CN1313431C - Method of preparing metal ion less adipic acid by nitric acid oxidation of cyclohexane oxidation liquid pickling water - Google Patents
Method of preparing metal ion less adipic acid by nitric acid oxidation of cyclohexane oxidation liquid pickling water Download PDFInfo
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- CN1313431C CN1313431C CNB2004100729319A CN200410072931A CN1313431C CN 1313431 C CN1313431 C CN 1313431C CN B2004100729319 A CNB2004100729319 A CN B2004100729319A CN 200410072931 A CN200410072931 A CN 200410072931A CN 1313431 C CN1313431 C CN 1313431C
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Abstract
The present invention discloses a method of preparing adipic acid without metal ions by the nitric acid oxidation of cyclohexane oxidation liquid pickling water, which belongs to a technique of preparing adipic acid. The method comprises the following steps: washing a cyclohexane oxidation liquid at a normal temperature and normal pressure according to the mass ratio of 0.5 to 3.0 of water to the cyclohexane oxidation liquid; concentrating the washed acid water under reduced pressure to obtain concentrated pickling water; adding nitric acid at 60 to 100 DEG C, and carrying out oxidation reaction; crystallizing, filtering and drying the oxidized solution to obtain crude adipic acid; recrystallizing to obtain refining adipic acid whose purity is above 99.5%. The present invention has the advantages of simple reaction processes and low production cost; obtained adipic acid has high product purity and contains no metal ions, and the obtained adipic acid can be directly used as raw materials for synthetic fibers.
Description
Technical field
The present invention relates to a kind of cyclohexane oxidation liquid pickling water method of preparing metal ion less adipic acid by nitric acid oxidation, belong to the not technology of preparing of metal ion hexanodioic acid.
Background technology
At present, industrial preparation hexanodioic acid and hexanolactam all are to pass through air oxidation of cyclohexane, the method that at first prepares pimelinketone and hexalin is carried out, because the complicacy of atmospheric oxidation process except generating principal product pimelinketone and hexalin, is also wanted the diprotic acid of by-product about 10% simultaneously, monoprotic acid, alcohol acid, lactone, materials such as tar.The way that these by products wash with water is usually separated from reaction solution, because major part is an organic acid in the washing thing, therefore normal these washing water of title are acid washing water.
Processing to these acid washing waters, initial way of burning commonly used is handled in the industrial production, but for a factory that produces 100000 tons of hexanolactams or hexanodioic acid per year, the amount of by product is very big, it is too big directly to burn financial loss, and burning process itself has also caused secondary pollution to environment simultaneously.A kind of simple, the cheap novel process and the novel method that prepare and reclaim valuable by product from washing water are studied and explore always to cause people already constantly.
From top various patents both domestic and external as can be seen, people are main particularly wherein the hexanodioic acid of diprotic acid that reclaims from washing water, roughly can be divided into two class methods in these patents, and a class is the method that physics reclaims, and a class is the method for chemical recovery.The method that physics reclaims is simple, and cost recovery is low, but the purity of hexanodioic acid is not high, and the rate of recovery is also low; This situation mainly is used in the factory of hexanodioic acid as the finished product, because the not high filter cake of purity, can incorporate in the main flow material that pimelinketone and hexalin nitric acid oxidation prepare hexanodioic acid, and the overall yield that has increased hexanodioic acid is just passable.With the hexanolactam is the factory of the finished product, the method of physical treatment acid washing water is just improper, because the adipic acid product that resultant purity is not high can not be as commodity selling, so also need to carry out further chemical treatment method, two steps like this handle, increase hexanodioic acid preparation technology's complicacy and preparation cost on the contrary, therefore used chemically treated method more suitable in this case.
Chemical process prepares the patent of hexanodioic acid from the acid washing water of cyclohexane oxide solution quite a few, the nitric acid catalytic oxidation is a main stream approach wherein, because vanadium, the use of catalyzer such as copper, make inevitably in the hexanodioic acid of preparing and contain metal ion, and in many purposes of hexanodioic acid concentration of metal ions is required very strictness, especially as the fiber synthesis material, this has just limited the range of application of hexanodioic acid.
Summary of the invention
Purpose of the present invention just provides a kind of method with the cyclohexane oxidation liquid pickling water preparing metal ion less adipic acid by nitric acid oxidation, and this procedure is simple, the content height of hexanodioic acid.
The present invention realized by following technical proposals, a kind ofly prepares the not method of metal ion hexanodioic acid with the cyclohexane oxidation liquid pickling water nitric acid oxidation, it is characterized in that comprising following process:
1. under normal pressure, by water and cyclohexane oxide solution mass ratio is 0.5-3.0, water washs cyclohexane oxide solution, obtains containing the acid washing water that comprises hexanodioic acid, alcohol acid, lactone, superoxide and monocarboxylic acid mixture, and wherein organic mass content is 15-25%.
2. under normal pressure, with resin acid washing water is decoloured, or without decolouring, under normal pressure or decompression, concentrate then and obtain the gelled acid wash water, organic mass content is 45-55% in the gelled acid wash water, and wherein the content of hexanodioic acid is 70-85% in the organism, and the content of alcohol acid is 5-10%, the content of superoxide is 2-3%, and all the other are monocarboxylic acid and lactone.
