CN101665297B - Waste water treatment method in 1-naphthylamine-4-sodium sulfonate production process - Google Patents
Waste water treatment method in 1-naphthylamine-4-sodium sulfonate production process Download PDFInfo
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- CN101665297B CN101665297B CN2009101722930A CN200910172293A CN101665297B CN 101665297 B CN101665297 B CN 101665297B CN 2009101722930 A CN2009101722930 A CN 2009101722930A CN 200910172293 A CN200910172293 A CN 200910172293A CN 101665297 B CN101665297 B CN 101665297B
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Abstract
The invention introduces a waste water treatment method in 1-naphthylamine-4-sodium sulfonate production process, and is characterized by adding quantitative sulfuric acid in waste water, which contains 1-naphthylamine-4-sodium sulfonate, sodium carbonate and sodium sulfate and is produced by the 1-naphthylamine-4-sodium sulfonate production process, so as to convert sodium carbonate into sodium sulfate, then cooling to precipitate Na2SO4 crystalline hydrate and separate crystallization mother liquor, and continuing to use the mother liquor to neutralize the concentration of the reaction process and the proportion regulating solution. The invention solves the pollution to environment cause by the waste water produced by the 1-naphthylamine-4-sodium sulfonate production process, and basically realizes zero discharge of crystallization mother liquor; the treatment cost is low; the energy consumption is small; Na2SO4 and 1-naphthylamine-4-sodium sulfonate can be recycled; the mother liquor can continue to be used for neutralizing the regulating solution of the reaction process; and the raw material is saved.
Description
Technical field
The present invention relates to a kind of naphthalidine-4-sodium sulfonate production technology, particularly relate to a kind of naphthalidine-4-sodium sulfonate production process method of wastewater treatment.
Background technology
Naphthalidine-4-sodium sulfonate is a kind of azoic dyestuff intermediate, is used to produce N.W. Acid, also can be used as the antidote of nitrite and iodism etc.
At present, the main production method of naphthalidine-4-sodium sulfonate is to be produced by the methyl naphthylamine sulfonation method, its main production process is: methyl naphthylamine dissolving back and sulfuric acid are by vacuum suction sulfonation still, the sulfonated detailed process is, methyl naphthylamine at first generates the vitriol of methyl naphthylamine with sulfuric acid reaction, transposition generates naphthalidine-4-sulfonic acid under heating and vacuum condition then, and neutralization tank is put in water inlet; Add the alkali neutralization then and make naphthalidine-4-sodium sulfonate aqueous solution.Extract unreacted methyl naphthylamine and impurity with orthodichlorobenzene, remainder water solution enters concentrating pan, be concentrated to the proportion of processing requirement after, put into crystallizing pan, after the crystallization of crystallizing pan internal cooling, through promptly obtaining the crystalline hydrate body of canescence crystalline naphthalidine-4-sodium sulfonate behind the centrifuge dewatering.
But in the production process of naphthalidine-4-sodium sulfonate, the processing of sewage is the difficult problem of the numerous manufacturing enterprises of puzzlement always.In at present the most frequently used methyl naphthylamine sulfonation method production process, in the raffinate after the crystallization of crystallizing pan internal cooling, also residual have a large amount of naphthalidines-4-sodium sulfonate, excessive yellow soda ash and sodium sulfate.These waste liquids generally can continue to enter reaction system, the concentration that is used for regulating crystal solution, reaction solution etc., but after the recycle about three times, just can only discharge or handle as waste liquid.This waste liquid, general naphthalidine-4-sodium sulfonate content can be more than 10%, sodium sulfate about 10%, yellow soda ash about 5%.At present, what each producer generally adopted is that spraying drying, drying cylinder oven drying method etc. dispose waste liquid, but produces a large amount of mixing salt solidss; The energy consumption height, tankage mixing salt composition complexity can't be recycled, and easily causes once more and pollutes.Even waste liquid is delivered to sewage work, these waste liquids are because the salt concn height, the organic content height, and COD value is more than 10000, and colourity is more than 2000 times, and toxicity is big, also is difficult to handle, even also unusual costliness of processing cost.Therefore a lot of enterprises stealthily discharge waste water, and environment has been caused severe contamination.At present, the domestic manufacturing enterprise that how tame naphthalidine-4-sodium sulfonate is arranged, the yearly capacity of each producer is about 3000 tons, but the processing of waste water such as crystalline mother solution is not generally also had special effective measures.
