CN1059204C - Process for preparing dimethyl thio-ether and methylthio-alcohol - Google Patents
Process for preparing dimethyl thio-ether and methylthio-alcohol Download PDFInfo
- Publication number
- CN1059204C CN1059204C CN98114291A CN98114291A CN1059204C CN 1059204 C CN1059204 C CN 1059204C CN 98114291 A CN98114291 A CN 98114291A CN 98114291 A CN98114291 A CN 98114291A CN 1059204 C CN1059204 C CN 1059204C
- Authority
- CN
- China
- Prior art keywords
- sulfide
- methyl mercaptan
- sulfur
- dimethyl sulfide
- gas
- 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.)
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- QMMFVYPAHWMCMS-UHFFFAOYSA-N Dimethyl sulfide Chemical compound CSC QMMFVYPAHWMCMS-UHFFFAOYSA-N 0.000 title claims abstract description 125
- LSDPWZHWYPCBBB-UHFFFAOYSA-N Methanethiol Chemical compound SC LSDPWZHWYPCBBB-UHFFFAOYSA-N 0.000 title claims abstract description 81
- 238000004519 manufacturing process Methods 0.000 title description 6
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 claims abstract description 78
- RWSOTUBLDIXVET-UHFFFAOYSA-N Dihydrogen sulfide Chemical compound S RWSOTUBLDIXVET-UHFFFAOYSA-N 0.000 claims abstract description 36
- 229910000037 hydrogen sulfide Inorganic materials 0.000 claims abstract description 36
- 150000003464 sulfur compounds Chemical class 0.000 claims abstract description 26
- 239000007789 gas Substances 0.000 claims abstract description 20
- 238000006243 chemical reaction Methods 0.000 claims abstract description 16
- 238000002360 preparation method Methods 0.000 claims abstract description 13
- 238000000034 method Methods 0.000 claims abstract description 12
- 239000003054 catalyst Substances 0.000 claims abstract description 8
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 claims abstract description 7
- 239000007788 liquid Substances 0.000 claims abstract description 5
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical group [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 claims description 18
- 239000011593 sulfur Substances 0.000 claims description 18
- 229910052717 sulfur Inorganic materials 0.000 claims description 18
- VNWKTOKETHGBQD-UHFFFAOYSA-N methane Chemical compound C VNWKTOKETHGBQD-UHFFFAOYSA-N 0.000 claims description 10
- JJWKPURADFRFRB-UHFFFAOYSA-N carbonyl sulfide Chemical compound O=C=S JJWKPURADFRFRB-UHFFFAOYSA-N 0.000 claims description 8
- 239000000047 product Substances 0.000 claims description 8
- CURLTUGMZLYLDI-UHFFFAOYSA-N Carbon dioxide Chemical compound O=C=O CURLTUGMZLYLDI-UHFFFAOYSA-N 0.000 claims description 6
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 claims description 5
- 239000006227 byproduct Substances 0.000 claims description 5
- QGJOPFRUJISHPQ-NJFSPNSNSA-N carbon disulfide-14c Chemical compound S=[14C]=S QGJOPFRUJISHPQ-NJFSPNSNSA-N 0.000 claims description 5
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 5
- 229910001868 water Inorganic materials 0.000 claims description 5
- 239000000126 substance Substances 0.000 claims description 4
- 229910003158 γ-Al2O3 Inorganic materials 0.000 claims description 4
- 230000015572 biosynthetic process Effects 0.000 claims description 3
- 239000012267 brine Substances 0.000 claims description 3
- 229910002092 carbon dioxide Inorganic materials 0.000 claims description 3
- 239000001569 carbon dioxide Substances 0.000 claims description 3
- 238000011084 recovery Methods 0.000 claims description 3
- HPALAKNZSZLMCH-UHFFFAOYSA-M sodium;chloride;hydrate Chemical compound O.[Na+].[Cl-] HPALAKNZSZLMCH-UHFFFAOYSA-M 0.000 claims description 3
- 238000003786 synthesis reaction Methods 0.000 claims description 3
- 239000002912 waste gas Substances 0.000 claims description 3
- 239000003963 antioxidant agent Substances 0.000 claims description 2
- 230000003078 antioxidant effect Effects 0.000 claims description 2
- 239000003034 coal gas Substances 0.000 claims description 2
- 238000006477 desulfuration reaction Methods 0.000 claims description 2
- 230000023556 desulfurization Effects 0.000 claims description 2
- 230000014759 maintenance of location Effects 0.000 claims description 2
- 239000003345 natural gas Substances 0.000 claims description 2
- 229910052757 nitrogen Inorganic materials 0.000 claims description 2
