 1.) measure, with catalytic elements concentration (weight %) expression in the liquid.
2. diaryl carbonate output is shown with the g numerical table in the liquid (conduit 28) at the bottom of every kg tower per hour.
3. and the selectivity of diaryl carbonate is calculated with following formula:
The selectivity of diaryl carbonate (%)=(aromatic hydroxy compound is the first step selectivity (%) of benchmark) * (carbonate alkyl aryl ester is the 2nd a step selectivity (%) of benchmark) ÷ 100
Distillation tower is continuously sent into methylcarbonate through preheater 5 with the speed of 7.0kg/hr from introducing port 2 as the 1st continuous multi-stage distillation tower shown in the 2nd figure, p-cresol, Pb(OPh)
2The mixture that constitutes (methylcarbonate 46 weight %, p-cresol 54 weight %, Pb(OPh)
2Be 10mmol/kg), simultaneously from introducing port 8 ' through vaporizer 10 ' and conduit 11 send into the methylcarbonate of 2.8kg/hr, 205 ℃ of column bottom temperatures, tower top pressure 6kg/cm continuously
2-G, react with this, the gaseous constituent that will contain methyl alcohol from cat head 17 is through conduit 12, take out with conduit 12 with the speed of 5.0kg/hr continuously as phlegma condenser 13 back, simultaneously at the bottom of the tower through conduit 19 liquid at the bottom of taking-up contains the tower of carbonic acid methyl tolyl ester of 30 weight % continuously with the speed of 4.8kg/hr.
Use diethyl carbonate, phenol, Pb(OPh)
2Operate equally, obtain containing liquid at the bottom of the tower of carbonic acid ethyl phenyl ester of 28.8 weight %.
Distillation tower shown in the 1st figure is as the 2nd continuous multi-stage distillation tower, and liquid imports the 2nd the continuous multi-stage distillation tower so that the speed of 4.8kg/hr is continuous through preheater 5 and conduit 6 from introducing port 2 at the bottom of the tower of the 1st continuous multi-stage distillation tower.Simultaneously, liquid at the bottom of the aforementioned tower that contains the carbonic acid ethyl phenyl ester is sent into the speed of 5.0kg/hr continuously through identical introducing port 2.200 ℃ of the column bottom temperatures of the 2nd continuous multi-stage distillation tower, the pressure 200mmHg of cat head 17.From cat head 17, through conduit 12, condenser 13 and conduit 14 and 16 contain methylcarbonate, diethyl carbonate, the phlegma of Methyl ethyl carbonate with continuous taking-up of the speed of 7.7kg/hr.Simultaneously, liquid at the bottom of conduit 8 and 19 takes out tower continuously with the speed of 2.1kg/hr.88 weight % of liquid are diphenyl carbonate at the bottom of the tower, the carboxylol ester, and the diaryl carbonate that carbonic acid phenyltolyl base ester constitutes, its ratio of components is a diphenyl carbonate: the carboxylol ester: carbonic acid phenyltolyl ester reaches about 1: 1: 0.8.
Press the 1st continuous multi-stage distillation tower of embodiment 25 described same operations, liquid takes out continuously with the speed of 4.8kg/hr at the bottom of containing the tower of the carbonic acid methyl tolyl ester that is formed by methylcarbonate and p-cresol, then it is sent into continuously in the 2nd the continuous multi-stage distillation tower, in the 2nd continuous multi-stage distillation tower, send into carbonic acid aminomethyl phenyl ester continuously through conduit 19 simultaneously with the speed of 1.36kg/hr.The reaction conditions of the 2nd continuous multi-stage distillation tower is identical with embodiment 25.When adding carbonic acid aminomethyl phenyl ester, the amount of the methylcarbonate from the feeding liquid that conduit 2 imports reduces gradually, till the amount of 0.38kg/hr.And displacedly be that the methylcarbonate amount from the feeding liquid that conduit 6 is sent into increases 0.36kg/hr.Increase the growing amount that carries out carbonic acid methyl tolyl ester and carbonic acid aminomethyl phenyl ester methylcarbonate low-boiling by-products when carrying out transesterification in the 2nd the continuous multi-stage distillation tower internal reaction process with this.
