CN102757341A - Preparation method of ethyl acetate and/or isopropyl acetate - Google Patents
Preparation method of ethyl acetate and/or isopropyl acetate Download PDFInfo
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- CN102757341A CN102757341A CN2011101177823A CN201110117782A CN102757341A CN 102757341 A CN102757341 A CN 102757341A CN 2011101177823 A CN2011101177823 A CN 2011101177823A CN 201110117782 A CN201110117782 A CN 201110117782A CN 102757341 A CN102757341 A CN 102757341A
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Abstract
The invention provides a preparation method of ethyl acetate and/or isopropyl acetate. Catalytic dry gas from an oil refinery is used as a dilute ethylene and/or dilute propylene raw material and is introduced into a reaction system with a strong solid acidic catalyst to perform an addition esterification reaction so as to produce ethyl acetate and isopropyl acetate. The dry gas required by the method directly comes from a dry gas desulfurization treatment device of the refinery, the addition reaction pressure is low, continuous production of the ethyl acetate and isopropyl acetate can be realized by using dilute ethylene and/or dilute propylene, i.e., low-concentration ethylene and/or propylene, serving as raw material(s), the device investment is saved, the energy consumption is low, and the preparation method belongs to an advanced technology for new utilization of the catalytic dry gas.
Description
Technical field
The present invention relates to the preparation method of a kind of acetic acid second vinegar and/or Iso Butyl Acetate, or rather, be about a kind of be raw material is produced vinyl acetic monomer and/or Iso Butyl Acetate in the presence of solid acid catalyst method with rare ethene and/or propylene and acetic acid.
Technical background
Vinyl acetic monomer; Have another name called vinyl acetic monomer; Being one of most widely used fatty ester, having good solubility property, is a kind of drip-dry, fabulous industrial solvent; Also be a kind of important industrial chemicals, be widely used in productions such as cellulose acetate, ethyl cellulose, chlorinated rubber, ethene resin, cellulose acetate resin, viton; Also can be used for producing used in copy machines liquid nitrocellulose ink; In textile industry, be used as clean-out system; Be used as the fragrance extraction agent of special modification alcohol in the foodstuffs industry; Be most important spice additive in the perfume industry, can be used as the component of deodorant tune; Vinyl acetic monomer also can be used as the solvent of tackiness agent, the thinner of paint and the raw material of making medicine, dyestuff.
The solvent nature of Iso Butyl Acetate is very good; It both had been slightly soluble in water, was dissolved in various organic solvents again, was called as menstruum universale; 88 ℃ of its boiling points; Volatility is between vinyl acetic monomer, N-BUTYL ACETATE, and dissolving power is very strong, for multiple synthetic resins and natural resin good dissolving power is arranged; Being the fine solvent of many synthetic resins such as TKK 021, cellulose acetate, Nitrocellulose, PS, polyacrylic ester, Rohm tech inc, epoxy resin, also is the fine solvent of kauri(resin), abaca glue, rosin wet goods natural resin.
In recent years, because the environmental requirement increasingly stringent, the use that contains noxious solvents such as benzene, toluene, hydrochloric ether is restricted just gradually, and the consumption of environmentally friendly solvents such as ester class sharply increases, and vinyl acetic monomer, Iso Butyl Acetate product have become the market hot-sale products.
Industrial acetic acid ethyl ester main preparation methods has acetic acid esterification process, acetaldehyde condensation method and alcohol dehydrogenase method etc. in the world at present.Traditional acetic acid esterification process technology exists shortcomings such as equipment corrosion is serious, side reaction is many, waste reaction solution is hard to manage, production cost height progressively to be eliminated abroad; And the scale operation device mainly is acetaldehyde condensation method and alcohol dehydrogenase method, and the acetaldehyde condensation subtraction unit more than the more rich regional ton of acetaldehyde raw material has obtained using widely.Ethanol deoxidation method is the novel process of developing in recent years, at ethanol abundant and cheaply the area obtained popularization.
