CN109320410A - A kind of preparation method of formic acid - Google Patents
A kind of preparation method of formic acid Download PDFInfo
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- CN109320410A CN109320410A CN201811400918.XA CN201811400918A CN109320410A CN 109320410 A CN109320410 A CN 109320410A CN 201811400918 A CN201811400918 A CN 201811400918A CN 109320410 A CN109320410 A CN 109320410A
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- formic acid
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- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C51/00—Preparation of carboxylic acids or their salts, halides or anhydrides
- C07C51/09—Preparation of carboxylic acids or their salts, halides or anhydrides from carboxylic acid esters or lactones
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- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C67/00—Preparation of carboxylic acid esters
- C07C67/36—Preparation of carboxylic acid esters by reaction with carbon monoxide or formates
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- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C67/00—Preparation of carboxylic acid esters
- C07C67/48—Separation; Purification; Stabilisation; Use of additives
- C07C67/52—Separation; Purification; Stabilisation; Use of additives by change in the physical state, e.g. crystallisation
- C07C67/54—Separation; Purification; Stabilisation; Use of additives by change in the physical state, e.g. crystallisation by distillation
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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
Abstract
The invention discloses a kind of preparation methods of formic acid, the following steps are included: using methanol and carbon monoxide for raw material, enter methyl formate reaction tower in the presence of metal alkoxide is catalyst, under conditions of reaction temperature is 75~95 DEG C, reacting system pressure is 2.0~4.0MPa and synthesizes methyl formate raw material.Obtained methyl formate raw material enters methyl formate destilling tower, rectifying separation, overhead extraction methyl formate；Methyl formate and water enter hydrolysis reaction tower, and reaction is hydrolyzed under conditions of reaction temperature is 120~140 DEG C, reaction pressure is 1.0~1.8MPa, and tower top uses infinite reflux, obtains containing methyl formate, methanol, water and formic acid mixtures；The mixture enters hydrolysis tower, catalytic distillation separation, water and formic acid；Dry formic acid product is obtained through inorganic pervaporation UF membrane entering formic acid tower.Preparation method of the invention is simple, and environmental pollution is small, and equipment dependability is strong, can produce high-purity formic acid.
Description
Technical field
The present invention relates to a kind of production methods of Organic Chemicals, and in particular to a kind of preparation method of formic acid.
Background technique
Formic acid (chemical formula HCOOH, molecular formula CH2O2, molecular weight 46.03), popular name formic acid is simplest carboxylic acid.Nothing
The liquid of color and irritant smell.Weak electrolyte, 8.6 DEG C of fusing point, 100.8 DEG C of boiling point.It is acid very strong, it is corrosive, can pierce
Swash skin blistering.It is present in the secretion of bee class, certain ant classes and caterpillar.Organic Chemicals, also serve as disinfectant and
Preservative.Formic acid is widely used in chemical industry, medicine, pesticide, leather, weaving, print as important basic organic chemical industry raw material
The industries such as dye, rubber, plastics and feed.Since formic acid is ultimately breaks down into carbon dioxide and water, effect on environment is little；Simultaneously again
It is the optimum substituent of feed over the counter antibiotic, thus market demand is being continuously increased, price also raises up always, becomes carbon
The hot spot product of one chemistry.
Production method mainly has a sodium formate method, formamide method to formic acid earlier, but that there are the norm quotas of consumption is high, is produced into for technique
This height and there is the problems such as a large amount of by-products.
Summary of the invention
The purpose of the present invention is overcome the deficiencies of the prior art and provide a kind of preparation method of formic acid.
The present invention provides a kind of preparation methods of formic acid, comprising the following steps:
(1) it uses methanol and carbon monoxide for raw material, in the presence of metal alkoxide is catalyst, is reacted into methyl formate
Tower synthesizes methyl formate raw material, and reaction temperature is 75~95 DEG C, reacting system pressure is 2.0~4.0MPa.
(2) methyl formate raw material enters methyl formate destilling tower, catalytic distillation separation, overhead extraction methyl formate；
(3) methyl formate and water enter hydrolysis reaction tower, and reaction is hydrolyzed, and tower top uses infinite reflux, and reaction temperature is
120~140 DEG C, reaction pressure be 1.0~1.8MPa, obtain containing methyl formate, methanol, water and formic acid mixtures；
(4) methyl formate, methanol, water and formic acid mixtures enter hydrolysis tower, rectifying separation, and tower reactor obtains water and formic acid；
(5) water and formic acid enter formic acid tower, through inorganic pervaporation UF membrane, obtain dry formic acid product.
