CN113979948A - Method for recovering AABI from mother liquor of AABI reduction process - Google Patents
Method for recovering AABI from mother liquor of AABI reduction process Download PDFInfo
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- CN113979948A CN113979948A CN202111534607.4A CN202111534607A CN113979948A CN 113979948 A CN113979948 A CN 113979948A CN 202111534607 A CN202111534607 A CN 202111534607A CN 113979948 A CN113979948 A CN 113979948A
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- China
- Prior art keywords
- aabi
- mother liquor
- temperature
- reduction process
- filtering
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- 239000012452 mother liquor Substances 0.000 title claims abstract description 28
- 238000000034 method Methods 0.000 title claims abstract description 19
- 238000011946 reduction process Methods 0.000 title claims abstract description 17
- 238000001914 filtration Methods 0.000 claims abstract description 25
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims abstract description 20
- 239000012535 impurity Substances 0.000 claims abstract description 14
- WASQWSOJHCZDFK-UHFFFAOYSA-N diketene Chemical compound C=C1CC(=O)O1 WASQWSOJHCZDFK-UHFFFAOYSA-N 0.000 claims abstract description 11
- 239000003638 chemical reducing agent Substances 0.000 claims abstract description 10
- 239000000706 filtrate Substances 0.000 claims description 24
- 238000003756 stirring Methods 0.000 claims description 20
- NBIIXXVUZAFLBC-UHFFFAOYSA-N Phosphoric acid Chemical compound OP(O)(O)=O NBIIXXVUZAFLBC-UHFFFAOYSA-N 0.000 claims description 18
- 239000000047 product Substances 0.000 claims description 15
- 150000003839 salts Chemical class 0.000 claims description 10
- 229910000147 aluminium phosphate Inorganic materials 0.000 claims description 9
- 239000003963 antioxidant agent Substances 0.000 claims description 8
- 230000003078 antioxidant effect Effects 0.000 claims description 8
- 238000001816 cooling Methods 0.000 claims description 7
- 229910052799 carbon Inorganic materials 0.000 claims description 6
- DWAQJAXMDSEUJJ-UHFFFAOYSA-M Sodium bisulfite Chemical group [Na+].OS([O-])=O DWAQJAXMDSEUJJ-UHFFFAOYSA-M 0.000 claims description 5
- 238000010438 heat treatment Methods 0.000 claims description 5
- JVBXVOWTABLYPX-UHFFFAOYSA-L sodium dithionite Chemical compound [Na+].[Na+].[O-]S(=O)S([O-])=O JVBXVOWTABLYPX-UHFFFAOYSA-L 0.000 claims description 5
- 235000010267 sodium hydrogen sulphite Nutrition 0.000 claims description 5
- 239000002253 acid Substances 0.000 claims description 4
- 238000001035 drying Methods 0.000 claims description 3
- 238000006722 reduction reaction Methods 0.000 abstract description 7
- -1 5-aminobenzimidazole ketone Chemical class 0.000 abstract description 6
- 239000002351 wastewater Substances 0.000 abstract description 5
- 238000004519 manufacturing process Methods 0.000 abstract description 4
- 238000003889 chemical engineering Methods 0.000 abstract description 2
- 238000002425 crystallisation Methods 0.000 abstract description 2
- 230000008025 crystallization Effects 0.000 abstract description 2
- 238000003912 environmental pollution Methods 0.000 abstract description 2
- 239000012847 fine chemical Substances 0.000 abstract description 2
- 239000000463 material Substances 0.000 abstract description 2
- 238000004042 decolorization Methods 0.000 abstract 1
- 238000011033 desalting Methods 0.000 abstract 1
- 238000006243 chemical reaction Methods 0.000 description 2
- 238000000643 oven drying Methods 0.000 description 2
- 239000000049 pigment Substances 0.000 description 2
- 239000002699 waste material Substances 0.000 description 2
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 2
- KQNZKBRSEJLVEO-UHFFFAOYSA-N 3-oxo-n-(2-oxobenzimidazol-5-yl)butanamide Chemical compound C1=C(NC(=O)CC(=O)C)C=CC2=NC(=O)N=C21 KQNZKBRSEJLVEO-UHFFFAOYSA-N 0.000 description 1
- 230000010933 acylation Effects 0.000 description 1
- 238000005917 acylation reaction Methods 0.000 description 1
- 239000003513 alkali Substances 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 238000011031 large-scale manufacturing process Methods 0.000 description 1
- 238000002844 melting Methods 0.000 description 1
