CN106883107A - A kind of preparation of support type Ag catalyst and the technique for gas-phase photocatalysis partial oxidation ethanol synthesizing ethylene, acetaldehyde and acetone - Google Patents
A kind of preparation of support type Ag catalyst and the technique for gas-phase photocatalysis partial oxidation ethanol synthesizing ethylene, acetaldehyde and acetone Download PDFInfo
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- CN106883107A CN106883107A CN201710171340.4A CN201710171340A CN106883107A CN 106883107 A CN106883107 A CN 106883107A CN 201710171340 A CN201710171340 A CN 201710171340A CN 106883107 A CN106883107 A CN 106883107A
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- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C45/00—Preparation of compounds having >C = O groups bound only to carbon or hydrogen atoms; Preparation of chelates of such compounds
- C07C45/27—Preparation of compounds having >C = O groups bound only to carbon or hydrogen atoms; Preparation of chelates of such compounds by oxidation
- C07C45/29—Preparation of compounds having >C = O groups bound only to carbon or hydrogen atoms; Preparation of chelates of such compounds by oxidation of hydroxy groups
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- 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
- B01J23/38—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of noble metals
- B01J23/48—Silver or gold
- B01J23/50—Silver
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- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C5/00—Preparation of hydrocarbons from hydrocarbons containing the same number of carbon atoms
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- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
- Y02P20/00—Technologies relating to chemical industry
- Y02P20/50—Improvements relating to the production of bulk chemicals
- Y02P20/52—Improvements relating to the production of bulk chemicals using catalysts, e.g. selective catalysts
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Abstract
The invention provides a kind of chemical technology of utilization loaded nano Ag catalyst multi-products such as photocatalysis partial oxidation preparation of bio-ethylene, acetaldehyde and acetone under gas phase condition.Catalyst is with the mixed phase titanium dioxide of Detitanium-ore-type or anatase and a small amount of rutile as carrier, presoma with soluble silver salt as nano silver particles, sodium borohydride is reducing agent, prepare the nano-silver catalyst of titanium dichloride load, alcohol gas can be oxidized to the multi-products such as ethene, acetaldehyde, acetone by the catalyst under ultraviolet light in oxygen-containing atmosphere.This photocatalysis technique has ethanol conversion high, the characteristics of ethene, acetaldehyde, acetone selectively high.
Description
Technical field
The present invention relates to a kind of photochemical catalyst preparation and its at low temperature gas-phase photocatalysis partial oxidation producing ethylene with ethyl alcohol,
The application of the multi-products such as acetaldehyde, acetone, belongs to derived energy chemical and field of fine chemical, there is provided the preparation method of catalyst and catalysis
Reaction condition.
Background technology
Ethene is one of maximum chemical products of yield in the world, and ethylene industry is the core of petrochemical industry, ethene
Product accounts for more than the 75% of petroleum chemicals, is occupied an important position in national economy.In the world using ethylene yield as measurement
One of one important symbol of national oil development of chemical industry level.[Minhua Zhang. Ind. Eng. Chem. Res.
2013, 52, 9505−9514]
Traditional ethylene production mainly has oil ethene, coal ethene, methyl alcohol ethene, methane ethene and sugar grass
Ethene processed.Its petrochina propane ratio is larger.Coal ethene route flow is short, accessory substance is less, olefin yields are high, but lacks
Point is higher than petroleum base route water consume, CO2 discharges many.Thermocatalytic method ethanol turns catalyst for ethylene HZSM-5 zeolite
[Bi, J. D.; Guo, X. W.; Liu, M.; Wang, X. S. Catal. Today 2010,149, 143−147]
With H-ZSM-5 [Varisli, D.; Dogu, T.; Dogu, G. Chem. Eng. Sci. 2007, 62, 5349−
5352.] etc..
Acetaldehyde is used to manufacture acetic acid, aceticanhydride and synthetic resin.Primary synthetic methods have direct oxidation of ethylene to method, oxidation of ethanol
Method, acetylene direct hydration method, ethanol deoxidation method etc..Wherein the production of direct oxidation of ethylene to method acetaldehyde and industrialization, become master
Want method.Reason is abundant and cheap ethylene source, with reaction condition is gentle, the good, high income of selectivity, technological process it is simple
And three-protection design it is easy the features such as.
Acetone is industrially used for the industries such as explosive, plastics, rubber, fiber, process hides, grease, spray painting mainly as solvent
In, also can be used as things such as synthesis ketenes, aceticanhydride, iodoform, polyisoprene rubber, methyl methacrylate, chloroform, epoxy resin
The important source material of matter.The industrial production of acetone is based on cumene method.Acetone is produced by raw material of ethanol, zinc chromate is generally required
Make catalyst, reaction high temperature is higher, usually more than more than 400 DEG C.
