CN101829558B - Catalyst for directly preparing methyl methacrylate by reacting methyl propionate with formaldehyde and preparation method thereof - Google Patents
Catalyst for directly preparing methyl methacrylate by reacting methyl propionate with formaldehyde and preparation method thereof Download PDFInfo
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- CN101829558B CN101829558B CN2010101567849A CN201010156784A CN101829558B CN 101829558 B CN101829558 B CN 101829558B CN 2010101567849 A CN2010101567849 A CN 2010101567849A CN 201010156784 A CN201010156784 A CN 201010156784A CN 101829558 B CN101829558 B CN 101829558B
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Abstract
The invention aims to provide a catalyst for directly preparing methyl methacrylate by reacting methyl propionate with formaldehyde and a preparation method thereof. The catalyst is characterized in that the mass ratio of load metal of the catalyst to a carrier is Cs to Zr to Ce to SiO2 being (1-10):(0.005-0.5):(0.001-0.1):100; in the preparation process by an immersion method, a water-soluble nonionic surfactant is added to be used as a dispersing accelerator of an active component on the carrier surface; and the dispersion degree of the active component Cs on the carrier surface can be improved by changing the concentration or the kinds of the dispersing accelerator so as to improve the catalytic performance of the catalyst.
Description
Technical field:
The invention belongs to catalysis technical field, be specifically related to a kind of Catalysts and its preparation method of directly producing methyl methacrylate by methyl propionate and formolite reaction.
Background technology:
Methyl methacrylate (MMA) is a kind of important Organic Chemicals; Be the monomer of producing polymethyl methacrylate (lucite) and acrylic materials, also be widely used in different field such as coating, weaving, papermaking, leather, adhesive and medical functional high molecule material.
In the presence of metallic catalyst; The existing multinomial patent of reaction that methyl propionate and formolite reaction generate methyl methacrylate relates to; Disclosed like Lucite and Ineos Acrylics UK Ltd is main active component with Cs, adds the SiO of auxiliary agents such as B, Mg, Al, Zr, Ha, Ti, Fe
2Supported catalyst is seen US6476255, US6544924, US7053147, EP1243330A1, patents such as CN99805643.Mamoru Ai has studied Different Alkali metal (Na, K, Rb, Cs) and alkaline-earth metal (Mg, Ca, Ba) is carried on dissimilar carrier (SiO
2, SiO
2-Al
2O
3, Zeolite 13X, SiC, Active carbon, Ca (OH)
2) go up the catalytic performance of gained catalyst, investigated different catalyst and formed methyl propionate and formolite reaction are generated the influence that methyl methacrylate reacts.The result shows, with SiO
2During for carrier loaded active component, the catalytic effect of catalyst is best.
More than the catalyst of report all mainly adopts immersion process for preparing.As a kind of method for preparing catalyst that extensively adopts in the industry; Infusion process is that active component (containing co-catalyst) is penetrated into the porous carrier inner surface through the salting liquid form, fully behind the dipping, removes remaining liq; Carry out treatment process such as drying, roasting again, obtain loaded catalyst.The advantage of immersion process for preparing catalyst is that active component only is distributed on the carrier surface, and consumption is few, and utilization rate is high, and cost is low.For the Cs loaded catalyst of directly producing methyl methacrylate by methyl propionate and formolite reaction; Basic center is the main activated centre of catalyst; Basic center evenly distributes just can show best catalytic performance; This just requires in dipping preparation process, and active component reaches uniform deposition at carrier surface, and then obtains the loaded catalyst of high degree of dispersion.
Summary of the invention
The purpose of this invention is to provide a kind of Catalysts and its preparation method of directly producing methyl methacrylate by methyl propionate and formolite reaction.It is characterized in that the carried metal of catalyst and the mass ratio of carrier are: Cs: Zr: Ce: SiO
2=1～10: 0.005～0.5: 0.001～0.1: 100; In the immersion process for preparing process, add a certain amount of water-soluble nonionic type surfactant as the dispersion promoter of active component at carrier surface; Disperse the concentration or the kind of promoter to improve the decentralization of active component Cs through changing, thereby improve the catalytic performance of catalyst at carrier surface.
