CN105712903A - Dimethyl sulfate residue treatment method - Google Patents
Dimethyl sulfate residue treatment method Download PDFInfo
- Publication number
- CN105712903A CN105712903A CN201610038001.4A CN201610038001A CN105712903A CN 105712903 A CN105712903 A CN 105712903A CN 201610038001 A CN201610038001 A CN 201610038001A CN 105712903 A CN105712903 A CN 105712903A
- Authority
- CN
- China
- Prior art keywords
- dimethyl sulfate
- processing method
- sulfate
- exchange resin
- treatment method
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Granted
Links
- VAYGXNSJCAHWJZ-UHFFFAOYSA-N dimethyl sulfate Chemical group COS(=O)(=O)OC VAYGXNSJCAHWJZ-UHFFFAOYSA-N 0.000 title claims abstract description 44
- 238000000034 method Methods 0.000 title abstract description 18
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 claims abstract description 15
- 239000012043 crude product Substances 0.000 claims abstract description 12
- NWUYHJFMYQTDRP-UHFFFAOYSA-N 1,2-bis(ethenyl)benzene;1-ethenyl-2-ethylbenzene;styrene Chemical compound C=CC1=CC=CC=C1.CCC1=CC=CC=C1C=C.C=CC1=CC=CC=C1C=C NWUYHJFMYQTDRP-UHFFFAOYSA-N 0.000 claims abstract description 11
- 239000003054 catalyst Substances 0.000 claims abstract description 8
- 239000007800 oxidant agent Substances 0.000 claims abstract description 7
- 238000004821 distillation Methods 0.000 claims abstract description 6
- 238000005886 esterification reaction Methods 0.000 claims abstract description 6
- 230000007062 hydrolysis Effects 0.000 claims abstract description 6
- 238000006460 hydrolysis reaction Methods 0.000 claims abstract description 6
- 239000003456 ion exchange resin Substances 0.000 claims abstract description 6
- 229920003303 ion-exchange polymer Polymers 0.000 claims abstract description 6
- 239000007788 liquid Substances 0.000 claims abstract description 5
- QAOWNCQODCNURD-UHFFFAOYSA-L Sulfate Chemical compound [O-]S([O-])(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-L 0.000 claims description 15
- MHAJPDPJQMAIIY-UHFFFAOYSA-N Hydrogen peroxide Chemical group OO MHAJPDPJQMAIIY-UHFFFAOYSA-N 0.000 claims description 10
- NUJOXMJBOLGQSY-UHFFFAOYSA-N manganese dioxide Chemical group O=[Mn]=O NUJOXMJBOLGQSY-UHFFFAOYSA-N 0.000 claims description 10
- 238000003672 processing method Methods 0.000 claims description 10
- 230000001590 oxidative effect Effects 0.000 claims description 7
- 235000011149 sulphuric acid Nutrition 0.000 claims description 7
- 239000001117 sulphuric acid Substances 0.000 claims description 7
- 238000006243 chemical reaction Methods 0.000 claims description 6
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 6
- 239000003729 cation exchange resin Substances 0.000 claims description 5
- 230000006837 decompression Effects 0.000 claims description 5
- 230000032050 esterification Effects 0.000 claims description 5
- OSVXSBDYLRYLIG-UHFFFAOYSA-N dioxidochlorine(.) Chemical compound O=Cl=O OSVXSBDYLRYLIG-UHFFFAOYSA-N 0.000 claims description 4
- 239000004155 Chlorine dioxide Substances 0.000 claims description 2
- 239000003957 anion exchange resin Substances 0.000 claims description 2
- 235000019398 chlorine dioxide Nutrition 0.000 claims description 2
- 239000012286 potassium permanganate Substances 0.000 claims description 2
- 239000000126 substance Substances 0.000 abstract description 2
- 239000012452 mother liquor Substances 0.000 abstract 2
- 238000006266 etherification reaction Methods 0.000 abstract 1
- 239000002440 industrial waste Substances 0.000 abstract 1
- 238000005292 vacuum distillation Methods 0.000 abstract 1
- QGZKDVFQNNGYKY-UHFFFAOYSA-N Ammonia Chemical compound N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 description 6
- 239000003513 alkali Substances 0.000 description 6
- 238000002347 injection Methods 0.000 description 4
- 239000007924 injection Substances 0.000 description 4
- 239000002912 waste gas Substances 0.000 description 4
- 229910021529 ammonia Inorganic materials 0.000 description 3
- 238000003912 environmental pollution Methods 0.000 description 3
- 239000002699 waste material Substances 0.000 description 3
- BFNBIHQBYMNNAN-UHFFFAOYSA-N ammonium sulfate Chemical compound N.N.OS(O)(=O)=O BFNBIHQBYMNNAN-UHFFFAOYSA-N 0.000 description 2
- 229910052921 ammonium sulfate Inorganic materials 0.000 description 2
- 235000011130 ammonium sulphate Nutrition 0.000 description 2
- 238000005516 engineering process Methods 0.000 description 2
- 239000012535 impurity Substances 0.000 description 2
- 230000009286 beneficial effect Effects 0.000 description 1
- 238000011109 contamination Methods 0.000 description 1
- 238000007599 discharging Methods 0.000 description 1
- 238000005008 domestic process Methods 0.000 description 1