Preferably, methanol described in step (1), carbon monoxide molar ratio be 2-2.5:1.
Preferably, methyl formate reaction tower reflux ratio is 1~8:1 in step (1), and theoretical cam curve is 8~40.
Preferably, methyl formate destilling tower is from top to bottom followed successively by catalyst reaction section and stripping section in step (2), and catalysis is anti-
Answering section theoretical cam curve is 10~50, and stripping section theoretical cam curve is 8~40.
Preferably, the raw materials components mole ratio of water and methyl formate is 3:1~5:1 in hydrolysis reaction tower 3 in step (3).
Preferably, the mixture of the extraction of step (2) methyl formate destilling tower methanol and methyl formate, is recycled to methyl formate
Reaction tower separation, reflux ratio 1-9:1, theoretical cam curve are 8~40.
Preferably, step (3) hydrolysis reaction tower obtains water-containing formic acid, is recycled to hydrolysis tower and further separates, reflux ratio be 1~
7:1, theoretical cam curve are 8~40.
Preferably, step (1) metal alkoxide used in it is sodium methoxide.
Preferably, step (5) formic acid column overhead recovered water is recycled to hydrolysis reaction tower recycling.
The present invention is described in further detail below.
(1) it uses methanol and carbon monoxide for raw material, in the presence of metal alkoxide is catalyst, is reacted into methyl formate
Tower synthesizes methyl formate raw material, and the methyl formate raw material produced from methyl formate reaction tower enters methyl formate destilling tower, at this
Tower separation, removes the methanol in methyl formate raw material, and the methanol and a small amount of catalyst of tower reactor extraction return to methyl formate reaction tower
It carries out methanol carbonyl and is combined to methyl formate, the methyl formate of overhead extraction enters hydrolysis reaction tower.
(2) methyl formate destilling tower is from top to bottom followed successively by catalyst reaction section and stripping section.Water is fed in the middle part of conversion zone,
Methyl formate is fed from conversion zone top, and reaction is hydrolyzed in methyl formate and water in conversion zone, generates methanol and formic acid, together
When reacting section catalyst also function to the effect of separation, tower top uses infinite reflux, and tower reactor produces formic acid first west, methanol, formic acid and water
Mixture, into hydrolysis tower.
(3) hydrolysis tower can in atmospheric operation, in order to preferably prevent formic acid resterification can also decompression separation, built-in filler or
The mixture of column plate, overhead extraction methanol and methyl formate is recycled to the separation of methyl formate destilling tower, tower reactor recovered water and formic acid
Into formic acid tower.
(4) formic acid tower is knockout tower, and overhead extraction water and a small amount of formic acid are recycled to hydrolysis reaction tower and one piece of water charging,
Through inorganic pervaporation UF membrane, built-in filler or column plate in formic acid tower, tower reactor extraction is concentration formic acid and high product.
The beneficial effects of the present invention are:
1, since catalyst reaction section reactant and product are that dynamic flows, and resin itself has centrifugation so that
The touch opportunity of formic acid and methanol significantly reduces, and effectively prevents resterification, improves one way hydrolysis conversion.
2, hydrolysis reaction tower is discharged control easier to operate using infinite reflux ratio using tower top, hydrolysis tower can be more preferable by first and
Formic acid first, which is separated from the mixture, to be come.
3, the aqueous formic acid of tower reactor extraction can be obtained pure by the inorganic pervaporation UF membrane in permeation evaporating device
95% or more formic acid product is spent, and avoids the use of entrainer or extractant using permeation evaporating device, alkali has lacked equipment
Investment cost, and energy consumption can be further decreased.
Therefore, the present invention provides new process to prepare formic acid by methanol conversion methyl formate hydrolysis, hydrolyzes improving
Conversion ratio has larger contribution in terms of reducing equipment investment and energy saving.
Detailed description of the invention
Fig. 1 is a kind of preparation method process flow chart of formic acid provided by the invention:
Wherein, 1 methyl formate reaction tower, 2 methyl formate destilling towers, 3. hydrolysis reaction towers, 4 hydrolysis towers, 5 formic acid towers.
