CN104003914A - Dimethyl sulfoxide preparation method - Google Patents
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- CN104003914A CN104003914A CN201310060248.2A CN201310060248A CN104003914A CN 104003914 A CN104003914 A CN 104003914A CN 201310060248 A CN201310060248 A CN 201310060248A CN 104003914 A CN104003914 A CN 104003914A
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Abstract
The invention provides a dimethyl sulfoxide preparation method. The method is characterized in that a liquid mixture contacts with a titanium silicate molecular sieve under oxidation reaction conditions to obtain a dimethyl sulfoxide-containing mixture, the liquid mixture contains dimethyl thioether and at least one peroxide, and the pH value of the liquid mixture is 5-9. The method can effectively improve the high effective utilization rate of an oxidant and the selectivity of dimethyl sulfoxide and the conversion rate of dimethyl thioether. The method having a good stability still realizes high effective utilization rate of the oxidant, high selectivity of dimethyl sulfoxide and high conversion rate of dimethyl thioether even long time operation is continuously carried out.
Description
Technical field
The present invention relates to a kind of method of preparing dimethyl sulfoxide (DMSO).
Background technology
Dimethyl sulfoxide (DMSO) (DMSO) is a kind of organic compounds containing sulfur, under normal temperature, is colourless transparent liquid, has the characteristics such as high polarity, high-hygroscopicity, flammable and high boiling point be non-proton.Dimethyl sulfoxide (DMSO) is water-soluble, ethanol, acetone, EC, it is the inert solvent that polarity is strong, be widely used as solvent and reaction reagent, for example, in acrylonitrile polymerization reaction as process solvent and the solvent that reels off raw silk from cocoons, as the synthetic of urethane and the solvent that reels off raw silk from cocoons, as the synthetic of polymeric amide, fluorochlorobenzene amine, polyimide and polysulfones.For example, and dimethyl sulfoxide (DMSO) has very high selectivity extracting ability, can be used as the extraction solvent that alkane separates with aromatic hydrocarbon: dimethyl sulfoxide (DMSO) can be used for the extracting of aromatic hydrocarbons or divinyl.Meanwhile, in medicine industry, dimethyl sulfoxide (DMSO) not only can be directly as raw material and the carrier of some drugs, and can also play anti-inflammatory analgetic, diuresis and the effect such as calm, therefore the active ingredient of Chang Zuowei analgesic drug product makes an addition in medicine.In addition, dimethyl sulfoxide (DMSO) also can be used as capacitor dielectric, frostproofer, brake solution and rare metal extracting agent etc.
Dimethyl sulfoxide (DMSO) generally adopts the preparation of dimethyl thioether oxidation style, according to the difference of used oxygenant and mode of oxidizing, generally includes nitric acid oxidation method, peroxide oxidation method, Ozonation, anonizing and nitrogen peroxide oxidation style.
The reaction conditions gentleness of peroxide oxidation method, equipment and process route is simple, and product does not need alkali to neutralize, and substantially pollution-free to environment.But in peroxide oxidation method, the price of oxygenant is high and consumption is large, has improved the production cost of dimethyl sulfoxide (DMSO), limit the range of application of peroxide oxidation method.
Therefore, in the time adopting peroxide oxidation method to prepare dimethyl sulfoxide (DMSO), improve effective rate of utilization, the transformation efficiency of dimethyl thioether and the selectivity of dimethyl sulfoxide (DMSO) of oxygenant, the production cost that reduces dimethyl sulfoxide (DMSO) is an important problem.
Summary of the invention
The object of the present invention is to provide a kind of method of preparing dimethyl sulfoxide (DMSO) using superoxide as oxygenant, the method can improve effective rate of utilization, dimethyl thioether transformation efficiency and the dimethyl sulfoxide (DMSO) selectivity of oxygenant effectively.
The invention provides a kind of method of preparing dimethyl sulfoxide (DMSO), the method is included under oxidation reaction condition, a kind of liquid mixture is contacted with HTS, obtain the mixture that contains dimethyl sulfoxide (DMSO), described liquid mixture contains dimethyl thioether and at least one superoxide, and the pH value of described liquid mixture is 5-9.
The method according to this invention, can improve the effective rate of utilization of oxygenant, selectivity and the dimethyl thioether transformation efficiency of dimethyl sulfoxide (DMSO) effectively.And the good stability of the method according to this invention, even if long-time continuous operation still can obtain high oxygenant effective rate of utilization, dimethyl sulfoxide (DMSO) selectivity and dimethyl thioether transformation efficiency.
Embodiment
The invention provides a kind of method of preparing dimethyl sulfoxide (DMSO), the method is included under oxidation reaction condition, a kind of liquid mixture is contacted with HTS, obtain the mixture that contains dimethyl sulfoxide (DMSO), described liquid mixture contains dimethyl thioether and at least one superoxide.
The method according to this invention, the pH value of described liquid mixture is 5-9.The liquid mixture that is 5-9 by pH value contacts with HTS, can improve effective rate of utilization, dimethyl thioether transformation efficiency and the dimethyl sulfoxide (DMSO) selectivity of oxygenant.And, contact with HTS by the liquid mixture that is 5-9 by pH value, even if move continuously for a long time, still can obtain high oxygenant effective rate of utilization, dimethyl thioether transformation efficiency and dimethyl sulfoxide (DMSO) selectivity.From the optionally angle of the effective rate of utilization of further raising oxygenant and the transformation efficiency of dimethyl thioether and dimethyl sulfoxide (DMSO), the pH value of described liquid mixture is 5.5-8.5.
The method according to this invention, can be adjusted to the pH value of liquid mixture within previously described scope by conventional the whole bag of tricks.Particularly, can regulate by add at least one basic cpd in described liquid mixture the pH value of described liquid mixture.Herein, the pH value that described alkaline matter refers to its aqueous solution is for being greater than 7 material.The specific examples of described alkaline matter can include but not limited to: ammonia (, NH
3), amine, quaternary ammonium hydroxide and M
1(OH)
n(wherein, M
1for basic metal or alkaline-earth metal, n is and M
1the identical integer of valency).
As described alkaline matter, ammonia can be introduced with the form of liquefied ammonia, also can introduce with aqueous solution form, can also introduce with the form of gas.Concentration as the ammonia (, ammoniacal liquor) of aqueous solution form is not particularly limited, and can be conventional selection, for example 1-36 % by weight.
