CN103708646B - A kind of Caprolactam industrial waste water treatment method - Google Patents
A kind of Caprolactam industrial waste water treatment method Download PDFInfo
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- CN103708646B CN103708646B CN201310716682.1A CN201310716682A CN103708646B CN 103708646 B CN103708646 B CN 103708646B CN 201310716682 A CN201310716682 A CN 201310716682A CN 103708646 B CN103708646 B CN 103708646B
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Abstract
The invention provides a kind of Caprolactam industrial waste water treatment method.The method 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, COD clearance can be made to reach 70% ~ 90% by two reactions of the present invention, biodegradability BOD/COD ratio is promoted to about 0.5 by before treatment 0.1.In addition, technical scheme of the present invention significantly reduces H for traditional Fenton process
2o
2consumption, cost is lower.
Description
Technical field
The present invention relates to technical field of sewage, be specifically related to a kind of Caprolactam industrial waste water treatment method.
Background technology
Hexanolactam is a kind of important chemical materials, and main application generates urethane by polymerization, can be processed into fiber, plastics, film etc. further.The main production process of domestic hexanolactam is toluene method and benzene method, but is finally all obtain hexanolactam by cyclohexanone-oxime liquid phase Beckmann rearrangement, and this technological reaction speed is fast, transformation efficiency is high, but its wastewater treatment difficulty produced is larger.Main containing compositions such as hexanolactam, sulphur ammonium, acetic acid, toluene, phenylformic acid, hexahydrobenzoic acid, hexahydrobenzoic acid sulfonic acid, hexahydrobenzene formic acid, hexanaphthenes in waste water, organism kinds is various, and COD value is high, and salts contg is high, and biodegradability is poor.
In prior art, chemical oxidization method process is adopted usually to Caprolactam Industry waste water, as Fenton process or wet oxidation process.Because the COD of caprolactam wastewater is 5000-30000mg/L, utilize Fenton process process can consume a large amount of H
2o
2, processing cost is higher; And wet oxidation rule exists defects such as equipment requirements is high, long reaction time, COD elimination factor are low.In addition, the some other treatment process also existing defects used in prior art.
Chinese invention patent " a kind for the treatment of process containing caprolactam wastewater and treatment unit thereof " (application number CN201110232634.6) discloses and a kind ofly utilizes aerobic and method that is anaerobic biochemical treatment system process caprolactam trade effluent, 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 influent quality is required that high, Caprolactam Industry waste water just can carry out biochemical treatment after having to pass through pre-treatment raising wastewater biodegradability.Therefore the method has larger limitation.
In addition, Chinese invention patent " toluene method produces the treatment process of caprolactam technology waste water " (application number CN201210107412.6) discloses a kind of wastewater of caprolactam production treatment process, first hexanolactam in waste water and hexahydrobenzoic acid sulfonate are purified and are reclaimed by the method, remain waste water after concentrated, burning disposal.The method can obtain the higher byproduct of added value from waste water, but in evaporation purification and concentration process, need to carry out underpressure distillation, and it is various containing organism kinds in caprolactam wastewater, COD value is between 100-300g/L, by the evaporation concentration energy consumption that extremely flammable needs are higher, virtually add cost.
In sum, prior art is desirable all 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, provides a kind of Caprolactam industrial waste water treatment method efficiently, is particularly useful for the wastewater treatment produced by cyclohexanone-oxime liquid phase Beckmann rearrangement production hexanolactam.
For realizing above technical purpose, the present invention by the following technical solutions:
A kind of Caprolactam industrial waste water treatment method, is characterized in that comprising the following steps:
1) with sulfuric acid, pending wastewater pH is adjusted to 1 ~ 6, after wherein throw out is fully separated out, removes precipitation;
2) waste water after step 1) being removed precipitation joins in batch tank reactor;
3) to step 2) described in reactor in add H
2o
2the aqueous solution, adds containing 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, prior to 40 ~ 80 DEG C of reaction 10min ~ 60min under whipped state, then raised temperature to 120 DEG C ~ 200 DEG C, continues reaction 1h ~ 5h.
Wherein, be preferably pending wastewater pH adjustment most 2 ~ 4 in step 1) with sulfuric acid; Step 2) in the waste water liquid amount that joins batch tank reactor be 50 ~ 60% of batch tank reactor volume; The method being filled with excessive oxygen or excess air described in step 3) is preferably oxygen or air is filled with by pressurization is disposable, and pressure is 1 ~ 1.5MPa; H described in step 3)
2o
2concentration of aqueous solution is preferably 30 ~ 50% (w/w); Whipped state described in step 1) 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, COD clearance can be made to reach 70% ~ 90% by two reactions of the present invention, biodegradability BOD/COD ratio is promoted to about 0.5 by before treatment 0.1.In addition, technical scheme of the present invention significantly reduces H for traditional Fenton process
2o
2consumption, cost is lower.
