CN104310520B - A kind of 4B acid producing waste water comprehensive processing method - Google Patents
A kind of 4B acid producing waste water comprehensive processing method Download PDFInfo
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- C07C309/46—Sulfonic acids having sulfo groups bound to carbon atoms of six-membered aromatic rings of a carbon skeleton containing nitrogen atoms, not being part of nitro or nitroso groups, bound to the carbon skeleton having the sulfo groups bound to carbon atoms of non-condensed six-membered aromatic rings
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Abstract
The present invention is a kind of 4B acid producing waste water comprehensive processing method, the method by 4B acid producing waste water after homogeneous all measures adjustment, with sulfonic acid substance in lewis alkalescence complexing extractant single extraction waste water, extraction phase alkali lye is stripped, regeneration Posterior circle is used in single extraction, and strip liquor reclaims 4B acid crude through acidifying.The extracting phase of single extraction is after adjust ph to alkalescence, reextraction Aniline class material is carried out with the acid complexing extractant of lewis, extraction phase acid solution is stripped, and regeneration Posterior circle is used in reextraction, and strip liquor adds alkaline reaction and reclaims para-totuidine crude product.The nearly water white transparency of waste water water outlet after twice extraction treatment, COD
crclearance > 95%, then water outlet can qualified discharge after biochemistry or oxidizing, flocculating process.Present invention process is reasonable in design, and it not only makes 4B acid producing waste water be governed, and achieves the recycling of resource in waste water.
Description
Technical field
The present invention relates to a kind of Chemicals factory effluent administering method, be exactly specifically first utilize lewis alkalescence complexing extractant by the 4B acid recovery in 4B acid producing waste water, para-totuidine in waste water reclaims by the acid complexing extractant of recycling lewis, realizes the comprehensive regulation of waste water.
Background technology
4B acid (4-aminotoluene-3-sulfonic acid) is a kind of important dyestuff intermediate, is usually used in manufacturing organic dye, the pigment such as bright red 6B, lithol red BK directions, reactive brilliant orange KR.4B acid through reduction, sulfonation and obtained, has baking process(of sulfonation) and solvent method two kinds of production technique by para-nitrotoluene usually.Containing a small amount of para-totuidine in 4B acid crude, para-totuidine is wrapped in 4B acid crude xln, and alkali-soluble acid analysis method refines 4B acid can make para-totuidine strong acid salt stay in crystalline mother solution.Simultaneously containing sulfonic group (-SO in 4B acid molecule
3and amido (-NH H)
2), there is strong, the water-soluble feature such as large of difficult degradation, polarity.Often produce 1 ton of 4B acid and will discharge a large amount of waste water, the CODcr value of waste water is at 8000 ~ 20000mg/l, and pH value is 0.5 ~ 1.5, simultaneously containing 4B acid 3000 ~ 5000mg/L, para-totuidine 300 ~ 800mg/L, directly discharges not only contaminate environment but also cause the wasting of resources.
At present, the treatment process of domestic 4B acid producing waste water mainly contains: extraction process, absorption method, method of enrichment, carbonization and burning method, membrane separation process, cold method, chemical oxidization method, electrolytic process, biochemical process and diazonium salt method etc.Adopt physisorphtion as higher in charcoal absorption cost, sorbent material easily saturated, be difficult to regeneration; Burning method also exists secondary pollution, problem that energy consumption is high; It is high to there is cost in direct chemical oxidization method and electrolytic process, invests large problem; Membrane separation process main drawback is the unstable properties of various film, and fenestra easily blocks; The 4B factory effluent difficulty of biochemical process process high density, highly acidity, high salinity and high chroma is large; And industrial chemicals useful in waste water all can not reclaim by above various method.Resin adsorption method can reclaim industrial chemicals in waste water, but process conditions and require high, short for high-concentration waste water-resin saturation time, backwash is frequent, and resin price is high, and plant investment is large.
Summary of the invention
Technical problem to be solved by this invention is for the deficiencies in the prior art, a kind of comprehensive processing method of 4B acid producing waste water is provided, utilize the method for complexometric extraction 4B acid and para-totuidine in 4B acid producing waste water to be reclaimed exactly, the improvement realizing waste water combines with resource reclaim.