- 230000008018 melting Effects 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 238000006396 nitration reaction Methods 0.000 description 1
- 230000003647 oxidation Effects 0.000 description 1
- 238000007254 oxidation reaction Methods 0.000 description 1
- 239000000843 powder Substances 0.000 description 1
- 239000002994 raw material Substances 0.000 description 1
- 238000011084 recovery Methods 0.000 description 1
- 238000007670 refining Methods 0.000 description 1
- 238000007363 ring formation reaction Methods 0.000 description 1
- 239000002904 solvent Substances 0.000 description 1
- 230000002194 synthesizing effect Effects 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07D—HETEROCYCLIC COMPOUNDS
- C07D235/00—Heterocyclic compounds containing 1,3-diazole or hydrogenated 1,3-diazole rings, condensed with other rings
- C07D235/02—Heterocyclic compounds containing 1,3-diazole or hydrogenated 1,3-diazole rings, condensed with other rings condensed with carbocyclic rings or ring systems
- C07D235/04—Benzimidazoles; Hydrogenated benzimidazoles
- C07D235/24—Benzimidazoles; Hydrogenated benzimidazoles with hetero atoms or with carbon atoms having three bonds to hetero atoms with at the most one bond to halogen, e.g. ester or nitrile radicals, directly attached in position 2
- C07D235/26—Oxygen atoms
Abstract
The invention belongs to the technical field of fine chemical engineering, and relates to a method for recovering AABI from mother liquor in an AABI reduction process, which comprises the steps of mother liquor acidity regulation, filtration, decolorization and reduction, dropwise addition, temperature reduction and filtration, wherein the wastewater is directly subjected to impurity removal and desalting through acidity regulation, then the crystallization process is skipped, a small amount of reducing agent is added to reduce oxidized 5-aminobenzimidazole ketone, then activated carbon is added to decolor and further remove impurities, and then diketene is dropwise added to react to generate an AABI product with low solubility to be separated out. The process is simple, and can be completed by using normal AABI production equipment without additionally arranging equipment, so that the cost is reduced; the invention can reduce the loss of materials, improve the yield of AABI, create higher economic value for enterprises, relieve the pressure of treating wastewater in the reduction step of AABI on the environment and reduce the environmental pollution.
Description
Technical Field
The invention belongs to the technical field of fine chemical engineering, and particularly relates to a method for recovering AABI from mother liquor of an AABI reduction process.
Background
AABI (5-acetoacetylaminobenzimidazolone), white-like powder, the molecular weight of 233 and the melting point of more than 350 ℃, and is mainly used as a raw material for synthesizing pigment yellow and pigment orange and the like.
At present, the production flow of domestic large-scale production of AABI mainly comprises four steps, namely cyclization, nitration, reduction and acylation, wherein a product in the reduction step is 5-aminobenzimidazole ketone, a large amount of water is used as a solvent in the step, the 5-aminobenzimidazole ketone has high water solubility, and more 5-aminobenzimidazole ketone is inevitably dissolved in a mother liquor (waste liquor) after the reaction is finished, so that the yield of the product is low and the cost is high. At present, loss is generally reduced by a mother liquor applying mode, but as the reaction process needs to be repeatedly neutralized by acid and alkali, salt and other impurities in the mother liquor can be increased along with the increase of the applying batch, the purity of the product can be reduced, the applying times can be limited so as to ensure the quality of the product, the mother liquor reaching the applying times has more salt and impurity contents, the dissolved 5-aminobenzimidazole ketone is recovered by using a traditional recovery method, the impurities are more and low, the oxidation phenomenon is serious, the direct production and use can not be carried out, the refining cost is high, and the repayment can not be carried out, so the mother liquor can only be used as wastewater for treatment, and the cost waste is caused.
