CN104230708A - Preparation method of methyl formate - Google Patents
Preparation method of methyl formate Download PDFInfo
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- CN104230708A CN104230708A CN201410530973.6A CN201410530973A CN104230708A CN 104230708 A CN104230708 A CN 104230708A CN 201410530973 A CN201410530973 A CN 201410530973A CN 104230708 A CN104230708 A CN 104230708A
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- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C67/00—Preparation of carboxylic acid esters
- C07C67/08—Preparation of carboxylic acid esters by reacting carboxylic acids or symmetrical anhydrides with the hydroxy or O-metal group of organic compounds
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J31/00—Catalysts comprising hydrides, coordination complexes or organic compounds
- B01J31/26—Catalysts comprising hydrides, coordination complexes or organic compounds containing in addition, inorganic metal compounds not provided for in groups B01J31/02 - B01J31/24
- B01J31/28—Catalysts comprising hydrides, coordination complexes or organic compounds containing in addition, inorganic metal compounds not provided for in groups B01J31/02 - B01J31/24 of the platinum group metals, iron group metals or copper
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J31/00—Catalysts comprising hydrides, coordination complexes or organic compounds
- B01J31/40—Regeneration or reactivation
- B01J31/4015—Regeneration or reactivation of catalysts containing metals
- B01J31/4023—Regeneration or reactivation of catalysts containing metals containing iron group metals, noble metals or copper
- B01J31/403—Regeneration or reactivation of catalysts containing metals containing iron group metals, noble metals or copper containing iron group metals or copper
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J2231/00—Catalytic reactions performed with catalysts classified in B01J31/00
- B01J2231/40—Substitution reactions at carbon centres, e.g. C-C or C-X, i.e. carbon-hetero atom, cross-coupling, C-H activation or ring-opening reactions
- B01J2231/49—Esterification or transesterification
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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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Abstract
The invention discloses a preparation method of methyl formate and belongs to the technical field of ester synthesis. According to the preparation method of the methyl formate, formic acid and methanol can react under the action of solid-phase catalyst to produce the methyl formate. The step of preparing the solid-phase catalyst comprises (a) adding kaolin into deionized water; (b) dissolving aluminum sulfate and copper sulfate into water to obtain solution, immersing the kaolin processed in the step (a) into the solution; (c) mixing cation exchange resin with a substance A and grinding the mixture to obtain a substance B; (d) preparing 30% carborane acid solution, immersing the substance B into the solution and taking the substance B out of the solution, drying the substance B in vacuum, roasting the substance B inside a muffle furnace, and grinding the substance B to obtain the solid-phase catalyst. The preparation method of the methyl formate is non-toxic and harmless, significantly improves the reaction velocity and is low in requirements on reaction conditions and energy consumption, and meanwhile, the catalyst is recyclable, so that the production cost can be effectively reduced, and the preparation method of the methyl formate is applicable to industrial production.
Description
Technical field
The invention belongs to the synthesis technical field of ester, specifically, relate to a kind of preparation method of methyl-formiate.
Background technology
Methyl-formiate, another name formic acid methyl ester is colourless dulcet volatile liquid.Miscible with ethanol, be dissolved in methyl alcohol, ether.Easy hydrolysis, the moisture in damp atmosphere also can make it be hydrolyzed.There is stronger hormesis to respiratory tract, eye, nose, pressure in chest, expiratory dyspnea can be caused.Methyl-formiate is the epochmaking intermediate of carbon geochemistry, and tool has been widely used, can directly with the smoke fumigant and the sterilant that deal with Yan grass, dried fruit, cereal etc.; Also the solvent of soluble cotton, cellulose acetate is commonly used for; Pharmaceutically, be commonly used for the synthesis material of the medicines such as sulfonic acid methyl pyrimidine, sulfonic acid Sulfamonomethoxine, anti-tussive agents dromethan.