Up-to-date vinyl acetic monomer industrial process is the ethene additive process; The employing pure ethylene is a raw material, anhydrous Glacial acetic acid min. 99.5 and ethene addition reaction under an acidic catalyst effect and direct synthesis for ethyl acetate, and this method technology is simple; Be suitable for scale operation, have remarkable economical property.Publication number 1953958 patents (method for preparing vinyl acetic monomer) disclosed a kind of in the presence of heteropolyacid catalyst through ethene and acetic acid and water being reacted prepare the method for vinyl acetic monomer; Wherein the concentration of reactants in the incoming flow that adds reactor drum is: the mol ratio of ethene and acetic acid is 6.0 to 12.2, the mol ratio of ethene and water be 8.0 to 17.0 and the mol ratio of acetic acid and water be 1.25 to 1.40.Have been found that relative concentration and process conditions, can reduce the relative populations of the methyl ethyl ketone (MEK, 2-butanone) that generates with needed vinyl acetic monomer, and therefore can prolong life of catalyst through controlling reactant carefully.
Yet above-mentioned acetic acid esterification process, acetaldehyde condensation method and alcohol dehydrogenase method are produced vinyl acetic monomer, and what use is not directly to be raw material with ethene.Even industrialized ethene additive process or publication number 1953958 patents are produced vinyl acetic monomer; They all are to be raw material with the pure ethylene; And the ethene production capacity wretched insufficiency of China; Domestic ethylene yield only accounted for about 40% of ethene equivalent demand in 2005, even also only can bring up to about 48% to this ratio in 2010.
At present, the manufacturer of external most Iso Butyl Acetates adopts traditional production process, and promptly acetic acid and Virahol are that the direct catalytic esterification of catalyzer is produced Iso Butyl Acetate with sulfuric acid.Novel process is promptly: the technological holder of acetic acid and the direct acetic acid synthesized isopropyl ester of propylene is BP Amoco Chemicals, Rhone-Poulenc Industris, Japan is clear and etc.But these technologies all are to be raw material with pure propylene, and the propylene production capacity wretched insufficiency of China estimates that China's propylene demand in 2013 is 2,200 ten thousand tons, but output is 16,000,000 tons.
In sum; This this industriallization or disclosed technology not only receive the restriction of ethene and propylene resource; And used ethylene raw price is also expensive, the more important thing is that this sampling device generally all can only be built by the ethylene unit owing to receive this properties influence of ethene inconvenience transportation.
On the other hand, along with the growth of China's oil-refining capacity, the about 5.5Mt of the annual by-product dry gas of oil refining apparatus such as petrochemical industry catalytic cracking, catalytic pyrolysis contains wherein that ethene reaches 1.0Mt, propylene reaches 0.13Mt.Aspect rare ethrel usefulness; Although in nearly 4 years, CNPC, Sinopec, China National Chemicals Import(Sinochem) subordinate enterprise and private enterprise utilize this part resource to adopt the Dalian Chemistry and Physics Institute of Chinese Academy of Sciences preparing ethylbenzene from dry gas technology to form the industrial scale of production capacity for 1.28Mt/a ethylbenzene; Amount to and spend 0.35Mt ethene; Obtained remarkable economic efficiency, but the ethene of remainder acts as a fuel still using with whole propylene resources, cause the waste of ethene and propylene resource.Therefore, the rare ethene of this part and rare propylene resource are still demanded comprehensive utilization urgently.
Summary of the invention
The preparation method who the purpose of this invention is to provide a kind of acetic acid second vinegar and/or Iso Butyl Acetate reclaims rare ethene and propylene in the dry gas, improves Utilization of Dry-Gas from Catalytic Cracking and is worth.