Ethyl acetate is widely used ester type compound, with excellent dissolubility, quick-drying, be can be used as organic molten
Agent.Ethyl acetate is also widely used for China Synthetic Rubber Industry, vinyl resin fiber element, typel element, butyl acetate, ethyl
The production of the products such as fiber, cellulose nitrate.[Liu Chong etc. compiles petrochemical industries handbook (three) Beijing:Chemical Industry Press,
1987: P259.].[Cheng Nenglin, Hu Shengwen solvents handbook (volume two) [M] Beijing:Chemical Industry Press, 1987:14-
15].Synthetic Methods of Ethyl Acetate generally has direct esterification, acetaldehyde condensation method, alcohol catalysis dehydriding, vinyl acetate esterification method
Deng.Wherein direct esterification has the following disadvantages：Reaction temperature is high, acetic acid utilization rate is low, side reaction easily occurs, while producing
Due to the severe corrosive of the catalyst concentrated sulfuric acid in journey, cause equipment corrosion serious, waste liquor contamination environment, accessory substance difficult treatment,
Cause production cost high.Acetaldehyde condensation method is limited by raw material acetaldehyde, and the preparation of catalyst hardly possible, facile hydrolysis, course of reaction need cooling.
Not only production procedure is simple for alcohol catalysis dehydriding, mild condition, product design are high, low production cost, and to equipment material
It is required that it is low, without acid-bearing wastewater and environmental pollution, be a kind of high yield, the synthetic route of corrosion-free, low cost of material.
The content of the invention
The purpose of the present invention is mainly to provide a kind of efficient Ag-TiO2Photochemical catalyst is prepared and its in low temperature（25-45
℃）, under gas phase and illumination condition by the multi-products such as partial oxidation of ethanol ethene, acetaldehyde and acetone chemical technology and reaction bar
Part.
The present invention is first by Ag-TiO2Photochemical catalyst is used for ethanol gas-phase photocatalysis partial oxidation ethene, acetaldehyde and third
The reaction of the multi-products such as ketone.Test result indicate that, catalyst has ethanol conversion and ethene higher, acetaldehyde, acetone
Selectivity.In the range of the experimental temperature and under illumination condition, ethanol conversion reaches more than 80%, ethene, acetone selectivity can
To reach 35-80%.
Catalyst Ag-TiO of the invention2By the silver and 95-99% of 1-5%（Mol ratio）Titanium dioxide constitute, titanium dioxide
Titanium crystal formation 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 soluble silver salt and be configured to the silver salt solution of 0.001mol/L with distilled water.
（2）With Ag:NaBH4=5:6（Mol ratio）Appropriate sodium borohydride is weighed, is dissolved in the distilled water of 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 silver salt solution of preparation is added dropwise to step（3）In the mixed solution for obtaining, while acute
Strong stirring is completed until reaction.Stopping is stirred and stands 24 hours.
（5）Centrifugation, washing is dried at 60 DEG C.
Specific surface area of catalyst prepared by the present invention is approached with the specific surface area of titanium dioxide precursor, 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.
Soluble silver salt as described above can be silver nitrate, silver acetate, silver perchlorate.
Catalyst of the invention is applied to the compounds such as gas-phase photocatalysis partial oxidation producing ethylene with ethyl alcohol, acetaldehyde, acetone
Reaction 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 is 15-50 DEG C, and ethanol/oxygen mole ratio is 1-6, ethanol volumn concentration 1-3%, and nitrogen is
Balance Air, 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 Ag-TiO2Catalyst is used for the chemical combination such as gas-phase photocatalysis partial oxidation of ethanol ethene, acetaldehyde and acetone
The reaction of thing.
Catalytic reaction temperature is 15-50 DEG C, is the work of the compounds such as current ethanol gaseous oxidation ethene, acetaldehyde, acetone
Reaction temperature minimum operation condition in skill.
Brief description of the drawings
Fig. 1 is the Ag-TiO for preparing2The solid uv-vis spectra of photochemical catalyst（UV-Vis）Figure
Fig. 2 is the Ag-TiO for preparing2The X-ray diffraction of photochemical catalyst（XRD）Collection of illustrative plates
Fig. 3 is the Ag-TiO for preparing2The transmission electron microscope of photochemical catalyst（TEM）Figure.
Specific embodiment
With reference to embodiment, the present invention is further illustrated, and the present invention includes but is not limited to the following examples.
Weigh 0.0075gNaBH4, it is dissolved in the distilled water of the advance ice bath coolings of 100ml, weigh 0.5 g titanium dioxides
Titanium（P25）Powder ultrasonic is scattered in above-mentioned solution.The 164ml 0.001mol/LAgNO that will be measured with vigorous stirring3It is water-soluble
Drop is added in above-mentioned solution, and stopping is stirred and stands 24h, centrifugation, and washing is vacuum dried 6h at 60 DEG C, obtains final product
2.56%Ag-TiO2Photochemical catalyst.In a similar manner, change the amount for adding titanium dioxide, different mol ratio can be prepared
Ag-TiO2Catalyst.
