CN103588636A - Method for preparing acrylic acid through hydrolyzation of methyl acrylate under catalysis of acidic resin - Google Patents
Method for preparing acrylic acid through hydrolyzation of methyl acrylate under catalysis of acidic resin Download PDFInfo
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Abstract
The invention discloses a method for hydrolyzing new-system methyl acrylate under catalysis of acidic resin. According to the method, SO3H-type strongly-acidic macroporous cation exchange resin is used as a catalyst, and the methyl acrylate and water are hydrolyzed under low-temperature and normal-pressures conditions to generate acrylic acid. In the course, the catalyst has the advantages of good mechanical strength, high exchange capacity, high exchange speed, mild reaction condition, freedom from corrosion of equipment, waste acid emission and pollution, environment-friendly property and the like; the catalyst can be used repeatedly after being activated, so that the production cost of the catalyst is reduced; and the catalyst is separated from products easily in catalytic reactions.
Description
Technical field:
The invention belongs to ester-type hydrolysis technical field, specifically refer to a kind of with SO
3h-type strongly acidic macroporous cation exchange resin is that the hydrolysis of catalyst methyl acrylate generates acrylic acid.
Background technology:
Vinylformic acid is important organic synthesis raw material and synthetic resins monomer, is the very fast vinyl monomer of polymerization velocity.Its great majority are in order to manufacture the esters of acrylic acids such as methyl acrylate, ethyl ester, butyl ester, hydroxyl ethyl ester.Vinylformic acid and acrylate can homopolymerization and copolymerization, also can with the monomer copolymerizations such as vinyl cyanide, vinylbenzene, divinyl, vinylchlorid and cis-butenedioic anhydride.Its polymkeric substance is for the synthesis of industrial sectors such as resin, sizing agent, synthetic rubber, synthon, super absorbent resin, pharmacy, leather, weaving, chemical fibre, building materials, water treatment, oil production, coating, as: for warp sizing material, sizing agent, water viscosifying agent, enamelled paper finishing agent and polyacrylate etc.
Current, the acrylic acid production of Chinese large-sized mainly adopts oxidation of propylene to make.Oxidation of propylene, propylene mixes by certain mol proportion with air and water vapour, under molybdenum bismuth series composite catalyst exists, oxidation makes propenal, then propenal is mixed by certain mol proportion with air and water vapour, under molybdenum-vanadium-tungsten series composite catalyst exists, oxidation makes vinylformic acid, this method technical maturity, but belong to petroleum path, raw materials cost is higher, and intermediate propenal is poisonous, by product is more, selectivity low (approximately 80%), yield not high (83～86%).In addition, China also adopted improvement Lei Peifa and acrylonitrile hydrolysis method to produce vinylformic acid in early days.The Lei Peifa of improvement, is solvent with tetrahydrofuran (THF), and the required acetylene of reaction is first dissolved in tetrahydrofuran (THF), under the catalyzer of nickelous bromide and cupric bromide composition exists, react with carbon monoxide and water, make vinylformic acid, temperature of reaction is 200-225 ℃, and reaction pressure is 8.11-10.13MPa; This method feature is: with tetrahydrofuran (THF), be solvent, can reduce the danger of autoclaving acetylene; Simultaneously catalyzer need not former Lei Peifa nickle carbonoxide used, only need nickel salt; Lei Peifayin it need compressive reaction to produce vinylformic acid all the time, and by vinylformic acid oxidation style, replaced gradually.Acrylonitrile hydrolysis method, vinyl cyanide first generates the vitriol of acrylamide with sulphuric acid hydrolysis, then hydrolysis generates vinylformic acid, by-product monoammonium sulfate; Though this method technique is simple, reaction temperature and, use a large amount of sulfuric acid, seriously polluted, the ammonium sulfate of a large amount of low values of by-product; Aggregate analysis be it seems, industrial employing oxidation of propylene is produced vinylformic acid, but tight slightly propylene supply and the propylene price raising up are affecting acrylic acid production, therefore, develop the new coal-based vinylformic acid production technology of low raw materials cost, will produce tremendous influence to the development of China's vinylformic acid industry.
