CN101391945B - Novel purification method for formic acid - Google Patents

Novel purification method for formic acid Download PDF

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Publication number
CN101391945B
CN101391945B CN2008101220183A CN200810122018A CN101391945B CN 101391945 B CN101391945 B CN 101391945B CN 2008101220183 A CN2008101220183 A CN 2008101220183A CN 200810122018 A CN200810122018 A CN 200810122018A CN 101391945 B CN101391945 B CN 101391945B
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formic acid
calcium chloride
purification
powder anhydrous
aqueous solution
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CN101391945A (en
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丁成荣
许莉
张翼
贺孝啸
谢思泽
来虎钦
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Jiang University Of Technology
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Jiang University Of Technology
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Abstract

The invention discloses a new method for formic acid purifying, which comprises the following steps: the aqueous solution of dilute formic acid with the mass concentration of more than 30 percent and anhydrous calcium chloride are mixed, heated to 80 distillation; and the mass ratio of the water in the aqueous solution of calcium chloride anhydrous and the aqueous solution of dilute formic acid is 1: 1.5 to 95 DEG C so as to lead the anhydrous calcium chloride to be dissolved, and then formic acid with high concentration is obtained through atmosphericto 1.8. The purifying method of formic acid is a process which has the advantages of simple and convenient operation, fastness, low cost and cleanness, thus being suitable for industrial production.