Disclosure of Invention
The invention aims to provide a method for recovering AABI from mother liquor of an AABI reduction process.
The technical scheme adopted by the invention for solving the technical problems is as follows: a method for recovering AABI from an AABI reduction process mother liquor comprising the steps of:
1) mother liquor acid regulation: adding phosphoric acid into the mother liquor of the AABI reduction process at normal temperature, adjusting the pH value to 4-4.5, stirring at normal temperature, and keeping the temperature to fully separate out impurities and salt, wherein the temperature is controlled to be not more than 35 ℃, and the time for keeping the temperature is 15-20 min;
2) and (3) filtering: keeping normal temperature for filtering, and filtering to remove impurities and salt, wherein the filtering temperature is not more than 35 ℃;
3) decoloring and reducing: adding reducing agent, antioxidant and active carbon into the filtered filtrate, heating to 90-95 deg.C under stirring, maintaining the temperature for 25-30min, filtering off active carbon, and collecting filtrate;
4) dropwise adding: controlling the temperature of the filtrate in the step 3) to be 80-85 ℃, dropwise adding diketene at a constant speed under stirring, stirring after dropwise adding, and keeping the temperature for 30 min;
5) cooling and filtering: cooling to a temperature of less than 45 ℃, filtering to obtain an AABI wet product, and drying to obtain an AABI dry product.
Further, the phosphoric acid in the step 1) is 85% phosphoric acid.
Further, the reducing agent added in the step 3) is sodium hydrosulfite, and the antioxidant is sodium bisulfite.
Further, the addition amounts of the reducing agent, the antioxidant and the activated carbon in the step 3) are as follows: every 1m31.6kg of reducing agent, 5kg of antioxidant and 4kg of active carbon are added into the mother liquor in the reduction process.
Further, the addition amount of the diketene in the step 4) is 1m343kg of diketene is added into the mother liquor of the reduction process.
The invention has the following beneficial effects: according to the invention, the acid is adjusted to directly remove impurities and salt from the wastewater, then the crystallization process is skipped, a small amount of reducing agent is added to reduce the oxidized 5-aminobenzimidazole ketone, then activated carbon is added to decolor and further remove impurities, and then diketene is added dropwise to react to generate an AABI product with low solubility to be separated out. The method has simple process, can be completed by using normal AABI production equipment, does not need to add new equipment, and reduces the cost; the invention can reduce the loss of materials, improve the yield of AABI, create higher economic value for enterprises, relieve the pressure of treating wastewater in the reduction step of AABI on the environment and reduce the environmental pollution.
Detailed Description
The following are specific examples of the present invention and further describe the technical solutions of the present invention, but the scope of the present invention is not limited to these examples. All changes, modifications and equivalents that do not depart from the spirit of the invention are intended to be included within the scope thereof.
Example 1
Adding 600ml of mother liquor of the AABI reduction step into a 1000ml flask, then adding 5.5g of 85% phosphoric acid, and adjusting the pH value to 4.5; stirring at 33 deg.C for about 15min to fully separate out impurities and salt, filtering with rapid filter paper, and collecting filtrate for further operation.
Transferring the filtrate into another 1000ml flask, adding 1.02g of sodium hydrosulfite and 3.01g of sodium bisulfite, stirring until the color of the filtrate changes from red to yellow, adding 2.5g of activated carbon, stirring, heating to 90-95 ℃, keeping the temperature for 25min, and performing hot filtration by using quick filter paper to obtain light yellow filtrate; transferring the filtrate into another 1000ml flask, controlling the temperature of the filtrate to be 80-85 ℃, and dropwise adding 26g of diketene at a constant speed under stirring for about 20 min; after the dripping is finished, controlling the temperature to be 80-85 ℃ and preserving the heat for 30 min; cooling to 44 deg.C, filtering with rapid filter paper to obtain wet AABI product, oven drying to obtain dry product 40.25g, and detecting purity to be 99.08%.