The hydrolysis of ester class is a kind of important chemical reaction, is extensively being applied to the every field of petrochemical iy produced, and wherein the hydrolysis of ritalin, NSC 11801 and propylene carbonate etc. has very important fundamental position especially.Process engineering institute of Beijing Chinese Academy of Sciences has proposed the new coal-based route of method of acetic acid acrylic acid synthesizing, uses methyl alcohol, acetic acid and aldehydes for raw material synthesizing methyl acrylate, and methyl acrylate is hydrolysis generation vinylformic acid under the effect of catalyzer again.The method raw material is easy to get, and cost is low, and technique is simple, is a kind of good method of development prospect.Wish to get vinylformic acid, the selection of hydrolysis reaction catalyzer is a most important step in this technique, so catalyst technology is that methyl acrylate is produced acrylic acid core.
At present, about the acrylic acid research report of methyl acrylate hydrolysis seldom, one piece that only has nineteen forty-four JACS to include is the article of catalyst hydrolysis with sulfuric acid, is specially: methyl acrylate is at H
2sO
4/ hydroquinone/HCO
2in H catalyst system, at 85-90 ℃, distill the generation vinylformic acid of 9-13h.Advantage widespread uses in ester-type hydrolysis such as the vitriol oil relies on its acid strong, excellent catalytic effect, stable in properties, water-absorbent is strong and cheap, very important all the time but it obtains more by product to the corrodibility of equipment and catalysis.
Based on above reason, it is more imperative than the substitute catalyzer of vitriol oil environmental protection in realizing industrialization, to find.Search finds, patent CN101234948A and CN102746138A propose to take the method for hydrolysis that ionic liquid carries out as catalyzer.The selectivity of ionic liquid is high, but its viscosity is larger, is difficult for and product separation.
Storng-acid cation exchange resin is that a kind of reaction conditions is gentle, side reaction is few, productive rate is high, can be continuously produced and segregative new catalytic material renewable with catalyzer.In field of catalytic reactions, be with a wide range of applications, the hydrolysis of methyl acetate hydrolysis, NSC 11801, Propylene Carbonate Water solution show that storng-acid cation exchange resin has that selectivity is good, operational condition is gentle and catalyzer such as can reuse at the advantage.
Therefore, the application based on storng-acid cation exchange resin in catalytic hydrolysis reaction, the present invention proposes a kind of with strongly-acid SO
3acrylic acid is prepared in the hydrolysis of H-type macropore cation resin catalyzing propone acid methyl esters, it is advantageous that physical strength is good, exchange capacity is high, exchange velocity is fast, and reaction conditions is gentle, corrosion-free to equipment, without spent acid, discharge, pollution-free, environmental friendliness, the advantage such as can reuse, there is industrialized application prospect.
Summary of the invention:
The object of the invention is under gentle condition, adopting macropore strong acid ion exchange resin is that catalyzer carries out the method for catalytic hydrolysis to methyl acrylate system.
It is the catalyzer of methyl acrylate hydrolysis that this synthetic method adopts strong-acid ion exchange resin, can make the hydrolysis of methyl acrylate carry out under normal pressure and lesser temps, and obtains higher methyl acrylate transformation efficiency and the selectivity of respective acids.
Reaction expression of the present invention is:
The present invention relates to catalyze and synthesize acrylic acid, it is characterized in that, in the catalytic hydrolysis reaction process of methyl acrylate, use acidic resins are catalyzer.This catalyzer can be hydrolyzed by catalyzing propone acid methyl esters, and Heat stability is good, physical strength is high, and has good selectivity, if use flow reactor catalytic hydrolysis reaction to reuse and to keep greater activity, there is very strong prospects for commercial application.
The catalyzer that catalyzed reaction of the present invention is used has dry and dry dividing, the 1-10% that undried catalyst levels is reaction solution, and the 1-9% that dry catalyst levels is reaction solution, dried preferred scope is between 2.5-8.5%.
