CN103193640A - Reactive distillation method for producing methyl methacrylate - Google Patents
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- CN103193640A CN103193640A CN2013101209607A CN201310120960A CN103193640A CN 103193640 A CN103193640 A CN 103193640A CN 2013101209607 A CN2013101209607 A CN 2013101209607A CN 201310120960 A CN201310120960 A CN 201310120960A CN 103193640 A CN103193640 A CN 103193640A
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Abstract
The invention relates to a reactive distillation method for producing methyl methacrylate. The method comprises steps of synthesizing the methyl methacrylate in a rectifying column; separating a target product from raw materials through azeotropic distillation while reacting, thereby obtaining an organic phase which does not contain methacrylic acid and is rich in methyl methacrylate from a column top and obtaining a solution which contains a great quantity of methacrylic acid from a column bottom; connecting a film evaporator with the column bottom in series; and further concentrating the heavy components of the column bottom so as to reduce the consumption of the methacrylic acid. An azeotropic distillation technology is utilized to separate the methyl methacrylate from acid; a whole rectifying system is integrated and coupled; one reacting and rectifying column is used to realize reacting and rectifying; tasks such as esterification, raw material and product separation and heavy component decomposition which need to be completed by a plurality of columns are completed at the same time; the organic phase which does not contain methacrylic acid and is rich in methyl methacrylate is obtained from the column top; and an original complicated technology is simplified.
Description
Technical field
The invention belongs to technical field of chemical synthesis, related to a kind of reactive distillation method of producing methyl methacrylate.
Technical background
(methyl methacrylate MMA), is colourless volatile liquid under the normal temperature, and has strong spicy flavour methyl methacrylate.Fusing point is-48.2 ℃, and boiling point is 100.3 ℃, and relative density is 1.009(20/4 ℃), refractive index is 1.412, flash-point is 11 ℃.Be slightly soluble in water, be soluble in ethanol etc.
Methyl methacrylate is a kind of important Organic Chemicals, it is most important industrialization product in the methyl acrylic ester, main application is to make various polymkeric substance and multipolymer, and MMA also is used for making the treating compound of resin, plastics, coating, tackiness agent, lubricant, timber and cork, penetrant, paper lustering agent, dyeing and printing auxiliary and the insulation pouring material etc. of motor coil simultaneously.
MMA can produce polymethylmethacrylate (PMMA) by polymerization, and PMMA is the homopolymer of MMA, is the most important end product of MMA, is commonly called as synthetic glass.PMMA has the good transparency, good shock-resistance, good electrical property, suitable rigidity, density and weathering resistance, chemical resistance is also fine.The PMMA optical property is very good, can see through 92% natural light (white light), transparency is equivalent to opticglass, because appearance transparent beauty, and good mechanical performance and electrical property arranged, therefore be widely used in aviation, electronics, electric, the optics articles for use, instrument, automobile, building, set lights, toy, stationery and LCD core parts are backlight with aspects such as tabula rasa and advertising sign boards, in addition, by the continuous research to the PMMA Application Areas, developed high temperature resistant at present, wear-resisting, antistatic, the PMMA inner core material that the PMMA of high-impact and photoconductive fiber are used etc.
MMA also can carry out copolymerization with vinyl acetate, vinyl cyanide, vinylbenzene, esters of acrylic acid and other methacrylic ester, obtains the polyester material of excellent property, for the production of paint, spinning sizing agent, papermaking, leather agent etc.Another main application fields of MMA is The Impact Modifiers for PVC ACR and MBS.PVC section bar, alloy material are widely used in fields such as traffic, building, furniture, and the PVC intensity after ACR and MBS modification is higher, and performance is better.
MMA also comprises aspect medical macromolecular materials, acrylic fibers second monomer, acrylic tackifier, unsaturated polyester cross-linking agent and the lubricated wet goods in the application of other consumer field.
The consumption structure of China MMA is at present: PMMA accounts for 60%, and plastic processing additives ACR and MBS account for 12%, and topcoating accounts for 23%, and other accounts for 5%.
