CN102941113B - Catalyst for synthesizing methyl acrylate by using methyl acetate and methylal and preparation method thereof - Google Patents
Catalyst for synthesizing methyl acrylate by using methyl acetate and methylal and preparation method thereof Download PDFInfo
- Publication number
- CN102941113B CN102941113B CN201210491886.5A CN201210491886A CN102941113B CN 102941113 B CN102941113 B CN 102941113B CN 201210491886 A CN201210491886 A CN 201210491886A CN 102941113 B CN102941113 B CN 102941113B
- Authority
- CN
- China
- Prior art keywords
- catalyst
- coagent
- preparation
- oxide
- carrier
- 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.)
- Active
Links
Abstract
The invention relates to a catalyst for synthesizing methyl acrylate by using methyl acetate and methylal and a preparation method thereof. The catalyst is composed of a main activity component, a coagent and a carrier, the main activity component is oxide of Cs, the coagent is one or a plurality of nitrate or oxide of Zr, B and Ce, and the carrier is mixture of one or a plurality of magnesium oxide, silica, titanium oxide, aluminum silicate and magnesium silicate. The preparation method comprises firstly weighting salt of the main activity component and the coagent, adding deionized water for dissolving and preparing an aqueous solution; then soaking the carrier in the aqueous solution to obtain a mixture; and finally shaping the mixture, drying and roasting to obtain the catalyst. The catalyst has acid-base dual functionality and can improve selectivity of yield of the methyl acrylate of a target product. A small quantity of Ce coagent is led in the catalyst to improve water-resistance of the catalyst, and reaction activity and activity stability of the catalyst are improved. The preparation method is simple and applicable to large-scale industrial application.
Description
Technical field
The present invention relates to the catalysis technical field of chemical industry, be specially the Catalysts and its preparation method of methyl acetate and methylal synthesis methyl acrylate.
Background technology
Methyl acrylate (MA) is a kind of important organic synthesis intermediate, also be the monomer of synthesising macromolecule copolymer, the high polymer making with methyl acrylate has good weather-proof, ultraviolet resistance, the characteristic such as water-fast, heat-resisting, be mainly used in the fields such as building, papermaking, leather, weaving, plastic processing, packaging material, daily-use chemical industry, water treatment, oil recovery, metallurgy, purposes is very extensive.
Methyl acetate is as the accessory substance in chemical process, in the production process of, polyvinyl alcohol synthetic at acetic acid and PTA, can produce in a large number.The methyl acetate of factory's by-product is mainly to enter atmosphere or drain into sewage-treatment plant with solvent waste water with reaction end gas at present; so no matter be from the viewpoint of environmental protection, the utilization of resources or economic worth, the methyl acetate recycling that relative price is cheap is all extremely urgent.Carry out the process study of methyl acetate synthesis methyl acrylate, contribute to solve the recycling problem of methyl acetate, meanwhile, also meet China's oil less, resource structures that poor, the coal of gas is many, consistent with the industrial policy of the synthetic large chemical products of the medium-term and long-term Non oil-based route of China.
Methyl acetate and methylal synthesis methyl acrylate, real reaction process is divided into two steps, and the first step is that dimethoxym ethane heats and resolves into formaldehyde and methyl alcohol under acid condition, and second step is that methyl acetate and formolite reaction generate methyl acrylate.First step decomposition reaction is simple, and key is second step reaction, and the direct synthesizing methyl acrylate of methyl acetate and formaldehyde is typical aldol reaction.Research shows, adopts solid base catalyst or difunction catalyst to have good catalytic effect to aldol reaction.
Summary of the invention
The object of the present invention is to provide a kind of energy catalyst for methyl acetate and methylal synthesis methyl acrylate.
Another object of the present invention is to provide the preparation method of above-mentioned catalyst.
Another object of the present invention is to provide the application of above-mentioned catalyst.
In order to realize foregoing invention object, the technical solution used in the present invention is as follows:
The catalyst of a kind of methyl acetate and methylal synthesis methyl acrylate, formed by main active component, coagent and carrier, the oxide that wherein the main active component in catalyst is Cs, the oxide of Cs is selected from any one in cesium carbonate, cesium nitrate or cesium acetate; Coagent is one or more in nitrate or the oxide of Zr, B, Ce, and carrier is one or more the mixture in magnesia, silica, titanium oxide, alumina silicate, magnesium silicate.