As described alkaline matter, amine refers to the hydrogen partial on ammonia or is all replaced by alkyl the material forming, comprises primary amine, secondary amine and tertiary amine.Described amine is specifically as follows the material shown in formula I and/or C
3-C
11heterocyclic amine,
(formula I)
In formula I, R
1, R
2and R
3can be H or C separately
1-C
6alkyl (as C
1-C
6alkyl), and R
1, R
2and R
3when different, be H.Herein, C
1-C
6the specific examples of alkyl can include but not limited to: methyl, ethyl, n-propyl, sec.-propyl, normal-butyl, sec-butyl, isobutyl-, the tertiary butyl, n-pentyl, isopentyl, tert-pentyl, neo-pentyl and n-hexyl.
The specific examples of amine can include but not limited to: methylamine, dimethylamine, Trimethylamine 99, ethamine, diethylamine, triethylamine, Tri N-Propyl Amine, di-n-propylamine, Tri-n-Propylamine, Isopropylamine, Diisopropylamine, n-butylamine, di-n-butyl amine, tri-n-butyl amine, sec-butylamine, diisobutyl amine, triisobutyl amine, tert-butylamine, n-amylamine, two n-amylamines, tri-n-amyl amine, neopentyl amine, isobutylcarbylamine, di-iso-amylamine, tri-isoamylamine, tertiary amylamine, normal hexyl Amine and n-octyl amine.
Described heterocyclic amine is on finger ring, to have the compound on nitrogen-atoms and this nitrogen-atoms with lone-pair electron.Described heterocyclic amine can be for example one or more in replacement or unsubstituted pyrroles, replacement or unsubstituted Pyrrolidine, replacement or unsubstituted pyridine, replacement or unsubstituted hexahydropyridine, replacement or unsubstituted imidazoles, replacement or unsubstituted pyrazoles, replacement or unsubstituted quinolines, replacement or unsubstituted dihydroquinoline, replacement or unsubstituted tetrahydroquinoline, replacement or unsubstituted decahydroquinoline, replacement or unsubstituted isoquinoline 99.9 and replacement or unsubstituted pyrimidine.
As described alkaline matter, quaternary ammonium hydroxide is specifically as follows the material shown in formula II,
(formula II)
In formula II, R
4, R
5, R
6and R
7can be C separately
1-C
6alkyl (as C
1-C
6alkyl).Described C
1-C
6the specific examples of alkyl can include but not limited to: methyl, ethyl, n-propyl, sec.-propyl, normal-butyl, sec-butyl, isobutyl-, the tertiary butyl, n-pentyl, neo-pentyl, isopentyl, tert-pentyl, n-hexyl.
The specific examples of described quaternary ammonium hydroxide can include but not limited to: Tetramethylammonium hydroxide, tetraethyl ammonium hydroxide, TPAOH (comprising four n-propyl ammonium hydroxide and tetra isopropyl ammonium hydroxide), TBAH (comprising 4-n-butyl ammonium hydroxide, four sec-butyl ammonium hydroxide, four isobutyl-ammonium hydroxide and tetra-tert ammonium hydroxide) and four pentyl ammonium hydroxide.
As described alkaline matter, M
1(OH)
nfor the oxyhydroxide of alkali-metal oxyhydroxide or alkaline-earth metal, for example, can be sodium hydroxide, potassium hydroxide, magnesium hydroxide, hydrated barta and calcium hydroxide.
The method according to this invention, described alkaline matter can directly add in described liquid mixture, adds in described liquid mixture after also described alkaline matter can being mixed with to solution.
The method according to this invention, described alkaline matter is preferably ammonia.Adopt ammonia as alkaline matter, can regulate on the one hand the pH value of described liquid mixture, ammonia is easy to remove on the other hand, increases burden can to follow-up separation and purification process.Meanwhile, adopt ammonia can also obtain higher oxygenant effective rate of utilization and dimethyl sulfoxide (DMSO) selectivity as alkaline matter.
The method according to this invention, HTS plays the effect as the catalyzer that dimethyl thioether is oxidized, and its concrete consumption is as the criterion can realize catalysis.Usually, the weight ratio of dimethyl thioether and described HTS can be 0.1-50:1.In the time that reaction is carried out in fixed-bed reactor, the weight hourly space velocity of described liquid mixture can be carried out appropriate selection according to the amount of the catalyzer that contains HTS loading in reactor.Usually, the weight hourly space velocity of described liquid mixture can be 0.1-500h
-1, be preferably 5-300h
-1.
HTS is the general name that titanium atom replaces a class zeolite of a part of Siliciumatom in lattice framework, can use chemical formula xTiO
2siO
2represent.The present invention is not particularly limited for the content of titanium atom in HTS, can be that the routine of this area is selected.Particularly, x can be 0.0001-0.04, is preferably 0.01-0.03, more preferably 0.015-0.025.
Described HTS can be the common HTS with various topological frameworks, for example: described HTS can be selected from 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 of hexagonal structure is (as Ti-MCM-41, Ti-SBA-15), the HTS (as Ti-MOR) of MOR structure, the HTS (as Ti-TUN) of TUN structure and the HTS (as Ti-ZSM-48) of other structure.
Preferably, described HTS is selected from HTS, the HTS of MEL structure and the HTS of BEA structure of MFI structure.More preferably, described HTS is the HTS of MFI structure.
From transformation efficiency, the effective rate of utilization of oxygenant and the optionally angle of dimethyl sulfoxide (DMSO) of further raising dimethyl thioether, the crystal grain of described HTS is hollow structure, the radical length of the cavity part 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 recording under the condition of 1 hour is at least 70 milligrams/grams, between the adsorption isothermal line of the nitrogen absorption under low temperature of this HTS and desorption isotherm, has hysteresis loop.The HTS that has this structure herein, is called hollow HTS.Described hollow HTS can be commercially available (be for example purchased from the trade mark of Sinopec Hunan Jianchang Petrochemical Co., Ltd be HTS molecular sieve), also can prepare according to disclosed method in CN1132699C.
The method according to this invention, according to the embodiment difference of reaction, can have different forms as the HTS of catalyzer.Particularly, can be molecular screen primary powder as the HTS of catalyzer, can be also the molecular sieve of moulding.
In the HTS of described moulding, the content of carrier can be that the routine of this area is selected.Usually, taking the total amount of the HTS of described moulding as benchmark, the content of described HTS can be 1-99 % by weight, and the content of described carrier can be 1-99 % by weight.Obtaining under the prerequisite of higher catalytic activity, from taking into account the angle of intensity of catalyzer, taking the total amount of the HTS of described moulding as benchmark, the content of described HTS is preferably 5-95 % by weight, more preferably 10-95 % by weight, more preferably 40-95 % by weight; The content of described carrier is preferably 5-95 % by weight, more preferably 5-90 % by weight, more preferably 5-60 % by weight.
