CN103224449B - A kind of method of recovery of benzoic acid from mother liquor or waste liquid - Google Patents
A kind of method of recovery of benzoic acid from mother liquor or waste liquid Download PDFInfo
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- CN103224449B CN103224449B CN201310153214.8A CN201310153214A CN103224449B CN 103224449 B CN103224449 B CN 103224449B CN 201310153214 A CN201310153214 A CN 201310153214A CN 103224449 B CN103224449 B CN 103224449B
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- liquid
- mother liquor
- waste
- lower floor
- recovery
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- 239000007788 liquid Substances 0.000 title claims abstract description 46
- WPYMKLBDIGXBTP-UHFFFAOYSA-N benzoic acid Chemical compound OC(=O)C1=CC=CC=C1 WPYMKLBDIGXBTP-UHFFFAOYSA-N 0.000 title claims abstract description 43
- 238000000034 method Methods 0.000 title claims abstract description 24
- 239000012452 mother liquor Substances 0.000 title claims abstract description 19
- 239000002699 waste material Substances 0.000 title claims abstract description 19
- 238000011084 recovery Methods 0.000 title claims abstract description 16
- 239000005711 Benzoic acid Substances 0.000 title claims abstract description 13
- 235000010233 benzoic acid Nutrition 0.000 title claims abstract description 13
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims abstract description 26
- 239000013078 crystal Substances 0.000 claims abstract description 23
- HEDRZPFGACZZDS-UHFFFAOYSA-N Chloroform Chemical compound ClC(Cl)Cl HEDRZPFGACZZDS-UHFFFAOYSA-N 0.000 claims abstract description 21
- 238000003756 stirring Methods 0.000 claims abstract description 17
- 229960001701 chloroform Drugs 0.000 claims abstract description 16
- 238000002425 crystallisation Methods 0.000 claims abstract description 14
- 230000008025 crystallization Effects 0.000 claims abstract description 14
- 238000000605 extraction Methods 0.000 claims abstract description 13
- 239000006228 supernatant Substances 0.000 claims abstract description 8
- 239000000706 filtrate Substances 0.000 claims description 12
- 239000012074 organic phase Substances 0.000 claims description 8
- 238000001291 vacuum drying Methods 0.000 claims description 8
- 241001473877 Biserrula isolate Species 0.000 claims description 5
- 238000001914 filtration Methods 0.000 claims description 4
- 239000012535 impurity Substances 0.000 claims description 4
- 238000000926 separation method Methods 0.000 claims description 4
- 239000002904 solvent Substances 0.000 claims description 4
- YMWUJEATGCHHMB-UHFFFAOYSA-N Dichloromethane Chemical compound ClCCl YMWUJEATGCHHMB-UHFFFAOYSA-N 0.000 abstract description 37
- XEKOWRVHYACXOJ-UHFFFAOYSA-N Ethyl acetate Chemical compound CCOC(C)=O XEKOWRVHYACXOJ-UHFFFAOYSA-N 0.000 abstract description 12
- 239000002351 wastewater Substances 0.000 abstract description 9
- 238000004064 recycling Methods 0.000 abstract description 3
- 238000009776 industrial production Methods 0.000 abstract description 2
- 239000010808 liquid waste Substances 0.000 abstract description 2
- 150000007524 organic acids Chemical class 0.000 abstract description 2
- 238000013517 stratification Methods 0.000 abstract description 2
- 239000002912 waste gas Substances 0.000 abstract description 2
- FJKROLUGYXJWQN-UHFFFAOYSA-N 4-hydroxybenzoic acid Chemical compound OC(=O)C1=CC=C(O)C=C1 FJKROLUGYXJWQN-UHFFFAOYSA-N 0.000 description 10
- 229940090248 4-hydroxybenzoic acid Drugs 0.000 description 5
- 239000003795 chemical substances by application Substances 0.000 description 5
- ISWSIDIOOBJBQZ-UHFFFAOYSA-N Phenol Chemical compound OC1=CC=CC=C1 ISWSIDIOOBJBQZ-UHFFFAOYSA-N 0.000 description 3
- KWYUFKZDYYNOTN-UHFFFAOYSA-M Potassium hydroxide Chemical compound [OH-].[K+] KWYUFKZDYYNOTN-UHFFFAOYSA-M 0.000 description 3
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 3
- CTQNGGLPUBDAKN-UHFFFAOYSA-N O-Xylene Chemical compound CC1=CC=CC=C1C CTQNGGLPUBDAKN-UHFFFAOYSA-N 0.000 description 2
- KBPLFHHGFOOTCA-UHFFFAOYSA-N caprylic alcohol Natural products CCCCCCCCO KBPLFHHGFOOTCA-UHFFFAOYSA-N 0.000 description 2
- 230000006378 damage Effects 0.000 description 2
- 239000000126 substance Substances 0.000 description 2
- VHUUQVKOLVNVRT-UHFFFAOYSA-N Ammonium hydroxide Chemical compound [NH4+].[OH-] VHUUQVKOLVNVRT-UHFFFAOYSA-N 0.000 description 1
- 235000011114 ammonium hydroxide Nutrition 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 238000006473 carboxylation reaction Methods 0.000 description 1
- 239000003814 drug Substances 0.000 description 1
- 238000001035 drying Methods 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 238000001704 evaporation Methods 0.000 description 1
