CN101899022A - Method for preparing epoxypropane by bionically catalyzing epoxidation of propylene - Google Patents
Method for preparing epoxypropane by bionically catalyzing epoxidation of propylene Download PDFInfo
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- CN101899022A CN101899022A CN2010102396486A CN201010239648A CN101899022A CN 101899022 A CN101899022 A CN 101899022A CN 2010102396486 A CN2010102396486 A CN 2010102396486A CN 201010239648 A CN201010239648 A CN 201010239648A CN 101899022 A CN101899022 A CN 101899022A
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- China
- Prior art keywords
- propylene
- general formula
- oxygen
- hydrogen
- propylene oxide
- Prior art date
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Links
- 125000004805 propylene group Chemical group [H]C([H])([H])C([H])([*:1])C([H])([H])[*:2] 0.000 title claims abstract description 76
- QQONPFPTGQHPMA-UHFFFAOYSA-N propylene Natural products CC=C QQONPFPTGQHPMA-UHFFFAOYSA-N 0.000 title claims abstract description 74
- GOOHAUXETOMSMM-UHFFFAOYSA-N Propylene oxide Chemical compound CC1CO1 GOOHAUXETOMSMM-UHFFFAOYSA-N 0.000 title claims abstract description 68
- 238000000034 method Methods 0.000 title claims abstract description 45
- 238000006735 epoxidation reaction Methods 0.000 title claims abstract description 17
- 238000006243 chemical reaction Methods 0.000 claims abstract description 61
- 239000001301 oxygen Substances 0.000 claims abstract description 34
- 229910052760 oxygen Inorganic materials 0.000 claims abstract description 34
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 claims abstract description 31
- 229910052751 metal Inorganic materials 0.000 claims abstract description 14
- 239000002184 metal Substances 0.000 claims abstract description 14
- 238000006555 catalytic reaction Methods 0.000 claims abstract description 11
- IEQIEDJGQAUEQZ-UHFFFAOYSA-N phthalocyanine Chemical compound N1C(N=C2C3=CC=CC=C3C(N=C3C4=CC=CC=C4C(=N4)N3)=N2)=C(C=CC=C2)C2=C1N=C1C2=CC=CC=C2C4=N1 IEQIEDJGQAUEQZ-UHFFFAOYSA-N 0.000 claims abstract description 7
- 239000003054 catalyst Substances 0.000 claims abstract description 5
- 239000007800 oxidant agent Substances 0.000 claims abstract description 4
- 239000002994 raw material Substances 0.000 claims abstract description 4
- HGINCPLSRVDWNT-UHFFFAOYSA-N Acrolein Chemical compound C=CC=O HGINCPLSRVDWNT-UHFFFAOYSA-N 0.000 claims description 44
- XEKOWRVHYACXOJ-UHFFFAOYSA-N Ethyl acetate Chemical compound CCOC(C)=O XEKOWRVHYACXOJ-UHFFFAOYSA-N 0.000 claims description 39
- 239000012752 auxiliary agent Substances 0.000 claims description 20
- 239000000460 chlorine Substances 0.000 claims description 19
- 239000001257 hydrogen Substances 0.000 claims description 13
- 229910052739 hydrogen Inorganic materials 0.000 claims description 13
- 229910052736 halogen Inorganic materials 0.000 claims description 10
- 150000002367 halogens Chemical group 0.000 claims description 10
- WEVYAHXRMPXWCK-UHFFFAOYSA-N Acetonitrile Chemical compound CC#N WEVYAHXRMPXWCK-UHFFFAOYSA-N 0.000 claims description 9
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical group OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 claims description 9
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 claims description 9
- -1 nitro, methyl Chemical group 0.000 claims description 9
- 229910052742 iron Inorganic materials 0.000 claims description 8
- 229910052748 manganese Inorganic materials 0.000 claims description 8
- 229910052801 chlorine Inorganic materials 0.000 claims description 7
- 125000004435 hydrogen atom Chemical group [H]* 0.000 claims description 7
- 125000002887 hydroxy group Chemical group [H]O* 0.000 claims description 7
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 6
- 125000003545 alkoxy group Chemical group 0.000 claims description 6
- 239000002904 solvent Substances 0.000 claims description 6
- YMWUJEATGCHHMB-UHFFFAOYSA-N Dichloromethane Chemical compound ClCCl YMWUJEATGCHHMB-UHFFFAOYSA-N 0.000 claims description 5
- 239000007788 liquid Substances 0.000 claims description 5
- STNJBCKSHOAVAJ-UHFFFAOYSA-N Methacrolein Chemical compound CC(=C)C=O STNJBCKSHOAVAJ-UHFFFAOYSA-N 0.000 claims description 4
- ATUOYWHBWRKTHZ-UHFFFAOYSA-N Propane Chemical compound CCC ATUOYWHBWRKTHZ-UHFFFAOYSA-N 0.000 claims description 4
- 125000004429 atom Chemical group 0.000 claims description 4
- 229910052802 copper Inorganic materials 0.000 claims description 4
- 229910052759 nickel Inorganic materials 0.000 claims description 4
- 229910052725 zinc Inorganic materials 0.000 claims description 4
- ZAMOUSCENKQFHK-UHFFFAOYSA-N Chlorine atom Chemical compound [Cl] ZAMOUSCENKQFHK-UHFFFAOYSA-N 0.000 claims description 3
- 125000003178 carboxy group Chemical group [H]OC(*)=O 0.000 claims description 3
- 229910052731 fluorine Inorganic materials 0.000 claims description 3
- 239000011737 fluorine Substances 0.000 claims description 3
