CN106955705A - A kind of gas-phase photocatalysis methanol and ethanol disposably synthesize the preparation and application of the copper catalyst of a variety of ester type compounds - Google Patents
A kind of gas-phase photocatalysis methanol and ethanol disposably synthesize the preparation and application of the copper catalyst of a variety of ester type compounds Download PDFInfo
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- CN106955705A CN106955705A CN201710204172.4A CN201710204172A CN106955705A CN 106955705 A CN106955705 A CN 106955705A CN 201710204172 A CN201710204172 A CN 201710204172A CN 106955705 A CN106955705 A CN 106955705A
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- copper
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- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 title claims abstract description 84
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 title claims abstract description 52
- 239000003054 catalyst Substances 0.000 title claims abstract description 34
- 239000010949 copper Substances 0.000 title claims abstract description 24
- 229910052802 copper Inorganic materials 0.000 title claims abstract description 16
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 title claims abstract description 14
- 238000007146 photocatalysis Methods 0.000 title claims abstract description 12
- 230000001699 photocatalysis Effects 0.000 title claims abstract description 12
- 238000002360 preparation method Methods 0.000 title claims abstract description 11
- 150000002148 esters Chemical class 0.000 title abstract description 12
- 150000001875 compounds Chemical class 0.000 title abstract description 9
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N Titan oxide Chemical compound O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 claims abstract description 41
- 238000006243 chemical reaction Methods 0.000 claims abstract description 28
- XEKOWRVHYACXOJ-UHFFFAOYSA-N Ethyl acetate Chemical compound CCOC(C)=O XEKOWRVHYACXOJ-UHFFFAOYSA-N 0.000 claims abstract description 25
- TZIHFWKZFHZASV-UHFFFAOYSA-N methyl formate Chemical compound COC=O TZIHFWKZFHZASV-UHFFFAOYSA-N 0.000 claims abstract description 22
- XBDQKXXYIPTUBI-UHFFFAOYSA-M Propionate Chemical compound CCC([O-])=O XBDQKXXYIPTUBI-UHFFFAOYSA-M 0.000 claims abstract description 14
- 239000004408 titanium dioxide Substances 0.000 claims abstract description 12
- QPLDLSVMHZLSFG-UHFFFAOYSA-N Copper oxide Chemical compound [Cu]=O QPLDLSVMHZLSFG-UHFFFAOYSA-N 0.000 claims abstract description 10
- 230000003647 oxidation Effects 0.000 claims abstract description 10
- 238000007254 oxidation reaction Methods 0.000 claims abstract description 10
- KXKVLQRXCPHEJC-UHFFFAOYSA-N acetic acid trimethyl ester Natural products COC(C)=O KXKVLQRXCPHEJC-UHFFFAOYSA-N 0.000 claims abstract description 9
- 239000002131 composite material Substances 0.000 claims abstract description 9
- WBJINCZRORDGAQ-UHFFFAOYSA-N formic acid ethyl ester Natural products CCOC=O WBJINCZRORDGAQ-UHFFFAOYSA-N 0.000 claims abstract description 6
- 239000011941 photocatalyst Substances 0.000 claims abstract description 6
- 239000012279 sodium borohydride Substances 0.000 claims abstract description 5
- 229910000033 sodium borohydride Inorganic materials 0.000 claims abstract description 5
- BERDEBHAJNAUOM-UHFFFAOYSA-N copper(I) oxide Inorganic materials [Cu]O[Cu] BERDEBHAJNAUOM-UHFFFAOYSA-N 0.000 claims abstract description 4
- 229960004643 cupric oxide Drugs 0.000 claims abstract description 4
- 229940112669 cuprous oxide Drugs 0.000 claims abstract description 4
- 150000001879 copper Chemical class 0.000 claims abstract 2
- 238000000034 method Methods 0.000 claims description 24
