CN103752305A - Catalyst, preparation method thereof, and method for production of methyl acrylate and co-production of methyl methacrylate by using catalyst - Google Patents
Catalyst, preparation method thereof, and method for production of methyl acrylate and co-production of methyl methacrylate by using catalyst Download PDFInfo
- Publication number
- CN103752305A CN103752305A CN201410022889.3A CN201410022889A CN103752305A CN 103752305 A CN103752305 A CN 103752305A CN 201410022889 A CN201410022889 A CN 201410022889A CN 103752305 A CN103752305 A CN 103752305A
- Authority
- CN
- China
- Prior art keywords
- carbon monoxide
- olefin polymeric
- methyl
- catalyst
- formaldehyde
- 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.)
- Granted
Links
Landscapes
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
- Catalysts (AREA)
Abstract
The invention relates to a catalyst composition for synthesis of methyl acrylate and co-production of methyl methacrylate by methyl acetate and formaldehyde, a preparation method of the catalyst composition and a method for production of methyl acrylate and co-production of methyl methacrylate by using the catalyst composition. The catalyst composition disclosed by the invention takes SiO2 as a catalyst carrier, and also comprises metal salts of Cs and Zr, and an oxide of Sb.
Description
Technical field
The present invention relates to a kind of carbon monoxide-olefin polymeric, its preparation method and use this carbon monoxide-olefin polymeric to produce the method for industrial chemicals, be specifically related to a kind of for carbon monoxide-olefin polymeric, its preparation method by methyl acetate and formaldehyde synthesizing methyl acrylate coproduction methyl methacrylate and use this carbon monoxide-olefin polymeric to produce the method for methyl acrylate coproduction methyl methacrylate.
Background technology
Methyl acrylate, as organic synthesis intermediate, is mainly also the monomer of synthesising macromolecule copolymer, for rubber, medicine, leather, papermaking, adhesive etc.The synthetic method of acrylic acid (ester) mainly contains: acrylonitrile hydrolysis method, oxidation of propylene and ketene process, wherein applying more is oxidation of propylene.In industrial production, adopt propylene oxidation to generate acrylic acid, and then esterification generate corresponding ester method and has accounted for 95% left and right.
Along with the growing tension of petroleum resources, propylene feedstocks source is restricted, and the Coal Chemical Industry produce market surpluses such as domestic acetic acid, formaldehyde, most manufacturing enterprises utilization of capacity deficiency, therefore develops Coal Chemical Industry raw material substitution process route synthesizing methyl acrylate and methyl methacrylate and has great importance.
The many R&D institutions of recent domestic have also carried out the research work take methyl acetate, formaldehyde as raw material synthesizing methyl acrylate.The Zhao Xin of Qiqihar University space etc., the Jing Tao of Harbin Institute of Technology, grand celebration China Tech and Daqing petrochemical Sun Wu sun and lift a sail and Institutes Of Technology Of Taiyuan's Zhang Zhiqiang etc. is all prepared and is studied in the application aspect methyl acetate and formaldehyde/methylal synthesis methyl acrylate at catalyst.
Methyl methacrylate is mainly used in during synthetic, the PVC auxiliary agent, coating of lucite etc. produce, and is important Organic Chemicals.The production of methyl methacrylate mainly adopts ACH method both at home and abroad at present, but the method exists, technological process is long, use hydrogen cyanide has the shortcomings such as severe toxicity.Other process routes have isobutene method, ethylene process, MGC method etc.Particularly, Lu Caite company has improved ethylene process, has proposed α technology, and this technology mainly comprises two courses of reaction: ethene and carbon monoxide, methyl alcohol react and generates methyl propionate under certain temperature and pressure; Methyl propionate and formolite reaction generate methyl methacrylate.
In process with methyl acetate and formaldehyde synthesizing methyl acrylate, can obtain a small amount of hydrogenation byproduct, i.e. methyl propionate, but due to the specificity of catalyst, in the prior art, this part accessory substance is difficult to be applied.And increased thus separation, the cost for purification of product, and the discharge of accessory substance, processing cost.In addition, because modern catalysts is of a great variety, expensive, mechanism is different, and therefore product complexity is various, therefore, also needs to develop carbon monoxide-olefin polymeric more, more targeted, that customize.
And the research of synthesizing methyl acrylate and methyl methacrylate there is not yet report take methyl acetate and formaldehyde as raw material simultaneously.