At present, the method for producing methyl-formiate mainly contains: methyl alcohol formic acid esterification method, Liquid Phase Methanol carbonylation method, methanol dehydrogenation method, methanol oxidation dehydriding, formaldehyde dimerization method, synthetic gas direct synthesis technique etc.Wherein industrialized method has methyl alcohol formic acid esterification method, Liquid Phase Methanol carbonylation method and methanol dehydrogenation method.Methanol dehydrogenation method, because of technology also non-fully matured, is not also promoted the use of at present.Liquid Phase Methanol carbonylation method is the main method of external scale operation methyl-formiate.And domestic still with methyl alcohol formic acid esterification method for main method, but this method technique existing is backward, energy consumption is high, equipment corrosion is serious.
Chinese Patent Application No.: 201410225179.0, the applying date: on May 26th, 2014, disclose a kind of patent document preparing methyl-formiate method by name, this invention enters Tishchenko reaction by formaldehyde gas or containing formaldehyde gas gas mixture in reactor, reacts complete and obtains described methyl-formiate.In this reaction, formaldehyde is very big to the body harm of people, sucks and people too much may be made carcinogenic, and speed of reaction is slow, and danger is large and consuming time, should not apply.Chinese Patent Application No.: 201410007283.2, the applying date: on 01 07th, 2014, disclose a kind of patent document of method of gas-phase methanol carbonyl compound formic acid methyl esters, this invention adopts fixed bed reaction technique, and material benzenemethanol, carbon monoxide, hydrogen and oxygen carry out vapor phase carbonylation and is obtained by reacting methyl-formiate under the effect of loaded nano platinum metals heterogeneous catalyst.Reaction raw materials is methyl alcohol (10%-50%), carbon monoxide (10%-50%), hydrogen (10%-30%), oxygen (5%-20%) by volume, be 500-5000h-1 in air speed, temperature of reaction is 323K-423K, and reaction pressure is react under 0.01Mpa-2Mpa.This reaction cost is higher, the easy poisoning reduction catalytic activity of catalyzer, and cyclic utilization rate is lower, is not suitable for suitability for industrialized production.
Summary of the invention
The problem that 1, will solve
Novel process for existing production methyl-formiate exists that raw material hazardness is large, cost is higher, catalyzer is easily poisoning and speed of reaction is reduced, and there is the problems such as technique is backward, energy consumption is high, equipment corrosion is serious in traditional formic acid methanol esterification method, the invention provides a kind of cost low, toxicological harmless, energy consumption is low and reaction efficiency is high, to the free from corrosion method preparing methyl-formiate of equipment.
2. technical scheme
In order to overcome the above problems, the concrete technical scheme that the present invention adopts is as follows:
A preparation method for methyl-formiate, the method adopts formic acid and methyl alcohol to react under the effect of solid-phase catalyst and generates methyl-formiate.
Further, preparation process is: get 20-28 part formic acid, 10-20 part methyl alcohol and 5-8 part solid-phase catalyst by mass fraction and fully mix, react, can obtain methyl-formiate at 30-50 DEG C, 101KPa.
Preferably, described solid catalyst component and mass fraction are: Zeo-karb 10-20 part, kaolin 30-50 part, carborane acid 30-40 part, Tai-Ace S 150 5-7 part and copper sulfate 8-12 part.
Preferably, the preparation process of described solid-phase catalyst is:
A kaolin that () gets 30-50 part is placed in deionized water, stir 3-4 hour, at 80 DEG C dry, sieve after grinding, get 25-40 object particle roasting 1.5-2 hour at 350 DEG C, be cooled to 25 DEG C for subsequent use;
B () is got the water that 5-7 part Tai-Ace S 150 and 8-12 part copper sulfate adds 100 parts and is mixed with solution, then the kaolin after process in step (a) is immersed, be heated to 80 DEG C, insulation, stir 4-5 hour, after stirring, cooling, then uses deionized water wash, and in the loft drier of 120 DEG C, drying obtains substance A in 4 hours;
C () is got 10-20 part Zeo-karb and is mixed with substance A, grind 0.5 hour, obtain substance B;
D carborane acid that () gets 30-40 part is made into the carborane acid solution that massfraction is 30 ﹪, substance B is immersed in this solution, stir 5-6 hour, from solution, take out final vacuum dry 3 hours, be placed in retort furnace roasting 2.5-4 hour again, namely grinding obtains solid-phase catalyst.