2.56%Ag-TiO prepared by the above method2Photochemical 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, using gas-chromatography
Detection product composition.Catalyst amount 0.02g, reaction temperature 15-50oC, unstripped gas 1% ethanol of composition, 0.5% oxygen,
98.5% nitrogen, raw gas flow 50ml/min, the L ﹒ g of air speed 150-1﹒ h-1。
Above catalyst carries out photocatalysis performance evaluation result and shows, the ethanol conversion of the reaction is up to 90%, second
Alkene, acetaldehyde, the yield of acetone can be controlled by adjusting reaction temperature and reactant ratio and oxygen content, its selectivity
It can be controlled in the range of 10% to 80%.The catalyst is high to ethanol conversion and ethene, acetaldehyde and acetone selectivity, stable reaction
Property is good, is excellent photochemical catalytic oxidation producing ethylene with ethyl alcohol, acetaldehyde, acetone catalyst.
Claims (1)
1. the method for the multi-products such as a kind of gas-phase photocatalysis partial oxidation preparation of bio-ethylene, acetaldehyde, acetone, it is characterised in that
The composition of catalyst, preparation method and catalytic reaction condition；Catalyst is the nano-Ag particles of titanium dichloride load, titanium dioxide
Active component is with nano-Ag particles；Titanium dioxide is the mixed phase structure of Detitanium-ore-type or anatase and a small amount of rutile, silver
Molar fraction be 2-6%；Catalyst is prepared using liquid-phase reduction method, water-soluble in the appropriate sodium borohydride through ice bath cooling
Titanium dioxide, ultrasound is added to be stirred continuously down after mixing in liquid, the soluble silver salt for being added dropwise over appropriate 0.001mol/L is water-soluble
Liquid, stops stirring and stands 24 hours after being added dropwise to complete, centrifugation is washed with distilled water, ethanol, is dried at 60 DEG C；Catalysis is anti-
It is 15-50 DEG C to answer temperature, ultraviolet light, and alcohol volume content is 1-3% in unstripped gas, and ethanol/oxygen ratio is CH5OH: O2=
1:1-6:1, Balance Air is nitrogen, air speed 100-400 l ﹒ g-1﹒ h-1。
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| CN201710171340.4A CN106883107A (en) | 2017-03-21 | 2017-03-21 | A kind of preparation of support type Ag catalyst and the technique for gas-phase photocatalysis partial oxidation ethanol synthesizing ethylene, acetaldehyde and acetone |
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| CN201710171340.4A CN106883107A (en) | 2017-03-21 | 2017-03-21 | A kind of preparation of support type Ag catalyst and the technique for gas-phase photocatalysis partial oxidation ethanol synthesizing ethylene, acetaldehyde and acetone |
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Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN111298788A (en) * | 2019-12-02 | 2020-06-19 | 上海纳米技术及应用国家工程研究中心有限公司 | Preparation method of silver-loaded colored one-dimensional mesoporous titanium dioxide, product and application thereof |
Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN103896765A (en) * | 2014-04-18 | 2014-07-02 | 内蒙古大学 | Preparation and application of supported nano Ag catalyst for synthesizing methyl formate by partially oxidizing methanol under gas-phase photocatalytic conditions |
| CN106883124A (en) * | 2017-03-30 | 2017-06-23 | 内蒙古大学 | A kind of preparation of silver catalyst and its method for disposably synthesizing various esters for gas-phase photocatalysis ethanol and methyl alcohol |
-
2017
- 2017-03-21 CN CN201710171340.4A patent/CN106883107A/en active Pending
Patent Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN103896765A (en) * | 2014-04-18 | 2014-07-02 | 内蒙古大学 | Preparation and application of supported nano Ag catalyst for synthesizing methyl formate by partially oxidizing methanol under gas-phase photocatalytic conditions |
| CN106883124A (en) * | 2017-03-30 | 2017-06-23 | 内蒙古大学 | A kind of preparation of silver catalyst and its method for disposably synthesizing various esters for gas-phase photocatalysis ethanol and methyl alcohol |
Non-Patent Citations (1)
| Title |
|---|
| XUZHUANG YANG, ET AL: "Photocatalytic oxidation of methanol to methyl formate in liquid phase over supported silver catalysts", 《CATALYSIS COMMUNICATIONS》 * |
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN111298788A (en) * | 2019-12-02 | 2020-06-19 | 上海纳米技术及应用国家工程研究中心有限公司 | Preparation method of silver-loaded colored one-dimensional mesoporous titanium dioxide, product and application thereof |
| CN111298788B (en) * | 2019-12-02 | 2022-07-12 | 上海纳米技术及应用国家工程研究中心有限公司 | Preparation method of silver-loaded colored one-dimensional mesoporous titanium dioxide, product and application thereof |
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Application publication date: 20170623 |