CN103880713A - Method for recycling bromaminic acid from production wastewater of reactive brilliant blue KN-R of vinyl sulfone type dye - Google Patents
Method for recycling bromaminic acid from production wastewater of reactive brilliant blue KN-R of vinyl sulfone type dye Download PDFInfo
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- CN103880713A CN103880713A CN201410153753.6A CN201410153753A CN103880713A CN 103880713 A CN103880713 A CN 103880713A CN 201410153753 A CN201410153753 A CN 201410153753A CN 103880713 A CN103880713 A CN 103880713A
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Abstract
The invention discloses a method for recycling bromaminic acid from production wastewater of reactive brilliant blue KN-R of a vinyl sulfone type dye, belonging to the field of wastewater treatment and resource recycle methods. The method mainly comprises the following steps: (A) adding potassium slat into to-be-treated bromaminic acid dye wastewater and uniformly stirring; (B) standing mixed liquid obtained in the step (A) and centrifuging to obtain a solid; (C) dripping a sodium carbonate solution into the solid obtained in the step (B) at a constant speed, uniformly stirring, and stopping adding the sodium carbonate solution when the solid is dissolved completely; (D) evaporating and crystalizing the mixed solution obtained in the step (C) to obtain the solid; (E) dissolving a solid mixture obtained in the step (D) with ethanol; and (F) filtering the mixed solution obtained in the step (E), and treating the filtrate through a reduced pressure distillation process to obtain a sodium bromamine solid. The method disclosed by the invention can be used for effectively treating the wastewater as well as recycling bromaminic acid in the wastewater, meets the requirements of environment-friendly production and is simple and convenient, easy to operate, low in cost and environmental friendly.
Description
Technical field
The invention belongs to the waste water treatment and its recovery method as resource field that in DYE PRODUCTION process, produce, more particularly, relate to the recovery method of bromamine acid in a kind of Vinyl-Sulfone Type dye activity brilliant blue KN-R factory effluent.
Background technology
Vinyl-sulfone reactive dyes is from nineteen fifty-seven listing existing history more than 50 years till now, the states such as China, Japan, Korea S, Switzerland, India and Russia are all in succession studied and develop vinyl-sulfone reactive dyes, vinyl-sulfone reactive dyes has developed into the first class in reactive dyestuffs at present, occupies very consequence in reactive dyestuffs commodity market and research field.Multiple kinds such as domestic existing Reactive Brilliant Blue KN-R, K-3R, K-BK, X-BR, X-3R, nearly ten thousand tons of yearly capacities.Synthesizing of this series dyes, normally under copper and ionic catalysis thereof, reacted with arylamine by bromamine acid and obtain, in process of production, in order to improve the utilization ratio of reactant, wherein a kind of reactant of the excessive interpolation of meeting, in Reactive Brilliant Blue KN-R reaction system, bromamine acid is exactly wherein a kind of, therefore produces in the processing wastewater producing in dyestuff process and can contain a large amount of unreacted bromamine acids.Bromamine acid, the actual sodium bromaminate that refers to, chemical name is 1-amino-4-bromo anthraquinone-2-sulfonic acid, is a kind of important anthraquinone dye intermediate, is widely used in the production of Chemicals.Produce and use procedure in, because it has higher water-solublely, very easily enter water body, cause the colourity of such waste water and COD higher, water body is caused to great pollution, serious harm HUMAN HEALTH.Therefore the improvement method of, studying and defining economical rationality, practicability and effectiveness has important practical significance and application value.
