CN101481304A - Process for preparing formic acid by hydrolyzing methyl formate - Google Patents
Process for preparing formic acid by hydrolyzing methyl formate Download PDFInfo
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- CN101481304A CN101481304A CNA2009100245830A CN200910024583A CN101481304A CN 101481304 A CN101481304 A CN 101481304A CN A2009100245830 A CNA2009100245830 A CN A2009100245830A CN 200910024583 A CN200910024583 A CN 200910024583A CN 101481304 A CN101481304 A CN 101481304A
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- formic acid
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- BDAGIHXWWSANSR-UHFFFAOYSA-N methanoic acid Natural products OC=O BDAGIHXWWSANSR-UHFFFAOYSA-N 0.000 title claims abstract description 87
- TZIHFWKZFHZASV-UHFFFAOYSA-N methyl formate Chemical compound COC=O TZIHFWKZFHZASV-UHFFFAOYSA-N 0.000 title claims abstract description 46
- OSWFIVFLDKOXQC-UHFFFAOYSA-N 4-(3-methoxyphenyl)aniline Chemical compound COC1=CC=CC(C=2C=CC(N)=CC=2)=C1 OSWFIVFLDKOXQC-UHFFFAOYSA-N 0.000 title claims abstract description 40
- 235000019253 formic acid Nutrition 0.000 title claims abstract description 40
- 230000003301 hydrolyzing effect Effects 0.000 title abstract description 3
- 238000004519 manufacturing process Methods 0.000 title abstract description 3
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 claims abstract description 110
- 238000006243 chemical reaction Methods 0.000 claims abstract description 44
- 238000000605 extraction Methods 0.000 claims abstract description 36
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 31
- 238000006460 hydrolysis reaction Methods 0.000 claims abstract description 29
- 230000007062 hydrolysis Effects 0.000 claims abstract description 28
- 230000003197 catalytic effect Effects 0.000 claims abstract description 22
- 238000010992 reflux Methods 0.000 claims description 20
- 239000003054 catalyst Substances 0.000 claims description 18
- 241000282326 Felis catus Species 0.000 claims description 17
- 238000005516 engineering process Methods 0.000 claims description 16
- 238000000895 extractive distillation Methods 0.000 claims description 13
- 239000003795 chemical substances by application Substances 0.000 claims description 12
- 238000007599 discharging Methods 0.000 claims description 9
- 238000011049 filling Methods 0.000 claims description 9
- 239000002253 acid Substances 0.000 claims description 8
- 239000003729 cation exchange resin Substances 0.000 claims description 7
- NWUYHJFMYQTDRP-UHFFFAOYSA-N 1,2-bis(ethenyl)benzene;1-ethenyl-2-ethylbenzene;styrene Chemical compound C=CC1=CC=CC=C1.CCC1=CC=CC=C1C=C.C=CC1=CC=CC=C1C=C NWUYHJFMYQTDRP-UHFFFAOYSA-N 0.000 claims description 6
- 239000002994 raw material Substances 0.000 claims description 5
- 238000004064 recycling Methods 0.000 claims description 4
- 239000011259 mixed solution Substances 0.000 claims description 3
- 238000000034 method Methods 0.000 abstract description 11
- 238000000926 separation method Methods 0.000 abstract description 6
- 238000005265 energy consumption Methods 0.000 abstract description 4
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 abstract 1
- 239000007864 aqueous solution Substances 0.000 abstract 1
- 230000006837 decompression Effects 0.000 abstract 1
- 239000000463 material Substances 0.000 description 15
- 239000000047 product Substances 0.000 description 8
- 230000009466 transformation Effects 0.000 description 5
- 238000005844 autocatalytic reaction Methods 0.000 description 4
- 239000000945 filler Substances 0.000 description 4
- 239000000243 solution Substances 0.000 description 4
- 230000006315 carbonylation Effects 0.000 description 2
- 238000005810 carbonylation reaction Methods 0.000 description 2
- 238000006555 catalytic reaction Methods 0.000 description 2
- 239000003480 eluent Substances 0.000 description 2
- 238000005342 ion exchange Methods 0.000 description 2
- 239000000126 substance Substances 0.000 description 2
- 238000010521 absorption reaction Methods 0.000 description 1
- 150000007933 aliphatic carboxylic acids Chemical class 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 229940023913 cation exchange resins Drugs 0.000 description 1
- 239000004568 cement Substances 0.000 description 1
