CN103992253A - Preparation method for generating electronic-grade dimethyl sulfide by use of industrial waste gas - Google Patents
Preparation method for generating electronic-grade dimethyl sulfide by use of industrial waste gas Download PDFInfo
- Publication number
- CN103992253A CN103992253A CN201410245820.7A CN201410245820A CN103992253A CN 103992253 A CN103992253 A CN 103992253A CN 201410245820 A CN201410245820 A CN 201410245820A CN 103992253 A CN103992253 A CN 103992253A
- Authority
- CN
- China
- Prior art keywords
- gas
- sulfide
- preparation
- grade dimethyl
- thioether
- 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
Landscapes
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
Abstract
The invention discloses a preparation method for generating electronic-grade dimethyl sulfide by use of industrial waste gas, belonging to the technical field of thioether compound preparation. In the method, the sulfide with hydrogen sulfide content being less than 30% in the industrial waste gas is purified to obtain 99.5% sulfide; the purified sulfide and methanol are used as raw materials and react in the presence of an alumino silica gel catalyst to generate gas, the gas is subjected to three-step cooling to obtain mixed liquid; and the mixed liquid is separated and rectified to obtain electronic-grade dimethyl sulfide with purity being higher than 99.5%. The method disclosed by the invention is of great significance for reducing environmental pollution and the relieving current and future urban haze climate; and meanwhile, a new way in term of raw material is provided for energy conservation and consumption reduction, and the reduction of product cost and the comprehensive utilization of resources are promoted.
Description
Technical field
The invention belongs to thio-ether type compounds preparing technical field, be specifically related to a kind of preparation method who utilizes industrial gaseous waste to generate electronic-grade dimethyl thioether.
Background technology
At present, prepare electronic-grade dimethyl thioether adopt hydrogen sulfide be raw material and methyl alcohol react prepare obtain.The raw material using is pure hydrogen sulfide, preparation consumes resources and the energy of pure hydrogen sulfide, dimethyl thioether preparation cost is high, meanwhile, in the refinement of oil, the fields such as the generating of coal produce a large amount of hydrogen sulfide, because its impurity is many, can not be utilized, produce serious atmospheric pollution, for producing the basic reason of haze weather.
Patent 98114291.5 discloses the preparation method of a kind of dimethyl thioether and thiomethyl alcohol, the sulfide of employing sulfide hydrogen 30-99% and methyl alcohol are as raw material, under the katalysis of aluminum oxide or alumino silica gel, reaction generates gas, obtain miscible liquid through cooling, after rectifying separation, obtain object product.The method is owing to containing more impurity in unstripped gas, the preheating again of need to first vaporizing, preheating temperature reaches 300 DEG C, consumes energy is high, to there is the variation of matter in required thing, it is cooling that the high-temperature gas that reaction generates directly passes through the icy salt solution of-18 DEG C, not only reduce the yield of dimethyl thioether in this process, also make much impurity not be filtered, affected the purity of dimethyl thioether.Also scientific and technological research and development lifting and social progress have been affected.
Summary of the invention
The present invention is directed to the defect of prior art, propose a kind of preparation method who utilizes industrial gaseous waste to generate electronic-grade dimethyl thioether.
A kind of preparation method who utilizes industrial gaseous waste to generate electronic-grade dimethyl thioether, be less than 30% industrial gaseous waste and purify containing hydrogen sulfide molar percentage, make the molar percentage of sulfide reach 99.5%, then with methanol mixed, sulphur in described sulfide and the mol ratio of methyl alcohol are 1: (0.5-2.1), be heated to 110-120 DEG C of preheating vaporization, forming gas enters in the reactor that spherical catalyst is housed, temperature of reaction 380-400 DEG C, the residence time is 1-3.5 second, the high-temperature gas that reaction generates is successively through 25 DEG C of recirculated waters, 9-11 DEG C of water at low temperature, the cooling liquid that obtains of icy salt solution of-20 DEG C, after ether water separator, leave standstill again layering after 20-40 minute, lower floor is water, upper strata is the thick thioether immiscible material of electronic-grade dimethyl thioether, the rectifying separation of dewatering again, the cut that intercepts 3-6 DEG C is thiomethyl alcohol, the cut that intercepts 42-45 DEG C is thick thioether, rectifying obtains mole percent level and is more than or equal to 99.5% electronic-grade dimethyl thioether again.
