CN104557628A - Method for oxidizing dimethyl sulfide - Google Patents
Method for oxidizing dimethyl sulfide Download PDFInfo
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- CN104557628A CN104557628A CN201310520898.0A CN201310520898A CN104557628A CN 104557628 A CN104557628 A CN 104557628A CN 201310520898 A CN201310520898 A CN 201310520898A CN 104557628 A CN104557628 A CN 104557628A
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Abstract
The invention provides a method for oxidizing dimethyl sulfide. The method comprises the steps that dimethyl sulfide and at least one peroxide are contacted with a titanium silicate molecular sieve to obtain a mixture containing dimethyl sulfoxide, wherein the titanium silicate molecular sieve is filled in tubes of a tubular reactor to form a catalyst bed; and a cooling medium is delivered into the space among tubes in the contacting process so as to exchange heat with the tubes. According to the method, in the process of oxidizing dimethyl sulfide to prepare dimethyl sulfoxide, reacting heat released in the reacting process is transferred in time, so that the conversion rate of dimethyl sulfide and the selectivity of dimethyl sulfoxide can be improved, and the effective utilization rate of oxidant can be effectively improved.
Description
Technical field
The present invention relates to a kind of method of cacodyl oxide base thioether.
Background technology
Dimethyl sulfoxide (DMSO) (DMSO) is a kind of organic compounds containing sulfur, is colourless transparent liquid under normal temperature, 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, such as, as process solvent and the solvent that reels off raw silk from cocoons in acrylonitrile polymerization reaction, as synthetic and the solvent that reels off raw silk from cocoons of urethane, as the synthetic of polymeric amide, fluoroaluminate glasses, polyimide and polysulfones.Further, dimethyl sulfoxide (DMSO) has very high selective extraction method ability, can be used as the Extraction solvent that alkane is separated with aromatic hydrocarbon, such as: dimethyl sulfoxide (DMSO) can be used for the extracting of aromatic hydrocarbons or divinyl.Meanwhile, in medicine industry, dimethyl sulfoxide (DMSO) not only directly as raw material and the carrier of some drugs, and can also play the effects such as anti-inflammatory analgetic, diuresis and calmness, and 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 dimethyl thioether oxidation style to prepare, and 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 of peroxide oxidation method is gentle, and 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 large, adds the production cost of dimethyl sulfoxide (DMSO), limits the range of application of peroxide oxidation method.
Therefore, when adopting peroxide oxidation method to prepare dimethyl sulfoxide (DMSO), improve the selectivity of the effective rate of utilization of oxygenant, the transformation efficiency of dimethyl thioether and dimethyl sulfoxide (DMSO), the production cost reducing dimethyl sulfoxide (DMSO) is an important problem.
Summary of the invention
The object of the invention is to overcome existing using superoxide as oxygenant, the oxygenant effective rate of utilization existed during dimethyl thioether oxidation preparation dimethyl sulfoxide (DMSO) is awaited the problem improved further, a kind of method of cacodyl oxide base thioether is provided, the method can not only obtain high dimethyl thioether transformation efficiency and dimethyl sulfoxide (DMSO) selectivity, and can obtain high oxygenant effective rate of utilization.
The invention provides a kind of method of cacodyl oxide base thioether, the method comprises and being contacted with HTS with at least one superoxide by dimethyl thioether, obtain the mixture containing dimethyl sulfoxide (DMSO), wherein, described HTS is seated in the tubulation interior formation beds of shell and tube reactor, the method is also included in the process of carrying out described contact, sends into heat-eliminating medium to carry out heat exchange with described tubulation to the space between tubulation.
Dimethyl thioether is being oxidized to prepare in the process of dimethyl sulfoxide (DMSO) by method according to the present invention, the reaction heat discharged in reaction process is shifted out in time, the transformation efficiency of dimethyl thioether and the selectivity of dimethyl sulfoxide (DMSO) can not only be improved, and effectively can improve the effective rate of utilization of oxygenant.
Embodiment
The invention provides a kind of method of cacodyl oxide base thioether, the method comprises and being contacted with HTS with at least one oxygenant by dimethyl thioether, obtains the mixture containing dimethyl sulfoxide (DMSO).
Method according to the present invention is carried out in shell and tube reactor, wherein, beds is formed in the tubulation described HTS being seated in shell and tube reactor, and in the process of carrying out described contact, heat-eliminating medium is sent into carry out heat exchange with described pipeline to the space between tubulation, thus the heat discharged in reaction process is shifted out in time, can effectively prevent beds inside from occurring temperature runaway phenomenon, and effectively improve the effective rate of utilization of oxygenant, the transformation efficiency of dimethyl thioether and the selectivity of dimethyl sulfoxide (DMSO) can also be improved simultaneously.
Described shell and tube reactor can be common various shell and tube reactors.The present invention is also not particularly limited for the specification of described shell and tube reactor, can be conventional selection.Particularly, the internal diameter of the tubulation of described shell and tube reactor can be 0.5-6cm, is preferably 1-5cm.The filling ratio of tubulation in reactor can be 5-95 volume %, is preferably 10-90 volume %, is generally 50-85%.Described filling ratio refers to the percent value of the cubic capacity of the space that tubulation occupies and reactor inner space.