- 229910052782 aluminium Inorganic materials 0.000 claims description 2
- 229910052804 chromium Inorganic materials 0.000 claims description 2
- 229910052749 magnesium Inorganic materials 0.000 claims description 2
- 230000001590 oxidative effect Effects 0.000 claims description 2
- 239000001294 propane Substances 0.000 claims description 2
- 150000003624 transition metals Chemical group 0.000 claims description 2
- 230000003197 catalytic effect Effects 0.000 abstract description 7
- 150000001875 compounds Chemical class 0.000 abstract 1
- 239000003960 organic solvent Substances 0.000 abstract 1
- 239000007789 gas Substances 0.000 description 20
- 238000004587 chromatography analysis Methods 0.000 description 19
- 239000000243 solution Substances 0.000 description 19
- 238000003756 stirring Methods 0.000 description 19
- 239000000047 product Substances 0.000 description 12
- 238000007254 oxidation reaction Methods 0.000 description 8
- 230000000052 comparative effect Effects 0.000 description 7
- YNQLUTRBYVCPMQ-UHFFFAOYSA-N Ethylbenzene Chemical compound CCC1=CC=CC=C1 YNQLUTRBYVCPMQ-UHFFFAOYSA-N 0.000 description 6
- 238000005660 chlorination reaction Methods 0.000 description 6
- XEEYBQQBJWHFJM-UHFFFAOYSA-N iron Substances [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 description 6
- NNPPMTNAJDCUHE-UHFFFAOYSA-N isobutane Chemical compound CC(C)C NNPPMTNAJDCUHE-UHFFFAOYSA-N 0.000 description 6
- 230000003647 oxidation Effects 0.000 description 6
- 150000001336 alkenes Chemical class 0.000 description 5
- 150000002431 hydrogen Chemical group 0.000 description 5
- 238000004519 manufacturing process Methods 0.000 description 5
- AMIMRNSIRUDHCM-UHFFFAOYSA-N Isopropylaldehyde Chemical compound CC(C)C=O AMIMRNSIRUDHCM-UHFFFAOYSA-N 0.000 description 4
- 239000003795 chemical substances by application Substances 0.000 description 4
- 125000001309 chloro group Chemical group Cl* 0.000 description 4
- 239000010949 copper Substances 0.000 description 4
- 230000000694 effects Effects 0.000 description 4
- 238000005516 engineering process Methods 0.000 description 4
- 239000007791 liquid phase Substances 0.000 description 4
- 125000000449 nitro group Chemical group [O-][N+](*)=O 0.000 description 4
- PEDCQBHIVMGVHV-UHFFFAOYSA-N Glycerine Chemical compound OCC(O)CO PEDCQBHIVMGVHV-UHFFFAOYSA-N 0.000 description 3
- DNIAPMSPPWPWGF-UHFFFAOYSA-N Propylene glycol Chemical compound CC(O)CO DNIAPMSPPWPWGF-UHFFFAOYSA-N 0.000 description 3
- JQRLYSGCPHSLJI-UHFFFAOYSA-N [Fe].N1C(C=C2N=C(C=C3NC(=C4)C=C3)C=C2)=CC=C1C=C1C=CC4=N1 Chemical compound [Fe].N1C(C=C2N=C(C=C3NC(=C4)C=C3)C=C2)=CC=C1C=C1C=CC4=N1 JQRLYSGCPHSLJI-UHFFFAOYSA-N 0.000 description 3
- 150000002924 oxiranes Chemical class 0.000 description 3
- 239000000126 substance Substances 0.000 description 3
- NIXOWILDQLNWCW-UHFFFAOYSA-N Acrylic acid Chemical compound OC(=O)C=C NIXOWILDQLNWCW-UHFFFAOYSA-N 0.000 description 2
- LYCAIKOWRPUZTN-UHFFFAOYSA-N Ethylene glycol Chemical compound OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 description 2
- OUUQCZGPVNCOIJ-UHFFFAOYSA-M Superoxide Chemical compound [O-][O] OUUQCZGPVNCOIJ-UHFFFAOYSA-M 0.000 description 2
- 239000002585 base Substances 0.000 description 2
- 239000003153 chemical reaction reagent Substances 0.000 description 2
- 150000001925 cycloalkenes Chemical class 0.000 description 2
- 150000002085 enols Chemical class 0.000 description 2
- 238000009776 industrial production Methods 0.000 description 2
- KQNPFQTWMSNSAP-UHFFFAOYSA-N isobutyric acid Chemical compound CC(C)C(O)=O KQNPFQTWMSNSAP-UHFFFAOYSA-N 0.000 description 2
- 150000002561 ketenes Chemical class 0.000 description 2
- 239000011664 nicotinic acid Substances 0.000 description 2
- JRZJOMJEPLMPRA-UHFFFAOYSA-N olefin Natural products CCCCCCCC=C JRZJOMJEPLMPRA-UHFFFAOYSA-N 0.000 description 2
- 238000002360 preparation method Methods 0.000 description 2
- 241000894007 species Species 0.000 description 2
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 2
- SMZOUWXMTYCWNB-UHFFFAOYSA-N 2-(2-methoxy-5-methylphenyl)ethanamine Chemical compound COC1=CC=C(C)C=C1CCN SMZOUWXMTYCWNB-UHFFFAOYSA-N 0.000 description 1
- RNDNSYIPLPAXAZ-UHFFFAOYSA-N 2-Phenyl-1-propanol Chemical compound OCC(C)C1=CC=CC=C1 RNDNSYIPLPAXAZ-UHFFFAOYSA-N 0.000 description 1
- VZIQXGLTRZLBEX-UHFFFAOYSA-N 2-chloro-1-propanol Chemical compound CC(Cl)CO VZIQXGLTRZLBEX-UHFFFAOYSA-N 0.000 description 1
- NLHHRLWOUZZQLW-UHFFFAOYSA-N Acrylonitrile Chemical compound C=CC#N NLHHRLWOUZZQLW-UHFFFAOYSA-N 0.000 description 1
- WKBOTKDWSSQWDR-UHFFFAOYSA-N Bromine atom Chemical compound [Br] WKBOTKDWSSQWDR-UHFFFAOYSA-N 0.000 description 1
- XUHQBYDWIWFNQY-UHFFFAOYSA-N C12=CC=C(N1)C=C1C=CC(=N1)C=C1C=CC(N1)=CC=1C=CC(N1)=C2.C2(=CC=CC=C2)[Cu](C2=CC=CC=C2)(C2=CC=CC=C2)C2=CC=CC=C2.[Br] Chemical class C12=CC=C(N1)C=C1C=CC(=N1)C=C1C=CC(N1)=CC=1C=CC(N1)=C2.C2(=CC=CC=C2)[Cu](C2=CC=CC=C2)(C2=CC=CC=C2)C2=CC=CC=C2.[Br] XUHQBYDWIWFNQY-UHFFFAOYSA-N 0.000 description 1
