CN1147437C - Method for treating waste water in dinaphthyl phenol production - Google Patents
Method for treating waste water in dinaphthyl phenol productionInfo
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- CN1147437C CN1147437C CNB001321293A CN00132129A CN1147437C CN 1147437 C CN1147437 C CN 1147437C CN B001321293 A CNB001321293 A CN B001321293A CN 00132129 A CN00132129 A CN 00132129A CN 1147437 C CN1147437 C CN 1147437C
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Abstract
The present invention discloses a method for treating wastewater in 2-naphthol production, which comprises the following steps that a), wastewater is oxidized to remove pollutants, oxidable sulfite, etc. in wastewater, so that weak acid is changed into strong acid, and the pH value of the wastewater is reduced; b), the oxidized wastewater is filtered to remove suspended impurities; c), the exchange adsorption and the elution are carried out through an ion exchange system, and naphthalenesulfonic acid as an intermediate body is recovered; d), the pH value of water adjusted with alkali is larger than 8, the chromaticity is removed, and the final water can be used as washing liquid and returns to the production process. The method of the present invention has the advantages of simple technology, efficient and economic treatment, etc. and has an obvious decolouring effect.
Description
Technical field
The present invention relates to the treatment process of beta naphthal factory effluent.
Background technology
Beta naphthal is important organic fine chemical synthetic intermediate, is mainly used in fields such as dyestuff, medicine, coating.It is to be raw material with the naphthalene, through chemical reaction processes such as oversulfonate, neutralization, replacements and prepare.Produce in the naphthols production process and contain the organic colorful wastewater with mineral compound of high density, wherein contain inorganicss such as a large amount of contains sodium sulfate, S-WAT, separate organic intermediate products such as incomplete naphthene sulfonic acid root, the component complexity.COD value of waste water (chemical oxygen demand (COD)) is up to 30000-40000mg/L, and wherein beta naphthal content is 15-20g/L, and sulfurous acid is 6000--10000mg/L, and colourity is 200-400 times (extension rate method, as follows).PH is 5-6 in the waste water.COD is mainly caused by the oxidation of inferior sulfate radical and naphthene sulfonic acid root in the waste water, and the high-concentration naphthalene sulfonic acid (17-18g/L) that especially contains is maximum to the COD contribution.Because in the beta naphthal production process, sulfuric acid reaction is incomplete, separation and strong brine washing etc. are saltoutd in employing, so waste water contains the salts substances (content is up to 10-15%) of high density.This kind discharge of wastewater feature intermittently discharged is measured less but pollution intensity is big.
To the dyestuff intermediate factory effluent of this high salt, high COD, high luminance relay, intractability is very big at present.Conventional materialization and biochemical process can't be handled.Usually adopt oxidative treatment, as high temperature wet catalysis, Fenton reagent oxidation method etc., but severe reaction conditions and oxygen consumption dosage are big, are difficult to economically realize.Also have and adopt extraction, charcoal absorption, membrane sepn, liquid film extraction, evaporation concentration, freezing concentrate or the like.But all there is the processing cost height in these methods, chromaticity removing effect is poor, separating effect is undesirable, complex technical process, be difficult to reclaim or reclaim shortcomings such as 2-naphthene sulfonic acid grade is low.The waste water treatment process that adopts resin absorption is also arranged, but there is obvious defects in this technology, adopts sulfuric acid to transfer pH, sulfurous acid reduces the adsorptive power of resin, and the COD clearance has only 85%, still can not be up to standard, and the almost infeasible biochemical processing process of following adopted.So far do not see economical and effective treatment process as yet.
Summary of the invention
The object of the present invention is to provide simple, the cost-effective beta naphthal production wastewater treatment of a kind of technology method.
Beta naphthal intermediate production wastewater treatment method of the present invention may further comprise the steps:
A) with the pollutents such as sulphite of waste water, make weak acid become strong acid, and waste water ph reduce through easy oxidation in the oxidation removal water;
B) waste water after the oxidation is removed suspended impurity after filtration;
C) exchange absorption-wash-out through ion exchange system, reclaim the intermediate naphthene sulfonic acid;
D) water outlet is regulated pH greater than 8 through alkali, removes colourity, and final outflow water can be used as washings and is back to production process.