Simultaneously, at the bottom of the tower of the 2nd continuous multi-stage distillation tower with the speed of 2kg/hr take out continuously contain 90 weight % by diphenyl carbonate, carboxylol ester, liquid at the bottom of the tower of the diaryl carbonate that carbonic acid phenyltolyl base ester constitutes.Diphenyl carbonate in the diaryl carbonate: carboxylol ester: the ratio of components of carbonic acid phenyltolyl base ester is about 1: 1: 0.75.
The 1st figure, the 2nd figure, the 3rd figure, the 4th figure, the 5th figure are the various technical process sketch chart of implementing the inventive method.
The 6th figure is a comparative example 1,2, the used reaction unit sketch chart of 3 described existing methods.
With continuous multi-stage distillation tower height speed of response, highly selective, the inventive method of making aryl carbonates with high yield continuously can be used for mass production in recent years effectively need not poisonous phosgene and its purposes poly carbonate aryl ester desired raw material very widely when making as engineering plastics, or need not make various isocyanic ester desired raw materials etc. by poisonous phosgene.
Claims (16)
1, the method for aryl carbonates or its mixture can be made continuously, wherein formula will be selected from
Dialkyl carbonate, formula
The carbonate alkyl aryl ester and the raw material of its mixture and be selected from formula Ar
1The aromatic hydroxy compound of OH,
2, the method for claim 1, it is characterized in that catalyzer is the catalyzer that dissolving obtains in the liquid phase, exist with dissolved state in the liquid phase in the continuous multi-stage distillation tower, and/or catalyzer is insoluble solid catalyst basically in the liquid phase, do not dissolve and the existence that distributes in the liquid phase in this continuous multi-stage distillation tower.
3, the method for claim 1 is characterized in that above-mentioned continuous multi-stage distillation tower as the 1st continuous multi-stage distillation tower, also is used in combination the 2nd continuous multi-stage distillation tower on this basis, and the raw material of sending into continuously in the 1st distillation tower is a formula
Dialkyl carbonate, reactant is formula Ar
1The aromatic hydroxy compound of OH, the aryl carbonates or its mixture product that contain from the high boiling reaction mixture that take out continuously the 1st distillation tower bottom are formula
(R
1And Ar
1With above-mentioned definition) carbonate alkyl aryl ester, the by product that the low-boiling reaction mixture that takes out continuously from the 1st distillation tower top contains is formula R
1The Fatty Alcohol(C12-C14 and C12-C18) of OH contains formula
(R wherein
1And Ar
1With above-mentioned definition) carbonate alkyl aryl ester and the above-mentioned high boiling reaction mixture and the formula of taking out continuously from the 1st continuous multi-stage distillation tower bottom
(R
3With R
1Identical or different, Ar
3With Ar
1Identical or different, but R
3And Ar
3Can not distinguish and be R simultaneously
1And Ar
1) the carbonate alkyl aryl ester reactant send into continuously in the 2nd the continuous multi-stage distillation tower, in the 2nd section continuous still battery tower, in the presence of catalyzer, carry out transesterification mutually with liquid phase or solution-air therebetween, make and contain formula
And Ar
3With above-mentioned definition) diaryl carbonate or the high boiling reaction mixture of its mixture, simultaneously this high boiling reaction mixture is taken out with liquid state continuously from the 2nd continuous multi-stage distillation tower bottom, and contain formula from the 2nd continuous multi-stage distillation tower top with gaseous state continuous still battery taking-up simultaneously
(R
1And R
3With above-mentioned definition) dialkyl carbonate or the low-boiling reaction mixture of its mixture by product.
4, the method for claim 3, it is characterized in that catalyzer is the catalyzer that dissolving obtains in the liquid phase, dissolving exists in the liquid phase at least 1 distillation tower of the 1st continuous multi-stage distillation tower and the 2nd continuous multi-stage distillation tower, and/or catalyzer is insoluble solid catalyst basically in the liquid phase, do not dissolve and the existence that distributes in the liquid phase in the 1st continuous multi-stage distillation tower and at least 1 distillation tower of the 2nd continuous multi-stage distillatory.