In oxide, the quality percentage composition of main active component is that 5%-30%, coagent quality percentage composition are 1%-5%, and all the other are vector contg, and its total percentage composition is 100%.
The preparation method of the catalyst of methyl acetate and methylal synthesis methyl acrylate, comprises the following steps:
(1) take the salt of main active component and coagent, add deionized water dissolving, being mixed with Cs ion concentration is 0.05mol/L-1.0mol/L, the aqueous solution that auxiliary agent ion concentration is 0.001mol/L-0.1mol/L;
(2) in proportion carrier is immersed in the aqueous solution of step (1) preparation, under normal temperature, flood 4-8 hour to obtain mixture;
(3) by the mixture of step (2) gained by the mode of roller forming or extruded moulding, dry 2-4 hour at 80-150 DEG C, then at 400-600 DEG C roasting 4-6 hour, make described catalyst.
Another preparation method of the catalyst of methyl acetate and methylal synthesis methyl acrylate, is characterized in that comprising the following steps:
(1) take the salt of main active component, add deionized water dissolving, be mixed with the aqueous solution that Cs ion concentration is 0.05mol/L-1.0mol/L;
(2) after carrier is fully mixed in proportion, add the solution of step (1) preparation to mediate, then by compressing tablet, spin or extruded moulding mode, dry 2-4 hour at 100-150 DEG C, roasting 3-5 hour at 300-500 DEG C, makes catalyst precarsor again;
(3) take the salt of coagent, add deionized water and dissolve, make the aqueous solution that ion concentration is 0.001mol/L-0.1mol/L;
(4) catalyst precarsor for preparing is immersed in salting liquid prepared by step (3), then normal temperature dipping 4～8 hours, dry 2-4 hour at 80-120 DEG C, then at 300-500 DEG C roasting 3-5 hour, make described catalyst.
Two kinds of catalyst shape that method is made, all can be made into the various shapes such as spherical, sheet, strip, column.
This catalyst reacts with methylal synthesis methyl acrylate for methyl acetate, and its reaction condition is: the mol ratio of dimethoxym ethane/methyl propionate is 1:2-1:12, and charging air speed is 1-10h
-1, reaction temperature is 340 DEG C-400 DEG C.Its reaction comprises two steps.Key reaction process is:
CH
3CH
2COOCH
3+HCHO?→?CH
2=C(CH
3)COOCH
3+H
2O
Compared with prior art, the invention has the beneficial effects as follows:
(1), catalyst is taking alkali metal Cs as main active component, then introduces acidic oxide ZrO
2or B
2o
3, to regulate the Acidity of Aikalinity of catalyst, make catalyst there is soda acid bi-functional, thereby improve the selective and yield of target product methyl acrylate;
(2), introduce a small amount of Ce auxiliary agent in catalyst, the water-resistance of catalyst be can improve simultaneously, catalyst reaction activity and activity stability improved;
(3), this method for preparing catalyst is simple, is applicable to heavy industrialization application.
Detailed description of the invention
Below in conjunction with detailed description of the invention, the present invention is described in further detail.
But this should be interpreted as to the scope of the above-mentioned theme of the present invention only limits to following embodiment.
embodiment 1:
(1) take cesium acetate 82.9g, zirconium nitrate 5.5g, cerous nitrate 5.0g adds 120mL deionized water dissolving, is made into the aqueous solution;
(2) take silica 1 70g, magnesia 28g, after mixing, add the solution of step (1) preparation to mediate, extruded moulding, dry 4h at 120 DEG C, roasting 4 hours at 400 DEG C, gets final product to obtain the catalyst of embodiment 1, is designated as MA-01.
Embodiment 2:
(1) take 56.1g cesium nitrate, boron oxide 4.0g, cerous nitrate 10.1g add 120mL deionized water dissolving, are made into the aqueous solution;
(2) take silica 1 70g, titanium oxide 24g, after mixing, add the solution of step (1) preparation to mediate, extruded moulding, dry 4h at 120 DEG C, roasting 4 hours at 450 DEG C, gets final product to obtain the catalyst of embodiment 2, is designated as MA-02.