3. to step 2 gelled acid wash water, add nitric acid down at 60-100 ℃ and carry out oxidizing reaction, the concentration of used nitric acid is 35-65%, and the consumption of nitric acid is that every 100g gelled acid wash water is the nitric acid of 30-80mL; Oxidation time is 0.5-3.0h, the oxidation liquid that is decoloured or do not have to decolour.
4. to the step 3 oxidation liquid that obtains decolouring, or the oxidation liquid that does not have decolouring is behind activated carbon decolorizing, 20-25 ℃ through crystallization, filter and make the thick hexanodioic acid that mass content is 90-95%.
5. the thick hexanodioic acid that step 4 is obtained, making mass content after carrying out recrystallization at 20-25 ℃ is smart hexanodioic acid more than 99.5%.
The invention has the advantages that reaction process is simple, production cost is low.The adipic acid product purity height that makes, and metal ion not can directly be used as synthetic fiber material.
Embodiment
Embodiment 1
Get the acid washing water of the cyclohexane oxide solution of 500mL, resin column by φ a 50 * 400mm decolours, acid washing water after the decolouring is concentrated at the pressure of 0.01-0.04MPa, the 105.3g organic content is 48% concentrated solution, concentrated solution is added in the reactor, under constant speed stirs, add 60mL, 65% nitric acid carries out oxidizing reaction, control reaction temperature is 85-90 ℃, keep reaction 3h, crystallisation by cooling then, filtration drying, get thick hexanodioic acid 36.5g, the purity of hexanodioic acid is 93.0%.Thick hexanodioic acid is dissolved in the hot water of 100mL, carries out recrystallization, filter, drying gets smart caproic acid 28.3g, and the purity of hexanodioic acid is 99.6%.
Embodiment 2
The concentrated solution of acid washing water of getting the 100g organic content and be 50% cyclohexane oxide solution is in reactor, the nitric acid of Dropwise 5 0mL65% carries out oxidizing reaction in 50min, control reaction temperature is 80-90 ℃, keep reaction 2h, adding the 10g activated carbon decolours, filtered while hot, mother liquor carries out crystallisation by cooling, filters, and gets the thick caproic acid of 28.3g, the purity of product is 94.2%, again thick hexanodioic acid is dissolved in the hot water of 100mL, carries out recrystallization, get the smart hexanodioic acid of 22.6g, the purity of hexanodioic acid is 99.5%, and product is a white.
Embodiment 3
The nitric acid that in reactor, adds 60mL65%, add water then and be made into 40% (quality) concentration, at 65 ℃, the dropping organic content is 48% cyclohexane oxidation liquid pickling water concentrated solution 101.3g, feed rate so that reaction bumping does not take place is control criterion, keep reaction 3.5h, decolour at 80 ℃ with the 10g gac then, reaction solution after the filtration is cooled to about 20 ℃, the hexanodioic acid that crystallization is gone out filters, drying, gets the thick hexanodioic acid of 29.3g, adds 100mL water and carries out recrystallization, get the smart hexanodioic acid of 23.8g, the purity of product is 98.1%.
Embodiment 4
The processing of at first resin column of acid washing water by φ a 50 * 400mm being decoloured, get the acid washing water after 315g decolours, under 0.001-0.05MPa pressure, concentrate, the 102.5g organic content is 51.5% concentrated solution, put into oxidation reactor then, at 60 ℃, drip the nitric acid of 30mL65%, keep reaction 3h, stopped reaction then, reaction solution is naturally cooled in air about 20 ℃, and hexanodioic acid crystallizes out from reaction solution, gets the thick hexanodioic acid of 36.2g behind the filtration drying, add 100mL water and carry out recrystallization, get the smart hexanodioic acid of 27.3g, the purity of product is 97.4%, and product is faint yellow.
Embodiment 5
The concentrated solution of getting the 100g organic content and be 52% cyclohexane oxidation liquid pickling water is in reactor, the nitric acid that drips 40mL 65% in 30min carries out oxidizing reaction, control reaction temperature is 50 ℃, keep reaction 3h, behind the stopped reaction reaction solution is naturally cooled to 20 ℃ in air, hexanodioic acid crystallizes out from reaction solution, get the thick hexanodioic acid of 40.2g behind the filtration drying, the content of hexanodioic acid is 84.32%, add 100mL water and carry out recrystallization, get the smart hexanodioic acid of 31.5g behind the filtration drying, the purity of product is 92.9%, and the color of product is yellow.
Embodiment 6
The concentrated solution of getting the 100g organic content and be 50% cyclohexane oxidation liquid pickling water is in reactor, the nitric acid that drips 70mL 65% in 30min carries out oxidizing reaction, control reaction temperature is 50 ℃, keep reaction 3h, then with the 10g gac at 70 ℃ of 3h that decolour, filtered while hot, reaction solution after the filtration is cooled to 20 ℃, then the hexanodioic acid that crystallization is gone out filter, drying, get the thick hexanodioic acid of 36.8g, add 100mL water and carry out recrystallization, get the smart hexanodioic acid of 28.6g, the purity of product is 96.5%.