Summary of the invention
Therefore, an object of the present invention is to provide a kind of carbon monoxide-olefin polymeric, its can be take methyl acetate and formaldehyde as raw material synthesizing methyl acrylate and methyl methacrylate simultaneously.
Another object of the present invention is to provide the preparation method of described carbon monoxide-olefin polymeric.
A further object of the present invention be to provide use described carbon monoxide-olefin polymeric take methyl acetate and formaldehyde as raw material the method for synthesizing methyl acrylate and methyl methacrylate simultaneously.
According to an aspect of the present invention, it provides a kind of for the carbon monoxide-olefin polymeric by methyl acetate and formaldehyde synthesizing methyl acrylate and methyl methacrylate, said composition comprises catalyst carrier and active component, wherein, described active component comprises the slaine of Cs and Zr, and the oxide of Sb, based on the quality of described carrier, in the metallic element quality in slaine and oxide, this carbon monoxide-olefin polymeric comprises 0.01%～0.5% Zr, 1%～35% Cs and 1%～40% Sb; Preferably include 0.02%～0.4% Zr, 2%～30% Cs and 5%～35% Sb; More preferably comprise 0.05%～0.15% Zr, 5%～25% Cs and 10%～30% Sb;
Preferably, the slaine of described Cs is cesium carbonate, cesium nitrate, cesium chloride or cesium sulfate;
Preferably, described catalyst carrier is SiO
2, Al
2o
3or the composition of the two; Be preferably particle diameter and be the microsphere particle of 50～100 microns;
Preferably, described carbon monoxide-olefin polymeric can further comprise transition metal oxide, and described transition metal oxide comprises the oxide of Zn or Ni etc.
According to another aspect of the present invention, the preparation method that it provides described carbon monoxide-olefin polymeric, specifically comprises the following steps:
(1) take Sb
2o
3, be mixed with deionized water the colloidal solution that antimony molar concentration is 0.05～5mol/L;
(2) by the mass ratio in composition mentioned above, take catalyst carrier, and under continuous stirring and 50～90 ℃ of conditions, make it mix with colloidal solution prepared in step (1), after dipping 5～24h, dry 2～5h at 80～130 ℃;
(3) by the mass ratio in composition mentioned above, take respectively the slaine of zirconium nitrate and caesium, being mixed with zirconium ion molar concentration is 0.005～0.5mol/L, the aqueous solution that cesium ion molar concentration is 0.05～5mol/L;
(4) under continuous stirring and 50～80 ℃ of conditions, by solution prepared in step (3) and the prepared solids mixing of step (2), after dipping 5～24h, in 80～130 ℃ of dry 2～5h, then at 400～500 ℃ of roasting 3～5h, obtain carbon monoxide-olefin polymeric.
Preferably, in step (3), the salt of transition metal Zn or Ni (being generally the salt corresponding with the slaine of Cs) is made up water in solution, wherein, the molar concentration of Zn or Ni ion is 0.01～2mol/L
Preferably, in above-mentioned steps (2), after dry at 400～500 ℃ of roasting 1～5h.
Preferably, in above-mentioned steps (2), the time of described dipping is 5～10 hours, and described dry temperature is 90～120 ℃, and the described dry time is 3～4 hours.
Preferably, in above-mentioned steps (4), the time of described dipping is 5～10 hours, and described dry temperature is 90～120 ℃, and the described dry time is 3～4 hours.
In above-mentioned preparation method, if dip time is too short, catalyst activity composition can not load on carrier fully, if dip time is oversize, the support structures of " active component-carrier " may change, and uneconomical.
In above-mentioned preparation method, if baking temperature is too low or drying time is too short, drying effect is insufficient, otherwise uneconomical.
In above-mentioned preparation method, in the situation that described carbon monoxide-olefin polymeric further comprises transition metal oxide, can further improve the selective of this carbon monoxide-olefin polymeric.
The invention provides the method for above-mentioned catalyst take methyl acetate and formaldehyde as raw material synthesizing methyl acrylate and methyl methacrylate of using, the method comprises: take methyl acetate and formaldehyde as raw material, depolymerizing agent using methyl alcohol as formaldehyde, adopt atmospheric fixed bed reaction, wherein, loaded catalyst is 1～10g, preferably 1～5g, more preferably 2.0g, and described catalyst is above-mentioned carbon monoxide-olefin polymeric, with the N of 80ml/min flow
2as dispersed gas; Wherein, the mol ratio of raw material methyl acetate and formaldehyde is 1:2～8:1, is preferably 1:1, and the mol ratio of methyl alcohol and methyl acetate is 1:2～3:1, is preferably 1.5:1.Finally adopt gas chromatographic analysis product composition.
