CN1164527A - Method for producing formic acid by using methanol-water rectifying tower residue produced in course of producing sodium hyposulfite - Google Patents
Method for producing formic acid by using methanol-water rectifying tower residue produced in course of producing sodium hyposulfite Download PDFInfo
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- CN1164527A CN1164527A CN 96118152 CN96118152A CN1164527A CN 1164527 A CN1164527 A CN 1164527A CN 96118152 CN96118152 CN 96118152 CN 96118152 A CN96118152 A CN 96118152A CN 1164527 A CN1164527 A CN 1164527A
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Abstract
The technological process for producing formic acid by using methanol-water rectifying tower residue produced in course of production of sodium hydrosulfite (Hydros) includes the following steps: acidizing residue (for example, making residue react with sulfuric acid) and converting the sodium formate in the residue to formic acid, then using ZYM mixed extracting agent to extract formic acid from the above-mentioned obtained dilute formic acid solution, and obtain extract phase in which formic acid is enriched, heating the extract phase and layering it so as to obtain 80% (wt%) formic acid solution; making it pass through such processes of rectifying or film-type evaporation to further obtainhigh-concentration formic acid product with more than 85% content. Said ivnented formic acid product can be extensively used in pharmaceutical industry and chemical industry, etc..
Description
The present invention relates to a kind of distillation residual liquid of discharging during vat powder is produced and recycle, and put forward the dense processing method that makes the formic acid product by extracting and separating after will sodium formiate wherein changing into formic acid.
As everyone knows, contain the sodium formiate of 80～120 grams per liters in the vat powder raffinate, and inorganic salt such as Sulfothiorine and S-WAT.Also has organism and some undetermined components and impurity such as bunte salts, sodium isethionate, ethylene glycol, ethylene glycol monomethyl ether.Lack effective treatment process before this raffinate is recycled, most producers have to discharge it, serious environment pollution.
In the prior art, have, remove organism oil phase and washing leaching cake, obtain the method for sodium formiate dry product the raffinate condensing crystal.The sodium formiate impurity that this method is produced is many, content is many, is difficult to find suitable purposes; Have in concentrating raffinate, to add methyl alcohol and sulfuric acid reacts, generate volatile methyl-formiate, the method that methyl-formiate reclaims after condensation, the methyl-formiate cost that this method is produced is higher, the no market competitiveness.
The method of traditional mode of production formic acid is to be raw material with industrial sodium formiate, making with strong sulfuric acid response behind the industrial sodium formiate depth drying.Also useful preparing aminic acid by methyl formate hydrolysis.Cost is all higher.
The objective of the invention is to utilize means such as extraction is the processing method that raw material is produced the formic acid product with the vat powder distillation residual liquid directly.Purpose is the vat powder distillation residual liquid is turned waste into wealth.When reducing pollution emissions, produce Chemicals formic acid with low cost.
The technical scheme that the present invention proposes is:
(1) utilizes one or more or its mixture in the high boiling point strong acid, under 40 ℃-60 ℃ temperature, be reacted to pH value below 1.9 with distillation residual liquid;
(2) below 30 ℃, from above-mentioned dark solvent, extract formic acid with ZYM hybrid extraction liquid, obtain gathering the extraction phase of formic acid;
(3) extraction phase gets formic acid solution through being heated to 190-205 ℃ after the condensation layering;
(4) above-mentioned formic acid solution is further carried densely through rectifying or membrane type infiltration evaporation, promptly gets the formic acid product of content greater than 85% (weight).
The present invention also has following characteristics: the used high boiling point strong acid of distillation residual liquid reaction is sulfuric acid; Distillation residual liquid can carry out earlier reacting with high boiling point strong acid after the evaporation concentration again; After the reaction of distillation residual liquid and high boiling point strong acid, available absorption or alkali cleaning method are being driven volatile matter such as clean sulfurous gas below 80 ℃.
