CN107353193A - A kind of preparation method of anhydrous formic acid - Google Patents
A kind of preparation method of anhydrous formic acid Download PDFInfo
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- CN107353193A CN107353193A CN201710582138.0A CN201710582138A CN107353193A CN 107353193 A CN107353193 A CN 107353193A CN 201710582138 A CN201710582138 A CN 201710582138A CN 107353193 A CN107353193 A CN 107353193A
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- formic acid
- methyl formate
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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
- C07C51/00—Preparation of carboxylic acids or their salts, halides or anhydrides
- C07C51/42—Separation; Purification; Stabilisation; Use of additives
- C07C51/43—Separation; Purification; Stabilisation; Use of additives by change of the physical state, e.g. crystallisation
- C07C51/44—Separation; Purification; Stabilisation; Use of additives by change of the physical state, e.g. crystallisation by distillation
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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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Abstract
The present invention relates to a kind of preparation method of anhydrous formic acid, comprise the following steps：(1) methanol and carbon monoxide are transported into reactor, it is lower to be reacted in the presence of catalyst, produce methyl formate mixed liquor；(2) sodium carbonate liquor is added into methyl formate mixed liquor, methyl formate is purified；(3) by methyl formate hydrolysis, the mixed solution containing formic acid is obtained；(4) mixed solution is delivered to rectifying in rectifying column, obtains formic acid；(5) boric acid fine powder is added in formic acid, be evaporated under reduced pressure, collected 22 25 DEG C/12 18mm fractions, be anhydrous formic acid.The preparation method of anhydrous formic acid provided by the invention, concise in technology, hydrolysis rate are fast, formic acid purity is high, formic acid purity can reach 99.5%, without other byproducts, can directly prepare anhydrous formic acid, water Han Liang≤0.02% of anhydrous formic acid.
Description
Technical field
The present invention relates to chemical production technical field, and in particular to a kind of preparation method of anhydrous formic acid.
Background technology
Formic acid, also referred to as formic acid, molecular formula HCOOH.Formic acid is colourless and has penetrating odor, and is corrosive, Ren Leipi
Can bubble redness after skin contact.Formic acid has the property of acid and aldehyde simultaneously.In chemical industry, formic acid be used for rubber, medicine,
Dyestuff, the industry of leather species.
Formic acid covered by J.-L. earliest-and Gay-Lussac oxalic acid decomposes and is made.1855~1856 years M. Bei Teluo sodium hydroxides
Sodium formate is directly made with carbon monoxide, formic acid is made from sodium formate with the method for hydrolysis at first in T. Ge De-Schmidt.This method in
Start within 1896 to be used for industrial production in Europe, small lot production so far is still with this method.American science Chevron Research Company (CRC), primary in 1980
Li Heng iron companies and Leo Nader company succeed in developing the method for methanol carbonyl metaplasia production formic acid, and have produced formic acid 20kt per year
Factory go into operation.Obtained in addition, formic acid can also be aoxidized to reclaim in the accessory substance of acetic acid processed by light oil.
In traditional formic acid preparation method, the not purified direct hydrolysis of methyl formate obtains formic acid, and hydrolysis rate is relatively low, system
It is not high for the formic acid purity gone out, waste more water resource.A kind of concise in technology is now provided, hydrolysis rate is fast, and formic acid purity is high,
Without other byproducts, the preparation method of the anhydrous formic acid of anhydrous formic acid can be directly prepared.
The content of the invention
The technical problems to be solved by the invention are：Fast a kind of concise in technology, hydrolysis rate, formic acid purity height, nothing are provided
Other byproducts, can directly prepare anhydrous formic acid anhydrous formic acid preparation method.
In order to solve the above technical problems, the technical scheme is that：A kind of preparation method of anhydrous formic acid, its feature exist
In comprising the following steps：.
(1) methanol and carbon monoxide are transported into reactor, in the presence of catalyst, control temperature at 65-80 DEG C,
Reacted under pressure 2.5-6.0MPa, produce methyl formate mixed liquor；
(2) in the presence of gas-liquid separator, sodium carbonate liquor, methanol soluble are added into the methyl formate mixed liquor
In the sodium carbonate liquor, methyl formate is insoluble, and methyl formate is purified；
(3) by the methyl formate hydrolysis, 115-125 DEG C of hydrolysis temperature, the weight ratio of water and methyl formate is 2-3：1,
Hydrolysis time is 1-3h, and pressure is the saturated vapor pressure of hydrolysis reaction system, obtains the mixed solution containing formic acid；
(4) mixed solution is delivered to rectifying in rectifying column, obtains formic acid；
(5) boric acid is put and gets rid of Shanghai high temperature and be dehydrated to bubble is no longer produced, gained fused mass is poured on iron plate one, puts drying
Cooled down in device, be then ground to powder, boric acid fine powder is added in the formic acid, place 72h, form lump, separate clear thorough liquid
It is evaporated under reduced pressure, collects 22-25 DEG C/12-18mm fractions, be anhydrous formic acid.