Through a large amount of experiments, applicant finds, the catalyst that uses above-mentioned composition during for the reaction of methyl acetate and formaldehyde, not only can obtain two kinds of products take methyl acetate and formaldehyde as raw material is synthetic, methyl acrylate and methyl methacrylate, thus accessory substance is converted into useful product; Meanwhile, also unexpectedly reduce the carbon deposition quantity of catalyst, catalyst has been had to certain activation, palingenesis, extended the service time of catalyst.
Through applicant, study discovery, above-mentioned reaction can be represented by following equation:
CH
3COOCH
3+HCHO→CH
2=CHCOOCH
3+H
2O （1）
C+H
2O→H
2+CO （2）
CH
2=CHCOOCH
3+H
2→CH
3CH
2COOCH
3 （3）
CH
3CH
2COOCH
3+HCHO→CH
2=CCH
3COOCH
3+H
2O； （4）
Reaction equation (1) and (4) represent to obtain respectively the reaction of methyl acrylate and methyl methacrylate product, and by reaction (2), have greatly reduced just the carbon deposition quantity of catalyst.
The specific embodiment
Following examples are only as the object of explanation, and scope of the present invention is not limited to following embodiment, in the situation that not departing from aim scope of the present invention, within alternate embodiment is included in technical scope of the present invention.
Embodiment mono-
(1) by 4.142g Sb
2o
3be mixed in 50ml there-necked flask with 25ml deionized water, be heated with stirring to 75 ℃, condensing reflux, adds 2ml stabilizing agent triethanolamine, after 10min, is warming up to 85 ℃, drips H
2o
23～4ml, continues to be stirred to solution clarification, obtains colloidal solution;
(2) take the SiO that 20.0g particle diameter is the microsphere particle of 50～100 microns
2carrier, under 70 ℃ of conditions, by the colloidal solution and the SiO that obtain in (1)
2carrier mixes, and after continuous stirring dipping 8h, in 90 ℃ of dry 2h, 450 ℃ of roasting 3h, obtain Sb/SiO
2;
(3) take 0.1235gZr (NO3)
45H
2o and 4.628gCsNO
3, be dissolved in 30ml deionized water;
(4) under 70 ℃ of conditions, the Sb/SiO by the mixed solution obtaining in (3) with (2) middle gained
2mix, after continuous stirring dipping 10h, in 90 ℃ of dry 2h, 450 ℃ of roasting 3h, obtain SiO
2the Cs-Zr-Sb composite catalyst of upper load.
Adopt the catalyst of preparation to carry out synthesizing methyl acrylate and methyl methacrylate reaction evaluating, adopt atmospheric fixed bed reaction, wherein, loaded catalyst is 2.0g, with the N of 80ml/min flow
2as dispersed gas.
Wherein, the mol ratio of raw material methyl acetate and formaldehyde is 1:1, and the mol ratio of methyl alcohol and methyl acetate is 1.5:1, and reaction temperature is 350 ℃, and charging air speed is 3h
-1.The evaluation result of this catalyst is: the conversion ratio of methyl acetate is 29.20%, methyl acrylate be selectively 78.98%, methyl methacrylate be selectively 12.57%.
Embodiment bis-:
Except in step (3), with 3.868g Cs
2cO
3replace CsNO
3in addition, with the preparation method's Kaolinite Preparation of Catalyst composition described in embodiment mono-.
Adopt the condition described in embodiment mono-to carry out synthesizing methyl acrylate and methyl methacrylate reaction evaluating to this catalyst, evaluation result is: the conversion ratio of methyl acetate is 23.41%, methyl acrylate be selectively 75.67%, methyl methacrylate be selectively 7.51%.
Embodiment tri-:
Except in step (1), by Sb
2o
3amount be increased to beyond 6.728g, with the preparation method's Kaolinite Preparation of Catalyst composition described in embodiment mono-.
Adopt the condition described in embodiment mono-to carry out synthesizing methyl acrylate and methyl methacrylate reaction evaluating to this catalyst, evaluation result is: the conversion ratio of methyl acetate is 32.75%, methyl acrylate be selectively 74.27%, methyl methacrylate be selectively 15.62%.