In the present invention, step a adopts atmospheric oxidation, makes sulfurous acid become sulfuric acid, reduces wastewater pH, helps resin absorption, adopts double bed series connection ion exchange system to exchange the absorption naphthene sulfonic acid.The atmospheric oxidation time is 2-4 hour, pH4-6.
In step c of the present invention, ion exchange system exchange flow velocity is 1-5BV/h, and regeneration velocity is 1-4BV/h, and regenerator is the NaOH solution of 4-8%, and regenerant consumption is 1-4BV.In step c, the ion exchange resin that uses in the ion exchange system is macropore highly basic, weakly-basic anion exchange or polymeric adsorbent.Ion exchange system generally adopts twin columns series connection ion exchange system.
Water outlet is regulated pH to 9-11 through alkali in steps d of the present invention.
Ultimate principle of the present invention is the beta naphthal factory effluent characteristics according to high dissolubility organism, supersalinity, high chroma, adopt purifies and separates technology from waste water, to remove the high density mineral sulfates, organic naphthene sulfonic acid in the adsorption and enrichment water, main handling principle is as follows:
The molecular weight of organic compound is big more, it is few more to contain oxygen, and every mole of complete oxidation requisite oxygen is many more, is reflected on the water-quality guideline, and it is higher to show as the COD value.With the naphthene sulfonic acid is example, if the ion exchange reaction that adopts equivalent to remove, every milliliter of resin (exchanging equivalent is 1) can reduce about COD 336mg, and the 100g resin can reduce COD 33600mg.Therefore adopt suitable separation, enrichment and purification process and in conjunction with production technology characteristic, separate and enrichment waste water in sulfonate, improve utilization rate of raw materials, be the key and the core of this type of waste water technology of processing.
The sulfite compound that also has that COD is had bigger contribution in the beta naphthal factory effluent, sulphite are readily oxidizable substances and have stronger volatility under acidic conditionss, can adopt oxidation stripping removal under direct oxidation or the acidic conditions, and reaction process is as follows:
Can adopt H
2SO
4Regulate pH＜3, the sulphite in the waste water is mainly with H at this moment
2SO
3And HSO
3 -Exist, can change into SO
2Gaseous volatilization falls, and reduce COD value of waste water, but acid consumption is bigger.Under higher pH condition, mainly based on oxidizing reaction, a little less than the volatilization of gas, and make full use of waste water acidity height, the characteristics that surge capability is strong are oxidized to strong acid sulfuric acid with weak acid sulfurous acid, to reduce the pH of waste water, help the absorption of resin.
Advantages such as ion-exchange has that selectivity is good, good separating effect, enrichment multiple height, simple to operate, stable effluent quality are widely used in pure water preparation and the chemical process.Especially integrate advantages such as separation, enrichment and purifying, be widely used in separation, enrichment and the purge process of chemical material.
Sulfonic acid is organic acid, acts on mutually with the cation exchange groups of ion exchange resin under acidic conditions:
(5)
X represents the number of H atom in the formula, 0＜x＜2; Y represents Ji-CH
3Number, 0＜y＜4.
Intermolecular interaction is actually a kind of Lewis Acids and Bases and interacts, and its reactive force also is eager to excel than hydrogen bond.Find in the experiment that anionite-exchange resin has higher selectivity (its selectivity is far above sulfate radical) to naphthene sulfonic acid root in the water under certain conditions, the satisfied mole that waits of exchange capacity exchanges.Therefore under alkaline condition, acid group ionization is dissolved in the solution again, and available highly basic reclaims naphthene sulfonic acid to adsorbing the resin regeneration after saturated.Foreign matter content is few in the naphthene sulfonic acid that reclaims, and the chemical reagent that adopts in treatment process is the raw material of production process, therefore need not separate again, can directly get back in the production process, has improved raw-material utilization ratio, reduces processing cost.
Because the water outlet behind the ion exchange column is regulated pH greater than 8, the high chroma material in the waste water is separated out with insolubles under alkaline condition, precipitates clarifying waste water by regulating pH, can be used as the washings circulation and is used for producing and treating processes.