Preferably, the catalyst described in step (1) is sodium methoxide, and the addition of the sodium methoxide is the methanol weight
5%.
Preferably, the reaction time of step (1) is 1-2h.
Preferably, the hydrolysis temperature is 120 DEG C, and the weight ratio of water and the methyl formate is 2：1, the hydrolysis time
For 1.5h.
Preferably, the method for step (4) described rectifying is, by the mixed solution and phthalic anhydride mixing infinite reflux
6h, then carry out rectifying.
Preferably, described be evaporated under reduced pressure of step (5) collects 23 DEG C/16mm fractions.
By adopting the above-described technical solution, the beneficial effects of the invention are as follows：
Methanol and carbon monoxide synthesize methyl formate in the presence of catalyst sodium methoxide；
Methyl formate purifies under sodium carbonate liquor, and methanol is dissolved in sodium carbonate liquor, methanol can be passed through into steaming after purification
Purification is evaporated, is reused；
Methyl formate is after purification, it is ensured that the amount of formic acid is continuously increased in hydrolytic process, will not be due to remnants first
Alcohol reduces the hydrolysis rate of methyl formate；
Boric acid is used in the preparation process of anhydrous formic acid, boric acid can reach the purpose of recycling by heating.
The preparation method of anhydrous formic acid provided by the invention, concise in technology, hydrolysis rate are fast, formic acid purity is high, formic acid is pure
Degree can reach 99.5%, without other byproducts, can directly prepare anhydrous formic acid, water Han Liang≤0.02% of anhydrous formic acid.
Embodiment
The following examples are only intended to illustrate the technical solution of the present invention more clearly, therefore is only used as example, and can not
Limited the scope of the invention with this.
In following examples, the addition of sodium methoxide is the 5% of methanol weight.
Embodiment 1
The preparation method of anhydrous formic acid：
(1) methanol and carbon monoxide are transported into reactor, in the presence of sodium methoxide, control temperature is at 65 DEG C, pressure
Reaction 1h is carried out under power 2.5MPa, produces methyl formate mixed liquor；
(2) in the presence of gas-liquid separator, sodium carbonate liquor is added into methyl formate mixed liquor, methanol soluble is in carbon
Acid sodium solution, methyl formate is insoluble, and methyl formate is purified；
(3) by methyl formate hydrolysis, 115 DEG C of hydrolysis temperature, the weight ratio of water and methyl formate is 2：1, hydrolysis time is
1h, pressure are the saturated vapor pressure of hydrolysis reaction system, obtain the mixed solution containing formic acid；
(4) by mixed solution and phthalic anhydride mixing infinite reflux 6h, rectifying is then carried out, obtains formic acid；
(5) boric acid is put and gets rid of Shanghai high temperature and be dehydrated to bubble is no longer produced, gained fused mass is poured on iron plate one, puts drying
Cooled down in device, be then ground to powder, boric acid fine powder is added in formic acid, place 72h, form lump, separated clear thorough liquid and carry out
It is evaporated under reduced pressure, collects 22 DEG C/12mm fractions, be anhydrous formic acid.
The purity of resulting anhydrous formic acid is detected as 99.5, and the water content of anhydrous formic acid is 0.02%.
Embodiment 2
The preparation method of anhydrous formic acid：
(1) methanol and carbon monoxide are transported into reactor, in the presence of sodium methoxide, control temperature is at 80 DEG C, pressure
Reaction 2h is carried out under power 6.0MPa, produces methyl formate mixed liquor；
(2) in the presence of gas-liquid separator, sodium carbonate liquor is added into methyl formate mixed liquor, methanol soluble is in carbon
Acid sodium solution, methyl formate is insoluble, and methyl formate is purified；
(3) by methyl formate hydrolysis, 125 DEG C of hydrolysis temperature, the weight ratio of water and methyl formate is 3：1, hydrolysis time is
3h, pressure are the saturated vapor pressure of hydrolysis reaction system, obtain the mixed solution containing formic acid；
(4) by mixed solution and phthalic anhydride mixing infinite reflux 6h, rectifying is then carried out, obtains formic acid；
(5) boric acid is put and gets rid of Shanghai high temperature and be dehydrated to bubble is no longer produced, gained fused mass is poured on iron plate one, puts drying
Cooled down in device, be then ground to powder, boric acid fine powder is added in formic acid, place 72h, form lump, separated clear thorough liquid and carry out
It is evaporated under reduced pressure, collects 25 DEG C/18mm fractions, be anhydrous formic acid.
