CN103708646A - Caprolactam industrial waste water treatment method - Google Patents
Caprolactam industrial waste water treatment method Download PDFInfo
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- CN103708646A CN103708646A CN201310716682.1A CN201310716682A CN103708646A CN 103708646 A CN103708646 A CN 103708646A CN 201310716682 A CN201310716682 A CN 201310716682A CN 103708646 A CN103708646 A CN 103708646A
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- waste water
- caprolactam
- wastewater treatment
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Abstract
The invention provides a caprolactam industrial waste water treatment method. The method has the characteristics that H2O2 is used as an oxidant on the basis of the traditional wet-type oxidation method, a high-efficient catalyst and appropriate reaction conditions are optimized, a better treatment effect can be achieved compared with the traditional wet-type oxidation method, the COD (chemical oxygen demand) removal rate can reach up to 70 to 90 percent through the two-step reaction, the biodegradability BOD (biological oxygen demand)/COD ratio is improved from 0.1 before the treatment to abount 0.5. In addition, by adopting the technical scheme, compared with the traditional fenton reagent method, the consumption of the H2O2 is remarkably reduced, and the cost is lower.
Description
Technical field
The present invention relates to technical field of sewage, be specifically related to a kind of Caprolactam Industry method of wastewater treatment.
Background technology
Hexanolactam is a kind of important chemical materials, and main application is to generate urethane by polymerization, can further be processed into fiber, plastics, film etc.The main production method of domestic hexanolactam is toluene method and benzene method, but is all finally to obtain hexanolactam by cyclohexanone-oxime liquid phase Beckmann rearrangement, and this technological reaction speed is fast, transformation efficiency is high, but the wastewater treatment difficulty of its generation is larger.In waste water, mainly contain the compositions such as hexanolactam, sulphur ammonium, acetic acid, toluene, phenylformic acid, hexahydrobenzoic acid, hexahydrobenzoic acid sulfonic acid, hexahydrobenzene formic acid, hexanaphthene, organism kinds is various, and COD value is high, and salts contg is high, and biodegradability is poor.
In prior art, to Caprolactam Industry waste water, conventionally adopt chemical oxidization method to process, as Fenton process or wet oxidation process.Because the COD of hexanolactam waste water is 5000-30000mg/L, utilize Fenton process processing can consume a large amount of H
2o
2, processing cost is higher; And the defect such as wet oxidation rule exists that equipment requirements is high, long reaction time, COD elimination factor are low.Also there is defect in some other treatment process of using in prior art in addition.
Chinese invention patent " a kind for the treatment of process and treatment unit thereof containing hexanolactam waste water " (application number CN201110232634.6) discloses a kind of method aerobic and anaerobic biological treatment system processing caprolactam trade effluent of utilizing, it is low that this biochemical method has working cost, treatment effect is good, the advantages such as non-secondary pollution, but its processing speed is excessively slow, cause biochemistry pool floor space excessive, and require high, Caprolactam Industry waste water after pre-treatment improves wastewater biodegradability, just can carry out biochemical treatment to influent quality.Therefore the method has larger limitation.
In addition, Chinese invention patent " toluene method is produced the treatment process of caprolactam technology waste water " (application number CN201210107412.6) discloses a kind of caprolactam production waste water treatment process, first the method reclaims the hexanolactam in waste water and the purification of hexahydrobenzoic acid sulfonate, remain waste water after concentrated, burning disposal.The method can obtain the byproduct that added value is higher from waste water, but in evaporation purification and concentration process, need to carry out underpressure distillation, and it is various in hexanolactam waste water, to contain organism kinds, COD value is between 100-300g/L, by evaporation concentration, to the higher energy consumption of flammable needs, virtually increased cost.
In sum, prior art is all desirable not to the utmost to the treatment effect of Caprolactam Industry waste water.
Summary of the invention
The present invention is intended to the technological deficiency for prior art, and a kind of efficient Caprolactam Industry method of wastewater treatment is provided, and is particularly useful for producing by cyclohexanone-oxime liquid phase Beckmann rearrangement the wastewater treatment that hexanolactam produces.
For realizing above technical purpose, the present invention by the following technical solutions:
A Caprolactam Industry method of wastewater treatment, is characterized in that comprising the following steps:
1) with sulfuric acid, pending wastewater pH is adjusted to 1～6, after throw out wherein is fully separated out, removes precipitation;
2) waste water of step 1) being removed after precipitation joins in tank reactor at intermittence;
3) to step 2) add H in described reactor
2o
2the aqueous solution, adds and contains Fe
3+or Fe
2+or Cu
+or Mn
2+or the catalyzer of iron powder or graphite or copper powder or manganese oxide, be filled with excessive oxygen or excess air, under whipped state, prior to 40～80 ℃ of reaction 10min～60min, the temperature to 120 that then raises ℃～200 ℃, continues reaction 1h～5h.