Example 2
Adding 600ml of mother liquor of the AABI reduction step into a 1000ml flask, then adding 5.5g of 85% phosphoric acid, and adjusting the pH value to 4.2; stirring at 30 deg.C for about 20min to fully separate out impurities and salt, filtering with rapid filter paper, and collecting filtrate for further operation.
Transferring the filtrate into another 1000ml flask, adding 1.01g of sodium hydrosulfite and 2.98g of sodium bisulfite, stirring until the color of the filtrate changes from red to yellow, then adding 2.5g of activated carbon, stirring, heating to 90-95 ℃, keeping the temperature for 30min, and performing hot filtration by using quick filter paper to obtain light yellow filtrate; transferring the filtrate into another 1000ml flask, controlling the temperature of the filtrate to be 80-85 ℃, and dropwise adding 26g of diketene at constant speed under stirring for about 22 min; after the dripping is finished, controlling the temperature to be 80-85 ℃ and preserving the heat for 30 min; cooling to 45 deg.C, filtering with rapid filter paper to obtain wet AABI product, oven drying to obtain dry AABI product 41.21g, and detecting purity to be 99.12%.
Example 3
Adding 600ml of mother liquor of the AABI reduction step into a 1000ml flask, then adding 5.5g of 85% phosphoric acid, and adjusting the pH value to 4; stirring at 32 deg.C for about 18min to fully separate out impurities and salt, filtering with rapid filter paper, and collecting filtrate for further operation.
Transferring the filtrate into another 1000ml flask, adding 1.02g of sodium hydrosulfite and 2.99g of sodium bisulfite, stirring until the color of the filtrate changes from red to yellow, adding 2.5g of activated carbon, stirring, heating to 90-95 ℃, keeping the temperature for 28min, and performing hot filtration by using quick filter paper to obtain light yellow filtrate; transferring the filtrate into another 1000ml flask, controlling the temperature of the filtrate to be 80-85 ℃, and dropwise adding 26g of diketene at constant speed under stirring for about 21 min; after the dripping is finished, controlling the temperature to be 80-85 ℃ and preserving the heat for 30 min; and (3) cooling to 43 ℃, filtering by using quick filter paper to obtain an AABI wet product, drying to obtain 42.01g of a dry product, and detecting the purity to be 99.11%.
The present invention is not limited to the above embodiments, and any structural changes made under the teaching of the present invention shall fall within the scope of the present invention, which is similar or similar to the technical solutions of the present invention.
The techniques, shapes, and configurations not described in detail in the present invention are all known techniques.
Claims (5)
1. A method for recovering AABI from an AABI reduction process mother liquor, comprising the steps of:
1) mother liquor acid regulation: adding phosphoric acid into the mother liquor of the AABI reduction process at normal temperature, adjusting the pH value to 4-4.5, stirring at normal temperature, and keeping the temperature to fully separate out impurities and salt, wherein the temperature is controlled to be not more than 35 ℃, and the time for keeping the temperature is 15-20 min;
2) and (3) filtering: keeping normal temperature for filtering, and filtering to remove impurities and salt, wherein the filtering temperature is not more than 35 ℃;
3) decoloring and reducing: adding reducing agent, antioxidant and active carbon into the filtered filtrate, heating to 90-95 deg.C under stirring, maintaining the temperature for 25-30min, filtering off active carbon, and collecting filtrate;
4) dropwise adding: controlling the temperature of the filtrate in the step 3) to be 80-85 ℃, dropwise adding diketene at a constant speed under stirring, stirring after dropwise adding, and keeping the temperature for 30 min;
5) cooling and filtering: cooling to a temperature of less than 45 ℃, filtering to obtain an AABI wet product, and drying to obtain an AABI dry product.