The present invention, after reaction completes, through the simple further transformation efficiency of augmenting response of methanol gas means of getting rid of, constantly can obtain corresponding product except methyl alcohol and after utilizing separation to remove unreacted water, just can make existing catalyzer recycle.
Easily polymerization of methyl acrylate itself in the present invention, one or more of thiodiphenylamine, phenols, arylamine class, ethers, quinones of take prevent vinylformic acid or methyl acrylate polymerization as stopper joins hydrolysis reaction system, and the add-on of stopper is 100mg-500mg/kg.
Acidic resins used herein are SO
3h-type large hole strong acid styrene system cation exchange resin, can generate acrylic acid system by catalytic hydrolysis methyl acrylate with this catalyzer.
Synthetic reaction condition of the present invention is as follows:
(1) acidifying catalyzer: successively remove floating matter with distilled water and methanol rinse catalyzer, with salt acid soak 3h, finally use distilled water rinsing to neutral again, the baking oven that is placed in 80 degree is dried, stand-by.
(2) weigh respectively methyl acrylate, water, stopper and catalyzer, water is with the molar content of ester than being 1:11-1:1, and the add-on of stopper is 100mg-500mg/kg.In the batch reactor of design temperature, add deionized water, catalyzer and stopper preheating, while synthermal preheating methyl acrylate in another container, when both temperature all reach temperature of reaction, methyl acrylate is added in batch reactor, start clock reaction.With stirring velocity and particle diameter, control the impact of eliminating external diffusion and internal diffusion, undried catalyst levels is the 1-10% of reaction solution, dry catalyst levels is the 1-9% of reaction solution, under the temperature of reaction condition of 50～75 ℃, measures at any time transformation efficiency and records starting time.
(2) for the quantivative approach of this experiment, use the gas-chromatography of PEG20W capillary column, this chromatographic column does not detect water peak, thereby used water is done thinner dilute sample, with acetone, as interior mark, demarcate the amount of methyl alcohol and methyl acrylate, with acetic acid, as the second internal standard substance, demarcate acrylic acid amount.
Positively effect of the present invention is: the present invention finds a kind of macropore strong acid cation exchange resin catalyst that is applicable to methyl acrylate hydrolyzation system, under the mild conditions of lower temperature normal pressure, efficient highly selective catalysis obtains vinylformic acid, is conducive to industrialized application.
Accompanying drawing explanation:
figure1,1. the experimental installation of the present invention's reaction, specifically comprise-there-necked flask (250ml); 2.-prolong; 3.-thermometer; 4.-power agitator; 5.-reaction solution
Embodiment:
The present invention illustrates by following examples, but the present invention is not limited to following embodiment, and before and after not departing from, under the scope of described aim, change is included in technical scope of the present invention.
Assembling and fixed reactor, the acidic resins D001 catalyzer then 13g not being dried and the methyl acrylate of 86g and 0.025g thiodiphenylamine join in the there-necked flask reactor of 250mL, start slowly to stir.There-necked flask is to be placed in the oil bath preheating that is heated to gradually 75 ℃, condensing reflux.Oil bath temperature and solution reach temperature of reaction stable after, then add the 54g water that is preheated in advance same temperature of reaction, tune up stirring velocity, start reaction.In reaction, timing sampling, records reflecting time, adds internal standard substance and thinner in sample, carries out chromatography of gases analysis, when the content of each component is constant in reaction system, shows that chemical reaction reaches balance.After experimental data, show, this catalyst property is good, and percent hydrolysis is 49.8%, and selectivity is more than 95%, and reacting balance time is 30h left and right.
Assembling and fixed reactor, in the there-necked flask reactor that the acidic resins NKC-9 catalyzer then 10g not being dried, the methyl acrylate of 86g and 0.025g Resorcinol join 250mL, start slowly to stir.There-necked flask is to be placed in the oil bath preheating that is heated to gradually 75 ℃, condensing reflux.Oil bath temperature and solution reach temperature of reaction stable after, then add the 54g water that is preheated in advance same temperature of reaction, tune up stirring velocity, start reaction.In reaction, timing sampling, records reflecting time, adds internal standard substance and thinner in sample, carries out chromatography of gases analysis, when the content of each component is constant in reaction system, shows that chemical reaction reaches balance.After experimental data, show, this catalyst property is good, and percent hydrolysis is 49.8%, and selectivity is more than 95%, and reacting balance time is 40h left and right.