5, claim 3 or 4 methods is characterized in that R
3With R
1Identical, Ar
3With Ar
1Difference is from the formula that contains of the 2nd continuous multi-stage distillation tower top taking-up
The low-boiling reaction mixture recirculation of dialkyl carbonate send in the 1st the continuous multi-stage distillation tower.
6, the method for claim 1 is characterized in that above-mentioned continuous multi-stage distillation tower as the 1st continuous multi-stage distillation tower, also is used in combination the 2nd continuous multi-stage distillation tower on this basis, and the raw material of sending into continuously in the 1st distillation tower is a formula
Dialkyl carbonate, reactant is formula Ar
1The aromatic hydroxy compound of OH, the aryl carbonates or its mixture product that contain from the high boiling reaction mixture that take out continuously the 1st distillation tower bottom are formula
The carbonate alkyl aryl ester of (R and Ar are with above-mentioned definition), the by product that the low-boiling reaction mixture that takes out continuously from the 1st distillation tower top contains is formula R
1The Fatty Alcohol(C12-C14 and C12-C18) of OH contains formula
Carbonate alkyl aryl ester and the above-mentioned high boiling reaction mixture that takes out continuously from the 1st continuous multi-stage distillation tower bottom is sent in the 2nd the continuous multi-stage distillation tower continuously, in the 2nd continuous still battery tower, in the presence of catalyzer, carry out intermolecular transesterification of the same race mutually, make and contain formula with liquid phase or solution-air
The high boiling reaction mixture of the diaryl carbonate of (Ar is with above-mentioned definition), simultaneously this high boiling reaction mixture is taken out with liquid state continuously from the 2nd continuous multi-stage distillation tower bottom, and contain formula from the 2nd continuous multi-stage distillation tower top with gaseous state continuous still battery taking-up simultaneously
The low-boiling reaction mixture of dialkyl carbonate by product.
7, the method for claim 6 is characterized in that the formula that contains of taking out from the 2nd continuous multi-stage distillation tower top
The lower boiling reaction product recirculation of dialkyl carbonate send in the 1st the continuous multi-stage distillation tower.
8, claim 6 or 7 method, it is characterized in that catalyzer is the catalyzer that dissolving obtains in the liquid phase, dissolving exists in the liquid phase at least 1 distillation tower of the 1st continuous multi-stage distillation tower and the 2nd continuous multi-stage distillation tower, and/or catalyzer is insoluble solid catalyst basically in the liquid phase, do not dissolve and the existence that distributes in the liquid phase in the 1st continuous multi-stage distillation tower and at least 1 distillation tower of the 2nd continuous multi-stage distillatory.
9, the method for claim 8, it is characterized in that catalyzer is the catalyzer that dissolving obtains in the liquid phase, dissolving exists in two distillation towers of the 1st continuous multi-stage distillation tower and the 2nd continuous multi-stage distillation tower, and the 1st and the 2nd the interior catalyzer separately of distillation tower can be identical or different.
10, claim 6 or 7 method, it is characterized in that 1 partly or entirely dissolving existence in liquid phase of the catalyzer of existence in the 1st the continuous multi-stage distillation tower, when the high boiling reaction mixture that takes out with liquid state from the 1st distillation tower bottom is sent into the 2nd continuous multi-stage distillation tower, the liquid high boiling point reaction mixture of this taking-up is imported the 1st evaporating pot, be divided into and contain formula
Carbonate alkyl aryl ester evaporant and contain the debris of catalyst-solvent after, part or all of this evaporant sent in the 2nd the continuous multi-stage distillation tower continuously, and part or all recirculation that will contain the debris of catalyst-solvent is simultaneously sent among the 1st the continuous multi-stage distillation tower.
11, claim 6 or 7 method, it is characterized in that the catalyzer that exists in the 2nd the continuous multi-stage distillation tower 1 partly or entirely in liquid phase dissolving exist, the liquid high boiling point reaction mixture that takes out from the 2nd continuous multi-stage distillation tower bottom imports the 2nd evaporating pot, is divided into and contains formula
Diaryl carbonate evaporant and contain the debris of catalyst-solvent after, part or all recirculation that contains the debris of catalyst-solvent is sent in the 2nd the continuous multi-stage distillation tower.