In recent years, along with the demand of China's synthetic glass, IT industry, automobile finish, furniture lacquer and PVC modifier A CR and the MMA of MBS rolls up, the expansion climax of a new round is arrived, and external numerous businessmans invest to China one after another and found the factory: the color special company of Britain's fine jade is installed on operation in 2005 years at 90,000 tons of/year MMA of Shanghai chemical industry park building; The mitsubishi rayon goes into operation at 70,000 tons of/year isobutylene oxidation method MMA devices of Guangdong Huizhou in July, 2006, expands production to 90,000 tons/year in 2007; Winning wound company is 110,000 tons/year in the MMA of Shanghai Chemical Industry Park construction machinery production capacity, and downstream unit comprises polymethylmethacrylate and methacrylic acid, and be constructed and put into operation in October, 2009.
The esterification that methacrylic acid and methyl alcohol carry out is a reversible reaction, be subjected to the restriction of the equilibrium constant, reaction conversion ratio is not high, there is an equilibrium conversion in the reaction process, industrially adopt the method for azeotropic distillation usually in order to improve the equilibrium conversion of methacrylic acid, in reaction process, product is separated, balance is moved right, improve reaction conversion ratio.Break molecular balance for the general method that removes water generation reaction that adopts of this technology, balance is moved to the direction that generates product.
Mitsubishi Co., Ltd. applies for a patent the method that CN1697822A discloses a kind of preparation (methyl) acrylate in China, under the effect of strongly acidic cation-exchange catalyzer with the pure esterification of (methyl) vinylformic acid and C1-C4 to generate (methyl) acrylate, reaction solution carries out rectifying, obtain (methyl) methyl acrylate, simultaneously unreacted (methyl) vinylformic acid is circulated.
Rohm GombH applies for a patent the method that CN101337889A discloses a kind of preparation (methyl) acrylate in China, and it mainly is that alcohol and lower boiling (methyl) vinylformic acid are carried out transesterification reaction in the presence of catalyzer.
US Patent No. 006025520A discloses the method for a kind of preparation (methyl) acrylate, this method is reacted the alcohol of (methyl) vinylformic acid and C1 ~ C3 under the effect of strong acid ion exchange resin, be reflected under the vacuum state and carry out, reaction solution is divided into the vapour-liquid two-phase, enter follow-up distillation system respectively and separate purification, obtain (methyl) acrylate product.
US Patent No. 4280010 discloses a kind of production method for preparing alkyl acrylate, and adopting sulfuric acid or organic sulfonic acid is catalyzer, in the distillation zone on reaction zone top the azeotropic mixture of alkyl acrylate, water and unreacted alkyl alcohol is separated.
European patent 0733617 is disclosed for adopting a reactor to carry out continuous esterification, and the water that generates in the reactor and alkyl ester are separated by reactor top rectifying tower as moisture azeotrope.
Chinese patent CN 101239909A discloses a kind of system (methyl) method for producing acrylic acid and equipment, this method is to make (methyl) vinylformic acid and alkanol reaction generate (methyl) acrylate under the effect of an acidic catalyst, in reaction process, 2 acid is transformed fully as far as possible, method by the alkali neutralization neutralizes to reaction solution then, with the acidity in the control product.
Above disclosed method all adopts reaction to add the technology of rectifying, adopt single reactor to carry out esterification, obtain the finished product by rectification and purification then, common this reactive mode needs to adopt the long residence time in order to obtain high conversion, cause required big reactor volume, reason is that methyl alcohol and water, methyl methacrylate form azeotrope equally because for making the reaction product vaporization, temperature of reactor is higher, reduced the reaction zone methanol concentration, esterification speed is reduced.In addition, do not have catalyzer in knockout tower, methyl alcohol can't react again, at a large amount of unreacted pure Returning reactors of back system recoveries, causes energy consumption to increase.In addition, for obtaining the organic phase of low methacrylic acid concentration, need to adopt additive method that methacrylic acid is separated, these methods comprise rectifying, absorption, neutralization etc.
Summary of the invention
In order to overcome the deficiencies in the prior art, the purpose of this invention is to provide a kind of reactive distillation method of producing methyl methacrylate.Specifically, this method is finished the synthetic of methyl methacrylate in a rectifying tower, in reaction, finish separating of target product and raw material by azeotropic distillation, obtain not contain the organic phase that is rich in methyl methacrylate of methacrylic acid at cat head, obtain containing the solution of a large amount of methacrylic acids in tower reactor, simultaneously at the tower reactor thin-film evaporator of connecting, to the further concentrate of the heavy component of tower reactor, to reduce the consumption of methacrylic acid.
