CN107032993A - A kind of gas-phase photocatalysis methanol and ethanol disposably synthesize the preparation and application of the Au catalyst of a variety of esters - Google Patents

A kind of gas-phase photocatalysis methanol and ethanol disposably synthesize the preparation and application of the Au catalyst of a variety of esters Download PDF

Info

Publication number
CN107032993A
CN107032993A CN201710322783.9A CN201710322783A CN107032993A CN 107032993 A CN107032993 A CN 107032993A CN 201710322783 A CN201710322783 A CN 201710322783A CN 107032993 A CN107032993 A CN 107032993A
Authority
CN
China
Prior art keywords
catalyst
methanol
ethanol
esters
gas
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.)
Pending
Application number
CN201710322783.9A
Other languages
Chinese (zh)
Inventor
杨绪壮
陈学涛
张伟达
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
Inner Mongolia University
Original Assignee
Inner Mongolia University
Priority date (The priority date 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 date listed.)
Filing date
Publication date
Application filed by Inner Mongolia University filed Critical Inner Mongolia University
Priority to CN201710322783.9A priority Critical patent/CN107032993A/en
Publication of CN107032993A publication Critical patent/CN107032993A/en
Pending legal-status Critical Current

Links

Classifications

    • CCHEMISTRY; METALLURGY
    • C07ORGANIC CHEMISTRY
    • C07CACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C67/00Preparation of carboxylic acid esters
    • C07C67/39Preparation of carboxylic acid esters by oxidation of groups which are precursors for the acid moiety of the ester
    • C07C67/40Preparation of carboxylic acid esters by oxidation of groups which are precursors for the acid moiety of the ester by oxidation of primary alcohols
    • BPERFORMING OPERATIONS; TRANSPORTING
    • B01PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01JCHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J23/00Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00
    • B01J23/38Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of noble metals
    • B01J23/48Silver or gold
    • B01J23/52Gold
    • BPERFORMING OPERATIONS; TRANSPORTING
    • B01PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01JCHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J35/00Catalysts, in general, characterised by their form or physical properties
    • B01J35/30Catalysts, in general, characterised by their form or physical properties characterised by their physical properties
    • B01J35/39Photocatalytic properties
    • BPERFORMING OPERATIONS; TRANSPORTING
    • B01PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01JCHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J35/00Catalysts, in general, characterised by their form or physical properties
    • B01J35/60Catalysts, in general, characterised by their form or physical properties characterised by their surface properties or porosity
    • B01J35/61Surface area
    • B01J35/61310-100 m2/g
    • BPERFORMING OPERATIONS; TRANSPORTING
    • B01PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01JCHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J35/00Catalysts, in general, characterised by their form or physical properties
    • B01J35/60Catalysts, in general, characterised by their form or physical properties characterised by their surface properties or porosity
    • B01J35/61Surface area
    • B01J35/615100-500 m2/g
    • CCHEMISTRY; METALLURGY
    • C07ORGANIC CHEMISTRY
    • C07CACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C67/00Preparation of carboxylic acid esters
    • C07C67/39Preparation of carboxylic acid esters by oxidation of groups which are precursors for the acid moiety of the ester

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)
  • Low-Molecular Organic Synthesis Reactions Using Catalysts (AREA)

Abstract

A kind of gas-phase photocatalysis methanol and ethanol disposably synthesize the preparation of the Au catalyst of a variety of esters and using photocatalysis partial oxidation methanol and ethanol prepare the experimental method and reaction condition of the compounds such as methyl formate, ethyl acetate, Ethyl formate, methyl acetate the invention provides a kind of preparation method of nano catalyst of titanium dichloride load and its under gas phase condition.Mixed phase titanium dioxide using Detitanium-ore-type or anatase and a small amount of rutile is carrier, using soluble gold salt as the presoma of gold, sodium borohydride is reducing agent, prepare the nano catalyst of titanium dichloride load, the catalyst, can be in oxygen-containing atmosphere by a variety of esters products such as methanol and ethanol mixed gas partial oxidation formic acid methyl esters, ethyl acetate, Ethyl formate, methyl acetate under ultraviolet light.Prepared catalyst has stability good, and methanol and ethanol conversion are high, the characteristics of total esters are selectively high.