According to method of the present invention, in contact reacts process to the space (namely, the shell side of shell and tube reactor) between tubulation in send into heat-eliminating medium.The kind of described heat-eliminating medium and consumption can be selected according to concrete reaction conditions, the temperature of the beds being positioned at the tube side of tubulation can be controlled to be as the criterion at predetermined temperature range.Usually, the heat transfer boundary condition of described heat-eliminating medium and described tubulation makes the temperature in beds be in the scope of 0-80 DEG C, is preferably in the scope of 20-60 DEG C, be generally be in 30-50 DEG C scope in.Described heat-eliminating medium is the flowing material with thermal conductive property, is specifically as follows water, alcohol, silicone oil etc., from ready availability and cost angularly, is preferably water.
According to method of the present invention, described 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 0.0001-0.05, is preferably 0.01-0.03, is more preferably 0.015-0.025.
Described HTS can for the common HTS with various topological framework, such as: described HTS can for being 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, one or more in the HTS (as Ti-TUN) of TUN structure and the HTS (as Ti-ZSM-48) of other structure.
Preferably, described HTS be selected from the HTS of the HTS of MFI structure, the HTS of MEL structure and BEA structure one or more.More preferably, described HTS is the HTS of MFI structure, as TS-1 molecular sieve.
From the optionally angle improving the transformation efficiency of dimethyl thioether, the effective rate of utilization of oxygenant and dimethyl sulfoxide (DMSO) further, at least part of described HTS is the HTS of MFI structure, and the crystal grain of this HTS is hollow structure, 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.Herein, the HTS with this structure is called hollow HTS.Described hollow HTS can be commercially available (be such as purchased from the trade mark of Sinopec Hunan Jianchang Petrochemical Co., Ltd be the molecular sieve of HTS), also method can prepare disclosed in CN1132699C.
In employing HTS as in the various full scale plants of catalyzer, as Ammoximation reaction, in hydroxylating and epoxidation reaction device, usually after plant running for some time, the catalytic activity of catalyzer declines, need to carry out in device or ex-situ regeneration, even if when carry out regenerating also be difficult to obtain satisfied active time, catalyzer is needed to draw off (namely from device, more catalyst changeout), and the catalyzer drawn off (namely, drawing off agent or spent catalyst) current treatment process normally piles up and buries, occupy valuable land resources and inventory space on the one hand, HTS production cost is higher on the other hand, directly pass into disuse and also result in great waste.The present inventor finds in research process, if these are drawn off agent (namely, the HTS drawn off) carry out contacting under oxidation reaction condition with oxygenant with dimethyl thioether after regeneration, still higher dimethyl thioether transformation efficiency and dimethyl sulfoxide (DMSO) selectivity can be obtained, and higher oxygenant effective rate of utilization can be obtained, in tandem reaction sequence dimethyl thioether transformation efficiency and dimethyl sulfoxide (DMSO) selectivity more stable.Therefore, according to method of the present invention, at least part of described HTS be preferably through regeneration the reaction unit using HTS as catalyzer draw off agent.Described draw off agent can for from various use HTS as the agent that draws off drawn off the reaction unit of catalyzer, such as can for draw off from oxidation reaction apparatus draw off agent.Particularly, draw off described in agent be Ammoximation reaction device draw off agent, hydroxylating device draw off agent and epoxidation reaction device draw off in agent one or more.More specifically, draw off described in agent can for cyclohexanone oxamidinating reaction unit draw off agent, phenol hydroxylation reaction unit draw off agent and propylene ring oxidation reaction device draw off in agent one or more.
Being not particularly limited drawing off the condition that agent carries out regenerating, appropriate selection can being carried out according to the source drawing off agent, such as: high-temperature roasting and/or solvent wash.
The activity drawing off agent through regeneration is different according to its source.Usually, the activity drawing off agent through regeneration can be the 5-95% of the activity of this HTS when fresh (that is, the activity of fresh titanium si molecular sieves).Preferably, the activity drawing off agent through regeneration can be the 10-90% of the activity of this HTS when fresh, the 10-50% of the activity more preferably when fresh.When the activity drawing off agent through regeneration is the 10-50% of the activity of this HTS when fresh, gratifying dimethyl thioether transformation efficiency and dimethyl sulfoxide (DMSO) selectivity can not only be obtained, and the oxygenant effective rate of utilization improved further can be obtained.The activity of described fresh titanium si molecular sieves is generally more than 90%, is generally more than 95%.
Described activity measures by the following method: will draw off through regeneration the catalyzer that agent and fresh titanium si molecular sieves are used as cyclohexanone oxamidinating reaction respectively, the condition of this Ammoximation reaction is: HTS, 36 % by weight ammoniacal liquor (with NH
3meter), the hydrogen peroxide of 30 % by weight is (with H
2o
2meter), the trimethyl carbinol and pimelinketone 1:7.5:10:7.5:10 in mass ratio, at atmosheric pressure in 80 DEG C of reaction 2h.The transformation efficiency that to calculate with non-fresh HTS and fresh titanium si molecular sieves be respectively pimelinketone during catalyzer, and using it as the activity of non-fresh HTS and fresh titanium si molecular sieves, wherein, transformation efficiency=[molar weight of the pimelinketone of (molar weight of the molar weight-unreacted pimelinketone of the pimelinketone added)/add] × 100% of pimelinketone.
