CN1033024C - Process for extraction of dicarboxylic acid and its esters from waste liquid after production of hexandioic acid - Google Patents
Process for extraction of dicarboxylic acid and its esters from waste liquid after production of hexandioic acid Download PDFInfo
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- CN1033024C CN1033024C CN 92106020 CN92106020A CN1033024C CN 1033024 C CN1033024 C CN 1033024C CN 92106020 CN92106020 CN 92106020 CN 92106020 A CN92106020 A CN 92106020A CN 1033024 C CN1033024 C CN 1033024C
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- acid
- esterification
- alcohol
- dicarboxylic acid
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Abstract
The present invention relates to a method for extracting dicarboxylic acid and ester thereof from waste liquid in the production of hexandioic acid. In the method, various chemical products, such as C4 to 6 dicarboxylic acid (21), refined C4 to 6 dicarboxylic ester (30), C4 to 6 monodicarboxylic ester (31), (32), (33), monodicarboxylic acid (butane diacid, glutaric acid and hexane diacid) (34), (35), (36), etc. which are prepared by evaporation, esterification, rectification and hydrolysis, are inland rare chemical products purified from waste liquid; waste is changed into valuables, and the problem that environment is polluted by waste is also solved. The present invention has the advantages of low production cost, advanced technique, less investment, high effectiveness and obvious economic and social benefit.
Description
The present invention relates to extract dicarboxylic acid and reaches the chemical process of its ester class of dicarboxylic acid production thus from hexane diacid preparation waste liquid.
At present, domestic recovery and utilization for hexane diacid preparation waste liquid found as yet; Many methods were abroad once arranged, as with urea complexation Separation and Recovery dicarboxylic acid, Japan's special permission communique clear-52-78818 and clear 52-78819; Useful recrystallization method, solvent extration, distillation method be Separation and Recovery in addition.These methods are documented among USpat, the Nos, 3290369,3329712,3338959,3511757.Aforesaid method, some is the product purity height, but yield is not high; Some is the yield height, and of low quality; Some just has been recovered to the mixture of Succinic Acid, pentanedioic acid, hexanodioic acid, and (this paper is hereinafter to be referred as C
4-6).
In order to overcome above-mentioned shortcoming, the purpose of this invention is to provide a kind of about by hexalin and pimelinketone in the presence of copper, vanadium ion, produce with nitric acid oxidation in the hexane diacid preparation waste liquid of being discharged in the production process of hexanodioic acid by evaporation, esterification, rectifying, hydrolysis and produce quality height, C that yield is high
4-6Dicarboxylic acid (Succinic Acid, pentanedioic acid, hexanodioic acid) and smart C
4-6Dicarboxylic ester (succinate, pentanedioic acid diester, di adipate mixture) and C
4-6Single dicarboxylic ester (succinate, glutarate, adipic acid ester) and single dicarboxylic acid multiple Chemicals such as (Succinic Acid, pentanedioic acid, hexanodioic acids).
Succinic Acid is market Chemicals in short supply, of many uses, expensive, and domestic common price reaches 18000 yuan/ton.
The pentanedioic acid Chemicals still belong to internal blank, and country need be from external import pentanedioic acid because of military project in 1978, and it is 450,000 yuan/ton that its price is amounted to Renminbi.
The present invention extracts domestic rare Chemicals from waste liquid, be to turn waste into wealth, and has both solved the waste pollution environmental problem, has reduced production cost of products again.This method technology advanced person, technology maturation, easy to operate, less investment, high efficiency have considerable economic and social benefit.
The present invention is described in further detail below in conjunction with drawings and Examples.
What accompanying drawing provided is process flow sheet of the present invention.
The present invention is by four step process methods: evaporation-esterification-rectifying-hydrolysis.
1, evaporation:
Evaporation technology is to concentrate, cool off, tie sheet and produce C
4-6Dicarboxylic acid mixture (21).
The waste liquid (20) that hexanodioic acid is produced is removed most of water (water content is less than 3%) through evaporation concentration.
The waste liquid (20) that hexanodioic acid production is discharged often contains 70-90% moisture, and by two polyphone climbing-film evaporators (1), (2), the material that comes out is fusion dicarboxylic acid (26) continuously.Its moisture can reach below 5%, and this strand material can directly enter does the processing of second step process in the esterifying kettle (5), also can water be deviate to less than 3% through a horizontal-type evaporator (3), becomes shred shape solid and makes C through a flaker (4) cooling junction plate then
4-6Dicarboxylic acid (21).