A kind of reactive distillation method of producing methyl methacrylate, in a rectifying tower, finish the synthetic of methyl methacrylate, in reaction, finish separating of target product and raw material by azeotropic distillation, obtain not contain the organic phase that is rich in methyl methacrylate of methacrylic acid at cat head, obtain containing the solution of a large amount of methacrylic acids in tower reactor, simultaneously at the tower reactor thin-film evaporator of connecting, to the further concentrate of the heavy component of tower reactor, to reduce the consumption of methacrylic acid; Described rectifying tower comprises three sections, is respectively rectifying section, conversion zone and stripping section; Carry out esterification at conversion zone methacrylic acid and methyl alcohol, the methyl methacrylate of Sheng Chenging, water and methyl alcohol are separated from liquid-phase reaction system by azeotropic distillation simultaneously; Carry out separating of methyl methacrylate, water and methyl alcohol and methacrylic acid at rectifying section and stripping section.
Wherein methacrylic acid is from the charging of conversion zone top, and methyl alcohol is from the conversion zone underfeed, and strong acid ion exchange resin is installed in the middle of the rectifying tower, and overhead condensation water, organic phase are partly refluxed to cat head respectively; The heavy constituent that conversion zone generates: the methacrylic acid of polymolecular polymerization and the esterification products of methyl alcohol and Michael addition adducts, in thin-film evaporator, be decomposed, the methacrylic acid of recovery, methyl methacrylate and part heavy component enter stripping section.
Wherein reactive distillation is to carry out in stage number is 30 ~ 110 rectifying tower, and the conversion zone stage number is 10 ~ 35, and the rectifying section stage number is 10 ~ 50, and the stripping section stage number is 10 ~ 25, and the column plate type is sieve plate, valve tray or bubble cap plate.
The catalyzer of described conversion zone adopts strong acid ion exchange resin, adopts the bale packing formula or adopts the heap formula of loosing.
Wherein butyl methacrylate be separating of methacrylic acid and heavy component in rectifying tower, to realize that by the azeotropic distillation that forms with water, methyl alcohol the aqueous-phase reflux ratio is 0.2 ~ 20, the organic phase reflux ratio is 1 ~ 30.
6, the reactive distillation method of production methyl methacrylate according to claim 1 is characterized in that: wherein carry out under the azeotropic distillation vacuum condition, pressure carries out under 15 ~ 60kPaA; The conversion zone temperature is 60 ~ 85 ℃
Wherein entering the methyl alcohol of reaction fractionating tower and the mol ratio of methacrylic acid is 1 ~ 2.0.
Stopper wherein is selected from one or more in 2,4 dimethyl 6 tert butyl phenol, Resorcinol, thiodiphenylamine, copper dibutyldithiocarbamate, nitroxyl free radical piperidines alcohol, the tetramethyl piperidine nitrogen oxygen free radical tris phosphite.
Beneficial effect of the present invention:
Change traditional reaction and added rectification process, utilize the characteristic of two kinds of binary azeotropes in the system, utilize the azeotropic distillation technology that methyl methacrylate is separated with acid, simultaneously whole rectifying system has been carried out integrated, coupling, reaction and rectifying are realized by a reaction fractionating tower, finished task of needing a plurality of towers just can finish before esterification, separate raw materials and product, the heavy component decomposition etc. simultaneously, and obtain not contain substantially the organic phase that is rich in methyl methacrylate of methacrylic acid at cat head, complicated originally technology is oversimplified.
Description of drawings
Accompanying drawing is produced the schematic flow sheet of the reactive distillation method of methyl methacrylate for the present invention.
Wherein, the rectifying section 1 of reaction fractionating tower, the conversion zone 2 of reaction fractionating tower, the stripping section 3 of reaction fractionating tower, pipeline 4, pipeline 5, pipeline 6, overhead condenser 7, cat head are subjected to flow container 8, pipeline 9, pipeline 10, pipeline 11, pipeline 12, pipeline 13, pipeline 14, pipeline 15, thin-film evaporator 16, pipeline 17, pipeline 18, tower reactor reboiler 19.