- 238000005119 centrifugation Methods 0.000 description 1
- 235000013339 cereals Nutrition 0.000 description 1
- 229920001429 chelating resin Polymers 0.000 description 1
- 239000012295 chemical reaction liquid Substances 0.000 description 1
- 239000007795 chemical reaction product Substances 0.000 description 1
- 239000012141 concentrate Substances 0.000 description 1
- 238000010924 continuous production Methods 0.000 description 1
- 230000007812 deficiency Effects 0.000 description 1
- 238000010586 diagram Methods 0.000 description 1
- 238000004043 dyeing Methods 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 150000002148 esters Chemical class 0.000 description 1
- 239000004744 fabric Substances 0.000 description 1
- 239000002638 heterogeneous catalyst Substances 0.000 description 1
- 239000004816 latex Substances 0.000 description 1
- 229920000126 latex Polymers 0.000 description 1
- 239000010985 leather Substances 0.000 description 1
- 238000005649 metathesis reaction Methods 0.000 description 1
- 238000004321 preservation Methods 0.000 description 1
- 239000000376 reactant Substances 0.000 description 1
- 239000011541 reaction mixture Substances 0.000 description 1
- 239000011347 resin Substances 0.000 description 1
- 229920005989 resin Polymers 0.000 description 1
- 239000007787 solid Substances 0.000 description 1
- 238000003786 synthesis reaction Methods 0.000 description 1
- 239000004753 textile Substances 0.000 description 1
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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
- Y02P20/10—Process efficiency
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- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
Abstract
The invention discloses a process for preparing formic acid by hydrolyzing methyl formate. Methyl formate containing methanol firstly enters a methyl formate tower for separation, methanol is extracted from the tower bottom, and the methyl formate extracted from the tower top enters a catalytic rectifying tower; methyl formate and water are hydrolyzed in the reaction section of the catalytic rectifying tower, the methyl formate and methanol extracted from the tower top are returned to the methyl formate tower for separation, and the formic acid aqueous solution extracted from the tower bottom enters the extraction rectifying tower; adding an extractant from the top of the extraction rectifying tower, extracting water from the top of the tower, and feeding the extractant, formic acid and a small amount of water extracted from the bottom of the tower into a reduced pressure rectifying tower; after decompression separation, the extractant extracted from the tower bottom is circulated to the extraction rectifying tower, and formic acid product with mass concentration of 85-99% is extracted from the tower top. The invention can lead the one-way hydrolysis conversion rate of the methyl formate to reach 70 to 99 percent, simultaneously shortens the process flow and saves the equipment investment and the energy consumption.
Description
Technical field
The present invention relates to a kind of technology of preparing aminic acid by methyl formate hydrolysis.
Background technology
Formic acid (Formic acid is called for short FA) is the simplest non-replacement aliphatic carboxylic acid, a kind of important basic Organic Chemicals.Have been widely used at aspects such as the preservation of organic synthesis, leather industry, textile and dyeing industry, green fodder and cereal, latex, cement.
At present in the formic acid industrial process, the most promising, most economical reasonably is the methyl formate hydrolysis method, and all to adopt the autocatalysis hydrolysis process be that the synthetic methyl-formiate direct hydrolysis under autocatalysis (product formic acid is as catalyzer) condition of methyl alcohol and CO carbonylation is produced formic acid.Tank reactor or tubular reactor are adopted in hydrolysis, but no matter which kind of type owing to be homogeneous reaction, suppressed the carrying out of positive reaction with reaction product formic acid as catalyzer, and has been subjected to the restriction of chemical equilibrium, cause the one way hydrolysis conversion generally not high.
