CN102553592A - High-dispersion silicon-loaded Cu-based catalyst and preparation method thereof - Google Patents
High-dispersion silicon-loaded Cu-based catalyst and preparation method thereof Download PDFInfo
- Publication number
- CN102553592A CN102553592A CN2012100713372A CN201210071337A CN102553592A CN 102553592 A CN102553592 A CN 102553592A CN 2012100713372 A CN2012100713372 A CN 2012100713372A CN 201210071337 A CN201210071337 A CN 201210071337A CN 102553592 A CN102553592 A CN 102553592A
- Authority
- CN
- China
- Prior art keywords
- copper
- loaded
- catalyst
- silicon
- high dispersive
- 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
Links
Images
Abstract
The invention belongs to the technical field of catalysts and preparation methods thereof, in particular to a high-dispersion silicon-loaded Cu-based catalyst for synthetizing ethyl acetate by utilizing an ethanol dehydrogenation reaction and a preparation method of the high-dispersion silicon-loaded Cu-based catalyst. The catalyst is prepared by using transition metal copper as an active ingredient and using SiO2 as a carrier, the copper is loaded on the SiO2 carrier in a high-dispersive way by adopting an ion exchange method, the mass ratio of metallic copper to the SiO2 is (0.01-0.1) : 1, and the metallic copper is in an amorphous state. The catalyst has the characteristics of lower copper loading, higher dispersion degree of an active center, better activity and stability, simple preparation process, low cost and environment friendliness. According to the catalyst disclosed by the invention, the preparation technology is simple, active species are highly dispersed, and the reaction activity of synthetizing the ethyl acetate by utilizing a one-step ethanol catalytic method is high under the condition of lower active ingredient loading capacity.
Description
Technical field
The invention belongs to the Catalysts and its preparation method technical field, particularly a kind of Cu of silicon load of the high dispersive that is used for alcohol dehydrogenase synthesizing ethyl acetate reaction is catalyst based and preparation method thereof.
Background technology
Ethyl acetate is a kind of important industrial chemicals and good organic solvent, has excellent dissolubility and quick-drying, is one of most widely used fatty acid ester.In textile industry, food industry, medical industry and perfumery, be widely used.Ethyl acetate is because its special performances is quite active in world's Chemical market.And along with the enhancing of environmental protection consciousness in the global range, people deepen the understanding of environmental hazard conventional solvent day by day, stop and limiting the field of using this kind solvent getting more and more with industry.Ethyl acetate is as selectable replace solvents, and demand will increase considerably.So still be that the domestic market is seen from the world no matter, all there is certain market potential in ethyl acetate.The catalyst that commercial production ethyl acetate is commonly used both at home and abroad at present has sulfuric acid, solid acid catalyst, heteropoly acid, noble metal etc., but the shortcoming of these catalyst is that equipment is had serious corrosivity, the waste liquor contamination environment, and production cost is high.Brazilian patent BR-8901776 discloses employing Metal Palladium/r-aluminium oxide catalyst and has obtained ethyl acetate by ethanol and oxygen.Chinese patent CN1349488A discloses palladium and heteropoly acid and salt thereof loaded to and has obtained catalyst on the carrier, is used for ethanol and oxygen prepared in reaction ethyl acetate.Chinese patent CN1781899A discloses with molecular sieve supported nm of gold as catalyst, uses oxygen to be oxidant, solvent-free oxidation ethanol preparation ethyl acetate down.
In general, the shortcoming of catalyst of reporting in the patent at present such as sulfuric acid, heteropoly acid, noble metal etc. is that contaminated environment, preparation cost are high, and under the condition that aerobic feeds, the danger of blast is arranged.
Summary of the invention
The technical problem that the present invention will solve is that a kind of copper-based catalysts and this Preparation of catalysts method that is used for the alcohol dehydrogenase synthesizing ethyl acetate is provided.The characteristics of this catalyst are lower copper load capacity, and the decentralization in activated centre is higher, and have activity and stable preferably, and catalyst preparation process is simple, and is cheap, environmental friendliness.
The silicon copper loaded of a kind of high dispersive that is used for the alcohol dehydrogenase synthesizing ethyl acetate of the present invention is catalyst based, be with transition metal copper as active component, SiO
2As carrier, adopt ion-exchange that copper is loaded to SiO
2On the carrier, metallic copper and SiO
2By mass ratio is 0.01～0.1: 1, and metallic copper is an amorphous state.Further, metallic copper and SiO
2Mass ratio be 0.03: 1.
