CN103435483A - Synthesis method for methyl acrylate from methyl acetate and formaldehyde - Google Patents
Synthesis method for methyl acrylate from methyl acetate and formaldehyde Download PDFInfo
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- CN103435483A CN103435483A CN2013102807862A CN201310280786A CN103435483A CN 103435483 A CN103435483 A CN 103435483A CN 2013102807862 A CN2013102807862 A CN 2013102807862A CN 201310280786 A CN201310280786 A CN 201310280786A CN 103435483 A CN103435483 A CN 103435483A
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Abstract
The invention relates to a synthesis method for methyl acrylate from methyl acetate and formaldehyde. According to the method, a catalyst is regenerated in a catalyst regenerator, the problem of rapid inactivation of the catalyst is overcome through coupling of a fluidized bed reactor and the catalyst regenerator, and continuous production is realized.
Description
Technical field
The present invention relates to a kind of method that is prepared methyl acrylate by ritalin and formaldehyde, particularly, the present invention relates to adopt the method for the synthesizing methyl acrylate of fluidized-bed process continous-stable.
Background technology
Methyl acrylate, another name loses the resin acid methyl esters, is the intermediate of organic synthesis, is also the monomer of synthesising macromolecule copolymer, is widely used in rubber, medicine, leather, papermaking, tackiness agent etc.Its demand is also going up year by year.The synthetic method of vinylformic 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 vinylformic acid, and then the method that esterification generates corresponding ester has accounted for 95% left and right.
Because the raw materials such as China's methyl alcohol, acetic acid are seriously superfluous, cheap, the exploitation derived product seems particularly important, and produce the annual byproduct ritalin produced of acetic acid plant of 200,000 tons per year, can reach 20,000-30,000 tons.The synthetic methyl acrylate by coal-based route that to utilize ritalin, formaldehyde be development of raw materials becomes a kind of new high added value derived product of ritalin and even acetic acid.
In recent years, domestic and international many R&D institutions also take ritalin, formaldehyde and have synthesized methyl acrylate as raw material.Wherein Harbin Institute of Technology and Qiqihar University have delivered the process patent CN 101575290 about catalyst segments filling 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 lifting a sail etc. all reaches and reports in the application aspect ritalin and formaldehyde/methylal synthesis methyl acrylate in the catalyzer preparation.No matter, because aldol condensation is to adopt basic catalyst or an acidic catalyst, all exist catalyst deactivation fast, the life-span is short, needs the problem of repeated regeneration.So no matter be to adopt the sectional type loading catalyst or adopt fixed bed all can not solve the problem of catalyzer rapid deactivation.
Summary of the invention
Due to the prior art above shortcomings, the purpose of this invention is to provide a kind of method that is prepared methyl acrylate by ritalin and formaldehyde, the method is reacted ritalin and formaldehyde in fluidized-bed reactor, decaying catalyst is regenerated in revivifier, thereby realized the coupling of fluidized-bed reactor and catalyst regenerator, to guarantee the conversion of continuous, stable ritalin and formaldehyde, reach continuously, stably manufactured, the purpose that reduces production costs.
Technical scheme
According to an aspect of the present invention, it provides a kind of method that is prepared methyl acrylate by ritalin and formaldehyde, the method comprises the following steps: make ritalin and formaldehyde and/or not necessarily methyl alcohol and/or not necessarily fluidized gas in mixing preheater, mix and preheating after enter fluidized-bed reactor with gaseous state and reacted to obtain methyl acrylate
Wherein, by being controlled at the valve between fluidized-bed reactor and catalyst regenerator, make the catalyzer of decaying catalyst from fluidized-bed reactor shifts out or make regeneration enter fluidized-bed reactor, thereby make decaying catalyst enter catalyst regenerator, regenerated, and the catalyzer after regeneration enters fluidized-bed reactor and reuses.