- 239000003209 petroleum derivative Substances 0.000 claims description 2
- 239000002994 raw material Substances 0.000 abstract description 15
- 238000003912 environmental pollution Methods 0.000 abstract description 2
- 230000000192 social effect Effects 0.000 abstract description 2
- CSDREXVUYHZDNP-UHFFFAOYSA-N alumanylidynesilicon Chemical compound [Al].[Si] CSDREXVUYHZDNP-UHFFFAOYSA-N 0.000 abstract 1
- 229910052593 corundum Inorganic materials 0.000 abstract 1
- 230000000694 effects Effects 0.000 abstract 1
- 238000000926 separation method Methods 0.000 abstract 1
- 229910001845 yogo sapphire Inorganic materials 0.000 abstract 1
- QGJOPFRUJISHPQ-UHFFFAOYSA-N Carbon disulfide Chemical compound S=C=S QGJOPFRUJISHPQ-UHFFFAOYSA-N 0.000 description 3
- 239000000203 mixture Substances 0.000 description 3
- 150000003568 thioethers Chemical class 0.000 description 3
- RAHZWNYVWXNFOC-UHFFFAOYSA-N Sulphur dioxide Chemical compound O=S=O RAHZWNYVWXNFOC-UHFFFAOYSA-N 0.000 description 2
- 238000009776 industrial production Methods 0.000 description 2
- 239000000463 material Substances 0.000 description 2
- 238000007670 refining Methods 0.000 description 2
- 239000002699 waste material Substances 0.000 description 2
- 238000006555 catalytic reaction Methods 0.000 description 1
- 150000001875 compounds Chemical class 0.000 description 1
- 238000001816 cooling Methods 0.000 description 1
- 229910001873 dinitrogen Inorganic materials 0.000 description 1
- 238000002309 gasification Methods 0.000 description 1
- 238000004064 recycling Methods 0.000 description 1
- 238000007086 side reaction Methods 0.000 description 1
Landscapes
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
Abstract
The present invention discloses a preparation method for dimethyl sulfide and methyl mercaptan. In the method, a sulfur compound containing 30% to 99%(mol%) of hydrogen sulfide and methanol are used as raw materials; under the action of r-Al2O3 or an aluminum silicon gel catalyst, gases generated from a reaction is cooled to obtain mixable liquid; a purpose product is obtained after separation by rectification. The present invention provides a new path for raw materials for preparing a purpose product, and has important social effects and economic effects on reducing product cost, comprehensively utilizing resources and reducing environmental pollution.
Description
The invention relates to a preparation method of thioether and mercaptan, in particular to a preparation method of dimethyl thioether and methyl mercaptan.
It is known that dimethyl sulfide and methyl mercaptan are prepared by reacting hydrogen sulfide as a raw material with methanol. However, in the prior art, the raw material hydrogen sulfide is pure hydrogen sulfide without other components, either in industrial production or in published documents. For example: the preparation of dimethyl sulfide by Elf Aguitain, which is prepared by reacting hydrogen sulfide with a content of more than 99% with methanol, is disclosed by U.S. Pat. No. 2647151, U.S. Pat. No. 773697 and handbook on the preparation of fine organic chemical industry (94 years, version 770 of scientific and technical literature publication), and the preparation of dimethyl sulfide and methyl mercaptan is carried out by using pure hydrogen sulfide as raw material. Thus, the use of pure hydrogen sulfide as raw material for preparing dimethyl sulfide requires refining and purifying impure hydrogen sulfide, which not only increases the refining process steps, but also increases the cost, and simultaneously generates new three wastes which can pollute the environment. At present, the process method for preparing dimethyl sulfide and methyl mercaptan by using the sulfur compound of hydrogen sulfide which is not pure and contains other components as the raw material is not implemented in the industrial production, and is not reported in the published documents.
The invention aims to provide a method for preparing dimethyl sulfide and methyl mercaptan, which uses a sulfur compound containing 30-99% (mol%) hydrogen sulfide as a raw material, simplifies the production process, reduces the cost and reduces the environmental pollution.