- YTZLDQDKVPVUID-UHFFFAOYSA-N C12=CC=C(N1)C=C1C=CC(=N1)C=C1C=CC(N1)=CC=1C=CC(N1)=C2.CC2=C(C=CC=C2)[Fe](C2=CC=CC=C2)(C2=CC=CC=C2)C2=CC=CC=C2 Chemical compound C12=CC=C(N1)C=C1C=CC(=N1)C=C1C=CC(N1)=CC=1C=CC(N1)=C2.CC2=C(C=CC=C2)[Fe](C2=CC=CC=C2)(C2=CC=CC=C2)C2=CC=CC=C2 YTZLDQDKVPVUID-UHFFFAOYSA-N 0.000 description 1
- YSJOIPWSKHSRTH-UHFFFAOYSA-N C12=CC=C(N1)C=C1C=CC(=N1)C=C1C=CC(N1)=CC=1C=CC(N1)=C2.[N+](=O)([O-])C2=C(C=CC=C2)[Ru](C2=CC=CC=C2)(C2=CC=CC=C2)C2=CC=CC=C2 Chemical compound C12=CC=C(N1)C=C1C=CC(=N1)C=C1C=CC(N1)=CC=1C=CC(N1)=C2.[N+](=O)([O-])C2=C(C=CC=C2)[Ru](C2=CC=CC=C2)(C2=CC=CC=C2)C2=CC=CC=C2 YSJOIPWSKHSRTH-UHFFFAOYSA-N 0.000 description 1
- VEXZGXHMUGYJMC-UHFFFAOYSA-M Chloride anion Chemical compound [Cl-] VEXZGXHMUGYJMC-UHFFFAOYSA-M 0.000 description 1
- 241001292396 Cirrhitidae Species 0.000 description 1
- 102000002004 Cytochrome P-450 Enzyme System Human genes 0.000 description 1
- MYMOFIZGZYHOMD-UHFFFAOYSA-N Dioxygen Chemical compound O=O MYMOFIZGZYHOMD-UHFFFAOYSA-N 0.000 description 1
- 102000004190 Enzymes Human genes 0.000 description 1
- 108090000790 Enzymes Proteins 0.000 description 1
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 1
- 101710198130 NADPH-cytochrome P450 reductase Proteins 0.000 description 1
- 241000208125 Nicotiana Species 0.000 description 1
- 235000002637 Nicotiana tabacum Nutrition 0.000 description 1
- 230000010718 Oxidation Activity Effects 0.000 description 1
- 239000004721 Polyphenylene oxide Substances 0.000 description 1
- 239000004743 Polypropylene Substances 0.000 description 1
- DKGAVHZHDRPRBM-UHFFFAOYSA-N Tert-Butanol Chemical compound CC(C)(C)O DKGAVHZHDRPRBM-UHFFFAOYSA-N 0.000 description 1
- XSWALQKVYPLUJA-UHFFFAOYSA-N [Ru].N1C(C=C2N=C(C=C3NC(=C4)C=C3)C=C2)=CC=C1C=C1C=CC4=N1 Chemical compound [Ru].N1C(C=C2N=C(C=C3NC(=C4)C=C3)C=C2)=CC=C1C=C1C=CC4=N1 XSWALQKVYPLUJA-UHFFFAOYSA-N 0.000 description 1
- 239000002253 acid Substances 0.000 description 1
- 125000003647 acryloyl group Chemical group O=C([*])C([H])=C([H])[H] 0.000 description 1
- 230000004913 activation Effects 0.000 description 1
- 239000003513 alkali Substances 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 238000009835 boiling Methods 0.000 description 1
- 239000012267 brine Substances 0.000 description 1
- GDTBXPJZTBHREO-UHFFFAOYSA-N bromine Substances BrBr GDTBXPJZTBHREO-UHFFFAOYSA-N 0.000 description 1
- 229910052794 bromium Inorganic materials 0.000 description 1
- 239000006227 byproduct Substances 0.000 description 1
- 150000001722 carbon compounds Chemical class 0.000 description 1
- 239000011203 carbon fibre reinforced carbon Substances 0.000 description 1
- MPMSMUBQXQALQI-UHFFFAOYSA-N cobalt phthalocyanine Chemical compound [Co+2].C12=CC=CC=C2C(N=C2[N-]C(C3=CC=CC=C32)=N2)=NC1=NC([C]1C=CC=CC1=1)=NC=1N=C1[C]3C=CC=CC3=C2[N-]1 MPMSMUBQXQALQI-UHFFFAOYSA-N 0.000 description 1
- 239000012141 concentrate Substances 0.000 description 1
- 238000011109 contamination Methods 0.000 description 1
- 238000001816 cooling Methods 0.000 description 1
- 238000005260 corrosion Methods 0.000 description 1
- 230000007797 corrosion Effects 0.000 description 1
- 230000018044 dehydration Effects 0.000 description 1
- 238000006297 dehydration reaction Methods 0.000 description 1
- 229910001882 dioxygen Inorganic materials 0.000 description 1
- 238000007599 discharging Methods 0.000 description 1
- 238000004090 dissolution Methods 0.000 description 1
- 238000004821 distillation Methods 0.000 description 1
- 239000003814 drug Substances 0.000 description 1
- 239000000839 emulsion Substances 0.000 description 1
- 238000005265 energy consumption Methods 0.000 description 1
- 235000013305 food Nutrition 0.000 description 1
- 238000005194 fractionation Methods 0.000 description 1
- 238000010438 heat treatment Methods 0.000 description 1
- RBTKNAXYKSUFRK-UHFFFAOYSA-N heliogen blue Chemical compound [Cu].[N-]1C2=C(C=CC=C3)C3=C1N=C([N-]1)C3=CC=CC=C3C1=NC([N-]1)=C(C=CC=C3)C3=C1N=C([N-]1)C3=CC=CC=C3C1=N2 RBTKNAXYKSUFRK-UHFFFAOYSA-N 0.000 description 1
- 150000002430 hydrocarbons Chemical class 0.000 description 1
- WGCNASOHLSPBMP-UHFFFAOYSA-N hydroxyacetaldehyde Natural products OCC=O WGCNASOHLSPBMP-UHFFFAOYSA-N 0.000 description 1
- LSACYLWPPQLVSM-UHFFFAOYSA-N isobutyric acid anhydride Chemical compound CC(C)C(=O)OC(=O)C(C)C LSACYLWPPQLVSM-UHFFFAOYSA-N 0.000 description 1
- 239000011777 magnesium Substances 0.000 description 1
- KIQQAJNFBLKFPO-UHFFFAOYSA-N magnesium;porphyrin-22,23-diide Chemical compound [Mg+2].[N-]1C(C=C2[N-]C(=CC3=NC(=C4)C=C3)C=C2)=CC=C1C=C1C=CC4=N1 KIQQAJNFBLKFPO-UHFFFAOYSA-N 0.000 description 1
- 239000000203 mixture Substances 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 238000005502 peroxidation Methods 0.000 description 1
- 229920000570 polyether Polymers 0.000 description 1
- 238000006116 polymerization reaction Methods 0.000 description 1
- 229920001155 polypropylene Polymers 0.000 description 1
