CN102642946A - Treatment method of waste water produced in process for producing caprolactam by utilizing toluene method - Google Patents
Treatment method of waste water produced in process for producing caprolactam by utilizing toluene method Download PDFInfo
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- CN102642946A CN102642946A CN2012101074126A CN201210107412A CN102642946A CN 102642946 A CN102642946 A CN 102642946A CN 2012101074126 A CN2012101074126 A CN 2012101074126A CN 201210107412 A CN201210107412 A CN 201210107412A CN 102642946 A CN102642946 A CN 102642946A
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Abstract
The invention provides a treatment method of waste water produced in process for producing caprolactam by utilizing a toluene method. The treatment method comprises the steps of: adding acetone into the waste water to be treated, implementing the filtering after solid is precipitated, washing the filter residue to gray white with absolute methanol, drying the absolute methanol to obtain cyclohexyl formate and sulfonate, and extracting the caprolactam. By utilizing the method, valuable organic substances and combustion pollutants in the waste water can be separated to obtain caprolactam and cyclohexyl formate and sulfonate, and chemical engineering products with high additional value can be obtained through subsequent further processing; and the content of organisms in the waste water also can be reduced, so that the treated waste water can be mixed with other waste water to be discharged after being further treated by a waste water treatment system, and residues after the separation and extraction can be used as fuel after being concentrated. The treatment method has good environmental-protection benefit and economic benefit.
Description
Technical field
The present invention relates to a kind of wastewater treatment method, relate in particular to a kind of toluene method and produce the caprolactam technology wastewater treatment method.
Background technology
Toluene method is produced has great amount of wastewater and by product to produce in the caprolactam technology process; These waste water complicated components; Principal pollutant have: hexanolactam, sulphur ammonium, toluene, phenylformic acid, cyclohexane carboxylic acid salt, hexahydrobenzoic acid sulphonate etc.; Wherein hexahydrobenzoic acid sulphonate is main chemical substance, also contains a small amount of hexanolactam and other chemical substances in addition.This organic dirty exhausted water is the black liquid of vicidity with bad smell, and complex chemical composition belongs to unmanageable high concentrated organic wastewater, and environment is had bigger pollution, can't directly discharge.Owing to contain organic matter in the organic sewage; Can be used as fuel and burn, main treatment process is a burning method both at home and abroad at present, but is difficult to the incendiary material owing to it contains; Must use special methods and equipment to burn; This method exists power consumption big, and valuable components does not have effective recycling in the waste liquid, to shortcomings such as environment and equipment contaminate are serious.Because the severe contamination property and the intractability of this waste water, seriously restricted the development that toluene method is produced the caprolactam technology project at present, therefore, effectively separate and handle this waste water and have important economic implications and social effect.
Summary of the invention
The objective of the invention is to provides a kind of toluene method to produce the caprolactam technology wastewater treatment method to the deficiency of above-mentioned prior art; Through this treatment process valuable organic substance in this organic waste water is separated with the Air thing; Reclaim purification hexanolactam and hexahydrobenzoic acid sulphonate, the hexahydrobenzoic acid sulphonate that wherein obtains can be converted into the Chemicals with high added value through follow-up deep processing; Can also reduce the organic content in the waste water through this treatment process; The waste water that makes toluene method produce to produce in the caprolactam technology process can efflux after Waste Water Treatment is further handled with incorporating into after other waste water mixes; And remainingly after treatment be difficult to isolating organic substance; Its fuel value can be used as fuel and burns at 5000-6000Kcal/Kg.
To achieve these goals, the present invention adopts following technical scheme:
A kind of toluene method is produced the caprolactam technology wastewater treatment method; It comprises the extraction separation of hexahydrobenzoic acid sulphonate, and concrete steps are following: in pending waste water, add solvent II acetone, its consumption is the 40-120% (mass percent) of wastewater quality; Treat to filter after solid is separated out; Collect filtrating and filter residue, to pearl, drying treatment obtains hexahydrobenzoic acid sulphonate bullion with anhydrous methanol washing filter residue.