Therefore, it is low to press for a kind of cost, reduce to pollute, and economic and reliable can make the method for wastewater treatment of Sustainable Development of Enterprises.
Summary of the invention
Technical problem to be solved by this invention is to propose a kind of naphthalidine-4-sodium sulfonate production process method of wastewater treatment, can recycle naphthalidine-4-sodium sulfonate product waste water thereby reach, and from waste water, reclaim naphthalidine-4-sodium sulfonate product and Na
2SO
4The purpose of crystalline hydrate.
For the purpose that realizes solving the problems of the technologies described above, the present invention has adopted following technical scheme:
A kind of naphthalidine of the present invention-4-sodium sulfonate production process method of wastewater treatment, it is characterized in that: in the naphthalidine that contains naphthalidine-4-sodium sulfonate, yellow soda ash, sodium sulfate-4-sodium sulfonate production process waste water, add quantitative sulfuric acid, yellow soda ash is converted into sodium sulfate, and cooling makes sodium sulfate become Na then
2SO
4The crystalline hydrate crystallization is separated out, and separates Na
2SO
4Crystalline hydrate and crystalline mother solution reclaim Na
2SO
4Crystalline mother solution behind the crystalline hydrate continues to serve as the concentration and the proportion regulator solution of neutralization reaction process.
A kind of naphthalidine of the present invention-4-sodium sulfonate production process method of wastewater treatment, its more specifically technical scheme can be: describedly in the naphthalidine that contains naphthalidine-4-sodium sulfonate, yellow soda ash, sodium sulfate-4-sodium sulfonate production process waste water, add quantitative sulfuric acid, its requirement is after adding sulfuric acid, the pH numerical range of gained liquid is 6.8～7.5, and best scope is 6.9～7.2.
A kind of naphthalidine of the present invention-4-sodium sulfonate production process method of wastewater treatment, its more specifically technical scheme can also be: describedly add quantitative sulfuric acid in the naphthalidine that contains naphthalidine-4-sodium sulfonate, yellow soda ash, sodium sulfate-4-sodium sulfonate production process waste water, feed rate and temperature of reaction are controlled at the CO that reaction is emitted
2Gas is comparatively even, avoids material acutely to seethe and gets final product, and can add sulfuric acid at normal temperatures, and the reaction end temp is controlled at and does not make Na
2SO
4Crystal of hydrate is separated out and is got final product, and generally is controlled at 25～50 ℃, and better scope is 30 ℃～40 ℃.
A kind of naphthalidine of the present invention-4-sodium sulfonate production process method of wastewater treatment, its more specifically technical scheme can also be: described cooling makes sodium sulfate become Na
2SO
4The Tc span of control that the crystalline hydrate crystallization is separated out is-3 ℃～22 ℃, and better scope is-1 ℃～20 ℃, and best scope is 0 ℃～15 ℃.
A kind of naphthalidine of the present invention-4-sodium sulfonate production process method of wastewater treatment, its more specifically technical scheme can also be: described separation Na
2SO
4The concrete grammar of crystalline hydrate and crystalline mother solution is a centrifugal separation.
A kind of naphthalidine of the present invention-4-sodium sulfonate production process method of wastewater treatment, its more specifically technical scheme can also be: described adding vitriolic concentration is 40%～98%.
A kind of naphthalidine of the present invention-4-sodium sulfonate production process method of wastewater treatment, its more specifically technical scheme can also be: described recovery Na
2SO
4Concentration and the concrete using method of proportion regulator solution that crystalline mother solution behind the crystalline hydrate continues to serve as the neutralization reaction process are that the reacted neutralizer of every 1000kg methyl naphthylamine adds recovery Na
2SO
4Crystalline mother solution 960～1120kg behind the crystalline hydrate; Concrete grammar is vitriol and the transposition generation naphthalidine-4-sulfonic acid that generates methyl naphthylamine in the methyl naphthylamine sulfonation reaction, after neutralization tank is put in water inlet, at first adds yellow soda ash the pH value is adjusted to 7.2～7.5, adds quantitative recovery Na then
2SO
4Crystalline mother solution behind the crystalline hydrate, water inlet is at last regulated the normal temperature density of neutralizer between 1.16～1.18.
