CN103288691B - A kind of method of dimethyl thioether oxidation - Google Patents
A kind of method of dimethyl thioether oxidation Download PDFInfo
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Abstract
The invention discloses the method for a kind of dimethyl thioether oxidation, the method comprises, and under oxidation reaction condition, by dimethyl thioether and oxidising agent, it is characterized in that, described oxygenant is the gas containing ozone.The method without the need to adding any inhibitor or initiator, has highly selective and higher ozone effective rate of utilization in unstripped gas, and particularly in the presence of a titanium-containing catalyst, its ozone effective rate of utilization has and significantly improves.In addition, procedure provided by the invention is simple and easy to control, is beneficial to suitability for industrialized production and application, relative to traditional method, instant invention overcomes the problems such as traditional processing technology complexity, equipment corrosion and noxious emission.
Description
Technical field
The invention relates to the method for a kind of dimethyl thioether oxidation.
Background technology
Dimethyl sulfoxide (DMSO) (DMSO) is a kind of organic compounds containing sulfur, English Dimethylsulfoxide, and molecular formula is (CH
3)
2sO is colourless transparent liquid under normal temperature, the characteristic such as have high polarity, high-hygroscopicity, flammable, high boiling point is non-proton.Water-soluble, ethanol, acetone, EC, it is the inert solvent that polarity is strong, be widely used as solvent and reaction reagent, there is very high selective extraction method ability, can be used as the Extraction solvent that alkane is separated with aromatic hydrocarbon, for aromatic hydrocarbons, Butadiene Extraction, particularly in acrylonitrile polymerization reaction, make process solvent and the solvent that reels off raw silk from cocoons, make urethane synthesis and the solvent that reels off raw silk from cocoons, make the synthetic of polymeric amide, fluoroaluminate glasses, polyimide and polysulfone resin.In medicine industry, dimethyl sulfoxide (DMSO) also can directly as raw material and the carrier of some drugs, and in addition, DMSO itself has the effects such as anti-inflammatory analgetic, diuresis, calmness, and the active ingredient of Chang Zuowei analgesic drug product makes an addition in medicine.Also capacitor dielectric, frostproofer, brake solution, rare metal extracting agent etc. can be made.
Dimethyl sulfone, another name methyl sulfonyl methane, English name: Dimethylsulfone, MethylSulfonylMethane (MSM) they are white crystalline powder, are soluble in ether water, ethanol, benzene, methyl alcohol and acetone, are slightly soluble in ether.Can not make potassium permanganate variable color under normal temperature, dimethyl sulfone can be oxidized to methylsulfonic acid by strong oxidizer.The dimethyl sulfone aqueous solution is in neutral.25 DEG C of microsublimations, accelerate to 60 DEG C of rate of sublimation, thus dimethyl sulfone product drying should carry out under cryogenic vacuum.
DMSO generally adopts dimethyl sulphide oxidation style to obtain, and because oxygenant used is different with mode of oxidizing, thus has different production technique.1, methyl alcohol dithiocarbonic anhydride method methyl alcohol and dithiocarbonic anhydride are raw material, with γ-Al
2o
3make catalyzer, first synthesizing dimethyl thioether, then be oxidized to obtain dimethyl sulfoxide (DMSO) with nitrogen peroxide (or nitric acid).2, nitrogen peroxide method generates dimethyl thioether with methyl alcohol and hydrogen sulfide under gama-alumina effect; Sulfuric acid and Sodium Nitrite react and generate nitrogen peroxide; Dimethyl thioether carries out liquid phase oxidizing reaction with nitrogen peroxide at 60 ~ 80 DEG C again and generates thick dimethyl sulfoxide (DMSO), also has direct oxygen to be oxidized, the thick dimethyl sulfoxide (DMSO) of same generation, then through underpressure distillation, refines and to obtain dimethyl sulfoxide (DMSO) finished product.This method is comparatively advanced production method.3, dimethyl sulfate ester process methyl-sulfate and sodium sulphite react, obtained dimethyl thioether; Sulfuric acid and Sodium Nitrite react and generate nitrogen peroxide; Dimethyl thioether and nitrogen peroxide are oxidized and obtain thick dimethyl sulfoxide (DMSO), then through neutralizing treatment, obtain smart dimethyl sulfoxide (DMSO) after distillation.In addition, by anodised method by dimethyl sulphide production dimethyl sulfoxide (DMSO), cost is higher, is unsuitable for scale operation.Also have and make buffer medium with acetone, dimethyl sulphide and hydrogen peroxide are reacted.As " research of dimethyl sulfoxide (DMSO) preparation technology " (chemistry world, 1st phase in 2003 36 pages) in report the research adopting hydrogen peroxide to be oxygenant acetone to be the dimethyl thioether oxidation preparation dimethyl sulfoxide (DMSO) of solvent, temperature of reaction 25 ~ 35 DEG C, dimethyl sulphide: hydrogen peroxide: acetone=3: 5: 5 (volume ratios), the reaction times wants 4.5h.Reaction times is longer, and sulfoxide selectivity also cannot ensure.