- 238000004519 manufacturing process Methods 0.000 claims description 12
- 239000007789 gas Substances 0.000 claims description 9
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 claims description 6
- 239000012153 distilled water Substances 0.000 claims description 6
- OGIDPMRJRNCKJF-UHFFFAOYSA-N titanium oxide Inorganic materials [Ti]=O OGIDPMRJRNCKJF-UHFFFAOYSA-N 0.000 claims description 6
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 6
- 238000006555 catalytic reaction Methods 0.000 claims description 5
- 238000003756 stirring Methods 0.000 claims description 5
- 239000003795 chemical substances by application Substances 0.000 claims description 4
- 238000005516 engineering process Methods 0.000 claims description 4
- 239000000203 mixture Substances 0.000 claims description 4
- 239000007864 aqueous solution Substances 0.000 claims description 3
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 claims description 3
- 229910052757 nitrogen Inorganic materials 0.000 claims description 3
- 239000001301 oxygen Substances 0.000 claims description 3
- 229910052760 oxygen Inorganic materials 0.000 claims description 3
- 239000000243 solution Substances 0.000 claims description 3
- -1 cuprous oxide compound Chemical class 0.000 claims description 2
- 238000013019 agitation Methods 0.000 claims 1
- PCHJSUWPFVWCPO-UHFFFAOYSA-N gold Chemical compound [Au] PCHJSUWPFVWCPO-UHFFFAOYSA-N 0.000 claims 1
- 229910052737 gold Inorganic materials 0.000 claims 1
- 239000010931 gold Substances 0.000 claims 1
- 239000012266 salt solution Substances 0.000 claims 1
- 239000004575 stone Substances 0.000 claims 1
- 229940108928 copper Drugs 0.000 abstract description 6
- KRFJLUBVMFXRPN-UHFFFAOYSA-N cuprous oxide Chemical compound [O-2].[Cu+].[Cu+] KRFJLUBVMFXRPN-UHFFFAOYSA-N 0.000 abstract description 3
- 239000003638 chemical reducing agent Substances 0.000 abstract description 2
- ZWYDDDAMNQQZHD-UHFFFAOYSA-L titanium(ii) chloride Chemical compound [Cl-].[Cl-].[Ti+2] ZWYDDDAMNQQZHD-UHFFFAOYSA-L 0.000 abstract 2
- BDAGIHXWWSANSR-UHFFFAOYSA-N methanoic acid Natural products OC=O BDAGIHXWWSANSR-UHFFFAOYSA-N 0.000 description 10
- 239000012071 phase Substances 0.000 description 10
- 239000000126 substance Substances 0.000 description 9
- 230000032050 esterification Effects 0.000 description 8
- 238000005886 esterification reaction Methods 0.000 description 8
- IKHGUXGNUITLKF-UHFFFAOYSA-N Acetaldehyde Chemical compound CC=O IKHGUXGNUITLKF-UHFFFAOYSA-N 0.000 description 6
- QTBSBXVTEAMEQO-UHFFFAOYSA-N Acetic acid Chemical compound CC(O)=O QTBSBXVTEAMEQO-UHFFFAOYSA-N 0.000 description 6
- 238000006356 dehydrogenation reaction Methods 0.000 description 6
- OSWFIVFLDKOXQC-UHFFFAOYSA-N 4-(3-methoxyphenyl)aniline Chemical compound COC1=CC=CC(C=2C=CC(N)=CC=2)=C1 OSWFIVFLDKOXQC-UHFFFAOYSA-N 0.000 description 5
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 description 5
- 235000019253 formic acid Nutrition 0.000 description 5
- 239000002994 raw material Substances 0.000 description 5
- 230000006315 carbonylation Effects 0.000 description 4
- 238000005810 carbonylation reaction Methods 0.000 description 4
- 230000008569 process Effects 0.000 description 4
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 description 3
- 239000011521 glass Substances 0.000 description 3
- 238000011160 research Methods 0.000 description 3
- JPVYNHNXODAKFH-UHFFFAOYSA-N Cu2+ Chemical compound [Cu+2] JPVYNHNXODAKFH-UHFFFAOYSA-N 0.000 description 2
- LCGLNKUTAGEVQW-UHFFFAOYSA-N Dimethyl ether Chemical compound COC LCGLNKUTAGEVQW-UHFFFAOYSA-N 0.000 description 2
- VGGSQFUCUMXWEO-UHFFFAOYSA-N Ethene Chemical compound C=C VGGSQFUCUMXWEO-UHFFFAOYSA-N 0.000 description 2