- 230000007613 environmental effect Effects 0.000 description 1
- 150000002148 esters Chemical class 0.000 description 1
- 239000003337 fertilizer Substances 0.000 description 1
- 239000012530 fluid Substances 0.000 description 1
- 238000010438 heat treatment Methods 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- 238000006386 neutralization reaction Methods 0.000 description 1
- 239000000843 powder Substances 0.000 description 1
- 239000010802 sludge Substances 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C303/00—Preparation of esters or amides of sulfuric acids; Preparation of sulfonic acids or of their esters, halides, anhydrides or amides
- C07C303/24—Preparation of esters or amides of sulfuric acids; Preparation of sulfonic acids or of their esters, halides, anhydrides or amides of esters of sulfuric acids
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
- C01B17/00—Sulfur; Compounds thereof
- C01B17/69—Sulfur trioxide; Sulfuric acid
- C01B17/90—Separation; Purification
Landscapes
- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Inorganic Chemistry (AREA)
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
Abstract
The invention belongs to the technical field of treatment of chemical industrial waste residues and relates to a dimethyl sulfate residue treatment method. The treatment method includes: subjecting dimethyl sulfate residues to hydrolysis, etherification and esterification reactions to obtain crude products of dimethyl sulfate; subjecting the crude products of dimethyl sulfate to reduced pressure distillation to separate dimethyl sulfate out and obtain black brown sulfuric acid mother liquor; performing vacuum distillation on the sulfuric acid mother liquor to increase concentration, and mixing with an oxidizing agent to react under the action of a catalyst to obtain light yellow transparent liquid; decolorizing the light yellow transparent liquid by an ion exchange resin system to obtain colorless transparent sulfuric acid. The dimethyl sulfate residue treatment method solves the problem of insufficiency in treatment of the dimethyl sulfate residues and has advantages of low equipment investment, mild process conditions, freeness of environment pollution, safety and environment friendliness.
Description
Technical field
The present invention relates to the processing method of a kind of dimethyl sulfate residue, belong to chemical sludge processing technology field.
Background technology
Producing substantial amounts of residue in the production process of dimethyl sulfate, its main component is dimethyl sulfate, sulphuric acid and other ester impurities and black body refuse, if directly discharging, environment can be caused severe contamination.In the method for current domestic process dimethyl sulfate residue, one is to be hydrolyzed by dimethyl sulfate residue, is then neutralized process with alkali liquor again；One is to adopt ammonia to be neutralized, and obtains ammonium sulfate.The subject matter of its existence is as follows:
(1) final treatment fluid is still black waste liquid, the black impurity of residue is not disposed, and simply waste residue has been carried out secondary transferring, could not thoroughly solve waste residue problem, still cannot use and discharge；
(2) although employing is first hydrolyzed the method adding alkali neutralization afterwards and eliminates environmental pollution, but processing cost can strengthen significantly, uneconomical；
(3) method adopting ammonia treatment, adds the consumption of ammonia, using ammonium sulfate as fertilizer sell time, owing to its acidity is relatively strong, substantially cannot use.
Summary of the invention
It is an object of the invention to provide the processing method of a kind of dimethyl sulfate residue, solve dimethyl sulfate residue treatment problem not thoroughly, have that process route is succinct, non-environmental-pollution, process feature thoroughly.
The processing method of dimethyl sulfate residue of the present invention, it is through hydrolysis by dimethyl sulfate residue, etherificate, dimethyl sulfate crude product is obtained after esterification, dimethyl sulfate crude product isolates dimethyl sulfate after decompression distillation, obtain the sulfate liquor of pitchy, sulfate liquor is carried out vacuum distilling to improve concentration, then under catalyst action, it is mixed with oxidant and reacts, obtain flaxen transparency liquid, water white sulphuric acid is obtained after ion exchange resin system decolours, the waste gas produced in course of reaction enters exhaust treatment system, by adopting the method that alkali liquor injection absorbs to carry out qualified discharge.