At present, the product that MSM is oxidized further as dimethyl sulfoxide (DMSO) is the principal by product that dimethyl sulfoxide (DMSO) is produced.In addition, MSM can also directly be obtained through nitric acid oxidation by dimethyl sulfoxide (DMSO).By dimethyl sulfoxide (DMSO) at 140-145 DEG C with nitric acid oxidation, cool after reaction terminates, filtration, obtains the crude product of white, needle-shaped crystals.Again through underpressure distillation, collect 138-145 DEG C of (98.42kPa) cut and be finished product.
Summary of the invention
The object of this invention is to provide the method for a kind of technique dimethyl thioether oxidation simple and with low cost.
In order to overcome the problems referred to above that prior art cacodyl oxide base thioether method exists, the present inventor conducts in-depth research, find: adopt ozone to carry out cacodyl oxide base thioether as oxygenant, the defects such as the operational condition that can overcome prior art existence on the one hand requires strictly, contaminate environment, and gratifying oxygenant effective rate of utilization can be obtained, this completes the present invention.
The invention discloses the method for a kind of dimethyl thioether oxidation, the method comprises, and under oxidation reaction condition, by dimethyl thioether and oxidising agent, it is characterized in that, described oxygenant is the gas containing ozone.
The method of dimethyl thioether oxidation provided by the invention, oxygenant is made with ozone, without the need to adding any inhibitor or initiator in unstripped gas, there is high object selectivity of product and higher ozone effective rate of utilization, particularly in the presence of a titanium-containing catalyst, its ozone effective rate of utilization has and significantly improves.In addition, procedure provided by the invention is simple and easy to control, is beneficial to suitability for industrialized production and application, relative to traditional method, instant invention overcomes the problems such as traditional processing technology complexity, equipment corrosion and noxious emission.
Embodiment
The invention discloses the method for a kind of dimethyl thioether oxidation, the method comprises, and under oxidation reaction condition, by dimethyl thioether and oxidising agent, it is characterized in that, described oxygenant is the gas containing ozone.
According to method of the present invention, adopt the gas containing ozone as oxygenant.(molecular formula is O to ozone
3, have another name called three atomic oxygens, be commonly called as " good fortune oxygen, super oxygen, oxygen of living ") at normal temperatures and pressures, for being nattier blue gas.The present inventor finds in research process, and adopt the gas containing ozone to carry out cacodyl oxide base thioether as oxygenant, have higher selectivity for dimethyl sulfoxide (DMSO) and sulfone, its simple process is easy, and operational condition is gentle.Further, ozone can disintegrate be oxygen at normal temperatures, can not produce and such as use hydrogen peroxide to carry out the shortcoming such as processing to the solution containing hydrogen peroxide as the needs faced during oxygenant.Therefore, according to the inventive method environmental friendliness.
According to method of the present invention, the described gas containing ozone can be ozone, can also be the mixed gas of ozone and diluent gas.According to method of the present invention, the described gas containing ozone is preferably the mixed gas of ozone and diluent gas, can regulate easily like this, thus control speed of reaction better to the concentration of ozone.
In the present invention, when the described gas containing ozone is the mixed gas of ozone and diluent gas, in described mixed gas, the concentration of ozone can carry out appropriate selection according to concrete oxidation reaction condition.Preferably, with the cumulative volume of described mixed gas for benchmark, in described mixed gas, the content of ozone is 1 more than volume %.More preferably, with the cumulative volume of described mixed gas for benchmark, in described mixed gas, the content of ozone is 5 more than volume %.Usually, with the cumulative volume of described mixed gas for benchmark, in described mixed gas, the content of ozone can be 5-80 volume %, is preferably 5-50 volume %, is more preferably 5-20 volume %.