- ZHNUHDYFZUAESO-UHFFFAOYSA-N Formamide Chemical compound NC=O ZHNUHDYFZUAESO-UHFFFAOYSA-N 0.000 description 2
- WQDUMFSSJAZKTM-UHFFFAOYSA-N Sodium methoxide Chemical compound [Na+].[O-]C WQDUMFSSJAZKTM-UHFFFAOYSA-N 0.000 description 2
- 230000005540 biological transmission Effects 0.000 description 2
- 238000009833 condensation Methods 0.000 description 2
- 230000005494 condensation Effects 0.000 description 2
- 229910001431 copper ion Inorganic materials 0.000 description 2
- XTVVROIMIGLXTD-UHFFFAOYSA-N copper(II) nitrate Chemical compound [Cu+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O XTVVROIMIGLXTD-UHFFFAOYSA-N 0.000 description 2
- 238000005260 corrosion Methods 0.000 description 2
- 230000007797 corrosion Effects 0.000 description 2
- 238000005286 illumination Methods 0.000 description 2
- 239000007788 liquid Substances 0.000 description 2
- 239000007787 solid Substances 0.000 description 2
- 241000894007 species Species 0.000 description 2
- 239000000758 substrate Substances 0.000 description 2
- 238000005406 washing Methods 0.000 description 2
- DKPFZGUDAPQIHT-UHFFFAOYSA-N Butyl acetate Natural products CCCCOC(C)=O DKPFZGUDAPQIHT-UHFFFAOYSA-N 0.000 description 1
- 239000001856 Ethyl cellulose Substances 0.000 description 1
- ZZSNKZQZMQGXPY-UHFFFAOYSA-N Ethyl cellulose Chemical compound CCOCC1OC(OC)C(OCC)C(OCC)C1OC1C(O)C(O)C(OC)C(CO)O1 ZZSNKZQZMQGXPY-UHFFFAOYSA-N 0.000 description 1
- 239000005977 Ethylene Substances 0.000 description 1
- 229910002651 NO3 Inorganic materials 0.000 description 1
- 241000208125 Nicotiana Species 0.000 description 1
- 235000002637 Nicotiana tabacum Nutrition 0.000 description 1
- 239000000020 Nitrocellulose Substances 0.000 description 1
- 238000002441 X-ray diffraction Methods 0.000 description 1
- FJWGYAHXMCUOOM-QHOUIDNNSA-N [(2s,3r,4s,5r,6r)-2-[(2r,3r,4s,5r,6s)-4,5-dinitrooxy-2-(nitrooxymethyl)-6-[(2r,3r,4s,5r,6s)-4,5,6-trinitrooxy-2-(nitrooxymethyl)oxan-3-yl]oxyoxan-3-yl]oxy-3,5-dinitrooxy-6-(nitrooxymethyl)oxan-4-yl] nitrate Chemical compound O([C@@H]1O[C@@H]([C@H]([C@H](O[N+]([O-])=O)[C@H]1O[N+]([O-])=O)O[C@H]1[C@@H]([C@@H](O[N+]([O-])=O)[C@H](O[N+]([O-])=O)[C@@H](CO[N+]([O-])=O)O1)O[N+]([O-])=O)CO[N+](=O)[O-])[C@@H]1[C@@H](CO[N+]([O-])=O)O[C@@H](O[N+]([O-])=O)[C@H](O[N+]([O-])=O)[C@H]1O[N+]([O-])=O FJWGYAHXMCUOOM-QHOUIDNNSA-N 0.000 description 1
- HGWOWDFNMKCVLG-UHFFFAOYSA-N [O--].[O--].[Ti+4].[Ti+4] Chemical compound [O--].[O--].[Ti+4].[Ti+4] HGWOWDFNMKCVLG-UHFFFAOYSA-N 0.000 description 1
- IKHGUXGNUITLKF-XPULMUKRSA-N acetaldehyde Chemical compound [14CH]([14CH3])=O IKHGUXGNUITLKF-XPULMUKRSA-N 0.000 description 1
- 230000000844 anti-bacterial effect Effects 0.000 description 1
- 239000003899 bactericide agent Substances 0.000 description 1
- 230000008901 benefit Effects 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 230000000903 blocking effect Effects 0.000 description 1
- 230000003197 catalytic effect Effects 0.000 description 1
- 239000001913 cellulose Substances 0.000 description 1
- 229920002678 cellulose Polymers 0.000 description 1
- 239000000919 ceramic Substances 0.000 description 1
- 230000008859 change Effects 0.000 description 1
- 238000004891 communication Methods 0.000 description 1
- 238000011109 contamination Methods 0.000 description 1
- 238000007796 conventional method Methods 0.000 description 1
- 238000001816 cooling Methods 0.000 description 1
- ORTQZVOHEJQUHG-UHFFFAOYSA-L copper(II) chloride Chemical compound Cl[Cu]Cl ORTQZVOHEJQUHG-UHFFFAOYSA-L 0.000 description 1
- ARUVKPQLZAKDPS-UHFFFAOYSA-L copper(II) sulfate Chemical compound [Cu+2].[O-][S+2]([O-])([O-])[O-] ARUVKPQLZAKDPS-UHFFFAOYSA-L 0.000 description 1
- OPQARKPSCNTWTJ-UHFFFAOYSA-L copper(ii) acetate Chemical compound [Cu+2].CC([O-])=O.CC([O-])=O OPQARKPSCNTWTJ-UHFFFAOYSA-L 0.000 description 1