Description

A kind of gas-phase photocatalysis methanol and ethanol disposably synthesize the Au catalyst of a variety of esters Preparation and application
Technical field
The present invention relates to a kind of preparation of photochemical catalyst and its at low temperature gas-phase photocatalysis partial oxidation ethanol and methanol The application of a variety of esters products is prepared, there is provided the preparation method of catalyst and catalysis are anti-for category derived energy chemical and field of fine chemical Answer condition.
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;Cause equipment corrosion serious, waste liquor contamination ring due to the severe corrosive of the catalyst concentrated sulfuric acid in production process simultaneously 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 15-50 DEG C, can be by under gas phase and illumination condition The high-efficiency titanium dioxide of the product such as methanol and ethanol gaseous mixture partial oxidation formic acid methyl esters, ethyl acetate, Ethyl formate, methyl acetate Change the nanogold Au-TiO of titanium load2Photochemical catalyst preparation method and application.
The present invention is first by Au-TiO2Photochemical catalyst is used for gas-phase photocatalysis partial oxidation methanol and ethanol gaseous mixture first The reaction of the products such as sour methyl esters, ethyl acetate, Ethyl formate, methyl acetate.Test result indicates that, catalyst has higher first Alcohol and ethanol conversion and total esters selectivity.In the range of experimental temperature and under illumination condition, methanol conversion reaches 60- More than 80%, ethanol conversion reaches more than 60-70%, and total esters selectively reach more than 75-95%, accessory substance have a small amount of ethene, Acetaldehyde and acetone.
The catalyst Au-TiO of the present invention2By 1-5 gold and 95-99%(Mol ratio)Titanium dioxide constitute, titanium dioxide Crystal formation is Detitanium-ore-type or anatase and a small amount of(Less than 25%)Rutile mixed phase is constituted.
The preparation method is that being prepared using chemical reduction method.
Preparation method is as follows.
(1)A certain amount of gold chloride is taken to be configured to 0.001 mol/l aqueous solution of chloraurate with distilled water.
(2)With Au:NaBH4=1:4(Mol ratio)Appropriate sodium borohydride is weighed, in the distilled water for being dissolved in advance ice bath cooling.
(3)A certain amount of titanium dioxide ultrasonic disperse is weighed in step(2)In the sodium borohydride aqueous solution of preparation, ice is kept Bath cooling continues to stir.
(4)By step(1)The aqueous solution of chloraurate of preparation is added dropwise to step(3)In obtained mixed solution, simultaneously It is stirred vigorously until reaction is completed.Stop stirring and standing 24 h.
(5)Centrifuge, washing, dried at 60 DEG C, catalyst is obtained after 400 DEG C of 1 h of calcining.
Specific surface area of catalyst and the specific surface area of titanium dioxide precursor prepared by the present invention is approached, typically in 50-300 m2/g。
Titanium dioxide as described above can be commercial mixed phase titanium dioxide P25, commercial anatase titanium dioxide ST- 01st, the mixed phase titanium dioxide of self-control Detitanium-ore-type or anatase and rutile.
Solubility gold salt as described above can be gold chloride, acetic acid gold, chlorauride.
The catalyst of the present invention is applied to gas-phase photocatalysis partial oxidation methanol and ethanol gaseous mixture methyl formate, acetic acid The reaction methods such as ethyl ester, Ethyl formate, methyl acetate are 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 is 15-50 DEG C, and methanol/ethanol/oxygen ratio is CH3OH:CH3CH2OH:O2=1:1:2-2:1:3, first Alcohol and alcohol volume content are 1-3%, and nitrogen is 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 Au-TiO2Catalyst is used for disposable gas-phase photocatalysis partial oxidation methanol and a variety of esters of ethanol system The reaction of compound.
Catalytic reaction temperature is 15-50 DEG C, is reaction in current methanol and ethanol gaseous oxidation ester type compound technique Temperature minimum operation condition.