The present invention is not particularly limited for the kind of described diluent gas, and described diluent gas can be such as at least one in oxygen, carbonic acid gas, nitrogen, argon gas, helium, neon and air.Preferably, described diluent gas is at least one in oxygen, carbonic acid gas, helium and air.According to the present invention, ozone can be mixed with above-mentioned diluent gas, thus the described mixed gas containing ozone of preparation; Because air contains oxygen, carbonic acid gas and nitrogen, also by ozone and air mixed, thus the mixed gas of ozone described in preparation, can be contained.According to method of the present invention, when adopting the on-the-spot generation ozone of ozonizer, oxygen can be adopted as the source of oxygen of described ozonizer, air also can be adopted to provide oxygen to described ozonizer.The smelly oxygen purity adopting oxygen to obtain as the source of oxygen of described ozonizer is higher, can obtain higher dimethyl thioether transformation efficiency and dimethyl sulfoxide (DMSO) and sulfone selectivity; Adopt air as the source of oxygen of described ozonizer, then can reduce running cost further.
According to method of the present invention, at the mixed gas that described oxygenant is ozone and diluent gas, and described diluent gas is when being two or more, the present invention is not particularly limited for the content of each diluent gas, as long as final contains in the gas of ozone, dimethyl thioether can be oxidized by the content of ozone, such as: the content of described ozone can be ozone content mentioned above.
One according to the present invention preferred embodiment in, the described gas containing ozone is the mixed gas of ozone or ozone and diluent gas, and with the cumulative volume of described mixed gas for benchmark, in described mixed gas, the content of ozone is 1 more than volume %, and described diluent gas is at least one in oxygen, carbonic acid gas, nitrogen, argon gas, helium, neon and air.One according to the present invention more preferred embodiment in, with the cumulative volume of described mixed gas for benchmark, in described mixed gas, the content of ozone is 5 more than volume %, and described diluent gas is at least one in oxygen, carbonic acid gas, helium and air.
Method according to the present invention is by adopting the gas containing ozone to realize preparing dimethyl sulfoxide (DMSO) and dimethyl sulfone with the operational condition of gentleness and higher selectivity as oxygenant, also can not produce the object of serious corrosion to equipment simultaneously.The present invention without particular requirement, can carry out appropriate selection according to concrete application scenario for the mol ratio of the ozone in dimethyl thioether and oxygenant.Under the condition of the transformation efficiency and object selectivity of product of guaranteeing dimethyl thioether, from the consumption reducing ozone further, and then reduction is set out according to the angle of the cost of method of the present invention further, the mol ratio of the ozone in described dimethyl thioether and oxygenant is preferably 1: 0.1-10, be more preferably 1: 0.1-5, more preferably 1: 0.5-5.
According to method of the present invention, the ratio of dimethyl sulfoxide (DMSO) and dimethyl sulfone in product can also be regulated and controled by controlling reaction conditions, as can by improve the ozone in dimethyl thioether and oxygenant mol ratio, improve temperature of reaction and reduce the selectivity that the measures such as quantity of solvent improve dimethyl sulfoxide (DMSO) in product, be i.e. the ratio of dimethyl sulfoxide (DMSO) and dimethyl sulfone in raising product.
According to method of the present invention, the contact of dimethyl thioether and oxygenant is preferably carried out in the presence of a titanium-containing catalyst.The present inventor finds in research process, when carrying out under existence at titanium-containing catalyst of the contact of dimethyl thioether and oxygenant, the transformation efficiency of the dimethyl thioether of the inventive method can be improved, particularly can increase substantially the selectivity of dimethyl sulfoxide (DMSO) in the effective rate of utilization of ozone and product.
According to method of the present invention, the consumption of described titanium-containing catalyst can carry out appropriate selection according to concrete application scenario.Preferably, in titanium dioxide, the mol ratio of described titanium-containing catalyst and dimethyl thioether is 1: 0.1-100.More preferably, in titanium dioxide, the mol ratio of described titanium-containing catalyst and dimethyl thioether is 1: 1-50.