In recent years, methyl formate hydrolysis technology has been done a large amount of research both at home and abroad.CN1066442A has developed a kind of continuous hydrolysis novel process of preparing aminic acid by methyl formate hydrolysis, make catalyzer with the hydrolyzed solution that partly returns and carry out self-catalyzed reaction, the ratio of rework solution need be effectively controlled in this invention, operates more loaded down with trivial detailsly, and partial reaction liquid returns and reduced throughput.CN1086508A in filling up the metathesis reactor (tubular or disc) of strongly-acid sulfonic group Zeo-karb as heterogeneous catalyst in 80～100 ℃ of following continuous hydrolysis methyl-formiates, and the mixed solution that generates is all sent into follow-up negative pressure knockout tower isolate thick formic acid, this invention has reduced water to ester ratio, improved transformation efficiency, continuous production, but reaction mixture need enter the quaternary knockout tower to be separated, and can not effectively prevent the resterification of methyl alcohol and formic acid.US6429333 utilizes the catalysis and the absorption attribute of exchange of solids material in the ion exchange bed, the hydrolysis methyl-formiate obtains formic acid and methyl alcohol, takes methyl alcohol out of with eluent simultaneously, and take place separating of formic acid and methyl alcohol, and then separation of methanol and eluent, this method has reduced the resterification of formic acid and methyl alcohol in reaction, improved percent hydrolysis, but ion exchange bed is comparatively complicated, be not easy to operation, and the methyl alcohol that washes away needs to separate again, and the discharging hydrolyzed solution also needs to separate complex process again.
Summary of the invention
The present invention is directed to existing methyl formate hydrolysis method, to produce the formic acid technical process long, and the one way hydrolysis conversion is not high, and the high deficiency of energy consumption provides a kind of technology of preparing aminic acid by methyl formate hydrolysis, shortens flow process, cuts down the consumption of energy raising methyl-formiate one way hydrolysis conversion.
The present invention's technical scheme that is adopted of dealing with problems is:
A kind of technology of preparing aminic acid by methyl formate hydrolysis, concrete steps are as follows:
(1) methyl-formiate that contains methyl alcohol enters methyl-formiate tower T1 and separates tower still extraction methyl alcohol, cat head extraction methyl-formiate;
(2) catalytic rectifying tower T2 is followed successively by catalyst reaction section, stripping section from top to bottom, from the methyl-formiate of T1 cat head extraction from the conversion zone bottom feed, water is from the conversion zone its top feed, methyl-formiate and water are in the catalyst reaction section reaction that is hydrolyzed, the discharging of tower still is an aqueous formic acid, and the methyl-formiate of cat head extraction separates with methanol loop to T1 tower;
(3) discharging of T2 tower still enters extractive distillation column T3 and separates, and extraction agent adds from this top of tower, and the discharging of tower still is the mixed solution of extraction agent, formic acid and less water, the cat head recovered water;
(4) discharging of T3 tower still enters rectification under vacuum tower T4 and separates, and the extraction agent of tower still extraction is circulated to extractive distillation column T3 recycling, cat head extraction formic acid product.
The methyl-formiate that contains methyl alcohol in the above-mentioned steps 1 is combined to methyl-formiate workshop section from methanol carbonyl, and methyl-formiate tower T1 reflux ratio is (0.5～5): 1, and theoretical plate number is 10～60.
Catalytic rectifying tower T2 catalyst reaction section theoretical plate number is 10～40 in the above-mentioned steps 2, the stripping section theoretical plate number is 10～50, the catalyzer of filling in the catalyst reaction section is a storng-acid cation exchange resin, the tower working pressure is 1～1.2atm, the raw materials components mole ratio of water and methyl-formiate is (1～8): 1, reflux ratio is (0.5～8): 1, the charging air speed be 0.05～1 cubic metre/(cubic meter reaction volume hour).
The methyl alcohol of tower still extraction returns methanol carbonyl and is combined to methyl-formiate workshop section in the above-mentioned steps 1.
Extractive distillation column T3 reflux ratio is (0.5～3) in the above-mentioned steps 3: 1, and theoretical plate number is 10～40, the cat head recovered water is circulated to catalytic rectifying tower T2 recycling.