- 239000013078 crystal Substances 0.000 description 1
- 238000011161 development Methods 0.000 description 1
- 235000014113 dietary fatty acids Nutrition 0.000 description 1
- 238000001035 drying Methods 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 238000005265 energy consumption Methods 0.000 description 1
- 150000002168 ethanoic acid esters Chemical class 0.000 description 1
- 229920001249 ethyl cellulose Polymers 0.000 description 1
- 235000019325 ethyl cellulose Nutrition 0.000 description 1
- 238000011156 evaluation Methods 0.000 description 1
- 229930195729 fatty acid Natural products 0.000 description 1
- 239000000194 fatty acid Substances 0.000 description 1
- 239000000835 fiber Substances 0.000 description 1
- 239000012847 fine chemical Substances 0.000 description 1
- 239000002316 fumigant Substances 0.000 description 1
- 238000004817 gas chromatography Methods 0.000 description 1
- 239000003254 gasoline additive Substances 0.000 description 1
- FUZZWVXGSFPDMH-UHFFFAOYSA-N hexanoic acid Chemical compound CCCCCC(O)=O FUZZWVXGSFPDMH-UHFFFAOYSA-N 0.000 description 1
- 230000007062 hydrolysis Effects 0.000 description 1
- 238000006460 hydrolysis reaction Methods 0.000 description 1
- 239000002917 insecticide Substances 0.000 description 1
- 239000007791 liquid phase Substances 0.000 description 1
- 229920001220 nitrocellulos Polymers 0.000 description 1
- 239000003960 organic solvent Substances 0.000 description 1
- 238000005839 oxidative dehydrogenation reaction Methods 0.000 description 1
- 239000004033 plastic Substances 0.000 description 1
- 229920003023 plastic Polymers 0.000 description 1
- 239000000843 powder Substances 0.000 description 1
- 239000002243 precursor Substances 0.000 description 1
- 238000012545 processing Methods 0.000 description 1
- 238000006722 reduction reaction Methods 0.000 description 1
- 239000011347 resin Substances 0.000 description 1
- 229920005989 resin Polymers 0.000 description 1
- 230000004044 response Effects 0.000 description 1
- 238000007086 side reaction Methods 0.000 description 1
- 229910052709 silver Inorganic materials 0.000 description 1
- 239000004332 silver Substances 0.000 description 1
- 239000011973 solid acid Substances 0.000 description 1
- 239000002904 solvent Substances 0.000 description 1
- 229910001220 stainless steel Inorganic materials 0.000 description 1
- 239000010935 stainless steel Substances 0.000 description 1
- 239000000725 suspension Substances 0.000 description 1
- 238000003786 synthesis reaction Methods 0.000 description 1
- 229920003051 synthetic elastomer Polymers 0.000 description 1
- 238000010189 synthetic method Methods 0.000 description 1
- 239000005061 synthetic rubber Substances 0.000 description 1
- 238000012360 testing method Methods 0.000 description 1
- 238000002371 ultraviolet--visible spectrum Methods 0.000 description 1
- 125000000391 vinyl group Chemical group [H]C([*])=C([H])[H] 0.000 description 1
- 229920002554 vinyl polymer Polymers 0.000 description 1
- 239000002699 waste material Substances 0.000 description 1
Classifications
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J23/00—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00
- B01J23/70—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper
- B01J23/72—Copper
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J23/00—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00
- B01J23/002—Mixed oxides other than spinels, e.g. perovskite
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J35/00—Catalysts, in general, characterised by their form or physical properties
- B01J35/30—Catalysts, in general, characterised by their form or physical properties characterised by their physical properties