According to method of the present invention, described titanium-containing catalyst can be various forms of titanium-containing catalyst.Preferably, described titanium-containing catalyst is at least one in molecular sieve containing titanium, the preformed catalyst of molecular sieve containing titanium, amorphous silicon titanium and titanium dioxide.More preferably, described titanium-containing catalyst is at least one in the HTS (as TS-1) of MFI structure, the HTS (as TS-2) of MEL structure, the HTS (as Ti-Beta) of BEA structure, the HTS (as Ti-MCM-22) of MWW structure, the HTS (as Ti-MCM-41, Ti-SBA-15) of hexagonal structure, the HTS (as Ti-MOR) of MOR structure, the HTS (as Ti-TUN) of TUN structure, the HTS (as Ti-ZSM-48) of other structures and titanium dioxide.More preferably, described titanium-containing catalyst is the HTS (as TS-1) of MFI structure.Above-mentioned molecular sieve can be commercially available, or adopts method well known in the art to synthesize, and repeats no more herein.
According to method of the present invention, described titanium-containing catalyst most preferably is the HTS of the MFI structure of hollow structure crystal grain, and the radical length of the chamber portion of this hollow structure is 5-300 nanometer, and described HTS is at 25 DEG C, P/P
0=0.10, adsorption time is that the benzene adsorptive capacity recorded under the condition of 1 hour is at least 70 milligrams/grams, there is hysteresis loop between the adsorption isothermal line of the nitrogen absorption under low temperature of this HTS and desorption isotherm.Hereinafter, the HTS of the type is called hollow HTS.
According to method of the present invention, the contact of dimethyl thioether and oxygenant is preferably carried out in the presence of solvent, the contact of dimethyl thioether and oxygenant can be made so more even, thus better control speed of response.The present invention is not particularly limited for the kind of described solvent, all kinds of SOLVENTS that described solvent can be commonly used for this area.Preferably, described solvent is water, C
1-C
10alcohol, C
3-C
10ketone, C
2-C
8nitrile and C
1-C
6carboxylic acid at least one.Such as, described solvent can be at least one in water, methyl alcohol, ethanol, n-propyl alcohol, Virahol, the trimethyl carbinol, isopropylcarbinol, acetone, butanone, acetonitrile and acetic acid.The present inventor finds unexpectedly in research process, is water, C at described solvent
1-C
4alcohol and/or C
3-C
8ketone time, the transformation efficiency of dimethyl thioether and the selectivity of dimethyl sulfoxide (DMSO) can be improved further.Further preferably, described solvent is preferably methyl alcohol, acetone, water or their mixing.
According to method of the present invention, the amount of described solvent can be the routine selection of this area.From the angle of cost reducing further method of the present invention, the mol ratio of described dimethyl thioether and solvent is preferably 1: 1-150, is more preferably 1: 1-100, and more preferably 1: 1-50.
According to method of the present invention, for described oxidation reaction condition without particular requirement, it can be conventional oxidation reaction condition.Under preferable case, described oxidation reaction condition comprises: temperature can be 0-180 DEG C, is preferably 20-160 DEG C, more preferably 20-120 DEG C; Pressure can be 0.1-3MPa, is preferably 0.1-2.5MPa, more preferably 0.1-2MPa.According to method of the present invention, the duration of contact of dimethyl thioether and oxygenant can carry out appropriate selection.Usually, the time of described contact can be 0.1-10 hour, is preferably 1-5 hour.It should be noted that, when at said temperatures, when can produce required pressure, described pressure can be autogenous pressure, when at said temperatures, when the pressure that described temperature produces does not reach required pressure, described pressure can apply pressure to realize by the external world, this is technology well known in the art, no longer describes in detail herein.
According to method of the present invention, ordinary method can be adopted dimethyl sulfone and dimethyl sulfoxide (DMSO) to be separated from the product of contact of dimethyl thioether and oxygenant.Such as: by described product of contact is carried out fractionation, thus dimethyl sulfoxide (DMSO) and dimethyl sulfone can be isolated.The method of described fractionation and condition are known in the field, repeat no more herein.