Description

The novel method that a kind of formic acid is purified
(1) technical field
The present invention relates to the new technology that a kind of formic acid is purified.
(2) background technology
Formic acid popular name formic acid is colourless liquid, and boiling point is 100.7 ℃, 8.4 ℃ of fusing points.Formic acid is used as reductive agent, condensing agent, formylation reagent and solvent on synthetic.
In the past, the existing bibliographical information of the method for purifying formic acid.As nineteen twenty-nine FRP report prepare anhydrous formic acid with Tetra hydro Phthalic anhydride and water-containing formic acid back flow reaction.This method principle is that Tetra hydro Phthalic anhydride can form phthalic acid with the water selective reaction; Thereby remove the water in the formic acid removal; But the deficiency of this method is a large amount of phthalic acids that reaction forms, and recycling is difficulty relatively, and economy and environment protection are brought pressure.Be reported in the new entrainer of adding in the water-containing formic acid like English Patent in 1948; The obvious weak point of these class methods is: entrainer propyl formate, tetryl formate etc. generally need prepare from anhydrous formic acid; The entrainer consumption is also bigger simultaneously, and production cost is higher.And for example Chinese patent report in 1992 utilizes SOCL 2The purification dilute formic acid; Its principle is that water and the sulfurous acid acyl chlorides selectivity in the dilute formic acid forms hydrogenchloride and sulfurous gas; Though this method can obtain the formic acid of high density, can cause certain pollution to environment, and in industrializing implementation, bring higher cost.Chinese bibliographical information boron trioxide method of purification in 2006 for another example, its principle boric anhydride (boron trioxide) forms boric acid with water reaction in the dilute formic acid, through distillation; Can obtain concentration formic acid and high, remaining boric acid can reuse through drying and dehydrating; But the boric acid drying and dehydrating becomes boric anhydride, and temperature just can carried out more than 300 ℃, and the industrializing implementation difficulty is bigger; And boric anhydride costs an arm and a leg, and production cost is too high.
(3) summary of the invention
The technical problem that the present invention will solve provides a kind of high-level efficiency, low cost, has the new technology of the formic acid purification of industrial value.
The technical scheme that the present invention adopts is:
A kind of method of purification of formic acid: mass concentration is mixed at 30%~50% the dilute formic acid aqueous solution and Calcium Chloride Powder Anhydrous, be heated to 80~95 ℃, make the Calcium Chloride Powder Anhydrous dissolving, obtain concentration formic acid and high through air distillation then; The amount of substance of water is than being 1:1.5~1.8 in the Calcium Chloride Powder Anhydrous that is added and the dilute formic acid aqueous solution.
Solubility property by calcium chloride can know that in 45~175 ℃ of TRs, calcium chloride mainly exists with the form of duohydrate under the normal pressure, so among the present invention, when being heated to 80~95 ℃, the water in the dilute formic acid combines with calcium chloride, mainly forms Calcium dichloride dihydrate.Reaction formula is following:
CaCl 2+2H 2O=CaCl 2·2H 2O
Thereby when air distillation, earlier formic acid is steamed, the mass concentration of the concentration formic acid and high of gained generally can reach more than 90%.
Further, after formic acid was reclaimed in air distillation, remaining calcium chloride solution can remove the crystal water in the calcium chloride through underpressure distillation, makes the calcium chloride evaporate to dryness, and the calcium chloride cover that obtains is used for next batch.Reaction formula is following:
CaCl 2·2H 2O=CaCl 2+2H 2O
Further, the condition of described underpressure distillation recovery calcium chloride is recommended as: 150~180 ℃ of temperature, vacuum tightness 0.09~0.095MPa.
Further again, heating is generally carried out under agitation condition among the present invention, and after Calcium Chloride Powder Anhydrous and dilute formic acid fed intake and finish, the heated and stirred time was generally at 2~5 hours.
Beneficial effect of the present invention is mainly reflected in:
A) can 30~50% dilute formic acid be purified to 90%~92% concentration formic acid and high;
B) in the technology of the present invention, only need dilute formic acid is added in the Calcium Chloride Powder Anhydrous, make its dissolving through heated and stirred, less demanding to service temperature; And formic acid boiling point low (100.7 ℃), distillation temperature reaches easily, and can distill out formic acid at short notice, easy and simple to handle so energy expenditure is low, technology is simple, is suitable for suitability for industrialized production;
C) Calcium Chloride Powder Anhydrous is cheap and easy to get, and it has replaced those water-retaining agent or entrainers of costing an arm and a leg and being difficult to obtain or environment is polluted, and remaining calcium chloride solution can repeat to apply mechanically through the underpressure distillation processed, and the technology cost reduced greatly.
To sum up, formic acid method of purification according to the invention is a technology easy and simple to handle, quick, low-cost, as to clean, and is suitable for suitability for industrialized production.
(4) embodiment
Below in conjunction with specific examples the present invention is described further.But protection scope of the present invention is not limited in this:
Embodiment 1:
To constant temperature oil bath is arranged; TM in 2000 milliliters of three mouthfuls of round-bottomed flasks of electronic stirring, adds 1554 gram (14.0 moles) Calcium Chloride Powder Anhydrouss; Formic acid solution 800 grams (amount of substance that wherein contains water in the formic acid is 22.2 moles) that add content 50% then; Under 80~95 ℃ of temperature, heated and stirred 5 hours makes the calcium chloride dissolving.After treating the calcium chloride dissolving,, collect 100~106 ℃ of cuts through the normal pressure distillation.Obtaining 409.6 gram content is 91.6% formic acid, the formic acid recovery 93.8%.With remaining calcium chloride solution, 150~180 ℃ of temperature, under the condition of vacuum tightness 0.09~0.095MPa, carry out the underpressure distillation dehydration, make the calcium chloride evaporate to dryness, cover is used for next batch.
Embodiment 2:
The Calcium Chloride Powder Anhydrous that in 1000 milliliters of three mouthfuls of round-bottomed flasks that constant temperature oil bath, TM, electronic stirring are arranged, adds 830 grams (7.5 moles), the formic acid solution 400 that adds content 44% then restrains (amount of substance that wherein contains water in the formic acid is 12.4 moles), under 80~95 ℃ of temperature; Heated and stirred 4 hours makes calcium chloride dissolving, treat the calcium chloride dissolving after; Air distillation; Collect 100~106 ℃ cut, obtaining 181.6 gram content is 91.1% formic acid, the formic acid recovery 94.0%.With remaining calcium chloride solution, 150~180 ℃ of temperature, under the condition of vacuum tightness 0.09~0.095MPa, carry out the underpressure distillation dehydration, make the calcium chloride evaporate to dryness, cover is used for next batch.
Embodiment 3:
The Calcium Chloride Powder Anhydrous that in 500 milliliters of three mouthfuls of round-bottomed flasks that constant temperature oil bath, TM, electronic stirring are arranged, adds 365 grams (3.3 moles), the formic acid solution 160 that adds content 40% then restrains (amount of substance that wherein contains water in the formic acid is 5.3 moles), under 80~95 ℃ of temperature; Heated and stirred 4 hours makes calcium chloride dissolving, treat the calcium chloride dissolving after; Air distillation; Collect 100~106 ℃ cut, obtaining 65.9 gram content is 90.8% formic acid, and the formic acid recovery is 93.5%.With remaining calcium chloride solution, 150~180 ℃ of temperature, under the condition of vacuum tightness 0.09~0.095MPa, carry out the underpressure distillation dehydration, make the calcium chloride evaporate to dryness, cover is used for next batch.
Embodiment 4:
The Calcium Chloride Powder Anhydrous that in 250 milliliters of three mouthfuls of round-bottomed flasks that constant temperature oil bath, TM, electronic stirring are arranged, adds 180 grams (1.6 moles), the formic acid solution 80 that adds content 36% then restrains (amount of substance that wherein contains water in the formic acid is 2.8 moles), under 80~95 ℃ of temperature; Heated and stirred 3 hours makes calcium chloride dissolving, treat the calcium chloride dissolving after; Air distillation; Collect 100~106 ℃ cut, obtaining 30.0 gram content is 90.9% formic acid, and the formic acid recovery is 94.7%.With remaining calcium chloride solution, 150~180 ℃ of temperature, under the condition of vacuum tightness 0.09~0.095MPa, carry out the underpressure distillation dehydration, make the calcium chloride evaporate to dryness, cover is used for next batch.
Embodiment 5:
The Calcium Chloride Powder Anhydrous that in 250 milliliters of three mouthfuls of round-bottomed flasks that constant temperature oil bath, TM, electronic stirring are arranged, adds 200 grams (1.8 moles), the formic acid solution 80 that adds content 30% then restrains (amount of substance that wherein contains water in the formic acid is 3.1 moles), under 80~95 ℃ of temperature; Heated and stirred 2 hours makes calcium chloride dissolving, treat the calcium chloride dissolving after; Air distillation; Collect 100~106 ℃ cut, obtaining 24.8 gram content is 90.1% formic acid, and the formic acid recovery is 93.2%.With remaining calcium chloride solution, 150~180 ℃ of temperature, under the condition of vacuum tightness 0.09~0.095MPa, carry out the underpressure distillation dehydration, make the calcium chloride evaporate to dryness, cover is used for next batch.