High dispersive silicon copper loaded of the present invention is catalyst based to be that complex compound with organic amine and mantoquita is a presoma, is carrier with silica, and organic amine is through playing the effect of dispersed activity component copper with the copper ion complexing.Simultaneously, be that complexing agent is the contrast experiment with ammoniacal liquor.
Ion-exchange is adopted in the catalyst based preparation of high dispersive silicon copper loaded of the present invention; Detailed process is: at first under stirring condition, organic amine is joined in the 0.05mol/L copper nitrate solution; Consumption 4～the 7ml of organic amine; The volume of copper nitrate solution is 30～50ml, treat that solution becomes navy blue and generates organic complex after, again with SiO
2Carrier joins in the above-mentioned organic complex solution, and to obtain high dispersive silicon copper loaded after (2～12 hours), washing (distilled water with 10～15 times of copper nitrate solution volumes carries out filtration washing), dry (under the room temperature under the condition drying 1～3 day), roasting (400～600 ℃ roasting 2～6 hours) step catalyst based through soaking successively.
SiO
2Carrier is commercial SiO
2Bead or mesoporous silicon material, mesoporous silicon material are SBA-15, MCM-41 molecular sieve etc.; Organic amine is diethylenetriamine, triethylene tetramine etc.
The Cu of silicon load of the present invention is catalyst based, and preparation technology is simple, the active specy high dispersive, and under than low activity component load capacity condition, catalysis ethanol one-step method synthesizing ethyl acetate reactivity is high.
The catalyst based method of in the ethanol with one-step method synthesizing ethyl acetate, using of the silicon copper loaded of high dispersive of the present invention is following: reaction is carried out in the fixed-bed micro-devices under normal pressure; Reactor is processed by stainless steel tube; Reactant is absolute ethyl alcohol (sample introduction flow velocity 2ml/h); Catalyst consumption is 2ml, and the sample introduction air speed of ethanol is 1h
-1(the reaction procatalyst needs under 300 ℃, to use H
2The gaseous mixture reductase 12 of/Ar volume ratio 10%～4h), reaction temperature is 250～320 ℃, and the reaction time is 4 hours, and reaction afterreaction thing and product are through the gas-chromatography on-line analysis.
Description of drawings
Fig. 1: the XRD spectra that uses the catalyst of different complexing agents;
As shown in the figure, the diffuse peaks about 22.7 ° belongs to unbodied SiO
2, we do not observe the diffraction maximum of CuO from figure, explain that CuO is in high dispersive and amorphous state.
Fig. 2: the TPR spectrogram that uses the catalyst of different complexing agents;
As shown in the figure, the reduction peak about 245 ℃ belongs to the reduction peak of the cupric oxide of high dispersive, and the reduction peak in 367～400 ℃ of scopes at high temperature place belongs to carrier has the Cu than strong interaction
2+Reduction.Consistent with the XRD characterization result, do not find the reduction of big particle diameter cupric oxide, explain with organic amine and make complexing agent, can not only improve the decentralization of active specy to a certain extent, simultaneously can also the enhanced activity species and the active force of carrier.
Fig. 3: the TEM photo (a, b, c: ammoniacal liquor, diethylenetriamine, triethylene tetramine) that uses the catalyst of different complexing agents;
As shown in the figure, assemble at the catalyst top CuO that with ammoniacal liquor is complexing agent, the aggregation extent of CuO weakens on the catalyst that with the diethylenetriamine is complexing agent, and CuO is dispersed in SiO on the catalyst that with the triethylene tetramine is complexing agent
2On the surface.It is the decentralization that complexing agent can improve active specy that TEM result further specifies with organic amine.
The specific embodiment
Comparative Examples 1:
1, Preparation of Catalyst
Get 0.45g Cu (NO
3)
23H
2O is dissolved in (concentration of copper nitrate solution is 0.05mol/L) in the 37mL distilled water, in solution, adds ammoniacal liquor to solution and is navy blue, takes by weighing 40～60 order SiO of 4g then
2Bead joins in the above-mentioned solution, soaks 6h, washs suction filtration afterwards with 450ml distilled water.Dry 2 days at ambient temperature, 400 ℃ of roasting 6h under air conditions.