Various content of the present invention and concentration if not otherwise specified, all are meant mass percentage content and concentration.
These technical schemes can be used in combination, thereby reach better technique effect.
Adopt the theoretical basis of technique scheme to be, by analyzing, the content of each material is in the waste liquid: naphthalidine-4-sodium sulfonate content can be more than 10%, sodium sulfate about 10%, yellow soda ash about 5%.Exist at the same time under the situation of three kinds of major ingredient, exist the more effect that interferes with each other, and these three kinds of compositions also can form crystal of hydrate and separate out, be unfavorable for further handling and utilizing, therefore, be necessary by reaction, make it be converted into two kinds of salts, be convenient to further processing.And from solubility curve, there is a tangible low solubility district in sodium sulfate at-5 ℃～22 ℃, particularly Na in-1 ℃～15 ℃ saturated solutions
2SO
4For concentration is 3%～11%, and sodium sulfate is under comparatively high temps, particularly more than 50 ℃, and Na in the saturated solution
2SO
4Concentration can be reached for more than 30%, and difference of them is very big, can separate out most Na with hydrate forms by the crystallisation by cooling method
2SO
4, and naphthalidine-4-sodium sulfonate is not separated out substantially, Na in the remaining mother liquor
2SO
4Content very low, major ingredient is useful naphthalidine-4-sodium sulfonate, can continue to serve as the concentration and the proportion regulator solution of sulfonation reaction post neutralization reaction process, thereby reaches the effect of recycle, accomplishes the zero release of crystalline mother solution.
By adopting technique scheme, the present invention has following beneficial effect:
A kind of naphthalidine of the present invention-4-sodium sulfonate production process method of wastewater treatment at first is to have solved naphthalidine-4-sodium sulfonate production process waste water pollution on the environment, has realized the crystalline mother solution water zero discharge substantially.
The second, saved highly energy-consuming processes such as spraying drying, drying cylinder oven drying method, processing cost is low, and energy consumption is little.
Three, turn waste into wealth Na
2SO
4And naphthalidine-4-sodium sulfonate obtains recycling, and reduces production costs, and saved raw material.
Four, after the processing, the concentration of the naphthalidine-4-sodium sulfonate of the crystalline mother solution that reclaims can be increased to 13%, the concentration of sodium sulfate can be reduced to about 8%, minimum can be about 4%, mother liquor water continues to serve as the concentration and the proportion regulator solution of sulfonation reaction post neutralization reaction process.
Description of drawings
Fig. 1 is naphthalidine-4-sodium sulfonate reaction principle figure.
Fig. 2 is naphthalidine-4-sodium sulfonate production process synoptic diagram.
Fig. 3 is naphthalidine of the present invention-4-sodium sulfonate production process method of wastewater treatment synoptic diagram.
Embodiment
Below in conjunction with description of drawings the specific embodiment of the present invention.Various content of the present invention if not otherwise specified, all is meant mass percentage content.
As shown in Figure 2, at naphthalidine-4-sodium sulfonate production process, methyl naphthylamine and sulfuric acid add the alkali neutralization and make naphthalidine-4-sodium sulfonate aqueous solution behind oversulfonate, extract unreacted methyl naphthylamine and impurity with orthodichlorobenzene then, can extract once more in case of necessity; The aqueous solution after the extraction is through filtering, concentrating, be concentrated to the proportion of processing requirement after, put into crystallizing pan, after the crystallization of crystallizing pan internal cooling, through promptly obtaining the crystalline hydrate body of canescence crystalline naphthalidine-4-sodium sulfonate after the dehydration.Can carry out secondary crystal in the time of necessary, be the present invention's naphthalidine to be processed-4-sodium sulfonate production process waste water through the mother liquor after the crystallization once or repeatedly.
As shown in Figure 3, naphthalidine of the present invention-4-sodium sulfonate production process method of wastewater treatment, at first in the waste liquid that contains naphthalidine-4-sodium sulfonate, yellow soda ash, sodium sulfate, add quantitative sulfuric acid, control reacted pH value and be near 7, yellow soda ash is converted into sodium sulfate, but makes sodium sulfate become Na through crystallisation by cooling then
2SO
4The crystalline hydrate crystallization is separated out, and enters running-out pit after separating out, and separates Na through whizzer then
2SO
4Crystalline hydrate crystallization and mother liquor, mother liquor enters withdrawing can, continues to serve as the concentration and the proportion regulator solution of sulfonation reaction post neutralization reaction process.
