CN106674010A - Process for preparing methyl methacrylate according to aldol condensation method - Google Patents
Process for preparing methyl methacrylate according to aldol condensation method Download PDFInfo
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- CN106674010A CN106674010A CN201510760777.2A CN201510760777A CN106674010A CN 106674010 A CN106674010 A CN 106674010A CN 201510760777 A CN201510760777 A CN 201510760777A CN 106674010 A CN106674010 A CN 106674010A
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- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C67/00—Preparation of carboxylic acid esters
- C07C67/30—Preparation of carboxylic acid esters by modifying the acid moiety of the ester, such modification not being an introduction of an ester group
- C07C67/333—Preparation of carboxylic acid esters by modifying the acid moiety of the ester, such modification not being an introduction of an ester group by isomerisation; by change of size of the carbon skeleton
- C07C67/343—Preparation of carboxylic acid esters by modifying the acid moiety of the ester, such modification not being an introduction of an ester group by isomerisation; by change of size of the carbon skeleton by increase in the number of carbon atoms
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- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
- Y02P20/00—Technologies relating to chemical industry
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- Y02P20/584—Recycling of catalysts
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Abstract
The invention relates to production of methyl methacrylate, in particular to a process for preparing methyl methacrylate according to an aldol condensation method, wherein the process is realized by connecting multiple reactors in series and in parallel. According to the process, the multiple reactors are connected in series, and a methyl propionate stream and multiple formaldehyde streams are fed, so that the effective conversion rate of a raw material formaldehyde can be well increased, and the single-cycle service life of a catalyst can be prolonged; the reactors of two series are connected in parallel, so that regeneration operation over the catalyst which is deactivated is realized without shutdown, and the whole system can run normally. Compared with the prior art, the process has the advantages that unfavorable factors such as the short service life of the aldol condensation catalyst and the high requirement on the catalyst during use of a fluidized bed are well eliminated, and the process has high application value and good economic benefits.
Description
Technical field
The present invention relates to methyl methacrylate production technology, and in particular to a kind of catalyst long service life, original
The technique that the high aldol condensation method of material utilization rate prepares methyl methacrylate.
Background technology
Methyl methacrylate (MMA) is important Organic Chemicals, is mainly used in lucite
(PMMA) production, is also widely used in the life of resin, plastics, coating, binding agent and various commercial auxiliaries
Produce.Between 2009-2013, the production capacity and the equal rapid growth of demand of China's MMA industries, production capacity is from 42
Ten thousand tons/year rise to 590,000 tons/year, annual average compound growth rate 7.0%；Demand rises to 69 from 470,000 tons/year
Ten thousand tons/year, annual average compound growth rate 8.0%.From the point of view of the country, demand is higher than the growth of production capacity.By downstream
The impact that industry drives, domestic 2014-2018 MMA aggregate demands are estimated to rise to 100 from 750,000 tons/year
Ten thousand tons/year, and same period production capacity only rises to 870,000 tons/year from 590,000 tons/year, the growth of demand is significantly higher than product
Can, therefore the situation that supply falls short of demand is still presented in coming years MMA.
At present domestic production MMA is mainly Acetone cyanohydrin method, and environmental pollution is serious, and technique falls behind.The whole world
Maximum lucite companies of MMA suppliers have adopted advanced alpha methods, shorten technological process, reduces cost
And beneficial to safety in production and environmental conservation.The technology is monopolized so far by foreign countries, and studies in China is less, mainly there is north
Capital rising sun sun Chemical Engineering Technology academy company limited, Southwest Research ＆ Design Institute of Chemical Industry Co., Ltd., Chinese Academy of Sciences's process
Graduate School of Engineering etc., and aldol condensation catalyst research and development aspect is concentrated mainly on, such as CN102962062A,
CN103551148B, CN102350336B, CN104525176A, CN101829558B etc..And aldol contracts
Close the base metal catalysts for adopting under the high temperature conditions, easily coking inactivation, thus cause catalyst service life compared with
It is short, the only fluidized-bed process application of rising sun sun chemical industry with this understanding, such as CN102775302A,
CN104513163A, is expected that by cyclic regeneration mode and catalyst activity is recovered.But fluid bed is relatively solid
For fixed bed, conversion ratio is low, higher to the intensity requirement of catalyst, easily causes catalyst efflorescence and loss, Gu
Body beaded catalyst is to pipe and the serious wear of container.Simultaneously as easily there are side reaction, effectively utilizes in formaldehyde
Rate is not high, therefore how to be effectively improved process conditions, extends catalyst service life, improves formaldehyde effectively utilizes
Rate, just becoming affects the key factor of production cost in industrial amplification process.
