CN103641568B - Comprehensive treatment method for waste sulfuric acid of sulfonated products - Google Patents
Comprehensive treatment method for waste sulfuric acid of sulfonated products Download PDFInfo
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- CN103641568B CN103641568B CN201310674504.7A CN201310674504A CN103641568B CN 103641568 B CN103641568 B CN 103641568B CN 201310674504 A CN201310674504 A CN 201310674504A CN 103641568 B CN103641568 B CN 103641568B
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Abstract
The invention relates to a comprehensive treatment method for waste sulfuric acid of sulfonated products. The comprehensive treatment method comprises the following steps: adding water and caustic calcined magnesite into the waste sulfuric acid of the sulfonated products, heating till the temperature achieves 80-90 DEG C, adding magnesite powder, reacting till the pH is 4-5, further adding the caustic calcined magnesite and reacting till the pH is 6.8-7; adding formaldehyde and urea into an obtained mixture, stirring for a period of time, further adding activated carbon, stirring, performing pressure filtration, crystallizing filtrate, centrifugating and drying to obtain magnesium sulfate heptahydrate; and calcining waste slag at the temperature of 600 DEG C-1000 DEG C to damage organic matters. The comprehensive treatment method provided by the invention has the advantages of simplicity in operation, low cost and easiness in implementation of industrialization. The production process can not only solve the pollution problem of a large amount of the waste sulfuric acid of the sulfonated products, but also reduce the cost, and further becomes an ideal process for solving the waste sulfuric acid of the sulfonated products.
Description
Technical field
The present invention relates to a kind of integrated conduct method of waste sulfuric acid of sulfonated products.
Background technology
In existing dyestuff intermediate production process, sulfonated product is the dyestuff intermediate commonly used the most, sulfuric acid or oleum are in sulfonation process, being sulphonating agent, is again reaction solvent, and sulfuric acid is all generally excessive greatly, therefore, removing product also produces a large amount of Waste Sulfuric Acid outward, and containing large amount of organic, processing costs is high.Emission of serious pollution of environment is puzzlement manufacturing enterprise a great problem.In recent years, the technology such as organic solvent sulfonation or sulphur trioxide sulphur occurred, but due to solvent recuperation and consumption increasing cost, the SO 3 sulfonated restriction being also subject to reaction substrate and solvent, applies not extensive.
Waste sulfuric acid of sulfonated products contains large amount of organic, and direct production magnesium sulfate can't meet the quality requirement, and even produces secondary pollution.
Summary of the invention
The object of the invention is to overcome above-mentioned deficiency and integrated conduct method that a kind of waste sulfuric acid of sulfonated products is provided, this kind of method pollute little, cost is low.
The technical scheme that the present invention takes is:
An integrated conduct method for waste sulfuric acid of sulfonated products, comprises step as follows:
(1) in waste sulfuric acid of sulfonated products water being joined and still be heated to temperature and reach 80-90 DEG C, add magnesite stone flour, reacting to pH is 4-5, then to add magnesia unslacked reaction be 6.8-7 to pH;
(2) in step (1) gained mixture, add formaldehyde, stir for some time, then add urea, gac stirring, press filtration, filtrate crystallisation, centrifugal, dry, dry to obtain magnesium sulfate heptahydrate, waste residue destroys organism 600 DEG C of-1000 DEG C of calcinings.
The Waste Sulfuric Acid that described waste sulfuric acid of sulfonated products is production 2, amino-3,6,8 naphthalene trisulfonic acids of 4-diamino benzene sulfonic acid, sulfonation para-ester, 2-produce.
Formaldehyde described in step (2) is the formalin of mass content 37%, and its consumption is 1%-5% of waste sulfuric acid of sulfonated products quality, and amount of urea is 10%-50% of formaldehyde quality.The additional proportion of gac is the 1%-3% of Waste Sulfuric Acid quality.
Stirring described in step (2) is first stir 0.5-1.5 hour, stirs 0.2-1 hour again after adding gac.
Residue after described calcining can be used to produce silicon-calcium-magnesium fertilizer.