Rectification under vacuum tower T4 reflux ratio is (0.5～4) in the above-mentioned steps 4: 1, and theoretical plate number is 10～50, the mass concentration of formic acid product is 85%～99%.
The present invention is described in further detail below in conjunction with accompanying drawing 1.
Methyl-formiate tower T1 is the knockout tower of methyl-formiate and methyl alcohol, interior filling conventional fillers or column plate, the methyl-formiate of producing from carbonylation of methanol workshop section that contains methyl alcohol is that material A enters this tower separation, further remove the methyl alcohol in the methyl-formiate, the methyl alcohol of tower still extraction is that material K returns methanol carbonyl and is combined to methyl-formiate workshop section, and the methyl-formiate of cat head extraction is that material B enters catalytic rectifying tower T2.
Catalytic rectifying tower T2 is divided into upper reaction section 1 and bottom stripping section 2, fill storng-acid cation exchange resin in the conversion zone, the filling of catalyzer, rolls into catalyst filling cylindraceous and ties up bag with wire cloth with little thin layer sack lining, stripping section filling conventional fillers or column plate.Water is that material C is from the conversion zone its top feed, material B is from the conversion zone bottom feed, methyl-formiate and the water reaction that is hydrolyzed in catalyst reaction section, generate methyl alcohol and formic acid, reacting section catalyst also plays isolating effect simultaneously, the methyl-formiate of cat head extraction and methyl alcohol are that material D returns the methyl-formiate tower and separates, and the formic acid of tower still extraction and water are that material E enters extractive distillation column T3.
Material E enters extractive distillation column T3, and interior filling conventional fillers or column plate, extraction agent are that material F adds from cat head, and the water of cat head extraction is that material G is circulated to catalytic rectifying tower, and extraction agent, formic acid and the less water of tower still extraction is that material H enters rectification under vacuum tower T4.
Material H enters rectification under vacuum tower T4, and interior filling conventional fillers or column plate, the extraction agent of tower still extraction are that material J is circulated to extractive distillation column, and the formic acid product that the cat head extraction contains less water is material I.
Beneficial effect:
(1) uses the storng-acid cation exchange resin catalytic hydrolysis reaction, do not need to carry out again prehydrolysis and obtain autocatalysis again behind the formic acid, do not need to adopt a large amount of excessive water to promote positive reaction to carry out yet and suppress reversed reaction, and will have hydrolytic reaction pot and hydrolyzed solution knockout tower, flasher or the low tower that boils in the technology now, all concentrate on a catalytic rectifying tower, make reaction carry out, shortened technical process with separating simultaneously.
(2) adopt formic acid autocatalysis hydrolysis all under High Temperature High Pressure, to carry out, and catalytic rectifying tower carry out, and makes operation be more prone to, and has saved energy consumption under normal pressure.
(3) because catalyst reaction section reactant and resultant all are dynamic flow, and resin itself has centrifugation, makes the touch opportunity of formic acid and methyl alcohol obviously reduce, and effectively prevented resterification, improved the one way hydrolysis conversion.
(4) under the operational condition of optimizing, the methyl formate hydrolysis transformation efficiency can reach more than 90%, has effectively improved one way hydrolysis conversion and catalytic rectifying tower still formic acid concn, and later separation is more prone to.
(5) this technology is operate continuously, has improved throughput, has reduced energy consumption.
Description of drawings
Fig. 1 is a preparing aminic acid by methyl formate hydrolysis process flow diagram provided by the invention:
Wherein, T1 methyl-formiate tower, T2 catalytic rectifying tower, T3 extractive distillation column, T4 formic acid tower, 1 catalyst reaction section, 2 stripping sections, 3 condensers, 4 reboilers, A contain the methyl-formiate of methyl alcohol, the B methyl-formiate, C water, D methyl alcohol and methyl-formiate, E formic acid and water, F replenishes extraction agent, G water, H extraction agent, formic acid and less water, I contains the formic acid product of less water, J extraction agent, K methyl alcohol.
Embodiment
The invention will be further described below by specific embodiment, but the present invention should be interpreted as and only limit to following embodiment.