Embodiment 1
A certain still naphthalidine-4-sodium sulfonate production process waste liquid wherein contains naphthalidine-4-sodium sulfonate 10.2%, sodium sulfate 9.9%, and yellow soda ash 4.7%, proportion are 1.20, gross weight is 2880kg.Under 20 ℃ of conditions, under the whipped state,, reacted 90 minutes to wherein adding 98% sulfuric acid 127.0kg, obtain the pH value and be 6.9 reaction solution.Then reaction solution is put into the crystallisation by cooling pot and cooled, separate out a large amount of Na gradually to 13 ℃
2SO
4Crystalline hydrate, the slurries after the crystallization are put in the whizzer, separate Na
2SO
4Crystalline hydrate and crystalline mother solution.Obtain Na
2SO
4Crystalline hydrate 470kg.Can wash Na with water in case of necessity
2SO
4Crystalline hydrate 1-3 time, and continue to dry.The naphthalidine of crystalline mother solution-4-sodium sulfonate 11.7%, sodium sulfate 8.6%, proportion are 1.172.The water of crystalline mother solution and washing continues to serve as the concentration and the proportion regulator solution of sulfonation reaction post neutralization reaction process.
A certain still naphthalidine-4-sodium sulfonate production process waste liquid wherein contains naphthalidine-4-sodium sulfonate 9.9%, sodium sulfate 9.8%, and yellow soda ash 5.1%, proportion are 1.19, gross weight is 2720kg.Under 40 ℃ of conditions, under the whipped state,, reacted 90 minutes to wherein adding 98% sulfuric acid 126kg, obtain the pH value and be 7.05 reaction solution.Then reaction solution is put into the crystallisation by cooling pot and cooled, separate out a large amount of Na gradually to 10 ℃
2SO
4The crystalline hydrate crystallization, will, the slurries after the crystallization are put in the whizzer, separate Na
2SO
4Crystalline hydrate crystallization and crystalline mother solution.Obtain Na
2SO
4Crystalline hydrate crystallization 530kg.Can wash Na with water in case of necessity
2SO
4Crystalline hydrate crystallization 1-3 time, and continue to dry.The naphthalidine of crystalline mother solution-4-sodium sulfonate 11.7%, sodium sulfate 6.8%, proportion are 1.172.The water of crystalline mother solution and washing continues to serve as the concentration and the proportion regulator solution of sulfonation reaction post neutralization reaction process.
Embodiment 3
A certain still naphthalidine-4-sodium sulfonate production process waste liquid wherein contains naphthalidine-4-sodium sulfonate 10.8%, sodium sulfate 9.9%, and yellow soda ash 4.8%, proportion are 1.18, gross weight is 2780kg.Under 20 ℃ of conditions, under the whipped state,, to react 80 minutes to wherein adding 98% sulfuric acid 125.8kg, 50 ℃ of outlet temperatures obtain the reaction solution of pH value 7.4.Reaction solution is put into the crystallisation by cooling pot cool, separate out a large amount of Na gradually to 0 ℃
2SO
4Crystalline hydrate, the slurries after the crystallization are put in the whizzer, separate Na
2SO
4Crystalline hydrate and crystalline mother solution.Obtain Na
2SO crystalline hydrate 693kg.Crystalline mother solution contains naphthalidine-4-sodium sulfonate 13.7%, and sodium sulfate 3.8%, proportion are 1.168.Crystalline mother solution continues to serve as the concentration and the proportion regulator solution of sulfonation reaction post neutralization reaction process.