In order to realize the purpose, the invention uses a sulfur compound containing 30-99% (mol%) hydrogen sulfide and methanol as raw materials, the sulfur and methanol in the sulfur compound are 1: 0.6-2.5(mol ratio), active alumina is used as a catalyst, the temperature is 350-.
The invention uses the sulfur compound containing 30-99% (mol%) hydrogen sulfide as raw material, the dimethyl sulfide and the methyl mercaptan are prepared by reaction with methanol, the sulfur compound containing the hydrogen sulfide of other components or the sulfur compound containing the hydrogen sulfide of other components recovered from tail gas of other products can be used as the raw material of the invention, in particular to the recycling of the sulfur-containing tail gas produced by utilizing the dimethyl sulfide, the sulfur-containing waste gas or the tail gas can be comprehensively utilized, thereby simplifying the production process, reducing the cost, reducing the pollution of the three wastes to the environment, simultaneously provides a feasible process method for producing dimethyl sulfide and methyl mercaptan by utilizing sulfur compounds containing other components of hydrogen sulfide, provides a new way for selecting raw materials for preparing the dimethyl sulfide and the methyl mercaptan, therefore, the preparation method of dimethyl sulfide and methyl mercaptan provided by the invention has positive economic and social effects.
The present invention will be described in detail with reference to examples
The invention takes sulfur compound containing other components of hydrogen sulfide and methanol to react under the catalysis of active alumina or active alumina catalyst containing other elements to generate dimethyl sulfide, and simultaneously obtains a byproduct of methyl mercaptan, wherein the chemical reaction equation is as follows:
main reaction
Side reaction
Sulfides of other components contained in the sulfur compounds of impure hydrogen sulfide,such as sulfur dioxide, mercaptan, thioether, carbonyl sulfide, etc., can take part in the reaction under the same conditions to obtain the target product. The chemical reaction equation is as follows:
as can be seen from the above chemical reaction formula, not only the hydrogen sulfide in the raw material, but also other components containing sulfur can produce the desired products dimethyl sulfide and methyl mercaptan under the same conditions.
The present invention uses 30-99% (mol%) of sulfur compound of hydrogen sulfide and methanol as raw material, and its preparation methodThe ratio (mol ratio) of sulfur to methanol in sulfur compound is 1: 0.6-2.5, and after gasification and preheating to 300 deg.C, the mixture is fed into the reactor filled with gamma-Al2O3Or in a reactor of the silica-alumina gel catalyst, the reaction temperature is 350-420 ℃, the retention time is 1.5-5 seconds, the gas generated by the reaction is cooled by ice brine at the temperature of-18 ℃ to obtain condensed liquid, the condensed liquid is stood for 10-20 minutes and then layered, the water at the lower layer is removed, the miscible substance of dimethyl sulfide and methyl mercaptan at the upper layer is distilled and separated, the distillate atthe temperature of 2.5-5.1 ℃ is intercepted to be methyl mercaptan, the distillate at the temperature of 37-39 ℃ is interceptedThe part is dimethyl sulfide.
The sulfur compound of hydrogen sulfide in 30-99 mol% is prepared with at least one of methyl sulfide, methyl mercaptan, carbon disulfide, carbonyl sulfide, methane, carbon dioxide, nitrogen and water.
The sulfur compound of 30-99% (mol%) hydrogen sulfide can be the sulfur-containing gas after desulfurization recovery of petroleum gas, natural gas, coal gas and synthetic gas.
The sulfur compounds of 30-99% (mol%) hydrogen sulfide may also be artificially formulated.
The sulfur-containing gas after the synthesis gas is desulfurized and recovered is the sulfur-containing gas recovered from the waste gas of carbon disulfide, methyl sulfide, methyl mercaptan and rubber antioxidant.
When the sulfur and methanol contained in the sulfur compound of 30-99% (mol%) of hydrogen sulfide are 1: 2.0-2.5(mol ratio), the main product is dimethyl sulfide, and the by-product is methyl mercaptan; when the mol ratio of sulfur to methanol is 1: 0.6-1.0, the main product is methyl mercaptan and the by-product is dimethyl sulfide.