The purity of resulting anhydrous formic acid is detected as 99.4, and the water content of anhydrous formic acid is 0.01%.
Embodiment 3
The preparation method of anhydrous formic acid：
(1) methanol and carbon monoxide are transported into reactor, in the presence of sodium methoxide, control temperature is at 70 DEG C, pressure
Reaction 1.5h is carried out under power 3MPa, produces methyl formate mixed liquor；
(2) in the presence of gas-liquid separator, sodium carbonate liquor is added into methyl formate mixed liquor, methanol soluble is in carbon
Acid sodium solution, methyl formate is insoluble, and methyl formate is purified；
(3) by methyl formate hydrolysis, 120 DEG C of hydrolysis temperature, the weight ratio of water and methyl formate is 2.5：1, hydrolysis time
For 2h, pressure is the saturated vapor pressure of hydrolysis reaction system, obtains the mixed solution containing formic acid；
(4) by mixed solution and phthalic anhydride mixing infinite reflux 6h, rectifying is then carried out, obtains formic acid；
(5) boric acid is put and gets rid of Shanghai high temperature and be dehydrated to bubble is no longer produced, gained fused mass is poured on iron plate one, puts drying
Cooled down in device, be then ground to powder, boric acid fine powder is added in formic acid, place 72h, form lump, separated clear thorough liquid and carry out
It is evaporated under reduced pressure, collects 23 DEG C/13mm fractions, be anhydrous formic acid.
The purity of resulting anhydrous formic acid is detected as 99.5, and the water content of anhydrous formic acid is 0.02%.
Embodiment 4
The preparation method of anhydrous formic acid：
(1) methanol and carbon monoxide are transported into reactor, in the presence of sodium methoxide, control temperature is at 75 DEG C, pressure
Reaction 1.5h is carried out under power 3.5MPa, produces methyl formate mixed liquor；
(2) in the presence of gas-liquid separator, sodium carbonate liquor is added into methyl formate mixed liquor, methanol soluble is in carbon
Acid sodium solution, methyl formate is insoluble, and methyl formate is purified；
(3) by methyl formate hydrolysis, 120 DEG C of hydrolysis temperature, the weight ratio of water and methyl formate is 2：1, hydrolysis time is
1.5h, pressure are the saturated vapor pressure of hydrolysis reaction system, obtain the mixed solution containing formic acid；
(4) by mixed solution and phthalic anhydride mixing infinite reflux 6h, rectifying is then carried out, obtains formic acid；
(5) boric acid is put and gets rid of Shanghai high temperature and be dehydrated to bubble is no longer produced, gained fused mass is poured on iron plate one, puts drying
Cooled down in device, be then ground to powder, boric acid fine powder is added in formic acid, place 72h, form lump, separated clear thorough liquid and carry out
It is evaporated under reduced pressure, collects 23 DEG C/16mm fractions, be anhydrous formic acid.
The purity of resulting anhydrous formic acid is detected as 99.5, and the water content of anhydrous formic acid is 0.01%.
Embodiment 5
The preparation method of anhydrous formic acid：
(1) methanol and carbon monoxide are transported into reactor, in the presence of sodium methoxide, control temperature is at 75 DEG C, pressure
Reaction 1.5h is carried out under power 4MPa, produces methyl formate mixed liquor；
(2) in the presence of gas-liquid separator, sodium carbonate liquor is added into methyl formate mixed liquor, methanol soluble is in carbon
Acid sodium solution, methyl formate is insoluble, and methyl formate is purified；
(3) by methyl formate hydrolysis, 121 DEG C of hydrolysis temperature, the weight ratio of water and methyl formate is 3：1, hydrolysis time is
2.5h, pressure are the saturated vapor pressure of hydrolysis reaction system, obtain the mixed solution containing formic acid；
(4) by mixed solution and phthalic anhydride mixing infinite reflux 6h, rectifying is then carried out, obtains formic acid；
(5) boric acid is put and gets rid of Shanghai high temperature and be dehydrated to bubble is no longer produced, gained fused mass is poured on iron plate one, puts drying
Cooled down in device, be then ground to powder, boric acid fine powder is added in formic acid, place 72h, form lump, separated clear thorough liquid and carry out
It is evaporated under reduced pressure, collects 24 DEG C/15mm fractions, be anhydrous formic acid.
The purity of resulting anhydrous formic acid is detected as 99.4, and the water content of anhydrous formic acid is 0.02%.