Embodiment 3:
(1) take 44.5g cesium nitrate and add 180mL deionized water dissolving, be made into the aqueous solution;
(2) take silica 280g, alumina silicate 90g, magnesium silicate 70g, after mixing, add the solution of step (1) preparation to mediate, roller forming, dry 4h at 120 DEG C, roasting 3 hours, makes catalyst precarsor at 600 DEG C;
(3) taking boron oxide 1.0g, zirconium nitrate 2.75g and cerous nitrate 5.1g is dissolved in 80mL deionized water, wiring solution-forming, take again the catalyst precarsor that 100g prepares, immerse in above-mentioned solution, normal temperature dipping 6h, dry 4h at 100 DEG C, roasting 4h at 500 DEG C, get final product to obtain the catalyst of embodiment 3, be designated as MA-03.
Embodiment 4-6:
(1) take respectively cerous nitrate 2.53g, boron oxide 2.0g and zirconium nitrate 2.75g and be dissolved in 80mL deionized water, be made into 3 parts of solution;
(2) take respectively again the catalyst precarsor that 100g embodiment 3 prepares, immerse in above-mentioned every part of solution, normal temperature dipping 6h, dry 4h at 100 DEG C, roasting 4h at 500 DEG C, gets final product to obtain the catalyst of embodiment 4-6, is designated as MA-04, MA-05 and MA-06.
Embodiment 7:
The activity rating of catalyst carries out on fixed-bed micro-devices, and raw material dimethoxym ethane adds thermal decomposition and generates formaldehyde and methyl alcohol under acid condition, after mixing with the methyl acetate of gasification, by carrier gas N
2send into conversion zone bed.Dimethoxym ethane/methyl acetate mol ratio=1:4, charging air speed is 8h
-1, reaction temperature is 380 DEG C.Test result is in table 1:
Table 1 catalyst activity evaluation result
| Catalyst numbering | MA-01 | MA-02 | MA-03 | MA-04 | MA-05 | MA-06 |
| Methyl acetate conversion ratio % | 31% | 36% | 24% | 16% | 21% | 27% |
| The selective % of methyl acrylate | 87% | 82% | 73% | 59% | 62% | 69% |
Embodiment 8:
Change the mol ratio of dimethoxym ethane and methyl acetate, MA-01 to MA-06 catalyst is carried out to activity rating test.Test condition: dimethoxym ethane/methyl acetate mol ratio=1:2, charging air speed is 10h
-1, reaction temperature is 380 DEG C.Test result is in table 2:
Table 2 catalyst activity evaluation result
| Catalyst numbering | MA-01 | MA-02 | MA-03 | MA-04 | MA-05 | MA-06 |
| Methyl acetate conversion ratio % | 37% | 42% | 25% | 19% | 26% | 31% |
| The selective % of methyl acrylate | 91% | 83% | 77% | 60% | 65% | 72% |
Claims (5)
1. the catalyst of a methyl acetate and methylal synthesis methyl acrylate, it is characterized in that: formed by main active component, coagent and carrier, the oxide that wherein the main active component in catalyst is Cs, coagent is any one or a few in nitrate or the oxide of Zr, B, Ce, and carrier is one or more the mixture in magnesia, silica, titanium oxide, alumina silicate, magnesium silicate; In oxide, the quality percentage composition of described main active component is that 5%-30%, coagent quality percentage composition are 1%-5%, the quality percentage composition that all the other are carrier.
2. catalyst according to claim 1, is characterized in that: the oxide of described Cs is selected from cesium acetate.
3. a preparation method for the catalyst of methyl acetate as claimed in claim 1 and methylal synthesis methyl acrylate, is characterized in that comprising the following steps:
(1) take the salt of main active component and coagent, add deionized water dissolving, being mixed with Cs ion concentration is 0.05mol/L-1.0mol/L, the aqueous solution that auxiliary agent ion concentration is 0.001mol/L-0.1mol/L;
(2) carrier is immersed in the aqueous solution of step (1) preparation, under normal temperature, flood 4-8 hour to obtain mixture;
(3) by the mixture of step (2) gained by roller forming or extruded moulding, dry 2-4 hour at 80-150 DEG C, then at 400-600 DEG C roasting 4-6 hour, make described catalyst.