- B01J35/39—Photocatalytic properties
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C67/00—Preparation of carboxylic acid esters
- C07C67/39—Preparation of carboxylic acid esters by oxidation of groups which are precursors for the acid moiety of the ester
- C07C67/40—Preparation of carboxylic acid esters by oxidation of groups which are precursors for the acid moiety of the ester by oxidation of primary alcohols
Landscapes
- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Engineering & Computer Science (AREA)
- Materials Engineering (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
- Catalysts (AREA)
Abstract
The invention provides a kind of preparation method of the copper-based composite photocatalyst of titanium dichloride load and its under gas phase condition, photocatalysis partial oxidation methanol and ethanol disposably prepare the reaction process of methyl formate, Ethyl formate, methyl acetate and ethyl acetate.Mixed phase titanium dioxide using Detitanium-ore-type or anatase and a small amount of rutile is carrier, and soluble copper salt is copper species（Metallic copper, cupric oxide, cuprous oxide）Presoma, sodium borohydride is reducing agent, the Nanometer Copper composite catalyst of titanium dichloride load is prepared, methanol and alcohol gas partial oxidation can disposably be synthesized methyl formate, Ethyl formate, methyl acetate and ethyl acetate by the catalyst under ultraviolet light in oxygenous atmosphere.Prepared catalyst has a good stability, high conversion rate, the characteristics of total ester type compound is selectively high.
Description
Technical field
The present invention relates to a kind of preparation of photochemical catalyst and its application, category derived energy chemical and field of fine chemical are main suitable
A variety of ester type compounds are disposably synthesized for gas-phase photocatalysis partial oxidation methanol/ethanol under low temperature（Methyl formate, formic acid second
Ester, methyl acetate, ethyl acetate) reaction there is provided the preparation method of catalyst and catalytic reaction process conditions.
Background technology
Methyl formate is described as " omnipotent chemical intermediate ", available for production formic acid, formamide and other tens kinds
Chemical products, can also be directly used as insecticide, bactericide, fumigant, agent for tobacco treatment and gasoline additive [G. Jenner.
Appl. Catal. A. 1995, 121, 25-44].Traditional methyl formate production method mainly has methanol esterification method, methanol
Carbonylation method, methanol dehydrogenation method and one-step method from syngas, wherein methanol dehydrogenation method include methanol direct dehydrogenation and oxidative dehydrogenation two
The method of kind.Esterification process technique falls behind, production cost is high, equipment corrosion is serious, and production technology is eliminated substantially；Carbonylation method reaction pressure
Power is high（4.0MPa）, complex process, catalyst sodium methoxide facile hydrolysis blocking pipeline and production cost it is high；One-step method from syngas is reacted
Pressure is high（The U.S. is more than 0.69MPa, domestic 4.0-5.0MPa）.
Compared with other conventional methods, traditional methanol dehydrogenation method has that raw material is single, reaction condition gentle, selecting response
Property and activity is high, the low advantage of equipment investment, thus receive significant attention.But conventional catalyst optimal reaction temperature is higher
（About 280 DEG C）, it is impossible to meet the requirement of low energy consumption.