It is described that to contain the component that hydrogen sulfide molar percentage is less than 30% industrial gaseous waste be hydrogen, dimethyl sulfide, methyl alcohol, thiomethyl alcohol, nitrogen, nitrogen peroxide, carbonic acid gas and water.
Describedly contain hydrogen sulfide molar percentage to be less than 30% industrial gaseous waste be the waste gas in refining of petroleum, tail gas after Sweet natural gas refines, coal gas is made the waste gas of methyl alcohol, the waste gas that synthetic ammonia generates, one or more after synthetic gas desulfurization reclaims in the gas of sulfur-bearing.
Described catalyzer is alumino silica gel.
Beneficial effect of the present invention: the present invention utilizes the sulphur-containing exhaust gas in industrial production, can reduce environmental pollution, alleviate current and city haze from now on, simultaneously, method preheating temperature of the present invention is low, energy efficient, adopts 3 grades of cooling steps, is improving on the productive rate basis of target product dimethyl thioether, improve again its purity, a kind of economical, efficient, the method for energy-conservation production dimethyl thioether.
Embodiment
Below in conjunction with specific embodiment, the present invention will be further described.
Embodiment 1
A kind of preparation method who utilizes industrial gaseous waste to generate electronic-grade dimethyl thioether, be less than 30% industrial gaseous waste and purify containing hydrogen sulfide molar percentage, make the molar percentage of sulfide reach 99.5%, then with methanol mixed, sulphur in described sulfide and the mol ratio of methyl alcohol are 1: 0.5, be heated to 110 DEG C of preheatings vaporization, forming gas enters in the reactor that spherical catalyst is housed, 380 DEG C of temperature of reaction, the residence time is 1～3.5 second, the high-temperature gas that reaction generates is successively through 25 DEG C of recirculated waters, 9 DEG C of water at low temperature, the cooling liquid that obtains of icy salt solution of-20 DEG C, after ether water separator, leave standstill again layering after 20 minutes, lower floor is water, upper strata is the thick thioether immiscible material of electronic-grade dimethyl thioether, the rectifying separation of dewatering again, the cut that intercepts 3-6 DEG C is thiomethyl alcohol, the cut that intercepts 42-45 DEG C is thick thioether, rectifying obtains mole percent level and is more than or equal to 99.5% electronic-grade dimethyl thioether again.
It is described that to contain the component that hydrogen sulfide molar percentage is less than 30% industrial gaseous waste be hydrogen, dimethyl sulfide, methyl alcohol, thiomethyl alcohol, nitrogen, nitrogen peroxide, carbonic acid gas and water.
Describedly contain hydrogen sulfide molar percentage to be less than 30% industrial gaseous waste be the waste gas in refining of petroleum.
In described target product, the yield of dimethyl thioether is 98.6% (% by weight), the yield of thiomethyl alcohol is 0.1% (% by weight), in target product, the content of each component is as follows: dimethyl sulphide ether content 99.7% (% by weight), thiomethyl alcohol 0.11% (% by weight), methyl alcohol 0.09% (% by weight), moisture content 0.09% (% by weight), sodium μ g/L≤50, potassium μ gL≤50, iron μ g/L≤50.