The content of the invention
The purpose of the present invention is exactly the defect in order to overcome above-mentioned prior art to exist and provides a kind of catalyst and use
The technique that the high aldol condensation method of life-span length, raw material availability prepares methyl methacrylate.
The purpose of the present invention can be achieved through the following technical solutions：A kind of aldol condensation method prepares methacrylic acid
The technique of methyl ester, adopts methyl propionate and formaldehyde source for raw material, individual anti-comprising 2n (n is 2～5 natural number)
Device is answered, is divided into two response series of X, Y, wherein series of X has n reactor, is respectively labeled as X serial
First reactor, X series second reactor, X series the 3rd reactor ... reactor is serially connected；Serial Y
There is n reactor, be respectively labeled as Y-series first reactor, Y-series second reactor, Y-series the 3rd
Reactor ..., reactor is serially connected；Series of X is in parallel with series Y；The technique specifically includes following step
Suddenly：
(1) raw material methyl propionate is entered from X series first reactors, is labeled as logistics a；Raw material formaldehyde source point
N stocks not from X series first reactor, X series second reactor, X series the 3rd reactor ... enter,
Be respectively labeled as logistics b, logistics c ...；Logistics a is reacted with logistics b into X series first reactors,
The reacted logistics of X series first reactors is entered into X series second reactors jointly Jing after heat exchange with logistics c
Row reaction, the reacted logistics of X series second reactors enters X series the 3rd jointly Jing after heat exchange with logistics d
Reactor is reacted, by that analogy, until the logistics after X the n-th reactor reactions of series is sent into Jing after heat exchange
Separative element carries out the separating-purifying of methyl methacrylate；
(2) after the catalyst performance in each reactor of series of X declines 30%, series Y, logistics a are started
Reacted into Y-series first reactor with logistics b, reacted logistics Jing of Y-series first reactor is changed
Reacted into Y-series second reactor jointly with logistics c after heat, Y-series second reactor is reacted
Logistics is reacted into the reactor of Y-series the 3rd jointly Jing after heat exchange with logistics d, by that analogy, until Y
Logistics after serial n-th reactor reaction sends into separative element Jing after heat exchange and carries out the separation of methyl methacrylate
Purification；Meanwhile, the catalyst in each reactor of series of X carries out at regeneration conditions regenerative operation；
(3) when the catalyst in each reactor of series of X completes regenerative operation, in treating each reactors of serial Y
After catalyst performance declines 30%, series of X is enabled, operate same step (1)；Meanwhile, each reactor of serial Y
In catalyst carry out regenerative operation at regeneration conditions.
(4) circulation carries out step (1), step (2), the operation of step (3), realizes that whole technique is continuous
Production, maintains stable operation.
Described formaldehyde source is one or more in formaldehyde, formalin, formaldehyde carbinol mixture, paraformaldehyde.
Described reactor is heat-insulating fixed bed reactors.
Identical catalyst is respectively arranged with each reactor, catalyst is base metal catalysts Cs/SiO2。
Described base metal catalysts Cs/SiO2For：Metal Cs is supported on carrier S iO2On, load capacity be 4～
20%, cesiated salt solution is immersed on silica support using infusion process is obtained.
Reaction condition in each reactor is：Temperature be 320～400 DEG C, pressure be normal pressure～1.0MPa, raw material
Methyl propionate is ((n+1)～20) with the mol ratio of formaldehyde:1.Preferable reaction temperature is 340～380 DEG C, most
Excellent temperature is 340～350 DEG C；It is preferred that reaction pressure is 0.4～0.8MPa, optimum pressure is 0.5～0.6MPa；
It is preferred that the mol ratio of methyl propionate and formaldehyde is 5～15:1, optimum molar ratio is 10～15:1；Liquid hourly space velocity (LHSV)
(0.5～9)/h, preferably 1～6/h, most preferably 1～3/h.
