CN102320635A - Comprehensive utilization method of waste sulfuric acid of sulfonated products - Google Patents
Comprehensive utilization method of waste sulfuric acid of sulfonated products Download PDFInfo
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- CN102320635A CN102320635A CN201110161609A CN201110161609A CN102320635A CN 102320635 A CN102320635 A CN 102320635A CN 201110161609 A CN201110161609 A CN 201110161609A CN 201110161609 A CN201110161609 A CN 201110161609A CN 102320635 A CN102320635 A CN 102320635A
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- acid
- sulfonated product
- comprehensive utilization
- sulfuric acid
- sulfur waste
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- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
- Y02P40/00—Technologies relating to the processing of minerals
- Y02P40/10—Production of cement, e.g. improving or optimising the production methods; Cement grinding
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- Curing Cements, Concrete, And Artificial Stone (AREA)
Abstract
The invention relates to a comprehensive utilization method of waste sulfuric acid of sulfonated products. The waste sulfuric acid of sulfonated products is heated to 80-110DEG C, magnesite powder and oxidant are added while agitating, and a mixture reacts until the pH is 6. Then, active carbon absorptive impurities are added for filtering, and filtrate is crystallized, centrifuged and dried to obtain magnesium sulfate heptahydrate. After filtering, slags are calcinated at a temperature of 600-1000DEG C to destroy organic substances. The method has the advantages that waste acid is sufficiently utilized, environment pollution is reduced, the organic substances are calcinated after the magnesium sulfate heptahydrate is produced, and secondary pollution is avoided. The method is an ideal technology for processing the waste sulfuric acid of sulfonated products.
Description
Technical field
The present invention relates to the useless vitriolic method of comprehensive utilization of a kind of sulfonated product.
Background technology
In existing dyestuff intermediate production process, sulfonated product is a dyestuff intermediate the most commonly used.Sulfuric acid or oleum are sulphonating agent in sulfonation process, are again reaction solvents, and sulfuric acid generally all is big excessive, therefore, removes outside the product, also produces a large amount of spent acid, contains large amount of organic, and processing costs is high.Emission of serious pollution of environment is a puzzlement manufacturing enterprise a great problem.In recent years, there were solvent sulfonation or technology such as SO 3 sulfonated to occur, but because solvent recuperation and consume and strengthen cost, the SO 3 sulfonated restriction that also receives reaction substrate and solvent is used not extensive.
Contain large amount of organic in the acid of sulfonated product sulfur waste, direct production sal epsom can't meet the quality requirement, even produces secondary pollution.
Summary of the invention
The objective of the invention is to overcome above-mentioned deficiency and provide a kind of sulfonated product vitriolic method of comprehensive utilization of giving up, this kind method pollute little, cost is low.
The technical scheme that the present invention takes is:
A kind of sulfonated product vitriolic method of comprehensive utilization of giving up; The acid of sulfonated product sulfur waste is heated to 80～110 ℃, under agitation adds magnesite stone flour, oxygenant, being reacted to pH is 6; Add charcoal absorption impurity then; Filter, the filtrating crystallization, centrifugal, dry MAGNESIUM SULPHATE HEPTAHYDRATE 99.5, filter the back residue and destroy organism 600～1000 ℃ of calcinings.
The sulfur waste acid that described sulfonated product sulfur waste acid produces for production 2,4-diamino benzene sulfonic acid, sulfonation para-ester, 2-amino-3,6,8-naphthalene trisulfonic acid.
Sulfuric acid in the acid of described sulfonated product sulfur waste (being that sulfuric acid rolls over hundred) is 1: 0.7～1 with wagnerite grain weight amount proportioning; The oxygenant consumption is the 1-5 ‰ of sulfuric acid quality in the acid of sulfonated product sulfur waste.
Described oxygenant is one or more in potassium permanganate, ydrogen peroxide 50, the Youxiaolin.
Residue after the described calcining is used for cement or cement brick production as cement additive.
The invention has the beneficial effects as follows:
1. made full use of sulfur waste acid, reduced environmental pollution, behind the production MAGNESIUM SULPHATE HEPTAHYDRATE 99.5, residue destroys organism through calcining, has avoided secondary pollution.
2. the residue staple after burning is calcium sulfate and silicate, can be used as cement additive, also can be used for cement brick production.This production process not only solves the pollution problem of a large amount of acid of sulfonated product, has reduced cost again, is to solve the desirable technology of the useless vitriolic of sulfonated product.