12, the method for claim 10, it is characterized in that the catalyzer that exists in the 2nd the continuous multi-stage distillation tower 1 partly or entirely in liquid phase dissolving exist, the liquid high boiling point reaction mixture that takes out from the 2nd continuous multi-stage distillation tower bottom imports the 2nd evaporating pot, is divided into and contains formula
Diaryl carbonate evaporant and contain the debris of catalyst-solvent after, part or all recirculation that contains the debris of catalyst-solvent is sent in the 2nd the continuous multi-stage distillation tower.
13, claim 1 or 2 method, it is characterized in that catalyzer is selected from lead compound, copper family metallic compound, alkali metal coordination compound, zine coordination compound, cadmium coordination compound, the iron family metal compound, the zirconium coordination compound, Lewis acid or Louis form compound, organo-tin compound and inorganic oxide.
14, the method for each of claim 3-12, it is characterized in that catalyzer is selected from lead compound, copper family metallic compound, alkali metal coordination compound, zine coordination compound, cadmium coordination compound, the iron family metal compound, the zirconium coordination compound, Lewis acid or Louis form compound, organo-tin compound and inorganic oxide.
15, the method for claim 1,2 or 13 is characterized in that the continuous multi-stage distillation tower is a tray column, packing tower or board-like-filler mixing column.
16, claim 3-12 and 14 each method is characterized in that the 1st continuous multi-stage distillation tower and the 2nd continuous multi-stage distillation tower can be respectively tray column, packing tower or board-like-filler mixing column.
Priority Applications (2)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP2406748A JPH0791234B2 (en) | 1990-12-26 | 1990-12-26 | Continuous production of aromatic carbonates |
| CN91101344.XA CN1030073C (en) | 1990-12-26 | 1991-03-08 | Process for preparing aromatic carbonate |
Applications Claiming Priority (2)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP2406748A JPH0791234B2 (en) | 1990-12-26 | 1990-12-26 | Continuous production of aromatic carbonates |
| CN91101344.XA CN1030073C (en) | 1990-12-26 | 1991-03-08 | Process for preparing aromatic carbonate |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN1064677A true CN1064677A (en) | 1992-09-23 |
| CN1030073C CN1030073C (en) | 1995-10-18 |
Family
ID=36764657
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN91101344.XA Expired - Lifetime CN1030073C (en) | 1990-12-26 | 1991-03-08 | Process for preparing aromatic carbonate |
Country Status (2)
| Country | Link |
|---|---|
| JP (1) | JPH0791234B2 (en) |
| CN (1) | CN1030073C (en) |
Cited By (8)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1077097C (en) * | 1995-09-22 | 2002-01-02 | 旭化成株式会社 | Process for the preparation of aromatic carbonate |
| CN100453520C (en) * | 2003-06-27 | 2009-01-21 | 旭化成化学株式会社 | Method for producing aromatic carbonate |
| CN101010284B (en) * | 2004-09-02 | 2011-06-22 | 旭化成化学株式会社 | Process for producing high-purity diphenyl carbonate on commercial scale |
| CN102531908A (en) * | 2011-12-21 | 2012-07-04 | 陕西省石油化工研究设计院 | Preparation method of methyl phenyl carbonic ester |
| CN106999924A (en) * | 2014-12-04 | 2017-08-01 | 国际壳牌研究有限公司 | Aromatic carbonate prepares the manufacture method of catalyst |
| CN107108449A (en) * | 2015-01-15 | 2017-08-29 | 国际壳牌研究有限公司 | Purposes of the composition comprising titanium or zirconium alkoxide or fragrant oxide in the preparation method of aromatic carbonate |
| CN109675630A (en) * | 2017-10-19 | 2019-04-26 | 中国石油化工股份有限公司 | The preparation and application of the monodisperse solid catalyst of diphenyl carbonate are prepared for transesterification |