Pending waste water ph is 8-9.Can be through under normal temperature and pressure conditions, regulating with NaOH solution.
As preferably, said exsiccant temperature is 40-50 ℃.
Treatment process of the present invention also comprises to be handled the hexahydrobenzoic acid sulphonate crude product refining that obtains; Concrete steps are following, and hexahydrobenzoic acid sulphonate bullion is water-soluble, and the mass ratio of itself and water is 1: 1.5-3; In solution, dropwise add the vitriol oil; Generate (the pH value is about 1-3) up to no longer including solid, its filtration is obtained the white plates crystal, drying treatment obtains cyclohexyl sulfo group formic acid.
Treatment process of the present invention also comprises the extraction separation of hexanolactam, and concrete steps are following: the filtrating to collecting is distilled under condition of normal pressure, and the cut of collecting 50-70 ℃ is a solvent II acetone, can reuse in the methods of the invention; Remaining liq distills under reduced pressure, adds the solvent I of residuum 20-30% (mass percent) then, and extracting and separating organic phase and water concentrate the organic phase that obtains, and obtain hexanolactam through vacuum drying treatment.
The I of solvent described in the above-mentioned steps is toluene, benzene or hexanaphthene.
As preferably, said vacuum drying actual conditions is 0.05-0.1MP, and temperature is 40-50 ℃.
Adopt the residue water after aforesaid method is handled after concentrating, to can be used as the fuel use.
Compared with prior art, the present invention has following advantage:
1, through aforesaid method, effectively separate and handled toluene method and produced the waste water that the caprolactam technology process is produced, cut down the consumption of energy, reduce pollution to environment.
2, can further develop its purposes to reclaiming the hexanolactam and the cyclohexyl sulfo group formic acid that obtain, have good benefits in environment and economic benefit.
3, the residuum behind the separation said extracted thing has the good combustion calorific value after concentrating, and can be used as fuel and uses, and creates economic benefit.
4, the inventive method is simple to operate, solvent for use benzene, toluene, hexanaphthene, methyl alcohol, acetone is all recyclable recycle and recovery method simple.
5, after treatment waste water can efflux after Waste Water Treatment is further handled with incorporating into after other waste water mixes, and can maximally utilise existing facility.
Description of drawings
Fig. 1 produces the processing flow chart of caprolactam technology waste water for toluene method of the present invention;
Fig. 2 cyclohexyl sulfo group formic acid
1The HNMR spectrogram;
The IR spectrogram of Fig. 3 cyclohexyl sulfo group formic acid;
Fig. 4 hexanolactam
1The HNMR spectrogram;
Fig. 5 hexanolactam
13The CNMR spectrogram;
The IR spectrogram of Fig. 6 hexanolactam.
Embodiment
Below in conjunction with embodiment the present invention is done further detailed explanation, but therefore the scope that the present invention requires to protect is not confined to the represented scope of embodiment.
Get the 100g toluene method and produce caprolactam technology waste water; The room temperature normal pressure is regulated the pH value to 8-9 with 20% (mass percent) NaOH solution down, adds solvent II acetone 60g, has solid to separate out; Batch filtration; Collect filtrating and filter residue, filter residue washs to pearl with anhydrous methanol 2g, weigh after the 40-50 ℃ of drying hexahydrobenzoic acid sulphonate bullion 9g.
Filtrating to collecting is distilled under normal pressure, collects 50-70 ℃ cut acetone, can reuse; Remaining liq distills down in reduced pressure (200-600mmHg) removes 60% (mass percent) moisture; Under the room temperature normal pressure, add the solvent I toluene 7g of residuum 20% (mass percent) then, carry out extracting and separating and obtain organic phase and water, concentrate organic phase; Weigh warp after the vacuum drying treatment
1HNMR,
13CNMR and IR identify that the gained material is a hexanolactam, and weight is 2.5g, and collection of illustrative plates is seen accompanying drawing 4-6 respectively.Water obtains black solid 30g through further concentrating with vacuum-drying.