Embodiment
Come this explanation is described further below in conjunction with drawings and Examples, but protection scope of the present invention is not limited to embodiment.Per-cents all among the embodiment are mass percent.
As shown in drawings, fresh methacrylic acid is sent into the top of conversion zone by pipeline 4, fresh methanol is sent into the conversion zone bottom by pipeline 5, methacrylic acid and first are joined the catalyst layer of enjoying on the conversion zone column plate and are reacted, the methyl methacrylate of Sheng Chenging and water simultaneously, methyl methacrylate, first alcohol and water distill from cat head under the effect of azeotropic; The overhead gas phase mixture is by pipeline 6, through being subjected to flow container 8(phase splitter at cat head after the condensation) in layering, isolate the organic phase that is rich in methyl methacrylate, first alcohol and water; The part water is back to cat head by pipeline 9, and as the component of the binary azeotropic system that forms methyl methacrylate, all the other waters are delivered to the back system by pipeline 10 and reclaimed methyl methacrylate and methyl alcohol operation; To cat head, this backflow can reduce the AA concentration of rectifying section to organic phase effectively by pipeline 12 partial reflux, and all the other organic phases are sent into back system recoveries methyl alcohol and purifying methyl acrylic methyl esters by pipeline 11; Tower bottoms returns tower reactor through pipeline 13 by reboiler, and the rectified heat load is provided; The part tower bottoms enters in the thin-film evaporator 16 through pipeline 15, reclaims methacrylic acid and part heavy component, and the material of recovery returns conversion zone through pipeline 14; Thin-film evaporator 16 bottom discharges system after pipeline 17 enters further handles, usually as waste material; The stopper of rectifying tower system adds cat head through pipeline 18.
High boiling point reactant methacrylic acid is from the charging of conversion zone top, lower boiling methyl alcohol is from the conversion zone underfeed, guaranteed that like this methacrylic acid that methyl alcohol in the liquid phase of conversion zone bottom maintains in the liquid phase on higher concentration, conversion zone top maintains higher concentration, two kinds of reactants all maintain relative higher concentration on the entire reaction section column plate thereby make, and the azeotrope of product formation simultaneously removes from system, and molecular balance is moved right faster.Pure and mild acid enters in the single reaction vessel of similar tower reactor in the present existing technology, and under same operation pressure, its temperature is higher than tower middle part temperature, so the concentration of methyl alcohol is relatively low, and speed of response is lower, and often reactor volume is bigger, the cost height.
The reaction fractionating tower stage number is 30 ~ 110, and wherein the conversion zone stage number is 10 ~ 35, and the rectifying section stage number is 10 ~ 50, and the stripping section stage number is 10 ~ 25.The conversion zone stage number is relevant with loadings, the conversion zone temperature of catalyzer.Loaded catalyst is more many, the conversion zone temperature is more high, and esterification speed is more fast, and the required reaction times is more short, and namely the total liquid holdup of required column plate is more little, and required conversion zone stage number is more few.But the loadings of catalyzer, when the conversion zone temperature is high, side reaction takes place easily, reduce the yield of methyl methacrylate, polymerization easily takes place in methacrylic acid and methyl methacrylate simultaneously.Preferred 6 ~ 30 of conversion zone stage number, preferred 50 ~ 80 ℃ of conversion zone temperature.The transformation efficiency of methacrylic acid is 70 ~ 99%, preferred 75 ~ 85%.For keeping the transformation efficiency of methacrylic acid, the mol ratio of the summation of methacrylic acid and methyl alcohol is 0.9 ~ 1.4, preferred 1.0 ~ 1.3.In the existing single esterifier technology, decompose therein for guaranteeing heavy component, temperature of reaction is generally higher, and at high temperature, under the sour environment, methyl alcohol easily dewaters and generates the side reaction of dme, has increased pure consumption.
Rectifying section and stripping section column plate type are sieve plate, valve tray or the bubble cap plate of macroporous plate, band downtake.The catalyst loading of conversion zone is on column plate, the type of feed of catalyzer on column plate can be the heap formula of loosing, also can adopt bundling type, the heap formula of loosing is easily loaded, cost is low, bundling type is difficult for filling, cost is higher, but can improve transformation efficiency and the selectivity of reaction, reduce consuming, the present invention preferentially adopts bundling type filling form.At conversion zone because adopt strong acid ion exchange resin, the preferential stainless steel of the material of column plate, optimal selection is 316L.