- 230000008020 evaporation Effects 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- 239000000203 mixture Substances 0.000 description 1
- XTAZYLNFDRKIHJ-UHFFFAOYSA-N n,n-dioctyloctan-1-amine Chemical compound CCCCCCCCN(CCCCCCCC)CCCCCCCC XTAZYLNFDRKIHJ-UHFFFAOYSA-N 0.000 description 1
- TVMXDCGIABBOFY-UHFFFAOYSA-N n-Octanol Natural products CCCCCCCC TVMXDCGIABBOFY-UHFFFAOYSA-N 0.000 description 1
- 239000000376 reactant Substances 0.000 description 1
- 230000001988 toxicity Effects 0.000 description 1
- 231100000419 toxicity Toxicity 0.000 description 1
Abstract
The present invention relates to the method for technical field of waste water processing recovery of benzoic acid from mother liquor or waste liquid in industrial production: add methylene dichloride or trichloromethane to containing in benzoic mother liquor or waste liquid, stir, stratification; Isolate lower floor's liquid, in supernatant liquid, add methylene dichloride or chloroform extraction, isolate lower floor's liquid, repeated several times, by all lower floors liquid, evaporative crystallization, dry, obtain coarse crystal; Coarse crystal is dissolved in methylene dichloride, trichloromethane, ethanol or ethyl acetate, stirs, isolates lower floor's liquid, evaporative crystallization, dry, obtains Benzoic Acid Crystal.The inventive method reduces organic acid content in mother liquor or waste liquid, reduces the difficulty of next step liquid waste disposal; From mother liquor or waste liquid, be recovered to pure phenylformic acid, turn waste into wealth; Do not produce waste water and waste gas, methylene dichloride and the recycling completely of ethanol energy; The phenylformic acid purity obtained is more than 95%, and in mother liquor or waste liquid, the benzoic rate of recovery reaches more than 85%.
Description
Technical field
The present invention relates to technical field of waste water processing in industrial production, particularly a kind of method of recovery of benzoic acid from mother liquor or waste liquid.
Background technology
Phenylformic acid is the organic monoacid that the industry such as chemical industry, medicine is commonly used, and its derivative is used for the industries such as medical treatment, food.No matter phenylformic acid is used for reactant or catalyzer, can have part phenylformic acid in the waste water after using.Waste water is caused to recycle.Moreover phenylformic acid price comparison is expensive, causes waste to a certain extent.
The patent No. is 200810019660.9; name is called the Chinese patent of " phenol in P-hydroxybenzoic acid processing wastewater and the recovery and treatment method of P-hydroxybenzoic acid "; disclose one extraction agent to extract P-hydroxybenzoic acid processing wastewater, reclaim phenol wherein and P-hydroxybenzoic acid simultaneously; Described extraction agent is: trioctylamine, tbp, dimethylbenzene or n-Octanol, or wherein two or more mixture; Extraction liquid alkaline substance solution is stripped, and described alkaline matter is selected from: potassium hydroxide, sodium hydroxide or aqua ammonia; Strip liquor returns production technique and carries out carboxylation reaction.In waste water the rate of recovery of P-hydroxybenzoic acid and phenol all close to 100%, COD clearance reaches 98.9%.But the extraction agent complicated components used, volatile, the smell is awful, toxicity is comparatively large, in removal process, loss is large, also easily causes damage to operator.
Summary of the invention
In order to solve above phenylformic acid reclaim in extraction agent select complexity and have the problem of certain harm, the invention provides a kind of method of recovery of benzoic acid from mother liquor or waste liquid using healthy extraction agent, the rate of recovery high.
The present invention is achieved by the following measures:
A method for recovery of benzoic acid from mother liquor or waste liquid, comprises the following steps:
A. add methylene dichloride or trichloromethane to containing in benzoic mother liquor or waste liquid, stir, stratification;
B. isolate lower floor's liquid, in supernatant liquid, add methylene dichloride or chloroform extraction, isolate lower floor's liquid, repeat this process several times, collect all lower floors liquid, evaporative crystallization, dry, obtain coarse crystal;
C. the coarse crystal obtained by step b, is dissolved in methylene dichloride, trichloromethane, ethanol or ethyl acetate, stirs, isolates lower floor's liquid, by isolated liquid evaporation crystallization, dry, obtains Benzoic Acid Crystal.