Wherein, it is preferred that technical scheme is as follows:
The described vacuum distilling that carried out by sulfate liquor is to improve concentration to 70-90wt%.
Reaction temperature when described sulfate liquor, catalyst and oxidant mixing react is 100-170 DEG C, and the response time is 1h.
Described catalyst is manganese dioxide.
Described oxidant is hydrogen peroxide, potassium permanganate or chlorine dioxide.
Described ion exchange resin is cation exchange resin or anion exchange resin.
Beneficial effects of the present invention is as follows:
(1) content of the dimethyl sulfate that the inventive method obtains is more than 98.5%, and sulfuric acid content is 60-70%；
(2) residue reacted after black powder sulfate liquor process by taking heating concentration, coordinating catalyst to carry out oxidative decoloration and ion exchange resin system, become water white sulphuric acid, it is possible to for market sale；
(3) equipment investment is few, process condition is gentle；
(4) environmental pollution, safety and environmental protection will not be produced.
Detailed description of the invention
Below in conjunction with embodiment, the present invention is described further.
Embodiment 1
By 1000kg dimethyl sulfate residue through hydrolysis, etherificate, 210kg dimethyl sulfate crude product is obtained after esterification, dimethyl sulfate crude product isolates 200kg dimethyl sulfate after decompression distillation, obtain the sulfate liquor that concentration is 60wt%, sulfate liquor is carried out vacuum distilling to improve concentration to 80wt%, then by itself and 20kg manganese dioxide, 80kg hydrogen peroxide mixes, 1h is reacted at 150 DEG C, after cation exchange resin system is decoloured, the water white sulphuric acid of 250kg is obtained after, the waste gas produced in course of reaction enters exhaust treatment system, by adopting the method that alkali liquor injection absorbs to carry out qualified discharge.
Embodiment 2
By 1000kg dimethyl sulfate residue through hydrolysis, etherificate, 210kg dimethyl sulfate crude product is obtained after esterification, dimethyl sulfate crude product isolates 200kg dimethyl sulfate after decompression distillation, obtain the sulfate liquor that concentration is 60wt%, sulfate liquor is carried out vacuum distilling to improve concentration to 70wt%, then by itself and 20kg manganese dioxide, 90kg hydrogen peroxide mixes, 1h is reacted at 170 DEG C, after cation exchange resin system is decoloured, the water white sulphuric acid of 270kg is obtained after, the waste gas produced in course of reaction enters exhaust treatment system, by adopting the method that alkali liquor injection absorbs to carry out qualified discharge.
Embodiment 3
By 1000kg dimethyl sulfate residue through hydrolysis, etherificate, 210kg dimethyl sulfate crude product is obtained after esterification, dimethyl sulfate crude product isolates 200kg dimethyl sulfate after decompression distillation, obtain the sulfate liquor that concentration is 60wt%, sulfate liquor is carried out vacuum distilling to improve concentration to 90wt%, then by itself and 20kg manganese dioxide, 70kg hydrogen peroxide mixes, 1h is reacted at 120 DEG C, after cation exchange resin system is decoloured, the water white sulphuric acid of 250kg is obtained after, the waste gas produced in course of reaction enters exhaust treatment system, by adopting the method that alkali liquor injection absorbs to carry out qualified discharge.
Claims (6)
1. the processing method of a dimethyl sulfate residue, it is characterized in that: dimethyl sulfate residue is obtained after hydrolysis, etherificate, esterification dimethyl sulfate crude product, dimethyl sulfate crude product isolates dimethyl sulfate after decompression distillation, obtain sulfate liquor, sulfate liquor is carried out vacuum distilling to improve concentration, then under catalyst action, it is mixed with oxidant and reacts, obtain flaxen transparency liquid, after ion exchange resin system decolours, obtain water white sulphuric acid.
2. the processing method of dimethyl sulfate residue according to claim 1, it is characterised in that: sulfate liquor is carried out vacuum distilling to improve concentration to 70-90wt%.
3. the processing method of dimethyl sulfate residue according to claim 1, it is characterised in that: reaction temperature when sulfate liquor, catalyst and oxidant mixing react is 100-170 DEG C, and the response time is 1h.
4. the processing method of dimethyl sulfate residue according to claim 3, it is characterised in that: catalyst is manganese dioxide.
5. the processing method of dimethyl sulfate residue according to claim 3, it is characterised in that: oxidant is hydrogen peroxide, potassium permanganate or chlorine dioxide.