At least part of HTS be through regeneration reaction unit draw off agent time, with the total amount of described HTS for benchmark, the content that reaction unit through regeneration draws off agent is preferably more than 5 % by weight, the effect better improving oxygenant effective rate of utilization can not only be obtained like this, and reaction process is more steadily easy to control, also can obtain higher dimethyl thioether transformation efficiency and dimethyl sulfoxide (DMSO) selectivity simultaneously.According to method of the present invention, even if whole HTS is the reaction unit through regenerating draw off agent (namely, the content of non-fresh HTS is 100 % by weight) time, still can obtain gratifying dimethyl thioether transformation efficiency, oxygenant effective rate of utilization and dimethyl sulfoxide (DMSO) selectivity.
According to method of the present invention, in a preferred embodiment, described HTS is hollow HTS and titanium-silicon molecular sieve TS-1, and described hollow HTS and titanium-silicon molecular sieve TS-1 filling order in described reaction zone makes dimethyl thioether successively contact with titanium-silicon molecular sieve TS-1 with described hollow HTS.Like this can not only extending catalyst steady running time further, the selectivity of dimethyl sulfoxide (DMSO) and the effective rate of utilization of oxygenant can also be improved further simultaneously.
This preferred embodiment in, the mass ratio of described hollow HTS and described titanium-silicon molecular sieve TS-1 can be 1-10:1, be preferably 1-5:1.
According to method of the present invention, described HTS can be the former powder of HTS, also can be shaping HTS, is preferably shaping HTS.
Described shaping HTS generally comprises HTS and the carrier (namely binding agent) for HTS being bonded together.The content of the middle HTS of described shaping HTS can be conventional selection.Usually, with the total amount of described shaping HTS for benchmark, the content of described HTS can be 5-95 % by weight, is preferably 10-95 % by weight, is more preferably 40-95 % by weight (as 40-85 % by weight); The content of described carrier can be 5-95 % by weight, is preferably 5-90 % by weight, is more preferably 5-60 % by weight (as 15-60 % by weight).Carrier in described shaping HTS can be conventional selection, as aluminum oxide and/or silicon oxide.The granular size of described shaping HTS is also not particularly limited, and can carry out appropriate selection according to concrete shape.As described in shaping HTS be spherical time, the median size of described shaping HTS can be 4-5000 micron, be preferably 5-2000 micron, be more preferably 40-600 micron, be generally 50-200 micron.Described median size is the volume average particle size adopting laser particle analyzer to measure.Conventional various methods can be adopted to prepare described shaping HTS.
One of the present invention preferred embodiment in, the preparation method of described shaping HTS comprises: under hydrolysis reaction condition, the silicoorganic compound that at least one can be occurred hydrolysis reaction contact with water with at least one water-soluble alkali, mix contacting the mixture obtained with the former powder of HTS, and the mixture containing the former powder of HTS obtained successively is carried out shaping and roasting.According to the shaping HTS that this embodiment obtains, not only there is higher intensity, and higher dimethyl thioether transformation efficiency and dimethyl sulfoxide (DMSO) selectivity can be obtained.
This preferred embodiment in, the consumption of the former powder of described silicoorganic compound, water-soluble alkali and HTS is can be as the criterion shaping for former for HTS powder, and the consumption of water is as the criterion smoothly can make hydrolysis reaction.From improving further the crushing strength of catalyzer of final preparation and dimethyl thioether transformation efficiency and dimethyl sulfoxide (DMSO) optionally angle, the mass ratio of the former powder of described HTS, silicoorganic compound, water-soluble alkali and water is preferably 100:10-2000:2-40:50-2000, be more preferably 100:100-500:5-40:50-2000, more preferably 100:100-500:5-40:50-500.
Described silicoorganic compound are not particularly limited, and can have hydrolyzable organic group, and can form the compound of silicon oxide by hydrolysis-condensation reaction on various Siliciumatom.Particularly, described silicoorganic compound can be selected from the siloxanes shown in formula I,
In formula I, R
1, R
2, R
3and R
4be 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 n-propyl silicate, positive isopropyl silicate and the positive positive butyl ester of silicic acid.
Described water-soluble alkali can for the conventional various alkali that can be dissolved in water.Such as: described water-soluble alkali can be chemical formula M
1(OH)
mthe compound represented, wherein, M
1can be basic metal, alkaline-earth metal, NH
4 +or quaternary ammonium group (that is, NH
4 +in hydrogen atom by alkyl replace formed group, described alkyl is preferably C
1-C
20alkyl, C
3-C
20cycloalkyl or C
6-C
20aryl), m is and M
1the 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, butanediamine, monoethanolamine, diethanolamine and trolamine.
Preferably, described water-soluble alkali is synthesis of titanium silicon molecular sieve template, can obtain higher dimethyl thioether transformation efficiency, dimethyl sulfoxide (DMSO) selectivity and oxygenant effective rate of utilization like this.Described synthesis of titanium silicon molecular sieve template can be the various compounds being used as template when synthesis of titanium silicon molecular sieve, as quaternary ammonium hydroxide and/or organic amine, is preferably quaternary ammonium hydroxide.Described quaternary ammonium hydroxide can be conventional selection, such as, can be the compound shown in formula II:
In formula II, R
5, R
6, R
7and R
8be 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
5, R
6, R
7and R
8be C separately
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
5, R
6, R
7and R
8be C separately
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-ethylcyclohexyl, 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 be as the criterion completely 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, the forming composition obtained is carried out condition that is dry and roasting and is also not particularly limited by the mixture forming containing HTS obtained, and can be the routine selection of this area.