Embodiment 1
The methyl-formiate raw material that contains methyl alcohol enters methyl-formiate tower T1 to be separated, reflux ratio 1, and theoretical plate number 50 obtains the methyl-formiate of mass content 95% after separating treatment; Control water and methyl-formiate mol ratio enter catalytic rectifying tower T2 at 1: 1, superficial velocity be 0.1 cubic metre/(cubic meter reaction volume hour), catalyzer is a D072 type macropore strong acid cation exchange resin, catalytic rectifying tower T2 catalyst reaction section theoretical plate number 15, stripping section theoretical plate number 20, reflux ratio 7, the methyl formate hydrolysis transformation efficiency reaches 70%; Extractive distillation column theoretical plate number 15, reflux ratio 3, rectification under vacuum tower theoretical plate number 20, reflux ratio 3 finally can obtain the formic acid product of mass content 90%.
Embodiment 2
The methyl-formiate raw material that contains methyl alcohol enters methyl-formiate tower T1 to be separated, reflux ratio 3, theoretical plate number 40, after separating treatment, obtain the methyl-formiate of mass content 98%, control water and methyl-formiate 4:1 in molar ratio enter catalytic rectifying tower T2, superficial velocity be 0.4 cubic metre/(cubic meter reaction volume hour), catalyzer is a D072 type macropore strong acid cation exchange resin, catalytic rectifying tower T2 catalyst reaction section theoretical plate number 25, stripping section theoretical plate number 30, reflux ratio 4, the methyl formate hydrolysis transformation efficiency reaches 80%, extractive distillation column theoretical plate number 25, reflux ratio 2, rectification under vacuum tower theoretical plate number 30, reflux ratio 2 finally can obtain the formic acid product of mass content 98%.
The methyl-formiate raw material that contains methyl alcohol enters methyl-formiate tower T1 to be separated, reflux ratio 4, theoretical plate number 20, after separating treatment, obtain the methyl-formiate of mass content 98%, control water and methyl-formiate 7:1 in molar ratio enter catalytic rectifying tower T2, superficial velocity be 0.8 cubic metre/(cubic meter reaction volume hour), catalyzer is Amberlyst 35 storng-acid cation exchange resins, catalytic rectifying tower T2 catalyst reaction section theoretical plate number 30, stripping section theoretical plate number 40, reflux ratio 1, the methyl formate hydrolysis transformation efficiency reaches 90%, extractive distillation column theoretical plate number 30, reflux ratio 1, rectification under vacuum tower theoretical plate number 40, reflux ratio 1 finally can obtain the formic acid product of mass content 95%.
Claims (8)
1. the technology of a preparing aminic acid by methyl formate hydrolysis, concrete steps are as follows:
(1) methyl-formiate that contains methyl alcohol enters methyl-formiate tower T1 and separates tower still extraction methyl alcohol, cat head extraction methyl-formiate;
(2) catalytic rectifying tower T2 is followed successively by catalyst reaction section, stripping section from top to bottom; From the methyl-formiate of T1 cat head extraction from the catalyst reaction section bottom feed, water is from the catalyst reaction section its top feed, methyl-formiate and water are in the catalyst reaction section reaction that is hydrolyzed, and the discharging of tower still is an aqueous formic acid, and the methyl-formiate of cat head extraction separates with methanol loop to T1 tower;
(3) discharging of T2 tower still enters extractive distillation column T3 and separates, and extraction agent adds from this top of tower, and the discharging of tower still is the mixed solution of extraction agent, formic acid and less water, the cat head recovered water;
(4) discharging of T3 tower still enters rectification under vacuum tower T4 and separates, and the extraction agent of tower still extraction is circulated to extractive distillation column T3 recycling, cat head extraction formic acid product.
2. technology according to claim 1 is characterized in that the methyl-formiate that contains methyl alcohol is combined to methyl-formiate workshop section from methanol carbonyl.
3. technology according to claim 1 is characterized in that methyl-formiate tower T1 reflux ratio is 0.5～5: 1, and theoretical plate number is 10～60.