According to method of the present invention, can adopt periodical operation, also can adopt operate continuously etc., feed way also can be any suitable mode well known by persons skilled in the art, and the present invention, does not repeat at this all without particular requirement one by one to this.During operate continuously, in the presence of a titanium-containing catalyst, be 10-10000h in ozone air speed
-1react under condition, ozone air speed is preferably 10-5000h
-1.
The invention will be further described for following embodiment, but therefore do not limit content of the present invention.
In embodiment, if not otherwise specified, used reagent is commercially available analytical reagent, and used reactor is universal 250mL stainless steel autoclave formula reactor.
In embodiment, ozone used provides for the NLO-15 type ozonizer produced by Fujian New Continent Environmental Protection Technology Co., Ltd, and ozone concn is adjustable, and maximum volume concentration can reach 80%.In following examples if not otherwise specified, source of oxygen is all used to prepare ozone.
In embodiment, HTS (TS-1) catalyzer used is the TS-1 sieve sample prepared by the method described in document [Zeolites, 1992, Vol.12 943-950 page], and titanium oxide content is 2.4 % by weight.
In embodiment, (Hunan Jianchang Petrochemical Co., Ltd manufactures the Industrial products of HTS described in hollow HTS HTS system CN1301599A used, be the HTS of MFI structure through X-ray diffraction analysis, there is hysteresis loop between the adsorption isothermal line of the nitrogen absorption under low temperature of this molecular sieve and desorption isotherm, crystal grain is hollow crystal grain and the radical length of chamber portion is 15-180 nanometer; This sieve sample at 25 DEG C, P/P
0=0.10, the benzene adsorptive capacity recorded under the adsorption time condition of 1 hour is 78 milligrams/gram), titanium oxide content is 2.5 % by weight.
In the present invention, adopt gas-chromatography to carry out the analysis of each composition in system, being undertaken quantitatively, all can refer to prior art and carrying out by correcting normalization method, calculating the evaluation index such as the transformation efficiency of reactant and the selectivity of product on this basis.
In an embodiment:
Embodiment 1
Under temperature is 60 DEG C and pressure is 0.5MPa, is oxygenant with ozone (15% volume ratio, all the other are oxygen), dimethyl thioether, ozone and solvent acetone are reacted according under the mol ratio of 1: 1: 1.The result of reacting 2 hours is as follows: dimethyl thioether transformation efficiency is 44%; Ozone effective rate of utilization is 58%; Dimethyl sulfoxide (DMSO) selectivity is 88%; Dimethyl sulfone selectivity is 11%.
Embodiment 2
Under temperature is 20 DEG C and pressure is 1.5MPa, is oxygenant with ozone (30% volume ratio, all the other are air), dimethyl thioether, ozone and solvent acetic acid are reacted according under the mol ratio of 1: 1: 5.The result of reacting 5 hours is as follows: dimethyl thioether transformation efficiency is 53%; Ozone effective rate of utilization is 61%; Dimethyl sulfoxide (DMSO) selectivity is 73%; Dimethyl sulfone selectivity is 25%.
Embodiment 3
Under temperature is 80 DEG C and pressure is 0.2MPa, is oxygenant with ozone (5% volume ratio, all the other are oxygen), dimethyl thioether, ozone and solvent methanol are reacted according under the mol ratio of 1: 2: 10.The result of reacting 2 hours is as follows: dimethyl thioether transformation efficiency is 57%; Ozone effective rate of utilization is 48%; Dimethyl sulfoxide (DMSO) selectivity is 78%; Dimethyl sulfone selectivity is 21%.
Embodiment 4
Under temperature is 40 DEG C and pressure is 0.1MPa, is oxygenant with ozone (15% volume ratio, all the other are oxygen), dimethyl thioether, ozone and solvent acetone are reacted according under the mol ratio of 1: 0.6: 50.The result of reacting 1 hour is as follows: dimethyl thioether transformation efficiency is 31%; Ozone effective rate of utilization is 64%; Dimethyl sulfoxide (DMSO) selectivity is 82%; Dimethyl sulfone selectivity is 17%.
Embodiment 5
The present embodiment illustrates reaction process in the presence of a catalyst and result.
