CN105523974A - Preparation method for dimethyl sulfone - Google Patents
Preparation method for dimethyl sulfone Download PDFInfo
- Publication number
- CN105523974A CN105523974A CN201410513984.3A CN201410513984A CN105523974A CN 105523974 A CN105523974 A CN 105523974A CN 201410513984 A CN201410513984 A CN 201410513984A CN 105523974 A CN105523974 A CN 105523974A
- Authority
- CN
- China
- Prior art keywords
- hts
- acid
- liquid mixture
- dimethyl
- weight
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Granted
Links
Landscapes
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
Abstract
The invention provides a preparation method for dimethyl sulfone. The method comprises the step of subjecting a liquid mixture to passing through a catalyst bed filled with at least one titanium-silicon molecular sieve in a fixed bed reactor under the condition of oxidation reaction so as to obtain a mixture containing dimethyl sulfone, wherein the liquid mixture comprises dimethyl sulfide and at least one peroxide; and the mol ratio of the peroxide to the dimethyl sulfide is more than 2: 1. According to the invention, with peroxide as an oxidant, the method has low corrosiveness to equipment, releases few environmental pollutants, can obtain high conversion rate of dimethyl sulfide and selectivity of dimethyl sulfone, and has high effective utilization rate of the oxidant at the same time.
Description
Technical field
The present invention relates to a kind of preparation method of dimethyl sulfone.
Background technology
Dimethyl sulfone is white crystalline powder, and soluble in water, ethanol, benzene, methyl alcohol and acetone, be slightly soluble in ether.Can not make potassium permanganate variable color under normal temperature, dimethyl sulfone can be oxidized to methylsulfonic acid by strong oxidizer.The dimethyl sulfone aqueous solution is in neutral.25 DEG C of microsublimations, accelerate to 60 DEG C of rate of sublimation, thus dimethyl sulfone product should carry out drying under cryogenic vacuum.
Dimethyl sulfone is used as organic synthesis high-temperature solvent and raw material, GC stationary liquid, analytical reagent, foodstuff additive and medicine in the industry.Dimethyl sulfone, as a kind of organic sulfide, has and strengthens the ability that human body produces Regular Insulin, also have promoter action simultaneously to the metabolism of carbohydrate, is the necessary material of human collagen albumen synthesis.Dimethyl sulfone can promote wound healing, also can work to the synthesis of the vitamins B needed for metabolism and neurological health, vitamins C, vitamin H and activation, be called as " naturally beautifying carbon species ".All dimethyl sulfone is contained in the skin of human body, hair, nail, bone, muscle and each organ, dimethyl sulfone is mainly present in ocean and soil at occurring in nature, absorbed as nutritive substance in plant-growth, the mankind can absorb from the foods such as veterinary antibiotics, fish, meat, egg, milk, health disorders will be caused once lack or disease occurs, it is the essential substance that human body maintains biological element sulphur balance, having therapeutic value and nourishing function to human body diseases, is the indispensable medicine of human survival and health care.Abroad dimethyl sulfone widely applied as the nutritious prod of equal importance with VITAMIN, the applied research of China to dimethyl sulfone is carried out not yet very well, and current product is mainly used in outlet.Therefore, dimethyl sulfone is not only a kind of new high-tech product, is also a kind of fine chemical product of high added value.Product is new, market potential is large, and benefit is given prominence to, and has wide production and application and development prospect.
At present, the product that dimethyl sulfone is oxidized further as dimethyl sulfoxide (DMSO) is the principal by product that dimethyl sulfoxide (DMSO) is produced.
In addition, dimethyl sulfone can also directly be obtained through nitric acid oxidation by dimethyl sulfoxide (DMSO).Concrete, can by dimethyl sulfoxide (DMSO) at 140-145 DEG C with nitric acid oxidation, cool after reaction terminates, filtration, obtains the crude product of white, needle-shaped crystals.Again through underpressure distillation, collect 138-145 DEG C of (98.42kPa) cut and be finished product.But the dimethyl sulfone yield of the method needs to improve further; Further, the method adopts nitric acid as oxygenant, and to the seriously corroded of equipment, release simultaneously contains waste gas and the acid-bearing wastewater of nitrogen peroxide, is unfavorable for environment protection.
Summary of the invention
The object of the present invention is to provide a kind of preparation method of new dimethyl sulfone, the method is using superoxide as oxygenant, little to the extent of corrosion of equipment, the waste gas waste water of generation is few, and can obtain high dimethyl thioether transformation efficiency, oxygenant effective rate of utilization and dimethyl sulfone selectivity.
The invention provides a kind of preparation method of dimethyl sulfone, under the method is included in oxidation reaction condition, in fixed-bed reactor, make a kind of liquid mixture by being filled with the beds of at least one HTS, obtain the mixture containing dimethyl sulfone, described liquid mixture contains dimethyl thioether and at least one superoxide, and the mol ratio of described superoxide and described dimethyl thioether is for being greater than 2:1.
Method of the present invention is using superoxide as oxygenant, with employing nitric acid as compared with oxygenant, low to the extent of corrosion of equipment, and the environmental pollutant of release are few.The more important thing is, method of the present invention can obtain high dimethyl thioether transformation efficiency and dimethyl sulfone selectivity, also has higher oxygenant effective rate of utilization simultaneously.