Get the pearl hexahydrobenzoic acid sulphonate bullion 10g of above-mentioned steps, be dissolved under the room temperature normal pressure in the 15g water, dropwise add the vitriol oil; Regulating the pH value has solid to generate to 1-3, and its filtration is obtained the white plates crystal, and 8.9g weighs after the drying; Product is a cyclohexyl sulfo group formic acid, its
1HNMR and IR identify and see accompanying drawing 2 and 3 respectively.
Get this organic waste water of 100g, regulate the pH value to 8-9 with NaOH under the room temperature normal pressure, add solvent II acetone 80g; Have solid to separate out, batch filtration is collected filtrating and filter residue; Filter residue washs to pearl with anhydrous methanol 2g, weigh after the 40-50 ℃ of drying hexahydrobenzoic acid sulphonate bullion 11g.
Filtrating to collecting is distilled under normal pressure, collects 50-70 ℃ cut acetone reuse; Remaining liq distills down in reduced pressure (200-600mmHg) removes 60% moisture (mass percent); The solvent I benzene 7g that under the room temperature normal pressure, adds residuum 20% (mass percent) then; Carry out extracting and separating and obtain organic phase and water; Concentrate organic phase, obtain hexanolactam 2.5g through vacuum drying treatment.Water obtains black solid 29g through further concentrating with vacuum-drying.
Get the pearl hexahydrobenzoic acid sulphonate bullion 10g of above-mentioned steps, be dissolved under the room temperature normal pressure in the 25g water, dropwise add the vitriol oil; Regulating pH value 1-3 has solid to generate; Its filtration is obtained the white plates crystal, and the 8.9g that weighs after the drying, product are cyclohexyl sulfo group formic acid.
Embodiment 3
Get this organic waste water of 100g, regulate the pH value to 8-9 with NaOH under the room temperature normal pressure, add solvent II acetone 120g; Have solid to separate out, batch filtration is collected filtrating and filter residue; Filter residue washs to pearl with anhydrous methanol 2g, weigh after the 40-50 ℃ of drying hexahydrobenzoic acid sulphonate bullion 12.5g.
Filtrating to collecting is distilled under normal pressure, collects 50-70 ℃ cut acetone reuse; Remaining liq distills down in reduced pressure (200-600mmHg) removes 60% moisture (mass percent); The solvent I hexanaphthene 10g that under the room temperature normal pressure, adds residuum 30% (mass percent) then; Carry out extracting and separating and obtain organic phase and water; Concentrate organic phase, obtain hexanolactam 2.2g through vacuum drying treatment.Water obtains black solid 30g through further concentrating with vacuum-drying.
Get the pearl hexahydrobenzoic acid sulphonate bullion 10g of above-mentioned steps, be dissolved under the room temperature normal pressure in the 30g water, dropwise add the vitriol oil; Regulating pH value 1-3 has solid to generate; Its filtration is obtained the white plates crystal, and the 8.5g that weighs after the drying, product are cyclohexyl sulfo group formic acid.
Vacuum-drying condition among the foregoing description 1-3 is 0.05-0.1MP, and temperature is 40-50 ℃.
Claims (8)
1. a toluene method is produced the caprolactam technology wastewater treatment method; Comprise: in pending waste water, add solvent II acetone; Its consumption is the 40-120% (mass percent) of wastewater quality, treats to filter after solid is separated out, and collects filtrating and filter residue; To pearl, drying treatment obtains hexahydrobenzoic acid sulphonate bullion with anhydrous methanol washing filter residue.
2. treatment process according to claim 1 is characterized in that, pending waste water ph is 8-9.
3. according to the treatment process described in the claim 2, it is characterized in that said exsiccant temperature is 40-50 ℃.