The invention has the beneficial effects as follows:
1. the script Waste Sulfuric Acid extremely harmful to environment is fully utilized, decrease environmental pollution.
2. after calcining, residue is used for producing silicon-calcium-magnesium fertilizer, achieves and makes full use of.
The feature of polymkeric substance can be generated with formaldehyde according to arylamine type organic, being reacted to pH with magnesite powder and Waste Sulfuric Acid is 4-5, neutralizing pH with magnesia unslacked is again 6.8-7, the organism adding formaldehyde and arylamine class forms insoluble polymer, thus after making arylamine type organic and oxymethylene polymerization, be deposited to from aqueous phase on waste residue, reach the object of organics removal.This method is simple to operate, and cost is low, is easy to realize industrialization.This production process not only solves the pollution problem of a large amount of Waste Sulfuric Acid of sulfonated product, again reduces cost, is the ideal technology solving waste sulfuric acid of sulfonated products.
Embodiment:
Further illustrate below in conjunction with embodiment.
Embodiment 1:
Add 960 part of 98% sulfuric acid in a kettle., 240 part of 105% sulfuric acid, the lower dropping 400 parts of mphenylenediamines of cooling, be no more than 80 DEG C after adding and add 2035 part of 105% sulfuric acid, 138 DEG C-142 DEG C are reacted three hours, reaction solution are put into 1200 parts of water, filter after stirring, obtain product 1125 parts, 3710 parts, Waste Sulfuric Acid mother liquor (sulfur acid 52.7%).
Aforesaid operations repeats 2 times.
Get 7000 parts, Waste Sulfuric Acid mother liquor obtained above, add 3000 parts of water, add magnesia unslacked about 500 parts, temperature reaches 80 DEG C, then adds 2000 parts of magnesite stone flours, and by the time basic bubble-free is emerged pH about 4-5, reaching pH with 400 parts of magnesia unslacked reactions is again 6.8, adds 150 part of 37% formaldehyde, stirs 1 hour, add about 60 parts of urea again, add gac about 150 parts, stir 0.5 hour, press filtration, filtrate crystallisation, centrifugal, dry, obtain magnesium sulfate heptahydrate, content 99.1%.
Embodiment 2:
Add 2500 part of 115% sulfuric acid in a kettle., 1100 part of 80% amino G salt is added under cooling, add rear direct temperature control 135-140 DEG C reaction 12 hours, be added to the water, adjust acidity of sulfuric acid about 40%, about add 4000 parts of water, cool to normal temperature, filter, obtain product 1425 parts, 6175 parts, Waste Sulfuric Acid mother liquor (sulfur acid 40.24%).
Aforesaid operations repeats 2 times.
Get 8000 parts, Waste Sulfuric Acid mother liquor obtained above and add 2000 parts of water, add magnesia unslacked about 500 parts, temperature reaches 85 DEG C, add 2000 parts of magnesite stone flours again, by the time basic bubble-free is emerged pH about 4-5, then reacts with 400 parts of magnesia unslackeds that to reach pH be 7, add 160 part of 37% formaldehyde, stir 1 hour, then add about 80 parts of urea, add gac about 150 parts, stir 0.5 hour, press filtration, filtrate crystallisation, centrifugal, dry, obtain magnesium sulfate heptahydrate, content 98.3%.
Embodiment 3
Add 2200 part of 105% sulfuric acid in a kettle., add 900 parts of para-esters under stirring, after adding, 120-125 DEG C are reacted 1 hour, add 200 part of 50% sulfuric acid, react 8 hours again, material drops to 40 DEG C, adds in frozen water, acid adjustment degree 30%, about with frozen water 4500 parts, drop to 0-5 DEG C, filter, obtain product 1538 parts, 6300 parts, Waste Sulfuric Acid mother liquor (sulfur acid 30.38%).
Aforesaid operations repeats 1 time.