Claims (1)
1. one kind with the cyclohexane oxidation liquid pickling water method of preparing metal ion less adipic acid by nitric acid oxidation, it is characterized in that comprising following process:
1) under the normal pressure, by water and cyclohexane oxide solution mass ratio is 0.5-3.0, water washs cyclohexane oxide solution, obtains containing the acid washing water that comprises hexanodioic acid, alcohol acid, lactone, superoxide and monocarboxylic acid mixture, and wherein organic mass content is 15-25%;
2) under the normal pressure, with resin acid washing water is decoloured, or without decolouring, under normal pressure or decompression, concentrate then and obtain the gelled acid wash water, organic mass content is 45-55% in the gelled acid wash water, and wherein the content of hexanodioic acid is 70-85% in the organism, and the content of alcohol acid is 5-10%, the content of superoxide is 2-3%, and all the other are monocarboxylic acid and lactone;
3) to step 2) the gelled acid wash water, add nitric acid down at 60-100 ℃ and carry out oxidizing reaction, the concentration of used nitric acid is 35-65%, the consumption of nitric acid is that every 100g gelled acid wash water is the nitric acid of 30-80mL; Oxidation time is 0.5-3.0 hour, the oxidation liquid that is decoloured or do not have to decolour;
4) to the step 3) oxidation liquid that obtains decolouring, or the oxidation liquid that does not have decolouring is behind activated carbon decolorizing, 20-25 ℃ through crystallization, filter and make the thick hexanodioic acid that mass content is 90-95%;
5) the thick hexanodioic acid that step 4) is obtained, making mass content after carrying out recrystallization at 20-25 ℃ is smart hexanodioic acid more than 99.5%.
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| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CNB2004100729319A CN1313431C (en) | 2004-11-26 | 2004-11-26 | Method of preparing metal ion less adipic acid by nitric acid oxidation of cyclohexane oxidation liquid pickling water |
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| Application Number | Priority Date | Filing Date | Title |
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| CNB2004100729319A CN1313431C (en) | 2004-11-26 | 2004-11-26 | Method of preparing metal ion less adipic acid by nitric acid oxidation of cyclohexane oxidation liquid pickling water |
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| CN1651391A CN1651391A (en) | 2005-08-10 |
| CN1313431C true CN1313431C (en) | 2007-05-02 |
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| CNB2004100729319A Expired - Fee Related CN1313431C (en) | 2004-11-26 | 2004-11-26 | Method of preparing metal ion less adipic acid by nitric acid oxidation of cyclohexane oxidation liquid pickling water |
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Families Citing this family (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN100450989C (en) * | 2006-09-18 | 2009-01-14 | 沈阳工业大学 | Method of preparing non-metallic ion 4,5,6-carbon diacid |
| CN102869642A (en) * | 2010-03-05 | 2013-01-09 | 莱诺维亚公司 | Adipic acid composition |
| CN102757332B (en) * | 2011-04-27 | 2015-07-01 | 中国石油化工集团公司 | Processing method of cyclohexane oxidation products |
| CN103787540B (en) * | 2014-01-16 | 2015-02-18 | 新疆蓝德精细石油化工股份有限公司 | BI waste liquor recycling method |
| CN104276937B (en) * | 2014-06-27 | 2016-09-28 | 重庆华峰化工有限公司 | Adipic acid and the method for C* binary acid is prepared by cyclohexane oxidation by-product |
Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| GB1123514A (en) * | 1966-03-24 | 1968-08-14 | Basf Ag | Production of adipic acid |
| JPS5524152A (en) * | 1978-08-09 | 1980-02-21 | Sumitomo Chem Co Ltd | Recovery of high purity adipic acid |
| US4227021A (en) * | 1977-05-14 | 1980-10-07 | Basf Aktiengesellschaft | Production of adipic acid from acidic wash waters |
| JPS5741456B2 (en) * | 1973-07-13 | 1982-09-03 | ||
| DE4428977A1 (en) * | 1994-08-16 | 1996-02-22 | Bayer Ag | Processing by-prod. stream from direct oxidn. of cyclohexane to adipic acid |
-
2004
- 2004-11-26 CN CNB2004100729319A patent/CN1313431C/en not_active Expired - Fee Related
Patent Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| GB1123514A (en) * | 1966-03-24 | 1968-08-14 | Basf Ag | Production of adipic acid |
| JPS5741456B2 (en) * | 1973-07-13 | 1982-09-03 | ||
| US4227021A (en) * | 1977-05-14 | 1980-10-07 | Basf Aktiengesellschaft | Production of adipic acid from acidic wash waters |
| JPS5524152A (en) * | 1978-08-09 | 1980-02-21 | Sumitomo Chem Co Ltd | Recovery of high purity adipic acid |
| DE4428977A1 (en) * | 1994-08-16 | 1996-02-22 | Bayer Ag | Processing by-prod. stream from direct oxidn. of cyclohexane to adipic acid |
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