Reaction fractionating tower adopts decompression operation, working pressure is 10～80kPaA, preferred operations pressure 20 ~ 65kPaA, most preferred working pressure is 30 ~ 60kPaA, compares with atmospheric operation, when guaranteeing that conversion zone is temperature required, reduce the service temperature of tower reactor, reduce the tendency that polymkeric substance produces, prolonged the driving cycle, can reduce the consumption of stopper simultaneously.
The composition of azeotrope is as shown in table 1 in the organic phase that is rich in methyl methacrylate that does not contain methacrylic acid substantially that cat head obtains, this system.According to table 1, the water yield that reaction generates can not satisfy the ratio of two yuan of azeotropes of methyl methacrylate, therefore reach certain azeotropic ratio by water, organic phase reflux amount, the methyl methacrylate that generates is all taken out of from cat head, thereby make the thin-film evaporator bottom discharge the heavy component that does not contain methyl methacrylate substantially, preferred aqueous-phase reflux ratio is 0.2～2.0, and optimum selection is 0.3～1.6.The control of the low methacrylic acid content of cat head realizes at rectifying section by a certain amount of organic phase reflux.The organic phase reflux ratio is 2.0～6.0, and preferred reflux ratio is 2.2～5.5, and optimum selection is 2.5～4.0.Backflow by water and organic phase makes the content of methacrylic acid in the cat head organic phase be no more than 10ppm, preferably is no more than 5ppm, and optimum is no more than 2ppm.
Table 1 azeotrope is formed and boiling point
From the stripping section to the tower reactor, the heavy component that reaction generates, as: two polymethyl acrylic acid, poly methacrylic acid with and with esterification products and the Michael addition adducts of methyl alcohol, concentration in liquid phase is more and more higher, and methyl methacrylate and methacrylic acid concentration in liquid phase reduces gradually, the tower reactor liquid effluent enters thin-film evaporator, and because tower bottoms is mainly the by product that reaction generates, the flow of this burst logistics is very little.The residence time of material in thin-film evaporator is very short, for fear of polymerization and the carbonization of heavy component, thin-film evaporator adopts vacuum operating, and working pressure is 1～20kPaA, preferential working pressure is 1～12kPaA, and most preferred working pressure is 2～10kPaA.The gas phase on thin-film evaporator top is through flowing into the reaction fractionating tower tower reactor certainly after the condensation.
In the entire reaction rectifying, can adopt stopper to suppress the formation of the polymkeric substance of methacrylic acid, methyl methacrylate and derivative thereof.Stopper is added by the cat head spray, stopper wherein is selected from one or more in 2,4 dimethyl 6 tert butyl phenol, Resorcinol, thiodiphenylamine, copper dibutyldithiocarbamate, nitroxyl free radical piperidines alcohol, the tetramethyl piperidine nitrogen oxygen free radical tris phosphite.The concentration of stopper is 200～5000ppm, and preferred concentration is 300～4000ppm, and most preferred inhibitor concentration is 500～2500ppm.
Reaction fractionating tower is the band downtake sieve-tray tower of a diameter 80mm, and wherein the conversion zone stage number is 15, and the rectifying section stage number is 25, and the stripping section stage number is 15, and full tower adopts the 316L stainless steel.Cat head is the condenser of two series connection, and first is the normal temperature water-cooled, and second is 5 ℃ of refrigerated waters, the second condenser gaseous phase outlet water ring vacuum pump.The glass quantizer of a 2000ml links to each other with the condenser downtake, and the outlet of quantizer water, organic phase divides two-way respectively, and one the tunnel returns cat head as refluxing through peristaltic pump, and one the tunnel enters water, organic phase storage tank respectively through under meter.Tower reactor is equipped with electrically heated cover and temperature control system, and tower reactor circulation and discharging are controlled by a toothed gear pump.The 500ml glass evaporators has stirring scratch board, and the bottom is sent system by a frequency conversion toothed gear pump with material, and gas phase is returned column plate of conversion zone foot.