In the present invention, the salt that described catalyzer is Cs, Zr, Mg or oxide compound or above-mentioned salt or hopcalite; Be preferably Cs-Zr salt or its oxide compound, Cs-Zr-Mg salt or its oxide compound; Described catalyzer is preferably used silicon dioxide carried.
The particle diameter of described support of the catalyst is at 30～300 microns, preferably 40～250 microns.
The method for preparing methyl acrylate provided by the invention further comprises following separation and/or circulation step:
Make reacted Product mix gas in fluidized-bed reactor enter the knockout tower separation, wherein, make unreacted ritalin, formaldehyde, methyl alcohol and/or fluidized gas return to the mixing preheater and circulated;
Thick product is separated from the knockout tower bottom, then enter treating tower and obtain the methyl acrylate product, the high boiling point materials such as heavy ester separate from bottom as by product.
In the present invention, the reaction conditions of described fluidized-bed reactor is: temperature is 250～450 ℃, and preferably temperature is 280～380 ℃; Pressure is normal pressure～1MPa; The mol ratio of ritalin and formaldehyde is 0.05～8, is preferably 0.5～4; The mol ratio of methyl alcohol and formaldehyde is 1:2～5:1, is preferably 1:1.5～3:1; Reaction velocity is 0.1～100h
-1, preferred 0.5～20.0h
-1.
In the present invention, preferably, described fluidized gas can be a kind of gas of being selected from nitrogen, argon gas and helium or the gas mixture of multiple gases.
In the present invention, carbon distribution content when decaying catalyst enters catalyst regenerator is 0.2～15wt%, is preferably 1～10wt%, more preferably 4～10wt%.
The catalyst regeneration condition of described catalyst regenerator is: temperature is 200～600 ℃, and the volume space velocity of regeneration gas is 10～1000h
-1, pressure is normal pressure～1MPa, the regenerative response time is 0.01～10h.
In the present invention, preferably, in described catalyst regenerator, regeneration gas can be and is selected from one or more in oxygen, air, nitrogen, hydrogen, methanol vapor, carbonic acid gas and water vapour.
The device for preparing methyl acrylate by ritalin and formaldehyde according to the present invention comprises: fluidized-bed reactor and catalyst regenerator, the catalyst outlet of fluidized-bed reactor is connected by pipeline with the catalyst inlet of catalyst regenerator, the catalyst inlet of fluidized-bed reactor is connected by pipeline with the catalyst outlet of catalyst regenerator, in the middle of pipeline, with valve, controls the residence time of catalyzer in each reactor.
Described fluidized-bed reactor comprises reaction raw materials and fluidized gas entrance; Gas distribution grid; Cylindrical shell; Interchanger; Expanding reach; The live catalyst entrance; Reacting product outlet; Cyclonic separator; The regenerated catalyst entrance; The decaying catalyst outlet; Decaying catalyst takes out control valve; Catalyzer takes out valve.
Described catalyst regenerator comprises the resurgent gases entrance; Gas distribution grid; Cylindrical shell; Heat collector; Expanding reach; Waste gas outlet; Cyclonic separator; The decaying catalyst entrance; The outlet of regeneration rear catalyst; The regenerated catalyst control valve.
The present invention adds a part of methyl alcohol in formaldehyde, can reduce on the one hand the generation of the by products such as formaldehyde autohemagglutination, can also suppress on the other hand the hydrolysis of methyl acrylate, ritalin, to prevent the selectivity that increases, reduces product of by product.
In sum, the beneficial effect that the present invention has is: this process using fluidized-bed reactor and revivifier, catalyzer is continuous flow realization response regenerative process between fluidized-bed and revivifier, greatly improved the utilising efficiency of catalyzer, realized the continuity of producing, effectively solved the short difficult problem of ritalin and formaldehyde reaction catalyst life, unreacted raw material enters mixing tank after separating simultaneously, enter again fluidized-bed reactor after preheating and reacted, reduce the loss of material that while adopting fixed bed, the raw material switching causes.This fluidized-bed process meets demand of industrial production, but the high reactivity of long term maintenance catalyzer, the service efficiency of raising catalyzer, the circulation of unreacting material has improved whole transformation efficiency, has increased economic benefit.