Embodiment
The invention provides a kind of preparation method of dimethyl sulfone, under the method is included in oxidation reaction condition, in fixed-bed reactor, make a kind of liquid mixture by being filled with the beds of at least one HTS, obtain the mixture containing dimethyl sulfone, described liquid mixture contains dimethyl thioether and at least one superoxide.
According to method of the present invention, described superoxide refers to the compound containing-O-O-key in molecular structure, can be hydrogen peroxide and/or organo-peroxide (as hydroperoxide and peracid).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 consumption of described superoxide is as the criterion dimethyl thioether can be oxidized into dimethyl sulfone.Usually, the mol ratio of described superoxide and described dimethyl thioether is for being greater than 2:1.Be preferably more than 2.5:1.The mol ratio of described superoxide and described dimethyl thioether can be below 20:1, as below 10:1, is preferably below 5:1.Preferably, the mol ratio of described superoxide and dimethyl thioether is 2.5-5:1.
According to method of the present invention, described liquid mixture can contain solvent, also can not contain solvent.From the degree of mixing improved further in reaction system between each reactant, enhanced dispersion and more easily to the angle that the severe degree of reaction regulates, described liquid mixture is preferably also containing at least one solvent.The kind of described solvent is not particularly limited.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.
The content of described solvent can be conventional selection.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 and the kind of solvent and the condition etc. of reaction have certain relation, and those skilled in the art can suitably select as the case may be.
Before making described liquid mixture and described HTS contact reacts, preferably also comprise according to method of the present invention and add at least one acid as pH value regulator in described liquid mixture, the addition of described acid makes the pH value of this liquid mixture be preferably 0.5-5.5, be more preferably 1-5 (as 2-5), the selectivity for dimethyl sulfone can be improved so further, higher dimethyl thioether transformation efficiency and oxygenant effective rate of utilization can also be obtained simultaneously.Although when described superoxide is peracid, the pH value of this liquid mixture, generally between 3.5-4, if add acid in described liquid mixture, being adjusted to lower than 3.5 to being not less than 1, still can obtaining above-mentioned effect by the pH value of described liquid mixture.The pH value of described liquid mixture refers at 25 DEG C and the pH value of the liquid mixture of 1 standard atmosphere pressure mensuration.
As pH value regulator, the kind of described acid can be conventional selection.Usually, for regulating the acid of the pH value of described liquid mixture to be mineral acid and/or organic acid, described organic acid can be carboxylic acid and/or sulfonic acid, as C
1-C
6aliphatic carboxylic acid, C
6-C
12aromatic carboxylic acid, C
1-C
6aliphatic sulfonic and C
6-C
12aromatic sulphonic acid.Described acid-specific can be one or more in hydrochloric acid, sulfuric acid, nitric acid, phosphoric acid, formic acid and acetic acid, is preferably hydrochloric acid and/or sulfuric acid.Pure acid can be used, also can use aqueous acid.Acid can be carried out with mixing of other component (as solvent) in dimethyl thioether and oxygenant and liquid mixture in reactor, also can carry out outside reactor.
The consumption of described acid is as the criterion so that the pH value of liquid mixture can be made to meet previously described requirement.
According to method of the present invention, described HTS can for the common HTS with various topological framework, such as: 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 two dimension 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 the HTS of the HTS of MFI structure, the HTS of MEL structure, the HTS of two-dimentional hexagonal structure and BEA structure.More preferably, described HTS is the HTS of MFI structure, as TS-1 molecular sieve.
One of the present invention preferred embodiment in, 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.The dimethyl thioether transformation efficiency, oxygenant effective rate of utilization and the dimethyl sulfone selectivity that improve further can be obtained according to this embodiment.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 Hunan Jianchang Petrochemical Co., Ltd be the molecular sieve of HTS), also method can prepare disclosed in CN1132699C.
According to this preferred embodiment, described HTS can be all hollow HTS, also can be the combination of the HTS of hollow HTS and other kind, such as, hollow HTS and the HTS (such as titanium-silicon molecular sieve TS-1) of other MFI structure, the HTS of two-dimentional hexagonal structure and the HTS of BEA structure be combinationally used.When the HTS of hollow HTS and other kind is combinationally used, preferably with the flow direction of described liquid mixture for benchmark, (namely described hollow HTS is positioned at the upstream of other HTS, described hollow HTS and other HTS filling order in described reaction zone makes described liquid mixture successively contact with other HTS with described hollow HTS), higher oxygenant effective rate of utilization and desirable oxidation selectivity of product can be obtained like this.The mass ratio of described hollow HTS and other HTS can be 1-10:1, is preferably 2-5:1.In actually operating, can by hollow HTS and other HTS layering being seated in fixed-bed reactor, and hollow HTS be made to be positioned at the upstream of other HTS and to realize.
When the HTS that described HTS is hollow HTS and other kind combinationally uses, preferably, described HTS is hollow HTS and titanium-silicon molecular sieve TS-1, with the flow direction of described liquid mixture for benchmark, described hollow HTS is positioned at the upstream (that is, described hollow HTS makes dimethyl thioether successively contact with titanium-silicon molecular sieve TS-1 with described hollow HTS with titanium-silicon molecular sieve TS-1 in described reaction zone filling order) of described titanium-silicon molecular sieve TS-1.Like this can not only extending catalyst steady running time further, selectivity and the oxygenant effective rate of utilization of dimethyl sulfone can also be improved further simultaneously.