H. Kominami etc. [H. Kominami, et al. Chem. Comm. 2010,11,426-429.] is reported
It is anti-that road realizes under ultraviolet light conditions gas phase oxidation dehydrogenation from methanol to methyl formate using anatase titanium dioxide
Should, at room temperature（25℃）Methyl formate conversion ratio nearly 10%, selectivity is more than 91%.The report such as Yang Xuzhuan is catalyzed using the silver of load
Agent realizes methanol to conversion [Xuzhuang Yang, the et al. Catalysis of methyl formate under liquid-phase condition
Communications. 2014, 43, 192-196]。
The production of methyl acetate mainly has using ethanol and formic acid as the direct esterification of raw material, using methanol as the methanol of raw material
Carbonylation method and methanol dehydrogenation method and Dimethyl ether carbonylation method etc..Direct esterification will be catalyzed using sulfuric acid or solid acid
Agent, other several method reaction temperatures are general more than 200 DEG C, and several MPas to tens MPas of pressure does not wait [Wu Wen Ping etc., acetic acid
Methyl esters study on the synthesis new development, gas chemical industry, 2004,29. C. Zuo, et. al, Industrial ＆
Engineering Chemistry Research,2014,53, 10540-10548. H. Xue, et al,Industrial
＆ Engineering Chemistry Research, 2013,52,11510-11515.], accessory substance is more.Ethyl formate
Catalyst for making direct esterification production is typically made of sulfuric acid using formic acid and ethanol as raw material, it is seriously polluted.Methyl acetate and Ethyl formate
Research report it is less.
Ethyl acetate is one of widely used fatty acid ester, maximum with excellent dissolubility, quick-drying
Function as organic solvent.Ethyl acetate is also widely used for China Synthetic Rubber Industry, vinyl resin fiber element, acetic acid esters
The production of the products such as cellulose, butyl acetate, ethyl cellulose, cellulose nitrate.[Liu Chong etc. compiles petrochemical industries handbook (three) north
Capital:Chemical Industry Press, 1987: P259.].[Cheng Nenglin, Hu Shengwen solvents handbook (volume two) [M] Beijing:Chemical industry
Publishing house, 1987:14-15].
Synthetic Methods of Ethyl Acetate generally has direct esterification, acetaldehyde condensation method, alcohol catalysis dehydriding, acetic acid
/ ethylene synthase esterification process etc..Wherein direct esterification has the following disadvantages：Reaction temperature is high, acetic acid utilization rate is low, Yi Fa
Raw side reaction；Simultaneously due to the severe corrosive of the catalyst concentrated sulfuric acid in production process, cause equipment corrosion serious, waste liquor contamination ring
Border, accessory substance processing is difficult, causes production cost high.Acetaldehyde condensation method is limited by raw material acetaldehyde, and prepared by catalyst hardly possible, the Yishui River
Solution, course of reaction need cooling.
The content of the invention
The purpose of the present invention is mainly to provide a kind of reaction temperature at 10-50 DEG C, can be by under gas phase and illumination condition
Methanol and partial oxidation of ethanol disposably synthesize the highly efficient titania of methyl formate, Ethyl formate, methyl acetate, ethyl acetate
The preparation method of the Nanometer Copper photochemical catalyst of load and the production technology for above-mentioned reaction.
The present invention is first by Cu-TiO2Photochemical catalyst（Wherein copper species are metallic copper, cupric oxide, cuprous oxide）For gas
Phase photocatalysis partial oxidation methanol and ethanol disposably synthesize the reaction of a variety of ester type compounds.Test result indicate that, catalyst
With higher methanol and ethanol conversion and total esters selectivity.In the range of experimental temperature and under illumination condition, conversion ratio
More than 50-70% is reached, total esters selectively reach more than 60-90%, and accessory substance has a small amount of ethene, acetaldehyde and acetone.
The catalyst Cu/TiO of the present invention2By 2-10% copper species（Metallic copper, cupric oxide, cuprous oxide）And 90-98%
Titanium dioxide constitute, titanium dioxide crystal form be Detitanium-ore-type or anatase with it is a small amount of（Less than 25%）Rutile mixed phase is constituted.
The preparation method of catalyst of the present invention is prepared using chemical reduction method.
Preparation method is as follows.