2, catalysis ethanol one-step method synthesizing ethyl acetate reaction
With the absolute ethyl alcohol is reactant, and sample introduction flow velocity 2ml/h, catalyst amount are 2ml, and reaction velocity is 1h
-1, react procatalyst H with 10% volume ratio under 300 ℃
2/ Ar gaseous mixture reductase 12 h; Reaction temperature is 270 ℃; Reactor is processed by stainless steel tube, is reflected under the normal pressure to carry out in the fixed-bed micro-devices, and the reaction afterproduct is through the content of Tianjin, island GC-14C gas-chromatography on-line analysis reactant and product; Ethanol conversion is 48%, and selectivity is 15%.
Embodiment 1:
1, Preparation of Catalyst
Get 0.45g Cu (NO
3)
23H
2O is dissolved in the 37mL distilled water, in solution, adds diethylenetriamine to solution and is navy blue, takes by weighing 40～60 order SiO of 4g then
2Particle joins in the above-mentioned solution, soaks 24h, and the distilled water with 10 times of copper nitrate solution volumes washs afterwards, suction filtration.Dry 1 day at ambient temperature, 500 ℃ of roasting 4h under air conditions.
2, catalysis ethanol one-step method synthesizing ethyl acetate reaction
With the absolute ethyl alcohol is reactant, and sample introduction flow velocity 2ml/h, catalyst amount are 2ml, and reaction velocity is 1h
-1, the reaction procatalyst is used 10%H under 300 ℃
2/ Ar gaseous mixture reductase 12 h, reaction temperature is 270 ℃, reactor is processed by stainless steel tube; Be reflected under the normal pressure and carry out in the fixed-bed micro-devices; The reaction back is through the content of Tianjin, island GC-14C gas-chromatography on-line analysis reactant and product, and ethanol conversion is 53%, and selectivity is 23%.
Embodiment 2:
1, Preparation of Catalyst
Get 0.45g Cu (NO
3)
23H
2O is dissolved in the 37mL distilled water, in solution, adds diethylenetriamine to solution and is navy blue, takes by weighing 40～60 order SiO of 4g then
2Particle joins in the above-mentioned solution, soaks 24h, and the distilled water with 15 times of copper nitrate solution volumes washs afterwards, suction filtration.Dry 3 days at ambient temperature, 600 ℃ of roasting 2h under air conditions.
2, catalysis ethanol one-step method synthesizing ethyl acetate reaction
With the absolute ethyl alcohol is reactant, and sample introduction flow velocity 2ml/h, catalyst amount are 2ml, and reaction velocity is 1h
-1, the reaction procatalyst is used 10%H under 300 ℃
2/ Ar gaseous mixture reductase 12 h; Reaction temperature is 300 ℃; Reactor is processed by stainless steel tube, is reflected under the normal pressure to carry out in the fixed-bed micro-devices, and the reaction afterproduct is through the content of Tianjin, island GC-14C gas-chromatography on-line analysis reactant and product; Ethanol conversion is 67%, and selectivity is 20%.
Embodiment 3:
1, Preparation of Catalyst
Get 0.45g Cu (NO
3)
23H
2O is dissolved in the 37mL distilled water, in solution, adds triethylene tetramine to solution and is navy blue, takes by weighing 40～60 order SiO of 4g then
2Particle joins in the above-mentioned solution, soaks 24h, and the distilled water with 13 times of copper nitrate solution volumes washs afterwards, suction filtration.Dry 2.5 days at ambient temperature, 450 ℃ of roasting 5h under air conditions.
2, catalysis ethanol one-step method synthesizing ethyl acetate reaction
With the absolute ethyl alcohol is reactant, and sample introduction flow velocity 2ml/h, catalyst amount are 2ml, and reaction velocity is 1h
-1, the reaction procatalyst is used 10%H under 300 ℃
2/ Ar gaseous mixture reductase 12 h; Reaction temperature is 270 ℃; Reactor is processed by stainless steel tube, is reflected under the normal pressure to carry out in the fixed-bed micro-devices, and the reaction afterproduct is through the content of Tianjin, island GC-14C gas-chromatography on-line analysis reactant and product; Ethanol conversion is 55%, and selectivity is 21%.
Claims (8)
1. the silicon copper loaded of a high dispersive is catalyst based, it is characterized in that: this catalyst be with transition metal copper as active component, SiO
2As carrier, adopt ion-exchange with the copper high dispersive load to SiO
2On the carrier, metallic copper and SiO
2Mass ratio be 0.01～0.1: 1, metallic copper is an amorphous state.
2. a kind of silicon copper loaded of high dispersive is catalyst based according to claim 1, it is characterized in that: metallic copper and SiO
2Mass ratio be 0.03: 1.