When the HTS that is moulding in described HTS, carrier can be common various heat-resistant inorganic oxides.Described heat-resistant inorganic oxide refers under oxygen or oxygen-containing atmosphere, and decomposition temperature is not less than the inorganic oxygen-containing compound of 300 DEG C (for example: decomposition temperature is 300-1000 DEG C).Particularly, described carrier can be one or more in aluminum oxide, silicon oxide, titanium oxide, magnesium oxide, zirconium white, Thorotrast, beryllium oxide and clay.
Can adopt the conventional the whole bag of tricks in this area to prepare the HTS of moulding.For example: after HTS can being mixed with support material, carry out moulding, and the forming composition obtaining is dried and optional roasting, thereby obtain the HTS of moulding.Described support material is selected from the precursor of heat-resistant inorganic oxide and heat-resistant inorganic oxide.The precursor of described heat-resistant inorganic oxide can be for forming the material of described heat-resistant inorganic oxide.For example, in the time that described heat-resistant inorganic oxide is aluminum oxide, described precursor can be various hydrated aluminum oxides; In the time that described heat-resistant inorganic oxide is silicon oxide, described precursor can be selected from various silicon sol and organo-siloxane.
One of the present invention preferred embodiment in, the preparation method of the HTS of described moulding comprises: under hydrolysis reaction condition, the silicoorganic compound that hydrolysis reaction can be occurred to at least one contact with water with at least one water-soluble alkali, the mixture that contact is obtained mixes with HTS, and the mixture that contains HTS obtaining is successively carried out to moulding and roasting.The HTS of the moulding obtaining according to this embodiment not only has higher intensity, thereby more wear-resistant and have higher anti-breaking capacity, and the bed of the HTS that contains this moulding has the higher anti-ability of caving in; And can obtain higher oxygenant effective rate of utilization, dimethyl thioether transformation efficiency and dimethyl sulfoxide (DMSO) selectivity.
This preferred embodiment in, the consumption of described silicoorganic compound, water-soluble alkali and HTS is HTS moulding can be as the criterion, the consumption of water is can make hydrolysis reaction be as the criterion smoothly.From finally crushing strength and dimethyl thioether transformation efficiency and the optionally angle of dimethyl sulfoxide (DMSO) of the HTS of the moulding of preparation of further raising, the mass ratio of described HTS, silicoorganic compound, water-soluble alkali and water is preferably 100:10-2000:2-40:50-2000, more preferably 100:100-500:5-40:50-1000, more preferably 100:100-500:5-40:50-500.
Described silicoorganic compound are not particularly limited, and can have hydrolyzable organic group on various Siliciumatoms, and can form the compound of silicon oxide by hydrolysis-condensation reaction.Particularly, described silicoorganic compound can be selected from the siloxanes shown in formula III,
In formula III, R
8, R
9, R
10and R
11can be C separately
1-C
4alkyl.Described C
1-C
4alkyl comprise C
1-C
4straight chained alkyl and C
3-C
4branched-chain alkyl, its specific examples can include but not limited to: methyl, ethyl, n-propyl, sec.-propyl, normal-butyl, sec-butyl, isobutyl-and the tertiary butyl.Preferably, described silicoorganic compound are selected from methyl silicate, tetraethoxy, positive silicic acid n-propyl, positive isopropyl silicate and the positive positive butyl ester of silicic acid.
Described water-soluble alkali can be the conventional various alkali that can be dissolved in water.For example: described water-soluble alkali can be chemical formula M
2(OH)
mthe compound representing, wherein, M
2can be basic metal, alkaline-earth metal, NH
4 +or quaternary ammonium group (, NH
4 +in hydrogen atom by alkyl replace form group, described alkyl is preferably C
1-C
20alkyl, C
3-C
20cycloalkyl or C
6-C
20aryl), m is and M
2the identical integer of valency; Described water-soluble alkali can be also various organic amine (being preferably fatty amine) and/or the hydramine (being preferably aliphatics hydramine) that can be dissolved in water, and its specific examples can include but not limited to: ethamine, propylamine and isomer thereof, butylamine and isomer thereof, butanediamine, monoethanolamine, diethanolamine and trolamine.
Preferably, described water-soluble alkali is synthesis of titanium silicon molecular sieve template, can obtain so higher dimethyl thioether transformation efficiency, dimethyl sulfoxide (DMSO) selectivity and oxygenant effective rate of utilization.Described synthesis of titanium silicon molecular sieve can be the various compounds that are used as template in the time of synthesis of titanium silicon molecular sieve by template, as quaternary ammonium hydroxide and/or organic amine, is preferably quaternary ammonium hydroxide.Described quaternary ammonium hydroxide can be conventional selection, for example, can be the compound shown in formula IV:
In formula IV, R
12, R
13, R
14and R
15can be C separately
1-C
20alkyl (comprise C
1-C
20straight chained alkyl and C
3-C
20branched-chain alkyl), C
3-C
20cycloalkyl or C
6-C
20aryl.Preferably, R
12, R
13, R
14and R
15c respectively does for oneself
1-C
10alkyl (comprise C
1-C
10straight chained alkyl and C
3-C
10branched-chain alkyl) and C
3-C
10cycloalkyl.Further preferably, R
12, R
13, R
14and R
15c respectively does for oneself
1-C
6alkyl (comprise C
1-C
6straight chained alkyl and C
3-C
6branched-chain alkyl).Described C
1-C
20the specific examples of alkyl can include but not limited to: one or more in methyl, ethyl, n-propyl, sec.-propyl, normal-butyl, sec-butyl, isobutyl-, the tertiary butyl, n-pentyl, neo-pentyl, isopentyl, tert-pentyl, n-hexyl, n-octyl, n-nonyl, positive decyl, n-undecane base, dodecyl, n-tridecane base, n-tetradecane base, Pentadecane base, n-hexadecyl, Octadecane base and NSC 62789 base.Described C
6-C
20the example of aryl can include but not limited to: phenyl, naphthyl, 4-aminomethyl phenyl and 4-ethylphenyl.Described C
3-C
20the example of cycloalkyl can include but not limited to: cyclopropyl, cyclopentyl, cyclohexyl, 4-methylcyclohexyl, 4-ethyl cyclohexyl, 4-n-propyl cyclohexyl and 4-normal-butyl cyclohexyl.
The example of described quaternary ammonium hydroxide can include but not limited to: TPAOH (comprising four n-propyl ammonium hydroxide and tetra isopropyl ammonium hydroxide), tetraethyl ammonium hydroxide, Tetramethylammonium hydroxide and TBAH (comprising 4-n-butyl ammonium hydroxide, four sec-butyl ammonium hydroxide, four isobutyl-ammonium hydroxide and tetra-tert ammonium hydroxide).
