CN101481304B - Process for preparing aminic acid by methyl formate hydrolysis - Google Patents
Process for preparing aminic acid by methyl formate hydrolysis Download PDFInfo
- Publication number
- CN101481304B CN101481304B CN2009100245830A CN200910024583A CN101481304B CN 101481304 B CN101481304 B CN 101481304B CN 2009100245830 A CN2009100245830 A CN 2009100245830A CN 200910024583 A CN200910024583 A CN 200910024583A CN 101481304 B CN101481304 B CN 101481304B
- Authority
- CN
- China
- Prior art keywords
- tower
- methyl
- formiate
- extraction
- methyl formate
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Expired - Fee Related
Links
Images
Classifications
-
- 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
Abstract
The invention discloses a process for preparing methanoic acid by methyl formate hydrolysis. The process comprises the following steps: methyl formate containing methanol is firstly sent to a methyl formate tower for separation, the methanol is extracted at the tower bottom, and the methyl formate extracted at the tower top is sent to a catalytic rectification tower; the methyl formate hydrolyzeswith water in a reaction section of the catalytic rectification tower, the methyl formate extracted at the tower top and the methanol are returned to the methyl formate tower for separation, and methanoic acid aqueous solution extracted at the tower bottom is sent to an extraction rectification tower; an extractant is added from the top of the extraction rectification tower, the water is extracted at the tower top, the extractant, the methanoic acid and a small quantity of the water which are extracted at the tower bottom are sent to a vacuum rectification tower; and the extractant extracted at the tower bottoms circulates to the extraction rectification tower after decompression and separation, and the methanoic acid product with 85%-99% mass concentration is extracted at the tower top. The process can cause the one-way hydrolysis conversion rate of the methyl formate to reach 70%-99%, shortens process flow and saves equipment investment and 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 received 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 all send into follow-up negative pressure knockout tower to the mixed solution that generates and isolate thick formic acid; This invention has reduced water to ester ratio, has improved transformation efficiency, continuous production; But reaction mixture need get into 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 absorption attribute of exchange of solids material in the ion exchange bed, and the hydrolysis methyl-formiate obtains formic acid and methyl alcohol, takes methyl alcohol out of with eluent simultaneously; 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, is 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 following:
(1) the methyl-formiate entering methyl-formiate tower T1 that contains methyl alcohol 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 top fed; 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) T2 tower still discharging entering extractive distillation column T3 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) T3 tower still discharging entering rectification under vacuum tower T4 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 strongly acidic cationic exchange resin, and the tower 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).
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%.
1 couple of the present invention makes further detailed description below in conjunction with accompanying drawing.
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 gets into 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 gets into catalytic rectifying tower T2.
Catalytic rectifying tower T2 is divided into upper reaction section 1 and bottom stripping section 2; Fill strongly acidic cationic 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 top fed; Material B is from the conversion zone bottom feed; Methyl-formiate and the water reaction that is hydrolyzed in catalyst reaction section generates methyl alcohol and formic acid, and 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 gets into extractive distillation column T3.
Material E gets into 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 gets into rectification under vacuum tower T4.
Material H gets into 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 strongly acidic cationic exchange resin catalytic hydrolysis reaction; Do not need to carry out again prehydrolysis and obtain autocatalysis again behind the formic acid; Need not adopt a large amount of excessive water to promote positive reaction to carry out yet and suppresses reversed reaction, and will have in the technology hydrolytic reaction pot and hydrolyzed solution knockout tower, flasher now or hang down the tower that boils, 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 HTHP, 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 operation optimized condition, 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 condensing surfaces, 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
Through concrete embodiment the present invention is done further description below, but should the present invention be interpreted as and only limit to following embodiment.
Embodiment 1
The methyl-formiate raw material that contains methyl alcohol gets into 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 get into 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 gets into methyl-formiate tower T1 and separates reflux ratio 3, theoretical plate number 40; After separating treatment, obtain the methyl-formiate of mass content 98%, control water and methyl-formiate got into catalytic rectifying tower T2 in 4: 1 in molar ratio, superficial velocity be 0.4 cubic metre/(cubic metre 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%.
Embodiment 3
The methyl-formiate raw material that contains methyl alcohol gets into methyl-formiate tower T1 and separates reflux ratio 4, theoretical plate number 20; After separating treatment, obtain the methyl-formiate of mass content 98%, control water and methyl-formiate got into catalytic rectifying tower T2 in 7: 1 in molar ratio, superficial velocity be 0.8 cubic metre/(cubic metre reaction volume hour); Catalyzer is Amberlyst 35 strongly acidic cationic 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 (7)
1. the technology of a preparing aminic acid by methyl formate hydrolysis, concrete steps are following:
(1) the methyl-formiate entering methyl-formiate tower T1 that contains methyl alcohol 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 top fed; 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; Wherein among the catalytic rectifying tower T2; The catalyst reaction section theoretical plate number is 10～40, and the stripping section theoretical plate number is 10～50, and the catalyzer of filling in the catalyst reaction section is a strongly acidic cationic exchange resin; Working pressure is 1～1.2atm; The raw materials components mole ratio of water and methyl-formiate is 1～8: 1, and reflux ratio is 0.5～8: 1, the charging air speed be 0.05～1 cubic metre/(cubic meter reaction volume hour);
(3) T2 tower still discharging entering extractive distillation column T3 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) T3 tower still discharging entering rectification under vacuum tower T4 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 is characterized in that extractive distillation column T3 reflux ratio is 0.5～3: 1, theoretical plate number 10～40.
5. 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.
