CN108863863A - A method of producing dimethyl sulfoxide - Google Patents
A method of producing dimethyl sulfoxide Download PDFInfo
- Publication number
- CN108863863A CN108863863A CN201810635896.9A CN201810635896A CN108863863A CN 108863863 A CN108863863 A CN 108863863A CN 201810635896 A CN201810635896 A CN 201810635896A CN 108863863 A CN108863863 A CN 108863863A
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- China
- Prior art keywords
- dimethyl sulfoxide
- reaction
- hydrogen sulfide
- crude product
- methanol
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- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C315/00—Preparation of sulfones; Preparation of sulfoxides
- C07C315/02—Preparation of sulfones; Preparation of sulfoxides by formation of sulfone or sulfoxide groups by oxidation of sulfides, or by formation of sulfone groups by oxidation of sulfoxides
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C319/00—Preparation of thiols, sulfides, hydropolysulfides or polysulfides
- C07C319/14—Preparation of thiols, sulfides, hydropolysulfides or polysulfides of sulfides
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- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
Abstract
The invention discloses a kind of methods for producing dimethyl sulfoxide, include the following steps：The preparation of S1 raw material, S2 hybrid reaction, S3 preparation process, the processing and refining of S4 product, the present invention are compared with the conventional method for producing dimethyl sulfoxide, by using Titanium Sieve Molecular Sieve, so that the conversion ratio of dimethyl sulfide improves, and during the reaction, it is easy to separate its gas-liquid, the utilization rate of oxidant is effectively raised, so that improving the selectivity of dimethyl sulfoxide during preparing dimethyl sulfoxide.
Description
Technical field
The invention belongs to dimethyl sulfoxide field of production, and more specifically more particularly to a kind of production dimethyl is sub-
The method of sulfone.
Background technique
Dimethyl sulfoxide (DMSO) is a kind of organic compounds containing sulfur, is colourless transparent liquid under room temperature, have it is highly polar,
Characteristics, the dimethyl sulfoxides such as high-hygroscopicity, flammable and higher boiling be non-proton are dissolved in water, ethyl alcohol, acetone, ether and chloroform, are pole
Property strong atent solvent, solvent and reaction reagent are widely used as, for example, being used as process solvent and pumping in acrylonitrile polymerization reaction
Silk solvent, the synthetic as polyurethane and the solvent that reels off raw silk from cocoons, the conjunction as polyamide, fluoroaluminate glasses, polyimides and polysulfones
At solvent, also, dimethyl sulfoxide has very high selective extraction method ability, and it is molten to can be used as the extraction that alkane is separated with aromatic hydrocarbon
Agent, such as：Dimethyl sulfoxide can be used for the extracting of aromatic hydrocarbons or butadiene, meanwhile, in medical industry, dimethyl sulfoxide not only may be used
With the raw material and carrier directly as some drugs, and the effects of anti-inflammatory analgetic, diuresis and calmness can also be played, therefore often make
It is made an addition in drug for the active component of analgesic drug product, in addition, dimethyl sulfoxide also can be used as capacitor dielectric, antifreezing agent, brake
Oil and rare metal extracting agent etc., control of the used consersion unit for the temperature and time of reaction during preparation
It is that automatic intelligent is controlled, does not need worker and be operated manually, but during the preparation process, how to improve dimethyl
The selectivity of the conversion ratio of thioether, the effective rate of utilization of oxidant and dimethyl sulfoxide is problem to be solved.
Summary of the invention
The purpose of the present invention is to provide a kind of methods for producing dimethyl sulfoxide, to solve to propose in above-mentioned background technique
The problem of.
To achieve the above object, the present invention provides the following technical solutions：
A method of dimethyl sulfoxide is produced, is included the following steps：
The preparation of S1, raw material, hydrogen sulfide and methanol, and the mass ratio of the two is 1：1, catalyst γ-Al2O3, sulfuric acid, Asia
Sodium nitrate, oxygen, nitric oxide；
S2, hybrid reaction, by step S1 hydrogen sulfide and methanol mix, then be added catalyst γ-Al2O3Into
Obtained mixture is filtered by row hybrid reaction, obtains the mixture containing dimethyl sulfide；
Obtained crude product is carried out gas-liquid separation processing, then Titanium Sieve Molecular Sieve is placed in containing sulphur by S3, preparation process
The methanol solution for changing hydrogen, is being stirred, and then it is added from the middle part of oxidizing tower, when setting pressure is 1.5MPa,
Crude product is added from the middle part of carbonoxide, on the basis of the total amount of material in reactor, the content of catalyst is total weight
15%, the molar ratio of methanol and hydrogen sulfide is 40 in liquid phase feed：1, the molar ratio of dimethyl sulfide and hydrogen sulfide is 2：1, instead
Answering the temperature in system is 45 DEG C, is carried out continuously reaction in 150 hours, separates to its product, cooling treatment；
The processing and refining of S4, product are reacted with sulfuric acid and sodium nitrite nitrogen dioxide, resulting nitrogen dioxide is made first
Pure oxygen and nitrogen dioxide and dimethyl disulfide stand-by as oxidant after cold system, water removal, then producing pressure-swing absorption apparatus
Ether is put into oxidizing tower according to a certain percentage, is aoxidized at 40 ± 5 DEG C, and tail gas is discharged through oxidizing tower top, and tower bottom obtains DMSO
Then crude product is neutralized with 30% caustic soda with kettle in crude product, is neutralized to PH=8, is evaporated by crude product, evaporation is de-
The DMSO fine work that content is 99% or more can be obtained in salt, vacuum distillation dehydration and three tower continuous stills.