| CN111389452A (en) * | 2018-12-31 | 2020-07-10 | 中国石油化工股份有限公司 | Catalyst for synthesizing diphenyl carbonate, preparation method and process thereof |
Families Citing this family (11)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US5731453A (en) * | 1996-03-12 | 1998-03-24 | Ube Industries, Ltd. | Process for producing a diaryl carbonate |
| SG54571A1 (en) * | 1996-09-27 | 1998-11-16 | Ube Industries | Process for producing diaryl carbonate |
| US5922827A (en) * | 1996-09-27 | 1999-07-13 | Ube Industries, Ltd. | Process for producing a polycarbonate |
| JP2005517003A (en) | 2002-02-05 | 2005-06-09 | エルジー・ケム・リミテッド | Continuous production method of aromatic carbonate using heterogeneous catalyst and reaction apparatus thereof |
| EA009715B1 (en) | 2004-07-13 | 2008-02-28 | Асахи Касеи Кемикалз Корпорейшн | Industrial process for producing aromatic carbonate |
| EA010066B1 (en) | 2004-08-25 | 2008-06-30 | Асахи Касеи Кемикалз Корпорейшн | Process for producing high-purity diphenyl carbonate on commercial scale |
| KR100870851B1 (en) | 2004-09-17 | 2008-11-27 | 아사히 가세이 케미칼즈 가부시키가이샤 | Industrial process for separating out by-produced alcohols |
| BRPI0515041B1 (en) | 2004-10-14 | 2015-06-09 | Asahi Kasei Chemicals Corp | Process for the production of high purity diaryl carbonate and process for the production of aromatic polycarbonate by transesterification with an aromatic dihydroxy compound |
| JP4195717B2 (en) | 2004-12-24 | 2008-12-10 | 旭化成ケミカルズ株式会社 | Method for producing aromatic carbonate |
| US7288668B2 (en) * | 2005-11-17 | 2007-10-30 | Catalytic Distillation Technologies | Process for making diaryl carbonate |
| KR101042069B1 (en) * | 2006-11-09 | 2011-06-16 | 주식회사 엘지화학 | Method for preparing aromatic carbonate and reaction equipment for the same |
-
1990
- 1990-12-26 JP JP2406748A patent/JPH0791234B2/en not_active Expired - Lifetime
-
1991
- 1991-03-08 CN CN91101344.XA patent/CN1030073C/en not_active Expired - Lifetime
Cited By (10)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1077097C (en) * | 1995-09-22 | 2002-01-02 | 旭化成株式会社 | Process for the preparation of aromatic carbonate |
| CN100453520C (en) * | 2003-06-27 | 2009-01-21 | 旭化成化学株式会社 | Method for producing aromatic carbonate |
| CN101010284B (en) * | 2004-09-02 | 2011-06-22 | 旭化成化学株式会社 | Process for producing high-purity diphenyl carbonate on commercial scale |
| CN102531908A (en) * | 2011-12-21 | 2012-07-04 | 陕西省石油化工研究设计院 | Preparation method of methyl phenyl carbonic ester |
| CN106999924A (en) * | 2014-12-04 | 2017-08-01 | 国际壳牌研究有限公司 | Aromatic carbonate prepares the manufacture method of catalyst |
| CN106999924B (en) * | 2014-12-04 | 2019-11-29 | 国际壳牌研究有限公司 | Aromatic carbonate prepares the manufacturing method of catalyst |
| CN107108449A (en) * | 2015-01-15 | 2017-08-29 | 国际壳牌研究有限公司 | Purposes of the composition comprising titanium or zirconium alkoxide or fragrant oxide in the preparation method of aromatic carbonate |
| CN109675630A (en) * | 2017-10-19 | 2019-04-26 | 中国石油化工股份有限公司 | The preparation and application of the monodisperse solid catalyst of diphenyl carbonate are prepared for transesterification |
| CN111389452A (en) * | 2018-12-31 | 2020-07-10 | 中国石油化工股份有限公司 | Catalyst for synthesizing diphenyl carbonate, preparation method and process thereof |
| CN111389452B (en) * | 2018-12-31 | 2023-04-07 | 中国石油化工股份有限公司 | Catalyst for synthesizing diphenyl carbonate, preparation method and process thereof |
Also Published As
| Publication number | Publication date |
|---|---|
| JPH0791234B2 (en) | 1995-10-04 |
| JPH04224547A (en) | 1992-08-13 |
| CN1030073C (en) | 1995-10-18 |
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