The present invention is the open first method of utilizing vat powder raffinate direct production formic acid a kind of with practical value that proposes.No similar prior art.Can be at this with close prior art---the processing method of utilizing raffinate to produce methyl-formiate is done a contrast:
Concentrate the methyl alcohol that adds excessive 5%-10% (comparing) in the raffinate with stoichiometry, in the input enamel reaction still, drip the sulfuric acid of 90-98%, control reaction temperature is at 60 ℃-80 ℃, make it to take place serial reaction, generate volatile matters such as sulfurous gas and methyl-formiate.The methyl-formiate that condensation is got off is thrown go back to the vat powder system, or purifies and sell.
The present invention compares with this technology, and significant difference and obvious superiority are arranged: 1. technical difficulty is different.Methyl-formiate is water insoluble, and boiling point low (being 31.6 ℃), and is volatile, also more easily separated and purification.And this programme is produced formic acid, and its boiling point is 100.5 ℃ and only differs from 0.5 ℃ for 100.0 ℃, extremely difficult the separation with water.And the two complete miscibility can form blend again, and azeotropic is formed formic acid 77.5%, water 22.5% (weight).Therefore it is very difficult greater than the formic acid product technology of 85% (weight) dilute formic acid to be carried dense one-tenth content.The present invention is by screening and definite optimum extractant, and avoiding the azeotropic composition is the key of success of the present invention; 2. to produce the formic acid cost low in the present invention, and the market competitiveness is strong, and economic benefit outclass the methyl-formiate method.
Below by specific embodiment the present invention is carried out more detailed description.
Example 1: in a Florence flask, add 2000 milliliters of vat powder distillation residual liquids, insert one on the soft rubber ball and fill 90% vitriolic separating funnel.Raffinate slowly drips sulfuric acid after being cooled to normal temperature, and control reaction temperature is 40 ℃-60 ℃, and question response no longer includes a large amount of bubbles and generates (SO
2Driven clean) and the solution pH value less than stopping to drip sulfuric acid at 1.9 o'clock.Under agitation slowly be warmed up to 101～105 ℃, make solution evaporation, after 30 ℃ of cooling water condensation, collect 1500ml distillation lime set.This lime set is for containing the formic acid dilute solution of 3%～5% (weight).This dilute solution 30 ℃ down and the ZYM extraction agent carry out continuous countercurrent extraction, can obtain being enriched with the extraction phase of formic acid.Extraction phase is heated to 190～205 ℃, and the condensation layering can obtain the formic acid solution about 80% (weight).Again 80% formic acid solution is carried out rectifying, about 100～105 ℃ of tower still can be carried dense one-tenth content greater than about 150～200 grams of the formic acid solution of 85% (weight).
Example 2: reaction process is with example.Reaction residue, solution by filter wherein sulfur granule and other suspended substance after go and ZYM extraction agent counter-current extraction.With the formic acid solution of example 1 acquisition greater than 85% (weight).Extraction agent after just separating may be polluted by organic impurity.Contaminated extraction agent and a large amount of distilled water can be mixed vibration, take out again after the layering and reuse.
Example 3: earlier evaporation concentration is carried out in the worn-out mouthful of heating in flask of 2000 milliliters of raffinates.The raffinate temperature is controlled at below 110 ℃, makes it to steam half moisture content, obtains about 1000 milliliters of concentrated raffinates.React, extract, carry dense with example 1 again.This example can steam 6%～10% (weight) dilute formic acid solution, and row is handled again.Can obtain content equally greater than 85% formic acid solution.
Example 4: with example 1.But it is dense that 80% (weight) formic acid solution that obtains after the condensation layering is carried with the infiltration evaporation of membrane separation technique, also can obtain content greater than about 150～200 grams of 85% formic acid solution.