3. the catalyst based preparation method of silicon copper loaded of the described high dispersive of claim 1; It is characterized in that: at first under stirring condition, organic amine is joined in the 0.05mol/L copper nitrate solution; Consumption 4～the 7ml of organic amine, the volume of copper nitrate solution are 30～50ml, again with SiO
2Carrier joins in the above-mentioned organic complex solution, and is catalyst based through obtaining high dispersive silicon copper loaded after immersion, washing, drying, the roasting.
4. the catalyst based preparation method of silicon copper loaded of high dispersive as claimed in claim 3 is characterized in that: SiO
2Carrier is commercial SiO
2Bead or mesoporous silicon material.
5. the catalyst based preparation method of silicon copper loaded of high dispersive as claimed in claim 4, it is characterized in that: mesoporous silicon material is SBA-15 molecular sieve or MCM-41 molecular sieve.
6. the catalyst based preparation method of silicon copper loaded of high dispersive as claimed in claim 3, it is characterized in that: organic amine is diethylenetriamine or triethylene tetramine.
7. the catalyst based preparation method of silicon copper loaded of high dispersive as claimed in claim 3, it is characterized in that: the time of immersion is 2～12 hours; Be that distilled water with 10～15 times of copper nitrate solution volumes carries out filtration washing; It is dry 1～3 day at ambient temperature; Be 400～600 ℃ of roastings 2～6 hours.
8. the catalyst based application in preparation ethyl acetate of the silicon copper loaded of claim 1 or 2 described a kind of high dispersive.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN2012100713372A CN102553592A (en) | 2012-03-18 | 2012-03-18 | High-dispersion silicon-loaded Cu-based catalyst and preparation method thereof |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN2012100713372A CN102553592A (en) | 2012-03-18 | 2012-03-18 | High-dispersion silicon-loaded Cu-based catalyst and preparation method thereof |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| CN102553592A true CN102553592A (en) | 2012-07-11 |
Family
ID=46400992
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN2012100713372A Pending CN102553592A (en) | 2012-03-18 | 2012-03-18 | High-dispersion silicon-loaded Cu-based catalyst and preparation method thereof |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN102553592A (en) |
Cited By (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN103880660A (en) * | 2014-03-12 | 2014-06-25 | 江苏大学 | Method for preparing ethyl acetate by catalyzing ethanol for directly dehydrogenizing at normal gas phase pressure |
| CN103880661A (en) * | 2014-03-12 | 2014-06-25 | 江苏大学 | Method of preparing ethyl acetate by catalyzing alcohol to directly dehydrogenize |
| CN104646058A (en) * | 2015-02-09 | 2015-05-27 | 山东师范大学 | Copper-containing complex catalyst and preparation method and application thereof |
| CN107952459A (en) * | 2017-12-07 | 2018-04-24 | 万华化学集团股份有限公司 | The synthetic method of big annulenones and a kind of catalyst and its application |
| CN111530461A (en) * | 2020-05-28 | 2020-08-14 | 中国科学院兰州化学物理研究所 | Low-load high-dispersion single-active-site Cu catalyst and preparation method and application thereof |
Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US20020001977A1 (en) * | 2000-03-29 | 2002-01-03 | Gole James L. | Silicon based nanospheres and nanowires |
| CN1644239A (en) * | 2003-11-26 | 2005-07-27 | 戴维加工技术有限公司 | Catalyst |
-
2012
- 2012-03-18 CN CN2012100713372A patent/CN102553592A/en active Pending
Patent Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US20020001977A1 (en) * | 2000-03-29 | 2002-01-03 | Gole James L. | Silicon based nanospheres and nanowires |
| CN1644239A (en) * | 2003-11-26 | 2005-07-27 | 戴维加工技术有限公司 | Catalyst |
Non-Patent Citations (2)
| Title |
|---|
| 《化学研究》 20101130 吴实等 "中孔二氧化硅担载铜(II) 配合物催化剂的制备及其对甲醇脱氢制甲酸甲酯的催化活性" 第39-44页 1-8 第21卷, 第6期 * |
| 吴实等: ""中孔二氧化硅担载铜(II) 配合物催化剂的制备及其对甲醇脱氢制甲酸甲酯的催化活性"", 《化学研究》 * |
Cited By (8)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN103880660A (en) * | 2014-03-12 | 2014-06-25 | 江苏大学 | Method for preparing ethyl acetate by catalyzing ethanol for directly dehydrogenizing at normal gas phase pressure |
| CN103880661A (en) * | 2014-03-12 | 2014-06-25 | 江苏大学 | Method of preparing ethyl acetate by catalyzing alcohol to directly dehydrogenize |