Embodiment 3
Assembling and fixed reactor, in the there-necked flask reactor that the acidic resins D072 catalyzer then 7g not being dried, the methyl acrylate of 86g and 0.03g Resorcinol join 250mL, start slowly to stir.There-necked flask is to be placed in the oil bath preheating that is heated to gradually 75 ℃, condensing reflux.Oil bath temperature and solution reach temperature of reaction stable after, then add the 54g water that is preheated in advance same temperature of reaction, tune up stirring velocity, start reaction.In reaction, timing sampling, records reflecting time, adds internal standard substance and thinner in sample, carries out chromatography of gases analysis, when the content of each component is constant in reaction system, shows that chemical reaction reaches balance.After experimental data, show, this catalyst property is good, and percent hydrolysis is 49.8%, and selectivity is more than 95%, and reacting balance time is 50h left and right.
Assembling and fixed reactor, acidic resins D072 catalyzer, 48.8636g methyl acrylate and the 0.035g Resorcinol then 9.2857g not being dried joins in the there-necked flask reactor of 250mL, starts slowly to stir.There-necked flask is to be placed in the oil bath preheating that is heated to gradually 75 ℃, condensing reflux.Oil bath temperature and solution reach temperature of reaction stable after, then add the 51.1364g water that is preheated in advance same temperature of reaction, tune up stirring velocity, start reaction.In reaction, timing sampling, records reflecting time, adds internal standard substance and thinner in sample, carries out chromatography of gases analysis, when the content of each component is constant in reaction system, shows that chemical reaction reaches balance.After experimental data, show, this catalyst property is good, and percent hydrolysis is 54.68%, and selectivity is more than 95%, and reacting balance time is 35h left and right.
Assembling and fixed reactor, the acidic resins DIAION then 9.2857g not being dried
tMcatalyzer and 48.8636g methyl acrylate and 0.025g Resorcinol join in the there-necked flask reactor of 250mL, start slowly to stir.There-necked flask is to be placed in the oil bath preheating that is heated to gradually 65 ℃, condensing reflux.Oil bath temperature and solution reach temperature of reaction stable after, then add the 51.1364g water that is preheated in advance same temperature of reaction, tune up stirring velocity, start reaction.In reaction, timing sampling, records reflecting time, adds internal standard substance and thinner in sample, carries out chromatography of gases analysis, when the content of each component is constant in reaction system, shows that chemical reaction reaches balance.After experimental data, show, this catalyst property is good, and percent hydrolysis is 49.98%, and selectivity is more than 95%, and reacting balance time is 45h left and right.
Embodiment 6
Assembling and fixed reactor, acidic resins 732 catalyzer that then 9.2857g were not dried and 48.8636g methyl acrylate and 0.03g Resorcinol join in the there-necked flask reactor of 250mL, start slowly to stir.There-necked flask is to be placed in the oil bath preheating that is heated to gradually 55 ℃, condensing reflux.Oil bath temperature and solution reach temperature of reaction stable after, then add the 51.1364g water that is preheated in advance same temperature of reaction, tune up stirring velocity, start reaction.In reaction, timing sampling, records reflecting time, adds internal standard substance and thinner in sample, carries out chromatography of gases analysis, when the content of each component is constant in reaction system, shows that chemical reaction reaches balance.After experimental data, show, when temperature of reaction is 55 ℃, the reaction times, while being 60h, reaction did not also reach balance.