Each catalyst reactor regeneration condition is：Temperature is 330～450 DEG C, and pressure is normal pressure～0.5MPa,
Regeneration atmosphere is N2And O2Gaseous mixture, wherein O2Content 1～10%.
It is catalyst deactivation to original initial activity that catalyst in each reactor needs the mark of regenerative operation
70%, the mark for terminating catalyst regeneration is the O in reactor A n exit2Content reaches 1%.
Compared with prior art, beneficial effects of the present invention are embodied in following several respects：
(1) by the series connection of reactor, to the disposable charging of methyl propionate, PARA FORMALDEHYDE PRILLS(91,95) source batch feed, can protect
Demonstrate,prove methyl propionate in each reactor feed much excessive, can so improve the utilization rate of formaldehyde, excessive propanoic acid first
Ester reusable edible Jing after rectification separation.
(2) formaldehyde is the key factor for causing the coking inactivation of catalyst, and the present invention improves the utilization rate of formaldehyde, because
This reduces the coking shrinkage of catalyst, improves the monocycle service life of catalyst.
(3) by the parallel connection of reactor series, it is ensured that the on-line regeneration of deactivation catalyst, whole system is made
It is not parking, maintain stable operation.
Description of the drawings
Fig. 1 is the flow chart of the technique of the present invention.
Specific embodiment
Embodiments of the invention are elaborated below, the present embodiment enters under premised on technical solution of the present invention
Row is implemented, and gives detailed embodiment and specific operating process, but protection scope of the present invention is not limited to down
The embodiment stated.
Embodiment 1
As shown in figure 1, X series and Y-series have three reactors, i.e. n=3, therefore, formaldehyde source is divided into
3 parts of chargings.Methyl propionate and formaldehyde are adopted in the present embodiment for raw material, by the series connection of multiple stage reactor with it is in parallel
To realize, following steps are specifically included：
X series reactors input reaction, Y-series reactor is waited and come into operation.
Methyl propionate 1 and first strand of formaldehyde 2 enter X series first after heat exchanger HA1 heating and react jointly
Device A1, reaction temperature is 330 DEG C, and reaction pressure is 0.6MPa, and methyl propionate is 10 with the mol ratio of formaldehyde:1,
Liquid hourly space velocity (LHSV) is 1.8/h；The X reacted materials of series first reactor A1 Jing after heat exchanger EA1 coolings, with
X series second reactors A2 are entered jointly with second strand of formaldehyde 3, and reaction temperature is 355 DEG C, and reaction pressure is
0.5MPa, methyl propionate is 9 with the mol ratio of formaldehyde:1, liquid hourly space velocity (LHSV) is 1.8/h；X series second reactors
The reacted materials of A2 enter X series the 3rd and react jointly Jing after heat exchanger EA2 coolings with the 3rd strand of formaldehyde 4
Device A3, reaction temperature is 365 DEG C, and reaction pressure is 0.4MPa, and methyl propionate is 8 with the mol ratio of formaldehyde:1,
Liquid hourly space velocity (LHSV) is 1.8/h；Dominant response product stream of X the 3rd reactor As 3 of series Jing after heat exchanger EA3 coolings
8, send into rectification separative element, wherein methyl propionate recycling, the purification of target product methyl methacrylate
Out as product.
When catalyst deactivation is to original initial activity 70% in X series reactors, stops X series reactors and enter
Material, begins to use Y-series reactor, its operation process conditions and X serial reaction operating procedure condition phases
Together, the reactor B 3 of Y-series the 3rd primary product 9 out sends into rectification separative element.Now X series is carried out
Catalyst regenerates, i.e., successively order passes through A1, A2, A3 reactor to regeneration gas 5 (1%O2+99%N2),
Regeneration temperature is 330～400 DEG C, and pressure is followed successively by 0.3MPa, 0.2MPa, 0.1MPa, and gas space velocity is 3000/h,
Until O in A3 reactor outlet gas 62Content reach 1% after regeneration ending, wait next time input reaction.
When Y-series catalyst reactor deactivation is to original initial activity 70%, stops Y-series reactor and enter
Material, begins to use X series reactors, and now Y-series carry out catalyst regeneration, and regeneration is as serial in X
Equally.Treat O in B3 reactor outlet gas 72Y-series regeneration ending when content reaches 1%, waits next time
Input reaction.