- 150000004032 porphyrins Chemical class 0.000 description 1
- 150000003254 radicals Chemical class 0.000 description 1
- 238000007127 saponification reaction Methods 0.000 description 1
- 238000001577 simple distillation Methods 0.000 description 1
- HPALAKNZSZLMCH-UHFFFAOYSA-M sodium;chloride;hydrate Chemical compound O.[Na+].[Cl-] HPALAKNZSZLMCH-UHFFFAOYSA-M 0.000 description 1
- 238000003746 solid phase reaction Methods 0.000 description 1
- 125000006158 tetracarboxylic acid group Chemical group 0.000 description 1
- IUVXCVGGLRYGFE-UHFFFAOYSA-N tetraphenyl-lambda5-arsane hydrochloride Chemical compound C1=CC=C(C=C1)[AsH](C2=CC=CC=C2)(C3=CC=CC=C3)C4=CC=CC=C4.Cl IUVXCVGGLRYGFE-UHFFFAOYSA-N 0.000 description 1
- 229910052723 transition metal Inorganic materials 0.000 description 1
- 239000000080 wetting agent Substances 0.000 description 1
Classifications
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
- Y02P20/00—Technologies relating to chemical industry
- Y02P20/50—Improvements relating to the production of bulk chemicals
- Y02P20/52—Improvements relating to the production of bulk chemicals using catalysts, e.g. selective catalysts
Landscapes
- Epoxy Compounds (AREA)
Abstract
The invention discloses a method for preparing epoxypropane by bionically catalyzing the epoxidation of propylene. In the method, the propylene is used as a raw material, oxygen is used as an oxidizing agent, a certain amount of organic solvent and aid is added, metal phthalocyanine or a metalloporphyrin compound is used as a catalyst and catalytic reaction is performed at the temperature of between 30 and 140 DEG C under the pressure of between 0.3 and 3.0MPa so as to obtain the epoxypropane. The method has the advantages of mild reaction conditions, good catalytic effect, high selectivity of the epoxypropane, simple process and the like.
Description
Technical field
The present invention relates to a kind of preparation method of propylene oxide, specifically, relate to a kind of method of preparing epoxypropane by bionically catalyzing epoxidation of propylene.
Background technology
Propylene oxide (PO) is the third-largest organic chemical industry's product that output is only second to polypropylene and vinyl cyanide in the acryloyl derivative.The propylene oxide purposes is very extensive, except being used to produce polyether glycol and the glycerol, also can be used for producing propylene glycol, nonionogenic tenside, oil field emulsion splitter, farm chemical emulgent and wetting agent etc. at present.The derivative of propylene oxide also is widely used in industries such as automobile, building, food, tobacco, medicine and makeup.Along with the expansion of propylene oxide purposes and the continuous growth of downstream product consumption, market increases year by year to the demand of propylene oxide.
At present, the main method of industrial production propylene oxide is chlorohydrination and conjugated oxidation (also claim the indirect oxidation method, or be the Halcon method), and these two kinds of methods account for more than 99% of world's overall throughput.Chlorohydrination is that propylene and chlorine, water reaction back are generated propylene chlorohydrin, obtains propylene oxide through saponification reaction then under the alkali lye effect.This method has been the main method of producing PO since being developed by U.S. associating carbon compound company and carry out industrial production the thirties in 20th century always.The shortcoming of this method is to produce a large amount of brine wastes and organic chloride in process of production, and equipment corrosion and blowdown are serious.
Conjugated oxidation divides Trimethylmethane method and ethylbenzene method.Trimethylmethane (or ethylbenzene) generates Trimethylmethane superoxide (or ethylbenzene superoxide) through peroxidation, generates PO with the propylene reaction again, simultaneously the coproduction trimethyl carbinol (or Alpha-Methyl phenylethyl alcohol).This method " three wastes " discharging is few, and shortcoming is the device that long flow path, investment are big, should not build middle and small scale, because the coproduction product is many, is subjected to market factor restriction serious.
In recent years, both at home and abroad the investigator is devoted to always that flow process is simple, by product is few and the research of the green catalysis technology of free of contamination production PO.Molecular oxygen is cheap and easy to get and pollution-free, is optimal oxygen source, so the direct epoxidation of propylene-oxygen is the focus that people study.But mostly concentrate on the gas-solid phase reaction with the Ag series catalyzer to catalyse of modification at present, required severe reaction conditions need higher temperature and pressure, and the selectivity of propylene oxide is still needed also and will further be improved.