Embodiment 7
Assembling and fixed reactor, the acidic resins D001MB catalyzer then 9.2857g not being dried and 82.7g methyl acrylate and 0.025g Resorcinol join in the there-necked flask reactor of 250mL, start slowly to stir.There-necked flask is to be placed in the oil bath preheating that is heated to gradually 65 ℃, condensing reflux.Oil bath temperature and solution reach temperature of reaction stable after, then add the 17.3g water that is preheated in advance same temperature of reaction, tune up stirring velocity, start reaction.In reaction, timing sampling, records reflecting time, adds internal standard substance and thinner in sample, carries out chromatography of gases analysis, when the content of each component is constant in reaction system, shows that chemical reaction reaches balance.After experimental data, show, percent hydrolysis is 30.01%, and selectivity is more than 95%, and reacting balance time is 48h left and right.
Embodiment 8
Assembling and fixed reactor, the acidic resins 001*7 catalyzer then 9.2857g not being dried and 61.43g methyl acrylate and 0.015g Resorcinol join in the there-necked flask reactor of 250mL, start slowly to stir.There-necked flask is to be placed in the oil bath preheating that is heated to gradually 55 ℃, condensing reflux.Oil bath temperature and solution reach temperature of reaction stable after, then add the 38.57g water that is preheated in advance same temperature of reaction, tune up stirring velocity, start reaction.In reaction, timing sampling, records reflecting time, adds internal standard substance and thinner in sample, carries out chromatography of gases analysis, when the content of each component is constant in reaction system, shows that chemical reaction reaches balance.After experimental data, show, after experimental data, show, percent hydrolysis is 36.5%, and selectivity is more than 95%, and reacting balance time is 50h left and right.
Embodiment 9
Assembling and fixed reactor, in the there-necked flask reactor that the acidic resins D072 catalyzer then 6.9324g being dried, the water of 63.0029g and 0.03g Resorcinol join 250mL, start slowly to stir.There-necked flask is to be placed in the oil bath preheating that is heated to gradually 70 ℃, condensing reflux.Oil bath temperature and solution reach temperature of reaction stable after, then add the 43.6597g methyl acrylate that is preheated in advance same temperature of reaction, tune up stirring velocity, start reaction.In reaction, timing sampling, records reflecting time, adds internal standard substance and thinner in sample, carries out chromatography of gases analysis, when the content of each component is constant in reaction system, shows that chemical reaction reaches balance.After experimental data, show, this catalyst property is good, and percent hydrolysis is 71%, and selectivity is more than 95%, and reacting balance time is 30h left and right.
Embodiment 10
Assembling and fixed reactor, in the there-necked flask reactor that the acidic resins D032 catalyzer then 6.9324g being dried, the water of 63.0091g and 0.035g Resorcinol join 250mL, start slowly to stir.There-necked flask is to be placed in the oil bath preheating that is heated to gradually 65 ℃, condensing reflux.Oil bath temperature and solution reach temperature of reaction stable after, then add the 43.6643g methyl acrylate that is preheated in advance same temperature of reaction, tune up stirring velocity, start reaction.In reaction, timing sampling, records reflecting time, adds internal standard substance and thinner in sample, carries out chromatography of gases analysis, when the content of each component is constant in reaction system, shows that chemical reaction reaches balance.After experimental data, show, this catalyst property is good, and percent hydrolysis is 69.5%, and selectivity is more than 95%, and reacting balance time is 40h left and right.
Embodiment 11
Assembling and fixed reactor, the acidic resins D001 catalyzer then 6.9324g being dried, the water of 63.0415g and 0.0252g join in the there-necked flask reactor of 250mL with Resorcinol, start slowly to stir.There-necked flask is to be placed in the oil bath preheating that is heated to gradually 50 ℃, condensing reflux.Oil bath temperature and solution reach temperature of reaction stable after, then add the 43.6496g methyl acrylate that is preheated in advance same temperature of reaction, tune up stirring velocity, start reaction.In reaction, timing sampling, records reflecting time, adds internal standard substance and thinner in sample, carries out chromatography of gases analysis, when the content of each component is constant in reaction system, shows that chemical reaction reaches balance.After experimental data, show, percent hydrolysis is 30%, and selectivity is more than 95%, and reacting balance time is 55h left and right.
Embodiment 12
By fresh resin and used the resin of manipulation of regeneration to carry out Infrared Characterization, before and after finding to use, in resin, the charateristic avsorption band of sulfonate radical is substantially unchanged.