In the present invention, unless otherwise indicated outside, all per-cent all refers to weight percent.
The formaldehyde used in the present invention also can replace with anhydrous paraformaldehyde/paraformaldehyde or anhydrous formaldehyde, because the application's reaction has water to generate, therefore adopts paraformaldehyde/paraformaldehyde to promote reaction to move right, and improves productive rate.Paraformaldehyde/paraformaldehyde can depolymerization obtain formaldehyde under the application's reaction conditions.
The step of formaldehyde depolymerization is, is at first a certain proportion of paraformaldehyde, paraformaldehyde, anhydrous formaldehyde and methyl alcohol (ratio is at 1.5:1 to 1:5), and (60-120 ℃) stirring regular hour (1-3h) at a certain temperature can obtain.
The accompanying drawing explanation
Fig. 1 is the schematic diagram that is prepared the fluidizer of methyl acrylate by ritalin and formaldehyde of the present invention;
Fig. 2 is fluidized-bed reactor and the catalyst regenerator schematic diagram that is prepared methyl acrylate by ritalin and formaldehyde of the present invention;
Wherein, fluidized-bed reactor part: 1: reaction raw materials and fluidized gas entrance; 2: gas distribution grid; 3: cylindrical shell; 4: interchanger; 5: expanding reach; 6: the live catalyst entrance; 7: reacting product outlet; 8: cyclonic separator; 9: the regenerated catalyst entrance; 10: the decaying catalyst outlet; 11: decaying catalyst takes out control valve; 12: catalyzer takes out valve.
Catalyst regeneration part: 1 ': resurgent gases entrance; 2 ': gas distribution grid; 3 ': cylindrical shell; 4 ': heat collector; 5 ': expanding reach; 7 ': waste gas outlet; 8 ': cyclonic separator; 9 ': the decaying catalyst entrance; 10 ': the outlet of regeneration rear catalyst; 11 ': the regenerated catalyst control valve.
Embodiment
The medicine cesium nitrate used in following examples, magnesium nitrate, zirconium nitrate are all purchased in traditional Chinese medicines reagent, and silica supports is purchased in Nanjing unification company, then according to required carrier size, is sieved.Then adopt same volume dipping method dipping, after dipping, at 100-120 ℃ of dry 5h, after 350-450 ℃ of roasting 5h, be used catalyzer, methyl alcohol, formaldehyde is all from rising sun sun chemical industry company limited.
Embodiment
Embodiment mono-: catalyzer is silicon dioxide carried Cs-Zr salt or its oxide compound, and Cs content is that 10%, Zr content is 1%, and the particle diameter of silica supports is 150-250 microns.Mixing the preheater temperature is 300 ℃, and temperature of reaction is 330 ℃, and the mol ratio of acetic acid methyl esters ︰ first aldehyde ︰ methyl alcohol is 1 ︰ 1 ︰ 1.5, and fluidized gas is nitrogen, and its air speed is 5h
-1, pressure is 0.05MPa; The temperature of catalyst regenerator is 420 ℃, and the nitrogen that the oxygenous amount of take is 1% carries out coke-burning regeneration as resurgent gases, and its air speed is 30h
-1, pressure is 0.1MPa; The residence time of catalyzer in fluidized-bed reactor is 4 hours, and carbon distribution content when catalyzer enters revivifier is 4wt%, and the recovery time is 4 hours, and after regeneration, carbon content is 0.1%; The molar yield of ritalin is 14.5%, and mole selectivity of methyl acrylate is 92.8%.