The methyl alcohol of 320g/h is sent into the bottom column plate of conversion zone by pipeline 5, and the fresh methacrylic acid of 800g/h is sent into conversion zone plate topmost by pipeline 4.The aqueous solution of the nitroxyl free radical piperidines alcohol (ZJ-701) of 2.5% concentration adds cat head with 30g/h by pipeline 18.Tower top pressure is set 45kPaA.The aqueous-phase reflux amount is set 100g/h, and the organic phase reflux amount is set 1550g/h.The tower reactor temperature is set 60 ℃, and the tower reactor internal circulating load is set at 7800g/h.
Per hour to cat head organic phase and the sampling analysis of still liquid, to determine that total system reaches stable state, pick up counting after stablizing and weigh.Cat head organic phase discharging 1230g/h, wherein methyl methacrylate content 88.5%, methanol content 4.0%, methacrylic acid content 4ppm; Cat head water discharging 180g/h, wherein methanol content 5.3%, methyl methacrylate content 2.1%; Methacrylic acid content 5ppm.The reaction conversion ratio 93% of this method methacrylic acid,, the reaction yield of AEB is 98%, cat head organic phase AA content is 4ppm.
Claims (8)
1. reactive distillation method of producing methyl methacrylate, it is characterized in that: in a rectifying tower, finish the synthetic of methyl methacrylate, in reaction, finish separating of target product and raw material by azeotropic distillation, obtain not contain the organic phase that is rich in methyl methacrylate of methacrylic acid at cat head, obtain containing the solution of a large amount of methacrylic acids in tower reactor, simultaneously at the tower reactor thin-film evaporator of connecting, to the further concentrate of the heavy component of tower reactor, to reduce the consumption of methacrylic acid; Described rectifying tower comprises three sections, is respectively rectifying section, conversion zone and stripping section; Carry out esterification at conversion zone methacrylic acid and methyl alcohol, the methyl methacrylate of Sheng Chenging, water and methyl alcohol are separated from liquid-phase reaction system by azeotropic distillation simultaneously; Carry out separating of methyl methacrylate, water and methyl alcohol and methacrylic acid at rectifying section and stripping section.
2. the reactive distillation method of production methyl methacrylate according to claim 1, it is characterized in that: wherein methacrylic acid is from the charging of conversion zone top, methyl alcohol is from the conversion zone underfeed, strong acid ion exchange resin is installed in the middle of the rectifying tower, and overhead condensation water, organic phase are partly refluxed to cat head respectively; The heavy constituent that conversion zone generates: the methacrylic acid of polymolecular polymerization and the esterification products of methyl alcohol and Michael addition adducts, in thin-film evaporator, be decomposed, the methacrylic acid of recovery, methyl methacrylate and part heavy component enter stripping section.
3. the reactive distillation method of production methyl methacrylate according to claim 1, it is characterized in that: wherein reactive distillation is to carry out in stage number is 30 ~ 110 rectifying tower, the conversion zone stage number is 10 ~ 35, the rectifying section stage number is 10 ~ 50, the stripping section stage number is 10 ~ 25, and the column plate type is sieve plate, valve tray or bubble cap plate.
4. the reactive distillation method of production methyl methacrylate according to claim 1 is characterized in that: the catalyzer employing strong acid ion exchange resin of described conversion zone, the diffusing heap formula of employing bale packing formula or employing.
5. the reactive distillation method of production methyl methacrylate according to claim 1, it is characterized in that: wherein butyl methacrylate be separating of methacrylic acid and heavy component in rectifying tower, to realize by the azeotropic distillation that forms with water, methyl alcohol, the aqueous-phase reflux ratio is 0.2 ~ 20, and the organic phase reflux ratio is 1 ~ 30.
6. the reactive distillation method of production methyl methacrylate according to claim 1, it is characterized in that: wherein carry out under the azeotropic distillation vacuum condition, pressure carries out under 15 ~ 60kPaA; The conversion zone temperature is 60 ~ 85 ℃.
7. the reactive distillation method of production methyl methacrylate according to claim 1, it is characterized in that: wherein entering the methyl alcohol of reaction fractionating tower and the mol ratio of methacrylic acid is 1 ~ 2.0.