The objective of the invention is to realize through following technical scheme: contain the plant catalytic cracking or the catalysis drying gas of low-concentration ethane and/or propylene, directly share split by a certain percentage gets into the placed in-line addition esterifier of multistage, and acetic acid is got into by first reactor drum.Reactor drum is divided into n conversion zone (n=2-10 is generally n=3-5), and two conversion zones wherein will be arranged at least, in each reactor drum acidic solid catalyst is housed, and each reactor configurations has bypass; Ethene, propylene carry out alkene-acetic acid direct addition reaction generation vinyl acetic monomer and Iso Butyl Acetate in the dry gas in reactive system, and reaction product is discharged by last reactor drum.
Specific embodiments of the present invention be in the presence of solid acid catalyst in the virgin gas alkene and acetic acid carry out the addition esterification, generate vinyl acetic monomer and Iso Butyl Acetate, comprise the steps:
(1) be raw material with the catalysis drying gas (comprising catalytic cracking, catalytic pyrolysis and thermal cracker) that contains low-concentration ethane and/or propylene;
(2) addition esterification adopts n fixed-bed reactor is composed in series reactive system; N=2-10 is equipped with acidic solid catalyst in each reactor drum, and is provided with bypass; Acetic acid is got into by first reactor drum; Dry gas share split by a certain percentage gets into each reactor drum, in reactive system, carries out virgin gas-acetic acid direct addition esterification, and reaction product is discharged reactive system by last reactor drum;
(3) low-concentration ethane and/or propylene are at 130-200 ℃, 2.0-3.0MPa, acetic acid and the molar ratio 1.3-4.4 of ethene+propylene, the weight hourly space velocity 0.1-0.37h of ethene+propylene
-1Condition under, contact with solid acid catalyst and to be converted into vinyl acetic monomer and/or Iso Butyl Acetate;
Vinyl acetic monomer proposed by the invention and Iso Butyl Acetate synthetic technology, raw material acetic acid is made up of two portions, and a part is fresh acetic acid, and another part can be an isolated circulation acetic acid in the reacted elute.Material dilute ethylene, propylene are the catalysis drying gas that contains low-concentration ethane and propylene from refinery's device, and or else this dry gas needs special purified from the dry gas desulfurizer of refinery, only otherwise contain free-water, H
2S content＜20mg/m
3, CO
2＜6% volume gets final product.
Vinyl acetic monomer proposed by the invention and Iso Butyl Acetate synthetic technology, the reactor drum of employing are various forms of fixed-bed reactor, like cartridge reactor, shell-and-tube reactor, radial reactor etc.Reactor drum can be an adiabatic reactor, also can be isothermal reactor.As select adiabatic reactor, then between reactor drum, should establish interchanger, so that take out heat of reaction.
The preparation vinyl acetic monomer proposed by the invention and the reactive system of Iso Butyl Acetate comprise two or more reactor drums.Number of reactors is also many, and alkene charging segments is many more, and temperature of reaction control is good more, and reaction effect is good more, but the manufacturing expense of reactor drum is also high more.Therefore, generally select 2-10 reactor drum, better select 2-6 reactor drum, preferably select 3-5 reactor drum.Each reactor drum should be provided with other pipe, helps catalyst change like this.In case the catalyst deactivation of certain reactor drum just can let material pass through other pipe, catalyst changeout or carry out catalyst regeneration more under the situation of not influence process running.