The metalloporphyrin title complex is effective stand-in of cytochrome P 450 monooxygenases, and oxygen is had very high activation capacity, can realize the high-selectivity oxidation of hydrocarbon compound under the condition of gentleness.It is catalyzer that Chinese patent ZL200310110533.7 discloses a kind of mixture with metalloporphyrin and transition metal salt, method with chemical oxidizing agent or Oxygen Catalytic Oxidation olefin production enol and ketenes, epoxide, the product of this method is mainly based on enol and ketenes, and the selectivity of epoxide is about 30% in the product.
Chinese patent CN1915983 discloses catalysis of metalloporphyrin C
6-C
10Alkene, C
6-C
10Liquid olefin epoxidations such as cycloolefin prepare the method for epoxide, and this method is co-conducer with the isobutyric aldehyde, and isobutyric aldehyde itself also is oxidized to the dehydration of isopropylformic acid or isopropylformic acid and generates isobutyric anhydride, therefore make reaction system product complexity.The alkene that is fit to this method in addition mainly is cycloolefin or the alkene that is in a liquid state under the normal temperature and pressure, and there is no obvious catalytic effect for the epoxidation of gas alkene such as propylene.
Therefore, developing a kind of is raw material with the propylene, and oxygen is oxygenant, and mild condition, technology is simple, selectivity is high propylene oxide production technology will have crucial application prospect.
Summary of the invention
The object of the present invention is to provide a kind of quasi-enzyme catalytic agent bionic catalysis propylene liquid phase epoxidation to prepare the method for propylene oxide.
For realizing purpose of the present invention; The technical scheme that adopts is: take gaseous propylene as raw material; Take oxygen as oxidant; Add the organic liquid solvent; Add auxiliary agent; Take metal phthalocyanine with general formula (I) structure, general formula (II) or (III) μ-oxygen of the monokaryon metalloporphyrin of structure or general formula (IV) structure-dinuclear metalloporphyrin as catalyst; Being controlled at reaction temperature is 30～140 ℃; Reaction pressure is to carry out catalytic reaction under the condition of 0.3～3.0MPa to obtain expoxy propane; The mol ratio of propylene and auxiliary agent is 1: 0.05～1: 10
General formula (I)
General formula (II)
General formula (III)
General formula (IV)
M in the general formula (I)
1Be transition metal atoms Fe, Co, Mn, Ni, Cu, Zn or Cr, R is hydrogen or carboxyl or sulfonic group; M in the general formula (II)
2Be atoms metal Mg, Al, Fe, Co, Mn, Ni, Cu or Zn, X is halogen or hydrogen, R
1, R
2, R
3, R
4And R
5All be selected from hydrogen, halogen, nitro, methyl, hydroxyl, alkoxyl group or sulfonic group; M in the general formula (III)
3Be atoms metal Fe, Co, Mn or Ru, X is halogen or hydrogen, R
1, R
2, R
3, R
4And R
5All be selected from hydrogen, halogen, nitro, methyl, hydroxyl, alkoxyl group or sulfonic group, dentate X
1Be chlorine; M in the general formula (IV)
4Be atoms metal Fe, Co, Mn or Ru, R
1, R
2, R
3, R
4And R
5All be selected from hydrogen, halogen, nitro, methyl, hydroxyl, alkoxyl group or sulfonic group.
In the method for above-mentioned preparing epoxypropane by bionically catalyzing epoxidation of propylene, preferred propenal of described auxiliary agent or methacrolein.
In the method for above-mentioned preparing epoxypropane by bionically catalyzing epoxidation of propylene, described propylene and auxiliary agent mol ratio be preferably 1: 0.5～and 1: 5.
In above-mentioned preparing epoxypropane by bionically catalyzing epoxidation of propylene preparation method, described solvent is preferably ethanol or ethyl acetate or acetonitrile.
The preferred catalyst concn of the inventive method is 5～100ppm, and preferred temperature of reaction is 60～100 ℃, and preferred reaction pressure is 1.0～2.0MPa, and the mol ratio of preferred propylene and oxygen is 1: 1～1: 5.
The present invention has at first synthesized quasi-enzyme catalytic agent such as metal phthalocyanine, metalloporphyrin, and catalyzer is solved homogeneously in the solvent, adds auxiliary agent, makes propylene and oxygen carry out catalyzed reaction under the effect of catalyzer and makes propylene oxide.The auxiliary agent that adds is the propenal or derivatives thereof, its objective is to make system be easy to generate free radical, can make that oxygen is easier to be activated, thereby can accelerate the epoxidation speed of propylene and improve the selectivity of propylene oxide.In addition, the adding of auxiliary agent can make the oxygen activity species that generate in the reaction process have suitable electron density, and the easier attack carbon-carbon double bond of oxygen activity species of appropriate electronic density is arranged, rather than the α hydrogen of attack propylene, therefore help epoxidation reaction, improved the selectivity of propylene oxide.In addition, the consumption of auxiliary agent is all influential to the selectivity of propylene conversion and propylene oxide, if amount of auxiliary is excessive, the self-polymerization reaction takes place auxiliary agent easily; On the contrary, amount of auxiliary is crossed the low formation that then is unfavorable for oxidation activity thing in the reaction system.
The selecting property of propylene oxide choosing all is higher than 96% under the various reaction conditionss of the present invention, and other products mainly contain vinylformic acid or derivatives thereof, the intact auxiliary agent propenal or derivatives thereof of unreacted that auxiliary agent is transformed in the reaction system.Because propylene oxide and propenal, acrylic acid boiling point differ bigger, just various products can be separated with simple distillation procedure.
Compared with prior art, the present invention has following beneficial effect:
What 1, the present invention adopted is that the direct process for epoxidation of propylene and oxygen prepares propylene oxide, has avoided shortcomings such as environment that use chlorohydrination or conjugated oxidation bring, product complexity.