Embodiment tetra-:
Except in step (3), by CsNO
3amount be increased to beyond 7.287g, with the preparation method's Kaolinite Preparation of Catalyst composition described in embodiment mono-.
Adopt the condition described in embodiment mono-to carry out synthesizing methyl acrylate and methyl methacrylate reaction evaluating to this catalyst, evaluation result is: the conversion ratio of methyl acetate is 35.83%, methyl acrylate be selectively 79.33%, methyl methacrylate be selectively 13.28%.
Embodiment five:
Except in step (3), with 3.997g CsCl, replace CsNO
3in addition, with the preparation method's Kaolinite Preparation of Catalyst composition described in embodiment mono-.
Adopt the condition described in embodiment mono-to carry out synthesizing methyl acrylate and methyl methacrylate reaction evaluating to this catalyst, evaluation result is: the conversion ratio of methyl acetate is 22.31%, methyl acrylate be selectively 80.56%, methyl methacrylate be selectively 10.37%.
Embodiment six:
Except in step (3), with 2.531g Cs
2sO
4replace CsNO
3in addition, with the preparation method's Kaolinite Preparation of Catalyst composition described in embodiment mono-.
Adopt the condition described in embodiment mono-to carry out synthesizing methyl acrylate and methyl methacrylate reaction evaluating to this catalyst, evaluation result is: the conversion ratio of methyl acetate is 23.47%, methyl acrylate be selectively 75.39%, methyl methacrylate be selectively 13.87%.
Embodiment seven:
Adopt the carbon monoxide-olefin polymeric that described in embodiment tri-prepared by preparation method to carry out synthesizing methyl acrylate and methyl methacrylate reaction evaluating, wherein, the mol ratio of raw material methyl acetate and formaldehyde is 2:1, the mol ratio of methyl alcohol and methyl acetate is 1:1, reaction temperature is 350 ℃, and charging air speed is 3h
-1.The evaluation result of this catalyst is: the conversion ratio of methyl acetate is 22.17%, methyl acrylate be selectively 79.23%, methyl methacrylate be selectively 10.31%.
Embodiment eight:
Adopt the carbon monoxide-olefin polymeric that described in embodiment tri-prepared by preparation method to carry out synthesizing methyl acrylate and methyl methacrylate reaction evaluating, wherein, the mol ratio of raw material methyl acetate and formaldehyde is 1:1, the mol ratio of methyl alcohol and methyl acetate is 1:1.5, reaction temperature is 330 ℃, and charging air speed is 3h
-1.The evaluation result of this catalyst is: the conversion ratio of methyl acetate is 21.84%, methyl acrylate be selectively 77.39%, methyl methacrylate be selectively 7.42%.
Embodiment nine:
Adopt the carbon monoxide-olefin polymeric that described in embodiment tri-prepared by preparation method to carry out synthesizing methyl acrylate and methyl methacrylate reaction evaluating, wherein, the mol ratio of raw material methyl acetate and formaldehyde is 1:1, the mol ratio of methyl alcohol and methyl acetate is 1:1.5, reaction temperature is 370 ℃, and charging air speed is 3h
-1.The evaluation result of this catalyst is: the conversion ratio of methyl acetate is 33.74%, methyl acrylate be selectively 77.26%, methyl methacrylate be selectively 10.50%.
Embodiment ten:
Adopt the carbon monoxide-olefin polymeric that described in embodiment tri-prepared by preparation method to carry out synthesizing methyl acrylate and methyl methacrylate reaction evaluating, wherein, the mol ratio of raw material methyl acetate and formaldehyde is 1:1, the mol ratio of methyl alcohol and methyl acetate is 1:1.5, reaction temperature is 350 ℃, and charging air speed is 5h
-1.The evaluation result of this catalyst is: the conversion ratio of methyl acetate is 23.49%, methyl acrylate be selectively 82.17%, methyl methacrylate be selectively 9.26%.
Embodiment 11:
Except among step (3), further add 0.915g Zn (NO
3)
26H
2beyond O, with the preparation method's Kaolinite Preparation of Catalyst composition described in embodiment mono-.
Adopt the condition described in embodiment mono-to carry out synthesizing methyl acrylate and methyl methacrylate reaction evaluating to this catalyst, evaluation result is: the conversion ratio of methyl acetate is 28.73%, methyl acrylate be selectively 85.21%, methyl methacrylate be selectively 11.37%.