Method for preparing catalyst of the present invention specifically comprises the steps:
(1) takes by weighing zirconium nitrate and cerous nitrate by mass ratio Zr: Ce=0.005～0.5: 0.001～0.1, the aqueous solution that to be mixed with zirconium, the total ion molar concentration of cerium be 0.001mol/L～0.1mol/L;
(2) under continuous stirring and 30～80 ℃, press mass ratio Zr: SiO
2=0.005～0.5: 100 take by weighing SiO
2, mix with (1) prepared solution, behind dipping 5～24h, 100～150 ℃ of dryings, not roasting or in 400～500 ℃ of roasting 1～6h;
(3) press mass ratio Cs: SiO
2Take by weighing cesium carbonate or cesium nitrate at=1～10: 100, is mixed with the aqueous solution that the cesium ion molar concentration is 0.05mol/L～5mol/L;
(4) according to 0.02%～2% of liquid quality fraction, in (3) prepared solution, add and disperse promoter, stir, fully mix;
(5) down (4) prepared solution is mixed with (2) prepared solid continuous stirring and 30～80 ℃, flood 5～24h after, 100～150 ℃ of dryings in 400～500 ℃ of roasting 2～6h, promptly get catalyst.
The dispersion promoter that the present invention selected for use is one or more among water miscible nonionic surface active agent Tween, OP, PEG200, PEG400, the PEG600.
Use the prepared catalyst of the present invention can the catalysis methyl propionate and formolite reaction directly produce methyl methacrylate, reaction equation is following:
CH
3CH
2COOCH
3+HCHO→CH
2＝C(CH
3)COOCH
3+H
2O
Reaction generally under the intensification condition, is carried out in 250-400 ℃ scope usually.In order to make reaction generate more ester, reaction is carried out under the condition like the methyl alcohol existence generally in related alcohols.
The present invention compared with prior art has the following advantages: catalyst has added nonionic surface active agent as disperseing promoter in the process of dipping preparation; Disperse the adding of promoter that the dipping process of reactive metal Cs on carrier played certain guiding function; Can optimize the dispersiveness of active component on carrier, and then improve the catalytic performance of catalyst.
The specific embodiment
The present invention is through following examples explanation, but the present invention is not limited to subordinate embodiment, and under the scope of said aim, alternate embodiment is included in the technical scope of the present invention before and after not breaking away from.
Embodiment 1
(1) with the Zr (NO of 0.015g
3)
45H
2Ce (the NO of O and 0.004g
3)
36H
2O is dissolved in the 20.0ml deionized water;
(2) take by weighing 20.0g SiO
2Carrier is under continuous stirring and 40 ℃, with solution and SiO in (1)
2Carrier mixes, behind the dipping 8h, and 110 ℃ of dry 2h, 450 ℃ of roasting 3h get Zr-Ce/SiO
2
(3) take by weighing 0.982g Cs
2CO
3Be dissolved in the 20ml deionized water; Take by weighing the PEG200 of 0.051g, join in the above-mentioned cesium carbonate aqueous solution, stir, fully mix;
(4) under continuous stirring and 40 ℃, with gained Zr-Ce/SiO in the mixed solution that obtains in (3) and (2)
2Mix, behind the dipping 8h, 110 ℃ of dry 2h, 450 ℃ of roasting 3h get Cs-Zr-Ce/SiO
2Catalyst.
Embodiment 2
Catalyst is formed according to embodiment 1, and in step (3), the quality of PEG200 is respectively 0.102g.
Embodiment 3
Preparation of Catalyst is according to embodiment 1, in step (3) with 1.175g CsNO
3Replaced C s
2CO
3
Embodiment 4
Preparation of Catalyst is according to embodiment 2, in step (3) with 1.175g CsNO
3Replaced C s
2CO
3
The catalytic performance test of catalyst is carried out on fixed-bed micro-devices, and formaldehyde uses formalin, inlet amount mol ratio methyl propionate: formaldehyde: methyl alcohol=1: 0.2: 1.3, and with flow 35ml/min N
2Be diluent gas, with catalyst at 300 ℃ down behind the dry 30min, with the mixture and the N of reactant
2Pass through catalyst.After charging is stable, temperature of reactor is elevated to 350 ℃, through GC on-line analysis catalyst activity and selectivity.