2, the selectivity height of propylene oxide of the present invention, simple, the easy row of operation, product separate easily.
3, the present invention has used with the metal phthalocyanine and the metal porphyrins of biological enzyme similar structures and has made catalyzer, the epoxidation reaction of propylene and oxygen is carried out in liquid phase, therefore reaction conditions gentleness has reduced the energy consumption of production process, and security simultaneously also is improved.
Embodiment
The present invention is described further below in conjunction with embodiment and Comparative Examples, but protection scope of the present invention is not limited to the scope that embodiment represents.
The propylene ring oxidation reaction that the present invention carries out mainly is to utilize quasi-enzyme catalytic agent such as metal phthalocyanine, metalloporphyrin, with propylene and oxygen dissolution in solvent, adding auxiliary agent, under the katalysis of catalyzer, carry out the liquid-phase catalysis reaction, propylene and auxiliary agent mol ratio be preferably 1: 0.5～and 1: 5; Temperature of reaction is preferably 60～100 ℃ between 30～140 ℃; Reaction pressure is 0.3～3.0MPa, is preferably 1.0～2.0MPa.
Used reagent is commercially available analytical reagent in embodiment and the Comparative Examples.
Quasi-enzyme catalytic agent such as used metal phthalocyanine, metalloporphyrin is by prior art (Alder AD, et al.J.Org.Chem.1967,32,476 in embodiment and the Comparative Examples; Wang LZ etal.Org.Process Res.Dev.2006,10,757) described method is prepared.
The process of embodiment 1-16 explanation bionic catalysis propylene liquid phase epoxidation has wherein been introduced the sepn process of product among the embodiment 1, the sepn process among the embodiment of back is as embodiment 1.
Embodiment 1
Contain 0.1mmol cobalt phthalocyanine (R=H in the general formula (I), M at 25mL
1In=Co) the methanol solution, adding the propenal of 0.01mol, charge into the propylene of 0.8MPa and the oxygen of 1.2MPa respectively, is to carry out stirring reaction under 30 ℃ in temperature, and through gas chromatographic analysis, propylene conversion is 35%, and the selectivity of propylene oxide is 96%.With the reaction solution cooling, pour into and carry out heating in water bath fractionation by distillation propylene oxide in the matrass after reaction finishes, the control bath temperature is 35 ℃, collects product propylene, and its yield is 30%.
Embodiment 2
Contain 1.0 * 10 at 25mL
-3Mmol tetracarboxylic copper phthalocyanine (R=COOH in the general formula (I), M
1In=Cu) the acetonitrile solution, adding the 5.0mmol propenal, charge into the propylene of 0.1MPa and the oxygen of 0.2MPa respectively, is to carry out stirring reaction under 50 ℃ in temperature, and through gas chromatographic analysis, propylene conversion is 38%, and the selectivity of propylene oxide is 97%.After separate purifying, yield is 33% propylene oxide.
Embodiment 3
Contain 1.0 * 10 at 50mL
-3The adjacent chlorine tetraphenyl of mmol iron porphyrin (R in the general formula (II)
1=Cl, R
2=R
3=R
4=R
5=H, M
2=Fe in ethyl acetate solution X=H), adds the methacrolein of 0.1mol, charging into the propylene of 0.8MPa and the oxygen of 2.2MPa respectively, is to carry out stirring reaction under 90 ℃ in temperature, through gas chromatographic analysis, propylene conversion is 45%, and the selectivity of propylene oxide is 96%.After separate purifying, yield is 41% propylene oxide.
Embodiment 4
Contain 1.0 * 10 at 25mL
-4Mmol is to nitro tetraphenyl manganoporphyrin (R in the general formula (II)
3=NO
2, R
1=R
2=R
4=R
5=H, M
2=Mn in toluene solution X=H), adds the propenal of 0.5mol, charging into the propylene of 0.8MPa and the air of 1.6MPa respectively, is to carry out stirring reaction under 120 ℃ in temperature, through gas chromatographic analysis, propylene conversion is 46%, and the selectivity of propylene oxide is 98%.After separate purifying, yield is 42% propylene oxide.
Embodiment 5
Contain 5.0 * 10 at 25mL
-4Mmol 2,6-dichloro tetraphenyl cobalt porphyrin (R in the general formula (II)
1=R
5=Cl, R
2=R
3=R
4=H, M
2=Co in dichloromethane solution X=H), adds the 2-fluorine propenal of 0.3mol, charging into the propylene of 0.8MPa and the oxygen of 0.4MPa respectively, is to carry out stirring reaction under 140 ℃ in temperature, through gas chromatographic analysis, propylene conversion is 43%, and the selectivity of propylene oxide is 99%.After separate purifying, yield is 40% propylene oxide.
Embodiment 6
Contain 5.0 * 10 at 50mL
-3Mmol tetraphenyl magnesium porphyrin (R in the general formula (II)
1=R
2=R
3=R
4=R
5=H, M
2=Mg, N X=H) is in the dinethylformamide solution, adding the propenal of 0.2mol, charge into the propylene of 0.2MPa and the oxygen of 0.3MPa respectively, is to carry out stirring reaction under 80 ℃ in temperature, through gas chromatographic analysis, propylene conversion is 37%, and the selectivity of propylene oxide is 98%.After separate purifying, yield is 34% propylene oxide.
Embodiment 7
Contain 2.0 * 10 at 25mL
-3Mmol O-methoxy tetraphenyl manganoporphyrin (R in the general formula (II)
1=OCH
3, R
2=R
3=R
4=R
5=H, M
2=Mn in ethyl acetate solution X=H), adds the propenal of 0.2mmol, charging into the propylene of 0.3MPa and the air of 1.5MPa respectively, is to carry out stirring reaction under 70 ℃ in temperature, through gas chromatographic analysis, propylene conversion is 41%, and the selectivity of propylene oxide is 98%.After separate purifying, yield is 37% propylene oxide.