Particularly, described shaping mode can be extrusion, spraying, round as a ball, compressing tablet or their combination.Described shaping catalyzer can have common different shape, such as, can be spherical, bar shaped, annular, cloverleaf pattern, honeycombed or butterfly etc., preferably spherical.
Under the normal condition of this area, forming composition can be carried out drying, such as can be dry by described forming composition at the temperature of 80-250 DEG C, under the condition of normal pressure or decompression.
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 such as air atmosphere or oxygen atmosphere.
According to method of the present invention, the consumption of described HTS is as the criterion can realize catalysis.Usually, the weight hourly space velocity of dimethyl thioether can be 0.1-500h
-1, be preferably 5-300h
-1(as 5-100h
-1).
According to method of the present invention, the tubulation of shell and tube reactor can also load filler further, and filling filler can adjust the amount of catalyzer in beds, thus regulates the treatment capacity of speed of response and reactor.The content of described filler can carry out appropriate selection according to the treatment capacity of the speed of response of expection and reactor, is as the criterion can meet concrete service requirements.Usually, in described beds, the content of filler can be 5-70 % by weight, is preferably 30-70 % by weight, is more preferably 30-50 % by weight.
The present invention is not particularly limited for the kind of described filler, for conventional various fillers, such as, can be selected from Raschig ring, Pall ring, cascade ring, arc saddle, square saddle and metal ring Intalox saddle.The specific examples of described filler can be θ ring and/or β ring.
When described beds is also filled with filler, can described filler and described catalyzer be seated in fixed-bed reactor with the form of the mixture of the two; Also can the beds formed by catalyzer and the packing layer interval formed by filler be seated in the tubulation of shell and tube reactor; The combination of above-mentioned two kinds of modes can also be adopted.
According to method of the present invention, described superoxide refers to the compound containing-O-O-key in molecular structure, 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 obtained.Described peracid refers to the organic oxacid containing-O-O-key in molecular structure.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 reduce separation costs further like this.The hydrogen peroxide existed in a variety of manners that described hydrogen peroxide can be commonly used for this area.
From the angle improved further according to the security of method of the present invention, preferably use the hydrogen peroxide existed as an aqueous solution according to method of the present invention.According to method of the present invention, when described hydrogen peroxide provides as an aqueous solution, the concentration of described aqueous hydrogen peroxide solution can be the normal concentration of this area, such as: 20-80 % by weight.The aqueous solution that concentration meets the hydrogen peroxide of above-mentioned requirements can adopt ordinary method to prepare, and also can be commercially available, such as: can for can be commercially available the hydrogen peroxide of 30 % by weight, the hydrogen peroxide of 50 % by weight or 70 % by weight hydrogen peroxide.
The mol ratio of described dimethyl thioether and described superoxide can be 1:0.2-2.Preferably, the mol ratio of described dimethyl thioether and described superoxide is 1:1-1.5.
According to method of the present invention, described contact is preferably carried out in the presence of at least one solvent.Described solvent can either dissolve dimethyl thioether and superoxide or mixing both promoting 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.
The consumption of described solvent can carry out appropriate selection according to the consumption of dimethyl thioether and superoxide.Preferably, the mass ratio of dimethyl thioether and described solvent is 1:0.1-20.More preferably, the mass ratio of dimethyl thioether and described solvent is 1:1-10.
According to method of the present invention, in a preferred embodiment, the mixture contacted with described HTS contains dimethyl thioether, as the superoxide of oxygenant and optional solvent, method of the present invention preferably adds at least one alkaline matter to by this mixture, the interpolation of described alkaline matter even makes the pH of this mixture be 5-9, can improve the effective rate of utilization of oxygenant, dimethyl thioether transformation efficiency and dimethyl sulfoxide (DMSO) selectivity so further.Further, making pH value be that the mixture of 5-9 contacts with HTS by adding alkaline matter, even if operate 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 improving the effective rate of utilization of oxygenant, the transformation efficiency of dimethyl thioether and dimethyl sulfoxide (DMSO) further, the addition of described alkaline matter makes the pH value of the mixture contacted with described HTS be 6-8.Described pH value measures under the condition of the temperature of 25 DEG C and 1 standard atmospheric pressure.
Herein, described alkaline matter refer to the pH value of its aqueous solution be greater than 7 material.The specific examples of described alkaline matter can include but not limited to: ammonia (that is, NH
3), amine, quaternary ammonium hydroxide and M
2(OH)
n(wherein, M
2for basic metal or alkaline-earth metal, n is and M
2the identical integer of valency).
As described alkaline matter, ammonia can be introduced with the form of liquefied ammonia, also can introduce in form of an aqueous solutions, can also introduce with the form of gas.Concentration as the ammonia (that is, ammoniacal liquor) of aqueous solution form is not particularly limited, and can be conventional selection, such as 1-36 % by weight.