Embodiment 4
A certain still naphthalidine-4-sodium sulfonate production process waste liquid wherein contains naphthalidine-4-sodium sulfonate 10.1%, sodium sulfate 10.1%, and yellow soda ash 5.1%, proportion are 1.20, gross weight is 2760kg.Under 23 ℃ of conditions, under the whipped state,, to react 85 minutes to wherein adding 40% sulfuric acid 330kg, the end reaction temperature is 40 ℃, obtains the pH value and be 7.2 reaction solution.Then reaction solution is put into the crystallisation by cooling pot and cooled, separate out a large amount of Na gradually to 5 ℃
2SO
4The crystalline hydrate crystallization, the slurries after the crystallization are put in the whizzer, separate Na
2SO
4Crystalline hydrate and crystalline mother solution.Obtain Na
2SO
4Crystalline hydrate 645kg.Can wash Na with water in case of necessity
2SO
4Crystalline hydrate 1-3 time, and continue to dry.The naphthalidine of crystalline mother solution-4-sodium sulfonate 12.7%, sodium sulfate 4.6%, proportion are 1.169.The water of crystalline mother solution and washing continues to serve as the concentration and the proportion regulator solution of neutralization reaction process.
Claims (6)
1. naphthalidine-4-sodium sulfonate production process method of wastewater treatment, it is characterized in that: in the naphthalidine that contains naphthalidine-4-sodium sulfonate, yellow soda ash, sodium sulfate-4-sodium sulfonate production process waste water, add quantitative sulfuric acid, yellow soda ash is converted into sodium sulfate, and cooling makes sodium sulfate become Na then
2SO
4The crystalline hydrate crystallization is separated out, and separates Na
2SO
4Crystalline hydrate and crystalline mother solution reclaim Na
2SO
4Crystalline mother solution behind the crystalline hydrate continues to serve as the concentration and the proportion regulator solution of neutralization reaction process.
2. according to the described naphthalidine of claim 1-4-sodium sulfonate production process method of wastewater treatment, it is characterized in that: describedly add quantitative sulfuric acid in the naphthalidine that contains naphthalidine-4-sodium sulfonate, yellow soda ash, sodium sulfate-4-sodium sulfonate production process waste water, its control condition is that the pH numerical range of gained liquid is 6.8～7.5.
3. according to the described naphthalidine of claim 1-4-sodium sulfonate production process method of wastewater treatment, it is characterized in that: describedly add quantitative vitriolic reaction process in the naphthalidine that contains naphthalidine-4-sodium sulfonate, yellow soda ash, sodium sulfate-4-sodium sulfonate production process waste water, its reaction end temp is 25 ℃～50 ℃.
4. according to the described naphthalidine of claim 1-4-sodium sulfonate production process method of wastewater treatment, it is characterized in that: described cooling makes sodium sulfate become Na
2SO
4The Tc that the crystalline hydrate crystallization is separated out is-3 ℃～22 ℃.
5. according to the described naphthalidine of claim 1-4-sodium sulfonate production process method of wastewater treatment, it is characterized in that: described separation Na
2SO
4The method of crystalline hydrate and crystalline mother solution is a centrifugal separation.
6. according to the described naphthalidine of claim 1-4-sodium sulfonate production process method of wastewater treatment, it is characterized in that: described adding vitriolic concentration is 40%～98%.
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| CN102452769B (en) * | 2010-11-01 | 2013-09-25 | 中国石油化工股份有限公司 | Processing method for waste alkali liquor in ethylene unit |
| CN102616891B (en) * | 2011-12-31 | 2014-07-09 | 广东先导稀材股份有限公司 | Method for treating sewage containing sodium sulfate and sodium chloride |
| CN103524384B (en) * | 2013-10-21 | 2016-04-20 | 金能科技股份有限公司 | In a kind of sulfonate solution, inorganic salt sodium sulfate carries salt processing method |
| CN104193046A (en) * | 2014-07-11 | 2014-12-10 | 奈曼明州化工科技有限公司 | Method for recycling and reusing active turquoise blue dye production wastewater |
| CN109761405B (en) * | 2019-02-01 | 2021-11-16 | 浙江科菲科技股份有限公司 | Comprehensive recovery and zero-discharge process of sulfate carbonate binary system high-salt nickel-containing wastewater |
| CN110015796B (en) * | 2019-04-01 | 2021-07-02 | 河海大学 | Zero-discharge treatment system and process for nickel hydrometallurgy wastewater of mixed high-salt system |
| CN110642754A (en) * | 2019-10-10 | 2020-01-03 | 沁阳市季晨化工有限公司 | Preparation process of 1-naphthylamine-4-sodium sulfonate |
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