CN102649689A - Method for parking reactor - Google Patents
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- CN102649689A CN102649689A CN2011100453065A CN201110045306A CN102649689A CN 102649689 A CN102649689 A CN 102649689A CN 2011100453065 A CN2011100453065 A CN 2011100453065A CN 201110045306 A CN201110045306 A CN 201110045306A CN 102649689 A CN102649689 A CN 102649689A
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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
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- Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
- Y02P20/00—Technologies relating to chemical industry
- Y02P20/50—Improvements relating to the production of bulk chemicals
- Y02P20/52—Improvements relating to the production of bulk chemicals using catalysts, e.g. selective catalysts
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Abstract
The invention relates to a method for parking a reactor, and mainly solves the technical problems in the prior art that during the parking of the reactor, the activity of a catalyst is reduced, and the selectivity of the hydrogenated product, namely ethylene glycol is low. Through the adoption of the technical scheme that oxalic ester and hydrogen are taken as raw materials, a copper contained solid oxide is taken as a catalyst, and the method comprises the following steps: (a) the temperature is kept to 180 to 260 DEG C, the pressure is 0.2 to 10 MPa, and the volume space velocity of hydrogen is 200 to 8,000 hours<-1>, the feeding of oxalic ester in the reactor is stopped step by step within 0.1 to 40 hours; (b), under the hydrogen atmosphere, the feeding stop is kept for 0.2 to 30 hours; (c) the reaction temperature is reduced to 20 to 100 DEG C within 1 to 60 hours; and (d) reaction gas is replaced with conversion gas, wherein the conversion gas is selected from at least one of nitrogen, methane, helium or argon, and the invention solves the problems, and can be used for parking the reactor in the industrial production of increasing the yield of ethylene glycol.
Description
Technical field
The present invention relates to a kind of method of reactor shutdowns, particularly about improving the method for reactor shutdowns in dimethyl oxalate hydrogenation or the oxalic acid diethyl ester hydrogenation preparing ethylene glycol process.
Background technology
Terepthaloyl moietie (EG) is a kind of important Organic Chemicals; Be mainly used in and produce trevira, frostproofer, unsaturated polyester resin, lubricant, softening agent, nonionogenic tenside and explosive etc.; Can be used for industries such as coating, soup, brake fluid and printing ink in addition; Solvent and medium as ammonium pertorate are used to produce special solvent glycol ether etc., and purposes very extensively.
At present; Direct hydration method or the legal operational path of pressurized water are all adopted in domestic and international large-scale terepthaloyl moietie production; This technology is that oxyethane and water are made into mixed aqueous solution by 1: 20～22 (mol ratios), and in 130～180 ℃, 1.0～2.5MPa reacted 18～30 minutes down in fixed-bed reactor; Oxyethane all is converted into alcohol mixture; The aqueous glycol solution content that generates carry through the multiple-effect evaporator dehydration then and obtain terepthaloyl moietie dense the separation with rectification under vacuum, but production equipment need be provided with a plurality of vaporizers greatly about 10% (massfraction); Consume lot of energy and be used for dehydration, cause that the technological process of production is long, equipment is many, energy consumption is high, directly influence the production cost of terepthaloyl moietie.Since the seventies in 20th century; Both at home and abroad some major companies that mainly produce terepthaloyl moietie all are devoted to the Synthesis of Ethylene Glycol by Catalytic Hydration Study on Technology; Mainly contain shell company, U.S. UCC company and Dow company, the Mitsubishi chemical company of Ying He, domestic Shanghai Petroleum Chemical Engineering Institute, Nanjing University of Technology etc.What representative was wherein arranged is the heterogeneous catalysis hydration method of Shell company and the homogeneous catalysis hydration method of UCC company.Shell company has reported that from 1994 quaternary ammonium type acid carbonate anionite-exchange resin carries out the exploitation of EO catalytic hydration technology as catalyzer; Obtain EO transformation efficiency 96%～98%; The test-results of EG selectivity 97%～98%; Develop the poly organic silicon alkane ammonium salt loaded catalyst of similar silicon dioxide skeleton and the epoxide hydrating process under the catalysis thereof in 1997 again, obtained better conversion rate and selectivity.The UCC company of the U.S. has mainly developed two kinds of hydration catalysts: a kind of is the anionic catalyst that