Technical problem to be solved by this invention is realized by following technical scheme.The present invention is a kind of 4B acid producing waste water comprehensive processing method, and its step is as follows:
(1) carry out homogeneous after being filtered by 4B acid producing waste water and all measure adjustment, compare 1 ~ 5: 1 abundant mixing with lewis basic extractant by profit under normal temperature and pressure and carry out single extraction in 3 ~ 5 minutes, namely extracting phase after layering extracts rear water and send reextraction, and extraction phase and loaded extractant send reextraction operation to regenerate;
(2) under normal pressure, the extraction phase of above-mentioned single extraction is fully mixed 10 ~ 20 minutes with alkali lye at 50 DEG C ~ 80 DEG C, reextraction caustic dosage is to control to be as the criterion 8.5 ~ 9.5 by pH end point values, sulfonate solution after layering send strip liquor acidifying recovery system, and the extraction agent after regeneration recycles in single extraction;
(3) above-mentioned reextraction gained sulfonate solution delivers to strip liquor acidifying recovery system, adds mineral acid stirring reaction to pH value 1 ~ 3, is cooled to normal temperature, filters to obtain 4B acid crude;
(4) namely the extracting phase after single extraction is extracted rear water and add alkali adjust ph 7.5 ~ 10.5, compare 1 ~ 5: 1 abundant mixing with lewis acidic extractant by profit under normal temperature and pressure and carry out reextraction in 3 ~ 5 minutes, extracting phase after layering and the rear water of secondary extraction send biochemistry or oxidizing, flocculating process qualified discharge, and the extraction phase of reextraction and loaded extractant send reextraction operation to regenerate;
(5) under normal pressure by reextraction extraction phase and inorganic acid fluid 50 DEG C ~ 80 DEG C abundant hybrid reactions 10 ~ 20 minutes, reextraction acid adding amount is to control to be as the criterion 2 ~ 4 by pH end point values, aniline salt solution after layering send lower step recovery system, and the extraction agent after regeneration recycles in reextraction;
(6) above-mentioned reextraction gained aniline salt solution sends into strip liquor alkalization recovery system, and add mineral alkali stirring reaction to pH value 12 ~ 13, layering obtains para-totuidine crude product.
In the technical scheme of the above 4B acid producing waste water comprehensive processing method of the present invention, further preferred technical scheme or technical characteristic as follows:
1. in step (1), described extraction agent is lewis alkalescence complexing extractant, is made up of complexing agent and thinner.Complexing agent is selected from that phosphoric acid ester, alkyl oxygen are Phosphorus, mixtures of one or more compositions in alkyl amine, and thinner is selected from mixtures of one or more compositions in fat hydrocarbon, aromatic hydrocarbons.Thinner is selected from the mixture of one or more compositions in fat hydrocarbon, aromatic hydrocarbons.Described complexing agent preferred alkyl tertiary amines; The described preferred normal hexane of fat hydrocarbon thinner or kerosene, the described preferred benzene of aromatic hydrocarbons thinner, toluene or dimethylbenzene.
2., in step (3), (5), described mineral acid is selected from sulfuric acid, hydrochloric acid, nitric acid or phosphoric acid.Further preferably sulfuric acid or hydrochloric acid, most preferably mass concentration is the sulfuric acid of 10% ~ 98% or the hydrochloric acid of 10% ~ 31%.
3. in step (2), (4) and (6), described alkali lye can use inorganic alkali lye conventional in prior art, preferred caustic soda, soda ash, oxygen potassium oxide or sodium hydrogen carbonate solution, the caustic soda of further preferred mass concentration 10% ~ 50% or potassium hydroxide solution.
4., in step (4), described extraction agent is the acid complexing extractant of lewis, and complexing agent is selected from the acid mixture containing one or more compositions in phosphorus extractant, and thinner is selected from the mixture of one or more compositions in fat hydrocarbon, aromatic hydrocarbons.Preferred P204 or P507 of described complexing agent; Described fat hydrocarbon thinner is selected from normal hexane or kerosene, and described aromatic hydrocarbons thinner is selected from benzene, toluene or dimethylbenzene.
5. in step (1), 4B acid waste water is after extracting and demixing, and upper strata is extraction phase (loaded extractant), and lower floor is extracting phase (after extraction water); In step (2), extraction phase (loaded extractant) is after reextraction layering, and upper strata is the extraction agent through regeneration, and return extracting system recycle, lower floor is sulfonate solution.