（1）Take a certain amount of mantoquita with distilled water with 1:10 proportional arrangement is stirred into the aqueous solution containing copper ion；
（2）A certain amount of titanium dioxide ultrasonic disperse is weighed in distilled water, and adds step（1）The copper ions of preparation it is molten
In liquid, 15 min are stirred；
（3）With Cu:NaBH4=1:2（Mol ratio）Appropriate sodium borohydride is weighed, is dissolved in distilled water, it is under fast stirring that its is fast
Speed is added in above-mentioned mixed liquor, stirs 24 h；
(4) centrifuge, washing, dried at 50 DEG C, obtain catalyst.
Specific surface area of catalyst and the specific surface area of titanium dioxide precursor prepared by the present invention is approached, typically in 50-
300m2/g；
Titanium dioxide as described above can be commercial mixed phase titanium dioxide P25, commercial anatase titanium dioxide ST-01, from
The mixed phase titanium dioxide of Detitanium-ore-type or anatase and rutile processed.
Mantoquita as described above can be the one or more of copper nitrate, copper chloride, copper acetate, copper sulphate.
The catalyst of the present invention is applied to the reaction that gas-phase photocatalysis methanol/ethanol disposably synthesizes a variety of ester type compounds
Method is as follows：
Catalyst fines is sprayed on a solid surface, and the solid can be glass, stainless steel, plastics, ceramics, and light source is ultraviolet
Light or sunshine, reaction temperature are 10-50 DEG C, and oxygen volumn concentration is 1-5% or so, methanol volumn concentration 1-
2%, ethanol volumn concentration 1-2%, nitrogen are Balance Air, and reaction velocity is 100-400 L.g-1.h-1.
Compared with the prior art the present invention has following innovation and feature：
First by Cu-TiO2Catalyst disposably synthesizes methyl formate, formic acid for gas-phase photocatalysis partial oxidation methanol/ethanol
Ethyl ester, methyl acetate, acetic acid ethyl reaction.
Catalytic reaction temperature is 10-50 DEG C, is a variety of ester type compound reaction temperatures of current partial oxidation methanol/ethanol system
Minimum operation condition.
Operating condition.
Brief description of the drawings：
Fig. 1 is the CuO liquid uv-vis spectras prepared（UV-Vis）Figure；
Fig. 2 is the Cu/TiO prepared2The X x ray diffractions of composite photo-catalyst（XRD）Collection of illustrative plates；
Fig. 3 is the Cu/TiO prepared2The transmission electron microscope of composite photo-catalyst（TEM）Figure；
Fig. 4 is the Cu/TiO prepared2The high-resolution-ration transmission electric-lens of composite photo-catalyst（TEM）Figure.
Embodiment
With reference to embodiment, the present invention is further illustrated, and the present invention includes but is not limited to the following examples.
Measure 10 mL 0.01mol/L Cu (NO3)2The aqueous solution is in 500 ml round-bottomed flasks；Weigh 0.4 g P25 bis-
Titanium dioxide powder ultrasonic disperse is then added in above-mentioned solution in 5 ml distilled water, stirring；Weigh 0.0038 g NaBH4,
It is dissolved in 5 ml distilled water and is quickly adding into the suspension of above-mentioned titanium dioxide and copper nitrate；Continue to stir 24 h,
Centrifuge, washing, be dried in vacuo 6 h at 50 DEG C, produce 2%Cu/TiO2Composite photo-catalyst.In a similar manner, change and add
Enter P25 amount, prepare different mol ratio（4%、6%、8%、10%）Cu/TiO2Composite catalyst.
2%Cu/TiO prepared by the above method2Composite catalyst is sprayed on the glass substrate, and will scribble catalyst
Substrate of glass is placed in photo catalysis reactor, be passed through reactor feed gas and open uviol lamp start reaction, utilize gas-chromatography
Detect the composition of reaction end gas.Catalyst amount 0.02g, 10-50 DEG C of reaction temperature, unstripped gas 1% methanol of composition, 1% ethanol,
2% oxygen, 96% nitrogen, the ml/min of raw gas flow 55, the L.g of air speed 150-1.h-1。
Above catalyst carries out photocatalysis performance evaluation result and shows that the methanol or ethanol conversion of the catalyst are
More than 70%, the selectivity of total ester type compound is up to 90%.The Catalyst Conversion and selectivity are high, and reaction stability is good, is excellent
The catalyst of good photochemical catalytic oxidation methanol and a variety of ester type compounds of ethanol system.