Claims (1)

1. a kind of gas-phase photocatalysis partial oxidation methanol and ethanol gaseous mixture prepare methyl formate, ethyl acetate, Ethyl formate, second The method of the multi-products such as sour methyl esters, it is characterised in that composition, preparation method and the reaction condition of catalyst;Catalyst is by two Titania oxide supported nanogold is constituted, and titanium dioxide and nanogold particle are active component;Titanium dioxide is sharp in catalyst The mixed phase structure of titanium ore type or anatase and a small amount of rutile, golden molar fraction is 1-5%;Catalyst uses liquid-phase reduction side Prepared by method, titanium dioxide is added in the appropriate sodium borohydride aqueous solution cooled down through ice bath, and ultrasound is stirred continuously down after mixing, Appropriate 0.001 mol/l aqueous solution of chloraurate is added dropwise, stops stirring after being added dropwise to complete and stands 24 h, centrifuge, use Distilled water, ethanol are washed, and are dried at 60 DEG C, are obtained Au-TiO2Photochemical catalyst;Catalytic reaction is in 15-50 DEG C and ultraviolet light Lower to carry out, methanol and alcohol volume content are 1-3% in unstripped gas, and methanol/ethanol/oxygen ratio is CH3OH: O2=2:1:1-1:1: 3, Balance Air is nitrogen, air speed 100-400 l ﹒ g-1﹒ h-1
CN201710322783.9A 2017-05-09 2017-05-09 A kind of gas-phase photocatalysis methanol and ethanol disposably synthesize the preparation and application of the Au catalyst of a variety of esters Pending CN107032993A (en)

Priority Applications (1)

Application Number Priority Date Filing Date Title
CN201710322783.9A CN107032993A (en) 2017-05-09 2017-05-09 A kind of gas-phase photocatalysis methanol and ethanol disposably synthesize the preparation and application of the Au catalyst of a variety of esters

Applications Claiming Priority (1)

Application Number Priority Date Filing Date Title
CN201710322783.9A CN107032993A (en) 2017-05-09 2017-05-09 A kind of gas-phase photocatalysis methanol and ethanol disposably synthesize the preparation and application of the Au catalyst of a variety of esters

Publications (1)

Publication Number Publication Date
CN107032993A true CN107032993A (en) 2017-08-11

Family

ID=59538429

Family Applications (1)

Application Number Title Priority Date Filing Date
CN201710322783.9A Pending CN107032993A (en) 2017-05-09 2017-05-09 A kind of gas-phase photocatalysis methanol and ethanol disposably synthesize the preparation and application of the Au catalyst of a variety of esters

Country Status (1)

Country Link
CN (1) CN107032993A (en)

Cited By (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN106946639A (en) * 2017-03-30 2017-07-14 内蒙古大学 A kind of Au catalyst preparation and its for gas-phase photocatalysis ethanol synthesizing ethylene, acetaldehyde, acetone method
CN108579794A (en) * 2018-04-02 2018-09-28 新疆大学 The molecular sieve catalyst of gold-supported is used to convert the method that methanol is methyl acetate
CN110681380A (en) * 2019-10-22 2020-01-14 吉林师范大学 Preparation of high-efficiency hydrogen production catalyst Au-HSTiO by liquid phase reduction2Method (2)

Citations (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN103894192A (en) * 2014-04-18 2014-07-02 内蒙古大学 Preparation and application of supported gold-silver alloy catalyst for synthesizing methyl formate by selectively oxidizing methanol under gas-phase photocatalytic conditions
CN103922929A (en) * 2014-04-18 2014-07-16 内蒙古大学 Preparation and application of load-type nanometer Au catalyst capable of synthesizing methyl formate by gas phase photocatalytic selectivity oxidation of methyl alcohol

Patent Citations (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN103894192A (en) * 2014-04-18 2014-07-02 内蒙古大学 Preparation and application of supported gold-silver alloy catalyst for synthesizing methyl formate by selectively oxidizing methanol under gas-phase photocatalytic conditions
CN103922929A (en) * 2014-04-18 2014-07-16 内蒙古大学 Preparation and application of load-type nanometer Au catalyst capable of synthesizing methyl formate by gas phase photocatalytic selectivity oxidation of methyl alcohol