6. in step (4), after reextraction layering, upper strata is the extraction phase (loaded extractant) of reextraction to single extraction extracting phase (after extraction water), and lower floor is the extracting phase (after extraction water) of reextraction; In step (5), the extraction phase (loaded extractant) of reextraction is after reextraction layering, and upper strata is the extraction agent through regeneration, and return extracting system recycle, lower floor is aniline salt solution.
The method of the invention can adopt the mode process of periodical operation or operate continuously.Described 4B acid producing waste water, containing 4B acid 3000 ~ 5000mg/L, para-totuidine 300 ~ 800mg/L in former water, waste water ph 0.5 ~ 1.5, CODcr value is at 8000 ~ 20000mg/l.Through aforesaid method process, after extraction, water outlet pH value 4 ~ 5, CODcr is lower than 500mg/l, CODcr clearance > 95%, and in waste water, 4B acid and the para-totuidine rate of recovery are all greater than 90%.
The present invention adopts complex-extracting method, and first utilize lewis alkalescence complexing extractant 4B acid extraction in waste water to be reclaimed, the acid complexing extractant of recycling lewis by the para-totuidine extraction and recovery in waste water, thus reduces the CODcr content in waste water, COD
crclearance > 95%, water nearly water white transparency of water outlet after biochemical or oxidizing, flocculating process after extraction, can qualified discharge, effectively realizes the comprehensive regulation of 4B acid producing waste water and recycling.Present invention process is reasonable in design, and it not only makes 4B acid producing waste water be governed, and achieves the recycling of resource in waste water.
Accompanying drawing explanation
Fig. 1 is the process flow diagram of 4B acid producing waste water comprehensive processing method of the present invention.
Embodiment
Referring to accompanying drawing, further describe concrete technical scheme of the present invention, so that those skilled in the art understands the present invention further, and do not form the restriction to its right.
Embodiment 1, with reference to Fig. 1, a kind of 4B acid producing waste water comprehensive processing method, its step is as follows:
(1) carry out homogeneous after being filtered by 4B acid producing waste water and all measure adjustment, compare 1: 1 abundant mixing with lewis basic extractant by profit under normal temperature and pressure and carry out single extraction in 3 minutes, namely extracting phase after layering extracts rear water and send reextraction, and extraction phase and loaded extractant send reextraction operation to regenerate;
(2) under normal pressure, the extraction phase of above-mentioned single extraction is fully mixed 20 minutes with alkali lye at 50 DEG C, reextraction caustic dosage is to control to be as the criterion 8.5 by pH end point values, sulfonate solution after layering send strip liquor acidifying recovery system, and the extraction agent after regeneration recycles in single extraction;
(3) above-mentioned reextraction gained sulfonate solution sends into strip liquor acidifying recovery system, adds mineral acid stirring reaction to pH value 1, is cooled to normal temperature, filters to obtain 4B acid crude;
(4) namely the extracting phase after single extraction is extracted rear water and add alkali adjust ph 7.5, compare 1: 1 abundant mixing with lewis acidic extractant by profit under normal temperature and pressure and carry out reextraction in 3 minutes, extracting phase after layering and the rear water of secondary extraction send biochemistry or oxidizing, flocculating process qualified discharge, and the extraction phase of reextraction and loaded extractant send reextraction operation to regenerate;
(5) under normal pressure by reextraction extraction phase and inorganic acid fluid 50 DEG C of abundant hybrid reactions 10 minutes, reextraction acid adding amount is to control to be as the criterion 2 by pH end point values, aniline salt solution after layering send strip liquor alkalization recovery system, and the extraction agent after regeneration recycles in reextraction;
(6) above-mentioned reextraction gained aniline salt solution sends into strip liquor alkalization recovery system, and add mineral alkali stirring reaction to pH value 12, layering obtains para-totuidine crude product.