Take TS-1 as catalyzer, the molar ratio of catalyzer and dimethyl thioether is 1: 100, and ozone volume space velocity is 20h
-1, other reaction conditions is with embodiment 4.The result of reacting 1 hour is as follows: dimethyl thioether transformation efficiency is 45%; Ozone effective rate of utilization is 81%; Dimethyl sulfoxide (DMSO) selectivity is 89%; Dimethyl sulfone selectivity is 11%.
Embodiment 6
The present embodiment illustrates reaction process in the presence of a catalyst and result.
React according to the reaction conditions of embodiment 5, unlike substituting TS-1 with HTS for catalyzer.The result of reacting 1 hour is as follows: dimethyl thioether transformation efficiency is 48%; Ozone effective rate of utilization is 86%; Dimethyl sulfoxide (DMSO) selectivity is 91%; Dimethyl sulfone selectivity is 9%.
Embodiment 7
The present embodiment illustrates reaction process in the presence of a catalyst and result.
Reacting according to the reaction conditions of embodiment 6, is 60 DEG C unlike temperature of reaction.The result of reacting 1 hour is as follows: dimethyl thioether transformation efficiency is 52%; Ozone effective rate of utilization is 84%; Dimethyl sulfoxide (DMSO) selectivity is 95%; Dimethyl sulfone selectivity is 5%.
Embodiment 8
React according to the reaction conditions of embodiment 4, change 1: 2: 50 into unlike by the mol ratio of dimethyl thioether, ozone and solvent acetone.The result of reacting 1 hour is as follows: dimethyl thioether transformation efficiency is 94%; Ozone effective rate of utilization is 82%; Dimethyl sulfoxide (DMSO) selectivity is 68%; Dimethyl sulfone selectivity is 31%.
Embodiment 9
React according to the reaction conditions of embodiment 8, change 1: 2: 10 into unlike by the mol ratio of dimethyl thioether, ozone and solvent acetone.The result of reacting 1 hour is as follows: dimethyl thioether transformation efficiency is 96%; Ozone effective rate of utilization is 85%; Dimethyl sulfoxide (DMSO) selectivity is 76%; Dimethyl sulfone selectivity is 23%.
Embodiment 10
React according to the reaction conditions of embodiment 4, change acetonitrile into unlike by solvent.The result of reacting 1 hour is as follows: dimethyl thioether transformation efficiency is 25%; Ozone effective rate of utilization is 61%; Dimethyl sulfoxide (DMSO) selectivity is 80%; Dimethyl sulfone selectivity is 20%.
Embodiment 11
Under temperature is 50 DEG C and pressure is 1.0MPa, is oxygenant with ozone (20% volume ratio, all the other are air), dimethyl thioether, ozone and aqueous solvent are reacted according under the mol ratio of 1: 0.3: 3.The result of reacting 4 hours is as follows: dimethyl thioether transformation efficiency is 21%; Ozone effective rate of utilization is 73%; Dimethyl sulfoxide (DMSO) selectivity is 75%; Dimethyl sulfone selectivity is 24%.
Embodiment 12
Under temperature is 100 DEG C and pressure is 1.0MPa, is oxygenant with ozone (10% volume ratio, all the other are the carbon dioxide and oxygen of volume ratio 7: 10), dimethyl thioether, ozone and solvent acetone are reacted according under the mol ratio of 1: 0.7: 25.The result of reacting 3 hours is as follows: dimethyl thioether transformation efficiency is 46%; Ozone effective rate of utilization is 60%; Dimethyl sulfoxide (DMSO) selectivity is 75%; Dimethyl sulfone selectivity is 24%.
Embodiment 13
The present embodiment illustrates reaction process in the presence of a catalyst and result.
With TiO
2for catalyzer (commercially available, Detitanium-ore-type), the molar ratio of catalyzer and dimethyl thioether is 1: 20, is 1000h at ozone volume space velocity
-1, other reaction conditions is with embodiment 12.The result of reacting 2 hours is as follows: dimethyl thioether transformation efficiency is 54%; Ozone effective rate of utilization is 89%; Dimethyl sulfoxide (DMSO) selectivity is 90%; Dimethyl sulfone selectivity is 10%.