6. the processing method of dimethyl sulfate residue according to claim 1, it is characterised in that: ion exchange resin is cation exchange resin or anion exchange resin.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201610038001.4A CN105712903B (en) | 2016-01-20 | 2016-01-20 | The processing method of dimethyl suflfate residue |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201610038001.4A CN105712903B (en) | 2016-01-20 | 2016-01-20 | The processing method of dimethyl suflfate residue |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN105712903A true CN105712903A (en) | 2016-06-29 |
| CN105712903B CN105712903B (en) | 2018-06-05 |
Family
ID=56147446
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN201610038001.4A Expired - Fee Related CN105712903B (en) | 2016-01-20 | 2016-01-20 | The processing method of dimethyl suflfate residue |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN105712903B (en) |
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN109534302A (en) * | 2018-11-13 | 2019-03-29 | 乳源东阳光电化厂 | A kind of method and its application for removing dimethyl sulfate in sulfuric acid |
Citations (8)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| GB122498A (en) * | 1918-01-31 | 1919-01-30 | Walter Norman Haworth | Improvements in and relating to the Preparation of Dimethyl Sulphate. |
| US1401693A (en) * | 1918-11-19 | 1921-12-27 | Haworth Walter Norman | Preparation of dimethyl sulfate |
| CN1775718A (en) * | 2005-12-14 | 2006-05-24 | 武汉青江化工股份有限公司 | Production process for recovering methanol and sulfuric acid from dimethyl sulfate waste residue |
| CN101142171A (en) * | 2005-03-14 | 2008-03-12 | 阿克佐诺贝尔股份有限公司 | Removal of residual sulfur dioxide from dimethyl sulfate |
| CN101357753A (en) * | 2008-08-15 | 2009-02-04 | 中国蓝星（集团）总公司 | Method for depriving dimethyl sulfate from sulphuric acid solution |
| CN102249953A (en) * | 2011-05-20 | 2011-11-23 | 山东兴辉化工有限公司 | Method for converting dimethyl sulfate waste residue into dimethyl sulfate product |
| CN103570591A (en) * | 2013-11-08 | 2014-02-12 | 湖北远大富驰医药化工股份有限公司 | Method for removing residues out of dimethyl sulfate |
| CN105036090A (en) * | 2015-04-23 | 2015-11-11 | 扬州祥发资源综合利用有限公司 | High-COD waste sulfuric acid recycling treatment process technology |
-
2016
- 2016-01-20 CN CN201610038001.4A patent/CN105712903B/en not_active Expired - Fee Related
Patent Citations (8)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| GB122498A (en) * | 1918-01-31 | 1919-01-30 | Walter Norman Haworth | Improvements in and relating to the Preparation of Dimethyl Sulphate. |
| US1401693A (en) * | 1918-11-19 | 1921-12-27 | Haworth Walter Norman | Preparation of dimethyl sulfate |
| CN101142171A (en) * | 2005-03-14 | 2008-03-12 | 阿克佐诺贝尔股份有限公司 | Removal of residual sulfur dioxide from dimethyl sulfate |
| CN1775718A (en) * | 2005-12-14 | 2006-05-24 | 武汉青江化工股份有限公司 | Production process for recovering methanol and sulfuric acid from dimethyl sulfate waste residue |
| CN101357753A (en) * | 2008-08-15 | 2009-02-04 | 中国蓝星（集团）总公司 | Method for depriving dimethyl sulfate from sulphuric acid solution |
| CN102249953A (en) * | 2011-05-20 | 2011-11-23 | 山东兴辉化工有限公司 | Method for converting dimethyl sulfate waste residue into dimethyl sulfate product |
| CN103570591A (en) * | 2013-11-08 | 2014-02-12 | 湖北远大富驰医药化工股份有限公司 | Method for removing residues out of dimethyl sulfate |
| CN105036090A (en) * | 2015-04-23 | 2015-11-11 | 扬州祥发资源综合利用有限公司 | High-COD waste sulfuric acid recycling treatment process technology |
Non-Patent Citations (1)
| Title |
|---|
| 吴慰思: "硫酸二甲酯精馏残液的处理", 《硫酸工业》 * |
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN109534302A (en) * | 2018-11-13 | 2019-03-29 | 乳源东阳光电化厂 | A kind of method and its application for removing dimethyl sulfate in sulfuric acid |
Also Published As
| Publication number | Publication date |
|---|---|
| CN105712903B (en) | 2018-06-05 |
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| C06 | Publication | ||
| PB01 | Publication | ||
| C10 | Entry into substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| GR01 | Patent grant | ||
| GR01 | Patent grant | ||
| CF01 | Termination of patent right due to non-payment of annual fee | ||
| CF01 | Termination of patent right due to non-payment of annual fee |
Granted publication date: 20180605 |