Described method, in step a, the volume ratio of methylene dichloride or trichloromethane and mother liquor or waste liquid is 1-1.5:1.
Described method, in step c, the mass ratio of coarse crystal and methylene dichloride, trichloromethane, ethanol or ethyl acetate is 1:5-10.
Described method, first filters after stirring in described step a and step c.
Described method, adds methylene dichloride or chloroform extraction in the supernatant liquid in step b, methylene dichloride or trichloromethane are 1-1.5 times of supernatant liquid volume.
Described method, the evaporative crystallization temperature in step b and step c is 20-100 DEG C.
Described method, in step b and step c, drying conditions is 20 DEG C-25 DEG C ,-0.1MPa.
Described method, the methylene dichloride of evaporative crystallization in recycling step b and step c.
Beneficial effect of the present invention:
The inventive method reduces organic acid content in mother liquor or waste liquid, reduces the difficulty of next step liquid waste disposal; Be recovered to pure phenylformic acid in from mother liquor or waste liquid, turn waste into wealth; Do not produce waste water and waste gas, methylene dichloride and the recycling completely of ethanol energy; The phenylformic acid purity obtained is more than 95%, and in mother liquor or waste liquid, the benzoic rate of recovery reaches 85%-99%.
Embodiment
For a better understanding of the present invention, further illustrate below in conjunction with specific embodiment.
embodiment 1:
A. benzoated trade effluent 100g(is detected wherein containing phenylformic acid 0.20g) join in reactor, add 150g methylene dichloride, stir 20-30min.Filter under whipped state, the mechanical impurity in system is filtered out, collect filtrate, filtrate is left standstill phase-splitting;
B. isolate lower floor's liquid, in supernatant liquid, add 100g dichloromethane extraction, stir 20-30min, leave standstill phase-splitting, isolate lower floor's liquid, repeat this process three times, collect all lower floors liquid, put into evaporative crystallizer, 40 DEG C of evaporative crystallizations, 20 DEG C-25 DEG C,-0.1MPa vacuum-drying, obtain coarse crystal, methylene dichloride will be collected, and uses for next batch solvent;
C. the coarse crystal obtained by step b, is dissolved in ethanol, and coarse crystal and ethanol mass ratio are 1:5, fully stir 40-60min, collecting by filtration filtrate, standing separation goes out lower floor's organic phase, by isolated organic phase evaporative crystallization, 20 DEG C-25 DEG C ,-0.1MPa vacuum-drying, obtains Benzoic Acid Crystal.Detecting purity is 96.55%, and the rate of recovery is 86.6%.
embodiment 2:
A. benzoated mother liquor 100g(is detected wherein containing phenylformic acid 0.25g) join in reactor, add 100g methylene dichloride, stir 20-30min.Filter under whipped state, the mechanical impurity in system is filtered out, collect filtrate, filtrate is left standstill phase-splitting;
B. isolate lower floor's liquid, in supernatant liquid, add 150g extraction into ethyl acetate, stir 20-30min, leave standstill phase-splitting, isolate lower floor's liquid, repeat this process four times, collect all lower floors liquid, put into evaporative crystallizer, 60 DEG C of evaporative crystallizations, 20 DEG C-25 DEG C,-0.1MPa vacuum-drying, obtain coarse crystal, methylene dichloride will be collected, and uses for next batch solvent;
C. the coarse crystal obtained by step b, is dissolved in ethanol, and coarse crystal and ethanol mass ratio are 1:10, fully stir 40-60min, collecting by filtration filtrate, standing separation goes out lower floor's organic phase, by isolated organic phase evaporative crystallization, 20 DEG C-25 DEG C ,-0.1MPa vacuum-drying, obtains Benzoic Acid Crystal.Detecting purity is 96.55%, and the rate of recovery is 88.9%.
embodiment 3:
A. benzoated mother liquor 100g(is detected wherein containing phenylformic acid 0.32g) join in reactor, add 150g trichloromethane, stir 20-30min.Filter under whipped state, the mechanical impurity in system is filtered out, collect filtrate, filtrate is left standstill phase-splitting;
B. isolate lower floor's liquid, in supernatant liquid, add 150g chloroform extraction, stir 20-30min, leave standstill phase-splitting, isolate lower floor's liquid, repeat this process five times, collect all lower floors liquid, put into evaporative crystallizer, 60 DEG C of evaporative crystallizations, 20 DEG C-25 DEG C,-0.1MPa vacuum-drying, obtain coarse crystal, trichloromethane will be collected, and uses for next batch solvent;
C. the coarse crystal obtained by step b, is dissolved in ethanol, and coarse crystal and ethanol mass ratio are 1:8, fully stir 40-60min, collecting by filtration filtrate, standing separation goes out lower floor's organic phase, by isolated organic phase evaporative crystallization, 20 DEG C-25 DEG C ,-0.1MPa vacuum-drying, obtains Benzoic Acid Crystal.Detecting purity is 98.05%, and the rate of recovery is 96.45%.