Embodiment 2, with reference to Fig. 1, a kind of H acid producing waste water comprehensive processing method, its step is as follows:
(1) all adjustment is measured with carrying out homogeneous after being filtered by 4B acid producing waste water, compare 5: 1 abundant mixing with lewis basic extractant by profit under normal temperature and pressure and carry out single extraction in 5 minutes, namely extracting phase after layering extracts rear water and send reextraction, and extraction phase and loaded extractant send reextraction operation to regenerate;
(2) under normal pressure, the extraction phase of above-mentioned single extraction is fully mixed 10 minutes with alkali lye at 80 DEG C, reextraction caustic dosage is to control to be as the criterion 9.5 by pH end point values, sulfonate solution after layering send strip liquor acidifying recovery system, and the extraction agent after regeneration recycles in single extraction;
(3) above-mentioned reextraction gained sulfonate solution sends into strip liquor acidifying recovery system, adds mineral acid stirring reaction to pH value 3, is cooled to normal temperature, filters to obtain 4B acid crude;
(4) namely the extracting phase after single extraction is extracted rear water and add alkali adjust ph 10.5, compare 5: 1 abundant mixing with lewis acidic extractant by profit under normal temperature and pressure and carry out reextraction in 5 minutes, extracting phase after layering and the rear water of secondary extraction send biochemistry or oxidizing, flocculating process qualified discharge, and the extraction phase of reextraction and loaded extractant send reextraction operation to regenerate;
(5) under normal pressure by reextraction extraction phase and inorganic acid fluid 80 DEG C of abundant hybrid reactions 20 minutes, reextraction acid adding amount is to control to be as the criterion 4 by pH end point values, aniline salt solution after layering send strip liquor alkalization recovery system, and the extraction agent after regeneration recycles in reextraction;
(6) above-mentioned reextraction gained aniline salt solution sends into strip liquor alkalization recovery system, and add mineral alkali stirring reaction to pH value 13, layering obtains para-totuidine crude product.
Embodiment 3, with reference to Fig. 1, a kind of H acid producing waste water comprehensive processing method, its step is as follows:
(1) carry out homogeneous after being filtered by 4B acid producing waste water and all measure adjustment, compare 3: 1 abundant mixing with lewis basic extractant by profit under normal temperature and pressure and carry out single extraction in 4 minutes, namely extracting phase after layering extracts rear water and send reextraction, and extraction phase and loaded extractant send reextraction operation to regenerate;
(2) under normal pressure, the extraction phase of above-mentioned single extraction is fully mixed 15 minutes with alkali lye at 65 DEG C, reextraction caustic dosage is to control to be as the criterion 9 by pH end point values, sulfonate solution after layering send strip liquor acidifying recovery system, and the extraction agent after regeneration recycles in single extraction;
(3) above-mentioned reextraction gained sulfonate solution sends into strip liquor acidifying recovery system, adds mineral acid stirring reaction to pH value 2, is cooled to normal temperature, filters to obtain 4B acid crude;
(4) namely the extracting phase after single extraction is extracted rear water and add alkali adjust ph 9, compare 3: 1 abundant mixing with lewis acidic extractant by profit under normal temperature and pressure and carry out reextraction in 4 minutes, extracting phase after layering and the rear water of secondary extraction send biochemistry or oxidizing, flocculating process qualified discharge, and the extraction phase of reextraction and loaded extractant send reextraction operation to regenerate;
(5) under normal pressure by reextraction extraction phase and inorganic acid fluid 70 DEG C of abundant hybrid reactions 15 minutes, reextraction acid adding amount is to control to be as the criterion 3 by pH end point values, aniline salt solution after layering send lower step alkalization recovery system, and the extraction agent after regeneration recycles in reextraction;
(6) above-mentioned reextraction gained aniline salt solution sends into strip liquor alkalization recovery system, and add mineral alkali stirring reaction to pH value 11, layering obtains para-totuidine crude product;
Embodiment 4, in the step (1) of the technique of embodiment 1-3 described in any one, described mineral acid is selected from sulfuric acid, hydrochloric acid, nitric acid or phosphoric acid.
Embodiment 5, in the technique of embodiment 1-3 described in any one in step (1), described mineral acid is mass concentration is the sulfuric acid of 10% ~ 98% or the hydrochloric acid of 10% ~ 31%.
Embodiment 6, in the step (2) of the technique of embodiment 1-5 described in any one, described alkali lye is selected from caustic soda, soda ash, oxygen potassium oxide or sodium hydrogen carbonate solution.
Embodiment 7, in the step (2) of the technique of embodiment 1-6 described in any one, described alkali lye is selected from caustic soda, soda ash, oxygen potassium oxide or sodium hydrogen carbonate solution, and its mass concentration is 10%-50%.
Embodiment 8, in the step (2) of the technique of embodiment 1-6 described in any one, described inorganic alkali lye to be mass concentration be 10% ~ 50% caustic soda or potassium hydroxide solution.