So X and two series reactor circular response-regeneration of Y, are capable of achieving continuously running for device.
The catalyst adopted in the implementation case is for Cs/SiO2Catalyst, its collocation method is as follows：Ratio is weighed first
Surface area 250m2The silica support 200g of/g, weighs a certain amount of cesium carbonate and is configured to solution, by silicon oxide
After carrier impregnates stirring 24 hours in the solution, after at room temperature evacuation is dried 12 hours again under 120C
It is dried 24 hours, then roasting is obtained catalyst after 6 hours at 400 DEG C.Gained catalyst Cs weight contents
For 15%, balance of SiO2。
X is as shown in the table with each reactor reaction operating condition of Y-series.
| A is serial | Reaction temperature | Reaction pressure | Liquid hourly space velocity (LHSV) | Ester aldehyde ratio |
| A1 reactors | 320℃ | 0.6MPa | 1.8/h | 10:1 |
| A2 reactors | 345℃ | 0.5MPa | 1.8/h | 9:1 |
| A3 reactors | 375℃ | 0.4MPa | 1.8/h | 8:1 |
| B1 reactors | 320℃ | 0.6MPa | 1.8/h | 10:1 |
| B2 reactors | 345℃ | 0.5MPa | 1.8/h | 9:1 |
| B3 reactors | 375℃ | 0.4MPa | 1.8/h | 8:1 |
X is as shown in the table with each reactor regenerative operation condition of Y-series.
| A is serial | Regeneration temperature | Reaction pressure | Regeneration gas | Gas space velocity |
| A1 reactors | 330～400 DEG C | 0.3MPa | 1%O2+ 99%N2 | 3000/h |
| A2 reactors | 330～400 DEG C | 0.2MPa | 1%O2+ 99%N2 | 3000/h |
| A3 reactors | 330～400 DEG C | 0.1MPa | 1%O2+ 99%N2 | 3000/h |
| B1 reactors | 330～400 DEG C | 0.3MPa | 1%O2+ 99%N2 | 3000/h |
| B2 reactors | 330～400 DEG C | 0.2MPa | 1%O2+ 99%N2 | 3000/h |
| B3 reactors | 330～400 DEG C | 0.1MPa | 1%O2+ 99%N2 | 3000/h |
According to above-mentioned condition, the reaction result of each reactor is as follows：
Note:CMMAFor the space-time yield of methyl methacrylate, g/ (Kg.cat.h)；
XHCHOFor formaldehyde conversion efficiency, %.
The reaction effect of different time sections is investigated in X and Y-series separate clocking.
Can be shown that by above-mentioned investigation result of the test, after sectional feeding formaldehyde, the monocycle service life of catalyst
Up to 600hr (activity is reduced to 70%).
Embodiment 2
As a comparison, and investigated catalyst monocycle service life of the formaldehyde not after sectional feeding, i.e. n=1's
Situation.Effect is as follows.
Reactor reaction operating condition is as shown in the table.
| Reaction temperature | Reaction pressure | Liquid hourly space velocity (LHSV) | Ester aldehyde ratio | |
| A1 reactors | 345℃ | 0.6MPa | 0.6/h | 3.33:1 |
Reactor reaction operating result is as shown in the table.
Note:YMMAFor the space-time yield of methyl methacrylate, g/ (Kg.cat.h)；
XHCHOFor formaldehyde conversion efficiency, %.
Embodiment 1 and embodiment 2 test result indicate that, (clump 1.8/h drops to former 1/3 to reduce catalyst loading
As little as 0.6/h), ester aldehyde ratio is from 10:1 is reduced to 3.33:1, that is, ensure the processed in units amount of the catalyst of the reactor
Catalyst processed in units amount after merging with original three reactors of X series is consistent, then after 250h,
Catalyst activity reduces to the 70% of original initial activity, i.e. life-span monocycle with respect to the shortening of formaldehyde batch feed.
Embodiment 3
Investigate the situation of n=5, catalyst position 20%Cs/SiO2.