6. technology according to claim 1 is characterized in that step (3) cat head recovered water is circulated to catalytic rectifying tower T2 recycling.
7. technology according to claim 1 is characterized in that the mass concentration of the described formic acid product of step (4) is 85%～99%.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN2009100245830A CN101481304B (en) | 2009-02-20 | 2009-02-20 | Process for preparing aminic acid by methyl formate hydrolysis |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN2009100245830A CN101481304B (en) | 2009-02-20 | 2009-02-20 | Process for preparing aminic acid by methyl formate hydrolysis |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN101481304A CN101481304A (en) | 2009-07-15 |
| CN101481304B true CN101481304B (en) | 2012-07-04 |
Family
ID=40878617
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN2009100245830A Expired - Fee Related CN101481304B (en) | 2009-02-20 | 2009-02-20 | Process for preparing aminic acid by methyl formate hydrolysis |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN101481304B (en) |
Families Citing this family (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 |
| EP2747883B1 (en) | 2011-08-27 | 2017-02-15 | Taminco | Process of formic acid production by hydrolysis of methyl formate |
| CN102617321B (en) * | 2012-03-12 | 2014-05-07 | 浙江大学 | Method for producing methanoic acid by hydrolyzing methyl formate |
| 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 |
Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1380273A (en) * | 2002-03-01 | 2002-11-20 | 福州大学 | Methyl acetate hydrolysis process and its equipment |
| CN1396898A (en) * | 2000-01-24 | 2003-02-12 | 巴斯福股份公司 | Method for producing anhydrous formic acid |
| CN1407960A (en) * | 1999-10-13 | 2003-04-02 | 苏舍化学技术有限公司 | Process and devices for hydrolytically obtaining carboxylic acid and alcohol from corresponding carboxylate |
| CN101186575A (en) * | 2007-12-04 | 2008-05-28 | 南京工业大学 | Methyl acetate catalysis rectification hydrolysis technique |
-
2009
- 2009-02-20 CN CN2009100245830A patent/CN101481304B/en not_active Expired - Fee Related
Patent Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1407960A (en) * | 1999-10-13 | 2003-04-02 | 苏舍化学技术有限公司 | Process and devices for hydrolytically obtaining carboxylic acid and alcohol from corresponding carboxylate |
| CN1396898A (en) * | 2000-01-24 | 2003-02-12 | 巴斯福股份公司 | Method for producing anhydrous formic acid |
| CN1380273A (en) * | 2002-03-01 | 2002-11-20 | 福州大学 | Methyl acetate hydrolysis process and its equipment |
| CN101186575A (en) * | 2007-12-04 | 2008-05-28 | 南京工业大学 | Methyl acetate catalysis rectification hydrolysis technique |
Non-Patent Citations (1)
| Title |
|---|
| 王成习.催化精馏塔内甲酸甲酯水解制甲酸的研究.《高校化学工程学报》.2006,第20卷(第6期),798-903. * |
Also Published As
| Publication number | Publication date |
|---|---|
| CN101481304A (en) | 2009-07-15 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN101481304B (en) | Process for preparing aminic acid by methyl formate hydrolysis | |
| US11299450B2 (en) | System and process for co-producing dimethyl carbonate and ethylene glycol | |
| CN106883121B (en) | Method for preparing anhydrous formic acid by hydrolyzing methyl formate | |
| CN101830806B (en) | Method and device for co-producing dimethyl carbonate and dimethyl oxalate | |
| CN103524345B (en) | Product separation process for preparing methyl acrylate from methyl acetate | |
| CN101684064B (en) | Environment-friendly process for producing dihydromyrcenol by using dihydromyrcene hydration reaction | |
| CN107162946A (en) | The method that continuous reaction rectification synthesizes isooctyl thioglycolate | |
| CN101186575B (en) | Methyl acetate catalysis rectification hydrolysis technique | |
| CN105461515B (en) | A kind of method that cyclopentanol is prepared by cyclopentene | |
| CN101786946B (en) | Methylal preparation device | |
| CN100564335C (en) | A kind of preparation method of formic acid | |
| CN111606780A (en) | Device and method for synthesizing cyclopentanol from cyclopentene | |
| CN102010321B (en) | Process for continuously producing isobutyric acid | |
| CN101481293A (en) | Catalytic hydrolysis process for by-product methyl acetate of purified terephthalic acid production | |
| CN106478586A (en) | The synthesis technique of ethylene carbonate | |
| CN100406419C (en) | Method for preparing dibasic alcohol | |
| CN102452934A (en) | Preparation method of sec-butyl acetate | |
| CN103588618B (en) | Ritalin hydrogenation produces reactive distillation method and the device of ethanol | |
| CN101805252A (en) | Process for producing formic acid | |
| CN101906020B (en) | Novel process for purifying 1,2-propylene glycol by ester exchange method | |
| CN104592027A (en) | Method for preparing methyl benzoate | |
| CN104447677B (en) | The preparation method of 4-hydroxyl-2,2-dimethyl-1,3-benzodioxole | |
| CN107973728A (en) | System and technique a kind of while that prepare methyl carbamate, dimethyl carbonate | |
| CN105585468B (en) | A method of cyclopentanone is prepared by raw material of cyclopentene | |
| CN102701920A (en) | Method for purifying vinyl isobutyl ether |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| C06 | Publication | ||
| PB01 | Publication | ||
| C10 | Entry into substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| C14 | Grant of patent or utility model | ||
| GR01 | Patent grant | ||
| CF01 | Termination of patent right due to non-payment of annual fee | ||
| CF01 | Termination of patent right due to non-payment of annual fee |
Granted publication date: 20120704 |