Claims (5)

1. the formic acid novel method of purifying; It is characterized in that said New Method of Purification is: with mass concentration is that 30%~50% the dilute formic acid aqueous solution and Calcium Chloride Powder Anhydrous mix; Be heated to 80~95 ℃, make the Calcium Chloride Powder Anhydrous dissolving, obtain the formic acid of high density then through air distillation; The amount of substance of water is than being 1:1.5~1.8 in the Calcium Chloride Powder Anhydrous that is added and the dilute formic acid aqueous solution.
2. formic acid New Method of Purification as claimed in claim 1 is characterized in that: after formic acid is reclaimed in air distillation, remaining calcium chloride solution through the underpressure distillation dehydration, is made the calcium chloride evaporate to dryness, the calcium chloride behind the evaporate to dryness is reused.
3. formic acid New Method of Purification as claimed in claim 1 is characterized in that: described heating is carried out under stirring condition.
4. formic acid New Method of Purification as claimed in claim 3 is characterized in that: churning time is 2~5 hours.
5. formic acid New Method of Purification as claimed in claim 1; It is characterized in that said method of purification step is following: with mass concentration is that 30%~50% the dilute formic acid aqueous solution injects the container that fills Calcium Chloride Powder Anhydrous, is heated to 80~95 ℃, stirs Calcium Chloride Powder Anhydrous is dissolved; Obtain the formic acid of high density then through air distillation; Remaining calcium chloride solution makes the calcium chloride evaporate to dryness through the underpressure distillation dehydration, and the calcium chloride behind the evaporate to dryness is reused; The amount of substance of water is than being 1:1.5~1.8 in the Calcium Chloride Powder Anhydrous that is added and the dilute formic acid aqueous solution.
CN2008101220183A 2008-10-27 2008-10-27 Novel purification method for formic acid Active CN101391945B (en)

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Publication number Priority date Publication date Assignee Title
CN104418723B (en) * 2013-08-20 2016-01-20 黄冈师范学院 The recovery method of trade effluent dilute formic acid and device
CN104774143B (en) * 2014-01-14 2016-08-24 曾舟华 The circulation recovery method of formic acid solvent in metronidazole production process
CN108203374A (en) * 2016-12-19 2018-06-26 曾舟华 Phosphorus pentoxide haze concentrates the method and device of dilute formic acid
CN108203377A (en) * 2016-12-20 2018-06-26 曾舟华 Polyphosphoric acids concentrates the simple and easy method and device of dilute formic acid
CN108203375A (en) * 2016-12-20 2018-06-26 曾舟华 The method that phosphorus pentoxide concentrates dilute formic acid
CN107032981B (en) * 2017-05-02 2018-07-03 山东博苑医药化学有限公司 A kind of method recycled containing sodium formate and sodium chloride mixing solid wastes recycling

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CN1063483A (en) * 1991-01-25 1992-08-12 北京农业大学 The novel process of preparation anhydrous formic acid
DE10002793A1 (en) * 2000-01-24 2001-07-26 Basf Ag Production of anhydrous formic acid involves hydrolysis of methyl formate followed by distillation, extraction with amide and further distillations, using the amide also as a foam suppressant in first distillation stage

Patent Citations (2)

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CN1063483A (en) * 1991-01-25 1992-08-12 北京农业大学 The novel process of preparation anhydrous formic acid
DE10002793A1 (en) * 2000-01-24 2001-07-26 Basf Ag Production of anhydrous formic acid involves hydrolysis of methyl formate followed by distillation, extraction with amide and further distillations, using the amide also as a foam suppressant in first distillation stage

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