X is as shown in the table with each reactor reaction operating condition of Y-series.
| A is serial | Reaction temperature | Reaction pressure | Liquid hourly space velocity (LHSV) | Ester aldehyde ratio |
| A1 reactors | 330℃ | 0.6MPa | 2.5/h | 15:1 |
| A2 reactors | 340℃ | 0.5MPa | 2.5/h | 14:1 |
| A3 reactors | 360℃ | 0.4MPa | 2.5/h | 13:1 |
| A4 reactors | 380℃ | 0.3MPa | 2.5/h | 12:1 |
| A5 reactors | 400℃ | 0.2MPa | 2.5/h | 11:1 |
| B1 reactors | 330℃ | 0.6MPa | 2.5/h | 15:1 |
| B2 reactors | 340℃ | 0.5MPa | 2.5/h | 14:1 |
| B3 reactors | 360℃ | 0.4MPa | 2.5/h | 13:1 |
| B4 reactors | 380℃ | 0.3MPa | 2.5/h | 12:1 |
| B5 reactors | 400℃ | 0.2MPa | 2.5/h | 11:1 |
Regeneration condition is similar to Example 1.
According to above-mentioned condition, the reaction result of each reactor is as follows：
Note:CMMAFor the space-time yield of methyl methacrylate, g/ (Kg.cat.h)；
XHCHOFor formaldehyde conversion efficiency, %.
The reaction effect of different time sections is investigated in X and Y-series separate clocking.
Claims (7)
1. the technique that a kind of aldol condensation method prepares methyl methacrylate, it is characterised in that adopt methyl propionate
It is raw material with formaldehyde source, comprising 2n (n is 1～5 natural number) individual reactor, is divided into two reactions of X, Y
Series, wherein series of X have n reactor, are respectively labeled as X series first reactor (A1), X serial
Serial 3rd reactor (A3) of second reactor (A2), X ... reactor is serially connected；Serial Y has n
Reactor, is respectively labeled as Y-series first reactor (B1), Y-series second reactor (B2), Y-series
3rd reactor (B3) ..., reactor is serially connected；Series of X is in parallel with series Y；The technique is concrete
Comprise the following steps：
(1) raw material methyl propionate is entered from X series first reactor (A1), is labeled as logistics a (1)；
Raw material formaldehyde source point n stocks are not from X series first reactor (A1), X series second reactor (A2), X
Serial 3rd reactor (A3) ... enter, be respectively labeled as logistics b (2), logistics c (3) ..., logistics
n+1；Logistics a (1) is reacted with logistics b (2) into X series first reactor (A1), and X is serial
The reacted logistics of first reactor (A1) enters X series second and reacts jointly Jing after heat exchange with logistics c (3)
Device (A2) is reacted, X series second reactor (A2) reacted logistics Jing after heat exchange with logistics d (4)
Enter X the 3rd reactors (A3) of series jointly to be reacted, by that analogy, until X the n-th reactors of series
(An) reacted logistics sends into separative element Jing after heat exchange and carries out the separating-purifying of methyl methacrylate；
(2) when in each reactor of series of X catalyst performance decline, start series Y, logistics a (1) and
Logistics b (2) is reacted into Y-series first reactor (B1), and Y-series first reactor (B1) is anti-
Logistics after answering is reacted into Y-series second reactor (B2) jointly Jing after heat exchange with logistics c (3),
The reacted logistics of Y-series second reactor (B2) enters Y-series the Jing after heat exchange jointly with logistics d (4)
Three reactors (B3) are reacted, by that analogy, until the reacted thing of the reactor of Y-series n-th (Bn)
Flowing through feeding separative element after heat exchange carries out the separating-purifying of methyl methacrylate；Meanwhile, series of X is respectively reacted
Catalyst in device carries out at regeneration conditions regenerative operation；
(3) when the catalyst in each reactor of series of X completes regenerative operation, in treating each reactors of serial Y
Catalyst performance declines, and enables series of X, operates same step (1)；Meanwhile, urging in each reactor of serial Y
Agent carries out at regeneration conditions regenerative operation.
2. a kind of aldol condensation method according to claim 1 prepares the technique of methyl methacrylate, and it is special
Levy and be, described formaldehyde source be the one kind in formaldehyde, formalin, formaldehyde carbinol mixture, paraformaldehyde or
It is several.