Specific embodiment
To make the objectives, technical solutions, and advantages of the present invention clearer, below in conjunction with specific embodiment, to this hair
Bright further description.
Embodiment 1
(1) methanol and carbon monoxide are raw material, in the presence of metal alkoxide is catalyst, into methyl formate reaction tower 1,
The methyl formate raw material methyl formate destilling tower 2 of generation separates, and reflux ratio 2, theoretical cam curve 50 is isolated to mass concentration
95% methyl formate；
(2) water and methyl formate molar ratio 1:1 are controlled and enters hydrolysis reaction tower 3, superficial linear velocity in a column is 0.5 cubic metre/(cube
Rice reaction volume hour), catalyst is D072 type macropore strong acid cation exchanger resin, the catalysis reaction of hydrolysis reaction tower 3
Section theoretical cam curve 20, stripping section theoretical cam curve 15, methyl formate one way hydrolysis conversion reach 60%；
(3) 4 reflux ratio 1.5 of hydrolysis tower, theoretical cam curve 35, tower reactor formic acid mass concentration 50%；
(4) formic acid tower 5 is overhead extraction water and a small amount of formic acid is recycled to hydrolysis reaction tower 3 and one piece of water charging, in first
Through inorganic pervaporation UF membrane in acid tower 5, reflux ratio 2, theoretical cam curve 50, mass concentration 95% is can be obtained in final tower top
Formic acid product.
Embodiment 2
(1) methanol and carbon monoxide are raw material, in the presence of metal alkoxide is catalyst, into methyl formate reaction tower 1,
The methyl formate raw material methyl formate destilling tower 2 of generation separates, and reflux ratio 5, theoretical cam curve 30 is isolated to mass concentration
95% methyl formate；
(2) water and methyl formate molar ratio 3:1 are controlled and enters hydrolysis reaction tower 3, superficial linear velocity in a column is 0.5 cubic metre/(cube
Rice reaction volume hour), catalyst is Amberlyst15 macropore strong acid cation exchanger resin, and hydrolysis reaction tower 3 is catalyzed
Conversion zone theoretical cam curve 40, stripping section theoretical cam curve 30, methyl formate one way hydrolysis conversion reach 80%；
(3) 4 reflux ratio 4 of hydrolysis tower, theoretical cam curve 30, tower reactor formic acid mass concentration 45%；
(4) formic acid tower 5 is overhead extraction water and a small amount of formic acid is recycled to hydrolysis reaction tower 3 and one piece of water charging, in first
Through inorganic pervaporation UF membrane in acid tower 5, reflux ratio 4, theoretical cam curve 30, mass concentration 95% is can be obtained in final tower top
Formic acid product.
Embodiment 3
(1) methanol and carbon monoxide are raw material, in the presence of metal alkoxide is catalyst, into methyl formate reaction tower 1,
The methyl formate raw material methyl formate destilling tower 2 of generation separates, and reflux ratio 8, theoretical cam curve 15 is isolated to mass concentration
95% methyl formate；
(2) water and methyl formate molar ratio 5:1 are controlled and enters hydrolysis reaction tower 3, superficial linear velocity in a column is 0.5 cubic metre/(cube
Rice reaction volume hour), catalyst is NKC-9 type macropore strong acid cation exchanger resin, the catalysis reaction of hydrolysis reaction tower 3
Section theoretical cam curve 60, stripping section theoretical cam curve 40, methyl formate one way hydrolysis conversion reach 90%；
(3) 4 reflux ratio 8 of hydrolysis tower, theoretical cam curve 20, tower reactor formic acid mass concentration 40%；
(4) formic acid tower 5 is overhead extraction water and a small amount of formic acid is recycled to hydrolysis reaction tower 3 and one piece of water charging, in first
Through inorganic pervaporation UF membrane in acid tower 5, reflux ratio 6, theoretical cam curve 20, mass concentration 92% is can be obtained in final tower top
Formic acid product.
Claims (9)
1. a kind of preparation method of formic acid, which comprises the following steps:
(1) use methanol and carbon monoxide for raw material, in the presence of metal alkoxide is catalyst, into methyl formate reaction tower 1
Methyl formate raw material is synthesized, reaction temperature is 75~95 DEG C, reacting system pressure is 2.0~4.0MPa.