| CN103880660B (en) * | 2014-03-12 | 2016-05-25 | 江苏大学 | Under a kind of ordinary-pressure gas-phase, catalysis ethanol direct dehydrogenation is prepared the method for ethyl acetate |
| CN103880661B (en) * | 2014-03-12 | 2016-05-25 | 江苏大学 | A kind of catalysis ethanol direct dehydrogenation is prepared the method for ethyl acetate |
| CN104646058A (en) * | 2015-02-09 | 2015-05-27 | 山东师范大学 | Copper-containing complex catalyst and preparation method and application thereof |
| CN107952459A (en) * | 2017-12-07 | 2018-04-24 | 万华化学集团股份有限公司 | The synthetic method of big annulenones and a kind of catalyst and its application |
| CN107952459B (en) * | 2017-12-07 | 2020-08-28 | 万华化学集团股份有限公司 | Method for synthesizing macrocyclic ketene, catalyst and application thereof |
| CN111530461A (en) * | 2020-05-28 | 2020-08-14 | 中国科学院兰州化学物理研究所 | Low-load high-dispersion single-active-site Cu catalyst and preparation method and application thereof |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN101138730B (en) | Catalyzer for oxalic ester hydrogenation for synthesizing glycolate and method of preparing the same | |
| CN102553592A (en) | High-dispersion silicon-loaded Cu-based catalyst and preparation method thereof | |
| CN104368358B (en) | It is a kind of suitable for the catalyst of butanedioic acid hydrogenation reaction and its preparation and process for selective hydrogenation | |
| CN102274724B (en) | High-activity catalyst used in hydrogenation reaction of aromatic nitro-compound and preparation method thereof | |
| CN104275185B (en) | A kind of cuprio hydrogenation catalyst preparation method without reduction activation | |
| CN102085479A (en) | Catalyst for hydro-conversion of mixed aqueous solution containing alcohol, aldehyde, acid and ester into alcohols | |
| CN103694116A (en) | Method for synthesizing methyl formate by gas-phase carbonylation of methyl alcohol | |
| CN102489315A (en) | Ruthenium catalyst, preparation method and application in synthesizing tetrahydrofurfuryl alcohol | |
| CN100364663C (en) | Supported nano Au catalyst and method for preparing the same | |
| CN103372453A (en) | Catalyst for synthesis of methyl glycolate and preparation method thereof | |
| CN103691442A (en) | Catalyst for synthesis of isobutanol from synthesis gas and preparation method of catalyst | |
| CN114853567B (en) | Catalyst for preparing low-carbon alcohol by converting carbon dioxide, and preparation method and application thereof | |
| CN103819295B (en) | The application of a kind of catalyzer in aromatic nitro compound selective hydrogenation | |
| CN102600900A (en) | Load-type gold-palladium bimetallic catalyst and preparation method thereof | |
| CN103638947B (en) | A kind of Ni/Ag/Cu/TiO 2the preparation of composite catalyst and application thereof | |
| CN101906038A (en) | Method for preparing ester by catalytic oxidization of 1,3-propanediol | |
| CN109647394B (en) | Catalyst for preparing unsaturated alcohol by selective hydrogenation of alpha, beta-unsaturated aldehyde and preparation method and application thereof | |
| CN102863335A (en) | Preparation method of diethyl succinate | |
| CN109422632A (en) | A kind of method of catalysis oxidation prenol isoamyl olefine aldehydr | |
| CN113926458B (en) | Preparation method of copper hydrogenation catalyst, catalyst prepared by preparation method and application of catalyst | |
| CN106807366B (en) | Core-shell catalyst for preparing lactic acid and pyruvic acid from glycerol, and preparation and application thereof | |
| CN110639511B (en) | Catalyst for carbon-carbon double bond hydrogenation of acrylate and application thereof | |
| CN106040246A (en) | Nickel-based catalyst and preparation method and application thereof in catalyzing selective hydrogenation of 1,4-butynediol to synthesize 1,4-butylene glycol | |
| CN101804347A (en) | Preparation method and purpose of supported nano-gold catalyst for cyclohexene oxide | |
| CN108047173A (en) | A kind of method for preparing gamma-valerolactone |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| C06 | Publication | ||
| PB01 | Publication | ||
| C10 | Entry into substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| WD01 | Invention patent application deemed withdrawn after publication | ||
| WD01 | Invention patent application deemed withdrawn after publication |
Application publication date: 20120711 |