4. a preparation method for the catalyst of methyl acetate as claimed in claim 1 and methylal synthesis methyl acrylate, is characterized in that comprising the following steps:
(1) take the salt of main active component, add deionized water dissolving, be mixed with the aqueous solution that Cs ion concentration is 0.05mol/L-1.0mol/L;
(2) after carrier is fully mixed in proportion, add the solution of step (1) preparation to mediate, then by compressing tablet, spin or extruded moulding mode, dry 2-4 hour at 100-150 DEG C, roasting 3-5 hour at 300-500 DEG C, makes catalyst precarsor again;
(3) take the salt of coagent, add deionized water and dissolve, make the aqueous solution that ion concentration is 0.001mol/L-0.1mol/L;
(4) catalyst precarsor for preparing is immersed in salting liquid prepared by step (3), then normal temperature dipping 4～8 hours, dry 2-4 hour at 80-120 DEG C, then at 300-500 DEG C roasting 3-5 hour, make described catalyst.
5. according to the application of the catalyst described in any one claim in claim 1-2, it is characterized in that: described catalyst reacts with methylal synthesis methyl acrylate for methyl acetate, its reaction condition is: the mol ratio of dimethoxym ethane/methyl acetate is 1:4 or 1:2, and corresponding charging air speed is 8h
-1or 10h
-1, reaction temperature is 380 DEG C.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201210491886.5A CN102941113B (en) | 2012-11-28 | 2012-11-28 | Catalyst for synthesizing methyl acrylate by using methyl acetate and methylal and preparation method thereof |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201210491886.5A CN102941113B (en) | 2012-11-28 | 2012-11-28 | Catalyst for synthesizing methyl acrylate by using methyl acetate and methylal and preparation method thereof |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN102941113A CN102941113A (en) | 2013-02-27 |
| CN102941113B true CN102941113B (en) | 2014-12-10 |
Family
ID=47724156
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN201210491886.5A Active CN102941113B (en) | 2012-11-28 | 2012-11-28 | Catalyst for synthesizing methyl acrylate by using methyl acetate and methylal and preparation method thereof |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN102941113B (en) |
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN106831417A (en) * | 2016-12-29 | 2017-06-13 | 沈阳化工大学 | A kind of method for preparing methyl acrylate |
| WO2021204789A3 (en) * | 2020-04-07 | 2021-12-30 | Arkema France | Recycling of polyacetal for the production of polyoxymethylene dialkyl ethers |
Families Citing this family (8)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN103551148B (en) * | 2013-10-29 | 2015-08-05 | 西南化工研究设计院有限公司 | A kind of resistance to water Catalysts and its preparation method for aldol condensation and application |
| 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 |
| CN104525176B (en) * | 2014-12-16 | 2017-05-17 | 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 |
| CN104475138B (en) * | 2014-12-18 | 2017-02-22 | 西南化工研究设计院有限公司 | Vanadium-phosphorus-zirconium-titanium composite oxide catalyst for synthesising acrylic acid (ester) as well as preparation method and application of vanadium-phosphorus-zirconium-titanium composite oxide catalyst |
| CN104874383B (en) * | 2015-04-30 | 2017-07-11 | 大连理工大学 | It is a kind of to be used to catalyze and synthesize difunction catalyst of methyl acrylate and preparation method thereof |
| CN107175094B (en) * | 2016-03-09 | 2020-08-18 | 上海浦景化工技术股份有限公司 | Composite carrier catalyst for aldol condensation and preparation method and application thereof |
| CN113751011A (en) * | 2020-06-05 | 2021-12-07 | 北京旭阳科技有限公司 | Aldol condensation catalyst composition, method for preparing same, and method for preparing methyl methacrylate using same |
| CN112371100B (en) * | 2020-11-07 | 2023-02-17 | 江苏大学 | Metal Cs modified B 2 O 3 Catalyst, preparation method and application thereof |