As described alkaline matter, amine refers to hydrogen partial on ammonia or is all replaced the material formed by alkyl, comprises primary amine, secondary amine and tertiary amine.Described amine is specifically as follows the material shown in formula III and/or C
3-C
11heterocyclic amine,
In formula III, R
9, R
10and R
11can be H or C separately
1-C
6alkyl (as C
1-C
6alkyl), and R
9, R
10and R
11be asynchronously 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 compound finger ring having nitrogen-atoms and this nitrogen-atoms has lone-pair electron.Described heterocyclic amine can be such as one or more in substituted or unsubstituted pyrroles, substituted or unsubstituted Pyrrolidine, substituted or unsubstituted pyridine, substituted or unsubstituted hexahydropyridine, substituted or unsubstituted imidazoles, substituted or unsubstituted pyrazoles, substituted or unsubstituted quinoline, substituted or unsubstituted dihydroquinoline, substituted or unsubstituted tetrahydroquinoline, substituted or unsubstituted decahydroquinoline, substituted or unsubstituted isoquinoline 99.9 and replacement and unsubstituted pyrimidine.
As described alkaline matter, quaternary ammonium hydroxide is specifically as follows the material shown in formula IV,
In formula IV, R
12, R
13, R
14and R
15can 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 and 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
2(OH)
nfor the oxyhydroxide of alkali-metal oxyhydroxide or alkaline-earth metal, such as, can be sodium hydroxide, potassium hydroxide, magnesium hydroxide, hydrated barta and calcium hydroxide.
According to method of the present invention, described alkaline matter can directly add in the tubulation of reactor, adds in the tubulation of reactor after also described alkaline matter can being mixed with solution.
According to method of the present invention, when being contacted with HTS with oxygenant by dimethyl thioether, the pressure in tubulation can be conventional selection.Usually, the pressure in described tubulation can be 0-3MPa, and be preferably 0.1-1.5MPa, described pressure is in gauge pressure.
The present invention is described in detail below in conjunction with embodiment and comparative example.The invention will be further described for following embodiment, but therefore do not limit the scope of the invention.
In following examples and comparative example, if not otherwise specified, used reagent is commercially available 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, the 1992,12nd volume, prepared by the method described in 943-950 page, and its titanium oxide content is 2.5 % by weight; Hollow HTS used is according to the preparation of method disclosed in CN1132699C, 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, the anti-crushing power of shaping catalyzer, according to the method specified in HG/T2783-1996, is the upper mensuration of common compact detector for strength of particles (purchased from Jiangsu Jiangyan City Guo Rui analytical instrument factory) of KD-3 in model.
In following examples 6,7 and 12, adopt the activity of following methods determination HTS:
By HTS, 36 % by weight ammoniacal liquor (with NH
3meter), the hydrogen peroxide of 30 % by weight is (with H
2o
2meter), the trimethyl carbinol and pimelinketone in mass ratio=1:7.5:10:7.5:10 mixing after at atmosheric pressure in 80 DEG C of stirring reactions after 2 hours, reactant is filtered, by gas-chromatography, liquid phase is analyzed, adopt the transformation efficiency of following formulae discovery pimelinketone and it can be used as the activity of HTS
The transformation efficiency of pimelinketone=[molar weight of the pimelinketone of (molar weight-unreacted pimelinketone molar weight of the pimelinketone added)/add] × 100%.
In following examples and comparative example, adopt gas-chromatography to analyze the content of each composition in the reaction solution obtained, adopt following formula to calculate dimethyl thioether transformation efficiency, oxygenant effective rate of utilization and dimethyl sulfoxide (DMSO) selectivity on this basis respectively.
X
thioether=[(m
o thioether-m
thioether)/m
o thioether] × 100% (formula V)
In formula V, X
thioetherrepresent the transformation efficiency of dimethyl thioether;
M
o thioetherrepresent the quality of the dimethyl thioether added;
M
thioetherrepresent the quality of unreacted dimethyl thioether.
S
sulfoxide=[n
sulfoxide/ (n
o thioether-n
thioether)] × 100% (formula VI)
In formula VI, S
sulfoxiderepresent the selectivity of dimethyl sulfoxide (DMSO);
N
o thioetherrepresent the molar weight of the dimethyl thioether added;
N
thioetherrepresent the molar weight of unreacted dimethyl thioether;
N
sulfoxiderepresent the molar weight of the dimethyl sulfoxide (DMSO) that reaction generates.
U
oxygenant=[n
sulfoxide/ (n
o oxygenant-n
oxygenant)] × 100% (formula VII)
In formula VII, U
oxygenantrepresent the effective rate of utilization of oxygenant;
N
o oxygenantrepresent the molar weight of the oxygenant added;
N
oxygenantrepresent the molar weight of unreacted oxygenant;
N
sulfoxiderepresent the molar weight of the dimethyl sulfoxide (DMSO) that reaction generates.
Embodiment 1-14 is for illustration of method of the present 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, in the mass ratio of the silicon sol of silicon-dioxide and water (comprising the water in silicon sol) for 1:0.2:1.5.By the mixture that obtains through spin granulation, and by the wet grain that obtains 550 DEG C of roastings 5 hours, thus obtain the shaping HTS (anti-crushing power is 81N) that volume average particle size is 200 μm.Wherein, in shaping HTS, the content of HTS is 80 % by weight.
(2) shaping HTS prepared by step (1) be seated in the tubulation (internal diameter of tubulation is 2cm, and the quantity of tubulation is 21, and the filling ratio of tubulation is 50%) of shell and tube reactor, height of formation is the beds of 1.5 meters.