Water outlet through ion-exchange mainly contains organic/inorganic substance sodium sulfate and sodium-chlor.These salt compounds are to saltout in the beta naphthal production process to separate and the main raw material of washing, but direct reuse saltout and washing procedure in production, finally realize the recovery of cycling utilization of wastewater and resource.
Specifically describe technical process of the present invention below in conjunction with accompanying drawing.
Description of drawings
Fig. 1 is the process flow sheet of the inventive method.
As shown in Figure 1, schedule of operation is: at first make waste water pass through the oxidation of stripping tower aeration stripping, hydraulic detention time is 3-4h, and the aeration stripping process keeps waste water to be little shape that boils, water outlet enters twin columns series connection ion exchange system after removing the suspended impurity particle after filtration, exchange absorption 2-naphthene sulfonic acid.It is saturated after the alkali lye wash-out reclaims the 2-naphthene sulfonic acid.The ion exchange system water outlet is adjusted pH to greater than 8, further removes the look qualified discharge, or direct reuse is as water of productive use, and remainder can be by producing waste heat evaporation, reclaim(ed) sulfuric acid salt.
The object of the invention mainly realizes by following aspect: 1, at first waste water is removed readily oxidizable substance in the water by the oxidation stripping, reach simultaneously the purpose of adjusting wastewater pH; 2, adopt large aperture ion exchange resin, double stage tandem is inverted ion exchange system and is carried out repeatedly naphthalene sulfonate in twin columns displacement exchange adsorption, the recycle-water; 3, process the colourity of water outlet and COD qualified discharge or as the industrial water reuse.
Method of the present invention has not only that equipment volume is little, technological process is simple, easily automatic control and easy and simple to handle, highly-efficient treatment and economic dispatch advantage, and has remarkable decolorizing effect. Adopt this method to process beta naphthal dyestuff intermediate factory effluent, the beta naphthal rate of recovery reaches more than 98%, and the COD clearance is more than 97%, and the colourity removal efficiency is more than 90%, water quality treatment reaches discharging standards or direct reuse production process, reduces the industrial water amount. The integrated treatment cost reclaims the economic worth of the industrial chemicals such as 2-naphthol dye intermediate and sodium sulphate at 90-100 yuan/ton about 25 yuan/tons, creating overall economic efficiency is 50-70 yuan/ton. Therefore, have significant society and economic benefit.
Below by instantiation the present invention is described in detail.
Embodiment
Embodiment 1
10 liters of chemical plant, Shanghai beta naphthal factory effluents.This wastewater pH 6.0 is Vandyke brown, and colourity is 400 times (extension rate methods), and COD is 33,000～35,000mg/L; Wherein 2-sodium naphthalene sulfonate content is about 18g/L, and inferior sulfate radical is about 30～35g/L.Waste water at first by aeration stripping post aeration stripping oxidation 2 hours, is measured water outlet COD value 25,000-27,000mg/L, clearance is about 20%.Inferior sulfate radical 0.5g/L, clearance reaches 98%.Water outlet is after filtration in the filtering water behind the impurity, with the one-level ion exchange column (250mL resin) of flow velocity 2BV/h, before water outlet, during 6BV, measure water outlet COD less than 100mg/L by being filled with macropore weak base type ion exchange resin, COD removes 99.9%, and treat effluent is up to standard.As water outlet COD during greater than 100mg/L, again with the water outlet of one-level exchange column by two ion exchange columns, the twin columns series connection is handled, and guarantees effluent characteristics.When one-level exchanging column resin water outlet COD matter reach water COD value into 95% the time, the one-level exchanging column resin is saturated.Close one-level exchange column inlet valve, this moment, water directly advanced the secondary ion exchange column.The one-level ion exchange column begins the clear water backwash, and the NaOH with 1.5BV 8% carries out resin elution regeneration with flow velocity 4BV/h then, and eluting rate is 98%.Regeneration finishes and with clear water resin rinsing to pH＜9 to be begun to connect the water outlet of secondary ion exchange column again and exchange the absorption operation.One-level backwash water and rinse water and factory effluent are mixed into the secondary ion exchange column, begin to connect the one-level exchange column after the saturated regeneration of secondary ion exchange column again and exchange the absorption operation, be inverted so repeatedly, circular flow, system's water outlet COD value is remained＜100mg/L, water outlet pH is 6.0, through alkali transfer to pH be 8.0 when above after remaining organic colourity thing precipitation separate out, the precipitation clarification, the water outlet qualified discharge, or as producing bath water in the reuse production process, resin alkali elutriant reclaims the 2-sodium naphthalene sulfonate after evaporation concentration.