According to above-described embodiment, can find out, by the catalyst with the present invention composition during for the reaction of methyl acetate and formaldehyde, can as raw material is synthetic, obtain two kinds of products take methyl acetate and formaldehyde, methyl acrylate and methyl methacrylate, thus accessory substance is converted into useful product.
Claims (10)
1. a carbon monoxide-olefin polymeric, this carbon monoxide-olefin polymeric comprises catalyst carrier and active component, wherein, described active component comprises the slaine of Cs, and the oxide of Zr and Sb, based on the quality of described carrier, in the metallic element quality in slaine and oxide, this carbon monoxide-olefin polymeric comprises 0.01%～0.5% Zr, 1%～35% Cs and 1%～40% Sb
Wherein, the slaine of described Cs is cesium carbonate, cesium nitrate, cesium chloride or cesium sulfate.
2. carbon monoxide-olefin polymeric according to claim 1, wherein, based on the quality of described carrier, in the metallic element quality in slaine and oxide, this carbon monoxide-olefin polymeric comprises 0.02%～0.4% Zr, 2%～30% Cs and 5%～35% Sb.
3. carbon monoxide-olefin polymeric according to claim 1, wherein, based on the quality of described carrier, in the metallic element quality in slaine and oxide, this carbon monoxide-olefin polymeric comprises 0.05%～0.15% Zr, 5%～25% Cs and 10%～30% Sb.
4. according to the carbon monoxide-olefin polymeric described in any one in claim 1-3, wherein, described catalyst carrier is SiO
2, Al
2o
3or the composition of the two.
5. according to the carbon monoxide-olefin polymeric described in any one in claim 1-3, wherein, described carbon monoxide-olefin polymeric further comprises the oxide of Zn or Ni, wherein, based on the quality of described carrier, in the metallic element quality in oxide, this carbon monoxide-olefin polymeric comprises 0.5%～20% Zn or Ni.
6. according to the preparation method of carbon monoxide-olefin polymeric described in any one in claim 1～3, comprise the following steps:
(1) take Sb
2o
3, be mixed with deionized water the colloidal solution that antimony molar concentration is 0.05～5mol/L;
(2) take catalyst carrier, and under continuous stirring and 50～90 ℃ of conditions, make described catalyst carrier mix with colloidal solution prepared in step (1), after dipping 5～24h, dry 2～5h at 80～130 ℃;
(3) take the slaine of zirconium nitrate and caesium, being mixed with zirconium ion molar concentration is 0.005～0.5mol/L, the aqueous solution that cesium ion molar concentration is 0.05～5mol/L;
(4) under continuous stirring and 50～80 ℃ of conditions, by solution prepared in step (3) and the prepared solids mixing of step (2), after dipping 5～24h, in 80～130 ℃ of dry 2～5h, then 400～500 ℃ of roasting 3～5h, obtain carbon monoxide-olefin polymeric
Wherein, the mass ratio of each component is with identical with the mass ratio of each component of carbon monoxide-olefin polymeric described in any one in claim 1～3.
7. preparation method according to claim 6, wherein,
In step (3), further the salt of transition metal Zn or Ni is made up water in solution, wherein, the salt of described Zn or Ni is the salt corresponding with the slaine of described Cs, and the molar concentration of described Zn or Ni ion is 0.01～2mol/L.
8. preparation method according to claim 6, wherein,
In described step (2), after dry at 400～500 ℃ of roasting 1～5h, and the time of described dipping be 5～10 hours, described dry temperature is 90～120 ℃, the described dry time is 3～4 hours, and
In above-mentioned steps (4), the time of described dipping is 5～10 hours, and described dry temperature is 90～120 ℃, and the described dry time is 3～4 hours.
9. the method take methyl acetate and formaldehyde as raw material synthesizing methyl acrylate and methyl methacrylate, the method comprises: take methyl acetate and formaldehyde as raw material, depolymerizing agent using methyl alcohol as formaldehyde, adopt atmospheric fixed bed reaction, wherein, loaded catalyst is 1～10g, and described catalyst is the carbon monoxide-olefin polymeric described in any one in claim 1-5, with the N of 80ml/min flow
2as dispersed gas, wherein, the mol ratio of raw material methyl acetate and formaldehyde is 1:2～2:1, and the mol ratio of methyl alcohol and methyl acetate is 1:2～3:1.