Embodiment
Embodiment 1:
In reaction kettle, add 960 part of 98% sulfuric acid, 240 part of 105% sulfuric acid, cooling drips 400 parts of mphenylenediamines down; Be no more than 80 ℃ after adding and add 2035 part of 105% sulfuric acid; 138～142 ℃ were reacted 3 hours, and reaction solution is put into 1200 parts of water, stirred after-filtration; Get 1125 parts of products, 3710 parts of sulfur waste acid mother liquors (sulfur acid 52.7%).
Aforesaid operations repeats 2 times.
Get 7000 parts of the above-mentioned sulfur waste acid mother liquors that obtains, add 3000 parts of water, be heated to 90 ℃, stirring down, 2800 parts of magnesite stone flours of adding (600 order) are reacted to about pH6; Add 8 parts of potassium permanganate, stirred 0.5 hour, add 150 parts of gacs again; Press filtration, the filtrating crystallization, centrifugal; Oven dry gets 8500 parts of MAGNESIUM SULPHATE HEPTAHYDRATE 99.5s, content 98.6%.
Embodiment 2:
2500 part of 115% sulfuric acid of adding in reaction kettle, cooling adds 1100 part of 80% amino G salt down, adds 135～140 ℃ of reactions of the direct temperature control in back 12 hours; Be added to the water, transfer acidity of sulfuric acid about 40%, add 4000 parts of water approximately; Cool to normal temperature; Filter, get 1425 parts of products, 6175 parts of sulfur waste acid mother liquors (sulfur acid 40.24%).
Aforesaid operations repeats 2 times.
Get 8000 parts of the above-mentioned sulfur waste acid mother liquors that obtains, add 2000 parts of water, subsequent operations gets 7360 parts of MAGNESIUM SULPHATE HEPTAHYDRATE 99.5s, content 98.3% with instance 1.
Embodiment 3
In reaction kettle, add 2200 part of 105% sulfuric acid, stir 900 parts of para-esters of adding down, add 120～125 ℃ of reactions in back 1 hour, add 200 part of 50% sulfuric acid; Reacted 8 hours, material drops to 40 ℃ again, adds in the frozen water; Acid adjustment degree 30% approximately with 4500 parts of frozen water, drops to 0～5 ℃; Filter, get 1538 parts of products, 6300 parts of sulfur waste acid mother liquors (sulfuric acid content 30.38%).
Aforesaid operations repeats 1 time.
Get 10000 parts in above-mentioned sulfur waste acid mother liquor mother liquor, be heated to 80 ℃, add 2400 parts of magnesite stone flours, the reaction subsequent operations gets 6950 parts of MAGNESIUM SULPHATE HEPTAHYDRATE 99.5s, content 98.7% with instance 1.
Claims (5)
1. the useless vitriolic method of comprehensive utilization of a sulfonated product is characterized in that, with sulfonated product sulfur waste acid direct heating to 80～110 ℃; Under agitation add magnesite stone flour, oxygenant; Being reacted to PH is 6, adds charcoal absorption impurity then, filters; The filtrating crystallization, centrifugal, dry MAGNESIUM SULPHATE HEPTAHYDRATE 99.5, filter the back residue and destroy organism 600～1000 ℃ of calcinings.
2. the sulfonated product according to claim 1 vitriolic method of comprehensive utilization of giving up is characterized in that the residue after the described calcining is used for cement or cement brick production as cement additive.
3. the sulfonated product according to claim 1 vitriolic method of comprehensive utilization of giving up is characterized in that, described sulfonated product sulfur waste acid is the sulfur waste acid of producing 2,4-diamino benzene sulfonic acid, sulfonation para-ester, 2-are amino-3,6, the 8-naphthalene trisulfonic acid produces.
4. the sulfonated product according to claim 1 vitriolic method of comprehensive utilization of giving up is characterized in that sulfuric acid and wagnerite grain weight amount proportioning are 1: 0.7～1 in the acid of described sulfonated product sulfur waste; The oxygenant consumption is the 1-5 ‰ of sulfuric acid quality in the acid of sulfonated product sulfur waste.