Family Cites Families (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| GB9807498D0 (en) * | 1998-04-08 | 1998-06-10 | Ici Plc | Production of unsaturated acids therfore and catalysts therfor |
| JP4497457B2 (en) * | 2003-06-03 | 2010-07-07 | 三菱レイヨン株式会社 | Method for producing catalyst for production of methacrylic acid ester |
| CN101829558B (en) * | 2010-04-27 | 2012-02-22 | 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 |
| CN102350336B (en) * | 2011-07-27 | 2013-03-27 | 北京旭阳化工技术研究院有限公司 | Zr-Cs series methyl methacrylate catalyst added with modification auxiliary agent and preparation method thereof |
-
2012
- 2012-11-28 CN CN201210491886.5A patent/CN102941113B/en active Active
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN106831417A (en) * | 2016-12-29 | 2017-06-13 | 沈阳化工大学 | A kind of method for preparing methyl acrylate |
| WO2021204789A3 (en) * | 2020-04-07 | 2021-12-30 | Arkema France | Recycling of polyacetal for the production of polyoxymethylene dialkyl ethers |
Also Published As
| Publication number | Publication date |
|---|---|
| CN102941113A (en) | 2013-02-27 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN102941113B (en) | Catalyst for synthesizing methyl acrylate by using methyl acetate and methylal and preparation method thereof | |
| CN102617518B (en) | One-step preparation method for tetrahydrofuran by employing maleic anhydride gas phase hydrogenation | |
| CN102962062B (en) | Catalyst for synthesis of methyl methacrylate by formaldehyde and methyl propionate and preparation method of catalyst | |
| CN100457263C (en) | Catalyst for synthesizing low-carbon carboxylate | |
| CN102145287B (en) | Preparation method of catalyst for synthesizing methanol from hydrogenated carbon dioxide | |
| CN103506107B (en) | The catalyst of methyl acetate and formaldehyde methyl acrylate and preparation method and application | |
| CN103638956A (en) | Catalyst for synthesizing methyl acrylate by trioxymethylene or paraformaldehyde and acetic acid and acetic acid aqueous solution, its preparation and its application method | |
| CN104475109A (en) | Catalyst for preparing sec-butyl alcohol and preparation method of catalyst | |
| CN105251496A (en) | Catalyst and method preparing dimethyl carbonate by using catalyst | |
| CN106470963A (en) | The manufacture method of the manufacture method of isobutene., the manufacture method of methacrylic acid and methyl methacrylate | |
| CN102863335B (en) | Preparation method of diethyl succinate | |
| CN101898946B (en) | Method for hydrogenolysis catalysis of glycerin | |
| CN107175094B (en) | Composite carrier catalyst for aldol condensation and preparation method and application thereof | |
| CN103191758A (en) | Pt-Cu catalyst for acetylene hydrochlorination, and preparation method of same | |
| CN103666770A (en) | Preparation method of epoxy modified castor oil | |
| CN103880661B (en) | A kind of catalysis ethanol direct dehydrogenation is prepared the method for ethyl acetate | |
| CN106256845A (en) | A kind of preparation method of high-molecular aliphatic polycarbonate | |
| CN102442992A (en) | Method for synthesizing glycerol carbonate with biodiesel based crude glycerine and dimethyl carbonate | |
| CN102806085B (en) | Preparation method of catalyst for co-generating of isopropanol and diisobutyl ketone through acetone hydrogenation and application | |
| CN106944050A (en) | A kind of catalyst for synthesizing 1,3 propane diols and its preparation method and application | |
| CN109678709B (en) | Efficient preparation of methyl 3-hydroxypropionate | |
| CN102173977A (en) | Cu/Al2O3 catalyst and preparation method thereof as well as method for catalyzing hydrolysis of glycerol | |
| CN105642351A (en) | Heteropolyacid ammonium salt catalyst and preparation method thereof | |
| CN109369366B (en) | Method for preparing lactic acid by catalytic dehydrogenation of glycerol | |
| CN102993131A (en) | Method for utilizing o-chlorocyclohexanol to prepare cyclohexene oxide by cyclization |
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 |