Claims (1)
1. a kind of gas-phase photocatalysis partial oxidation methanol and ethanol disposably prepare methyl formate, Ethyl formate, methyl acetate and
The method for preparing catalyst and production technology of ethyl acetate, it is characterised in that the composition of catalyst, preparation method and photocatalysis are anti-
Answer condition；The composition of catalyst:Metallic copper, cupric oxide and the cuprous oxide compound of nano titanium oxide load are photocatalysis
Agent, titanium dioxide and different types of copper species are active component；Titanium dioxide is Detitanium-ore-type or anatase and a small amount of gold
The mixed phase structure of red stone, the molar fraction of copper species is 2-10%；The preparation method of catalyst：In appropriate soluble copper salt solution
Titanium dioxide is added in solution, ultrasonic agitation rapidly joins a certain amount of sodium borohydride aqueous solution, stirs 24 h, centrifuges,
Washed with distilled water, ethanol, dried at 50 DEG C, obtain Cu/TiO2Composite photo-catalyst；Catalytic reaction condition：Ultraviolet light or
Sunshine irradiates, and reaction temperature is 10-50 DEG C, and methanol volume content is 1-2% or so in unstripped gas, and alcohol volume content is 1-
2% or so, the volume fraction about 1-5% of oxygen, Balance Air are nitrogen, air speed 100-400 L.g-1.h-1。
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Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN106883087A (en) * | 2017-03-21 | 2017-06-23 | 内蒙古大学 | A kind of Cu/TiO of volatile corrosion inhibitor film producing ethylene with ethyl alcohol, acetaldehyde and acetone2Catalyst and reaction process |
| CN110449154A (en) * | 2019-07-21 | 2019-11-15 | 内蒙古农业大学 | A kind of copper oxide and titanium dioxide heterogeneous knot composite catalyst and its preparation method and application |
| CN110813307A (en) * | 2019-11-12 | 2020-02-21 | 武汉工程大学 | P-n heterojunction type copper oxide-tungsten oxide material and preparation method and application thereof |
| CN113332981A (en) * | 2021-06-15 | 2021-09-03 | 华东理工大学 | Carbon dioxide reduction photocatalytic material, preparation method and application thereof |
Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN103864576A (en) * | 2014-03-28 | 2014-06-18 | 厦门大学 | Method of preparing ethylene glycol by photo-catalytic formaldehyde conversion |
| CN103894198A (en) * | 2014-04-18 | 2014-07-02 | 内蒙古大学 | Preparation and application of Cu/TiO2 composite catalyst for synthesizing methyl formate by partially oxidizing methanol under gas-phase photocatalytic conditions |
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Patent Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN103864576A (en) * | 2014-03-28 | 2014-06-18 | 厦门大学 | Method of preparing ethylene glycol by photo-catalytic formaldehyde conversion |
| CN103894198A (en) * | 2014-04-18 | 2014-07-02 | 内蒙古大学 | Preparation and application of Cu/TiO2 composite catalyst for synthesizing methyl formate by partially oxidizing methanol under gas-phase photocatalytic conditions |
Cited By (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN106883087A (en) * | 2017-03-21 | 2017-06-23 | 内蒙古大学 | A kind of Cu/TiO of volatile corrosion inhibitor film producing ethylene with ethyl alcohol, acetaldehyde and acetone2Catalyst and reaction process |
| CN110449154A (en) * | 2019-07-21 | 2019-11-15 | 内蒙古农业大学 | A kind of copper oxide and titanium dioxide heterogeneous knot composite catalyst and its preparation method and application |
| CN110813307A (en) * | 2019-11-12 | 2020-02-21 | 武汉工程大学 | P-n heterojunction type copper oxide-tungsten oxide material and preparation method and application thereof |
| CN110813307B (en) * | 2019-11-12 | 2022-09-02 | 武汉工程大学 | P-n heterojunction type copper oxide-tungsten oxide material and preparation method and application thereof |
| CN113332981A (en) * | 2021-06-15 | 2021-09-03 | 华东理工大学 | Carbon dioxide reduction photocatalytic material, preparation method and application thereof |
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