Embodiment bis-: catalyzer is silicon dioxide carried Cs-Zr-Mg salt or its oxide compound, and Cs content is that 13%, Zr content is that 0.5%, Mg content is 0.5%, and the particle diameter of silica supports is 150-250 microns.Mixing the preheater temperature is 330 ℃, and temperature of reaction is 340 ℃, and the mol ratio of acetic acid methyl esters ︰ first aldehyde ︰ methyl alcohol is 1 ︰ 1 ︰ 1.5, and fluidized gas is nitrogen, and its air speed is 10h
-1, pressure is 0.05MPa; The temperature of catalyst regenerator is 450 ℃, and the nitrogen that the oxygenous amount of take is 1% carries out coke-burning regeneration as resurgent gases, and its air speed is 30h
-1, pressure is 0.1MPa; The residence time of catalyzer in fluidized-bed reactor is 10 hours, and carbon distribution content when catalyzer enters revivifier is 5wt%, and the recovery time is 4 hours, and after regeneration, carbon content is 0.1%; The molar yield of ritalin is 18%, and mole selectivity of methyl acrylate is 90.5%.
Embodiment tri-: catalyzer is silicon dioxide carried Cs-Zr salt or its oxide compound, and Cs content is that 15%, Zr content is 0.5%, and the particle diameter of silica supports is 75-150 microns.Mixing the preheater temperature is 260 ℃, and temperature of reaction is 360 ℃, and the mol ratio of acetic acid methyl esters ︰ first aldehyde ︰ methyl alcohol is 0.5 ︰ 1 ︰ 1.5, and fluidized gas is nitrogen, and its air speed is 6h
-1, pressure is 0.05MPa; The temperature of catalyst regenerator is 450 ℃, and the nitrogen that the oxygenous amount of take is 1% carries out coke-burning regeneration as resurgent gases, and its air speed is 30h
-1, pressure is 0.1MPa; The residence time of catalyzer in fluidized-bed reactor is 8 hours, and carbon distribution content when catalyzer enters revivifier is 4.8wt%, and the recovery time is 4 hours, and after regeneration, carbon content is 0.1%; The molar yield 28% of ritalin, mole selectivity of methyl acrylate is 93%.
Claims (10)
1. a method that is prepared methyl acrylate by ritalin and formaldehyde, the method comprises the following steps: make ritalin and formaldehyde and/or not necessarily methyl alcohol and/or not necessarily fluidized gas in mixing preheater, mix and preheating after enter fluidized-bed reactor with gaseous state and reacted to obtain methyl acrylate
Wherein, by being controlled at the valve between fluidized-bed reactor and catalyst regenerator, make the catalyzer of decaying catalyst from fluidized-bed reactor shifts out or make regeneration enter fluidized-bed reactor, thereby make decaying catalyst enter catalyst regenerator, regenerated, and the catalyzer after regeneration enters fluidized-bed reactor and reuses.
2. method according to claim 1, wherein, the salt that described catalyzer is Cs, Zr, Mg or oxide compound or above-mentioned salt or hopcalite.
3. method according to claim 1, wherein, described catalyzer be take silicon dioxide microsphere as carrier.
4. method according to claim 1, wherein, the particle diameter of described support of the catalyst is at 30～300 microns.
5. method according to claim 1, wherein, the particle diameter of described support of the catalyst is at preferably 40～250 microns.
6. method according to claim 1, the method further comprises following separation and/or circulation step:
Make reacted Product mix gas in fluidized-bed reactor enter the knockout tower separation, wherein, make unreacted ritalin, formaldehyde, methyl alcohol and/or fluidized gas return to described mixing preheater and circulated;
Thick product is separated from the knockout tower bottom, then enter treating tower and obtain the methyl acrylate product, the high boiling point materials such as heavy ester separate from bottom as by product.
7. method according to claim 1, wherein, the reaction conditions of described fluidized-bed reactor is: temperature is 250～450 ℃; Pressure is normal pressure～1MPa; The mol ratio of ritalin and formaldehyde is 0.05～8; The mol ratio of methyl alcohol and formaldehyde is 1:2～5:1; Reaction velocity is 0.1～100h
-1.
8. method according to claim 1, wherein, described fluidized gas is selected from a kind of gas in nitrogen, argon gas and helium or the gas mixture of multiple gases.