Described hydrolysis reaction condition is not particularly limited, and can be conventional selection, can be hydrolyzed completely and be as the criterion with described silicoorganic compound.Usually, described hydrolysis reaction condition comprises: temperature can be 20-100 DEG C, and the time can be 0.5-10 hour.
In the present invention, being dried with the condition of roasting and being also not particularly limited by the mixture forming that contains HTS obtaining and by the forming composition obtaining, can be that the routine of this area is selected.
Particularly, the mode of described moulding can be extrusion, spraying, round as a ball, compressing tablet or their combination.The catalyzer of described moulding can have common different shape, for example, can be spherical, bar shaped, annular, cloverleaf pattern, honeycombed or butterfly etc., is preferably spherical.
Can under the normal condition of this area, forming composition be dried, for example can be at the temperature of 80-250 DEG C, under the condition of normal pressure or decompression, described forming composition is dry.
The condition of described roasting comprises: temperature can be 350-600 DEG C, and the time can be 0.5-12 hour.Described roasting is preferably carried out in oxygen-containing atmosphere, and described oxygen-containing atmosphere can be for example air atmosphere or oxygen atmosphere.
The granular size of the HTS of moulding is also not particularly limited, and can carry out appropriate selection according to concrete shape.As described in catalyzer while being spherical, the median size of described catalyzer can be 4-5000 micron, is preferably 5-2000 micron, more preferably 40-600 micron.Described median size is the volume average particle size that adopts laser particle analyzer to measure.
The method according to this invention, can carry out appropriate selection according to the amount of dimethyl thioether as the consumption of the superoxide of oxygenant.Usually, the mol ratio of dimethyl thioether and described superoxide is 1:0.1-4.The method according to this invention, by within the pH value of described liquid mixture be adjusted to meet previously described scope, even in the time of the large usage quantity of superoxide, still can obtain the selectivity of very high dimethyl sulfoxide (DMSO), in the product obtaining, the content of dimethyl sulfone is low.Preferably, the mol ratio of dimethyl thioether and described superoxide is 1:0.2-2.
Described superoxide refers in molecular structure the compound of contain-O-O-key, can be selected from hydrogen peroxide, hydroperoxide and peracid.Described hydroperoxide refer to that a hydrogen atom in hydrogen peroxide molecule is replaced by organic group and the material that obtains.Described peracid refers in molecular structure the organic oxacid of contain-O-O-key.The specific examples of described superoxide can include but not limited to: hydrogen peroxide, tertbutyl peroxide, dicumyl peroxide, cyclohexyl hydroperoxide, Peracetic Acid and Perpropionic Acid.Preferably, described oxygenant is hydrogen peroxide, can further reduce like this separation costs.Described hydrogen peroxide can be the conventional hydrogen peroxide existing with various forms in this area.From the angle of the security of further raising the method according to this invention, the method according to this invention is preferably used the hydrogen peroxide existing with aqueous solution form.The method according to this invention, in the time that described hydrogen peroxide provides with aqueous solution form, the concentration of described aqueous hydrogen peroxide solution can be the normal concentration of this area, for example: 20-80 % by weight.The aqueous solution that concentration meets the hydrogen peroxide of above-mentioned requirements can adopt ordinary method preparation, also can be commercially available, for example: can be hydrogen peroxide, the hydrogen peroxide of 50 % by weight or the hydrogen peroxide of 70 % by weight of 30 % by weight that can be commercially available.
The method according to this invention, described liquid mixture can also contain at least one solvent.Described solvent can either dissolve dimethyl thioether and superoxide or promote the two to mix for various, can promote again the liquid substance of dmso solution.Usually, described solvent can be selected from water, C
1-C
6alcohol, C
3-C
8ketone and C
2-C
6nitrile.The specific examples of described solvent can include but not limited to: water, methyl alcohol, ethanol, n-propyl alcohol, Virahol, the trimethyl carbinol, isopropylcarbinol, acetone, butanone and acetonitrile.Preferably, described solvent is selected from water and C
1-C
6alcohol.More preferably, described solvent is methyl alcohol and/or water.Can be the water in various sources as the water of solvent, be hydrogen peroxide at described oxygenant, and hydrogen peroxide is while providing with aqueous solution form, and the water in aqueous hydrogen peroxide solution can be used as solvent and uses.
The consumption of solvent can carry out appropriate selection according to the consumption of dimethyl thioether and oxygenant.Preferably, the weight ratio of dimethyl thioether and described solvent is 1:0.1-20.More preferably, the weight ratio of dimethyl thioether and described solvent is 1:1-10.The concrete consumption of solvent has certain relation with kind and the condition of reacting etc. of solvent, and those skilled in the art can suitably select as the case may be.
The method according to this invention, described oxidation reaction condition can be conventional selection, is as the criterion dimethyl thioether can be oxidized into dimethyl sulfoxide (DMSO).Usually, described oxidation reaction condition comprises: temperature can be 0-80 DEG C, is preferably 20-60 DEG C; Pressure can be 0-3MPa, is preferably 0.1-1.5MPa.Herein, pressure is gauge pressure.The method according to this invention, the time that described liquid mixture is contacted with HTS can be carried out appropriate selection according to the mode of contact.
The method according to this invention, can adopt periodical operation, also can adopt operate continuously, is not particularly limited.Feed way can be also any suitable way well known by persons skilled in the art.Particularly, in the time carrying out with andnon-continuous operation manner, dimethyl thioether, oxygenant, catalyzer and optional solvent can be added in reactor, react.In the time carrying out in a continuous manner, can in common various fixed-bed reactor or slurry bed reactor, carry out.
The method according to this invention can also comprise that the mixture that contains dimethyl sulfoxide (DMSO) that contact is obtained separates, to isolate dimethyl sulfoxide (DMSO) wherein.The present invention is not particularly limited for the method for isolating the dimethyl sulfoxide (DMSO) in the mixture that obtains of contact, can be the routine selection of this area.For example can carry out fractionation by the mixture that contact is obtained, thereby obtain dimethyl sulfoxide (DMSO).
The method according to this invention, using HTS as catalyzer, the pH value of the liquid mixture contacting with HTS is adjusted to 5-9(simultaneously and is preferably 5.5-8.5), can improve the effective rate of utilization of oxygenant and the selectivity of dimethyl sulfoxide (DMSO), can also obtain high dimethyl thioether transformation efficiency simultaneously.And the stability that the method according to this invention has also had, even if long-time continuous operation still can obtain high dimethyl thioether transformation efficiency, oxygenant effective rate of utilization and dimethyl sulfoxide (DMSO) selectivity.The one of the method according to this invention preferred embodiment, in the time adopting hollow HTS as catalyzer, the further velocity of diffusion of intensified response thing and product, further reduce the generation of side reaction, thereby can obtain higher oxygenant effective rate of utilization, dimethyl sulfoxide (DMSO) selectivity and dimethyl thioether selectivity.