Claims (4)
1, methyl alcohol---the method for the rectifying tower residue produced production formic acid of crystal is characterized in that in a kind of utilization production V-Brite B process:
(1) utilizes one or more or its mixture in the high boiling point strong acid, under 40 ℃-60 ℃ temperature, be reacted to pH value below 1.9 with distillation residual liquid;
(2) below 30 ℃, from above-mentioned solvent, extract formic acid with ZYM hybrid extraction liquid, obtain gathering the extraction phase of formic acid;
(3) extraction phase gets formic acid solution through being heated to 190-205 ℃ after the condensation layering;
(4) above-mentioned formic acid solution is further carried densely through rectifying or membrane type infiltration evaporation, promptly gets the formic acid product of content greater than 85% (weight).
2, the method for production formic acid according to claim 1 is characterized in that the high boiling point strong acid that reacts used with distillation residual liquid is sulfuric acid.
3, the method for production formic acid according to claim 1 and 2 is characterized in that distillation residual liquid can carry out earlier reacting with high boiling point strong acid after the evaporation concentration again.
4, according to the method for claim 1 or 2 or 3 described production formic acid, it is characterized in that: after the reaction of distillation residual liquid and high boiling point strong acid, available absorption or alkali cleaning method are being driven volatile matter such as clean sulfurous gas below 80 ℃.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN 96118152 CN1164527A (en) | 1996-05-08 | 1996-05-08 | Method for producing formic acid by using methanol-water rectifying tower residue produced in course of producing sodium hyposulfite |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN 96118152 CN1164527A (en) | 1996-05-08 | 1996-05-08 | Method for producing formic acid by using methanol-water rectifying tower residue produced in course of producing sodium hyposulfite |
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| Publication Number | Publication Date |
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| CN1164527A true CN1164527A (en) | 1997-11-12 |
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| Application Number | Title | Priority Date | Filing Date |
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| CN 96118152 Pending CN1164527A (en) | 1996-05-08 | 1996-05-08 | Method for producing formic acid by using methanol-water rectifying tower residue produced in course of producing sodium hyposulfite |
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Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102199417A (en) * | 2010-03-23 | 2011-09-28 | 张以河 | Technology for preparing mineral composite solid lubricant for well drilling on basis of by-products in chemical industry |
| CN103058146A (en) * | 2011-12-17 | 2013-04-24 | 湖北宜化化工股份有限公司 | Method for recycling residues of sodium dithionite |
| CN104177248A (en) * | 2014-08-25 | 2014-12-03 | 湖南中成化工有限公司 | Novel treatment technique of sodium hydrosulfite mother solution rectification raffinate |
| CN106748737A (en) * | 2016-11-16 | 2017-05-31 | 南京师范大学 | A kind of method of formic acid in azeotropic extraction rectifying concentration aqueous formic acid |
-
1996
- 1996-05-08 CN CN 96118152 patent/CN1164527A/en active Pending
Cited By (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102199417A (en) * | 2010-03-23 | 2011-09-28 | 张以河 | Technology for preparing mineral composite solid lubricant for well drilling on basis of by-products in chemical industry |
| CN102199417B (en) * | 2010-03-23 | 2016-01-20 | 中国地质大学（北京） | One prepares drilling well mineral composite solid lubricating agent technology based on chemical byproduct |
| CN103058146A (en) * | 2011-12-17 | 2013-04-24 | 湖北宜化化工股份有限公司 | Method for recycling residues of sodium dithionite |
| CN104177248A (en) * | 2014-08-25 | 2014-12-03 | 湖南中成化工有限公司 | Novel treatment technique of sodium hydrosulfite mother solution rectification raffinate |
| CN104177248B (en) * | 2014-08-25 | 2015-09-09 | 湖南中成化工有限公司 | A kind of distillation residual liquid treatment process of vat powder mother liquor |
| CN106748737A (en) * | 2016-11-16 | 2017-05-31 | 南京师范大学 | A kind of method of formic acid in azeotropic extraction rectifying concentration aqueous formic acid |
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