4. according to each described treatment process among the claim 1-3, it is characterized in that said method also comprises to be handled the hexahydrobenzoic acid sulphonate crude product refining that obtains; Concrete steps are following, and hexahydrobenzoic acid sulphonate bullion is water-soluble, and the mass ratio of itself and water is 1: 1.5-3; In solution, dropwise add the vitriol oil; Generate up to no longer including solid, its filtration is obtained the white plates crystal, drying treatment obtains cyclohexyl sulfo group formic acid.
5. according to each described treatment process among the claim 1-4, it is characterized in that said method also comprises distills under condition of normal pressure the filtrating of collecting, the cut of collecting 50-70 ℃ is a solvent II acetone, and is reusable in said method; Remaining liq distills under reduced pressure, adds the solvent I of residuum 20-30% (mass percent) then, and extracting and separating organic phase and water concentrate the organic phase that obtains, and obtain hexanolactam through vacuum drying treatment.
6. treatment process according to claim 5 is characterized in that, said solvent I is toluene, benzene or hexanaphthene.
7. according to the treatment process described in the claim 6, it is characterized in that said vacuum drying actual conditions is 0.05-0.1MP, temperature is 40-50 ℃.
8. according to each described treatment process among the claim 6-7, it is characterized in that said water can be used as fuel and uses after concentrating.
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Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN105836949A (en) * | 2016-05-05 | 2016-08-10 | 巨化集团技术中心 | Treatment method for benzene extraction raffinate in caprolactam production |
| CN112321044A (en) * | 2020-09-01 | 2021-02-05 | 福建钰融科技有限公司 | Purification liquid of waste stripping liquid and purification method and application thereof |
Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPS522065A (en) * | 1975-06-24 | 1977-01-08 | Ashizawa Tekko Kk | Method of drying caprolactam waste liquid through atomization |
| EP0396790A1 (en) * | 1989-05-09 | 1990-11-14 | Bayer Antwerpen N.V. | Process for the removal of nitrate and organic pollutants from effluents |
| CN1635008A (en) * | 2004-12-07 | 2005-07-06 | 天津大学 | Macromolecular grafted carbon black containing sulfonic groups and method for preparation |
| CN101618919A (en) * | 2008-06-30 | 2010-01-06 | 中国石油化工股份有限公司 | Method for processing waste water produced by caprolactam ammoximation process |
-
2012
- 2012-04-13 CN CN 201210107412 patent/CN102642946B/en active Active
Patent Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPS522065A (en) * | 1975-06-24 | 1977-01-08 | Ashizawa Tekko Kk | Method of drying caprolactam waste liquid through atomization |
| EP0396790A1 (en) * | 1989-05-09 | 1990-11-14 | Bayer Antwerpen N.V. | Process for the removal of nitrate and organic pollutants from effluents |
| CN1635008A (en) * | 2004-12-07 | 2005-07-06 | 天津大学 | Macromolecular grafted carbon black containing sulfonic groups and method for preparation |
| CN101618919A (en) * | 2008-06-30 | 2010-01-06 | 中国石油化工股份有限公司 | Method for processing waste water produced by caprolactam ammoximation process |
Non-Patent Citations (2)
| Title |
|---|
| 喻爱和 等: "甲苯法生产己内酰胺废液的综合利用工艺研究", 《现代化工》, vol. 29, no. 10, 20 October 2009 (2009-10-20), pages 76 - 79 * |
| 贺玉平 等: "1-磺酸基环己烷羧酸样本的制备与表征", 《化学试剂》, vol. 34, no. 3, 15 March 2012 (2012-03-15), pages 261 - 265 * |
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN105836949A (en) * | 2016-05-05 | 2016-08-10 | 巨化集团技术中心 | Treatment method for benzene extraction raffinate in caprolactam production |
| CN112321044A (en) * | 2020-09-01 | 2021-02-05 | 福建钰融科技有限公司 | Purification liquid of waste stripping liquid and purification method and application thereof |
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