CN105457634A - Copper-based catalyst and application thereof - Google Patents
Copper-based catalyst and application thereof Download PDFInfo
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- CN105457634A CN105457634A CN201510777940.6A CN201510777940A CN105457634A CN 105457634 A CN105457634 A CN 105457634A CN 201510777940 A CN201510777940 A CN 201510777940A CN 105457634 A CN105457634 A CN 105457634A
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- copper
- series catalyst
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- sodium metasilicate
- organic solvent
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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
- B01J23/70—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
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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
- B01J21/00—Catalysts comprising the elements, oxides, or hydroxides of magnesium, boron, aluminium, carbon, silicon, titanium, zirconium, or hafnium
- B01J21/06—Silicon, titanium, zirconium or hafnium; Oxides or hydroxides thereof
- B01J21/08—Silica
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- Organic Chemistry (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Catalysts (AREA)
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
Abstract
The present invention discloses a copper-based catalyst, which is prepared by reaction of sodium metasilicate and a copper source in an organic phase environment. Compared with the prior art, the copper-based catalyst of the present invention has the catalytic copper dispersedly immobilized on a silica gel carrier to expand the area of contact with the reaction substrate materials. Compared with the prior art, the copper-based catalyst has higher catalytic efficiency, requires more moderate catalytic conditions, and is in favor of industrial production. At the same time, the method of the present invention is completed under the condition of pure organic phase; by contrast, the obtained copper catalyst has higher catalytic efficiency than the one obtained in general water content conditions.
Description
Technical field
The invention belongs to catalyst field, be specifically related to a kind of Cu-series catalyst and application thereof.
Background technology
The low-carbon alkene such as ethene, propylene is raw material the most basic in petrochemical industry.For ethene, about there are the petrochemicals of 75% by ethylene production, it is mainly used to produce the multiple important Organic chemical products such as polyethylene, polyvinyl chloride, ethylene oxide/ethylene glycol, dichloroethanes, styrene, polystyrene, ethanol, vinyl acetate, in fact, ethylene yield has become the mark of a measurement national oil chemical engineering industry development level.
Statistics display, from nineteen ninety by 2003, China's ethene equivalent consumption figure increases by 12% every year, after this growth rate is more surprising, within 2003, China's ethene equivalent consumption figure is 1,350 ten thousand tons, within 2005, this numeral just reaches 1,876 ten thousand tons, has increased nearly 40% on foot between 2 years, and Chinese Market for Ethylene has become the country that global growth rate is the fastest, the growth duration is the longest.
In the technique of preparing ethylene, propylene and other functionalized olefin, the effect of catalyst has great impact for the productive rate of product and qualification rate.Cu-series catalyst is a kind of conventional catalyst in industrial production, but comparatively active because of it, and reducing power is comparatively strong, and therefore reaction condition is comparatively harsh.Improving Cu-series catalyst catalytic efficiency in the industrial production, is a current large study hotspot.
Summary of the invention
The technical problem to be solved in the present invention is to provide a kind of Cu-series catalyst, not high to solve the catalytic efficiency of prior art existence, the problems such as catalytic condition is harsh.
The technical problem that the present invention finally will solve is to provide the application of above-mentioned Cu-series catalyst.
For solving the problems of the technologies described above, the technical solution used in the present invention is as follows:
A preparation method for Cu-series catalyst, it comprises the steps:
(1) sodium metasilicate is dissolved in organic solvent, under the condition of nitrogen protection, in organic solvent, passes into hydrogen chloride gas, at 30 ~ 60 DEG C, react 3 ~ 6h;
(2) keep nitrogen protection condition, in the mixed system of step (1) gained, add copper source, at 40 ~ 45 DEG C, react 1 ~ 3h;
(3) in the mixed system of gained in step (2), add precipitating reagent, fully mix, after colloidal sol is complete, get gel;
(4) by after the gel detergent of gained in step (3), drying, roast, Cu-series catalyst is obtained.
Wherein, described sodium metasilicate is anhydrous sodium metasilicate.