4. technology according to claim 1, it is characterized in that among the catalytic rectifying tower T2, the catalyst reaction section theoretical plate number is 10～40, the stripping section theoretical plate number is 10～50, the catalyzer of filling in the catalyst reaction section is a storng-acid cation exchange resin, and working pressure is 1～1.2atm, and the raw materials components mole ratio of water and methyl-formiate is 1～8:1, reflux ratio is 0.5～8:1, the charging air speed be 0.05～1 cubic metre/(cubic meter reaction volume hour).
5. technology according to claim 1 is characterized in that extractive distillation column T3 reflux ratio is 0.5～3:1, theoretical plate number 10～40.
6. technology according to claim 1 is characterized in that rectification under vacuum tower T4 reflux ratio is 0.5～4:1, and theoretical plate number is 10～50.
7. technology according to claim 1 is characterized in that step (3) cat head recovered water is circulated to catalytic rectifying tower T2 recycling.
8. technology according to claim 1 is characterized in that the mass concentration of the described formic acid product of step (4) is 85%～99%.
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| CN2009100245830A CN101481304B (en) | 2009-02-20 | 2009-02-20 | Process for preparing formic acid by hydrolyzing methyl formate |
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| CN101481304B CN101481304B (en) | 2012-07-04 |
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Cited By (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101805252A (en) * | 2010-04-06 | 2010-08-18 | 南京工业大学 | Process for producing formic acid |
| CN102617321A (en) * | 2012-03-12 | 2012-08-01 | 浙江大学 | Method for producing methanoic acid by hydrolyzing methyl formate |
| WO2013030162A1 (en) | 2011-08-27 | 2013-03-07 | Taminco | Process of formic acid production by hydrolysis of methyl formate |
| CN104771924A (en) * | 2015-04-15 | 2015-07-15 | 中国科学院广州能源研究所 | Device and method for preparing coupled and rectified ethanol by furfural |
| CN114057563A (en) * | 2020-08-06 | 2022-02-18 | 天津华信化工技术有限公司 | Method for rectifying and hydrolyzing organic acid ester by slurry catalytic reaction |
Family Cites Families (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| DE60002597T2 (en) * | 1999-10-13 | 2004-08-05 | Sulzer Chemtech Ag | METHOD FOR THE HYDROLYTIC PRODUCTION OF A CARBOXYLIC ACID AND ALCOHOL FROM THE CORRESPONDING CARBOXYLATE |
| DE10002791A1 (en) * | 2000-01-24 | 2001-07-26 | Basf Ag | Production of anhydrous formic acid by hydrolyzing methyl formate comprises introducing methanol-containing methyl formate into distillation column used to distil hydrolysis mixture |
| CN1380273A (en) * | 2002-03-01 | 2002-11-20 | 福州大学 | Methyl acetate hydrolysis process and its equipment |
| CN101186575B (en) * | 2007-12-04 | 2010-04-14 | 南京工业大学 | Methyl acetate catalytic rectification hydrolysis process |
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2009
- 2009-02-20 CN CN2009100245830A patent/CN101481304B/en not_active Expired - Fee Related
Cited By (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101805252A (en) * | 2010-04-06 | 2010-08-18 | 南京工业大学 | Process for producing formic acid |
| WO2013030162A1 (en) | 2011-08-27 | 2013-03-07 | Taminco | Process of formic acid production by hydrolysis of methyl formate |
| CN102617321A (en) * | 2012-03-12 | 2012-08-01 | 浙江大学 | Method for producing methanoic acid by hydrolyzing methyl formate |
| CN102617321B (en) * | 2012-03-12 | 2014-05-07 | 浙江大学 | Method for producing methanoic acid by hydrolyzing methyl formate |
| CN104771924A (en) * | 2015-04-15 | 2015-07-15 | 中国科学院广州能源研究所 | Device and method for preparing coupled and rectified ethanol by furfural |
| CN104771924B (en) * | 2015-04-15 | 2016-06-08 | 中国科学院广州能源研究所 | A kind of devices and methods therefor of furfural preparation coupling ethanol rectification |
| CN114057563A (en) * | 2020-08-06 | 2022-02-18 | 天津华信化工技术有限公司 | Method for rectifying and hydrolyzing organic acid ester by slurry catalytic reaction |
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