Embodiment 2
A kind of preparation method who utilizes industrial gaseous waste to generate electronic-grade dimethyl thioether, be less than 30% industrial gaseous waste and purify containing hydrogen sulfide molar percentage, make the molar percentage of sulfide reach 99.5%, then with methanol mixed, sulphur in described sulfide and the mol ratio of methyl alcohol are 1: 1, be heated to 115 DEG C of preheatings vaporization, forming gas enters in the reactor that spherical catalyst is housed, 390 DEG C of temperature of reaction, the residence time is 2 seconds, the high-temperature gas that reaction generates is successively through 25 DEG C of recirculated waters, 10 DEG C of water at low temperature, the cooling liquid that obtains of icy salt solution of-20 DEG C, after ether water separator, leave standstill again layering after 30 minutes, lower floor is water, upper strata is the thick thioether immiscible material of electronic-grade dimethyl thioether, the rectifying separation of dewatering again, the cut that intercepts 3-6 DEG C is thiomethyl alcohol, the cut that intercepts 42-45 DEG C is thick thioether, rectifying obtains mole percent level and is more than or equal to 99.5% electronic-grade dimethyl thioether again.
It is described that to contain the component that hydrogen sulfide molar percentage is less than 30% industrial gaseous waste be hydrogen, dimethyl sulfide, methyl alcohol, thiomethyl alcohol, nitrogen, nitrogen peroxide, carbonic acid gas and water.
Describedly contain hydrogen sulfide molar percentage to be less than 30% industrial gaseous waste be the tail gas after Sweet natural gas refines.In described target product, the yield of dimethyl thioether is 99.0% (% by weight), the yield of thiomethyl alcohol is 0.1% (% by weight), in target product, the content of each component is as follows: dimethyl sulphide ether content 99.8% (% by weight), thiomethyl alcohol 0.01% (% by weight), methyl alcohol 0.09% (% by weight), moisture content 0.09% (% by weight), sodium μ g/L≤50, potassium μ g/L≤50, iron μ g/L≤50.
Embodiment 3
A kind of preparation method who utilizes industrial gaseous waste to generate electronic-grade dimethyl thioether, be less than 30% industrial gaseous waste and purify containing hydrogen sulfide molar percentage, make the molar percentage of sulfide reach 99.5%, then with methanol mixed, sulphur in described sulfide and the mol ratio of methyl alcohol are 1: 2, be heated to 120 DEG C of preheatings vaporization, forming gas enters in the reactor that spherical catalyst is housed, 400 DEG C of temperature of reaction, the residence time is 3.5 seconds, the high-temperature gas that reaction generates is successively through 25 DEG C of recirculated waters, 11 DEG C of water at low temperature, the cooling liquid that obtains of icy salt solution of-20 DEG C, after ether water separator, leave standstill again layering after 40 minutes, lower floor is water, upper strata is the thick thioether immiscible material of electronic-grade dimethyl thioether, the rectifying separation of dewatering again, the cut that intercepts 3-6 DEG C is thiomethyl alcohol, the cut that intercepts 42-45 DEG C is thick thioether, rectifying obtains mole percent level and is more than or equal to 99.5% electronic-grade dimethyl thioether again.
It is described that to contain the component that hydrogen sulfide molar percentage is less than 30% industrial gaseous waste be hydrogen, dimethyl sulfide, methyl alcohol, thiomethyl alcohol, nitrogen, nitrogen peroxide, carbonic acid gas and water.
The described hydrogen sulfide molar percentage that contains is less than the gas that 30% industrial gaseous waste is sulfur-bearing after synthetic gas desulfurization reclaims.
In described target product, the yield of dimethyl thioether is 98.9% (% by weight), the yield of thiomethyl alcohol is 0.05% (% by weight), in target product, the content of each component is as follows: dimethyl sulphide ether content 99.8% (% by weight), thiomethyl alcohol 0.01% (% by weight), methyl alcohol 0.08% (% by weight), moisture content 0.09% (% by weight), sodium μ g/L≤50, potassium μ g/L≤50, iron μ g/L≤50.