(2) methyl formate raw material enters methyl formate destilling tower 2, rectifying separation, overhead extraction methyl formate；
(3) methyl formate and water enter hydrolysis reaction tower 3, and reaction is hydrolyzed, and tower top uses infinite reflux, reaction temperature 120
~140 DEG C, reaction pressure be 1.0~1.8MPa, obtain containing methyl formate, methanol, water and formic acid mixtures；
(4) methyl formate, methanol, water and formic acid mixtures enter hydrolysis tower 4, catalytic distillation separation, and tower reactor obtains water and formic acid；
(5) water and formic acid enter formic acid tower 5, through inorganic pervaporation UF membrane, obtain dry formic acid product.
2. the preparation method of formic acid as described in claim 1, which is characterized in that methanol described in step 1), carbon monoxide rub
You are than being 2-2.5:1.
3. the preparation method of formic acid as described in claim 1, which is characterized in that 1 reflux ratio of methyl formate reaction tower is 1~8:1,
Theoretical cam curve is 8~40.
4. the preparation method of formic acid as described in claim 1, which is characterized in that methyl formate destilling tower 2 is from top to bottom followed successively by
Catalyst reaction section and stripping section, catalyst reaction section theoretical cam curve are 10~50, and stripping section theoretical cam curve is 8~40.
5. the preparation method of formic acid as described in claim 1, which is characterized in that in hydrolysis reaction tower 3 water and methyl formate into
Material molar ratio is 3:1~5:1.
6. the preparation method of formic acid as described in claim 1, which is characterized in that methyl formate destilling tower 2 produces methanol and formic acid
The mixture of methyl esters, is recycled to the separation of methyl formate reaction tower 1, reflux ratio 1-9:1, and theoretical cam curve is 8~40.
7. technique according to claim 1, it is characterised in that hydrolysis reaction tower 3 water-containing formic acid, be recycled to hydrolysis tower 4 into
The separation of one step, reflux ratio are 1~7:1, and theoretical cam curve is 8~40.
8. technique according to claim 1, it is characterised in that metal alkoxide used in it is sodium methoxide.
9. technique according to claim 1, it is characterised in that 5 overhead extraction water of formic acid tower is recycled to 3 weight of hydrolysis reaction tower
It is multiple to utilize.
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Citations (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1086508A (en) * | 1992-11-05 | 1994-05-11 | 萨尔斯吉特建筑公司 | The method for making of formic acid |
| CN1646469A (en) * | 2002-04-19 | 2005-07-27 | 巴斯福股份公司 | Method for producing methyl formate |
| CN101805252A (en) * | 2010-04-06 | 2010-08-18 | 南京工业大学 | Process for producing formic acid |
| WO2014080026A1 (en) * | 2012-11-26 | 2014-05-30 | Basf Se | Method for producing methyl formate by reacting methanol with carbon monoxide in the presence of a catalyst system which comprises alkali formate and alkali alcoholate |
| CN106883121A (en) * | 2017-02-16 | 2017-06-23 | 福州福大双众化工科技有限公司 | The method that methyl formate hydrolysis prepares anhydrous formic acid |
| CN107353193A (en) * | 2017-07-17 | 2017-11-17 | 衡阳屹顺化工有限公司 | A kind of preparation method of anhydrous formic acid |
-
2018
- 2018-11-22 CN CN201811400918.XA patent/CN109320410A/en active Pending
Patent Citations (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1086508A (en) * | 1992-11-05 | 1994-05-11 | 萨尔斯吉特建筑公司 | The method for making of formic acid |
| CN1646469A (en) * | 2002-04-19 | 2005-07-27 | 巴斯福股份公司 | Method for producing methyl formate |
| CN101805252A (en) * | 2010-04-06 | 2010-08-18 | 南京工业大学 | Process for producing formic acid |
| WO2014080026A1 (en) * | 2012-11-26 | 2014-05-30 | Basf Se | Method for producing methyl formate by reacting methanol with carbon monoxide in the presence of a catalyst system which comprises alkali formate and alkali alcoholate |
| CN106883121A (en) * | 2017-02-16 | 2017-06-23 | 福州福大双众化工科技有限公司 | The method that methyl formate hydrolysis prepares anhydrous formic acid |
| CN107353193A (en) * | 2017-07-17 | 2017-11-17 | 衡阳屹顺化工有限公司 | A kind of preparation method of anhydrous formic acid |
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Application publication date: 20190212 |