Wherein, in step 1), be preferably with sulfuric acid pending wastewater pH adjustment most 2～4; Step 2) liquid amount that in, waste water joins tank reactor is intermittently autoclave reactor volume intermittently 50～60%; The method that is filled with excessive oxygen or excess air described in step 3) is preferably oxygen or air by disposable being filled with of pressurizeing, and pressure is 1～1.5MPa; H described in step 3)
2o
2concentration of aqueous solution is preferably 30～50% (w/w); Described in step 1), whipped state is preferably mixing speed and is not less than 800r/min; Cationic catalyst described in step 3), is preferably sulfate radical with the negatively charged ion of its pairing.
The present invention introduces H on traditional wet oxidation process basis
2o
2as oxygenant, simultaneously preferred efficient catalyzer and suitable reaction conditions, more traditional wet oxidation process has better treatment effect, by two reactions of the present invention, can make COD clearance reach 70%～90%, biodegradability BOD/COD ratio is promoted to 0.5 left and right by 0.1 before processing.In addition technical scheme of the present invention remarkable H that reduced for traditional Fenton process,
2o
2consumption, cost is lower.
Embodiment
Embodiment 1
Getting the initial COD value of 800ml for the hexanolactam waste water of 11000mg/L, with the vitriol oil, regulate pH value to 2, produce precipitation in process, pack in Hastelloy reactor after removing precipitation after filtration, is 30% (w/w) H to adding 10g concentration in system
2o
2the aqueous solution, adds 0.67gFeSO
4make catalyzer, till being filled with pure oxygen to reacting kettle inner pressure and reaching 1MPa, be warming up to 70 ℃, under the condition of rotating speed 800r/min, react 30min; Be warming up to afterwards 170 ℃, reaction 2h.
Detecting after completion of the reaction COD value in waste water is 899mg/L, and clearance reaches 91.8%.
Embodiment 2
Getting the initial COD value of 800ml for the hexanolactam waste water of 9900mg/L, with the vitriol oil, regulate pH value to 4, produce precipitation in process, pack into after filtering intermittently in tank reactor, is the H of 40% (w/w) to adding 15g concentration in system
2o
2, 1.22gFe
2(SO
4)
3make catalyzer, till being filled with pure oxygen to reacting kettle inner pressure and reaching 1.1MPa, be warming up to 80 ℃, under the condition of rotating speed 1000r/min, react 40min; Be warming up to afterwards 180 ℃, reaction 3h.
Detecting after completion of the reaction COD value in waste water is 473mg/L, and clearance reaches 95.3%.
Embodiment 3
Getting the initial COD value of 800ml for the hexanolactam waste water of 6600mg/L, with the vitriol oil, regulate pH value to 5, produce precipitation in process, pack into after filtering intermittently in tank reactor, is the H of 30% (w/w) to adding 15g concentration in system
2o
2, 1.37gMnCl
2make catalyzer, be filled with ultrapure oxygen 1.2MPa, be warming up to 40 ℃, under the condition of rotating speed 1500r/min, react 10min, be warming up to afterwards 150 ℃, reaction 4h.
Detecting after completion of the reaction COD value in waste water is 463mg/L, and clearance is up to 95.3%.
Embodiment 4
Getting the initial COD value of 800ml for the hexanolactam waste water of 23000mg/L, with the vitriol oil, regulate pH value to 1, produce precipitation in process, pack into after filtering intermittently in tank reactor, is the H of 50% (w/w) to adding 30g concentration in system
2o
2, 2.08g iron powder is made catalyzer, is filled with ultrapure oxygen 1.3MPa, is warming up to 80 ℃, under the condition of rotating speed 1200r/min, reacts 60min; Be warming up to afterwards 130 ℃, reaction 1h.
Detecting after completion of the reaction COD value in waste water is 1530mg/L, and clearance reaches 93.3%.
Embodiment 5
Getting the initial COD value of 800ml for the hexanolactam waste water of 7280mg/L, with the vitriol oil, regulate pH value to 6, pack in Hastelloy reactor, is the H of 35% (w/w) to adding 17g concentration in system
2o
2, 1.73g manganese oxide is made catalyzer, is filled with ultrapure oxygen 1.5MPa, is warming up to 60 ℃, under the condition of rotating speed 900r/min, reacts 50min; Be warming up to afterwards 120 ℃, reaction 5h.