The solid acid catalyst that the present invention adopts comprises load or unsupported heteropolyacid (salt), strongly acidic cationic exchange resin, molecular sieve, SO42-/ZrO2 type solid super-strong acid etc.; And the combination of above-mentioned catalyzer; Such as, resin assembled heteropoly acid catalyzer and molecular sieve carried heteropolyacid (salt) catalyzer etc.As the resin of an acidic catalyst mainly is to obtain polystyrene resin by vinylbenzene-Vinylstyrene in the condition low suspension copolymerization that has pore-creating agent to exist, and then carries out with the vitriol oil, oleum or SO3 that sulfonation obtains.This resinoid can be synthetic according to existing knowledge, also can buy from market easily, and be D72 like the trade mark, D005, D006; D008, S54, Amberlyst 15, and Amberlyst 35, and Dowex 50; K2611, K2431, Puolite175, Puolite 275 resins such as grade.Selectable molecular sieve has Y series, ZSM is serial, MCM is serial, the serial equimolecular sieve of β.Selectable heteropolyacid comprises the heteropolyacid of Kegin structure, Dawson structure, Anderson structure, Silverton structure.At present commonly used what make catalyzer mainly is several kinds of heteropolyacids of keggin structure, like 12 phospho-wolframic acid (H
3PW12O40xH2O), 12 silicotungstic acids (H4SiW12O40xH2O), 12 phosphomolybdate (H3PMo12O40xH2O), 12 molybdovanaphosphoric acids (H3PMo12-yVyO40xH2O) etc.For heteropolyacid; Because its specific surface area is less and be difficult to independent moulding; Often need it be loaded on the suitable carriers, the available carrier of available carrier comprises metal oxide carriers such as silicon-dioxide, aluminum oxide, large pore molecular sieve, gac, through ion exchange resin of special processing or the like.
The compound method of vinyl acetic monomer provided by the present invention and Iso Butyl Acetate, reaction conditions is relevant with catalyzer that is adopted and desired reaction effect.In general, can adopt addition esterification condition to be: temperature of reaction 150-180 ℃, reaction pressure 2.5-3.0MPa, acetic acid and the molar ratio 2.5-3.0 of ethene+propylene, the weight hourly space velocity 0.15-0.3h of ethene
-1
The reactive system of preparation vinyl acetic monomer provided by the invention and Iso Butyl Acetate, acetic acid gets into from first reactor drum, and contains the dry gas segmentation entering reactor drum of low-concentration ethane and/or propylene.This kind sectional benefit is effectively to reduce the concentration of alkene; Avoid focus to produce, and can under the lower situation of total acid alkene, improve sour alkene ratio actual in the reactor drum; Uniformly temperature of reaction and high sour alkene are than helping suppressing the generation that alkene oligomerization reacts; Thereby the raising reaction preference reduces the product separation difficulty, and prevents catalyst deactivation.And behind the catalyst deactivation in certain reactor drum, can cut out through bypass and carry out catalyst change or regeneration, and needn't close down the entire reaction system.
The instance explanation
Below through embodiment the present invention and effect thereof are described further.
Before introducing specific examples, earlier dry gas raw material such as table 1 (the invention is not restricted to the raw material of this concentration of olefin), acetic acid, reactive system and the experimentation that instance adopted carried out necessary introduction.
Table 1, catalysis drying gas raw material are formed
| Component | H 2 | N 2 | O 2 | CO 2 | CH 4 | C 2H 6 | C 2H 4 | C 3H 6 | C 3H 8 | C 4 | C 5 |
| (WT％) | 2.51 | 27.05 | 1.22 | 5.65 | 21.87 | 18.29 | 19.60 | 2.31 | 0.42 | 0.77 | 0.26 |
From the catalysis drying gas total sulfur (H after refinery's desulfurization
2S) content≤20mg/Nm
3, do not contain free-water.After the desulfurization of oil refining apparatus dry gas, locate to adopt dress with cylinder for liquefied gas, deliver to this reactor assembly with the pneumatic diaphragm pump pressurization.Acetic acid is industrial top grade Glacial acetic acid min. 99.5.
Three fixed-bed reactor series connection are constituted reactive system; Reactor drum is the stainless steel tube (manufacturing of 316L stainless steel) of the outer jacketed heating system of φ 32 * 4 * 800mm; Acetic acid gets into reactive system by volume pump from first reactor drum; The dry gas that contains rare ethene and propylene is divided into three the tunnel through mass flowmeter entering reactor drum, and the temperature of reactor drum is controlled by electric heating system in the chuck.Six logical sampling valves all are equipped with in the outlet of every reactor drum, can online sampling analysis.Reaction was carried out 1000 hours continuously, through changing the inlet amount of operating parameters such as temperature of reaction, reaction pressure and dry gas, investigated result of the present invention in the operational process.