Embodiment 14
Under temperature is 100 DEG C and pressure is 2.0MPa, is oxygenant with ozone (15% volume ratio, all the other are isopyknic helium and oxygen), dimethyl thioether, ozone and solvent acetonitrile are reacted according under the mol ratio of 1: 1.5: 60.The result of reacting 1 hour is as follows: dimethyl thioether transformation efficiency is 87%; Ozone effective rate of utilization is 62%; Dimethyl sulfoxide (DMSO) selectivity is 90%; Dimethyl sulfone selectivity is 9%.
Embodiment 15
Reacting according to the reaction conditions of embodiment 14, substituting acetonitrile for solvent unlike utilizing methyl alcohol.The result of reacting 1 hour is as follows: dimethyl thioether transformation efficiency is 93%; Ozone effective rate of utilization is 68%; Dimethyl sulfoxide (DMSO) selectivity is 92%; Dimethyl sulfone selectivity is 7%.
Embodiment 16
The present embodiment illustrates reaction process in the presence of a catalyst and result.
Take HTS as catalyzer, the molar ratio of catalyzer and dimethyl thioether is 1: 10, and ozone volume space velocity is 100h
-1, other reaction conditions is with embodiment 14.The result of reacting 1 hour is as follows: dimethyl thioether transformation efficiency is 99%; Ozone effective rate of utilization is 89%; Dimethyl sulfoxide (DMSO) selectivity is 97%; Dimethyl sulfone selectivity is 3%.
Claims (3)
1. the method for a dimethyl thioether oxidation, the method is under oxidation reaction condition, by dimethyl thioether and oxidising agent, it is characterized in that, described contact exists at solvent and carries out under titanium-containing catalyst, the mol ratio of described dimethyl thioether and solvent is 1:1-50, described oxygenant is the gas containing ozone, the mol ratio of the ozone in described dimethyl thioether and oxygenant is 1:0.3-2, described solvent is water, methyl alcohol, acetone, at least one in acetonitrile and acetic acid, described oxidation reaction condition comprises: temperature is 20-100 DEG C, pressure is 0.1-1.5MPa, time is 0.1-10 hour, described titanium-containing catalyst is the HTS of MFI structure, and crystal grain is hollow structure, and the radical length of the chamber portion of this hollow structure is 5-300 nanometer, and described HTS is at 25 DEG C, P/P
0=0.10, adsorption time is that the benzene adsorptive capacity recorded under the condition of 1 hour is at least 70 milligrams/grams, hysteresis loop is there is between the adsorption isothermal line of the nitrogen absorption under low temperature of this HTS and desorption isotherm, described titanium-containing catalyst is in the mol ratio of titanium dioxide and dimethyl thioether for 1:10-100, and ozone air speed is 20-1000h
-1.
2. according to the method for claim 1, wherein, the said gas containing ozone is the mixed gas of ozone or ozone and diluent gas, and with the cumulative volume of described mixed gas for benchmark, in described mixed gas, the content of ozone is 1 more than volume %, and described diluent gas is at least one in oxygen, carbonic acid gas, nitrogen, argon gas, helium, neon and air.
3. according to the method for claim 2, wherein, with the cumulative volume of described mixed gas for benchmark, in described mixed gas, the content of ozone is 5 more than volume %, and described diluent gas is at least one in oxygen, carbonic acid gas, helium and air.
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| CN103288692B (en) * | 2012-02-29 | 2016-03-02 | 中国石油化工股份有限公司 | A kind of method being prepared dimethyl sulfone by dimethyl sulfoxide (DMSO) |
| 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 |
| CN104557631B (en) * | 2013-10-29 | 2016-08-17 | 中国石油化工股份有限公司 | A kind of method preparing dimethyl sulfoxide |
| CN104557625B (en) * | 2013-10-29 | 2017-01-25 | 中国石油化工股份有限公司 | Method for preparing dimethyl sulfone |
| CN105367463B (en) * | 2014-08-26 | 2017-06-30 | 中国石油化工股份有限公司 | It is a kind of while the method for producing dimethyl sulfone and dimethyl sulfoxide (DMSO) |
| CN107698472A (en) * | 2017-10-18 | 2018-02-16 | 辽宁省轻工设计院有限公司 | A kind of method that dimethyl sulfide prepares dimethyl sulfoxide (DMSO) |
| CN108863863A (en) * | 2018-06-20 | 2018-11-23 | 重庆兴发金冠化工有限公司 | A method of producing dimethyl sulfoxide |
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