10. method according to claim 9, wherein,
Described loaded catalyst is 1～5g, and the mol ratio of raw material methyl acetate and formaldehyde is 1:1, and the mol ratio of methyl alcohol and methyl acetate is 1.5:1.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201410022889.3A CN103752305B (en) | 2014-01-17 | 2014-01-17 | A kind of catalyst, its preparation method and use the method for this Catalyst Production methyl acrylate co-production methyl methacrylate |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201410022889.3A CN103752305B (en) | 2014-01-17 | 2014-01-17 | A kind of catalyst, its preparation method and use the method for this Catalyst Production methyl acrylate co-production methyl methacrylate |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN103752305A true CN103752305A (en) | 2014-04-30 |
| CN103752305B CN103752305B (en) | 2015-12-30 |
Family
ID=50519712
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN201410022889.3A Active CN103752305B (en) | 2014-01-17 | 2014-01-17 | A kind of catalyst, its preparation method and use the method for this Catalyst Production methyl acrylate co-production methyl methacrylate |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN103752305B (en) |
Cited By (10)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN104275172A (en) * | 2014-09-10 | 2015-01-14 | 江苏金聚合金材料有限公司 | High-stability catalyst for synthesizing methyl acrylate and preparation method of high-stability catalyst for synthesizing methyl acrylate |
| CN104525176A (en) * | 2014-12-16 | 2015-04-22 | 旭阳化学技术研究院有限公司 | Preparation method of Cs-based catalyst microsphere, microsphere prepared by adopting preparation method, and method for synthesizing (methyl) acrylic acid methyl ester by utilizing microsphere |
| CN106423159A (en) * | 2016-09-08 | 2017-02-22 | 万华化学集团股份有限公司 | Anti-carbon deposition aldol condensation catalyst, preparation method thereof and method for preparing methyl methacrylate by using catalyst |
| CN107721855A (en) * | 2017-10-13 | 2018-02-23 | 北京博迩科技有限公司 | A kind of method for preparing 3 methoxy methyl propionates |
| CN108097305A (en) * | 2016-11-25 | 2018-06-01 | 中国科学院大连化学物理研究所 | A kind of renovation process for the catalyst for being used to prepare acrylic acid and/or methyl acrylate |
| CN108097289A (en) * | 2016-11-25 | 2018-06-01 | 中国科学院大连化学物理研究所 | A kind of renovation process for the catalyst for being used to prepare acrylic acid and/or methyl acrylate |
| CN108097335A (en) * | 2016-11-25 | 2018-06-01 | 中国科学院大连化学物理研究所 | A kind of method that regeneration prepares the catalyst of unsaturated acids and/or unsaturated acid ester |
| CN112221482A (en) * | 2020-11-03 | 2021-01-15 | 中触媒新材料股份有限公司 | Catalyst for synthesizing methyl acrylate or methyl methacrylate and application |
| CN112427031A (en) * | 2020-11-30 | 2021-03-02 | 中触媒新材料股份有限公司 | Preparation method and application of catalyst for synthesizing methyl acrylate/methyl methacrylate |
| CN113713819A (en) * | 2020-05-26 | 2021-11-30 | 北京旭阳科技有限公司 | Catalyst composition and preparation method and application thereof |
Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US4447641A (en) * | 1982-07-26 | 1984-05-08 | Standard Oil Company (Indiana) | Process for preparation of alpha, beta-unsaturated esters using AMS-1B borosilicate crystalline molecular sieve |
| WO2007014205A2 (en) * | 2005-07-25 | 2007-02-01 | Saudi Basic Industries Corporation | An integrated plant for producing 2-ethyl-hexanol and methacrylic acid and a method based thereon |
| CN101829558A (en) * | 2010-04-27 | 2010-09-15 | 中国科学院过程工程研究所 | Catalyst for directly preparing methyl methacrylate by reacting methyl propionate with formaldehyde and preparation method thereof |
| CN102962062A (en) * | 2012-12-11 | 2013-03-13 | 西南化工研究设计院有限公司 | Catalyst for synthesis of methyl methacrylate by formaldehyde and methyl propionate and preparation method of catalyst |
-
2014
- 2014-01-17 CN CN201410022889.3A patent/CN103752305B/en active Active