2, esterification:
Esterification technique is esterification, purifies and produce the smart C of senior solvent
4-6Dicarboxylic ester (30).
With fusion C
4-6Dicarboxylic acid (26) and the used alcohol of esterification are C
1-C
4Alcohol (23) in the alcohol carries out esterification.
This alcohol (23) is added one fusion C is housed
4-6In the esterifying kettle (5) of dicarboxylic acid (26), add catalyzer (22), catalyzer (22) is a kind of inorganic acids, solid super-strong acid is arranged, for example ZrO-TiO
2Type solid acid, liquid acid.Esterification is to be to carry out under 60-140 ℃ in temperature, reaction pressure is a normal pressure, esterification is constantly removed the water (27) that dereaction generated through a separation column (6), the recovery alcohol (24) after separating that comes out with water turns back in the esterifying kettle (5), make the reaction trend fully, esterification yield reaches more than 90%.
Material one thick C with reaction end in the esterifying kettle (5)
4-6Dicarboxylic ester (28) is removed a part of catalyzer and other impurity through filter (7), and its filtrate mainly is C
4-6Dicarboxylic ester (29).With this liquor C
4-6Dicarboxylic ester (29) steams tower (8) at the beginning of one, with the foreshot (comprising alcohol, water and other low boilers) of removing minute quantity, the tower still then leaves nonesterified C
4-6Heavy components such as dicarboxylic acid (19), it turns back in the esterifying kettle (5), and obtaining most of middle distillate is the very high smart C of purity
4-6Dicarboxylic ester (30) (mixture of succinate, pentanedioic acid diester, di adipate) is a kind of high-temperature solvent, especially C
4-6The dimethyl dicarboxylate.
3, rectifying:
Rectification process is smart C
4-6Dicarboxylic ester (30) is separated into single dicarboxylic ester to them through a rectifying tower (9): succinate (31), pentanedioic acid diester (32) and di adipate (33), for example dimethyl succinate, Methyl glutarate, dimethyl adipate or corresponding diethyl ester, di-n-butyl etc.Rectifying is under reduced pressure carried out.Rectifying tower still thing (37) turns back in the esterifying kettle (5).
4, hydrolysis:
Hydrolysis process is that one dicarboxylic ester (31), (32), (33) are put into hydrolysis kettle (16), (13), (10) respectively, adds a certain amount of water separately and is hydrolyzed, and then adds an amount of hydrolyst for the ester of facile hydrolysis not.(sulfuric acid that for example generally adds 1-10% the water yield).Hydrolysis reaction carries out under boiling temperature, takes out the alcohol (25) that reaction generates simultaneously continuously, and the hydrolysis reaction trend is finished, and the alcohol of taking-up (25) returns and is affixed in the esterification technique process.
Make after hydrolysis reaction finishes dicarboxylic acid solution crystallisation by cooling it, pass through filter (18), (15), (12) then separately and obtain pure corresponding single dicarboxylic acid: Succinic Acid (36), pentanedioic acid (35) and hexanodioic acid (34).
Filter the mother liquor (17), (14), (11) of gained, be used for the hydrolysis reaction of next batch separately.
Advantage of the present invention and good effect:
1, the separation of mixed dicarboxylic acid has been adopted through generating the way of ester, so yield Height, quality are also high.
2, esterification adopts the way of taking out water, and the esterification trend is finished, and With the situation of methyl alcohol or ethyl esterification, taking out water generally will be with benzene or toluene etc. as generation Aqua, the present invention then directly separates water and alcohol with a fractionating column, reaches and takes away The purpose of water is omitted one and is reclaimed benzene or toluene etc. with the trouble technology of aqua.
3, the temperature of esterification is that normal pressure carries out under the boiling point that is higher than alcohol, and reaction is established Standby simple, handling safety is because general low-carbon alcohols is being higher than under the condition of atmospheric boiling point The row reaction needs a pressure-resistant equipment, and appointed condition requires high, and cost of equipment is big, and Operate the reaction that low-boiling point alcohol with pressure is participated in, itself just has potential unsafe factor; It is an outstanding advantages that the present invention adopts normal pressure esterification.
4, general carboxylate adopts WATER-WASHING METHOD to obtain thick mixed ester with layering, inorganic Acid and catalyst separation are gone out, and this facture will be lost ester partly and nonesterified Dicarboxylic acids, but water lotion can only discard as waste liquid, also polluted environment; The present invention adopts Give distillation way extract mixed ester, exempted that WATER-WASHING METHOD is this gives two in the processing Individual shortcoming.