Using dimethyl thioether, the hydrogen peroxide as oxygenant and the methanol mixed as solvent, form liquid mixture.Then, described liquid mixture is sent into the beds contact reacts in the tubulation of shell and tube reactor and containing HTS.Wherein, in liquid mixture, the mol ratio of dimethyl thioether and oxygenant is 1:1, and the mass ratio of dimethyl thioether and solvent is 1:5, and the weight hourly space velocity of liquid mixture (in dimethyl thioether) is 100h
-1, the pressure in tubulation is 0.5MPa.In reaction process, in the shell side of reactor, send into water coolant, make the temperature in beds remain 30 DEG C.
Reaction is proceeded to 0.5 hour and the 100 little reaction mixtures obtained constantly carry out gas chromatographic analysis, and calculates the selectivity of the transformation efficiency of dimethyl thioether, the effective rate of utilization of oxygenant and dimethyl sulfoxide (DMSO).Result is listed in Table 1.
Embodiment 2
The method identical with embodiment 1 is adopted to be oxidized by dimethyl thioether, unlike, in step (1), replace titanium-silicon molecular sieve TS-1 by the hollow HTS of equivalent.Obtain the shaping HTS (anti-crushing power is 85N) that volume average particle size is 200 μm.Wherein, in shaping HTS, the content of hollow HTS is 80 % by weight.
Reaction is proceeded to 0.5 hour and the 100 little reaction mixtures obtained constantly carry out gas chromatographic analysis, and calculates the selectivity of the transformation efficiency of dimethyl thioether, the effective rate of utilization of oxygenant and dimethyl sulfoxide (DMSO).Result is listed in Table 1.
Embodiment 3
The method identical with embodiment 1 is adopted to be oxidized by dimethyl thioether, unlike, step (1) adopts following methods to prepare shaping HTS:
Under the condition of normal pressure (1 standard atmospheric pressure) and 30 DEG C, tetraethyl orthosilicate is joined in the TPAOH aqueous solution, stir after 2 hours and add hollow HTS continuation stirring 2 hours, wherein, the mass ratio of hollow HTS, tetraethyl orthosilicate, TPAOH and water is 100:130:20:250.By the mixture that obtains after spin granulation, 550 DEG C of roastings 5 hours, obtain the shaping HTS (anti-crushing power is 92N) that median size is 200 μm.Wherein, in shaping HTS, the content of HTS is 80 % by weight.
Reaction is proceeded to 0.5 hour and the 100 little reaction mixtures obtained constantly carry out gas chromatographic analysis, and calculates the selectivity of the transformation efficiency of dimethyl thioether, the effective rate of utilization of oxygenant and dimethyl sulfoxide (DMSO).Result is listed in Table 1.
Embodiment 4
The method identical with embodiment 1 is adopted to be oxidized by dimethyl thioether, unlike, in step (2), when obtaining liq mixture, also use ammoniacal liquor (concentration is 25 % by weight), it is 5.8 that the consumption of ammoniacal liquor makes the pH value of the liquid mixture finally obtained be the pH value that 6.0(does not add the liquid mixture of ammoniacal liquor).Reaction is proceeded to 0.5 hour and the 100 little reaction mixtures obtained constantly carry out gas chromatographic analysis, and calculates the selectivity of the transformation efficiency of dimethyl thioether, the effective rate of utilization of oxygenant and dimethyl sulfoxide (DMSO).Result is listed in Table 1.
Embodiment 5
The method identical with embodiment 1 is adopted to be oxidized by dimethyl thioether, unlike, in step (2), when obtaining liq mixture, also use ammoniacal liquor (concentration is 25 % by weight), the consumption of ammoniacal liquor makes the pH value of the liquid mixture finally obtained be 6.5.Reaction is proceeded to 0.5 hour and the 100 little reaction mixtures obtained constantly carry out gas chromatographic analysis, and calculates the selectivity of the transformation efficiency of dimethyl thioether, the effective rate of utilization of oxygenant and dimethyl sulfoxide (DMSO).Result is listed in Table 1.
Embodiment 6
The method identical with embodiment 1 is adopted to be oxidized by dimethyl thioether, unlike, in step (1), do not use titanium-silicon molecular sieve TS-1, but the regenerator using being carried out regenerating by the titanium-silicon molecular sieve TS-1 drawn off from cyclohexanone oxamidinating reaction process of equivalent and obtain, wherein, regeneration condition be at 550 DEG C in air atmosphere roasting 4h, the volume average particle size of this regenerator is 200 μm, the activity of this regenerator is 40%, its activity when fresh is 95%, the carrier of this regenerator is silicon-dioxide, in this regenerator, the content of titanium-silicon molecular sieve TS-1 is 80 % by weight.
Reaction is proceeded to 0.5 hour and the 100 little reaction mixtures obtained constantly carry out gas chromatographic analysis, and calculates the selectivity of the transformation efficiency of dimethyl thioether, the effective rate of utilization of oxygenant and dimethyl sulfoxide (DMSO).Result is listed in Table 1.
Embodiment 7
The method identical with embodiment 2 is adopted to be oxidized by dimethyl thioether, unlike, in step (1), do not use hollow HTS, but the regenerator using the hollow HTS drawn off from propylene ring oxidation reaction device being carried out regenerating of equivalent and obtain, wherein, regeneration condition be at 550 DEG C in air atmosphere roasting 4h, the activity of this catalyzer is 36%, its activity when fresh is 95%, the volume average particle size of this regenerator is 200 μm, and the carrier of this regenerator is silicon-dioxide, and the content of hollow HTS is 79 % by weight.