Patent Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US4447641A (en) * | 1982-07-26 | 1984-05-08 | Standard Oil Company (Indiana) | Process for preparation of alpha, beta-unsaturated esters using AMS-1B borosilicate crystalline molecular sieve |
| WO2007014205A2 (en) * | 2005-07-25 | 2007-02-01 | Saudi Basic Industries Corporation | An integrated plant for producing 2-ethyl-hexanol and methacrylic acid and a method based thereon |
| CN101829558A (en) * | 2010-04-27 | 2010-09-15 | 中国科学院过程工程研究所 | Catalyst for directly preparing methyl methacrylate by reacting methyl propionate with formaldehyde and preparation method thereof |
| CN102962062A (en) * | 2012-12-11 | 2013-03-13 | 西南化工研究设计院有限公司 | Catalyst for synthesis of methyl methacrylate by formaldehyde and methyl propionate and preparation method of catalyst |
Non-Patent Citations (1)
| Title |
|---|
| 荆涛等: "Cs-Sb2O5/SiO2催化剂用于合成丙烯酸甲酯", 《化学工程》, vol. 38, no. 5, 31 May 2010 (2010-05-31) * |
Cited By (15)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN104275172A (en) * | 2014-09-10 | 2015-01-14 | 江苏金聚合金材料有限公司 | High-stability catalyst for synthesizing methyl acrylate and preparation method of high-stability catalyst for synthesizing methyl acrylate |
| CN104525176A (en) * | 2014-12-16 | 2015-04-22 | 旭阳化学技术研究院有限公司 | Preparation method of Cs-based catalyst microsphere, microsphere prepared by adopting preparation method, and method for synthesizing (methyl) acrylic acid methyl ester by utilizing microsphere |
| CN106423159B (en) * | 2016-09-08 | 2019-07-23 | 万华化学集团股份有限公司 | A kind of anti-carbon aldol condensation catalyst and preparation method thereof and method using the catalyst preparation methyl methacrylate |
| CN106423159A (en) * | 2016-09-08 | 2017-02-22 | 万华化学集团股份有限公司 | Anti-carbon deposition aldol condensation catalyst, preparation method thereof and method for preparing methyl methacrylate by using catalyst |
| CN108097305B (en) * | 2016-11-25 | 2020-09-04 | 中国科学院大连化学物理研究所 | Regeneration method of catalyst for preparing acrylic acid and/or methyl acrylate |
| CN108097289A (en) * | 2016-11-25 | 2018-06-01 | 中国科学院大连化学物理研究所 | A kind of renovation process for the catalyst for being used to prepare acrylic acid and/or methyl acrylate |
| CN108097335A (en) * | 2016-11-25 | 2018-06-01 | 中国科学院大连化学物理研究所 | A kind of method that regeneration prepares the catalyst of unsaturated acids and/or unsaturated acid ester |
| CN108097305A (en) * | 2016-11-25 | 2018-06-01 | 中国科学院大连化学物理研究所 | A kind of renovation process for the catalyst for being used to prepare acrylic acid and/or methyl acrylate |
| CN108097289B (en) * | 2016-11-25 | 2020-09-04 | 中国科学院大连化学物理研究所 | Regeneration method of catalyst for preparing acrylic acid and/or methyl acrylate |
| CN107721855A (en) * | 2017-10-13 | 2018-02-23 | 北京博迩科技有限公司 | A kind of method for preparing 3 methoxy methyl propionates |
| CN107721855B (en) * | 2017-10-13 | 2021-01-19 | 北京博迩科技有限公司 | Method for preparing 3-methoxy methyl propionate |
| CN113713819A (en) * | 2020-05-26 | 2021-11-30 | 北京旭阳科技有限公司 | Catalyst composition and preparation method and application thereof |
| CN113713819B (en) * | 2020-05-26 | 2023-12-01 | 北京旭阳科技有限公司 | Catalyst composition and preparation method and application thereof |
| CN112221482A (en) * | 2020-11-03 | 2021-01-15 | 中触媒新材料股份有限公司 | Catalyst for synthesizing methyl acrylate or methyl methacrylate and application |
| CN112427031A (en) * | 2020-11-30 | 2021-03-02 | 中触媒新材料股份有限公司 | Preparation method and application of catalyst for synthesizing methyl acrylate/methyl methacrylate |
Also Published As
| Publication number | Publication date |
|---|---|
| CN103752305B (en) | 2015-12-30 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN103752305B (en) | A kind of catalyst, its preparation method and use the method for this Catalyst Production methyl acrylate co-production methyl methacrylate | |
| CN101712590B (en) | Improved process for the oxidative dehydrogenation of ethane | |
| CN104549220B (en) | Catalyst for dehydrogenating low-carbon alkane | |