Example 1:
the sulfur compound with 95 percent (mol%) of hydrogen sulfide in tail gas recovery in carbon disulfide production contains other components: 1% of carbon disulfide, 0.3% of carbonyl sulfide, 0.6% of methane and 2.3% of nitrogen gas, and the raw material ratio is that the ratio of sulfur to methanol in sulfur-containing compound is 1: 2.02(mol ratio), and after the above-mentioned materials are gasified and preheated to 300 deg.C, the above-mentioned material is fed into a furnace filled with gamma-Al2O3Maintaining the reaction temperature of 400 deg.C in the reactor of catalyst for 2.5 s, cooling the generated gas with-18 deg.C brine ice to obtain condensate, standing for 10 min, layering, and removing water in the lower layerThe upper layer is the miscible substance of dimethyl sulfide and methyl mercaptan, and then rectification is carried out, the distillate at 2.5-5.1 ℃ is intercepted as methyl mercaptan, the yield to methanol is 8 percent (weight percent), the distillate at 37-39 ℃ is intercepted as dimethyl sulfide, and the yield to methanol is 89 percent (weight percent).
Example 2:
according to example 1, the yield of methyl mercaptan was 82% and the yield of dimethyl sulfide was 14% when the ratio of sulfur to methanol was 1: 0.9(mol ratio).
Example 3:
the tail gas for producing the dimethyl sulfide is recovered and directly reacted with methanol, and the tail gas composition is as follows according to the same conditions and steps of the embodiment 1: 30% (mol%) of hydrogen sulfide, 48% (mol%) of methyl mercaptan, 13.8% (mol%) of dimethyl sulfide, 4.2% of carbon dioxide, the other 4%, 9.7% (wt%) of methyl mercaptan, and 86.4% (wt%) of dimethyl sulfide.
Example 4:
according to example 1, the reaction temperature was 380 ℃, the residence time was 3.5 seconds, the catalyst was silica-alumina gel, the yield of methyl mercaptan was 8.8%, and the yield of dimethyl sulfide was 82.4%.
Example 5:
the hydrogen sulfide with the content of 99.5 percent reacts with the methanol qualified in the industrial grade, and the mixture ratio is that the hydrogen sulfide: methanol at 1: 2.02 mol ratio, gasifying, preheating to 300 deg.C, and adding gamma-Al2O3The catalyst was reacted at 400 ℃ for a residence time of 2.5 seconds to give a yield of methylmercaptan (to methanol) of 7.5% by weight and dimethyl sulfide of 91.1% by weight.
As can be seen from the above examples, the reaction of pure hydrogen sulfide with methanol and the reaction of a sulfur compound containing 30 to 99% (mol%) of hydrogen sulfide with methanol, the yield of dimethyl sulfide to methanol obtained by the former is only 2.5 to 8.7% higher than that of the latter, but the cost of the former is 3 to 10 times higher than that of the latter, so the reaction of the recovered sulfur compound containing 30 to 90% (mol%) of hydrogen sulfide with methanol to prepare dimethyl sulfide and methyl mercaptan has great social and economic significance in reducing the product cost, comprehensively utilizing, reducing pollution and the like.
Claims (6)
1. A method for preparing dimethyl sulfide and methyl mercaptan is characterized in that; it is prepared with sulfur compound containing 30-99 mol% hydrogen sulfide and methanol in the molar ratio of 1 to 0.6-2.5, and through gasifying, preheating to 300 deg.c, adding gamma-Al2O3Or in a reactor of the silica-alumina gel catalyst, the reaction temperature is 350-420 ℃, the retention time is 1.5-5 seconds, the gas generated by the reaction is cooled by ice brine at the temperature of-18 ℃ to obtain condensed liquid, the condensed liquid is stood for 10-20 minutes and then layered, the water at the lower layer is removed, the miscible substance of dimethyl sulfide and methyl mercaptan at the upper layer is distilled and separated, the distillate at the temperature of 2.5-5.1 ℃ is intercepted as methyl mercaptan, and the distillate at the temperature of 37-39 ℃ is intercepted as dimethyl sulfide.
2. The process according to claim 1 for the preparation of dimethyl sulfide and methylmercaptan, characterized in that: the sulfur compound of hydrogen sulfide with the molar percentage of 30-99 percent is prepared from at least one of methyl sulfide, methyl mercaptan, carbon disulfide, carbonyl sulfide, methane, carbon dioxide, nitrogen and water.