is carried on the ion exchange resin, mainly is molybdate, tungstate, vannadate and triphenylphosphine complex catalyst; Another kind is the molybdate composite catalyst.In two kinds of Application of Catalyst examples, the TM catalyzer of spent ion exchange resin DOWEXWSA21 preparation is hydration under 9: 1 the condition in the mol ratio of water and EO, and the EG yield is 96%.Using the molybdate composite catalyst, is hydration under 5: 1 the condition in the mol ratio of water and EO, and the EG yield is 96.6%.Catalysis method greatly reduces the water ratio; Simultaneously can obtain high EO transformation efficiency and high EG selectivity; But also there is certain problem aspect Preparation of Catalyst, regeneration and life-span, not enough like catalyst stability, preparation is quite complicated, be difficult to recycle; Have also can be in product residual a certain amount of anionic metal, need to increase corresponding apparatus and separate.NSC 11801 method synthesizing glycol is by oxyethane and carbonic acid gas synthesizing ethylene carbonate, obtains terepthaloyl moietie with the NSC 11801 hydrolysis again.The US4508927 patent proposes separately to carry out esterification and hydrolysis reaction.The two-step process that the US4500559 of U.S. Halcon-SD company proposes is that the mixture that comes from reactor drum is through resorber; With the carbonic acid gas extracting oxyethane under the criticality, obtain oxyethane, carbonic acid gas again; Water mixture contacts synthetic BC with catalyst for esterification reaction such as Organohalogen compounds, sulfohalides; BC is admitted to hydrolysis reactor then, and hydrolysis obtains terepthaloyl moietie and carbonic acid gas under same catalyst action, and the terepthaloyl moietie yield is up to 99%.Japanese Patent JP571006631 has proposed the EO-EC-EG novel process of industrially scalable; Patent introduces oxyethane and the carbonic acid gas esterification is in the presence of catalyzer KI; 160 ℃ are carried out esterification; Transformation efficiency is 99.9%, and the selectivity of terepthaloyl moietie is 100%, and the NSC 11801 legal system is equipped with the terepthaloyl moietie technology no matter aspect transformation efficiency and selectivity; Still all than present BO direct hydration method bigger advantage is being arranged aspect production process raw material consumption and the energy expenditure, technical in ethylene glycol is a kind of method that maintains the leading position.But this method still is raw material with the oil, and need build the terepthaloyl moietie production equipment again, and this glycol unit to new construction is more suitable, and on original production unit was undergone technological transformation, it was favourable to be not so good as catalytic hydration.
Document CN101138725A discloses a kind of Catalysts and its preparation method of oxalic ester hydrogenation synthesizing of ethylene glycol, and it is active ingredient with the metallic copper, and zinc is auxiliary agent, adopt the coprecipitation method preparation, but the document is not mentioned the concrete grammar of reactor shutdowns.
Document " petrochemical complex " was rolled up the 340th～343 page of the 4th phase in 2007 the 36th and has been introduced a kind of employing Cu/SiO
2Carry out the research of hydrogenation of dimethyl oxalate to synthesizing ethylene glycol reaction, but the concrete grammar of reactor shutdowns is not mentioned in the same existence of this catalyzer.
At present, from world wide, petroleum resources day is becoming tight, and oil price fluctuation in the world's is bigger, and the resource general layout of China can be summarized as few oil, weak breath, many coals.Development carbon one chemical industry not only can make full use of Sweet natural gas and coal resource, reduces the dependence of petroleum import and can alleviate environmental stress, is unusual important field of research.With the carbon monoxide is the feedstock production barkite, is a very attractive Coal Chemical Industry route with preparing glycol by hydrogenating oxalate then.Now both at home and abroad to being that the research of feedstock production barkite has obtained good effect with the carbon monoxide, industrial production is ripe.And, still have more need of work further investigation with preparing glycol by hydrogenating oxalate, and the activity of especially better guard catalyst, the effective parking methods of reactor drum etc. are important subject.
Summary of the invention
Technical problem to be solved by this invention is to exist in the document to cause catalyst activity to reduce the technical problem that the reaction product glycol selectivity is low in the reactor shutdowns process in the past.A kind of method of new reactor shutdowns is provided.This method has catalyst activity and keeps good, the advantage that glycol selectivity is high.