Describe the present invention in detail below in conjunction with embodiment and comparative example.
In following examples and comparative example, if not otherwise specified, reagent used is commercially available analytical reagent.
In following examples and comparative example, pressure is all in gauge pressure.
In following examples, titanium-silicon molecular sieve TS-1 used is according to Zeolites, 1992, the 12 volumes, and prepared by the method described in 943-950 page, and its titanium oxide content is 2.5 % by weight.
In following examples, hollow HTS used is prepared according to disclosed method in Chinese patent CN1132699C, by analysis, this HTS is MFI structure, between the adsorption isothermal line of the nitrogen absorption under low temperature of this HTS and desorption isotherm, have hysteresis loop, crystal grain is that the radical length of hollow crystal grain and cavity part is 15-180 nanometer; This HTS sample is at 25 DEG C, P/P
0=0.10, adsorption time is that the benzene adsorptive capacity recording under the condition of 1 hour is 78 milligrams/gram, and its titanium oxide content is 2.5 % by weight.
In following examples and comparative example, the hydrogen peroxide of use is the hydrogen peroxide of 30 % by weight.
In following examples and comparative example, adopt gas-chromatography to analyze the content of each composition in the reaction solution obtaining, adopt respectively on this basis following formula to calculate transformation efficiency, the effective rate of utilization of oxygenant and the selectivity of dimethyl sulfoxide (DMSO) of dimethyl thioether.
X
thioether=[(m
o thioether-m
thioether)/m
o thioether] × 100% (V)
In formula V, X
thioetherrepresent the transformation efficiency of dimethyl thioether;
M
o thioetherrepresent the quality of the dimethyl thioether adding;
M
thioetherrepresent the quality of unreacted dimethyl thioether.
S
sulfoxide=[n
sulfoxide/ (n
o thioether-n
thioether)] × 100% (VI)
In formula VI, S
sulfoxiderepresent the selectivity of dimethyl sulfoxide (DMSO);
N
o thioetherrepresent the molar weight of the dimethyl thioether adding;
N
thioetherrepresent the molar weight of unreacted dimethyl thioether;
N
sulfoxiderepresent the molar weight of the dimethyl sulfoxide (DMSO) obtaining.
U
oxygenant=[n
sulfoxide/ (n
o oxygenant-n
oxygenant)] × 100% (VII)
In formula VII, U
oxygenantrepresent the effective rate of utilization of oxygenant;
N
o oxygenantrepresent the molar weight of the oxygenant adding;
N
oxygenantrepresent the molar weight of unreacted oxygenant;
N
sulfoxiderepresent the molar weight of the dimethyl sulfoxide (DMSO) obtaining.
Embodiment 1-20 is used for illustrating the method according to this invention.
Embodiment 1
(1) titanium-silicon molecular sieve TS-1 is mixed with silicon sol (dioxide-containing silica is 30 % by weight) and water, wherein, titanium-silicon molecular sieve TS-1, taking the silicon sol of silicon-dioxide and the weight ratio of water as 1:0.2:1.5.By the mixture obtaining through spin granulation, and by the wet grain obtaining 550 DEG C of roastings 5 hours, thereby obtain the catalyzer that median size is 200 μ m.Wherein, in catalyzer, the content of HTS is 80 % by weight.
(2) catalyst loading of being prepared by step (1), in fixed-bed reactor, forms beds, and wherein, the quantity of beds is 1 layer.
By dimethyl thioether, hydrogen peroxide and methanol mixed, form liquid mixture.In liquid mixture, add ammoniacal liquor (concentration is 25 % by weight), the pH value of liquid mixture is adjusted to 6.5.Then the beds contact reacts of, described liquid mixture being sent in fixed-bed reactor and being contained HTS.Wherein, in liquid mixture, the mol ratio of dimethyl thioether and hydrogen peroxide is 1:1, and the weight ratio of dimethyl thioether and methyl alcohol is 1:5, and the weight hourly space velocity of liquid mixture is 100h
-1.Temperature in beds is 30 DEG C, and the pressure in fixed-bed reactor is 0.5MPa.
Reaction mixture reaction being started latter 0.5 hour and obtain for 150 hours carries out gas chromatographic analysis, and calculates transformation efficiency, the effective rate of utilization of oxygenant and the selectivity of dimethyl sulfoxide (DMSO) of dimethyl thioether.Result is listed in table 1.
Embodiment 2
Adopt the method identical with embodiment 1 to prepare dimethyl sulfoxide (DMSO), different, with the titanium-silicon molecular sieve TS-1 in the hollow HTS replacement embodiment 1 of equivalent.The selectivity of the transformation efficiency of the dimethyl thioether calculating, the effective rate of utilization of oxygenant and dimethyl sulfoxide (DMSO) is listed in table 1.
Comparative example 1
Adopt the method identical with embodiment 1 to prepare dimethyl sulfoxide (DMSO), different, omit the step that regulates the pH value of liquid mixture with ammoniacal liquor.The selectivity of the transformation efficiency of the dimethyl thioether calculating, the effective rate of utilization of oxygenant and dimethyl sulfoxide (DMSO) is listed in table 1.
Embodiment 3
Adopt the method identical with embodiment 2 to prepare dimethyl sulfoxide (DMSO), different is, adopt following methods Kaolinite Preparation of Catalyst: under the condition of normal pressure (1 standard atmospheric pressure) and 40 DEG C, tetraethyl orthosilicate is joined in the TPAOH aqueous solution, stirring after 2 hours adds hollow HTS to continue to stir 1 hour, wherein, the mass ratio of hollow HTS, tetraethyl orthosilicate, TPAOH and water is 100:200:20:250.The mixture obtaining, after spin granulation, 550 DEG C of roastings 5 hours, is obtained to the catalyzer that median size is 200 μ m.Wherein, in catalyzer, the content of HTS is 60 % by weight.
The selectivity of the transformation efficiency of the dimethyl thioether calculating, the effective rate of utilization of oxygenant and dimethyl sulfoxide (DMSO) is listed in table 1.
Table 1
Embodiment 4
(1) hollow HTS is mixed with silicon sol (dioxide-containing silica is 30 % by weight) and water, wherein, hollow HTS, taking the silicon sol of silicon-dioxide and the weight ratio of water as 1:0.1:1.By the mixture obtaining through spin granulation, and by the wet grain obtaining 580 DEG C of roastings 4 hours, thereby obtain the catalyzer that median size is 300 μ m.Wherein, in catalyzer, the content of HTS is 70 % by weight.