Embodiment 8
Contain 1.0 * 10 at 25mL
-3Mmol eight bromine tetraphenyl copper porphyrins (R in the general formula (II)
1=R
2=R
3=R
4=R
5=H, M
2=Cu in ethyl acetate solution X=Br), adds the propenal of 0.03mol, charging into the propylene of 0.6MPa and the oxygen of 1.0MPa respectively, is to carry out stirring reaction under 50 ℃ in temperature, through gas chromatographic analysis, propylene conversion is 42%, and the selectivity of propylene oxide is 99%.After separate purifying, yield is 39% propylene oxide.
Embodiment 9
Contain 1.5 * 10 at 25mL
-3The mmol chlorination is to nitro tetraphenyl ruthenium porphyrin (R in the general formula (III)
3=NO
2, R
1=R
2=R
4=R
5=H, M
3=Ru, X=H, X
1In=Cl) the ethyl acetate solution, add the 2-fluorine propenal of 0.2mol, charge into the propylene of 0.4MPa and the oxygen of 0.6MPa respectively, in temperature is to carry out stirring reaction under 60 ℃, through gas chromatographic analysis, propylene conversion is 46%, and the selectivity of propylene oxide is 96%.After separate purifying, yield is 43% propylene oxide.
Embodiment 10
Contain 0.8 * 10 at 25mL
-3The adjacent hydroxyl tetraphenyl of mmol chlorination manganoporphyrin (R in the general formula (III)
1=OH, R
2=R
3=R
4=R
5=H, M
3=Mn, X=H, X
1In=Cl) the methanol solution, adding the propenal of 0.3mol, charge into the propylene of 0.4MPa and the oxygen of 0.6MPa respectively, is to carry out stirring reaction under 90 ℃ in temperature, and through gas chromatographic analysis, propylene conversion is 35%, and the selectivity of propylene oxide is 97%.After separate purifying, yield is 31% propylene oxide.
Embodiment 11
Contain 1.8 * 10 at 25mL
-3Mmol 3,4-disulfonic acid base tetraphenylarsonium chloride base iron porphyrin (R in the general formula (III)
2=R
4=SO
3H, R
1=R
3=R
5=H, M
3=Fe, X=H, X
1In=Cl) the ethyl acetate solution, add the propenal of 6.0mmol, charge into the propylene of 0.6MPa and the air of 0.8MPa respectively, in temperature is to carry out stirring reaction under 60 ℃, through gas chromatographic analysis, propylene conversion is 37%, and the selectivity of propylene oxide is 99%.After separate purifying, yield is 35% propylene oxide.
Embodiment 12
Contain 0.5 * 10 at 25mL
-3The adjacent chlorine tetraphenyl of mmol chlorination manganoporphyrin (R in the general formula (III)
1=Cl, R
2=R
3=R
4=R
5=H, M
3=Mn, X=H, X
1In=Cl) the ethyl acetate solution, add the methacrolein of 0.3mol, charge into the propylene of 0.5MPa and the oxygen of 1.0MPa respectively, in temperature is to carry out stirring reaction under 80 ℃, through gas chromatographic analysis, propylene conversion is 38%, and the selectivity of propylene oxide is 99%.After separate purifying, yield is 36% propylene oxide.
Embodiment 13
Contain 1.5 * 10 at 50mL
-3(the R in the general formula (III) of methyl tetraphenyl iron porphyrin between the mmol chlorination
2=CH
3, R
1=R
3=R
4=R
5=H, M
3=Fe, X=H, X
1In=Cl) the ethyl acetate solution, add the propenal of 0.06mol, charge into the propylene of 0.6MPa and the oxygen of 1.8MPa respectively, in temperature is to carry out stirring reaction under 100 ℃, through gas chromatographic analysis, propylene conversion is 40%, and the selectivity of propylene oxide is 96%.After separate purifying, yield is 36% propylene oxide.
Embodiment 14
Contain 0.6 * 10 at 25mL
-3The adjacent nitro tetraphenyl of mmol eight bromine chlorinations manganoporphyrin (R in the general formula (III)
1=NO
2, R
2=R
3=R
4=R
5=H, M
3=Mn, X=Br, X
1In=Cl) the ethyl acetate solution, add the propenal of 0.5mol, charge into the propylene of 0.8MPa and the oxygen of 1.6MPa respectively, in temperature is to carry out stirring reaction under 80 ℃, through gas chromatographic analysis, propylene conversion is 41%, and the selectivity of propylene oxide is 99%.After separate purifying, yield is 39% propylene oxide.
Embodiment 15
Contain 0.8 * 10 at 25mL
-4Mmol μ-oxygen-double-core tetraphenyl manganoporphyrin (R in the general formula (IV)
1=R
2=R
3=R
4=R
5=H, M
4In=Mn) the ethanolic soln, adding the propenal of 0.08mol, charge into the propylene of 0.4MPa and the oxygen of 1.2MPa respectively, is to carry out stirring reaction under 60 ℃ in temperature, and through gas chromatographic analysis, propylene conversion is 37%, and the selectivity of propylene oxide is 99%.After separate purifying, yield is 35% propylene oxide.
Embodiment 16
Contain 1.5 * 10 at 25mL
-4The adjacent chlorine tetraphenyl of mmol μ-oxygen-double-core iron porphyrin (R in the general formula (IV)
1=Cl, R
2=R
3=R
4=R
5=H, M
4In=Fe) the ethyl acetate solution, add the propenal of 0.8mol, charge into the propylene of 0.8MPa and the oxygen of 1.2MPa respectively, in temperature is to carry out stirring reaction under 80 ℃, through gas chromatographic analysis, propylene conversion is 36%, and the selectivity of propylene oxide is 99%.After separate purifying, yield is 33% propylene oxide.
Comparative Examples 1-3 illustrates the reaction result of the propylene ring oxidation reaction of carrying out with different amount of auxiliary.