Embodiment 6
The preparation method of anhydrous formic acid：
(1) methanol and carbon monoxide are transported into reactor, in the presence of sodium methoxide, control temperature is at 72 DEG C, pressure
Reaction 1h is carried out under power 5MPa, produces methyl formate mixed liquor；
(2) in the presence of gas-liquid separator, sodium carbonate liquor is added into methyl formate mixed liquor, methanol soluble is in carbon
Acid sodium solution, methyl formate is insoluble, and methyl formate is purified；
(3) by methyl formate hydrolysis, 120 DEG C of hydrolysis temperature, the weight ratio of water and methyl formate is 2.5：1, hydrolysis time
For 2.5h, pressure is the saturated vapor pressure of hydrolysis reaction system, obtains the mixed solution containing formic acid；
(4) by mixed solution and phthalic anhydride mixing infinite reflux 6h, rectifying is then carried out, obtains formic acid；
(5) boric acid is put and gets rid of Shanghai high temperature and be dehydrated to bubble is no longer produced, gained fused mass is poured on iron plate one, puts drying
Cooled down in device, be then ground to powder, boric acid fine powder is added in formic acid, place 72h, form lump, separated clear thorough liquid and carry out
It is evaporated under reduced pressure, collects 22 DEG C/17mm fractions, be anhydrous formic acid.
The purity of resulting anhydrous formic acid is detected as 99.4, and the water content of anhydrous formic acid is 0.01%.
Various embodiments above is merely illustrative of the technical solution of the present invention, rather than its limitations；Although with reference to foregoing each reality
Example is applied the present invention is described in detail, it will be understood by those within the art that：It still can be to foregoing each
Technical scheme described in embodiment is modified, and either carries out equivalent substitution to which part or all technical characteristic；And
These modifications are replaced, and the essence of appropriate technical solution is departed from the scope of various embodiments of the present invention technical scheme, its
It all should cover among the claim of the present invention and the scope of specification.
Claims (6)
1. a kind of preparation method of anhydrous formic acid, it is characterised in that comprise the following steps：
(1) methanol and carbon monoxide are transported into reactor, in the presence of catalyst, control temperature is at 65-80 DEG C, pressure
Reacted under 2.5-6.0MPa, produce methyl formate mixed liquor；
(2) in the presence of gas-liquid separator, sodium carbonate liquor is added into the methyl formate mixed liquor, methanol soluble is in institute
Sodium carbonate liquor is stated, methyl formate is insoluble, and methyl formate is purified；
(3) by the methyl formate hydrolysis, 115-125 DEG C of hydrolysis temperature, the weight ratio of water and methyl formate is 2-3：1, hydrolysis
Time is 1-3h, and pressure is the saturated vapor pressure of hydrolysis reaction system, obtains the mixed solution containing formic acid；
(4) mixed solution is delivered to rectifying in rectifying column, obtains formic acid；
(5) boric acid is put and gets rid of Shanghai high temperature and be dehydrated to bubble is no longer produced, gained fused mass is poured on iron plate one, put in drier
Cooling, is then ground to powder, boric acid fine powder is added in the formic acid, places 72h, forms lump, separates clear thorough liquid and carries out
It is evaporated under reduced pressure, collects 22-25 DEG C/12-18mm fractions, be anhydrous formic acid.
2. the preparation method of anhydrous formic acid as claimed in claim 1, it is characterised in that：Catalyst described in step (1) is first
Sodium alkoxide, the addition of the sodium methoxide are the 5% of the methanol weight.
3. the preparation method of anhydrous formic acid as claimed in claim 1, it is characterised in that：The reaction time of step (1) is 1-2h.
4. the preparation method of anhydrous formic acid as claimed in claim 1, it is characterised in that：The hydrolysis temperature be 120 DEG C, water and
The weight ratio of the methyl formate is 2：1, the hydrolysis time is 1.5h.
5. the preparation method of anhydrous formic acid as claimed in claim 1, it is characterised in that：The method of step (4) described rectifying is,
By the mixed solution and phthalic anhydride mixing infinite reflux 6h, rectifying is then carried out.
6. the preparation method of anhydrous formic acid as claimed in claim 1, it is characterised in that：Described be evaporated under reduced pressure of step (5) is collected
23 DEG C/16mm fractions.
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Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN109320410A (en) * | 2018-11-22 | 2019-02-12 | 湖南湘硕化工有限公司 | A kind of preparation method of formic acid |
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| Publication number | Priority date | Publication date | Assignee | Title |
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| CN109320410A (en) * | 2018-11-22 | 2019-02-12 | 湖南湘硕化工有限公司 | A kind of preparation method of formic acid |
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