At present, the method for processing bromamine acid waste water both at home and abroad has physico-chemical process and biological process.Physico-chemical process mainly contains resin adsorption method (for example China Patent No.: 200410014646.1, open day on January 12nd, 2005, disclosed name is called the improvement of bromamine acid class reactive dyestuffs factory effluent and the patent document of its recovery method as resource), electrochemical oxidation process (for example China Patent No.: 200910029887.6, open day on August 19th, 2009, disclosed name is called a kind of patent document of electrochemical oxidation method for treating of wastewater containing anthraquinone dye) etc., these methods have all obtained certain treatment effect, but have the problems such as energy consumption is high, secondary pollution is serious.Biological process receives much concern with advantages such as its economic environmental protection, current research mainly concentrates on following 2 aspects: the screening of bromamine acid efficient degrading bacterial strain and degradation characteristic and be added to and in reactor, carry out biological reinforced processing, biological process is better to the chromaticity removing effect of bromamine acid, but easily there is autoxidation phenomenon, form and be difficult to biodegradable yellow intermediate product.As, patent of invention CN101391856A discloses a kind of method of bromamine acid aerobic biomineralization, this method is mainly added efficient adsorption material in aerobic reactor, utilize the microorganism growing on sorbing material to carry out absorption degradation to bromamine acid, thereby avoid its generation autoxidation to reach the object of thorough mineralising.But due to wastewater from chemical industry component complexity, concentration is higher, has bio-toxicity, aerobe system microbiological treatment, is difficult to reach processing requirement up to standard.
By paper and patent retrieval, at present the method for the bromamine acid in conventional Dye Wastewater Treatment is all react bromamine acid as general organism degrade or adsorb with sorbent material, do not find bromamine acid to carry out the report of effective recycling, and because the impurity in Vinyl-Sulfone Type dye activity brilliant blue KN-R factory effluent is more, interfering factors is too many, also cannot use ordinary method to reclaim, also do not have pertinent literature to give those skilled in the art with enlightenment, this certainly will be a kind of huge waste of resource.
Summary of the invention
1. the problem that will solve
, not environmental protection high for bromamine acid processing cost in current waste water in dye production and the low problem of recovery utilization rate, the invention provides the recovery method of bromamine acid in a kind of Vinyl-Sulfone Type dye activity brilliant blue KN-R factory effluent, not only reclaim active principle bromamine acid in waste water, save enterprise's production cost, and realized the cleaner production of DYE PRODUCTION technique, the target of resource recycling.
2. technical scheme
In order to address the above problem, the technical solution adopted in the present invention is as follows:
In Vinyl-Sulfone Type dye activity brilliant blue KN-R factory effluent, a recovery method for bromamine acid, the steps include:
A) in pending bromamine acid waste water from dyestuff, add sylvite, stir, obtain mixed solution;
B) by steps A) in mixed solution leave standstill, the centrifugal solid that obtains;
C) to step B) at the uniform velocity drip sodium carbonate solution in the solid that obtains, stir, after dissolving completely, solid stops adding sodium carbonate solution, obtain sodium bromaminate, salt of wormwood and sodium carbonate mixture;
D) by step C) the mixing solutions evaporative crystallization that obtains, obtain the solid mixture of sodium bromaminate, salt of wormwood and sodium carbonate;
E) by step D) evaporate the solid mixture dissolve with ethanol obtaining, sodium bromaminate is dissolved in ethanol, and salt of wormwood, sodium carbonate are insoluble to ethanol, obtain mixing solutions;
F) by step e) mixing solutions that obtains filters, and the filtrate obtaining is sodium bromaminate ethanolic soln, and filter residue is salt of wormwood and sodium carbonate solid, and filtrate decompression distillation is got final product to obtain to sodium bromaminate solid.
Preferably, described steps A) in the sylvite that adds be Repone K or saltpetre, temperature of reaction is 10-30 DEG C, churning time is 15-20min;
Preferably, described steps A) in amount and the waste water of the sylvite that adds the molar weight of bromamine acid than being (1.1-1.2): 1;
Preferably, described step B) in time of repose be 10min, centrifugal speed is 1000r/min, centrifugation time is 15min;
Preferably, described step C) in reaction conditions be 10-30 DEG C, the sodium carbonate solution mass concentration of dropping is 10-15%;
Preferably, described step F) in the ethanolic soln that obtains of underpressure distillation recycle and reuse, the salt of wormwood obtaining and sodium carbonate solid recycle and reuse.
The application that Repone K or saltpetre reclaim bromamine acid in Vinyl-Sulfone Type dye activity brilliant blue KN-R factory effluent.