Reaction is proceeded to 0.5 hour and the 100 little reaction mixtures obtained constantly carry out gas chromatographic analysis, and calculates the selectivity of the transformation efficiency of dimethyl thioether, the effective rate of utilization of oxygenant and dimethyl sulfoxide (DMSO).Result is listed in Table 1.
Embodiment 8
The method identical with embodiment 1 is adopted to be oxidized by dimethyl thioether, unlike, in step (2), under the condition that the loadings of shaping HTS is constant in every root tubulation, in tubulation, first load shaping HTS prepared by embodiment 2, shaping HTS prepared by embodiment of recharging 1, wherein, the mass ratio of shaping HTS prepared by embodiment 2 and shaping HTS prepared by embodiment 1 is 1:1.Reaction is proceeded to 0.5 hour and the 100 little reaction mixtures obtained constantly carry out gas chromatographic analysis, and calculates the selectivity of the transformation efficiency of dimethyl thioether, the effective rate of utilization of oxygenant and dimethyl sulfoxide (DMSO).Result is listed in Table 1.
Table 1
Embodiment 9
(1) under the condition of normal pressure (1 standard atmospheric pressure) and 40 DEG C, tetraethyl orthosilicate is joined in the TPAOH aqueous solution, stir after 2 hours and add hollow HTS continuation stirring 1 hour, wherein, the mass ratio of hollow HTS, tetraethyl orthosilicate, TPAOH and water is 100:400:30:200.By the mixture that obtains after spin granulation, 550 DEG C of roastings 5 hours, obtain the shaping HTS (resistant to breakage power is 112N) that median size is 60 μm.Wherein, in this shaping HTS, the content of HTS is 40 % by weight.
(2) shaping HTS prepared by step (1) be seated in the tubulation (internal diameter of tubulation is 5cm, and the quantity of tubulation is 16, and the filling ratio of tubulation is 75%) of shell and tube reactor, height of formation is the beds of 2 meters.
Dimethyl thioether, the Perpropionic Acid as oxygenant and the water as solvent are mixed, forms liquid mixture.Then, in this liquid mixture, add pyridine, make the pH value of this liquid mixture be 7.0.Then, described liquid mixture is sent into the beds contact reacts in the tubulation of shell and tube reactor and containing HTS.Wherein, in liquid mixture, the mol ratio of dimethyl thioether and oxygenant is 1:0.5, and the mass ratio of dimethyl thioether and solvent is 1:1, and the weight hourly space velocity of liquid mixture (in dimethyl thioether) is 10.0h
-1, the pressure in tubulation is 1.5MPa.In reaction process, in the shell side of reactor, send into water coolant, make the temperature in beds remain 45 DEG C.
Reaction is proceeded to 0.5 hour and the 100 little reaction mixtures obtained constantly carry out gas chromatographic analysis, and calculates the selectivity of the transformation efficiency of dimethyl thioether, the effective rate of utilization of oxygenant and dimethyl sulfoxide (DMSO).Result is listed in table 2.
Embodiment 10
(1) hollow HTS is mixed with silicon sol (dioxide-containing silica is 30 % by weight) and water, wherein, hollow HTS, in the mass ratio of the silicon sol of silicon-dioxide and water for 1:0.5:5.By the mixture that obtains through mist projection granulating, and by the wet grain that obtains 550 DEG C of roastings 5 hours, thus obtain the shaping HTS (resistant to breakage power is 107N) that median size is 100 μm.Wherein, in this shaping HTS, the content of HTS is 65 % by weight.
(2) shaping HTS prepared by step (1) be seated in the tubulation (internal diameter of tubulation is 1cm, and the quantity of tubulation is 108, and the filling ratio of tubulation is 83%) of shell and tube reactor, height of formation is the beds of 1.2 meters.
Dimethyl thioether, the tertbutyl peroxide as oxygenant and the acetone as solvent are mixed, forms liquid mixture.Then, in this liquid mixture, add sodium hydroxide, make the pH value of this liquid mixture be 8.0.Then, described liquid mixture is sent into the beds contact reacts in the tubulation of shell and tube reactor and containing HTS.Wherein, in liquid mixture, the mol ratio of dimethyl thioether and oxygenant is 1:1.5, and the mass ratio of dimethyl thioether and solvent is 1:5, and the weight hourly space velocity of liquid mixture (in dimethyl thioether) is 5.0h
-1, the pressure in tubulation is 1.0MPa.In reaction process, in the shell side of reactor, send into water coolant, make the temperature in beds remain 35 DEG C.
Reaction is proceeded to 0.5 hour and the 100 little reaction mixtures obtained constantly carry out gas chromatographic analysis, and calculates the selectivity of the transformation efficiency of dimethyl thioether, the effective rate of utilization of oxygenant and dimethyl sulfoxide (DMSO).Result is listed in table 2.
Embodiment 11
The method identical with embodiment 10 is adopted to be oxidized by dimethyl thioether, unlike, in step (2), the consumption of sodium hydroxide makes the pH value of liquid mixture be 9.0.
Reaction is proceeded to 0.5 hour and the 100 little reaction mixtures obtained constantly carry out gas chromatographic analysis, and calculates the selectivity of the transformation efficiency of dimethyl thioether, the effective rate of utilization of oxygenant and dimethyl sulfoxide (DMSO).Result is listed in table 2.