Claims (4)
1. a preparation method who utilizes industrial gaseous waste to generate electronic-grade dimethyl thioether, it is characterized in that, be less than 30% industrial gaseous waste and purify containing hydrogen sulfide molar percentage, make the molar percentage of sulfide reach 99.5%, then with methanol mixed, sulphur in described sulfide and the mol ratio of methyl alcohol are 1: (0.5-2.1), be heated to 110-120 DEG C of preheating vaporization, forming gas enters in the reactor that spherical catalyst is housed, temperature of reaction 380-400 DEG C, the residence time is 1-3.5 second, the high-temperature gas that reaction generates is successively through 25 DEG C of recirculated waters, 9-11 DEG C of water at low temperature, the cooling liquid that obtains of icy salt solution of-20 DEG C, after ether water separator, leave standstill again layering after 20-40 minute, lower floor is water, upper strata is the thick thioether immiscible material of electronic-grade dimethyl thioether, the rectifying separation of dewatering again, the cut that intercepts 3-6 DEG C is thiomethyl alcohol, the cut that intercepts 42-45 DEG C is thick thioether, rectifying obtains mole percent level and is more than or equal to 99.5% electronic-grade dimethyl thioether again.
2. a kind of preparation method who utilizes industrial gaseous waste to generate electronic-grade dimethyl thioether according to claim 1, it is characterized in that, described in to contain the component that hydrogen sulfide molar percentage is less than 30% industrial gaseous waste be hydrogen, dimethyl sulfide, methyl alcohol, thiomethyl alcohol, nitrogen, nitrogen peroxide, carbonic acid gas and water.
3. a kind of preparation method who utilizes industrial gaseous waste to generate electronic-grade dimethyl thioether according to claim 1, it is characterized in that, describedly contain hydrogen sulfide molar percentage to be less than 30% industrial gaseous waste be the waste gas in refining of petroleum, tail gas after Sweet natural gas refines, coal gas is made the waste gas of methyl alcohol, the waste gas that synthetic ammonia generates, one or more after synthetic gas desulfurization reclaims in the gas of sulfur-bearing.
4. a kind of preparation method who utilizes industrial gaseous waste to generate electronic-grade dimethyl thioether according to claim 1, is characterized in that, described catalyzer is alumino silica gel.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201410245820.7A CN103992253B (en) | 2014-06-05 | 2014-06-05 | A kind of preparation method utilizing industrial gaseous waste to generate electronic-grade dimethyl thioether |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201410245820.7A CN103992253B (en) | 2014-06-05 | 2014-06-05 | A kind of preparation method utilizing industrial gaseous waste to generate electronic-grade dimethyl thioether |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN103992253A true CN103992253A (en) | 2014-08-20 |
| CN103992253B CN103992253B (en) | 2016-03-02 |
Family
ID=51306622
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN201410245820.7A Expired - Fee Related CN103992253B (en) | 2014-06-05 | 2014-06-05 | A kind of preparation method utilizing industrial gaseous waste to generate electronic-grade dimethyl thioether |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN103992253B (en) |
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN105693573A (en) * | 2016-03-11 | 2016-06-22 | 湖北兴发化工集团股份有限公司 | Method and device for producing sodium thiomethoxide from by-product obtained through synthesis of dimethyl sulfide |
Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US2910506A (en) * | 1956-11-28 | 1959-10-27 | Pure Oil Co | Process of preparing low molecular weight alkyl monosulfides |
| CN1217326A (en) * | 1998-09-03 | 1999-05-26 | 田锡义 | Process for preparing dimethyl thio-ether and methylthio-alcohol |
| CN1486786A (en) * | 2002-09-30 | 2004-04-07 | 中国石化集团齐鲁石油化工公司 | Catalyst for synthesizing dimethyl thioether and its prepn |
-
2014
- 2014-06-05 CN CN201410245820.7A patent/CN103992253B/en not_active Expired - Fee Related