Wherein, in above-mentioned preparation method, in step (1) ~ (3), agents useful for same is all through anhydrous process.
Wherein, in above-mentioned preparation method, in step (1) and (2), reaction is all placed on shaking table to be carried out.
In step (1), described organic solvent is pyridine or methyl-sulfoxide.
In step (1), the weight ratio of sodium metasilicate and organic solvent is 1:50 ~ 200.
In step (1), the mol ratio of sodium metasilicate and hydrogen chloride is 1:1.5 ~ 3.5.
In step (2), described copper source is copper chloride or cupric phosphate.
In step (2), in sodium metasilicate and copper source, the mol ratio of copper is 50 ~ 75:1.
In step (3), described precipitating reagent is polyacrylamide or ferric sulfate; Wherein, the mass ratio of precipitating reagent and sodium metasilicate is 1:600 ~ 750.
In step (4), the method for washing is for using deionized water rinsing 2 ~ 3 times, and dry method is for using sodium sulfite dry, and the method for roast is roasting 1 ~ 1.5h at 600 ~ 700 DEG C.
The Cu-series catalyst that above-mentioned preparation method prepares is also within protection scope of the present invention.
Above-mentioned Cu-series catalyst in the application of catalyst field also within protection scope of the present invention.
Beneficial effect: compared with prior art, the present invention has following advantage:
Cu-series catalyst in the present invention, is fixed on silica-gel carrier by the copper dispersion playing catalytic action, expands itself and the contact area of reacting bed material.Compared with prior art, the catalytic efficiency of this Cu-series catalyst is higher, and required catalytic condition milder, is conducive to industrial production.Meanwhile, the inventive method completes under pure organic phase condition, and through contrast, more general aqueous conditions, gained Cu-series catalyst catalytic efficiency is higher.
Detailed description of the invention
According to following embodiment, the present invention may be better understood.But those skilled in the art will readily understand, the content described by embodiment only for illustration of the present invention, and should can not limit the present invention described in detail in claims yet.
The preparation of embodiment 1 catalyst
Preparation method:
(1) anhydrous sodium metasilicate is dissolved in methyl-sulfoxide, under the condition of nitrogen protection, in methyl-sulfoxide, passes into hydrogen chloride gas, on shaking table, react 4h at 45 DEG C;
(2) keep nitrogen protection condition, in the mixed system of step (1) gained, add copper chloride, on shaking table, react 1h at 40 DEG C;
(3) in the mixed system of gained in step (2), add polyacrylamide, fully mix, after colloidal sol is complete, get gel;
(4) by the gel of gained in step (3) with after deionized water rinsing 2 ~ 3 times, dry with sodium sulfite, finally at 700 DEG C, after roasting 1h, obtain Cu-series catalyst.
In step (1) ~ (3), agents useful for same is all through anhydrous process.
In step (1), the weight ratio of anhydrous sodium metasilicate and organic solvent is 1:100.
In step (1), the mol ratio of anhydrous sodium metasilicate and hydrogen chloride is 1:3.
In step (2), in anhydrous sodium metasilicate and copper chloride, the mol ratio of copper is 60:1.
In step (3), the mass ratio of polyacrylamide and anhydrous sodium metasilicate is 1:700.
Comparative example 1
Preparation method is with embodiment 1, and difference is, sodium metasilicate used is metasilicate pentahydrate sodium.
Comparative example 2
Preparation method is with embodiment 1, and difference is, methyl-sulfoxide is replaced with water.
Embodiment 2
The Cu-series catalyst prepared in embodiment 1, comparative example 1 and comparative example 2 is used for the reaction of catalysis ethanol and oxygen.According to the conversion of reaction rate, if the catalytic efficiency of Cu-series catalyst is 1 in embodiment 1, the catalytic efficiency in comparative example 1 is 0.8, and the catalytic efficiency in comparative example 2 is 0.6.