Instance 1
The silicon dioxide carried phospho-wolframic acid cesium salt of 30g (Cs respectively packs in three reactor drums
2.5H
0.5PW
12O
40/ SiO
2) catalyzer, with continuous first reactor drum that feeds of the speed of 30g/h, dry gas divides three stocks not with 5g/h with Glacial acetic acid min. 99.5,5g/h, and the speed of 5g/h gets into three reactor drums such as first, second grade, and the total feed of dry gas is 15g/h, for C
2 =+ C
3 =Total sour alkene mol ratio is 4.42, for C
2 =+ C
3 =Total feed weight air speed 0.11h
-1, be 150 ℃ in temperature of reaction, reaction pressure 2.0MPa reacts.The question response situation is stablized constant back (approximately needing 15h), analyzes through the six-way valve on-line sampling.
Operation result shows that behind system stability, the vertex temperature of reactor bed is respectively: 152 ℃ of one anti-155 ℃, two reactions, three anti-148 ℃.Calculate according to the 3rd reactor outlet product analysis result: the total conversion rate of ethene is 77.5%, and conversion of ethylene is that the selectivity of vinyl acetic monomer is 91.6%, and the selectivity that is converted into superimposed alkene is 8.4%; The total conversion rate of propylene is 88.2%, and the selectivity that propylene is converted into Iso Butyl Acetate is 92.6%, and the selectivity that is converted into superimposed alkene is 7.4%; Do not detect heavy hydrocarbon greater than C8.
Instance 2
The silicon dioxide carried phospho-wolframic acid cesium salt of 30g (Cs respectively packs in three reactor drums
2.5H
0.5PW
12O
40/ SiO
2) catalyzer, with continuous first reactor drum that feeds of the speed of 30g/h, dry gas divides three stocks not with 10g/h with Glacial acetic acid min. 99.5,5g/h, and the speed of 5g/h gets into three reactor drums such as first, second grade, and the total feed of dry gas is 20g/h, for C
2 =+ C
3 =Total sour alkene mol ratio is 3.31, for C
2 =+ C
3 =Total feed weight air speed 0.15h
-1, be 150 ℃ in temperature of reaction, reaction pressure 2.0MPa reacts.The question response situation is stablized constant back (approximately needing 15h), analyzes through the six-way valve on-line sampling.
Operation result shows that behind system stability, the vertex temperature of reactor bed is respectively: 153 ℃ of one anti-157 ℃, two reactions, three anti-148 ℃.Calculate according to the 3rd reactor outlet product analysis result: the total conversion rate of ethene is 76.5%, and conversion of ethylene is that the selectivity of vinyl acetic monomer is 92.6%, and the selectivity that is converted into superimposed alkene is 7.4%; The total conversion rate of propylene is 87.2%, and the selectivity that propylene is converted into Iso Butyl Acetate is 93.4%, and the selectivity that is converted into superimposed alkene is 6.6%; Do not detect heavy hydrocarbon greater than C8.
Instance 3
The silicon dioxide carried phospho-wolframic acid cesium salt of 30g (Cs respectively packs in three reactor drums
2.5H
0.5PW
12O
40/ SiO
2) catalyzer, with continuous first reactor drum that feeds of the speed of 30g/h, dry gas divides three stocks not with 15g/h with Glacial acetic acid min. 99.5,10g/h, and the speed of 5g/h gets into three reactor drums such as first, second grade, and the total feed of dry gas is 30g/h, for C
2 =+ C
3 =Total sour alkene mol ratio is 2.21, for C
2 =+ C
3 =Total feed weight air speed 0.22h
-1, be 170 ℃ in temperature of reaction, reaction pressure 2.5MPa reacts.The question response situation is stablized constant back (approximately needing 15h), analyzes through the six-way valve on-line sampling.