Embodiment 9, in the step (1) of the technique of embodiment 1-8 described in any one, described extraction agent is lewis alkalescence complexing extractant, complexing agent is selected from that phosphoric acid ester, alkyl oxygen are Phosphorus, mixtures of one or more compositions in alkyl amine, and thinner is selected from mixtures of one or more compositions in fat hydrocarbon, aromatic hydrocarbons.Thinner is selected from the mixture of one or more compositions in fat hydrocarbon, aromatic hydrocarbons.
Embodiment 10, in the technique of embodiment 1-8 described in any one, described complexing agent is selected from alkyl tert amine; Described fat hydrocarbon thinner is selected from normal hexane or kerosene, and described aromatic hydrocarbons thinner is selected from benzene, toluene or dimethylbenzene.
Embodiment 11, in the step (4) of the technique of embodiment 1-10 described in any one, described extraction agent is the acid complexing extractant of lewis, complexing agent is selected from the mixture of acid one or more compositions containing phosphorus extractant, and thinner is selected from the mixture of one or more compositions in fat hydrocarbon, aromatic hydrocarbons.
Embodiment 12, in the technique of embodiment 1-10 described in any one, described complexing agent is selected from P204 or P507; Described fat hydrocarbon thinner is selected from normal hexane or kerosene, and described aromatic hydrocarbons thinner is selected from benzene, toluene or dimethylbenzene.
Embodiment 13, the comprehensive processing method experiment one of periodical operation formula H acid producing waste water:
In the dye chemical industry factory 4B acid producing waste water of Suzhou, CODcr reaches 16740mg/l, and 4B acid 4682mg/L, para-totuidine 680mg/L, pH value 1.25, outward appearance is that brownish black is opaque.Extraction process is sent after regulating by homogeneous, all amount.
(1) by the above-mentioned 4B acid producing waste water pump delivery of certain volume in single extraction still, the lewis basic extractant that add same volume at 1: 1 is compared by profit, open and stir, stir fully mixing in 5 minutes, leave standstill 0.5 hour again, after layering, lower floor's extracting phase (after extraction water) is discharged and is sent reextraction, the waste water ph about 4 after extraction.Upper strata oil reservoir is that extraction phase (stay in still and wait regeneration of stripping by loaded extractant.
(2) open extraction kettle to stir, stir above-mentioned extraction phase (loaded extractant), open and be steam heated to 80 DEG C, slowly add 30% caustic soda soln, alkali lye dosage is as the criterion with pH value in still simultaneously, control reextraction endpoint pH 9.0, alkali lye adds rear continuation stirring 10 minutes, leaves standstill 0.5 little layered, discharges lower floor's strip liquor (sodium sulfonate solution) to 4B acid recovery system, upper strata oil reservoir is the extraction agent after regeneration, recycles in next extracting operation.
(3) by the above-mentioned strip liquor pump delivery of a constant volume in reactor, open and stir, drip 31% hydrochloric acid, to reactor during material liquid pH value 1, stop dripping hydrochloric acid, logical cooling water temperature crystallization, filters to obtain 4B acid crude with whizzer.Filtrate returns one-level extraction.
(4) by the extracting phase of the above-mentioned single extraction of certain volume (after extraction water) by 30% caustic soda adjust ph 9.0, by pump delivery in reextraction still, the lewis acidic extractant that add same volume at 1: 1 is compared by profit, open and stir, stir fully mixing in 5 minutes, leave standstill 0.5 hour again, after layering, lower floor's extracting phase (after extraction water) is discharged and is sent biochemistry or oxidizing, flocculating qualified discharge, the waste water ph about 4 after extraction.Upper strata oil reservoir is extraction phase (loaded extractant), stays in still and waits regeneration of stripping.
(5) open reextraction still to stir, stir above-mentioned extraction phase (loaded extractant), open and be steam heated to 80 DEG C, slowly add 31% hydrochloric acid soln, hydrochloric acid dosage is as the criterion with pH value in still simultaneously, control reextraction endpoint pH 3.0, hydrochloric acid adds rear continuation stirring 10 minutes, leaves standstill 0.5 little layered, discharges lower floor's strip liquor (aniline salt solution) to para-totuidine recovery system, upper strata oil reservoir is the extraction agent after regeneration, recycles in next extracting operation.
(6) by the above-mentioned strip liquor pump delivery of a constant volume in reactor, open and stir, drip 30% caustic soda soln, to reactor during material liquid pH value to 12, stop dripping caustic soda, logical cooling water temperature, stratification 0.5 hour, discharge lower floor's waste back-cycling to reextraction, release upper strata oil reservoir and obtain para-totuidine crude product.