Claims (6)
1, a kind of beta naphthal production wastewater treatment method is characterized in that may further comprise the steps in order:
A) with the sulphite staining thing of waste water, make weak acid become strong acid, and waste water ph reduce through easy oxidation in the oxidation removal water;
B) waste water after the oxidation is removed suspended impurity after filtration;
C) exchange absorption-wash-out through ion exchange system, reclaim the intermediate naphthene sulfonic acid;
D) water outlet is regulated pH greater than 8 through alkali, removes colourity, and final outflow water can be used as washings and is back to production process.
2, in accordance with the method for claim 1, wherein step a adopts atmospheric oxidation, makes sulfurous acid become sulfuric acid.
3, in accordance with the method for claim 2, wherein the atmospheric oxidation time is 2-4 hour, pH4-6.
4, in accordance with the method for claim 1, be 1-5BV/h wherein at step c intermediate ion exchange system exchange flow velocity, regeneration velocity is 1-4BV/h, and regenerator is the NaOH solution of 4-8%, and regenerant consumption is 1-4BV.
5, in accordance with the method for claim 1, wherein making spent ion exchange resin in ion exchange system described in the step c is macropore highly basic, weak base anion-exchange resin.
6, in accordance with the method for claim 1, wherein in steps d water outlet regulate pH to 9-11 through alkali.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CNB001321293A CN1147437C (en) | 2000-12-14 | 2000-12-14 | Method for treating waste water in dinaphthyl phenol production |
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| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CNB001321293A CN1147437C (en) | 2000-12-14 | 2000-12-14 | Method for treating waste water in dinaphthyl phenol production |
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| CN1358678A CN1358678A (en) | 2002-07-17 |
| CN1147437C true CN1147437C (en) | 2004-04-28 |
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| CNB001321293A Expired - Fee Related CN1147437C (en) | 2000-12-14 | 2000-12-14 | Method for treating waste water in dinaphthyl phenol production |
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Families Citing this family (8)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101544381B (en) * | 2009-04-30 | 2011-04-20 | 江苏华达化工集团有限公司 | Method for producing ammonium sulphate by waste water produced in alpha naphthol production |
| CN102633399B (en) * | 2012-04-19 | 2013-09-04 | 中蓝连海设计研究院 | Comprehensive treatment and resource utilization technology of 2-naphthol production wastewater |
| CN102838232B (en) * | 2012-09-03 | 2013-09-11 | 济宁阳光煤化有限公司 | Process for processing 2-sodium naphthalene sulfonate mother liquor by blowing and resin absorption |
| CN102964001A (en) * | 2012-11-20 | 2013-03-13 | 武汉工程大学 | High-phenol content wastewater treatment technology |
| CN103408092B (en) * | 2013-08-02 | 2015-01-07 | 浙江吉华集团股份有限公司 | Treatment method for production wastewater of sulfonic acid group dye and dye intermediate of sulfonic acid group dye |
| CN104671501B (en) * | 2015-02-13 | 2016-06-22 | 威士邦（厦门）环境科技有限公司 | The process for cleanly preparing of a kind of washings high-quality reuse of dyeing and complete set of equipments |
| CN105800849A (en) * | 2016-04-21 | 2016-07-27 | 江苏久吾高科技股份有限公司 | Wastewater treatment process and device of sulfonic dye and dye intermediate |
| CN106277609A (en) * | 2016-08-30 | 2017-01-04 | 枣阳市众成化工有限公司 | A kind of benzene produces sewage disposal system and the method for m-dichlorobenzene |
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