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 sulfone selectivity can be obtained, and higher oxygenant effective rate of utilization can be obtained, in tandem reaction sequence dimethyl thioether transformation efficiency and dimethyl sulfone 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 in the reaction unit (being generally the reaction unit except thioether oxidation 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 more preferably 30-50% of the activity of this HTS when fresh.When the activity drawing off agent through regeneration is the 30-50% of the activity of this HTS when fresh, gratifying dimethyl thioether transformation efficiency and dimethyl sulfone 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 by weight 1:7.5:10:7.5:10, at atmosheric pressure in 80 DEG C of reaction 2h.Calculate to draw off agent and the fresh titanium si molecular sieves transformation efficiency as pimelinketone during catalyzer respectively, and using it as the activity drawing off agent 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 sulfone 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 drawing off agent is 100 % by weight) time, still can obtain gratifying dimethyl thioether transformation efficiency, oxygenant effective rate of utilization and dimethyl sulfone selectivity.
According to method of the present invention, before described HTS is contacted with described liquid mixture, preferably at least part of described HTS is contacted with at least one acid as properties-correcting agent.Like this improve further dimethyl sulfone optionally simultaneously, can also work-ing life of extending catalyst further, the running cost of reduction the inventive method further.For clearly object, hereinafter, the HTS contacted with acid is called the HTS of modification.
The content of the HTS of described modification can be selected according to concrete use occasion.Described HTS can be all the HTS of modification, can be also partly the HTS of modification.Usually, with the total amount of described HTS for benchmark, the content of the HTS of described modification is preferably more than 10 % by weight.
As properties-correcting agent, described acid is general acid, can be one or more in mineral acid, organic acid and acid-salt.Described organic acid can be carboxylic acid and/or sulfonic acid, as C
1-C
6aliphatic carboxylic acid, C
6-C
12aromatic carboxylic acid, C
1-C
6aliphatic sulfonic and C
6-C
12aromatic sulphonic acid.Preferably, described acid is one or more in acetic acid, hydrochloric acid, sulfuric acid, phosphoric acid, nitric acid, perchloric acid and Hydrogen bromide.Described acid preferably provides in form of an aqueous solutions, and in aqueous acid, the concentration of acid can be selected according to the kind of acid, is not particularly limited, and usually, in aqueous acid, the concentration of acid can be 0.01-50 % by weight, is preferably 10-35 % by weight.
With compared with the HTS before acid treatment, the condition processed HTS with acid is to make in ultraviolet-visible (UV-Vis) spectrum of the HTS after contacting, the peak height of the absorption peak between 240-300nm reduces more than 2% and (is generally 2-20%, as 3-8%), reduce by more than 1% (being generally 1-10%, as 1.5-3%) with the pore volume of static determination of nitrogen adsorption.
Usually, HTS is in silicon-dioxide, and the mol ratio of described HTS and described acid can be 1:0.01-10, is preferably 1:0.05-8, is more preferably 1:0.1-5.Described contact can be carried out at the temperature of 0-200 DEG C, preferably 20-180 DEG C, more preferably 50-100 DEG C.The time of described contact can be selected according to the kind of the temperature of contact and acid.Usually, the time of described contact can be 0.1-72 hour, is preferably 0.5-24 hour (as 5-24 hour).
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.Shaping HTS contains carrier (namely binding agent) and HTS, and wherein, the content of carrier forms the formed body with some strength be as the criterion HTS can be bonded together.Usually, with the total amount of described shaping HTS for benchmark, the content of HTS can be 5-95 % by weight, is preferably 10-95 % by weight, be more preferably 40-95 % by weight, more preferably 60-95 % by weight (as 70-90 % 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, more preferably 5-40 % by weight (as 10-30 % by weight).The carrier of described shaping HTS can be conventional selection, as aluminum oxide and/or silicon oxide.The method preparing described shaping HTS is known in the field, no longer describes in detail herein.The granular size of described shaping HTS is also not particularly limited, and can carry out appropriate selection according to concrete shape.Usually, the median size of described shaping HTS can be 4-5000 micron, is preferably 5-2000 micron, is more preferably 100-1000 micron.Described median size is volume average particle size, and laser particle analyzer can be adopted to measure.
According to method of the present invention, HTS is as catalyzer, and its consumption is as the criterion can realize catalysis.In actual mechanical process, the consumption of HTS can be represented with the weight hourly space velocity of liquid mixture.Usually, the weight hourly space velocity of described liquid mixture can be 0.1-500h
-1, be preferably 5-300h
-1(as 100-200h
-1).Described weight hourly space velocity with whole HTS of loading in fixed-bed reactor for benchmark.
According to method of the present invention, can also load filler further in fixed-bed reactor, 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 fixed-bed reactor; The combination of above-mentioned two kinds of modes can also be adopted.