| CN104056652B (en) | A kind of hud typed ZSM-5 molecular sieve pellet catalyst | |
| CN102553624B (en) | Preparation method of catalyst for synthesizing methacrylic acid | |
| CN103801280A (en) | Cs-supported silica-based catalyst and preparation method and application thereof | |
| CN104056654B (en) | A kind of ZSM-5 molecular sieve compositions, preparation method and application thereof | |
| CN102350336A (en) | Zr-Cs series methyl methacrylate catalyst added with modification auxiliary agent and preparation method thereof | |
| CN103769148A (en) | Acrolein oxidation to acrylic acid catalyst, preparation method and application of catalyst | |
| CN104837799A (en) | Catalytic conversion of bio-mass derivable aliphatic alcohols to valuable alkenes or oxygenates | |
| CN106699601B (en) | One-step method for synthesizing of the one kind to (neighbour) hydroxy-phenylformonitrile | |
| CN107175094B (en) | Composite carrier catalyst for aldol condensation and preparation method and application thereof | |
| JP2018500148A (en) | Catalyst for glycerol dehydration reaction, method for producing the same, and method for producing acrolein using the catalyst | |
| CN101279910A (en) | A kind of preparation method of acrylic acid | |
| CN110639492A (en) | Catalyst for preparing methyl acrylate from methyl acetate and formaldehyde and application thereof | |
| CN105944757A (en) | Catalyst for synthesizing vinyl acetate with acetylene process, preparation method and vinyl acetate synthesizing method | |
| CN103664634B (en) | For loaded catalyst prepared by 1,2 propane diamine | |
| CN107445833B (en) | Method for synthesizing glyoxylic ester by oxidizing glycolate | |
| CN109772356B (en) | Acrylonitrile catalyst and preparation method and application thereof | |
| CN112774658A (en) | Acid-base bifunctional catalyst for synthesizing methyl acrylate from methyl acetate and formaldehyde and preparation method thereof | |
| CN113877560A (en) | Synthesis method of methyl acrylate and solid base catalyst thereof | |
| CN103274887B (en) | Method for synthesizing 1,3-butadiene by using Bi/Mo/Ce three-component composite oxide catalyst | |
| CN105582964B (en) | A kind of O composite metallic oxide catalyst and its preparation method and application | |
| TWI645899B (en) | Method for producing ethylene from ethanol raw material | |
| CN107445832A (en) | The method of ethyl glycolate oxidation generation glyoxylic ester |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| C06 | Publication | ||
| PB01 | Publication | ||
| C10 | Entry into substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| C14 | Grant of patent or utility model | ||
| GR01 | Patent grant | ||
| CB03 | Change of inventor or designer information |
Inventor after: Zhang Yingwei Inventor after: Zhang Lingwei Inventor after: Dang Weirong Inventor after: Wang Yaohong Inventor after: Wang Peng Inventor after: Sun Changjiang Inventor before: Zhang Yingwei Inventor before: Zhang Lingwei Inventor before: Wang Yaohong Inventor before: Wang Peng Inventor before: Sun Changjiang |
|
| CB03 | Change of inventor or designer information | ||
| TR01 | Transfer of patent right |
Effective date of registration: 20180531 Address after: 061113 west side of Xu Yang Street, north of Bohai Road, Bohai New District, Hebei Patentee after: Cangzhou Xu Yang science and Technology Co., Ltd. Address before: 100070 building 21, zone 188, South Fourth Ring Road, Fengtai District, Beijing. Patentee before: Xuyang Chemical Technology Research Institute Co., Ltd. |
|
| TR01 | Transfer of patent right | ||
| TR01 | Transfer of patent right |
Effective date of registration: 20190513 Address after: 100070 301, 3 floor, 21 building, 188 District, South Fourth Ring Road, Fengtai District, Beijing. Patentee after: BEIJING RISUN TECHNOLOGY CO., LTD. Address before: 061113 west side of Xu Yang Street, north of Bohai Road, Bohai New District, Hebei Patentee before: Cangzhou Xu Yang science and Technology Co., Ltd. |
|
| TR01 | Transfer of patent right |