9. method according to claim 1, wherein, carbon distribution content when described decaying catalyst enters catalyst regenerator is 0.2～15wt%.
10. method according to claim 1, wherein, the catalyst regeneration condition of described catalyst regenerator is: temperature is 200～600 ℃, the volume space velocity of regeneration gas is 10～1000h
-1, pressure is normal pressure～1MPa, the regenerative response time is 0.01～10h; And
In described catalyst regenerator, regeneration gas can be and is selected from one or more in oxygen, air, nitrogen, hydrogen, methanol vapor, carbonic acid gas and water vapour.
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Cited By (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN104513163A (en) * | 2014-12-16 | 2015-04-15 | 北京旭阳化工技术研究院有限公司 | Method for producing methyl methacrylate by methyl acetate and formaldehyde |
| CN104926644A (en) * | 2015-04-28 | 2015-09-23 | 中国科学院过程工程研究所 | Fluidized bed method for directly preparing acrylic acid by using acetic acid and methyl aldehyde as raw materials |
| 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 |
| CN109232247A (en) * | 2018-11-12 | 2019-01-18 | 西南化工研究设计院有限公司 | A kind of method of methyl acetate and formaldehyde aldol condensation methyl methacrylate |
| CN111333508A (en) * | 2020-04-17 | 2020-06-26 | 湖北三里枫香科技有限公司 | Production process of acrylic ester |
| CN112705274A (en) * | 2019-10-24 | 2021-04-27 | 中国石油化工股份有限公司 | Catalyst regeneration and formaldehyde recovery method |
| CN114478254A (en) * | 2020-10-23 | 2022-05-13 | 中国石油化工股份有限公司 | Composite catalyst bed layer, method for preparing methyl acrylate and application |
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| CN102126949A (en) * | 2011-01-26 | 2011-07-20 | 齐齐哈尔大学 | Method for synthesizing methyl acrylate |
| CN102775302A (en) * | 2012-08-03 | 2012-11-14 | 北京旭阳化工技术研究院有限公司 | Method for preparing methyl methacrylate from methyl propionate and formaldehyde |
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2013
- 2013-07-05 CN CN2013102807862A patent/CN103435483A/en active Pending
Patent Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
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| CN102126949A (en) * | 2011-01-26 | 2011-07-20 | 齐齐哈尔大学 | Method for synthesizing methyl acrylate |
| CN102775302A (en) * | 2012-08-03 | 2012-11-14 | 北京旭阳化工技术研究院有限公司 | Method for preparing methyl methacrylate from methyl propionate and formaldehyde |
Cited By (9)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN104513163A (en) * | 2014-12-16 | 2015-04-15 | 北京旭阳化工技术研究院有限公司 | Method for producing methyl methacrylate by methyl acetate and formaldehyde |
| CN104926644A (en) * | 2015-04-28 | 2015-09-23 | 中国科学院过程工程研究所 | Fluidized bed method for directly preparing acrylic acid by using acetic acid and methyl aldehyde as raw materials |
| 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 |
| CN109232247A (en) * | 2018-11-12 | 2019-01-18 | 西南化工研究设计院有限公司 | A kind of method of methyl acetate and formaldehyde aldol condensation methyl methacrylate |
| CN109232247B (en) * | 2018-11-12 | 2020-06-30 | 西南化工研究设计院有限公司 | Method for preparing methyl methacrylate by aldol condensation of methyl acetate and formaldehyde |
| CN112705274A (en) * | 2019-10-24 | 2021-04-27 | 中国石油化工股份有限公司 | Catalyst regeneration and formaldehyde recovery method |
| CN111333508A (en) * | 2020-04-17 | 2020-06-26 | 湖北三里枫香科技有限公司 | Production process of acrylic ester |
| CN114478254A (en) * | 2020-10-23 | 2022-05-13 | 中国石油化工股份有限公司 | Composite catalyst bed layer, method for preparing methyl acrylate and application |
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Application publication date: 20131211 |