Operation result shows that behind system stability, the vertex temperature of reactor bed is respectively: 168 ℃ of one anti-173 ℃, two reactions, three anti-164 ℃.Calculate according to the 3rd reactor outlet product analysis result: the total conversion rate of ethene is 76.2%, and conversion of ethylene is that the selectivity of vinyl acetic monomer is 92.8%, and the selectivity that is converted into superimposed alkene is 7.2%; The total conversion rate of propylene is 86.2%, and the selectivity that propylene is converted into Iso Butyl Acetate is 94.2%, and the selectivity that is converted into superimposed alkene is 5.8%; Do not detect heavy hydrocarbon greater than C8.
Instance 4
The silicon dioxide carried phospho-wolframic acid cesium salt of 30g (Cs respectively packs in three reactor drums
2.5H
0.5PW
12O
40/ SiO
2) catalyzer, with continuous first reactor drum that feeds of the speed of 30g/h, dry gas divides three stocks not with 15g/h with Glacial acetic acid min. 99.5,15g/h, and the speed of 10g/h gets into three reactor drums such as first, second grade, and the total feed of dry gas is 40g/h, for C
2 =+ C
3 =Total sour alkene mol ratio is 1.66, for C
2 =+ C
3 =Total feed weight air speed 0.29h
-1, be 180 ℃ in temperature of reaction, reaction pressure 2.5MPa reacts.The question response situation is stablized constant back (approximately needing 10h), analyzes through the six-way valve on-line sampling.
Operation result shows that behind system stability, the vertex temperature of reactor bed is respectively: 183 ℃ of one anti-186 ℃, two reactions, three anti-176 ℃.Calculate according to the 3rd reactor outlet product analysis result: the total conversion rate of ethene is 75.5%, and conversion of ethylene is that the selectivity of vinyl acetic monomer is 93.2%, and the selectivity that is converted into superimposed alkene is 6.8%; The total conversion rate of propylene is 85.6%, and the selectivity that propylene is converted into Iso Butyl Acetate is 95.2%, and the selectivity that is converted into superimposed alkene is 4.8%; Do not detect heavy hydrocarbon greater than C8.
Instance 5
The silicon dioxide carried phospho-wolframic acid cesium salt of 30g (Cs respectively packs in three reactor drums
2.5H
0.5PW
12O
40/ SiO
2) catalyzer, with continuous first reactor drum that feeds of the speed of 30g/h, dry gas divides three stocks not with 25g/h with Glacial acetic acid min. 99.5,15g/h, and the speed of 10g/h gets into three reactor drums such as first, second grade, and the total feed of dry gas is 50g/h, for C
2 =+ C
3 =Total sour alkene mol ratio is 1.32, for C
2 =+ C
3 =Total feed weight air speed 0.37h
-1, be 180 ℃ in temperature of reaction, reaction pressure 3.0MPa reacts.The question response situation is stablized constant back (approximately needing 15h), analyzes through the six-way valve on-line sampling.
Operation result shows that behind system stability, the vertex temperature of reactor bed is respectively: 183 ℃ of one anti-187 ℃, two reactions, three anti-177 ℃.Calculate according to the 3rd reactor outlet product analysis result: the total conversion rate of ethene is 74.6%, and conversion of ethylene is that the selectivity of vinyl acetic monomer is 93.8%, and the selectivity that is converted into superimposed alkene is 6.2%; The total conversion rate of propylene is 84.8%, and the selectivity that propylene is converted into Iso Butyl Acetate is 95.9%, and the selectivity that is converted into superimposed alkene is 4.1%; Do not detect heavy hydrocarbon greater than C8.