(2) catalyst loading of being prepared by step (1), in fixed-bed reactor, forms beds, and wherein, the quantity of beds is 1 layer.
Dimethyl thioether, hydrogen peroxide and acetone are mixed, form liquid mixture.In liquid mixture, add ammoniacal liquor (concentration is 25 % by weight), the pH value of liquid mixture is adjusted to 7.0.Then the beds contact reacts of, described liquid mixture being sent in fixed-bed reactor and being contained HTS.Wherein, in liquid mixture, the mol ratio of dimethyl thioether and hydrogen peroxide is 1:1, and the weight ratio of dimethyl thioether and acetone is 1:10, and the weight hourly space velocity of liquid mixture is 200h
-1.Temperature in beds is 50 DEG C, and the pressure in fixed-bed reactor is 0.1MPa.
Reaction mixture reaction being started latter 0.5 hour and obtain for 150 hours carries out gas chromatographic analysis, and calculates transformation efficiency, the effective rate of utilization of oxygenant and the selectivity of dimethyl sulfoxide (DMSO) of dimethyl thioether.Result is listed in table 2.
Embodiment 5
(1) titanium-silicon molecular sieve TS-1 is mixed with silicon sol (dioxide-containing silica is 30 % by weight) and water, wherein, titanium-silicon molecular sieve TS-1, taking the silicon sol of silicon-dioxide and the weight ratio of water as 1:0.5:5.By the mixture obtaining through mist projection granulating, and by the wet grain obtaining 550 DEG C of roastings 5 hours, thereby obtain the catalyzer that median size is 80 μ m.Wherein, in catalyzer, the content of HTS is 60 % by weight.
(2) catalyst loading of being prepared by step (1), in fixed-bed reactor, forms beds, and wherein, the quantity of beds is 1 layer.
Dimethyl thioether, hydrogen peroxide and water are mixed, form liquid mixture.In liquid mixture, add ammoniacal liquor (concentration is 25 % by weight), the pH value of liquid mixture is adjusted to 8.0.Then the beds contact reacts of, described liquid mixture being sent in fixed-bed reactor and being contained HTS.Wherein, in liquid mixture, the mol ratio of dimethyl thioether and hydrogen peroxide is 1:2, and the weight ratio of dimethyl thioether and water is 1:2, and the weight hourly space velocity of liquid mixture is 10h
-1.Temperature in beds is 40 DEG C, and the pressure in fixed-bed reactor is 0.2MPa.
Reaction mixture reaction being started latter 0.5 hour and obtain for 150 hours carries out gas chromatographic analysis, and calculates transformation efficiency, the effective rate of utilization of oxygenant and the selectivity of dimethyl sulfoxide (DMSO) of dimethyl thioether.Result is listed in table 2.
Table 2
Embodiment 6
(1) hollow HTS is mixed with silicon sol (dioxide-containing silica is 30 % by weight) and water, wherein, hollow HTS, taking the silicon sol of silicon-dioxide and the weight ratio of water as 1:0.05:0.5.By the mixture obtaining through spin granulation, and by the wet grain obtaining 550 DEG C of roastings 5 hours, thereby obtain the catalyzer that median size is 600 μ m.Wherein, in catalyzer, the content of HTS is 95 % by weight.
(2) catalyst loading of being prepared by step (1), in fixed-bed reactor, forms beds, and wherein, the quantity of beds is 1 layer.
By dimethyl thioether, Peracetic Acid and methanol mixed, form liquid mixture.In liquid mixture, add ammoniacal liquor (concentration is 25 % by weight), the pH value of liquid mixture is adjusted to 7.5.Then the beds contact reacts of, described liquid mixture being sent in fixed-bed reactor and being contained HTS.Wherein, in liquid mixture, the mol ratio of dimethyl thioether and Peracetic Acid is 1:0.5, and the weight ratio of dimethyl thioether and methyl alcohol is 1:5, and the weight hourly space velocity of liquid mixture is 10h
-1.Temperature in beds is 30 DEG C, and the pressure in fixed-bed reactor is 1.5MPa.
Reaction mixture reaction being started latter 0.5 hour and obtain for 150 hours carries out gas chromatographic analysis, and calculates transformation efficiency, the effective rate of utilization of oxygenant and the selectivity of dimethyl sulfoxide (DMSO) of dimethyl thioether.Result is listed in table 3.
Embodiment 7
Adopt the method identical with embodiment 6 to prepare dimethyl sulfoxide (DMSO), different, the pH value of liquid mixture is adjusted to 6.5.The selectivity of the transformation efficiency of the dimethyl thioether calculating, the effective rate of utilization of oxygenant and dimethyl sulfoxide (DMSO) is listed in table 3.
Embodiment 8
Adopt the method identical with embodiment 6 to prepare dimethyl sulfoxide (DMSO), different, not to use ammoniacal liquor to regulate the pH value of liquid mixture, but use the aqueous solution (concentration is 25 % by weight) of NaOH to regulate the pH value of liquid mixture.The selectivity of the transformation efficiency of the dimethyl thioether calculating, the effective rate of utilization of oxygenant and dimethyl sulfoxide (DMSO) is listed in table 3.
Embodiment 9
Adopt the method identical with embodiment 6 to prepare dimethyl sulfoxide (DMSO), different, the pH value of liquid mixture is adjusted to 8.5.The selectivity of the transformation efficiency of the dimethyl thioether calculating, the effective rate of utilization of oxygenant and dimethyl sulfoxide (DMSO) is listed in table 3.
Embodiment 10
Adopt the method identical with embodiment 6 to prepare dimethyl sulfoxide (DMSO), different, the pH value of liquid mixture is adjusted to 5.5.The selectivity of the transformation efficiency of the dimethyl thioether calculating, the effective rate of utilization of oxygenant and dimethyl sulfoxide (DMSO) is listed in table 3.
Comparative example 2
Adopt the method identical with embodiment 6 to prepare dimethyl sulfoxide (DMSO), different, omit the step that regulates the pH value of liquid mixture with ammoniacal liquor.The selectivity of the transformation efficiency of the dimethyl thioether calculating, the effective rate of utilization of oxygenant and dimethyl sulfoxide (DMSO) is listed in table 3.
Table 3
Embodiment 11
(1) hollow HTS is mixed with silicon sol (dioxide-containing silica is 30 % by weight) and water, wherein, hollow HTS, taking the silicon sol of silicon-dioxide and the weight ratio of water as 1:0.1:5.By the mixture obtaining through mist projection granulating, and by the wet grain obtaining 550 DEG C of roastings 5 hours, thereby obtain the catalyzer that median size is 80 μ m.Wherein, in catalyzer, the content of HTS is 90 % by weight.