Table 1 evaluating catalyst result
Claims (1)
1. directly produce methyl methacrylate Preparation of catalysts method by methyl propionate and formolite reaction for one kind, it is characterized in that the carried metal of catalyst and the mass ratio of carrier are: Cs: Zr: Ce: SiO
2=1～10: 0.005～0.5: 0.001～0.1: 100; Said methyl methacrylate Preparation of catalysts method comprises the steps:
(1) takes by weighing zirconium nitrate and cerous nitrate by mass ratio Zr: Ce=0.005～0.5: 0.001～0.1, the aqueous solution that to be mixed with zirconium, the total ion molar concentration of cerium be 0.001mol/L～0.1mol/L;
(2) under continuous stirring and 30～80 ℃, press mass ratio Zr: SiO
2=0.005～0.5: 100 take by weighing SiO
2, mix with (1) prepared solution, behind dipping 5～24h, 100～150 ℃ of dryings, not roasting or in 400～500 ℃ of roasting 1～6h;
(3) press mass ratio Cs: SiO
2Take by weighing cesium carbonate or cesium nitrate at=1～10: 100, is mixed with the aqueous solution that the cesium ion molar concentration is 0.05mol/L～5mol/L;
(4) according to 0.02%～2% of liquid quality fraction; In (3) prepared solution among the water miscible nonionic surface active agent Tween of adding, OP, PEG200, PEG400, the PEG600 one or more are as disperseing promoter; Stir, fully mix;
(5) down (4) prepared solution is mixed with (2) prepared solid continuous stirring and 30～80 ℃, flood 5～24h after, 100～150 ℃ of dryings in 400～500 ℃ of roasting 2～6h, promptly get catalyst.
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| Application Number | Priority Date | Filing Date | Title |
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| CN2010101567849A CN101829558B (en) | 2010-04-27 | 2010-04-27 | Catalyst for directly preparing methyl methacrylate by reacting methyl propionate with formaldehyde and preparation method thereof |
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| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN2010101567849A CN101829558B (en) | 2010-04-27 | 2010-04-27 | Catalyst for directly preparing methyl methacrylate by reacting methyl propionate with formaldehyde and preparation method thereof |
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|---|---|
| CN101829558A CN101829558A (en) | 2010-09-15 |
| CN101829558B true CN101829558B (en) | 2012-02-22 |
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Cited By (1)
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| CN102941113A (en) * | 2012-11-28 | 2013-02-27 | 西南化工研究设计院有限公司 | Catalyst for synthesizing methyl acrylate by using methyl acetate and methylal and preparation method thereof |
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| 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 |
| CN102962062B (en) * | 2012-12-11 | 2014-09-17 | 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 |
| CN103638956A (en) * | 2013-11-14 | 2014-03-19 | 中国科学院过程工程研究所 | Catalyst for synthesizing methyl acrylate by trioxymethylene or paraformaldehyde and acetic acid and acetic acid aqueous solution, its preparation and its application method |
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| CN105195186A (en) * | 2015-10-09 | 2015-12-30 | 中国科学院过程工程研究所 | Preparation method of wear-resistant microsphere catalyst for acrylic acid (ester) fluidized bed |
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| CN109225192A (en) * | 2018-08-15 | 2019-01-18 | 中国科学院兰州化学物理研究所 | A kind of load type metal catalyst of polymer modification and its preparation method and application |
| CN109364908B (en) * | 2018-11-12 | 2020-05-19 | 西南化工研究设计院有限公司 | Preparation of catalyst for preparing methyl methacrylate by aldol condensation, catalyst and application |
| CN110975929A (en) * | 2019-12-06 | 2020-04-10 | 中国科学院大连化学物理研究所 | Preparation method and application of catalyst for synthesizing methyl methacrylate |
| 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 |
| CN113509921B (en) * | 2021-07-16 | 2023-03-17 | 中国科学院兰州化学物理研究所 | Bifunctional catalyst system and application thereof |
| CN115814779B (en) * | 2021-10-31 | 2024-02-09 | 浙江新和成股份有限公司 | Porous catalyst, preparation method and application thereof |
| CN117205909A (en) * | 2023-09-05 | 2023-12-12 | 中国科学院过程工程研究所 | Preparation method and application of polymer modified aldol condensation catalyst |
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| US6476255B1 (en) * | 1997-10-29 | 2002-11-05 | Lucite International Uk Limited | Production of esters |
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| CN102941113A (en) * | 2012-11-28 | 2013-02-27 | 西南化工研究设计院有限公司 | Catalyst for synthesizing methyl acrylate by using methyl acetate and methylal and preparation method thereof |
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| CN101829558A (en) | 2010-09-15 |
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