According to method of the present invention, described oxidation reaction condition can be conventional selection, is as the criterion dimethyl thioether can be oxidized into dimethyl sulfone.Usually, described oxidation reaction condition comprises: temperature can be 0-160 DEG C, is preferably 20-120 DEG C (as 30-80 DEG C); Pressure can be 0-3MPa, is preferably 0.1-1.5MPa.Herein, pressure is gauge pressure.
Method of the present invention is not particularly limited for the type of described fixed-bed reactor, can be common various forms of fixed-bed reactor.Method of the present invention is also not particularly limited for the filling form of HTS in fixed-bed reactor, can be conventional selection.
Can also comprise according to method of the present invention the mixture containing dimethyl sulfone contact obtained to be separated, to isolate dimethyl sulfone wherein.The present invention is not particularly limited for the method isolating the dimethyl sulfone contacted in the mixture that obtains, can be the routine selection of this area.Such as by carrying out fractionation by contacting the mixture obtained, thus dimethyl sulfone can be obtained.
Describe the present invention in detail below in conjunction with 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, and HTS used is fresh titanium si molecular sieves, and pressure is all in gauge pressure.
In following examples, titanium-silicon molecular sieve TS-1 used is according to Zeolites, and prepared by the method described in 1992, Vol.12:943-950, its titanium oxide content is 2.5 % by weight; Hollow HTS used is be the hollow HTS of HTS purchased from the trade mark of Hunan Jianchang Petrochemical Co., Ltd, and its titanium oxide content is 2.5 % by weight; HTS Ti-MCM-41 used is that prepared by the method described in 1994,147-148, its titanium oxide content is 3 % by weight according to Corma etc. at Chem.Commun.; HTS Ti-Beta used is that prepared by the method described in 1997,677-678, its titanium oxide content is 2.6 % by weight according to TakashiTatsumi etc. at J.Chem.Soc.Chem.Commun..
In embodiment 3 and 17, static nitrogen adsorption method and solid ultraviolet-visible diffuse reflectance spectroscopy is adopted to characterize the pore volume of the HTS after before modified and ultraviolet absorption peak respectively.Wherein, solid UV-Vis diffuse reflection spectroscopy (UV-Vis) records on SHIMADZUUV-3100 type ultraviolet-visible spectrometer; Pore volume measures on the static n2 absorption apparatus of the ASAP2405 type of Micromeritics company.
In following examples, adopt the Mastersizer2000 type laser fineness gage be purchased from Malvern company of Britain to measure median size, wherein, median size is volume average particle size.
In following examples, adopt vapor-phase chromatography to analyze the content of each composition in the reaction solution obtained, adopt following formula to calculate the selectivity of the transformation efficiency of dimethyl thioether, the effective rate of utilization of oxygenant and dimethyl sulfone on this basis respectively:
Dimethyl thioether transformation efficiency (%)=[molar weight of the dimethyl thioether of (molar weight of the molar weight-unreacted dimethyl thioether of the dimethyl thioether added)/add] × 100%;
Oxygenant effective rate of utilization (%)=[molar weight/(molar weight of the molar weight-unreacted oxygenant of the oxygenant added) of the dimethyl sulfone that 2 × reaction generates] × 100%;
Dimethyl sulfone selectivity (%)=[molar weight/(molar weight-unreacted dimethyl thioether molar weight of the dimethyl thioether added) of the dimethyl sulfone that reaction generates] × 100%.
Embodiment 13,14 and 16-18 adopt following methods to measure the activity of catalyzer:
By catalyzer, 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 after 80 DEG C of stirring reaction 2h, reactant is filtered, analyze with the composition of vapor-phase chromatography to the liquid phase obtained, adopt the transformation efficiency of following formulae discovery pimelinketone and it can be used as the activity of this catalyzer
The transformation efficiency (%) of pimelinketone=[molar weight of the pimelinketone of (molar weight of the molar weight-unreacted pimelinketone of the pimelinketone added)/add] × 100%.
Embodiment 1-18 is for illustration of method of the present invention.
Embodiment 1
(1) titanium-silicon molecular sieve TS-1 is mixed with silicon sol (silica content is 30 % by weight) and water, wherein, titanium-silicon molecular sieve TS-1, in the weight ratio of the silicon sol of silicon oxide and water 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 catalyzer (being designated as C1) that volume average particle size is 200 μm.Wherein, in catalyzer, the content of titanium-silicon molecular sieve TS-1 is 80 % by weight.
(2) catalyst loading step (1) prepared, in isometrical fixed-bed reactor, forms beds.By dimethyl thioether, hydrogen peroxide (being the hydrogen peroxide of 30 % by weight) and methanol mixed, form liquid mixture.Then, described liquid mixture to be sent in fixed-bed reactor and to flow through beds.Wherein, in liquid mixture, the mol ratio of dimethyl thioether and hydrogen peroxide is 1:3, 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.
Gas chromatographic analysis is carried out in reaction 0.5 hour and the reaction mixture that obtains for 100 hours, and calculates dimethyl thioether transformation efficiency, oxygenant effective rate of utilization and dimethyl sulfone selectivity.Result is listed in Table 1.
Embodiment 2
The method identical with embodiment 1 is adopted to prepare dimethyl sulfone, unlike, in step (1), the hollow HTS of titanium-silicon molecular sieve TS-1 equivalent replaces, thus obtains the catalyzer (being designated as C2) that volume average particle size is 200 μm.Wherein, in catalyzer, the content of HTS is 80 % by weight.