4B acid producing waste water is after twice extraction, and water outlet water white transparency, CODcr is down to 364mg/l, 4B acid 32mg/L, para-totuidine 12mg/L.
Embodiment 14, continuous operation type 4B acid producing waste water comprehensive processing method experiment two:
Chemical plant, Zhejiang 4B acid producing waste water outward appearance is that brownish black is opaque, and CODcr reaches 18720mg/l, 4B acid 4867mg/L, para-totuidine 738mg/L, pH value 0.97.Extraction process is sent after regulating by homogeneous, all amount.
(1) homogeneous is all measured the 4B acid producing waste water regulated and lewis basic extractant pump delivery, through under meter adjust flux, compare 2: 1 by profit, deliver to static mixer and fully mix, continuously flow into band whipping appts extractor, 15 minutes abundant stirring reaction time; Continuously flow into quantizer, 40 minutes residence time, after layering, lower floor's extracting phase (after extraction water) delivers to reextraction continuously, and upper strata oil reservoir is extraction phase (loaded extractant), and continus convergence is to loaded extractant basin.
(2) above-mentioned loaded extractant and mass concentration 25% caustic soda soln use pump delivery respectively, after under meter adjust flux, through preheater preheats, continuously flow into the back wash extractor of band heating and stirring device, maintain the temperature at 70 DEG C, fully be uniformly mixed reaction after 20 minutes, continuously flow into the quantizer of band heating and heat-insulating device, 40 minutes residence time, after stratification, the strip liquor (sodium sulfonate solution) of lower floor delivers to 4B acid recovery system continuously, and upper strata oil reservoir is the extraction agent regenerated after back extraction, continus convergence, to extraction agent basin, recycles in single extraction.
(3) by the above-mentioned strip liquor pump continus convergence of certain volume in acidification reaction still, open stir, drip 70% sulfuric acid, keep material liquid pH value in reactor to be 1 ~ 3, continuously flow into crystallization kettle, logical cooling water temperature crystallization, filter to obtain 4B acid crude with whizzer, filtrate sends one-level extraction back to.
(4) by the extracting phase of the above-mentioned single extraction of certain volume (after extraction water) by 30% caustic soda adjust ph 10.0, pump delivery is reinstated with lewis acidic extractant one, through under meter adjust flux, 2: 1 are compared by profit, deliver to static mixer fully to mix, continuously flow into band whipping appts extractor, 20 minutes abundant stirring reaction time; Continuously flow into quantizer, 40 minutes residence time, after layering, lower floor's extracting phase (after extraction water) delivers to biochemistry or oxidizing, flocculating qualified discharge continuously, and upper strata oil reservoir is extraction phase (loaded extractant), and continus convergence is to loaded extractant basin.
(5) above-mentioned loaded extractant and mass concentration 70% sulphuric acid soln use pump delivery respectively, after under meter adjust flux, through preheater preheats, continuously flow into the back wash extractor of band heating and stirring device, maintain the temperature at 70 DEG C, fully be uniformly mixed reaction after 20 minutes, continuously flow into the quantizer of band heating and heat-insulating device, 40 minutes residence time, after stratification, the strip liquor (aniline salt solution) of lower floor delivers to para-totuidine recovery system continuously, and upper strata oil reservoir is the extraction agent regenerated after back extraction, continus convergence, to extraction agent basin, recycles in reextraction.
(6) by the above-mentioned strip liquor pump continus convergence of certain volume in reactor, open and stir, drip 30% caustic soda, material liquid pH value in reactor is kept to be 12 ~ 13, continuously flow into quantizer, 0.5 hour layering residence time, discharge lower floor's waste back-cycling continuously to reextraction, upper strata oil reservoir continuous overflow goes out to obtain para-totuidine crude product.
4B acid producing waste water is after twice extraction, and the nearly water white transparency of water outlet, CODcr is down to 376mg/l, 4B acid 27mg/L, para-totuidine 16mg/L.