3. beneficial effect
Than prior art, beneficial effect of the present invention is:
(1) the present invention is reacted with bromamine acid and is generated bromamine acid potassium precipitation by Repone K or saltpetre, bromamine acid potassium precipitation is reacted generation sodium bromaminate again with saturated solution of sodium carbonate, obtain sodium bromaminate by evaporative crystallization and ethyl alcohol recrystallization, different from conventional process waste water in dye production technique, the present invention can reclaim the active principle bromamine acid in waste water, avoid the wasting of resources, and reduce this COD value of waste water, reduce its intractability, save enterprise's production cost, the cleaner production of DYE PRODUCTION technique and the target of resource recycling are realized, emphasis has been avoided the interference problem of other impurity in Vinyl-Sulfone Type dye activity brilliant blue KN-R factory effluent,
(2) the present invention precipitates the bromamine acid in coupling alcohol solvent recrystallization method recovery waste water in dye production by sylvite, salt of wormwood and sodium carbonate solid and ethanol can recirculation utilizations, realize greenization, circulationization to containing bromamine acid wastewater treatment process in Vinyl-Sulfone Type dye activity brilliant blue KN-R, not only save production cost for enterprise self, strengthen enterprise's competitive power in the industry, and met the industry development trend of environment protection and energy-saving and emission-reduction; Cost recovery is low and income is high, is a kind of method of wastewater treatment of environmental protection, meets green production requirement;
(3) recovery method of the present invention is easy, easy to operate, and bromamine acid recovering effect is obvious.
Brief description of the drawings
Fig. 1 is process flow sheet of the present invention.
Embodiment
Describe the present invention below in conjunction with specific embodiment.
Embodiment 1
As shown in Figure 1, the recovery method of bromamine acid in a kind of Vinyl-Sulfone Type dye activity brilliant blue KN-R factory effluent, its treatment step is:
A) to adding 2.55kg Repone K in the pending bromamine acid waste water from dyestuff of 250L, (in the amount of the sylvite of interpolation and waste water, the molar weight of bromamine acid is than being (1.1-1.2): between 1, all can, those skilled in the art can predict this scope by the present embodiment and all can, no longer exhaustive at this), at 10-20 DEG C, 60rpm stirs 15min; Pending bromamine acid waste water from dyestuff is the waste water that Zhejiang produces the chemical plant discharge of Vinyl-Sulfone Type dye activity brilliant blue KN-R, in waste water, contain bromamine acid 50300mg/L, sodium bicarbonate 0.5%(massfraction), toluene 0.1%(massfraction), dimethylbenzene 0.05%(massfraction), and a small amount of 2-sulfonic acid (lower than 0.01%, massfraction) etc.;
B) by steps A) the standing 10min of middle mixed solution, obtain solid with the centrifugal 15min of 1000r/min;
C) to step B) at the uniform velocity to drip mass concentration in the solid that obtains be 10% sodium carbonate solution 16.5L, at 10-20 DEG C, 60rpm stirs, and after solid dissolves completely, stops adding sodium carbonate solution, obtains sodium bromaminate, salt of wormwood and sodium carbonate mixture;
D) by step C) the mixing solutions evaporative crystallization that obtains, obtain the solid mixture of sodium bromaminate, salt of wormwood and sodium carbonate;
E) by step D) evaporate the solid mixture dissolve with ethanol obtaining, sodium bromaminate is dissolved in ethanol, and salt of wormwood, sodium carbonate are insoluble to ethanol, obtain mixing solutions;
F) by step e) mixing solutions that obtains filters, the filtrate obtaining after filtration is sodium bromaminate ethanolic soln, filter residue is the solid mixture of salt of wormwood and sodium carbonate, the sodium bromaminate solid obtaining after filtrate decompression distillation is 12.1kg, ethanolic soln and salt of wormwood and the equal recycle and reuse of sodium carbonate solid.In waste water after treatment, contain bromamine acid 2080mg/L, the bromamine acid rate of recovery reaches 95.9%.