The result of reacting 0.5 hour and obtain for 100 hours is listed in Table 1.
Embodiment 3
The method identical with embodiment 1 is adopted to prepare dimethyl sulfone, unlike, the titanium-silicon molecular sieve TS-1 of step (1) replaces with the titanium-silicon molecular sieve TS-1 of equivalent modification, and wherein, the titanium-silicon molecular sieve TS-1 of modification adopts following methods preparation:
Titanium-silicon molecular sieve TS-1 is mixed with hydrochloric acid (mass concentration is the aqueous solution of 36 % by weight), by the mixture that obtains 90 DEG C of stirring reactions 5 hours, filter after the temperature of the reaction mixture obtained is down to room temperature, the solid matter obtained is dried to constant weight at 120 DEG C, obtains the HTS of modification.Wherein, titanium-silicon molecular sieve TS-1 is with SiO
2meter, the mol ratio of HTS and HCl is 1:0.2.Through characterizing, compared with raw material HTS, the peak height of the absorption peak in the UV-Vis spectrum of the HTS of the modification obtained between 240-300nm reduces 3.1%, reduces 1.6% by the pore volume of static determination of nitrogen adsorption.
The result of reacting 0.5 hour and obtain for 150 hours is listed in Table 1.
Embodiment 4
The method identical with embodiment 1 is adopted to prepare dimethyl sulfone, unlike, in step (2), also in liquid mixture, add hydrochloric acid, so that the pH value of liquid mixture is adjusted to 5.0 from 5.7.
The result of reacting 0.5 hour and obtain for 120 hours is listed in Table 1.
Embodiment 5
The method identical with embodiment 1 is adopted to prepare dimethyl sulfone, unlike, in step (2), under the condition that the total filling amount of catalyzer is constant, two beds are formed in fixed-bed reactor, be designated as the first beds and the second beds respectively, the upper surface of the first beds connects with the lower surface of the second beds, with the flow direction of liquid mixture in fixed-bed reactor for benchmark, (namely first beds is positioned at the upstream of the second beds, liquid mixture first flows through the first beds, flow through the second beds again), described first beds loading catalyst C2, described second beds loading catalyst C1, and the weight ratio of catalyzer C2 and catalyzer C1 is 2:1.
The result of reacting 0.5 hour and obtain for 200 hours is listed in Table 1.
Embodiment 6
The method identical with embodiment 5 is adopted to prepare dimethyl sulfone, unlike, under the condition that the total filling amount of catalyzer is constant, make in step (2), the weight ratio of catalyzer C2 and catalyzer C1 is 5:1.
The result of reacting 0.5 hour and obtain for 200 hours is listed in Table 1.
Embodiment 7
The method identical with embodiment 5 is adopted to prepare dimethyl sulfone, unlike, under the condition that the loadings of catalyzer C1 and catalyzer C2 is constant, loading catalyst C1 in the first beds, loading catalyst C2 in the second beds.
The result of reacting 0.5 hour and obtain for 80 hours is listed in Table 1.
Embodiment 8
The method identical with embodiment 5 is adopted to prepare dimethyl sulfone, unlike, under the condition that the total filling amount of catalyzer is constant, make the weight ratio of catalyzer C2 and catalyzer C1 be 1:1.
The result of reacting 0.5 hour and obtain for 120 hours is listed in Table 1.
Embodiment 9
The method identical with embodiment 5 is adopted to prepare dimethyl sulfone, unlike, under the condition that the total filling amount of catalyzer is constant, make the weight ratio of catalyzer C2 and catalyzer C1 be 10:1.
The result of reacting 0.5 hour and obtain for 140 hours is listed in Table 1.
Embodiment 10
The method identical with embodiment 6 is adopted to prepare dimethyl sulfone, unlike, the catalyzer C3 of catalyzer C1 equivalent replaces, and the preparation method of catalyzer C3 is as follows:
HTS Ti-Beta is mixed with silicon sol (silica content is 30 % by weight) and water, wherein, HTS Ti-Beta, in the weight ratio of the silicon sol of silicon oxide and water 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 catalyzer C3 that median size is 200 μm.Wherein, in catalyzer C3, the content of HTS Ti-Beta is 80 % by weight.
The result of reacting 0.5 hour and obtain for 130 hours is listed in Table 1.
Embodiment 11
The method identical with embodiment 6 is adopted to prepare dimethyl sulfone, unlike, the catalyzer C4 of catalyzer C1 equivalent replaces, and the preparation method of catalyzer C4 is as follows:
HTS Ti-MCM-41 is mixed with silicon sol (silica content is 30 % by weight) and water, wherein, HTS Ti-MCM-41, in the weight ratio of the silicon sol of silicon oxide and water 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 catalyzer C4 that median size is 200 μm.Wherein, in catalyzer C4, the content of HTS Ti-MCM-41 is 80 % by weight.
The result of reacting 0.5 hour and obtain for 120 hours is listed in Table 1.
Table 1
The result of table 1 shows, adopts method of the present invention to prepare dimethyl sulfone, can obtain high dimethyl thioether transformation efficiency, oxygenant effective rate of utilization and dimethyl sulfone selectivity.