(2) catalyst loading of being prepared by step (1), in fixed-bed reactor, forms beds, and wherein, the quantity of beds is 1 layer.
Dimethyl thioether, tertbutyl peroxide and acetonitrile are mixed, form liquid mixture.In liquid mixture, add ammoniacal liquor (concentration is 25 % by weight), the pH value of liquid mixture is adjusted to 7.5.Then the beds contact reacts of, described liquid mixture being sent in fixed-bed reactor and being contained HTS.Wherein, in liquid mixture, the mol ratio of dimethyl thioether and tertbutyl peroxide is 1:0.2, and the weight ratio of dimethyl thioether and acetonitrile is 1:2, and the weight hourly space velocity of liquid mixture is 10h
-1.Temperature in beds is 20 DEG C, and the pressure in fixed-bed reactor is 0.1MPa.
Reaction mixture reaction being started latter 0.5 hour and obtain for 150 hours carries out gas chromatographic analysis, and calculates transformation efficiency, the effective rate of utilization of oxygenant and the selectivity of dimethyl sulfoxide (DMSO) of dimethyl thioether.Result is listed in table 4.
Embodiment 12
(1) titanium-silicon molecular sieve TS-1 is mixed with silicon sol (dioxide-containing silica is 30 % by weight) and water, wherein, titanium-silicon molecular sieve TS-1, taking the silicon sol of silicon-dioxide and the weight ratio of water as 1:0.08:0.8.By the mixture obtaining through spin granulation, and by the wet grain obtaining 550 DEG C of roastings 5 hours, thereby obtain the catalyzer that median size is 400 μ m.Wherein, in catalyzer, the content of HTS is 92 % by weight.
(2) catalyst loading of being prepared by step (1), in fixed-bed reactor, forms beds, and wherein, the quantity of beds is 1 layer.
By dimethyl thioether, Perpropionic Acid and methanol mixed, form liquid mixture.In liquid mixture, add ammoniacal liquor (concentration is 25 % by weight), the pH value of liquid mixture is adjusted to 7.5.Then the beds contact reacts of, described liquid mixture being sent in fixed-bed reactor and being contained HTS.Wherein, in liquid mixture, the mol ratio of dimethyl thioether and Perpropionic Acid is 1:2, and the weight ratio of dimethyl thioether and methyl alcohol is 1:10, and the weight hourly space velocity of liquid mixture is 10h
-1.Temperature in beds is 30 DEG C, and the pressure in fixed-bed reactor is 2.5MPa.
Reaction mixture reaction being started latter 0.5 hour and obtain for 150 hours carries out gas chromatographic analysis, and calculates transformation efficiency, the effective rate of utilization of oxygenant and the selectivity of dimethyl sulfoxide (DMSO) of dimethyl thioether.Result is listed in table 1.
Comparative example 3
Adopt the method identical with embodiment 12 to prepare dimethyl sulfoxide (DMSO), different, omit the step that regulates the pH value of liquid mixture with ammoniacal liquor.The selectivity of the transformation efficiency of the dimethyl thioether calculating, the effective rate of utilization of oxygenant and dimethyl sulfoxide (DMSO) is listed in table 4.
Embodiment 13
Adopt the method identical with embodiment 12 to prepare dimethyl sulfoxide (DMSO), different, use the hollow HTS of equivalent to replace the titanium-silicon molecular sieve TS-1 in embodiment 12.The selectivity of the transformation efficiency of the dimethyl thioether calculating, the effective rate of utilization of oxygenant and dimethyl sulfoxide (DMSO) is listed in table 4.
Table 4
Embodiment 14
(1) hollow HTS is mixed with silicon sol (dioxide-containing silica is 30 % by weight) and water, wherein, hollow HTS, taking the silicon sol of silicon-dioxide and the weight ratio of water as 1:0.5:5.By the mixture obtaining through mist projection granulating, and by the wet grain obtaining 550 DEG C of roastings 5 hours, thereby obtain the catalyzer that median size is 100 μ m.Wherein, in catalyzer, the content of HTS is 45 % by weight.
(2) catalyst loading of being prepared by step (1), in fixed-bed reactor, forms beds, and wherein, the quantity of beds is 1 layer.
By dimethyl thioether, hydrogen peroxide and methanol mixed, form liquid mixture.In liquid mixture, add ammoniacal liquor (concentration is 25 % by weight), the pH value of liquid mixture is adjusted to 8.5.Then the beds contact reacts of, described liquid mixture being sent in fixed-bed reactor and being contained HTS.Wherein, in liquid mixture, the mol ratio of dimethyl thioether and hydrogen peroxide is 1:1, and the weight ratio of dimethyl thioether and methyl alcohol is 1:4, and the weight hourly space velocity of liquid mixture is 250h
-1.Temperature in beds is 40 DEG C, and the pressure in fixed-bed reactor is 0.8MPa.
Reaction mixture reaction being started latter 0.5 hour and obtain for 150 hours carries out gas chromatographic analysis, and calculates transformation efficiency, the effective rate of utilization of oxygenant and the selectivity of dimethyl sulfoxide (DMSO) of dimethyl thioether.Result is listed in table 5.
Embodiment 15
Adopt the method identical with embodiment 14 to prepare dimethyl sulfoxide (DMSO), different, the mol ratio of dimethyl thioether and oxygenant is 1:2.The selectivity of the transformation efficiency of the dimethyl thioether calculating, the effective rate of utilization of oxygenant and dimethyl sulfoxide (DMSO) is listed in table 5.
Embodiment 16
Adopt the method identical with embodiment 14 to prepare dimethyl sulfoxide (DMSO), different, the mol ratio of dimethyl thioether and oxygenant is 1:4.The selectivity of the transformation efficiency of the dimethyl thioether calculating, the effective rate of utilization of oxygenant and dimethyl sulfoxide (DMSO) is listed in table 5.
Comparative example 4
Adopt the method identical with embodiment 14 to prepare dimethyl sulfoxide (DMSO), different, omit the step that regulates the pH value of liquid mixture with ammoniacal liquor.The selectivity of the transformation efficiency of the dimethyl thioether calculating, the effective rate of utilization of oxygenant and dimethyl sulfoxide (DMSO) is listed in table 5.
Comparative example 5
Adopt the method identical with embodiment 15 to prepare dimethyl sulfoxide (DMSO), different, omit the step that regulates the pH value of liquid mixture with ammoniacal liquor.The selectivity of the transformation efficiency of the dimethyl thioether calculating, the effective rate of utilization of oxygenant and dimethyl sulfoxide (DMSO) is listed in table 5.
