CN105251495A - Composite catalyst and application thereof - Google Patents
Composite catalyst and application thereof Download PDFInfo
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- CN105251495A CN105251495A CN201510776852.4A CN201510776852A CN105251495A CN 105251495 A CN105251495 A CN 105251495A CN 201510776852 A CN201510776852 A CN 201510776852A CN 105251495 A CN105251495 A CN 105251495A
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- composite catalyst
- catalyst according
- sodium metasilicate
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- organic solvent
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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 discloses a composite catalyst which is obtained in the mode that sodium metasilicate and a metal source react under an organic phase environment. Compared with the prior art, the composite catalyst fixes copper and calcium which play a catalytic role to a silica-gel carrier in a scattered mode, and the contact area between the composite catalyst and a reaction backing material is expanded, the catalytic efficiency of the composite catalyst is higher, the required catalytic condition is milder, and industrial production is facilitated; meanwhile, a method is completed under a pure organic phase condition, and through comparison, the catalytic efficiency of the obtained composite catalyst is higher compared with a general water containing condition.
Description
Technical field
The invention belongs to catalyst field, be specifically related to a kind of composite 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.Copper system and calcium series catalysts are 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 composite 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 also will solve is to provide the application of above-mentioned composite 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 composite 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 67 ~ 75 DEG C, react 3 ~ 5h;
(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, composite 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 1:100 ~ 300.
In step (1), the mol ratio of sodium metasilicate and hydrogen chloride is 1:2 ~ 4.
In step (2), described source metal is CaCu 3 Ti 4 O.
In step (2), in sodium metasilicate and CaCu 3 Ti 4 O, the mol ratio of copper is 60 ~ 92:1.
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 500 ~ 800 DEG C.
The composite catalyst that above-mentioned preparation method prepares is also within protection scope of the present invention.
Above-mentioned composite 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:
Composite catalyst in the present invention, is fixed on silica-gel carrier by the copper and calcium dispersion that play catalytic action, expands itself and the contact area of reacting bed material.Compared with prior art, this composite catalyst can provide two kinds of catalytic metals simultaneously, and catalytic efficiency 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 composite 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 5h at 50 DEG C;
(2) keep nitrogen protection condition, in the mixed system of step (1) gained, add CaCu 3 Ti 4 O, on shaking table, react 4h at 70 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 composite 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 1:200.
In step (1), the mol ratio of anhydrous sodium metasilicate and hydrogen chloride is 1:3.
In step (2), in anhydrous sodium metasilicate and CaCu 3 Ti 4 O, the mol ratio of copper is 83:1.
In step (3), the mass ratio of polyacrylamide and anhydrous sodium metasilicate is 1:680.
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 composite catalyst prepared in embodiment 1, comparative example 1 and comparative example 2 is used for petroleum cracking prepare in the reaction of ethene.According to the conversion of reaction rate, if the catalytic efficiency of composite catalyst is 1 in embodiment 1, the catalytic efficiency in comparative example 1 is 0.72, and the catalytic efficiency in comparative example 2 is 0.32.
Claims (9)
1. a composite catalyst, is characterized in that, it prepares by the following 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 source metal, at 67 ~ 75 DEG C, react 3 ~ 5h;
(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, composite catalyst is obtained.
2. composite catalyst according to claim 1, is characterized in that, in step (1), described organic solvent is pyridine or methyl-sulfoxide.
3. composite catalyst according to claim 1, is characterized in that, in step (1), the weight ratio of sodium metasilicate and organic solvent is 1:100 ~ 300.
4. composite catalyst according to claim 1, is characterized in that, in step (1), the mol ratio of sodium metasilicate and hydrogen chloride is 1:2 ~ 4.
5. composite catalyst according to claim 1, is characterized in that, in step (2), described source metal is CaCu 3 Ti 4 O.
6. composite catalyst according to claim 1, is characterized in that, in step (2), in sodium metasilicate and CaCu 3 Ti 4 O, the mol ratio of copper is 60 ~ 92:1.
7. composite 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. composite 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 500 ~ 800 DEG C.
9. composite catalyst according to claim 1 is in the application of catalyst field.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201510776852.4A CN105251495A (en) | 2015-11-13 | 2015-11-13 | Composite catalyst and application thereof |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201510776852.4A CN105251495A (en) | 2015-11-13 | 2015-11-13 | Composite catalyst and application thereof |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| CN105251495A true CN105251495A (en) | 2016-01-20 |
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Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN201510776852.4A Pending CN105251495A (en) | 2015-11-13 | 2015-11-13 | Composite catalyst and application thereof |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN105251495A (en) |
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2015
- 2015-11-13 CN CN201510776852.4A patent/CN105251495A/en active Pending
Non-Patent Citations (2)
| Title |
|---|
| 朱洪法: "《催化剂载体制备及应用技术(第二版)》", 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: 20160120 |
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| RJ01 | Rejection of invention patent application after publication |