In order to solve the problems of the technologies described above, the technical scheme that the present invention adopts is following: a kind of method of reactor shutdowns is a raw material with barkite and hydrogen, and the cupric soild oxide is a raw material, and its reactor shutdowns in turn includes the following steps:
A) remain 180～260 ℃ in temperature, pressure is 0.2～10MPa, and the hydrogen volume air speed is 200～8000 hours
-1Under the condition, with progressively stopped reaction device barkite charging in 0.1～40 hour;
B) under there is atmosphere in hydrogen, kept 0.2～30 hour;
C) temperature of reactor was reduced to 20～100 ℃ with 1～60 hour;
D) use the inert gas replacement reactant gases;
Wherein, substitution gas is selected from least a in nitrogen, methane, helium or the argon gas.
Temperature maintenance preferable range is 190～250 ℃ in the technique scheme, and more preferably scope is 190～240 ℃; The volume space velocity preferable range is 300～6000 hours
-1, more preferably scope is 300～5000 hours
-1The pressure preferable range is 0.2～6.0MPa, and more preferably scope is 0.2～3.0MPa; With preferred time range 0.2～20 hour, more preferably time range was progressively stopped reaction device barkite charging in 0.2～10 hour; Under there was atmosphere in hydrogen, keeping preferred time range was 0.2～20 hour, and more preferably time range is for keeping 0.2～10 hour; It is 3～40 hours that temperature of reactor uses preferred time range, and more preferably time range is to reduce to 20～80 ℃ of preferred range in 3～30 hours, and more preferably TR is 20～70 ℃.
Cupric soild oxide support of the catalyst is selected from least a in silicon oxide or the aluminum oxide in the technique scheme; Active ingredient is selected from oxide compound or its mixture of metallic copper, copper.Barkite is selected from dimethyl oxalate or oxalic acid diethyl ester.
As everyone knows; Hydrogenation of oxalate for preparing ethylene glycol technology, hydrogenation catalyst are the keys of technology, the stability of this catalyzer; Its height to conversion of raw material and purpose product selectivity all determines the advance and the validity of hydrogenation of oxalate for preparing ethylene glycol technology; And the stability of catalyzer, its to the indexs such as height of conversion of raw material and purpose product selectivity except with Preparation of catalysts, outside processes such as filling are closely related; Also with the use of catalyzer, comprise and driving and methods such as parking are closely connected.The present invention in a large amount of research process and finds, is the oxalate hydrogenation catalyzer for copper, in the reactor shutdowns process; Stop the barkite charging earlier if adopt, keep for some time again, the method for under hydrogen atmosphere, progressively lowering the temperature again afterwards with hydrogen; For the protection of catalyst activity and optionally improve useful; Otherwise activity of such catalysts can be lost, and the selectivity of terepthaloyl moietie can reduce.This is because hydrogenation of oxalate for preparing ethylene glycol reacts its active site and Cu and Cu
+Synergy relevant, and this active site can keep or " fixing " preferably in atmosphere of hydrogen, and in the presence of barkite Cu and Cu
+The synergistic activity center can be interfered, especially under the condition of high temperature even can cause irreversible loss.
Adopt technical scheme of the present invention; With barkite and hydrogen is raw material, and the cupric soild oxide is a catalyzer, and its reactor shutdowns comprises the steps: that (a) remains 180～260 ℃ in temperature; Pressure is 0.2～10MPa, and the hydrogen volume air speed is 200～8000 hours
-1Under the condition, with progressively stopped reaction device barkite charging in 0.1～40 hour; (b) under there is atmosphere in hydrogen, kept 0.2～30 hour; (c) temperature of reactor was reduced to 20～100 ℃ with 1～60 hour; (d) with substitution gas replacement(metathesis)reaction gas; Wherein, Substitution gas is selected under at least a condition in nitrogen, methane, helium or the argon gas, and the catalyzer after stopping is through active revaluation; Its result is: the transformation efficiency of barkite is greater than 99%; The selectivity of terepthaloyl moietie can have been protected activity of such catalysts preferably greater than 97%, has obtained better technical effect.
Through embodiment the present invention is done further elaboration below, but be not limited only to present embodiment.