Preferably, the cooling of oxidizing tower is cooling using helix tube in step s3, external cooling with collet, general bottom
Temperature control is at 30-35 DEG C, and at 35-45 DEG C, head temperature is not more than 45 DEG C for middle portion temperature control.
Preferably, in step s 4, the acid waste water in the alkaline waste water and oxidation process in synthesis process, all uses lime
It is neutralized, is filtered when pH value reaches 6-9, and gas explosion oxidation is carried out to it, then using activated carbon adsorption to remove
Depollute object, discharges after reaching discharge standard, and DMSO reaction neutralizes the exhaust gas generated in sewage treatment, is sent to combustion furnace burning together
Fall.
Compared with prior art, the beneficial effects of the invention are as follows：The method phase of the present invention and conventional production dimethyl sulfoxide
Compare, by using Titanium Sieve Molecular Sieve, so that the conversion ratio of dimethyl sulfide improves, and during the reaction, it is easy to will
Its gas-liquid is separated, and the utilization rate of oxidant is effectively raised, so that mentioning during preparing dimethyl sulfoxide
The high selectivity of dimethyl sulfoxide.
Specific embodiment
In order to make the objectives, technical solutions, and advantages of the present invention clearer, below in conjunction with specific embodiment, to this
Invention is further elaborated.It should be appreciated that the specific embodiments described herein are merely illustrative of the present invention, not
For limiting the present invention.
A method of dimethyl sulfoxide is produced, is included the following steps：
The preparation of S1, raw material, hydrogen sulfide and methanol, and the mass ratio of the two is 1：1, catalyst γ-Al2O3, sulfuric acid, Asia
Sodium nitrate, oxygen, nitric oxide；
S2, hybrid reaction, by step S1 hydrogen sulfide and methanol mix, then be added catalyst γ-Al2O3Into
Obtained mixture is filtered by row hybrid reaction, obtains the mixture containing dimethyl sulfide；
Obtained crude product is carried out gas-liquid separation processing, then Titanium Sieve Molecular Sieve is placed in containing sulphur by S3, preparation process
The methanol solution for changing hydrogen, is being stirred, and then it is added from the middle part of oxidizing tower, when setting pressure is 1.5MPa,
Crude product is added from the middle part of carbonoxide, on the basis of the total amount of material in reactor, the content of catalyst is total weight
15%, the molar ratio of methanol and hydrogen sulfide is 40 in liquid phase feed：1, the molar ratio of dimethyl sulfide and hydrogen sulfide is 2：1, instead
Answering the temperature in system is 45 DEG C, is carried out continuously reaction in 150 hours, separates to its product, cooling treatment；
The processing and refining of S4, product are reacted with sulfuric acid and sodium nitrite nitrogen dioxide, resulting nitrogen dioxide is made first
Pure oxygen and nitrogen dioxide and dimethyl disulfide stand-by as oxidant after cold system, water removal, then producing pressure-swing absorption apparatus
Ether is put into oxidizing tower according to a certain percentage, is aoxidized at 40 ± 5 DEG C, and tail gas is discharged through oxidizing tower top, and tower bottom obtains DMSO
Then crude product is neutralized with 30% caustic soda with kettle in crude product, is neutralized to PH=8, is evaporated by crude product, evaporation is de-
The DMSO fine work that content is 99% or more can be obtained in salt, vacuum distillation dehydration and three tower continuous stills.
Specifically, the cooling of oxidizing tower is cooling using helix tube in step s3, it is external cooling with collet, general bottom
Temperature control is at 30-35 DEG C, and at 35-45 DEG C, head temperature is not more than 45 DEG C for middle portion temperature control.
Specifically, in step s 4, the acid waste water in alkaline waste water and oxidation process in synthesis process all uses lime
It is neutralized, is filtered when pH value reaches 6-9, and gas explosion oxidation is carried out to it, then using activated carbon adsorption to remove
Depollute object, discharges after reaching discharge standard, and DMSO reaction neutralizes the exhaust gas generated in sewage treatment, is sent to combustion furnace burning together
Fall.
The present invention is compared with the method and technology of conventional production dimethyl sulfoxide, by using Titanium Sieve Molecular Sieve, so that two
The conversion ratio of Dimethyl sulfide improves, and during the reaction, it is easy to separate its gas-liquid, effectively raise oxidation
The utilization rate of agent, so that improving the selectivity of dimethyl sulfoxide during preparing dimethyl sulfoxide.