Embodiment 12
The method identical with embodiment 10 is adopted to be oxidized by dimethyl thioether, unlike, step (1) does not use hollow HTS, but the regenerator obtained with equivalent the hollow HTS drawn off from cyclohexanone oxamidinating reaction process is carried out regenerating, wherein, regeneration condition be at 550 DEG C in air atmosphere roasting 4h, the activity of this regenerator is 9.5%, and its activity when fresh is 95%.The volume average particle size of this regenerator is 106 μm, and the carrier of this regenerator is silicon-dioxide, and the hollow HTS content in this regenerator is 65 % by weight.
Reaction is proceeded to 0.5 hour and the 100 little reaction mixtures obtained constantly carry out gas chromatographic analysis, and calculates the selectivity of the transformation efficiency of dimethyl thioether, the effective rate of utilization of oxygenant and dimethyl sulfoxide (DMSO).Result is listed in table 2.
Embodiment 13
The method identical with embodiment 10 is adopted to be oxidized by dimethyl thioether, unlike, the titanium-silicon molecular sieve TS-1 of step (1) middle equivalent replaces hollow HTS, thus prepares shaping HTS (resistant to breakage power is 99N).
Reaction is proceeded to 0.5 hour and the 100 little reaction mixtures obtained constantly carry out gas chromatographic analysis, and calculates the selectivity of the transformation efficiency of dimethyl thioether, the effective rate of utilization of oxygenant and dimethyl sulfoxide (DMSO).Result is listed in table 2.
Embodiment 14
The method identical with embodiment 10 is adopted to be oxidized by dimethyl thioether, unlike, in step (2), under the condition that the loadings of shaping HTS is constant in every root tubulation, in tubulation, first load shaping HTS prepared by embodiment 10, shaping HTS prepared by embodiment of recharging 13, wherein, the weight of shaping HTS prepared by embodiment 10 and shaping HTS prepared by embodiment 13 is 5:1.
Reaction is proceeded to 0.5 hour and the 100 little reaction mixtures obtained constantly carry out gas chromatographic analysis, and calculates the selectivity of the transformation efficiency of dimethyl thioether, the effective rate of utilization of oxygenant and dimethyl sulfoxide (DMSO).Result is listed in table 2.
Table 2
Claims (14)
1. the method for a cacodyl oxide base thioether, the method comprises and being contacted with HTS with at least one superoxide by dimethyl thioether, obtain the mixture containing dimethyl sulfoxide (DMSO), wherein, described HTS is seated in the tubulation interior formation beds of shell and tube reactor, the method is also included in the process of carrying out described contact, sends into heat-eliminating medium to carry out heat exchange with described tubulation to the space between tubulation.
2. method according to claim 1, wherein, the condition of described heat exchange makes the temperature of the beds in tubulation be in the scope of 0-80 DEG C.
3. method according to claim 1, wherein, at least part of described HTS be through regeneration the reaction unit using HTS as catalyzer draw off agent.
4. method according to claim 3, wherein, described in draw off agent be Ammoximation reaction device draw off agent, hydroxylating device draw off agent and epoxidation reaction device draw off in agent one or more.
5. method according to claim 1, wherein, the method also comprises adds at least one alkaline matter in the mixture contacted with described HTS, and the addition of described alkaline matter makes the pH value of this mixture be 5-9.
6. according to the method in claim 1 and 3-5 described in any one, wherein, described HTS is the HTS with MFI structure.
7. method according to claim 6, wherein, at least part of described HTS is hollow HTS, and the crystal grain of described hollow HTS is hollow structure, the radical length of the chamber portion of this hollow structure is 5-300nm, and described HTS is at 25 DEG C, P/P
0=0.10, adsorption time is the benzene adsorptive capacity that records under the condition of 1h is at least 70mg/g, there is hysteresis loop between the adsorption isothermal line of the nitrogen absorption under low temperature of this HTS and desorption isotherm.
8. method according to claim 7, wherein, described catalyzer is hollow HTS and titanium-silicon molecular sieve TS-1, and described hollow HTS and titanium-silicon molecular sieve TS-1 filling order in described pipeline makes dimethyl thioether successively contact with titanium-silicon molecular sieve TS-1 with described hollow HTS.
9. method according to claim 8, wherein, the mass ratio of described hollow HTS and described titanium-silicon molecular sieve TS-1 is 1-10:1.
10. according to the method in claim 1 and 3-5 described in any one, wherein, described HTS is shaping HTS.
11. methods according to claim 1 or 5, wherein, described contact is carried out in the presence of at least one solvent, and the mass ratio of dimethyl thioether and described solvent is 1:0.1-20.
12. methods according to claim 11, wherein, described solvent is selected from water, C
1-C
10alcohol, C
3-C
10ketone and C
2-C
10nitrile.
13. methods according to claim 1, wherein, the mol ratio of described dimethyl thioether and described superoxide is 1:0.2-2.
14. methods according to claim 1, wherein, the weight hourly space velocity of described dimethyl thioether is 0.1-500h
-1.
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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 |
| 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) |
| CN114805145A (en) * | 2022-04-22 | 2022-07-29 | 新疆广汇陆友硫化工有限公司 | Device and method for preparing dimethyl sulfoxide by oxidizing dimethyl sulfide with hydrogen peroxide |
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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 |
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| CN114805145A (en) * | 2022-04-22 | 2022-07-29 | 新疆广汇陆友硫化工有限公司 | Device and method for preparing dimethyl sulfoxide by oxidizing dimethyl sulfide with hydrogen peroxide |
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