Comparative example 6
Adopt the method identical with embodiment 16 to prepare dimethyl sulfoxide (DMSO), different, omit the step that regulates the pH value of liquid mixture with ammoniacal liquor.The selectivity of the transformation efficiency of the dimethyl thioether calculating, the effective rate of utilization of oxygenant and dimethyl sulfoxide (DMSO) is listed in table 5.
Embodiment 17
Adopt the method identical with embodiment 14 to prepare dimethyl sulfoxide (DMSO), different, adopt following methods Kaolinite Preparation of Catalyst:
Under the condition of normal pressure (1 standard atmospheric pressure) and 40 DEG C, tetraethyl orthosilicate is joined in the TPAOH aqueous solution, stirring after 2 hours adds hollow HTS to continue to stir 1 hour, wherein, the mass ratio of hollow HTS, tetraethyl orthosilicate, TPAOH and water is 100:400:30:200.The mixture obtaining, after spin granulation, 550 DEG C of roastings 5 hours, is obtained to the catalyzer that median size is 60 μ m.Wherein, in catalyzer, the content of HTS is 30 % by weight.
The selectivity of the transformation efficiency of the dimethyl thioether calculating, the effective rate of utilization of oxygenant and dimethyl sulfoxide (DMSO) is listed in table 5.
Embodiment 18
Adopt the method identical with embodiment 16 to prepare dimethyl sulfoxide (DMSO), different, adopt the method Kaolinite Preparation of Catalyst identical with embodiment 17.The selectivity of the transformation efficiency of the dimethyl thioether calculating, the effective rate of utilization of oxygenant and dimethyl sulfoxide (DMSO) is listed in table 5.
Embodiment 19
Adopt the method identical with embodiment 16 to prepare dimethyl sulfoxide (DMSO), different, adopt titanium-silicon molecular sieve TS-1 to replace hollow HTS.The selectivity of the transformation efficiency of the dimethyl thioether calculating, the effective rate of utilization of oxygenant and dimethyl sulfoxide (DMSO) is listed in table 5.
Table 5
Embodiment 20
By even to dimethyl thioether, hydrogen peroxide and methanol mixed, and the pH value of mixture is adjusted to 7.5 with ammoniacal liquor.Said mixture and hollow HTS are sent in reactor, followed stirring, react 2 hours.The mixture obtaining is filtered to the hollow HTS being recycled and the liquid phase that contains dimethyl sulfoxide (DMSO).Wherein, reaction conditions comprises: the mol ratio of dimethyl thioether and hydrogen peroxide is 1:2, and the mass ratio of dimethyl thioether and hollow HTS is 1:1, and the mass ratio of dimethyl thioether and methyl alcohol is 1:5; Temperature in reactor is 60 DEG C, and pressure is 0.8MPa.
The hollow HTS reclaiming is proceeded to react with sending in reactor after dimethyl thioether, hydrogen peroxide and methanol mixed according to the method described above again next time.Wherein, HTS recycles 100 times.
In reaction process, detect the composition of the mixture of at every turn exporting from reactor, and calculate dimethyl thioether transformation efficiency, oxygenant effective rate of utilization and dimethyl sulfoxide (DMSO) selectivity.Wherein, the result of the 1st time and the 100th time is listed in table 6.
Comparative example 7
Adopt the method identical with embodiment 20 to prepare dimethyl sulfoxide (DMSO), different, omit the step that regulates the pH value of mixture with ammoniacal liquor.Transformation efficiency, the effective rate of utilization of oxygenant and the selectivity of dimethyl sulfoxide (DMSO) of the dimethyl thioether of calculate the 1st time and the 100th time are listed in table 6.
Table 6
Claims (11)
1. prepare the method for dimethyl sulfoxide (DMSO) for one kind, the method is included under oxidation reaction condition, a kind of liquid mixture is contacted with at least one HTS, obtain the mixture that contains dimethyl sulfoxide (DMSO), described liquid mixture contains dimethyl thioether and at least one superoxide, and the pH value of described liquid mixture is 5-9.
2. method according to claim 1, wherein, the pH value of described liquid mixture is 5.5-8.5.
3. method according to claim 1 and 2, wherein, regulates the pH value of described liquid mixture by add at least one basic cpd in described liquid mixture.
4. method according to claim 3, wherein, described basic cpd is selected from ammonia, quaternary ammonium hydroxide and M
1(OH)
n, M
1for basic metal or alkaline-earth metal, n is and M
1the identical integer of valency.
5. method according to claim 1, wherein, described HTS is the HTS with MFI structure.
6. method according to claim 5, wherein, the crystal grain of described HTS is hollow structure, the radical length of the cavity part 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 recording under the condition of 1 hour is at least 70 milligrams/grams, between the adsorption isothermal line of the nitrogen absorption under low temperature of this HTS and desorption isotherm, has hysteresis loop.
7. method according to claim 1, wherein, described superoxide is selected from hydrogen peroxide, hydroperoxide and peracid.
8. method according to claim 1, wherein, described superoxide is selected from hydrogen peroxide, tertbutyl peroxide, isopropyl benzene hydroperoxide, cyclohexyl hydroperoxide, Peracetic Acid and Perpropionic Acid.
9. method according to claim 1, wherein, described liquid mixture also contains at least one solvent, and the weight ratio of dimethyl thioether and described solvent is 1:0.1-20.
10. method according to claim 9, wherein, described solvent is selected from water, C
1-C
10alcohol, C
3-C
10ketone and C
2-C
10nitrile.
11. methods according to claim 1, wherein, the weight ratio of dimethyl thioether and described HTS is 0.1-50:1; The mol ratio of dimethyl thioether and described superoxide is 1:0.1-4; Described oxidation reaction condition comprises: temperature is 0-80 DEG C; In gauge pressure, pressure is 0-3MPa.
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| CN105439924A (en) * | 2014-09-29 | 2016-03-30 | 中国石油化工股份有限公司 | Preparation method of dimethyl sulfoxide |
| CN105985273A (en) * | 2015-03-06 | 2016-10-05 | 中国石油化工股份有限公司 | Method for preparing dimethyl sulfoxide |
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| Publication number | Priority date | Publication date | Assignee | Title |
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| CN105439924A (en) * | 2014-09-29 | 2016-03-30 | 中国石油化工股份有限公司 | Preparation method of dimethyl sulfoxide |
| CN105439924B (en) * | 2014-09-29 | 2017-06-30 | 中国石油化工股份有限公司 | A kind of preparation method of dimethyl sulfone |
| CN105985273A (en) * | 2015-03-06 | 2016-10-05 | 中国石油化工股份有限公司 | Method for preparing dimethyl sulfoxide |
| CN105985273B (en) * | 2015-03-06 | 2018-02-23 | 中国石油化工股份有限公司 | A kind of method for preparing dimethyl sulfoxide (DMSO) |
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