Claims (9)
1. acidic resins are prepared an acrylic acid for methyl acrylate system catalytic hydrolysis, it is characterized in that, using methyl acrylate and water is reactant, in batch reactor, take acidic resins as catalyzer, and temperature of reaction is 50-75 ℃, and the reaction times is 30-60h.
2. method according to claim 1, is characterized in that, described acid resin catalyst is SO
3h-type large hole strong acid styrene system cation exchange resin.
3. method according to claim 1 and 2, is characterized in that, the consumption of described catalyzer is that undried catalyst levels is the 1-10% (wt) of reaction solution, the 1-10% that dry catalyst levels is reaction solution (wt).
4. method according to claim 1 and 2, is characterized in that, described catalyzer has acidifying and not-acidified dividing.
5. method according to claim 1 and 2, is characterized in that, reaction unit is batch reactor.
6. method according to claim 1 and 2, is characterized in that, the water of described reaction and the mol ratio of methyl acrylate are 11:1～1:1.
7. method according to claim 1 and 2, it is characterized in that, for stoping the polymerization of vinylformic acid or methyl acrylate, hydrolyzation system has added stopper, it is thiodiphenylamine, phenols, arylamine class, ethers, quinones one or more, and the add-on stopper/reaction solution of stopper is 100mg-500mg/kg.
8. method according to claim 1 and 2, is characterized in that service temperature is below 100 ℃, and working pressure is normal pressure or decompression or pressurization.
9. method according to claim 1 and 2, is characterized in that using the catalyzer of for some time, with anhydrous methanol, soaks 3～5h, and after oven dry, activity returns to the activity before use substantially.
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Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO2019207264A1 (en) | 2018-04-27 | 2019-10-31 | Arkema France | Recovery of (meth)acrylic resin by depolymerization and hydrolysis |
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| US7041199B1 (en) * | 1999-10-13 | 2006-05-09 | Sulzer Chemtech Ag | Process and device for hydrolytically obtaining a carboxylic acid alcohol from the corresponding carboxylate |
| CN101065343A (en) * | 2004-11-17 | 2007-10-31 | 旭化成化学株式会社 | Oxidation catalyst and oxidation method |
| CN101696162A (en) * | 2009-10-30 | 2010-04-21 | 华南理工大学 | Method for preparing glutaric acid from dimethyl glutarate |
| DE102011076642A1 (en) * | 2011-05-27 | 2012-11-29 | Evonik Röhm Gmbh | Process for the preparation of methacrylic acid |
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2013
- 2013-11-14 CN CN201310566003.7A patent/CN103588636A/en active Pending
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| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPH04198151A (en) * | 1990-11-28 | 1992-07-17 | Mitsubishi Gas Chem Co Inc | Production of methacrylic acid |
| US7041199B1 (en) * | 1999-10-13 | 2006-05-09 | Sulzer Chemtech Ag | Process and device for hydrolytically obtaining a carboxylic acid alcohol from the corresponding carboxylate |
| CN1454886A (en) * | 2002-05-01 | 2003-11-12 | 罗姆和哈斯公司 | Improved method for preparing methyl-propenoic acid and methyl acrylate |
| CN1541991A (en) * | 2003-04-29 | 2004-11-03 | 中国石油化工股份有限公司 | Hydrolysis method of esters |
| CN101065343A (en) * | 2004-11-17 | 2007-10-31 | 旭化成化学株式会社 | Oxidation catalyst and oxidation method |
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Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO2019207264A1 (en) | 2018-04-27 | 2019-10-31 | Arkema France | Recovery of (meth)acrylic resin by depolymerization and hydrolysis |
| FR3080623A1 (en) * | 2018-04-27 | 2019-11-01 | Arkema France | (METH) ACRYLIC RESIN VALORIZATION BY DEPOLYMERIZATION AND HYDROLYSIS |
| US11739192B2 (en) | 2018-04-27 | 2023-08-29 | Arkema France | Recovery of (meth) acrylic resin by depolymerization and hydrolysis |
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Application publication date: 20140219 |