Cited By (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN106946639A (en) * 2017-03-30 2017-07-14 内蒙古大学 A kind of Au catalyst preparation and its for gas-phase photocatalysis ethanol synthesizing ethylene, acetaldehyde, acetone method
CN108579794A (en) * 2018-04-02 2018-09-28 新疆大学 The molecular sieve catalyst of gold-supported is used to convert the method that methanol is methyl acetate
CN110681380A (en) * 2019-10-22 2020-01-14 吉林师范大学 Preparation of high-efficiency hydrogen production catalyst Au-HSTiO by liquid phase reduction2Method (2)

Similar Documents

Publication Publication Date Title
CN103922929B (en) A kind of preparation of supported nano-Au catalyst of gas-phase photocatalysis selective oxidation methanol-fueled CLC methyl-formiate and application thereof
CN103896765B (en) Preparation and the application thereof of the loaded nano Ag catalyst of the synthetic methyl formate of a kind of gas-phase photocatalysis partial oxidation methyl alcohol
CN108250069B (en) Preparation method of isooctanoic acid
CN107032993A (en) A kind of gas-phase photocatalysis methanol and ethanol disposably synthesize the preparation and application of the Au catalyst of a variety of esters
CN106955705A (en) 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
TWI476047B (en) Preparation of pyruvate
CN111875479B (en) Application of acidic ionic liquid in high-selectivity synthesis of borneol
CN103894198A (en) Preparation and application of Cu/TiO2 composite catalyst for synthesizing methyl formate by partially oxidizing methanol under gas-phase photocatalytic conditions
CN103894192B (en) A kind of preparation of load type gold silver alloy catalyst of gas-phase photocatalysis selective oxidation methanol-fueled CLC methyl formate and application thereof
CN113198492B (en) Catalyst for preparing pyruvate by photocatalytic oxidation of lactate and method thereof
CN102452871B (en) Method for catalytic oxidation of cyclic ketone
CN106883087A (en) A kind of Cu/TiO of volatile corrosion inhibitor film producing ethylene with ethyl alcohol, acetaldehyde and acetone2Catalyst and reaction process
CN102452894B (en) Method for catalytic oxidation of cyclic ketone by nanometer Beta molecule sieve
CN102452918B (en) Method for preparing corresponding dicarboxylic acid by catalytic oxidation of hydroxy acid
CN102964230B (en) Method for preparing benzaldehyde from methylbenzene through liquid-phase catalytic oxidation
CN106883124A (en) A kind of preparation of silver catalyst and its method for disposably synthesizing various esters for gas-phase photocatalysis ethanol and methyl alcohol
CN107056614A (en) A kind of preparation of electrum catalyst and its method for disposably synthesizing a variety of esters for gas-phase photocatalysis methanol and ethanol
CN106883123A (en) A kind of gas-phase photocatalysis methyl alcohol and ethanol disposably synthesize the preparation and application of the silver-bearing copper composite catalyst of various ester type compounds
CN106883107A (en) A kind of preparation of support type Ag catalyst and the technique for gas-phase photocatalysis partial oxidation ethanol synthesizing ethylene, acetaldehyde and acetone
CN106946639A (en) A kind of Au catalyst preparation and its for gas-phase photocatalysis ethanol synthesizing ethylene, acetaldehyde, acetone method
CN102942548B (en) Delta-dodecalactone synthesis method
CN107540520B (en) Method for preparing pyromellitic acid or trimellitic acid from pinacol
CN114950518B (en) Cobalt/tubular graphite phase carbon nitride composite material and preparation method and application thereof
CN103435477A (en) Novel method for synthesizing para-ethoxybenzoic acid
CN102260170B (en) Method for microwave pipeline production of butyl acetate

Legal Events

Date Code Title Description
PB01 Publication
PB01 Publication
SE01 Entry into force of request for substantive examination
SE01 Entry into force of request for substantive examination
RJ01 Rejection of invention patent application after publication

Application publication date: 20170811

RJ01 Rejection of invention patent application after publication