Embodiment
[embodiment 1]
Taking by weighing specific surface is silica support 500 grams of 200 meters squared per gram; According to 30% reactive metal copper and 5% promoter metal zinc content configuration catalyzer; Its step is following: choose cupric nitrate and zinc nitrate; Be made into steeping fluid according to Cu and Zn charge capacity, silica support is flooded 24 hours in this solution after, vacuum-drying at room temperature 12 hours solids.Again with solid 120 ℃ dry 12 hours down, after 450 ℃ of roastings 4 hours, gas (hydrogen molar content 20%, nitrogen molar content 80%) 200 ml/min that feed the hydrogen mixture obtain required catalyzer 450 ℃ of activation 6 hours.
Take by weighing above-mentioned cupric soild oxide catalyst sample 20 grams, in the fixed-bed reactor of packing into, the employing dimethyl oxalate is a raw material, 210 ℃ of temperature of reaction, and reaction pressure 3.0MPa, reaction velocity 0.5 hour
-1, reactive hydrogen/ester mol ratio is to react 10 hours under 80: 1 the condition, and its reaction result is that the transformation efficiency of barkite is 100%, and the selectivity of terepthaloyl moietie is 95.2%; Adopt following steps to stop afterwards: (a) remain 180 ℃ in temperature, pressure is 3.0MPa, and the hydrogen volume air speed is 300 hours
-1Under the condition, with progressively stopped reaction device barkite charging in 1 hour; (b) under there is atmosphere in hydrogen, kept 5 hours; (c) temperature of reactor was reduced to 30 ℃ with 50 hours; (d) use the nitrogen replacement reactant gases.Afterwards, still adopting dimethyl oxalate is raw material, 210 ℃ of temperature of reaction, and reaction pressure 3.0MPa, reaction velocity 0.5 hour
-1, reactive hydrogen/ester mol ratio is to react 10 hours under 80: 1 the condition, and its reaction result is that the transformation efficiency of barkite is 100%, and the selectivity of terepthaloyl moietie is 96.1%.
[embodiment 2]
According to catalyzer and each step and the condition of [embodiment 1], the step of just stopping is following: (a) remain 260 ℃ in temperature, pressure is 2.0MPa, and the hydrogen volume air speed is 3000 hours
-1Under the condition, with progressively stopped reaction device barkite charging in 20 hours; (b) under there is atmosphere in hydrogen, kept 10 hours; (c) temperature of reactor was reduced to 60 ℃ with 20 hours; (d) with methane gas replacement(metathesis)reaction gas.Afterwards, still adopting dimethyl oxalate is raw material, 210 ℃ of temperature of reaction, and reaction pressure 3.0MPa, reaction velocity 0.5 hour
-1, reactive hydrogen/ester mol ratio is to react 10 hours under 80: 1 the condition, and its reaction result is that the transformation efficiency of barkite is 100%, and the selectivity of terepthaloyl moietie is 97.1%.
[embodiment 3]
According to catalyzer and each step and the condition of [embodiment 1], the step of just stopping is following: (a) remain 230 ℃ in temperature, pressure is 1.0MPa, and the hydrogen volume air speed is 6000 hours
-1Under the condition, with progressively stopped reaction device barkite charging in 2 hours; (b) under there is atmosphere in hydrogen, kept 4 hours; (c) temperature of reactor was reduced to 30 ℃ with 15 hours; (d) use the argon replaces reactant gases.Afterwards, still adopting dimethyl oxalate is raw material, 210 ℃ of temperature of reaction, and reaction pressure 3.0MPa, reaction velocity 0.5 hour
-1, reactive hydrogen/ester mol ratio is to react 10 hours under 80: 1 the condition, and its reaction result is that the transformation efficiency of barkite is 100%, and the selectivity of terepthaloyl moietie is 95.8%.
[embodiment 4]
According to catalyzer and each step and the condition of [embodiment 1], the step of just stopping is following: (a) remain 190 ℃ in temperature, pressure is 0.5MPa, and the hydrogen volume air speed is 3000 hours
-1Under the condition, with progressively stopped reaction device barkite charging in 0.5 hour; (b) under there is atmosphere in hydrogen, kept 10 hours; (c) temperature of reactor was reduced to 25 ℃ with 2 hours; (d) use the helium replacement reactant gases.Afterwards, still adopting dimethyl oxalate is raw material, 210 ℃ of temperature of reaction, and reaction pressure 3.0MPa, reaction velocity 0.5 hour
-1, reactive hydrogen/ester mol ratio is to react 10 hours under 80: 1 the condition, and its reaction result is that the transformation efficiency of barkite is 100%, and the selectivity of terepthaloyl moietie is 95.3%.