Result by last embodiment can find out, provided by the invention is that the process that raw material is produced vinyl acetic monomer and Iso Butyl Acetate has following characteristics with rare ethene and propylene and acetic acid:
1, can adopt the ethene of lower concentration in the catalysis drying gas and/or propylene is raw material;
2, the addition esterifier has adopted alkene sectional tandem reactor, helps obtaining high sour alkene ratio, guarantees conversion of olefines and improves selectivity, prolongs the single-pass operation cycle of catalyzer simultaneously.
3, between each esterifier, adopt the direct charging of cold dry gas material, also can control reaction temperature rising with imitating, suppress the generation of side reaction.
Claims (7)
1. the preparation method of acetic acid second vinegar and/or Iso Butyl Acetate, be in the presence of solid acid catalyst in the virgin gas alkene and acetic acid carry out the addition esterification, generate vinyl acetic monomer and Iso Butyl Acetate, it is characterized in that:
(1) be raw material with the catalysis drying gas (comprising catalytic cracking, catalytic pyrolysis and thermal cracker) that contains low-concentration ethane and/or propylene;
(2) addition esterification adopts n fixed-bed reactor is composed in series reactive system; N=2-10 is equipped with acidic solid catalyst in each reactor drum, and is provided with bypass; Acetic acid is got into by first reactor drum; Dry gas share split by a certain percentage gets into each reactor drum, in reactive system, carries out virgin gas-acetic acid direct addition esterification, and reaction product is discharged reactive system by last reactor drum;
(3) low-concentration ethane and/or propylene are at 130-200 ℃, 2.0-3.0MPa, acetic acid and the molar ratio 1.3-4.4 of ethene+propylene, the weight hourly space velocity 0.1-0.37h of ethene+propylene
-1Condition under, contact with solid acid catalyst and to be converted into vinyl acetic monomer and/or Iso Butyl Acetate.
2. according to the described method of claim 1, it is characterized in that: raw materials used dry gas does not contain free-water, H
2S content＜20mg/m
3, CO
2＜6% volume, raw material do not need special purified again.
3. according to the described method of claim 1, it is characterized in that: addition esterification condition is temperature of reaction 150-180 ℃, reaction pressure 2.5-3.0MPa, acetic acid and the molar ratio 2.5-3.0 of ethene, the weight hourly space velocity 0.15-0.3h of ethene
-1
4. according to the described method of claim 1, it is characterized in that described acidic solid catalyst is carried heteropoly acid (salt), strongly acidic cationic exchange resin, molecular sieve, SO
4 2-/ ZrO
2Type solid super-strong acid, or their combination.
5. according to the described method of claim 1, it is characterized in that the share split charging is adopted in described dry gas charging, but acetic acid is got into by first reactor drum.
6. according to the described method of claim 1, it is characterized in that the reactor drum of described anabolic reaction system comprises various forms of solid-bed reactors, like shell and tube reactor, cartridge reactor, radial reactor etc., and each reactor drum is provided with bypass.
7. according to the described method of claim 1, it is characterized in that the number of the fixed-bed reactor of anabolic reaction system is n=3～5.
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Cited By (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN103214367A (en) * | 2013-05-09 | 2013-07-24 | 江苏瑞佳化学有限公司 | Continuous production device and method for isopropyl acetate |
| CN103342640A (en) * | 2013-07-04 | 2013-10-09 | 中国海洋石油总公司 | Method for synthesizing secbutyl acetate by acetic acid and mixed C4 |
| CN106800509A (en) * | 2015-11-26 | 2017-06-06 | 中国石油化工股份有限公司 | A kind of production method of isopropyl acetate |
| CN109456179A (en) * | 2017-09-06 | 2019-03-12 | 中国科学院大连化学物理研究所 | A kind of method that oil refinery dry gas prepares ethyl acetate |
| CN115784884A (en) * | 2022-12-20 | 2023-03-14 | 广东欧凯新材料有限公司 | Method for preparing methyl propionate by catalyzing ethylene in dry gas |
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