The foregoing is only a preferred embodiment of the present invention, but scope of protection of the present invention is not limited thereto,
Anyone skilled in the art in the technical scope disclosed by the present invention, according to the technique and scheme of the present invention and its
Inventive concept is subject to equivalent substitution or change, should be covered by the protection scope of the present invention.
Claims (3)
1. a kind of method for producing dimethyl sulfoxide, which is characterized in that include the following steps：
The preparation of S1, raw material, hydrogen sulfide and methanol, and the mass ratio of the two is 1：1, catalyst γ-Al2O3, sulfuric acid, nitrous acid
Sodium, oxygen, nitric oxide；
S2, hybrid reaction, by step S1 hydrogen sulfide and methanol mix, then be added catalyst γ-Al2O3It is mixed
Reaction is closed, obtained mixture is filtered, the mixture containing dimethyl sulfide is obtained；
Obtained crude product is carried out gas-liquid separation processing, then Titanium Sieve Molecular Sieve is placed in containing hydrogen sulfide by S3, preparation process
Methanol solution, be stirred, then by its from the middle part of oxidizing tower be added, setting pressure be 1.5MPa when, will be thick
Product is added from the middle part of carbonoxide, and on the basis of the total amount of material in reactor, the content of catalyst is total weight 15%, liquid
The molar ratio of methanol and hydrogen sulfide is 40 in phase raw material：1, the molar ratio of dimethyl sulfide and hydrogen sulfide is 2：1, in reaction system
Temperature be 45 DEG C, be carried out continuously reaction in 150 hours, its product separated, cooling treatment；
The processing and refining of S4, product are reacted with sulfuric acid and sodium nitrite nitrogen dioxide is made first, and resulting nitrogen dioxide is through cold
It is stand-by as oxidant after system, water removal, the pure oxygen of then producing pressure-swing absorption apparatus and nitrogen dioxide and dimethyl sulfide by
Certain ratio is put into oxidizing tower, is aoxidized at 40 ± 5 DEG C, and tail gas is discharged through oxidizing tower top, and tower bottom obtains DMSO crude product,
Then it is neutralized with kettle with 30% caustic soda in crude product, is neutralized to PH=8, is evaporated by crude product, evaporative desalination subtracts
Distillation dehydration and three tower continuous stills are pressed, the DMSO fine work that content is 99% or more can be obtained.
2. a kind of method for producing dimethyl sulfoxide according to claim 1, it is characterised in that：Oxidizing tower in step s3
Cooling it is cooling using helix tube, external cooling with collet, the temperature control of general bottom is at 30-35 DEG C, middle portion temperature control
At 35-45 DEG C, head temperature is not more than 45 DEG C.
3. a kind of method for producing dimethyl sulfoxide according to claim 1, it is characterised in that：In step s 4, it synthesizes
The acid waste water in alkaline waste water and oxidation process in the process, is all neutralized with lime, is carried out when pH value reaches 6-9
Filter, and gas explosion oxidation is carried out to it, then using activated carbon adsorption to remove pollutant, discharged after reaching discharge standard,
DMSO reaction neutralizes the exhaust gas generated in sewage treatment, is sent to combustion furnace burn-up together.
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| CN201810635896.9A CN108863863A (en) | 2018-06-20 | 2018-06-20 | A method of producing dimethyl sulfoxide |
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| CN201810635896.9A CN108863863A (en) | 2018-06-20 | 2018-06-20 | A method of producing dimethyl sulfoxide |
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Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN111978217A (en) * | 2020-09-21 | 2020-11-24 | 冷冰 | Preparation method of electronic grade dimethyl sulfoxide |
Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102527300A (en) * | 2012-02-20 | 2012-07-04 | 兖矿鲁南化肥厂 | Safety production device and process for dimethyl sulfide oxidation reaction |
| CN103288691A (en) * | 2012-02-29 | 2013-09-11 | 中国石油化工股份有限公司 | Method for oxidizing dimethyl sulfide |
| CN103787931A (en) * | 2012-10-29 | 2014-05-14 | 中国石油化工股份有限公司 | Production method of dimethyl sulfoxide |
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2018
- 2018-06-20 CN CN201810635896.9A patent/CN108863863A/en active Pending
Patent Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102527300A (en) * | 2012-02-20 | 2012-07-04 | 兖矿鲁南化肥厂 | Safety production device and process for dimethyl sulfide oxidation reaction |
| CN103288691A (en) * | 2012-02-29 | 2013-09-11 | 中国石油化工股份有限公司 | Method for oxidizing dimethyl sulfide |
| CN103787931A (en) * | 2012-10-29 | 2014-05-14 | 中国石油化工股份有限公司 | Production method of dimethyl sulfoxide |
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN111978217A (en) * | 2020-09-21 | 2020-11-24 | 冷冰 | Preparation method of electronic grade dimethyl sulfoxide |
| CN111978217B (en) * | 2020-09-21 | 2022-10-21 | 冷冰 | Preparation method of electronic grade dimethyl sulfoxide |
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