The present invention has overcome traditional microbiological deterioration method of wastewater treatment, utilizes sylvite precipitation coupling ethyl alcohol recrystallization mode to reclaim bromamine acid in waste water, and not only utilization of waste material, saves production cost, and reduced this COD value of waste water, reduces its intractability, the present invention is precipitated → stirred by sylvite, and salt → ethyl alcohol recrystallization → underpressure distillation (ethanol is applied mechanically) is analysed in the dissolve → evaporation of centrifugal → sodium carbonate, in Vinyl-Sulfone Type dye activity brilliant blue KN-R, contain bromamine acid wastewater treatment process and realize greenization, circulationization, not only save production cost for enterprise self, strengthen enterprise's competitive power in the industry, and meet the industry development trend of environment protection and energy-saving and emission-reduction, find through investigation, the bromamine acid wastewater flow rate that contains that the chemical plant emission of Zhejiang production Vinyl-Sulfone Type dye activity brilliant blue KN-R goes out is about 50t/d, bromamine acid market value is 70000 yuan/t, if the method providing in employing the present invention is recycled, can be enterprise and save approximately 160,000 yuan/d of bromamine acid raw materials cost left and right.
Embodiment 2
A recovery method for bromamine acid in Vinyl-Sulfone Type dye activity brilliant blue KN-R factory effluent, its treatment step is:
A) in the pending bromamine acid waste water from dyestuff of 250L, add 3.45kg saltpetre, at 20-30 DEG C, 60rpm stirs 15min; Pending bromamine acid waste water from dyestuff is the waste water that Suzhou produces the chemical plant discharge of Vinyl-Sulfone Type dye activity brilliant blue KN-R, in waste water, contain bromamine acid 51100mg/L, sodium bicarbonate 0.5%(massfraction), toluene 0.1%(massfraction), dimethylbenzene 0.05%(massfraction), and a small amount of 2-sulfonic acid (lower than 0.01%, massfraction) etc.;
B) by steps A) the standing 10min of middle mixed solution, obtain solid with the centrifugal 15min of 1000r/min;
C) to step B) at the uniform velocity to drip mass concentration in the solid that obtains be 15% sodium carbonate solution 11.0L, at 20-30 DEG C, 60rpm stirs, and after solid dissolves completely, stops adding sodium carbonate solution, obtains sodium bromaminate, salt of wormwood and sodium carbonate mixture;
D) by step C) the mixing solutions evaporative crystallization that obtains, obtain the solid mixture of sodium bromaminate, salt of wormwood and sodium carbonate;
E) by step D) evaporate the solid mixture dissolve with ethanol obtaining, sodium bromaminate is dissolved in ethanol, and salt of wormwood, sodium carbonate are insoluble to ethanol, obtain mixing solutions;
F) by step e) mixing solutions that obtains filters, the filtrate obtaining is sodium bromaminate ethanolic soln, filter residue is salt of wormwood and sodium carbonate solid, the sodium bromaminate solid 12.2kg obtaining after filtrate decompression distillation, ethanolic soln and salt of wormwood and the equal recycle and reuse of sodium carbonate solid.In waste water after treatment, contain bromamine acid 1960mg/L, the bromamine acid rate of recovery reaches 96.1%.
Embodiment 3
With embodiment 1, difference is, steps A) in the addition of Repone K be 2.78kg; Churning time is 20min, step C) in added the sodium carbonate solution that 11.0L mass concentration is 15%; The method of the present embodiment can will be down to 1945mg/L from 50300mg/L, the rate of recovery 96.13% containing the bromamine acid content in bromamine acid waste water.
Embodiment 4
With embodiment 2, difference is, steps A) in the addition of saltpetre be 3.76kg; Churning time is 20min, step C) in added the sodium carbonate solution that 16.5L mass concentration is 10%; The method of the present embodiment can will be down to 1958mg/L from 50300mg/L, the rate of recovery 96.11% containing the bromamine acid content in bromamine acid waste water.
Embodiment 5
With embodiment 1, difference is to contain bromamine acid 58400mg/L, steps A in pending Vinyl-Sulfone Type dye activity brilliant blue KN-R factory effluent) in amount and the waste water of interpolation of Repone K the molar weight of bromamine acid than being 1.2:1; Step C) in added the sodium carbonate solution that 12.0L mass concentration is 13%; The method of the present embodiment is the bromamine acid rate of recovery 97.24% from Vinyl-Sulfone Type dye activity brilliant blue KN-R factory effluent.