Preferably, described Zeo-karb is strongly acidic styrene type cation exchange resin.
The recovery method of the solid-phase catalyst used in a kind of preparation method of methyl-formiate, to the steps include: used solid-phase catalyst to immerse quality be the massfraction of 1/3 of solid-phase catalyst quality is in the carborane acid solution of 30 ﹪, final vacuum is taken out dry 3 hours from solution, be placed in retort furnace roasting 2.5-4 hour again, grind the solid-phase catalyst be recycled.
The recovery method of the solid-phase catalyst used in a kind of preparation method of methyl-formiate, its step is identical with above, difference is the Potassium aluminum sulfate dodecahydrate adding the quality 1/5 equaling carborane acid in carborane acid solution, then vacuum-drying is placed on roasting 1.5-2 hour in retort furnace for 2 hours, grinds the solid-phase catalyst be recycled.
Parts all above all refers to mass fraction, and the portion of arbitrary substance in full all represents material identical in quality.
3. beneficial effect
Compared to prior art, beneficial effect of the present invention is:
(1) solid-phase catalyst of the present invention have employed Zeo-karb, kaolin, carborane acid, Tai-Ace S 150 and copper sulfate, this solid-phase catalyst form stable, reaction conditions requires low, carborane acid catalytic activity under cupric ion and aluminum ions effect of load significantly improves, increase the number that proton contacts with nonpolar reactant, this reaction can be carried out at a lower temperature, only need 30-50 DEG C, simultaneously less demanding for pressure, carry out under 101KPa condition, workable, energy consumption has been saved in this reaction simultaneously greatly, and kaolin is cheap and easy to get, effectively reduce cost, and non-oxidative, corrodibility is minimum, effectively decrease the generation of by product.
(2) the present invention adopts special technique by the load of Tai-Ace S 150 and copper sulfate on kaolin and resin, contribute to the absorption to reactant, and adsorption strength is moderate, active centre can be departed from very soon after reaction terminates, accelerate speed of reaction, Zeo-karb can the concentration of acid in equilibrium catalyst, and can absorb moisture, promotes that reaction is carried out to positive dirction.
(3) strongly acidic styrene type cation exchange resin used of the present invention can not only provide proton when reacting and starting, can also reaction carry out for some time after with the proton generation exchange interaction in solution, make the hydrogen ion in solid-phase catalyst can remain on a more stable state, catalyzer is recycled.
(4) used catalyst of the present invention easily reclaims after using, just reusable through process, has greatly saved cost.
(5) recovery method of used catalyst of the present invention, easy and simple to handle, and cost is low, is conducive to recycling of catalyzer, energy-conserving and environment-protective.
Embodiment
Below in conjunction with specific embodiment, the present invention is described in detail.