8. the reactive distillation method of production methyl methacrylate according to claim 1, it is characterized in that: stopper wherein is selected from one or more in 2,4 dimethyl 6 tert butyl phenol, Resorcinol, thiodiphenylamine, copper dibutyldithiocarbamate, nitroxyl free radical piperidines alcohol, the tetramethyl piperidine nitrogen oxygen free radical tris phosphite.
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| CN104383705A (en) * | 2014-10-31 | 2015-03-04 | 青岛万泰生物科技有限公司 | Tube type up-down circulating heating methyl ester distillation system and processing technology thereof |
| CN104447307A (en) * | 2014-10-31 | 2015-03-25 | 青岛万泰生物科技有限公司 | Preparation method of methyl oleate, rectification equipment and treatment process thereof |
| CN104557538A (en) * | 2014-12-04 | 2015-04-29 | 江门谦信化工发展有限公司 | Industrial production method for producing butyl acrylate by in-column reaction rectification |
| CN105111081A (en) * | 2015-08-11 | 2015-12-02 | 中国石油集团东北炼化工程有限公司吉林设计院 | Method for reducing methylacrylic acid content in methyl methacrylate |
| CN105801408A (en) * | 2016-05-13 | 2016-07-27 | 中建安装工程有限公司 | Reaction distillation device and method for producing high-purity n-butyl acrylate |
| CN107056617A (en) * | 2017-01-03 | 2017-08-18 | 福州大学 | A kind of rectification process and equipment for producing methyl methacrylate |
| CN110935188A (en) * | 2019-12-18 | 2020-03-31 | 万华化学集团股份有限公司 | Continuous rectification separation method and device for hydroxyethyl (meth) acrylate crude product |
| CN111559816A (en) * | 2019-02-13 | 2020-08-21 | 中国石油天然气股份有限公司 | Method for treating wastewater of methyl methacrylate device |
| CN113457186A (en) * | 2020-03-30 | 2021-10-01 | 中石油吉林化工工程有限公司 | Method for improving separation effect of crude MMA (methyl methacrylate) separation tower |
| CN114835543A (en) * | 2022-03-17 | 2022-08-02 | 北京安胜瑞力科技有限公司 | Long-chain olefin synthesis system and synthesis process for synthesizing long-chain olefin by applying same |
| CN114890890A (en) * | 2022-05-09 | 2022-08-12 | 中建安装集团有限公司 | Process for recovering methacrylic acid or/and ester residual liquid thereof by catalytic cracking coupled rectification |
Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US5360926A (en) * | 1992-10-22 | 1994-11-01 | Sumitomo Chemical Company, Limited | Process for producing methyl methacrylate |
| CN102249913A (en) * | 2011-05-17 | 2011-11-23 | 上海华谊丙烯酸有限公司 | Preparation method of butyl acrylate |
-
2013
- 2013-04-09 CN CN2013101209607A patent/CN103193640A/en active Pending
Patent Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US5360926A (en) * | 1992-10-22 | 1994-11-01 | Sumitomo Chemical Company, Limited | Process for producing methyl methacrylate |
| CN102249913A (en) * | 2011-05-17 | 2011-11-23 | 上海华谊丙烯酸有限公司 | Preparation method of butyl acrylate |
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| CN104447307A (en) * | 2014-10-31 | 2015-03-25 | 青岛万泰生物科技有限公司 | Preparation method of methyl oleate, rectification equipment and treatment process thereof |
| CN104383705A (en) * | 2014-10-31 | 2015-03-04 | 青岛万泰生物科技有限公司 | Tube type up-down circulating heating methyl ester distillation system and processing technology thereof |
| CN104447307B (en) * | 2014-10-31 | 2017-01-11 | 青岛万泰生物科技有限公司 | Preparation method of methyl oleate, rectification equipment and treatment process thereof |
| CN104557538A (en) * | 2014-12-04 | 2015-04-29 | 江门谦信化工发展有限公司 | Industrial production method for producing butyl acrylate by in-column reaction rectification |
| CN105111081B (en) * | 2015-08-11 | 2017-04-19 | 中国石油集团东北炼化工程有限公司吉林设计院 | Method for reducing methylacrylic acid content in methyl methacrylate |
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