Embodiment 6
With embodiment 2, difference is to contain bromamine acid 4970mg/L, steps A in pending Vinyl-Sulfone Type dye activity brilliant blue KN-R factory effluent) in amount and the waste water of interpolation of saltpetre the molar weight of bromamine acid than being 1.2:1; Step C) in added the sodium carbonate solution that 16.7L mass concentration is 10%; The method of the present embodiment is the bromamine acid rate of recovery 97.09% from Vinyl-Sulfone Type dye activity brilliant blue KN-R factory effluent.
Claims (7)
1. a recovery method for bromamine acid in Vinyl-Sulfone Type dye activity brilliant blue KN-R factory effluent, the steps include:
A) in pending bromamine acid waste water from dyestuff, add sylvite, stir, obtain mixed solution;
B) by steps A) in mixed solution leave standstill, the centrifugal solid that obtains;
C) to step B) at the uniform velocity drip sodium carbonate solution in the solid that obtains, stir, after dissolving completely, solid stops adding sodium carbonate solution, obtain sodium bromaminate, salt of wormwood and sodium carbonate mixture;
D) by step C) the mixing solutions evaporative crystallization that obtains, obtain the solid mixture of sodium bromaminate, salt of wormwood and sodium carbonate;
E) by step D) evaporate the solid mixture dissolve with ethanol obtaining, sodium bromaminate is dissolved in ethanol, and salt of wormwood, sodium carbonate are insoluble to ethanol, obtain mixing solutions;
F) by step e) mixing solutions that obtains filters, and the filtrate obtaining is sodium bromaminate ethanolic soln, and filter residue is salt of wormwood and sodium carbonate solid, and filtrate decompression distillation is got final product to obtain to sodium bromaminate solid.
2. the recovery method of bromamine acid in a kind of Vinyl-Sulfone Type dye activity brilliant blue KN-R factory effluent according to claim 1, it is characterized in that: described steps A) in add sylvite be Repone K or saltpetre, temperature of reaction is 10-30 DEG C, and churning time is 15-20min.
3. the recovery method of bromamine acid in a kind of Vinyl-Sulfone Type dye activity brilliant blue KN-R factory effluent according to claim 2, is characterized in that: described steps A) in amount and the waste water of the sylvite that adds the molar weight of bromamine acid than being (1.1-1.2): 1.
4. the recovery method of bromamine acid in a kind of Vinyl-Sulfone Type dye activity brilliant blue KN-R factory effluent according to claim 1, is characterized in that: described step B) in time of repose be 10min, centrifugal speed is 1000r/min, centrifugation time is 15min.
5. according to the recovery method of bromamine acid in a kind of Vinyl-Sulfone Type dye activity brilliant blue KN-R factory effluent described in any one in claim 1-4, it is characterized in that: described step C) in reaction conditions be 10-30 DEG C, the sodium carbonate solution mass concentration of dropping is 10-15%.
6. the recovery method of bromamine acid in a kind of Vinyl-Sulfone Type dye activity brilliant blue KN-R factory effluent according to claim 5, it is characterized in that: described step F) in underpressure distillation the ethanolic soln recycle and reuse, the salt of wormwood obtaining and the recycle and reuse of sodium carbonate solid that obtain.
7. the application that Repone K or saltpetre reclaim bromamine acid in Vinyl-Sulfone Type dye activity brilliant blue KN-R factory effluent.
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| CN101481531A (en) * | 2008-12-12 | 2009-07-15 | 天津市德凯化工有限公司 | Preparation of reactive dye KN-R |
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| US20120118833A1 (en) * | 2010-11-12 | 2012-05-17 | Korea Institute Of Science And Technology | Method and apparatus for enhanced photocatalytic oxidative decolorization of wastewater containing reactive anthraquinone dye |
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2014
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| EP0153599B1 (en) * | 1984-02-11 | 1988-03-02 | Bayer Ag | Triphenedioxazine vinylsulfonyl dyestuffs |
| DE4422160A1 (en) * | 1994-06-24 | 1996-01-04 | Hoechst Ag | C.I. Reactive Blue 19 direct synthesis in good yield and purity |
| CN1141914A (en) * | 1994-09-24 | 1997-02-05 | 山东省招远化工总厂 | Refining technology of high-purity sodium bromaminate |
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| CN101538417A (en) * | 2008-12-12 | 2009-09-23 | 天津市德凯化工有限公司 | Method for preparing acid blue 260 |
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