Embodiment 1
A preparation method for methyl-formiate, the steps include:
A kaolin that () gets 30 parts (in the present embodiment, every part refers to 100g) is placed in the deionized water of 5L, stirs 3 hours, dries, sieve after grinding at 80 DEG C, gets the roasting 2 hours at 350 DEG C of 25-40 object particle, be cooled to 25 DEG C for subsequent use;
B () is got the water that 6 parts of Tai-Ace S 150 and 8 parts of copper sulfate adds 100 parts and is mixed with solution, then the kaolin after process in step (a) is immersed, be heated to 80 DEG C, insulation, stir 4 hours, after stirring, cooling, then uses deionized water wash, washing and filtering, obtains substance A in 4 hours by the material drying in the loft drier of 120 DEG C after filtering;
C () is got 20 parts of Zeo-karbs (model is the strongly acidic styrene type cation exchange resin of Amberlite IR-120) and is mixed with the substance A obtained in step (b), grind 0.5 hour, obtain substance B;
D carborane acid that () gets 35 parts is made into the carborane acid solution that massfraction is 30 ﹪, the substance B obtained in step (c) is immersed in this solution, stir 5 hours, final vacuum is taken out dry 3 hours from solution, be placed in retort furnace roasting again 3 hours, namely grinding obtains solid-phase catalyst.
E () gets 23 parts of formic acid, 15 parts of methyl alcohol, and in 6 parts of steps (d), the solid-phase catalyst of preparation fully mixes, and reacts at 40-45 DEG C, 101KPa, after reaction 30min, obtains methyl-formiate.
By gas chromatography analysis method, the composition of analytical reaction thing and product, the productive rate of methyl-formiate is 98 ﹪, and reaction efficiency is high, and most importantly raw material hazardness is little, cost is low, catalyzer nontoxicity.
Embodiment 2
A preparation method for methyl-formiate, the steps include:
A kaolin that () gets 45 parts (in the present embodiment, every part refers to 100g) is placed in the deionized water of 6L, stir 3.5 hours, dry at 80 DEG C, sieve after grinding, get the roasting 1.5 hours at 350 DEG C of 25-40 object particle, be cooled to 25 DEG C for subsequent use;
B () is got 5 parts of Tai-Ace S 150 and 12 parts of copper sulfate and is joined in the water of 100 parts and be mixed with solution, then the kaolin after process in step (a) is immersed, be heated to 80 DEG C, insulation, stir 5 hours, after stirring, cooling, then uses deionized water wash, and in the loft drier of 120 DEG C, drying obtains substance A in 4 hours;
C () is got 10 parts of Zeo-karbs (selecting 732 strongly acidic styrene type cation exchange resins of Langfang Si Chuan Chemical Co., Ltd.) and is mixed with substance A, grind 0.5 hour, obtain substance B;
D carborane acid that () gets 40 parts is made into the carborane acid solution that massfraction is 30 ﹪, substance B is immersed in this solution, stir 5.5 hours, from solution, take out final vacuum dry 3 hours, be placed in retort furnace roasting again 4 hours, namely grinding obtains solid-phase catalyst.
E () gets 28 parts of formic acid, 20 parts of methyl alcohol, and in 8 parts of steps (d), the solid-phase catalyst of preparation fully mixes, and reacts at 30-35 DEG C, 101KPa, after reaction 50min, obtains methyl-formiate.
By gas chromatography analysis method, the composition of analytical reaction thing and product, the productive rate of methyl-formiate is 97.5 ﹪.
Embodiment 3
A preparation method for methyl-formiate, the steps include:
A kaolin that () gets 50 parts (in the present embodiment, every part refers to 100g) is placed in the deionized water of 5L, stirs 4 hours, dries, sieve after grinding at 80 DEG C, gets the roasting 1.8 hours at 350 DEG C of 25-40 object particle, be cooled to 25 DEG C for subsequent use;
B () is got the water that 7 parts of Tai-Ace S 150 and 10 parts of copper sulfate adds 100 parts and is mixed with solution, then the kaolin after process in step (a) is immersed, be heated to 80 DEG C, insulation, stir 4.5 hours, after stirring, cooling, then uses deionized water wash, and in the loft drier of 120 DEG C, drying obtains substance A in 4 hours;
C () is got 10-20 part Zeo-karb and is mixed with substance A, grind 0.5 hour, obtain substance B;
D carborane acid that () gets 30 parts is made into the carborane acid solution that massfraction is 30 ﹪, substance B is immersed in this solution, stir 6 hours, from solution, take out final vacuum dry 3 hours, be placed in retort furnace roasting again 2.5 hours, namely grinding obtains solid-phase catalyst.E () gets 20 parts of formic acid, 10 parts of methyl alcohol, and in 6 parts of steps (d), the solid-phase catalyst of preparation fully mixes, and reacts at 30-35 DEG C, 101KPa, after reaction 40min, obtains methyl-formiate.