Embodiment 1 and embodiment 3 are compared and can find out, use the HTS of sour modification as catalyzer, with directly HTS is used as compared with catalyzer, higher dimethyl sulfone selectivity can be obtained, the parallel-adder settle-out time of the HTS as catalyzer can also be extended simultaneously further.
Embodiment 1 and embodiment 4 are compared and can find out, by the pH value of the liquid mixture of acid adjustment and catalyst exposure, better reaction effect can be obtained.
Embodiment 12
(1) titanium-silicon molecular sieve TS-1 is mixed with silicon sol (silica content is 30 % by weight) and water, wherein, titanium-silicon molecular sieve TS-1, in the weight ratio of the silicon sol of silicon oxide and water for 1:0.15:5.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 catalyzer that median size is 500 μm.Wherein, in catalyzer, the content of HTS is 85 % by weight.
(2) catalyst loading step (1) prepared is in isometrical fixed-bed reactor, and form beds, wherein, the quantity of beds is 1 layer.
Dimethyl thioether, hydrogen peroxide (being the hydrogen peroxide of 30 % by weight) and acetone are mixed, forms liquid mixture.Then, described liquid mixture to be sent in fixed-bed reactor and to flow through beds.Wherein, in liquid mixture, the mol ratio of dimethyl thioether and hydrogen peroxide is 1:4, and the weight ratio of dimethyl thioether and acetone is 1:2, and the weight hourly space velocity of liquid mixture is 150h
-1.Temperature in beds is 80 DEG C, and the pressure in fixed-bed reactor is 1.5MPa.
Gas chromatographic analysis is carried out in reaction 1 hour and the reaction mixture that obtains for 100 hours, and calculates dimethyl thioether transformation efficiency, oxygenant effective rate of utilization and dimethyl sulfone selectivity.Result is listed in table 2.
Embodiment 13
The method identical with embodiment 12 is adopted to prepare dimethyl sulfone, unlike, the catalyzer be seated in fixed-bed reactor is carried out regenerating obtaining by the preformed catalyst drawn off from cyclohexanone oxamidinating reaction process (fresh dose adopt the method identical with embodiment 12 step (1) prepare), and regeneration condition is: at 550 DEG C in air atmosphere roasting 4h.The activity of regenerated catalyst is 45%, and its activity when fresh is 95%.
The result of reacting 1 hour and obtain for 180 hours is listed in table 2.
Embodiment 14
The method identical with embodiment 13 is adopted to prepare dimethyl sulfone, unlike, in step (2), also in liquid mixture, add phosphoric acid, so that the pH value of liquid mixture is adjusted to 2 from 5.6.
The result of reacting 1 hour and obtain for 200 hours is listed in table 2.
Table 2
Embodiment 15
(1) hollow HTS is mixed with silicon sol (silica content is 30 % by weight) and water, wherein, hollow HTS, in the weight ratio of the silicon sol of silicon oxide and water for 1:0.1:8.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 catalyzer that median size is 100 μm.Wherein, in catalyzer, the content of hollow HTS is 90 % by weight.
(2) catalyst loading step (1) prepared is in fixed-bed reactor, and form beds, wherein, the quantity of beds is 1 layer.
Dimethyl thioether, hydrogen peroxide (being the hydrogen peroxide of 40 % by weight), acetonitrile and hydrochloric acid (concentration is 20 % by weight) are mixed, form liquid mixture, the pH value of liquid mixture is adjusted to 3.0 from 5.8 by the consumption of hydrochloric acid.Then, described liquid mixture to be sent in fixed-bed reactor and to flow through beds.Wherein, in liquid mixture, the mol ratio of dimethyl thioether and hydrogen peroxide is 1:2.5, and the weight ratio of dimethyl thioether and acetonitrile is 1:10, and the weight hourly space velocity of liquid mixture is 200h
-1.Temperature in beds is 20 DEG C, and the pressure in fixed-bed reactor is 0.5MPa.
Gas chromatographic analysis is carried out in reaction 1 hour and the reaction mixture that obtains for 120 hours, and calculates dimethyl thioether transformation efficiency, oxygenant effective rate of utilization and dimethyl sulfone selectivity.Result is listed in table 3.
Embodiment 16
The method identical with embodiment 15 is adopted to prepare dimethyl sulfone, unlike, in step (2), the catalyzer be seated in fixed-bed reactor is the shaping hollow HTS drawn off from phenol hydroxylation reaction unit (fresh dose adopts the method identical with embodiment 15 step (1) to prepare) carried out regenerating obtaining, its activity is 30%, activity when fresh is 96%, and regeneration condition is: at 570 DEG C in air atmosphere roasting 4h.
The result of reacting 1 hour and obtain for 200 hours is listed in table 3.
Embodiment 17
The method identical with embodiment 16 is adopted to prepare dimethyl sulfone, unlike, carry out acid treatment by after the shaping hollow HTS regeneration drawn off from phenol hydroxylation reaction unit, be then seated in fixed-bed reactor and form beds, wherein acid-treated method is as follows:
The agent that draws off after regeneration is mixed with acetic acid (mass concentration is the aqueous solution of 32 % by weight), by the mixture that obtains 60 DEG C of stirring reactions 24 hours, filter after the temperature of the reaction mixture obtained is down to room temperature, the solid matter obtained is dried to constant weight at 120 DEG C, obtains the HTS of modification.Wherein, HTS is with SiO
2meter, HTS and CH
3the mol ratio of COOH is 1:5.Through characterizing, and draw off compared with agent after regeneration, the absorption peak peak height in the UV-Vis spectrum of the HTS of modification between 240-300nm reduces 5.5%, reduces 2.2% by the pore volume of static determination of nitrogen adsorption.