2. The method for recovering AABI from an AABI reduction process mother liquor of claim 1, wherein the phosphoric acid in step 1) is 85% phosphoric acid.
3. The method for recovering AABI from an AABI reduction process mother liquor as claimed in claim 1, wherein the reducing agent added in step 3) is sodium hydrosulfite and the antioxidant is sodium bisulfite.
4. The method for recovering AABI from an AABI reduction process mother liquor of claim 1, wherein the reducing agent, the antioxidant and the activated carbon are added in the amount of: every 1m31.6kg of reducing agent, 5kg of antioxidant and 4kg of active carbon are added into the mother liquor in the reduction process.
5. The method for recovering AABI from an AABI reduction process mother liquor as in claim 1, wherein the amount of diketene added in step 4) is per 1m343kg of diketene is added into the mother liquor of the reduction process.
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| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202111534607.4A CN113979948B (en) | 2021-12-15 | 2021-12-15 | Method for recovering AABI from AABI reduction process mother liquor |
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| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202111534607.4A CN113979948B (en) | 2021-12-15 | 2021-12-15 | Method for recovering AABI from AABI reduction process mother liquor |
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| Publication Number | Publication Date |
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| CN113979948A true CN113979948A (en) | 2022-01-28 |
| CN113979948B CN113979948B (en) | 2024-02-06 |
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Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101307023A (en) * | 2008-05-23 | 2008-11-19 | 东营市天正化工有限公司 | Production process of 5-acetyl acetamino benzimidazolone |
| CN106397332A (en) * | 2016-08-30 | 2017-02-15 | 山东汇海医药化工有限公司 | Method for treating 5-nitrobenzimidazolone mother liquor by reduction with iron powder |
| CN109232435A (en) * | 2018-11-01 | 2019-01-18 | 山东汇海医药化工有限公司 | A kind of preparation method of high-purity 5-acetoacetamido benzimidazolone |
| CN110845424A (en) * | 2019-12-11 | 2020-02-28 | 山东汇海医药化工有限公司 | Preparation method of 5-acetoacetylaminobenzimidazolone |
| CN113277983A (en) * | 2021-04-13 | 2021-08-20 | 东营市天正化工有限公司 | Treatment method of 5-aminobenzimidazole ketone mother liquor |
-
2021
- 2021-12-15 CN CN202111534607.4A patent/CN113979948B/en active Active
Patent Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101307023A (en) * | 2008-05-23 | 2008-11-19 | 东营市天正化工有限公司 | Production process of 5-acetyl acetamino benzimidazolone |
| CN106397332A (en) * | 2016-08-30 | 2017-02-15 | 山东汇海医药化工有限公司 | Method for treating 5-nitrobenzimidazolone mother liquor by reduction with iron powder |
| CN109232435A (en) * | 2018-11-01 | 2019-01-18 | 山东汇海医药化工有限公司 | A kind of preparation method of high-purity 5-acetoacetamido benzimidazolone |
| CN110845424A (en) * | 2019-12-11 | 2020-02-28 | 山东汇海医药化工有限公司 | Preparation method of 5-acetoacetylaminobenzimidazolone |
| CN113277983A (en) * | 2021-04-13 | 2021-08-20 | 东营市天正化工有限公司 | Treatment method of 5-aminobenzimidazole ketone mother liquor |
Non-Patent Citations (2)
| Title |
|---|
| 天津大学化工系: "5-乙酰乙酰氨基苯并咪唑酮的合成", 染料工业, no. 2, pages 204 - 3 * |
| 马洪庆等: "5-乙酰乙酰氨基苯并咪唑酮的合成工艺优化", 第六届全国精细化工清洁生产技术发展研讨会, pages 55 * |
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| CN113979948B (en) | 2024-02-06 |
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