Get 10000 parts, above-mentioned Waste Sulfuric Acid mother liquor, be heated to 80 DEG C, add 2400 parts of magnesite stone flours, add magnesia unslacked about 500 parts, temperature reaches 80 DEG C, then adds 2000 parts of magnesite stone flours, and by the time basic bubble-free is emerged pH about 4, reaching pH with 400 parts of magnesia unslacked reactions is again 6.8, adds 100 part of 37% formaldehyde, stirs 1 hour, add about 40 parts of urea again, add gac about 150 parts, stir 0.5 hour, press filtration, filtrate crystallisation, centrifugal, dry, obtain magnesium sulfate heptahydrate, content 98.7%.
Claims (3)
1. an integrated conduct method for waste sulfuric acid of sulfonated products, is characterized in that, comprises step as follows:
(1) waste sulfuric acid of sulfonated products is added water, magnesia unslacked is heated to temperature and reaches 80-90 DEG C, add magnesite stone flour, reacting to pH is 4-5, then to add magnesia unslacked reaction be 6.8-7 to pH; The Waste Sulfuric Acid that described waste sulfuric acid of sulfonated products is production 2, amino-3,6,8 naphthalene trisulfonic acids of 4-diamino benzene sulfonic acid, sulfonation para-ester, 2-produce;
(2) in step (1) gained mixture, formaldehyde is added, stir for some time, add urea again, gac stirs, press filtration, the additional proportion of gac is the 1%-3% of Waste Sulfuric Acid quality, filtrate crystallisation, centrifugal, dry, dry to obtain magnesium sulfate heptahydrate, waste residue destroys organism 600 DEG C of-1000 DEG C of calcinings; Described formaldehyde is the formalin of mass content 37%, and its consumption is 1%-5% of waste sulfuric acid of sulfonated products quality, and amount of urea is 10%-50% of formaldehyde quality.
2. the integrated conduct method of a kind of waste sulfuric acid of sulfonated products according to claim 1, is characterized in that, the stirring described in step (2) is first stir 0.5-1.5 hour, stirs 0.2-1 hour again after adding gac.
3. the integrated conduct method of a kind of waste sulfuric acid of sulfonated products according to claim 1, is characterized in that, the residue after described calcining can be used to produce silicon-calcium-magnesium fertilizer.
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| RU2206394C1 (en) * | 2002-08-26 | 2003-06-20 | Институт угля и углехимии СО РАН | Method of preparing nanostructured carbon material |
| CN101367533A (en) * | 2007-08-16 | 2009-02-18 | 苏州麒麟医药化学研发有限公司 | Process for preparing magnesium sulphate heptahydrate in treatment of industrial waste sulphuric acid liquid |
| CN101481098A (en) * | 2008-12-12 | 2009-07-15 | 天津市德凯化工有限公司 | Method for processing sulphonation waste acid from reactive dye production |
| CN101481097A (en) * | 2008-12-12 | 2009-07-15 | 天津市德凯化工有限公司 | Method for processing waste acid from sulphonation ester production |
| CN102320635A (en) * | 2011-06-16 | 2012-01-18 | 青岛奥盖克化工有限公司 | Comprehensive utilization method of waste sulfuric acid of sulfonated products |
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Patent Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| RU2206394C1 (en) * | 2002-08-26 | 2003-06-20 | Институт угля и углехимии СО РАН | Method of preparing nanostructured carbon material |
| CN101367533A (en) * | 2007-08-16 | 2009-02-18 | 苏州麒麟医药化学研发有限公司 | Process for preparing magnesium sulphate heptahydrate in treatment of industrial waste sulphuric acid liquid |
| CN101481098A (en) * | 2008-12-12 | 2009-07-15 | 天津市德凯化工有限公司 | Method for processing sulphonation waste acid from reactive dye production |
| CN101481097A (en) * | 2008-12-12 | 2009-07-15 | 天津市德凯化工有限公司 | Method for processing waste acid from sulphonation ester production |
| CN102320635A (en) * | 2011-06-16 | 2012-01-18 | 青岛奥盖克化工有限公司 | Comprehensive utilization method of waste sulfuric acid of sulfonated products |
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