The result of reacting 1 hour and obtain for 250 hours is listed in table 3.
Embodiment 18
The method identical with embodiment 15 is adopted to prepare dimethyl sulfone, unlike, in step (2), the catalyzer be seated in fixed-bed reactor is the shaping hollow HTS drawn off from propylene ring oxidation reaction device (fresh dose adopts the method identical with embodiment 15 step (1) to prepare) carried out regenerating obtaining, its activity is 40%, activity when fresh is 96%, and regeneration condition is: at 570 DEG C in air atmosphere roasting 4h.
The result of reacting 1 hour and obtain for 200 hours is listed in table 3.
Table 3
The result of embodiment 13,14 and 16-18 shows, even if at least partly catalyst source is in drawing off agent using HTS as the reaction unit of catalyzer, method of the present invention also can obtain high dimethyl thioether transformation efficiency, oxygenant effective rate of utilization and dimethyl sulfone selectivity; And in tandem reaction sequence, the activity of catalyzer is more stable.
Claims (15)
1. the preparation method of a dimethyl sulfone, under the method is included in oxidation reaction condition, in fixed-bed reactor, make a kind of liquid mixture by being filled with the beds of at least one HTS, obtain the mixture containing dimethyl sulfone, described liquid mixture contains dimethyl thioether and at least one superoxide, and the mol ratio of described superoxide and described dimethyl thioether is for being greater than 2:1.
2. method according to claim 1, wherein, before contacting with described liquid mixture, contacts 0.1-72 hour with at least one acid by least part of described HTS at the temperature of 0-200 DEG C.
3. method according to claim 2, wherein, HTS is in silicon-dioxide, and the mol ratio of described HTS and described acid is 1:0.01-10.
4. according to the method in claim 2 or 3, wherein, described acid is selected from acetic acid, hydrochloric acid, sulfuric acid, phosphoric acid, nitric acid, perchloric acid and Hydrogen bromide.
5. according to the method in claim 1-3 described in any one, wherein, at least part of described HTS be through regeneration the reaction unit using HTS as catalyzer draw off agent, 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.
6. according to the method in claim 1-3 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 5-300 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.
8. method according to claim 7, wherein, described HTS is hollow HTS and titanium-silicon molecular sieve TS-1, and with the flow direction of described liquid mixture for benchmark, described hollow HTS is positioned at the upstream of described titanium-silicon molecular sieve TS-1.
9. method according to claim 8, wherein, the weight ratio of described hollow HTS and described titanium-silicon molecular sieve TS-1 is 1-10:1.
10. method according to claim 1, wherein, described liquid mixture is also containing at least one solvent, and the weight ratio of dimethyl thioether and described solvent is 1:0.1-20.
11. methods according to claim 10, wherein, described solvent is selected from water, C
1-C
10alcohol, C
3-C
10ketone and C
2-C
10nitrile.
12. according to the method in claim 1,2,10 and 11 described in any one, and wherein, the method also comprises adds at least one acid in described liquid mixture, and the addition of described acid makes the pH value of this liquid mixture be 0.5-5.5.
13. methods according to claim 1, wherein, the mol ratio of described superoxide and dimethyl thioether is 2.5-5:1.
14. methods according to claim 1 or 13, wherein, described superoxide is selected from hydrogen peroxide, hydroperoxide and peracid.