Patent Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US2910506A (en) * | 1956-11-28 | 1959-10-27 | Pure Oil Co | Process of preparing low molecular weight alkyl monosulfides |
| CN1217326A (en) * | 1998-09-03 | 1999-05-26 | 田锡义 | Process for preparing dimethyl thio-ether and methylthio-alcohol |
| CN1486786A (en) * | 2002-09-30 | 2004-04-07 | 中国石化集团齐鲁石油化工公司 | Catalyst for synthesizing dimethyl thioether and its prepn |
Non-Patent Citations (1)
| Title |
|---|
| 天津市跃进化工厂: "《二甲基亚砜的制造》", 30 April 1973, article "二甲硫醚合成系统的主要设备", pages: 64-90 * |
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN105693573A (en) * | 2016-03-11 | 2016-06-22 | 湖北兴发化工集团股份有限公司 | Method and device for producing sodium thiomethoxide from by-product obtained through synthesis of dimethyl sulfide |
Also Published As
| Publication number | Publication date |
|---|---|
| CN103992253B (en) | 2016-03-02 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN104096707B (en) | Semi-dry desulphurization ash resource utilization method | |
| CN103523764B (en) | A kind of reduce the method for magnalium impurity in phosphoric acid by wet process | |
| CN103991882B (en) | The fluorine in phosphoric acid by wet process liquid phase is utilized to prepare the method for Potassium monofluoride | |
| CN105600990B (en) | Method for recycling sulfur, ammonium sulfate and catalyst by utilizing coke oven gas desulfurization and decyanation waste liquid | |
| CN103638688B (en) | A kind of recoverying and utilizing method synthesizing phosgene in n-butyl isocyanate thermo-optical reaction end gas | |
| CN103466579B (en) | The method of the complete water-soluble monoammonium phosphate of Wet-process Phosphoric Acid Production | |
| CN103420394A (en) | Method for preparing X-type molecular sieve with rice husks serving as silicon source | |
| CN204400624U (en) | A kind of production system for the preparation of high purity liquid carbonic acid gas | |
| CN104386713B (en) | A kind of method of Repone K and ammonium sulfate preparing potassium sulfate | |
| CN104087354A (en) | Process of preparing synthetic natural gas by using yellow phosphorus tail gas | |
| CN104986817A (en) | Method for treating sewage containing sulfur and ammonia during alternation working procedure of synthetic ammonia by using steam stripping method | |
| CN108439452A (en) | A kind of purifying technique of low-grade fluorite | |
| CN105413429A (en) | Method for separating and purifying lime kiln tail gas | |
| CN103992253B (en) | A kind of preparation method utilizing industrial gaseous waste to generate electronic-grade dimethyl thioether | |
| CN103553078B (en) | Technology for preparing ammonium sulfate by high-efficiency ammonia desulphurization and crystallization | |
| CN105439870B (en) | A kind of N of recovery, the method for N ' dicyclohexylurea (DCU)s recycling | |
| CN102836627B (en) | One-step process energy-saving and water-saving cleaning technology for converting smoke carbon dioxide into ardealite | |
| CN102659102B (en) | Technology and device for preparing industrial carbon monoxide with water gas | |
| CN109135818A (en) | The preparation method and production equipment of slag oil desulfurization method and petroleum coke | |
| CN115006982A (en) | Method for desulfurizing and carbon-fixing coal-fired flue gas by using carbide slag slurry | |
| CN103344471A (en) | Polysilicon pretreatment method regulating dropwise addition concentration of nitric acid | |
| CN102952589A (en) | Method for removing acid gas out of raw gas or shifted gas of raw gas | |
| CN106139823B (en) | A kind of comprehensive reutilization method of coal chemical industry transformation condensate liquid stripping tail gas | |
| CN102923720A (en) | Method for preparing nanometer white carbon black through comprehensively utilizing sodium chloride wastewater | |
| CN106219577A (en) | A kind of method utilizing smoke-gas wet desulfurization intermediate product calcium sulfite to prepare sodium sulfite |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| C06 | Publication | ||
| PB01 | Publication | ||
| C10 | Entry into substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| C14 | Grant of patent or utility model | ||
| 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: 20160302 Termination date: 20200605 |