Embodiment
Embodiment 1
Getting the initial COD value of 800ml is the caprolactam wastewater of 11000mg/L, regulates pH value to 2 with the vitriol oil, produces precipitation in process, and load in Hastelloy reactor after removing precipitation after filtration, in system, add 10g concentration is 30% (w/w) H
2o
2the aqueous solution, adds 0.67gFeSO
4make catalyzer, be filled with pure oxygen to reacting kettle inner pressure reaches 1MPa, be warming up to 70 DEG C, under the condition of rotating speed 800r/min, react 30min; Be warming up to 170 DEG C afterwards, reaction 2h.
Detecting COD value in waste water is after completion of the reaction 899mg/L, and clearance reaches 91.8%.
Embodiment 2
Getting the initial COD value of 800ml is the caprolactam wastewater of 9900mg/L, regulates pH value to 4 with the vitriol oil, produces precipitation in process, loads in batch tank reactor after filtering, adds the H that 15g concentration is 40% (w/w) in system
2o
2, 1.22gFe
2(SO
4)
3make catalyzer, be filled with pure oxygen to reacting kettle inner pressure reaches 1.1MPa, be warming up to 80 DEG C, under the condition of rotating speed 1000r/min, react 40min; Be warming up to 180 DEG C afterwards, reaction 3h.
Detecting COD value in waste water is after completion of the reaction 473mg/L, and clearance reaches 95.3%.
Embodiment 3
Getting the initial COD value of 800ml is the caprolactam wastewater of 6600mg/L, regulates pH value to 5 with the vitriol oil, produces precipitation in process, loads in batch tank reactor after filtering, adds the H that 15g concentration is 30% (w/w) in system
2o
2, 1.37gMnCl
2make catalyzer, be filled with ultrapure oxygen 1.2MPa, be warming up to 40 DEG C, under the condition of rotating speed 1500r/min, react 10min, be warming up to 150 DEG C afterwards, reaction 4h.
Detecting COD value in waste water is after completion of the reaction 463mg/L, and clearance is up to 95.3%.
Embodiment 4
Getting the initial COD value of 800ml is the caprolactam wastewater of 23000mg/L, regulates pH value to 1 with the vitriol oil, produces precipitation in process, loads in batch tank reactor after filtering, adds the H that 30g concentration is 50% (w/w) in system
2o
2, 2.08g iron powder makees catalyzer, is filled with ultrapure oxygen 1.3MPa, is warming up to 80 DEG C, under the condition of rotating speed 1200r/min, react 60min; Be warming up to 130 DEG C afterwards, reaction 1h.
Detecting COD value in waste water is after completion of the reaction 1530mg/L, and clearance reaches 93.3%.
Embodiment 5
Getting the initial COD value of 800ml is the caprolactam wastewater of 7280mg/L, regulates pH value to 6 with the vitriol oil, loads in Hastelloy reactor, adds the H that 17g concentration is 35% (w/w) in system
2o
2, 1.73g manganese oxide makees catalyzer, is filled with ultrapure oxygen 1.5MPa, is warming up to 60 DEG C, under the condition of rotating speed 900r/min, react 50min; Be warming up to 120 DEG C afterwards, reaction 5h.
Detecting COD value in waste water is after completion of the reaction 664mg/L, and clearance reaches 90.9%.
Above the embodiment of the present invention has been described in detail, but described content is only preferred embodiment of the present invention, not in order to limit the present invention.All make in application range of the present invention any amendment, equivalent to replace and improvement etc., all should be included within protection scope of the present invention.
Claims (3)
1. a Caprolactam industrial waste water treatment method, is characterized in that comprising the following steps:
1) with sulfuric acid, pending wastewater pH is adjusted to 1 ~ 6, after wherein throw out is fully separated out, removes precipitation;
2) by step 1) remove precipitation after waste water join in batch tank reactor, liquid amount is 50 ~ 60% of batch tank reactor volume;
3) to step 2) described in reactor in add H
2o
2the aqueous solution, adds containing Fe
3+or Fe
2+or Cu
+or Mn
2+or the catalyzer of iron powder or graphite or copper powder or manganese oxide, in reactor, excessive oxygen or excess air is filled with to pressure for 1 ~ 1.5MPa in the disposable mode be filled with, prior to 40 ~ 80 DEG C of reaction 10min ~ 60min under whipped state, then raised temperature to 120 DEG C ~ 200 DEG C, continues reaction 1h ~ 5h.
2. a kind of Caprolactam industrial waste water treatment method according to claim 1, is characterized in that step 1) in sulfuric acid, pending wastewater pH is adjusted to 2 ~ 4.
3. a kind of Caprolactam industrial waste water treatment method according to claim 1, is characterized in that step 3) described H
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 CN103708646A (en) | 2014-04-09 |
| CN103708646B true CN103708646B (en) | 2015-10-28 |
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| 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 |
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 |
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