Claims (1)
1. the method for recovery of benzoic acid from mother liquor or waste liquid, is characterized in that comprising the following steps:
A. the mother liquor 100g detected wherein containing phenylformic acid 0.32g is joined in reactor, add 150g trichloromethane, stir 20-30min, filter under whipped state, the mechanical impurity in system is filtered out, collect filtrate, filtrate is left standstill phase-splitting;
B. isolate lower floor's liquid, in supernatant liquid, add 150g chloroform extraction, stir 20-30min, leave standstill phase-splitting, isolate lower floor's liquid, repeat this process five times, collect all lower floors liquid, put into evaporative crystallizer, 60 DEG C of evaporative crystallizations, 20 DEG C-25 DEG C,-0.1MPa vacuum-drying, obtain coarse crystal, trichloromethane will be collected, and uses for next batch solvent;
C. coarse crystal step b obtained, be dissolved in ethanol, coarse crystal and ethanol mass ratio are 1:8, fully stir 40-60min, collecting by filtration filtrate, standing separation goes out lower floor's organic phase, by isolated organic phase evaporative crystallization, and 20 DEG C-25 DEG C,-0.1MPa vacuum-drying, obtain Benzoic Acid Crystal, detecting purity is 98.05%, and the rate of recovery is 96.45%.
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| Application Number | Priority Date | Filing Date | Title |
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| CN201310153214.8A CN103224449B (en) | 2013-04-28 | 2013-04-28 | A kind of method of recovery of benzoic acid from mother liquor or waste liquid |
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| CN201310153214.8A CN103224449B (en) | 2013-04-28 | 2013-04-28 | A kind of method of recovery of benzoic acid from mother liquor or waste liquid |
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| CN103224449A CN103224449A (en) | 2013-07-31 |
| CN103224449B true CN103224449B (en) | 2015-09-02 |
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| CN114105754B (en) * | 2021-12-02 | 2024-02-27 | 湖北科林博伦新材料有限公司 | Organic sodium salt treatment process and device in toluene oxidation process |
Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US6211404B1 (en) * | 1996-09-30 | 2001-04-03 | Nippon Steel Chemical Co., Ltd. | Method of refining benzoic acid |
| CN102701959A (en) * | 2012-06-05 | 2012-10-03 | 山东大学 | Novel method for extracting benzoic acid from TA (Terephthalic Acid) residues |
-
2013
- 2013-04-28 CN CN201310153214.8A patent/CN103224449B/en active Active
Patent Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US6211404B1 (en) * | 1996-09-30 | 2001-04-03 | Nippon Steel Chemical Co., Ltd. | Method of refining benzoic acid |
| CN102701959A (en) * | 2012-06-05 | 2012-10-03 | 山东大学 | Novel method for extracting benzoic acid from TA (Terephthalic Acid) residues |
Non-Patent Citations (1)
| Title |
|---|
| PTA装置废渣及废钯的回收利用;张海清等;《聚酯工业》;20000630;第13卷(第2期);第29-31页 * |
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Address after: Shengquan Industrial Park 250204 Shandong city of Ji'nan province Zhangqiu City Diao Town Industrial Development Zone Applicant after: CARBOTANG LTD. Address before: Shengquan Industrial Park 250204 Shandong city of Ji'nan province Zhangqiu City Diao Town Industrial Development Zone Applicant before: JINAN KABOTANG BIOTECHNOLOGY Co.,Ltd. |
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Address after: 250204 Shengquan Industrial Park, Diaozhen Industrial Development Zone, Zhangqiu City, Shandong Province Patentee after: CARBOTANG BIOTECH CO.,LTD. Address before: 250204 Shengquan Industrial Park, Diaozhen Industrial Development Zone, Zhangqiu City, Jinan City, Shandong Province Patentee before: CARBOTANG LTD. |
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Address after: 250204 Diaozhen Street Chemical Industrial Park, Zhangqiu District, Jinan City, Shandong Province Patentee after: Jinan Carbotang Biotech Co.,Ltd. Address before: 250204 Shengquan Industrial Park, Diaozhen Industrial Development Zone, Zhangqiu City, Shandong Province Patentee before: CARBOTANG BIOTECH CO.,LTD. |