Comparative Examples 1
Contain 1.0 * 10 at 25mL
-4The adjacent nitro tetraphenyl of mmol manganoporphyrin (R in the general formula (II)
1=NO
2, R
2=R
3=R
4=R
5=H, M
2=Mn in toluene solution X=H), does not add auxiliary agent, charges into the propylene of 0.8MPa and the air of 1.2MPa respectively, is to carry out stirring reaction under 90 ℃ in temperature, and through gas chromatographic analysis, propylene conversion is 2%, and the selectivity of propylene oxide is 58%.
Comparative Examples 2
Contain 1.0 * 10 at 25mL
-4The adjacent chlorine tetraphenyl of mmol chlorination ruthenium porphyrin (R in the general formula (III)
1=Cl, R
2=R
3=R
4=R
5=H, M
3=Mn, X=H, X
1In=Cl) the ethyl acetate solution, add the 3.0mmol propenal, charge into the propylene of 0.8MPa and the air of 1.2MPa (propylene and auxiliary agent mol ratio are preferably 1: 0.03) respectively, in temperature is to carry out stirring reaction under 80 ℃, through gas chromatographic analysis, propylene conversion is 6%, and the selectivity of propylene oxide is 80%.
Comparative Examples 3
Contain 1.0 * 10 at 25mL
-4Mmol is to nitro tetraphenyl manganoporphyrin (R in the general formula (II)
3=NO
2, R
1=R
2=R
4=R
5=H, M
2=Mn, X=H) in the ethyl acetate solution, add the 1.5mol propenal, charge into the propylene of 0.8MPa and the air of 1.2MPa (propylene and auxiliary agent mol ratio are preferably 1: 15) respectively, in temperature is to carry out stirring reaction under 90 ℃, through gas chromatographic analysis, propylene conversion is 3%, and the selectivity of propylene oxide is 65%.
Claims (10)
1. the method for a preparing epoxypropane by bionically catalyzing epoxidation of propylene; It is characterized in that take gaseous propylene as raw material; Take oxygen as oxidant; Add the organic liquid solvent; Add auxiliary agent; Take metal phthalocyanine with general formula (I) structure, general formula (II) or (III) μ-oxygen of the monokaryon metalloporphyrin of structure or general formula (IV) structure-dinuclear metalloporphyrin as catalyst; Being controlled at reaction temperature is 30～140 ℃; Reaction pressure is to carry out catalytic reaction under the condition of 0.3～3.0MPa to obtain expoxy propane; The mol ratio of propylene and auxiliary agent is 1: 0.05～1: 10
General formula (I)
General formula (II)
General formula (III)
General formula (IV)
M in the general formula (I)
1Be transition metal atoms Fe, Co, Mn, Ni, Cu, Zn or Cr, R is hydrogen or carboxyl or sulfonic group; M in the general formula (II)
2Be atoms metal Mg, Al, Fe, Co, Mn, Ni, Cu or Zn, X is halogen or hydrogen, R
1, R
2, R
3, R
4And R
5All be selected from hydrogen, halogen, nitro, methyl, hydroxyl, alkoxyl group or sulfonic group; M in the general formula (III)
3Be atoms metal Fe, Co, Mn or Ru, X is halogen or hydrogen, R
1, R
2, R
3, R
4And R
5All be selected from hydrogen, halogen, nitro, methyl, hydroxyl, alkoxyl group or sulfonic group, dentate X
1Be chlorine; M in the general formula (IV)
4Be atoms metal Fe, Co, Mn or Ru, R
1, R
2, R
3, R
4And R
5All be selected from hydrogen, halogen, nitro, methyl, hydroxyl, alkoxyl group or sulfonic group.
2. method according to claim 1 is characterized in that described auxiliary agent is selected from least a in propenal, methacrolein or the 2-fluorine propenal.
3. method according to claim 1, the mol ratio that it is characterized in that propylene and auxiliary agent is 1: 0.5～1: 5.
4. method according to claim 1 is characterized in that described organic liquid solvent is selected from methyl alcohol, ethanol, ethyl acetate, acetonitrile, toluene, methylene dichloride or N, at least a in the dinethylformamide.
5. method according to claim 1, the temperature that it is characterized in that catalyzed reaction is 30～140 ℃.
6. method according to claim 5, the temperature that it is characterized in that catalyzed reaction is 60～100 ℃.
7. method according to claim 1, the total pressure that it is characterized in that propylene and oxygen is 0.3～3.0MPa.
8. method according to claim 7, the total pressure that it is characterized in that propylene and oxygen is 1.0～2.0MPa.
9. method according to claim 1, the mol ratio that it is characterized in that propylene and oxygen is 1: 0.5～1: 5.
10. method according to claim 1 is characterized in that catalyst concn is 1～100ppm.
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| CN102807469A (en) * | 2012-08-22 | 2012-12-05 | 山东科技大学 | Method for preparing tertiary butanol by oxidizing iso-butane |
| CN103450144A (en) * | 2013-09-12 | 2013-12-18 | 中山大学 | Method for preparing epsilon-caprolactone through biomimetic catalysis of cyclohexanone oxidation |
| CN105001183A (en) * | 2015-07-29 | 2015-10-28 | 中山大学惠州研究院 | Method for co-producing epoxypropane and furoic acid |
| CN105085438A (en) * | 2015-07-31 | 2015-11-25 | 中山大学惠州研究院 | Preparation method of propylene epoxide |
| CN107903164A (en) * | 2017-10-24 | 2018-04-13 | 山东联创互联网传媒股份有限公司 | The method for preparing organic acid and epoxy butane at the same time |
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| CN105001183A (en) * | 2015-07-29 | 2015-10-28 | 中山大学惠州研究院 | Method for co-producing epoxypropane and furoic acid |
| CN105001183B (en) * | 2015-07-29 | 2017-12-19 | 中山大学惠州研究院 | A kind of method of coproduction expoxy propane and furancarboxylic acid |
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| CN105085438B (en) * | 2015-07-31 | 2018-08-21 | 中山大学惠州研究院 | A kind of preparation method of propylene oxide |
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