3. The process according to claim 1 for the preparation of dimethyl sulfide and methyl mercaptan, characterized in that: the sulfur compound of hydrogen sulfide with the molar percentage of 30-99 percent is sulfur-containing gas after the desulfurization recovery of petroleum gas, natural gas, coal gas and synthesis gas.
4. The process according to claim 1 for the preparation of dimethyl sulfide and methyl mercaptan, characterized in that: the sulfur compound of hydrogen sulfide with the molar percentage of 30-99 percent is artificially prepared.
5. The process according to claim 1 for the preparation of dimethyl sulfide and methyl mercaptan, characterized in that: when the molar ratio of sulfur to methanol in the sulfur compound containing 30-99% of hydrogen sulfide in terms of molar percentage is 1: 2.0-2.5, the main product is dimethyl sulfide, and the by-product is methyl mercaptan; when the molar ratio of sulfur to methanol in the sulfur compound containing 30-99% of hydrogen sulfide in terms of molar percentage is 1: 0.6-1.0, the main product is methyl mercaptan, and the by-product is dimethyl sulfide.
6. The process for the preparation of dimethyl sulfide and methyl mercaptan as claimed in claim 1 or 3, wherein: the sulfur-containing gas after the synthesis gas is desulfurized and recovered is the sulfur-containing gas recovered from the waste gas of carbon disulfide, methyl sulfide, methyl mercaptan and rubber antioxidant.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN98114291A CN1059204C (en) | 1998-09-03 | 1998-09-03 | Process for preparing dimethyl thio-ether and methylthio-alcohol |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN98114291A CN1059204C (en) | 1998-09-03 | 1998-09-03 | Process for preparing dimethyl thio-ether and methylthio-alcohol |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN1217326A CN1217326A (en) | 1999-05-26 |
| CN1059204C true CN1059204C (en) | 2000-12-06 |
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Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN98114291A Expired - Lifetime CN1059204C (en) | 1998-09-03 | 1998-09-03 | Process for preparing dimethyl thio-ether and methylthio-alcohol |
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| Country | Link |
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| CN (1) | CN1059204C (en) |
Families Citing this family (9)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN100337741C (en) * | 2003-08-13 | 2007-09-19 | 中国科学院大连化学物理研究所 | Active alumina catalyst, and its preparation method and use |
| CN102659648B (en) * | 2012-04-28 | 2014-07-30 | 重庆紫光天化蛋氨酸有限责任公司 | Method and system for separating mixed liquid containing dimethyl sulfide and methyl mercaptan |
| CN103787931B (en) * | 2012-10-29 | 2016-12-21 | 中国石油化工股份有限公司 | A kind of method producing dimethyl sulfoxide |
| CN104557627B (en) * | 2013-10-29 | 2017-02-08 | 中国石油化工股份有限公司 | Method for preparing dimethyl sulfone |
| CN103992253B (en) * | 2014-06-05 | 2016-03-02 | 刘成旭 | A kind of preparation method utilizing industrial gaseous waste to generate electronic-grade dimethyl thioether |
| CN108794362B (en) * | 2017-04-28 | 2020-06-16 | 中国石油化工股份有限公司 | Method for producing dimethyl sulfoxide from hydrogen sulfide |
| CN113527159B (en) * | 2020-04-17 | 2023-03-28 | 中国石油化工股份有限公司 | Method for utilizing refinery acid gas |
| CN113149877A (en) * | 2021-04-26 | 2021-07-23 | 新疆兴发化工有限公司 | Production process of dimethyl sulfide |
| CN114591205A (en) * | 2022-03-26 | 2022-06-07 | 河南君合新材料科技有限公司 | Process for joint production of methyl mercaptan and methyl sulfide |
Citations (2)
| 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 |
| GB1417532A (en) * | 1973-11-30 | 1975-12-10 | Rhone Progil | Process for the manufacture of methyl mercaptan |
-
1998
- 1998-09-03 CN CN98114291A patent/CN1059204C/en not_active Expired - Lifetime
Patent Citations (2)
| 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 |
| GB1417532A (en) * | 1973-11-30 | 1975-12-10 | Rhone Progil | Process for the manufacture of methyl mercaptan |
Also Published As
| Publication number | Publication date |
|---|---|
| CN1217326A (en) | 1999-05-26 |
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