[embodiment 5]
According to catalyzer and each step and the condition of [embodiment 1], the step of just stopping is following: (a) remain 200 ℃ in temperature, pressure is 0.2MPa, and the hydrogen volume air speed is 2000 hours
-1Under the condition, with progressively stopped reaction device barkite charging in 1 hour; (b) under there is atmosphere in hydrogen, kept 8 hours; (c) temperature of reactor was reduced to 35 ℃ with 6 hours; (d) with high-purity hydrogen replacement(metathesis)reaction gas.Afterwards, still adopting dimethyl oxalate is raw material, 210 ℃ of temperature of reaction, and reaction pressure 3.0MPa, reaction velocity 0.5 hour
-1, reactive hydrogen/ester mol ratio is to react 10 hours under 80: 1 the condition, and its reaction result is that the transformation efficiency of barkite is 100%, and the selectivity of terepthaloyl moietie is 95.9%.
[embodiment 6]
According to the catalyzer of [embodiment 1], the employing oxalic acid diethyl ester is a raw material, 210 ℃ of temperature of reaction, and reaction pressure 3.0MPa, reaction velocity 0.5 hour
-1, reactive hydrogen/ester mol ratio is to react 10 hours under 80: 1 the condition, and its reaction result is that the transformation efficiency of barkite is 100%, and the selectivity of terepthaloyl moietie is 96.1%; Adopt following steps to stop afterwards: (a) remain 220 ℃ in temperature, pressure is 0.8MPa, and the hydrogen volume air speed is 2000 hours
-1Under the condition, with progressively stopped reaction device barkite charging in 0.2 hour; (b) under there is atmosphere in hydrogen, kept 10 hours; (c) temperature of reactor was reduced to 35 ℃ with 12 hours; (d) with high-purity hydrogen replacement(metathesis)reaction gas.Afterwards, still adopting oxalic acid diethyl ester is raw material, 210 ℃ of temperature of reaction, and reaction pressure 3.0MPa, reaction velocity 0.5 hour
-1, reactive hydrogen/ester mol ratio is to react 10 hours under 80: 1 the condition, and its reaction result is that the transformation efficiency of barkite is 100%, and the selectivity of terepthaloyl moietie is 96.8%.
[comparative example 1]
According to each step and the operational condition of [embodiment 5], the mode that just adopts hydrogen and barkite raw material to stop synchronously, concrete steps are following: (a) remain 200 ℃ in temperature, pressure is 0.2MPa, and the hydrogen volume air speed is 2000 hours
-1Under the condition, with progressively stopped reaction device hydrogen and barkite charging in 1 hour; (b) temperature of reactor was reduced to 35 ℃ with 6 hours; Afterwards, still adopting dimethyl oxalate is raw material, 210 ℃ of temperature of reaction, and reaction pressure 3.0MPa, reaction velocity 0.5 hour
-1, reactive hydrogen/ester mol ratio is to react 10 hours under 80: 1 the condition, and its reaction result is that the transformation efficiency of barkite is 97.5%, and the selectivity of terepthaloyl moietie is 90.2%.
[comparative example 2]
According to each step and the operational condition of [embodiment 4], just adopt and stop hydrogen earlier, stop the parking mode of barkite raw material again, concrete steps are following: (a) remain 190 ℃ in temperature, pressure is 0.5MPa, and the hydrogen volume air speed is 3000 hours
-1Under the condition, with 0.5 hour stopped reaction device hydrogen feed progressively; (b) in the presence of barkite, kept 1 hour; (c) temperature of reactor was reduced to 25 ℃ with 2 hours; (d) use the nitrogen replacement reactor drum.Afterwards, still adopting dimethyl oxalate is raw material, 210 ℃ of temperature of reaction, and reaction pressure 3.0MPa, reaction velocity 0.5 hour
-1, reactive hydrogen/ester mol ratio is to react 10 hours under 80: 1 the condition, and its reaction result is that the transformation efficiency of barkite is 90%, and the selectivity of terepthaloyl moietie is 88.6%.