5. according to claim 1 or the useless vitriolic method of comprehensive utilization of 4 described sulfonated products, it is characterized in that described oxygenant is one or more in potassium permanganate, ydrogen peroxide 50, the Youxiaolin.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
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| CN201110161609A CN102320635A (en) | 2011-06-16 | 2011-06-16 | Comprehensive utilization method of waste sulfuric acid of sulfonated products |
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| CN201110161609A CN102320635A (en) | 2011-06-16 | 2011-06-16 | Comprehensive utilization method of waste sulfuric acid of sulfonated products |
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| CN102320635A true CN102320635A (en) | 2012-01-18 |
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| CN201110161609A Pending CN102320635A (en) | 2011-06-16 | 2011-06-16 | Comprehensive utilization method of waste sulfuric acid of sulfonated products |
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Cited By (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN103641568A (en) * | 2013-12-11 | 2014-03-19 | 青岛奥盖克化工股份有限公司 | Comprehensive treatment method for waste sulfuric acid of sulfonated products |
| CN104016385A (en) * | 2014-05-18 | 2014-09-03 | 天津理工大学 | Method for preparing magnesium sulfate and magnesium silico calcium sulfur fertilizer by utilizing alkylated waste sulfuric acid |
| CN105174234A (en) * | 2015-09-15 | 2015-12-23 | 中国科学院过程工程研究所 | Resource-oriented utilization method of waste concentrated sulfuric acids |
| CN105712907A (en) * | 2016-03-11 | 2016-06-29 | 楚源高新科技集团股份有限公司 | Cleaning sulfonation technology adopted in H acid production process |
| CN107438582A (en) * | 2015-03-31 | 2017-12-05 | 罗门哈斯公司 | Handle sulfuric acid |
| CN107572599A (en) * | 2017-09-14 | 2018-01-12 | 江苏远征化工有限公司 | A kind of method that sulfonation para-ester acid pickle prepares PAFS |
| CN109809447A (en) * | 2019-03-27 | 2019-05-28 | 宋纯 | The recovery method of Waste Sulfuric Acid |
Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1092040A (en) * | 1994-02-25 | 1994-09-14 | 黄军梁 | Method for extracting light magnesia from asbestos tailings |
| KR20010097371A (en) * | 2000-04-21 | 2001-11-08 | 우명우 | Manufacturing magnesium sulfate by waste sulfuric acid. |
| 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 |
| CN101698491A (en) * | 2009-08-17 | 2010-04-28 | 陈玉芳 | Magnesium sulfate and manufacturing method thereof |
-
2011
- 2011-06-16 CN CN201110161609A patent/CN102320635A/en active Pending
Patent Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1092040A (en) * | 1994-02-25 | 1994-09-14 | 黄军梁 | Method for extracting light magnesia from asbestos tailings |
| KR20010097371A (en) * | 2000-04-21 | 2001-11-08 | 우명우 | Manufacturing magnesium sulfate by waste sulfuric acid. |
| 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 |
| CN101698491A (en) * | 2009-08-17 | 2010-04-28 | 陈玉芳 | Magnesium sulfate and manufacturing method thereof |
Cited By (8)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN103641568A (en) * | 2013-12-11 | 2014-03-19 | 青岛奥盖克化工股份有限公司 | Comprehensive treatment method for waste sulfuric acid of sulfonated products |
| CN103641568B (en) * | 2013-12-11 | 2015-04-15 | 青岛奥盖克化工股份有限公司 | Comprehensive treatment method for waste sulfuric acid of sulfonated products |
| CN104016385A (en) * | 2014-05-18 | 2014-09-03 | 天津理工大学 | Method for preparing magnesium sulfate and magnesium silico calcium sulfur fertilizer by utilizing alkylated waste sulfuric acid |
| CN107438582A (en) * | 2015-03-31 | 2017-12-05 | 罗门哈斯公司 | Handle sulfuric acid |
| CN105174234A (en) * | 2015-09-15 | 2015-12-23 | 中国科学院过程工程研究所 | Resource-oriented utilization method of waste concentrated sulfuric acids |
| CN105712907A (en) * | 2016-03-11 | 2016-06-29 | 楚源高新科技集团股份有限公司 | Cleaning sulfonation technology adopted in H acid production process |
| CN107572599A (en) * | 2017-09-14 | 2018-01-12 | 江苏远征化工有限公司 | A kind of method that sulfonation para-ester acid pickle prepares PAFS |
| CN109809447A (en) * | 2019-03-27 | 2019-05-28 | 宋纯 | The recovery method of Waste Sulfuric Acid |
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Application publication date: 20120118 |