By gas chromatography analysis method, the composition of analytical reaction thing and product, the productive rate of methyl-formiate is 99.1 ﹪.Can find by contrasting above embodiment, in embodiment 2, the molar mass ratio of formic acid and methyl alcohol is less than 1, and in embodiment 3, the molar mass ratio of formic acid and methyl alcohol is greater than 1, illustrate that the molar mass of this solid-phase catalyst at formic acid and methyl alcohol is than being greater than when 1, the productive rate of methyl-formiate is higher.
Embodiment 4
After solid-phase catalyst uses for some time, speed of response and efficiency can reduce, it is in the carborane acid solution of 1/3 of solid-phase catalyst quality that solid-phase catalyst used in embodiment 1 is immersed quality, wherein in carborane acid solution, the massfraction of carborane acid is 30 ﹪, final vacuum is taken out dry 3 hours from solution, be placed in retort furnace roasting 2.5-4 hour again, grind the solid-phase catalyst be recycled.The solid-phase catalyst reclaimed still can continue to use as the solid catalyst in step (e) in enforcement 1, and reaction times and efficiency are still identical with new.
Embodiment 5
After solid-phase catalyst uses for some time, speed of response and efficiency can reduce, it is that in the carborane acid solution of 1/3 of solid-phase catalyst quality, (massfraction of the total soluble matters in carborane acid solution is wherein 30 ﹪ that solid-phase catalyst used in embodiment 1 is immersed quality, solute is carborane acid and Potassium aluminum sulfate dodecahydrate, wherein the quality of Potassium aluminum sulfate dodecahydrate equals 1/5 of the quality of carborane acid), then from solution, final vacuum is taken out dry 2 hours, be placed in retort furnace roasting again 1.5-2 hour (fewer than the used time of embodiment 4), grind the solid-phase catalyst be recycled.The solid-phase catalyst reclaimed still can continue to use as the solid catalyst in step (e) in enforcement 2, and reaction times and efficiency are still identical with new.
Claims (7)
1. a preparation method for methyl-formiate, is characterized in that, the method adopts formic acid and methyl alcohol to react under the effect of solid-phase catalyst and generates methyl-formiate.
2. the preparation method of a kind of methyl-formiate according to claim 1, it is characterized in that, described step is: get 20-28 part formic acid, 10-20 part methyl alcohol and 5-8 part solid-phase catalyst by mass fraction and fully mix, at 30-50 DEG C, 101KPa reacts, and obtains methyl-formiate.
3. the preparation method of a kind of methyl-formiate according to claim 1, it is characterized in that, described solid catalyst component and mass fraction are: Zeo-karb 10-20 part, kaolin 30-50 part, carborane acid 30-40 part, Tai-Ace S 150 5-7 part and copper sulfate 8-12 part.
4. the preparation method of a kind of methyl-formiate according to claim 1, is characterized in that, the preparation process of described solid-phase catalyst is:
A kaolin that () gets 30-50 part by mass fraction is placed in deionized water, stir 3-4 hour, at 80 DEG C dry, sieve after grinding, get 25-40 object particle roasting 1.5-2 hour at 350 DEG C, be cooled to 25 DEG C for subsequent use;
B () is got the water that 5-7 part Tai-Ace S 150 and 8-12 part copper sulfate adds 100 parts and is mixed with solution, then the kaolin after process in step (a) is immersed, be heated to 80 DEG C, insulation, stir 4-5 hour, after stirring, cooling, then uses deionized water wash, and in the loft drier of 120 DEG C, drying obtains substance A in 4 hours;
C () is got 10-20 part Zeo-karb and is mixed with substance A, grind 0.5 hour, obtain substance B;
D carborane acid that () gets 30-40 part is made into the carborane acid solution that massfraction is 30 ﹪, substance B is immersed in this solution, stir 5-6 hour, from solution, take out final vacuum dry 3 hours, be placed in retort furnace roasting 2.5-4 hour again, namely grinding obtains solid-phase catalyst.