Claims (6)
1. the method for a reactor shutdowns is a raw material with barkite and hydrogen, and the cupric soild oxide is a catalyzer, and its reactor shutdowns in turn includes the following steps:
A) remain 180～260 ℃ in temperature, pressure is 0.2～10MPa, and the hydrogen volume air speed is 200～8000 hours
-1Under the condition, with progressively stopped reaction device barkite charging in 0.1～40 hour;
B) under there is atmosphere in hydrogen, kept 0.2～30 hour;
C) temperature of reactor was reduced to 20～100 ℃ with 1～60 hour;
D) use the inert gas replacement reactant gases;
Wherein, substitution gas is selected from least a in nitrogen, methane, helium or the argon gas.
2. according to the method for the said reactor shutdowns of claim 1, it is characterized in that temperature remains 190～250 ℃, volume space velocity is 300～6000 hours
-1, pressure was 0.2～6.0MPa, with progressively stopped reaction device barkite charging in 0.2～20 hour; Under there is atmosphere in hydrogen, kept 0.2～20 hour; Temperature of reactor was reduced to 20～80 ℃ with 3～40 hours.
3. according to the method for the said reactor shutdowns of claim 2, it is characterized in that temperature remains 190～240 ℃, volume space velocity is 300～5000 hours
-1, pressure was 0.2～3.0MPa, with progressively stopped reaction device barkite charging in 0.2～10 hour; Under there is atmosphere in hydrogen, kept 0.2～10 hour; Temperature of reactor was reduced to 20～70 ℃ with 3～30 hours.
4. according to the method for the said reactor shutdowns of claim 1, it is characterized in that cupric soild oxide support of the catalyst is selected from least a in silicon oxide or the aluminum oxide; Active ingredient is selected from oxide compound or its mixture of metallic copper, copper.
5. according to the method for the said reactor shutdowns of claim 1, it is characterized in that barkite is selected from dimethyl oxalate or oxalic acid diethyl ester.
6. according to the method for the said reactor shutdowns of claim 1, it is characterized in that substitution gas is selected from nitrogen.
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| CN201110045306.5A CN102649689B (en) | 2011-02-25 | 2011-02-25 | Method for parking reactor |
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| CN201110045306.5A CN102649689B (en) | 2011-02-25 | 2011-02-25 | Method for parking reactor |
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| CN102649689B CN102649689B (en) | 2014-08-13 |
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Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN108084003A (en) * | 2016-11-19 | 2018-05-29 | 中国石油化工股份有限公司 | A kind of occasional shutdowns method of methylisobutanone synthesized from acetone technique |
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| US4551565A (en) * | 1981-01-26 | 1985-11-05 | Ube Industries, Ltd. | Process for the production of ethylene glycol and/or glycollic acid esters, and catalyst therefor |
| CN101475442A (en) * | 2008-12-18 | 2009-07-08 | 中国石油化工股份有限公司 | Method for preparing ethylene glycol from oxalic ester |
| CN101475441A (en) * | 2008-12-18 | 2009-07-08 | 中国石油化工股份有限公司 | Method for preparing ethylene glycol from oxalic ester |
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2011
- 2011-02-25 CN CN201110045306.5A patent/CN102649689B/en active Active
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| US4551565A (en) * | 1981-01-26 | 1985-11-05 | Ube Industries, Ltd. | Process for the production of ethylene glycol and/or glycollic acid esters, and catalyst therefor |
| CN101475442A (en) * | 2008-12-18 | 2009-07-08 | 中国石油化工股份有限公司 | Method for preparing ethylene glycol from oxalic ester |
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| Title |
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| 黄维捷等: "草酸二甲酯加氢制乙二醇Cu/SiO2催化剂的制备与改性", 《工业催化》 * |
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN108084003A (en) * | 2016-11-19 | 2018-05-29 | 中国石油化工股份有限公司 | A kind of occasional shutdowns method of methylisobutanone synthesized from acetone technique |
| CN108084003B (en) * | 2016-11-19 | 2020-10-27 | 中国石油化工股份有限公司 | Temporary shutdown method for process for synthesizing methyl isobutyl ketone from acetone |
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