Claims (7)
1. a 4B acid producing waste water comprehensive processing method, is characterized in that, its step is as follows:
(1) carry out homogeneous after being filtered by 4B acid producing waste water and all measure adjustment, compare 1 ~ 5: 1 abundant mixing with lewis basic extractant by profit under normal temperature and pressure and carry out single extraction in 3 ~ 5 minutes, namely extracting phase after layering extracts rear water and send reextraction, and extraction phase and loaded extractant send reextraction operation to regenerate;
(2) under normal pressure, the extraction phase of above-mentioned single extraction is fully mixed 10 ~ 20 minutes with alkali lye at 50 DEG C ~ 80 DEG C, reextraction caustic dosage is to control to be as the criterion 8.5 ~ 9.5 by pH end point values, sulfonate solution after layering send strip liquor acidifying recovery system, and the extraction agent after regeneration recycles in single extraction;
(3) above-mentioned reextraction gained sulfonate solution delivers to strip liquor acidifying recovery system, adds mineral acid stirring reaction to pH value 1 ~ 3, is cooled to normal temperature, filters to obtain 4B acid crude;
(4) namely the extracting phase after single extraction is extracted rear water and add alkali adjust ph 7.5 ~ 10.5, compare 1 ~ 5: 1 abundant mixing with lewis acidic extractant by profit under normal temperature and pressure and carry out reextraction in 3 ~ 5 minutes, extracting phase after layering and the rear water of secondary extraction send biochemistry or oxidizing, flocculating process qualified discharge, and the extraction phase of reextraction and loaded extractant send reextraction operation to regenerate;
(5) under normal pressure by reextraction extraction phase and inorganic acid fluid 50 DEG C ~ 80 DEG C abundant hybrid reactions 10 ~ 20 minutes, reextraction acid adding amount is to control to be as the criterion 2 ~ 4 by pH end point values, aniline salt solution after layering send strip liquor alkalization recovery system, and the extraction agent after regeneration recycles in reextraction;
(6) above-mentioned reextraction gained aniline salt solution sends into strip liquor alkalization recovery system, and add mineral alkali stirring reaction to pH value 12 ~ 13, layering obtains para-totuidine crude product;
In described lewis alkalescence complexing extractant: complexing agent is selected from that phosphoric acid ester, alkyl oxygen are Phosphorus, mixtures of one or more compositions in alkyl amine, and thinner is selected from mixtures of one or more compositions in fat hydrocarbon, aromatic hydrocarbons;
In the acid complexing extractant of described lewis: complexing agent is selected from the mixture of acid one or more compositions containing phosphorus extractant, and thinner is selected from the mixture of one or more compositions in fat hydrocarbon, aromatic hydrocarbons.
2. method according to claim 1, is characterized in that: in described lewis alkalescence complexing extractant: complexing agent is selected from alkyl tert amine; Described fat hydrocarbon thinner is selected from normal hexane or kerosene, and described aromatic hydrocarbons thinner is selected from benzene, toluene or dimethylbenzene.
3. method according to claim 1, is characterized in that: in step (3), (5), described mineral acid is selected from sulfuric acid, hydrochloric acid, nitric acid or phosphoric acid.
4. method according to claim 3, is characterized in that: in step (3), (5), and described mineral acid is mass concentration is the sulfuric acid of 10% ~ 98% or the hydrochloric acid of 10% ~ 31%.
5. method according to claim 1, is characterized in that: in step (2), (4) and (6), described alkali lye is selected from caustic soda, soda ash, oxygen potassium oxide or sodium hydrogen carbonate solution.
6. method according to claim 5, is characterized in that: in step (2), (4) and (6), and described alkali lye is caustic soda or the potassium hydroxide solution of mass concentration 10% ~ 50%.
7. method according to claim 1, is characterized in that: in the acid complexing extractant of described lewis: complexing agent is selected from P204 or P507; Described fat hydrocarbon thinner is selected from normal hexane or kerosene, and described aromatic hydrocarbons thinner is selected from benzene, toluene or dimethylbenzene.
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| CN102603025A (en) * | 2012-03-31 | 2012-07-25 | 中国中化股份有限公司 | Method for processing wastewater produced in reactive dye production by utilizing complexing extraction technology |
| CN104086462A (en) * | 2014-07-25 | 2014-10-08 | 潍坊沃尔特科技有限公司 | Method for extracting m-phthalic acid-5-sodium sulfonate from trimonomer production wastewater |
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| CN102603025A (en) * | 2012-03-31 | 2012-07-25 | 中国中化股份有限公司 | Method for processing wastewater produced in reactive dye production by utilizing complexing extraction technology |
| CN104086462A (en) * | 2014-07-25 | 2014-10-08 | 潍坊沃尔特科技有限公司 | Method for extracting m-phthalic acid-5-sodium sulfonate from trimonomer production wastewater |
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