Claims (1)
1, a kind of method of from hexane diacid preparation waste liquid, extracting dicarboxylic acid and ester class thereof that relates to; It is characterized in that it being to produce C by operations such as evaporation, esterification, rectifying, hydrolysis
4-6Dicarboxylic acid and ester class thereof, catalyzer (22) used in esterification is a kind of mineral acid, comprises solid super-strong acid, as ZrO-TiO
2The type solid acid, the temperature of esterification is 60-140 ℃, and esterification is constantly removed the water (27) that dereaction generated through a separation column (6), turns back in the esterifying kettle (5) through separating back recovery alcohol (24), make the reaction trend fully, the used alcohol of esterification is C
1-C
4Alcohol (23) in the alcohol, in this operation of hydrolysis, hydrolysis reaction carries out under boiling temperature, take out the alcohol (25) that reaction generates simultaneously continuously, the hydrolysis reaction trend is finished, the alcohol (25) that takes out turns back in the alcoholization operation, passes through strainer (18), (15), (12) resulting mother liquor (17), (14), (11) behind the resulting dicarboxylic acid solution of the hydrolysis reaction crystallisation by cooling separately, is used for the hydrolysis reaction of next batch separately.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN 92106020 CN1033024C (en) | 1992-01-15 | 1992-01-15 | Process for extraction of dicarboxylic acid and its esters from waste liquid after production of hexandioic acid |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN 92106020 CN1033024C (en) | 1992-01-15 | 1992-01-15 | Process for extraction of dicarboxylic acid and its esters from waste liquid after production of hexandioic acid |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN1067046A CN1067046A (en) | 1992-12-16 |
| CN1033024C true CN1033024C (en) | 1996-10-16 |
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| Application Number | Title | Priority Date | Filing Date |
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| CN 92106020 Expired - Fee Related CN1033024C (en) | 1992-01-15 | 1992-01-15 | Process for extraction of dicarboxylic acid and its esters from waste liquid after production of hexandioic acid |
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Families Citing this family (13)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US6291708B1 (en) * | 1999-04-28 | 2001-09-18 | A.E. Staley Manufacturing Co. | Process for production of organic acids and esters thereof |
| CN100410229C (en) * | 2006-08-18 | 2008-08-13 | 李强国 | Method of treating hexane diacid preparation waste liquid |
| CN101016245B (en) * | 2007-02-17 | 2010-08-04 | 青岛伊科思技术工程有限公司 | Preparing method for mixed dibasic acid ester from adipic acid production waste liquid and treatment method for the waste liquid |
| CN102211992B (en) * | 2011-04-18 | 2013-04-24 | 湖南百利工程科技股份有限公司 | Process for reclaiming dibasic acid from adipic acid production waste solution |
| CN103343147B (en) * | 2013-07-31 | 2014-12-31 | 山东兰典生物科技股份有限公司 | Method for preparing dibutyl succinate from cassava raw materials |
| KR20180019611A (en) * | 2015-06-23 | 2018-02-26 | 쉘 인터내셔날 리써취 마트샤피지 비.브이. | Apparatus and method for reactive distillation for wastewater treatment |
| CN105924345A (en) * | 2016-06-22 | 2016-09-07 | 江苏永安制药有限公司 | Preparation method for sodium phenylbutyrate |
| CN106117045A (en) * | 2016-06-22 | 2016-11-16 | 北京阳光诺和药物研究有限公司 | A kind of purification process of phenylbutyric acid |
| CN106810448A (en) * | 2017-01-10 | 2017-06-09 | 中国科学院过程工程研究所 | The processing system and processing method and purposes of waste liquid are produced in a kind of carbonyl synthesis acetic acid |
| CN106957223B (en) * | 2017-04-24 | 2019-11-26 | 上海华峰新材料研发科技有限公司 | A method of purifying C4~C6 dicarboxylic acid monomer from adipic acid by-product mixed dibasic acid |
| CN110283074A (en) * | 2019-07-29 | 2019-09-27 | 河南久圣化工有限公司 | A kind of process units and its production method of mixed dibasic acid dimethyl ester |
| CN110283075A (en) * | 2019-07-29 | 2019-09-27 | 河南久圣化工有限公司 | A kind of process units and method using adipic acid waste liquid production dimethyl glutarate |
| KR20220052926A (en) | 2019-08-30 | 2022-04-28 | 쉘 인터내셔날 리써취 마트샤피지 비.브이. | Method for making organic carbonates |
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- 1992-01-15 CN CN 92106020 patent/CN1033024C/en not_active Expired - Fee Related
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