5. the preparation method of a kind of methyl-formiate according to claim 3 or 4, is characterized in that, described Zeo-karb is strongly acidic styrene type cation exchange resin.
6. the recovery method of the solid-phase catalyst used in the preparation method of a kind of methyl-formiate according to claim 1, to the steps include: used solid-phase catalyst to immerse quality be the massfraction of 1/3 of solid-phase catalyst quality is in the carborane acid solution of 30 ﹪, final vacuum is taken out dry 3 hours from solution, be placed in retort furnace roasting 2.5-4 hour again, grind the solid-phase catalyst be recycled.
7. the recovery method of the solid-phase catalyst used in the preparation method of a kind of methyl-formiate according to claim 1, its step is identical with claim 6, difference is the Potassium aluminum sulfate dodecahydrate adding the quality 1/5 equaling carborane acid in carborane acid solution, then vacuum-drying is placed on roasting 1.5-2 hour in retort furnace for 2 hours, grinds the solid-phase catalyst be recycled.
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CN201510390363.5A CN105013539B (en) | 2014-10-10 | 2014-10-10 | Solid phase catalyst for preparing methyl formate, preparation method therefor and application thereof |
CN201410530973.6A CN104230708B (en) | 2014-10-10 | 2014-10-10 | A kind of preparation method of methyl-formiate |
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Cited By (2)
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CN106397191A (en) * | 2016-08-29 | 2017-02-15 | 吴琦琪 | Catalytic preparation method for methyl oleate |
CN106478416A (en) * | 2016-08-28 | 2017-03-08 | 安徽金邦医药化工有限公司 | A kind of preparation method of methyl formate |
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CN110777529A (en) * | 2019-11-25 | 2020-02-11 | 王言 | Preparation method of antibacterial agent for textile fabric |
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US2928853A (en) * | 1957-12-02 | 1960-03-15 | Houdry Process Corp | Esterification and catalysts therefor |
RU2377232C2 (en) * | 2007-03-28 | 2009-12-27 | Олег Николаевич Новиков | Method of producing methyl formate |
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CN1053390C (en) * | 1996-01-08 | 2000-06-14 | 焦佩玉 | Catalyst for esterification reaction and method for preparing same |
CN1136470A (en) * | 1996-01-08 | 1996-11-27 | 焦佩玉 | Catalyst for esterification reaction and its preparing method |
KR101049561B1 (en) * | 2009-09-08 | 2011-07-14 | 주식회사 엘지화학 | Manufacturing Method of (meth) acrylate |
CN101948385B (en) * | 2010-07-12 | 2013-12-11 | 江门谦信化工发展有限公司 | Method for composing butyl acetate |
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US2928853A (en) * | 1957-12-02 | 1960-03-15 | Houdry Process Corp | Esterification and catalysts therefor |
RU2377232C2 (en) * | 2007-03-28 | 2009-12-27 | Олег Николаевич Новиков | Method of producing methyl formate |
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Cited By (2)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
CN106478416A (en) * | 2016-08-28 | 2017-03-08 | 安徽金邦医药化工有限公司 | A kind of preparation method of methyl formate |
CN106397191A (en) * | 2016-08-29 | 2017-02-15 | 吴琦琪 | Catalytic preparation method for methyl oleate |
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CN105013539A (en) | 2015-11-04 |
CN104230708B (en) | 2015-12-09 |
CN105013539B (en) | 2017-04-19 |
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