Detecting after completion of the reaction COD value in waste water is 664mg/L, and clearance reaches 90.9%.
Above the embodiment of the present invention is had been described in detail, but described content is only preferred embodiment of the present invention, not in order to limit the present invention.All any modifications of making in application range of the present invention, be equal to and replace and improvement etc., within all should being included in protection scope of the present invention.
Claims (5)
1. a Caprolactam Industry method of wastewater treatment, is characterized in that comprising the following steps:
1) with sulfuric acid, pending wastewater pH is adjusted to 1～6, after throw out wherein is fully separated out, removes precipitation;
2) waste water of step 1) being removed after precipitation joins in tank reactor at intermittence;
3) to step 2) add H in described reactor
2o
2the aqueous solution, adds and contains Fe
3+or Fe
2+or Cu
+or Mn
2+or the catalyzer of iron powder or graphite or copper powder or manganese oxide, be filled with excessive oxygen or excess air, under whipped state, prior to 40～80 ℃ of reaction 10min～60min, the temperature to 120 that then raises ℃～200 ℃, continues reaction 1h～5h.
2. a kind of Caprolactam Industry method of wastewater treatment according to claim 1, is characterized in that with sulfuric acid, pending wastewater pH being adjusted to 2～4 in step 1).
3. a kind of Caprolactam Industry method of wastewater treatment according to claim 1, is characterized in that step 2) in the waste water liquid amount that joins tank reactor be intermittently autoclave reactor volume intermittently 50～60%.
4. a kind of Caprolactam Industry method of wastewater treatment according to claim 1, it is characterized in that the method that is filled with excessive oxygen or excess air described in step 3) be oxygen or air by disposable being filled with of pressurizeing, pressure is 1～1.5MPa.
5. a kind of Caprolactam Industry method of wastewater treatment according to claim 1, is characterized in that H described in step 3)
2o
2the concentration of the aqueous solution is 30～50% (w/w).
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| CN201310716682.1A CN103708646B (en) | 2013-12-16 | 2013-12-16 | A kind of Caprolactam industrial waste water treatment method |
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| CN201310716682.1A CN103708646B (en) | 2013-12-16 | 2013-12-16 | A kind of Caprolactam industrial waste water treatment method |
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| CN103708646A true CN103708646A (en) | 2014-04-09 |
| CN103708646B CN103708646B (en) | 2015-10-28 |
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Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN113087252A (en) * | 2019-12-23 | 2021-07-09 | 南京延长反应技术研究院有限公司 | Treatment system and method for caprolactam production wastewater |
Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| 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 |
| CN102219327A (en) * | 2011-05-10 | 2011-10-19 | 中南大学 | Membrane method treatment process for caprolactam waste water |
| CN102249394A (en) * | 2011-06-13 | 2011-11-23 | 清华大学 | Method for pre-treating coking wastewater by using iron powder and hydrogen peroxide |
| CN102351380A (en) * | 2011-08-15 | 2012-02-15 | 浙江华建尼龙有限公司 | Method and device for treating caprolactam-containing waste water |
| CN103332774A (en) * | 2013-07-10 | 2013-10-02 | 四川师范大学 | Method used for processing high-concentration degradation-resistant organic wastewater |
-
2013
- 2013-12-16 CN CN201310716682.1A patent/CN103708646B/en active Active
Patent Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| 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 |
| CN102219327A (en) * | 2011-05-10 | 2011-10-19 | 中南大学 | Membrane method treatment process for caprolactam waste water |
| CN102249394A (en) * | 2011-06-13 | 2011-11-23 | 清华大学 | Method for pre-treating coking wastewater by using iron powder and hydrogen peroxide |
| CN102351380A (en) * | 2011-08-15 | 2012-02-15 | 浙江华建尼龙有限公司 | Method and device for treating caprolactam-containing waste water |
| CN103332774A (en) * | 2013-07-10 | 2013-10-02 | 四川师范大学 | Method used for processing high-concentration degradation-resistant organic wastewater |
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN113087252A (en) * | 2019-12-23 | 2021-07-09 | 南京延长反应技术研究院有限公司 | Treatment system and method for caprolactam production wastewater |
| CN113087252B (en) * | 2019-12-23 | 2022-04-01 | 南京延长反应技术研究院有限公司 | Treatment system and method for caprolactam production wastewater |
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| CN103708646B (en) | 2015-10-28 |
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