3. a kind of aldol condensation method according to claim 1 prepares the technique of methyl methacrylate, and it is special
Levy and be, described reactor is heat-insulating fixed bed reactors.
4. a kind of aldol condensation method according to claim 1 prepares the technique of methyl methacrylate, and it is special
Levy and be, identical catalyst is respectively arranged with each reactor, catalyst is base metal catalysts Cs/SiO2。
5. a kind of aldol condensation method according to claim 4 prepares the technique of methyl methacrylate, and it is special
Levy and be, described base metal catalysts Cs/SiO2For：Metal Cs is supported on carrier S iO2On, load capacity is
4～20%, cesiated salt solution is immersed on silica support using infusion process is obtained.
6. a kind of aldol condensation method according to claim 1 prepares the technique of methyl methacrylate, and it is special
Levy and be, the reaction condition in each reactor is：Temperature is 320～400 DEG C, and pressure is normal pressure～1.0MPa,
Methyl propionate is ((n+1)～20) with the mol ratio of formaldehyde:1.
7. a kind of aldol condensation method according to claim 1 prepares the technique of methyl methacrylate, and it is special
Levy and be, each catalyst reactor regeneration condition is：Temperature is 330～450 DEG C, and pressure is normal pressure～0.5MPa,
Regeneration atmosphere is N2And O2Gaseous mixture, wherein O2Content 1～10%.
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Cited By (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN109320392A (en) * | 2018-11-15 | 2019-02-12 | 西南化工研究设计院有限公司 | A kind of fixed fluidized bed reaction of preparing propylene by dehydrogenating propane and regeneration technology |
| CN111574369A (en) * | 2020-06-08 | 2020-08-25 | 北京旭阳科技有限公司 | Method for preparing methyl methacrylate by condensing methyl propionate and formaldehyde aldol and multi-stage reaction system |
| CN113692398A (en) * | 2019-07-04 | 2021-11-23 | 株式会社Lg化学 | Process for the continuous production of diesters |
| CN114478244A (en) * | 2020-10-27 | 2022-05-13 | 中国石油化工股份有限公司 | Method for synthesizing methyl acrylate, catalyst and application |
| WO2023071490A1 (en) * | 2021-10-31 | 2023-05-04 | 浙江新和成股份有限公司 | Preparation method and apparatus for methyl methacrylate |
| CN111574369B (en) * | 2020-06-08 | 2024-05-17 | 北京旭阳科技有限公司 | Method for preparing methyl methacrylate by condensing methyl propionate and formaldehyde aldol and multistage reaction system |
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| 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 |
| CN103265394A (en) * | 2013-05-27 | 2013-08-28 | 神华集团有限责任公司 | Methanation reaction system and regeneration technology of methanation catalyst |
| 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 |
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| WO1999052628A1 (en) * | 1998-04-08 | 1999-10-21 | Ineos Acrylics Uk Limited | Production of unsaturated acids or esters thereof and catalysts therefor |
| 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 |
| CN103265394A (en) * | 2013-05-27 | 2013-08-28 | 神华集团有限责任公司 | Methanation reaction system and regeneration technology of methanation catalyst |
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Cited By (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN109320392A (en) * | 2018-11-15 | 2019-02-12 | 西南化工研究设计院有限公司 | A kind of fixed fluidized bed reaction of preparing propylene by dehydrogenating propane and regeneration technology |
| CN113692398A (en) * | 2019-07-04 | 2021-11-23 | 株式会社Lg化学 | Process for the continuous production of diesters |
| CN111574369A (en) * | 2020-06-08 | 2020-08-25 | 北京旭阳科技有限公司 | Method for preparing methyl methacrylate by condensing methyl propionate and formaldehyde aldol and multi-stage reaction system |
| CN111574369B (en) * | 2020-06-08 | 2024-05-17 | 北京旭阳科技有限公司 | Method for preparing methyl methacrylate by condensing methyl propionate and formaldehyde aldol and multistage reaction system |
| CN114478244A (en) * | 2020-10-27 | 2022-05-13 | 中国石油化工股份有限公司 | Method for synthesizing methyl acrylate, catalyst and application |
| WO2023071490A1 (en) * | 2021-10-31 | 2023-05-04 | 浙江新和成股份有限公司 | Preparation method and apparatus for methyl methacrylate |
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