Claims (9)
1. a Cu-series catalyst, is characterized in that, it prepares just like below method:
(1) sodium metasilicate is dissolved in organic solvent, under the condition of nitrogen protection, in organic solvent, passes into hydrogen chloride gas, at 30 ~ 60 DEG C, react 3 ~ 6h;
(2) keep nitrogen protection condition, in the mixed system of step (1) gained, add copper source, at 40 ~ 45 DEG C, react 1 ~ 3h;
(3) in the mixed system of gained in step (2), add precipitating reagent, fully mix, after colloidal sol is complete, get gel;
(4) by after the gel detergent of gained in step (3), drying, roast, Cu-series catalyst is obtained.
2. Cu-series catalyst according to claim 1, is characterized in that, in step (1), described organic solvent is pyridine or methyl-sulfoxide.
3. Cu-series catalyst according to claim 1, is characterized in that, in step (1), the weight ratio of sodium metasilicate and organic solvent is 1:50 ~ 200.
4. Cu-series catalyst according to claim 1, is characterized in that, in step (1), the mol ratio of sodium metasilicate and hydrogen chloride is 1:1.5 ~ 3.5.
5. Cu-series catalyst according to claim 1, is characterized in that, in step (2), described copper source is copper chloride or cupric phosphate.
6. Cu-series catalyst according to claim 1, is characterized in that, in step (2), in sodium metasilicate and copper source, the mol ratio of copper is 50 ~ 75:1.
7. Cu-series catalyst according to claim 1, is characterized in that, in step (3), described precipitating reagent is polyacrylamide or ferric sulfate; Wherein, the mass ratio of precipitating reagent and sodium metasilicate is 1:600 ~ 750.
8. Cu-series catalyst according to claim 1, it is characterized in that, in step (4), the method for washing is for using deionized water rinsing 2 ~ 3 times, dry method is for using sodium sulfite dry, and the method for roast is roasting 1 ~ 1.5h at 600 ~ 700 DEG C.
9. Cu-series catalyst according to claim 1 is in the application of catalyst field.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201510777940.6A CN105457634A (en) | 2015-11-13 | 2015-11-13 | Copper-based catalyst and application thereof |
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| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201510777940.6A CN105457634A (en) | 2015-11-13 | 2015-11-13 | Copper-based catalyst and application thereof |
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| CN105457634A true CN105457634A (en) | 2016-04-06 |
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Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US20080183020A1 (en) * | 2007-01-26 | 2008-07-31 | Carter Technologies | Catalytic conversion of alcohols to aldehydes and ketones |
| CN103633268A (en) * | 2012-08-22 | 2014-03-12 | 海洋王照明科技股份有限公司 | Preparation method of silicon dioxide composite separators |
| CN203870880U (en) * | 2014-05-14 | 2014-10-08 | 武守宇 | Simple experiment apparatus for oxidation of ethanol to acetaldehyde |
| CN104190396A (en) * | 2014-08-28 | 2014-12-10 | 无锡普爱德环保科技有限公司 | Preparation method of lithium-loaded silica gel catalyst |
-
2015
- 2015-11-13 CN CN201510777940.6A patent/CN105457634A/en active Pending
Patent Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US20080183020A1 (en) * | 2007-01-26 | 2008-07-31 | Carter Technologies | Catalytic conversion of alcohols to aldehydes and ketones |
| CN103633268A (en) * | 2012-08-22 | 2014-03-12 | 海洋王照明科技股份有限公司 | Preparation method of silicon dioxide composite separators |
| CN203870880U (en) * | 2014-05-14 | 2014-10-08 | 武守宇 | Simple experiment apparatus for oxidation of ethanol to acetaldehyde |
| CN104190396A (en) * | 2014-08-28 | 2014-12-10 | 无锡普爱德环保科技有限公司 | Preparation method of lithium-loaded silica gel catalyst |
Non-Patent Citations (2)
| Title |
|---|
| 朱洪法: "《催化剂载体制备及应用技术》", 31 October 2014, 石油工业出版社 * |
| 陆鼎一: "《化学故事新编》", 31 July 2007, 苏州大学出版社 * |
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Application publication date: 20160406 |