15. according to the method in claim 1,2,10 and 13 described in any one, and wherein, the weight hourly space velocity of described liquid mixture is 0.1-500h
-1; Described oxidation reaction condition comprises: temperature is 0-160 DEG C; In gauge pressure, pressure is 0-3MPa.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201410513984.3A CN105523974B (en) | 2014-09-29 | 2014-09-29 | A kind of preparation method of dimethyl sulfone |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201410513984.3A CN105523974B (en) | 2014-09-29 | 2014-09-29 | A kind of preparation method of dimethyl sulfone |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN105523974A true CN105523974A (en) | 2016-04-27 |
| CN105523974B CN105523974B (en) | 2017-08-22 |
Family
ID=55766546
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN201410513984.3A Active CN105523974B (en) | 2014-09-29 | 2014-09-29 | A kind of preparation method of dimethyl sulfone |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN105523974B (en) |
Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN108794360A (en) * | 2017-04-28 | 2018-11-13 | 中国石油化工股份有限公司 | A kind of production method of sulfone |
| CN109721514A (en) * | 2017-10-31 | 2019-05-07 | 中国石油化工股份有限公司 | A kind of preparation method of sulfone |
| CN109721516A (en) * | 2017-10-31 | 2019-05-07 | 中国石油化工股份有限公司 | A kind of sulfide oxidation method |
| CN109721515A (en) * | 2017-10-31 | 2019-05-07 | 中国石油化工股份有限公司 | A kind of preparation method of sulfone |
Citations (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2003128660A (en) * | 2001-10-22 | 2003-05-08 | Showa Denko Kk | Oxidation method of carbon-carbon double bond and production method of oxidized compound using the same |
| US20040034258A1 (en) * | 2000-09-29 | 2004-02-19 | Showa Denko K.K. | Crystalline MWW-type titanosilicate catalyst for producing oxidized compound, production process for the catalyst, and process for producing oxidized compound by using the catalyst |
| US20040122243A1 (en) * | 2002-12-24 | 2004-06-24 | Wataru Oguchi | Process for oxidizing carbon-carbon double bond and process for producing oxidized compounds |
| CN1657168A (en) * | 2004-12-09 | 2005-08-24 | 华东师范大学 | Preparation method of acid modified titanium-containing molecular sieve |
| CN102838516A (en) * | 2012-09-25 | 2012-12-26 | 宁夏兴平精细化工股份有限公司 | Preparation method for sulfoxide and sulphone |
| CN105367463A (en) * | 2014-08-26 | 2016-03-02 | 中国石油化工股份有限公司 | Method for simultaneously producing dimethyl sulfone and dimethyl sulfoxide |
-
2014
- 2014-09-29 CN CN201410513984.3A patent/CN105523974B/en active Active
Patent Citations (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US20040034258A1 (en) * | 2000-09-29 | 2004-02-19 | Showa Denko K.K. | Crystalline MWW-type titanosilicate catalyst for producing oxidized compound, production process for the catalyst, and process for producing oxidized compound by using the catalyst |
| JP2003128660A (en) * | 2001-10-22 | 2003-05-08 | Showa Denko Kk | Oxidation method of carbon-carbon double bond and production method of oxidized compound using the same |
| US20040122243A1 (en) * | 2002-12-24 | 2004-06-24 | Wataru Oguchi | Process for oxidizing carbon-carbon double bond and process for producing oxidized compounds |
| CN1657168A (en) * | 2004-12-09 | 2005-08-24 | 华东师范大学 | Preparation method of acid modified titanium-containing molecular sieve |
| CN102838516A (en) * | 2012-09-25 | 2012-12-26 | 宁夏兴平精细化工股份有限公司 | Preparation method for sulfoxide and sulphone |
| CN105367463A (en) * | 2014-08-26 | 2016-03-02 | 中国石油化工股份有限公司 | Method for simultaneously producing dimethyl sulfone and dimethyl sulfoxide |
Non-Patent Citations (2)
| Title |
|---|
| SAHID HUSSAIN 等: "Borax-catalyzed and pH-controlled selective oxidation of organic sulfides by H2O2: and environmentally clean protocol", 《EUR.J.ORG.CHEM.》 * |
| 李金凤 等: "钛硅分子筛(TS-1)催化氧化二甲基硫醚制备二甲基砜的研究", 《广州化工》 * |
Cited By (8)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN108794360A (en) * | 2017-04-28 | 2018-11-13 | 中国石油化工股份有限公司 | A kind of production method of sulfone |
| CN108794360B (en) * | 2017-04-28 | 2020-05-19 | 中国石油化工股份有限公司 | Production method of sulfone |
| CN109721514A (en) * | 2017-10-31 | 2019-05-07 | 中国石油化工股份有限公司 | A kind of preparation method of sulfone |
| CN109721516A (en) * | 2017-10-31 | 2019-05-07 | 中国石油化工股份有限公司 | A kind of sulfide oxidation method |
| CN109721515A (en) * | 2017-10-31 | 2019-05-07 | 中国石油化工股份有限公司 | A kind of preparation method of sulfone |
| CN109721516B (en) * | 2017-10-31 | 2020-12-04 | 中国石油化工股份有限公司 | Thioether oxidation method |
| CN109721515B (en) * | 2017-10-31 | 2020-12-04 | 中国石油化工股份有限公司 | Preparation method of sulfone |
| CN109721514B (en) * | 2017-10-31 | 2020-12-04 | 中国石油化工股份有限公司 | Preparation method of sulfone |
Also Published As
| Publication number | Publication date |
|---|---|
| CN105523974B (en) | 2017-08-22 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN103288692B (en) | A kind of method being prepared dimethyl sulfone by dimethyl sulfoxide (DMSO) | |
| CN105523974A (en) | Preparation method for dimethyl sulfone | |
| CN105017103A (en) | Dimethyl sulfone preparation method | |
| CN104557627B (en) | Method for preparing dimethyl sulfone | |
| CN104945353A (en) | Alkene epoxidation reaction method capable of producing few byproducts | |
| CN104557624B (en) | Method for preparing dimethyl sulfone | |
| CN105523894B (en) | A kind of method of cyclohexene oxide | |
| CN104557625B (en) | Method for preparing dimethyl sulfone | |
| CN104557634B (en) | Method for producing dimethyl sulfone | |
| CN104557635B (en) | Method for oxidizing dimethyl sulfide | |
| CN105017106B (en) | A kind of method of cacodyl oxide base sulfoxide | |
| CN104557633A (en) | Method for preparing dimethyl sulfone | |
| CN105985269B (en) | A kind of method for preparing dimethyl sulfone | |
| CN105017104A (en) | Dimethyl sulfone preparation method | |
| CN105985272B (en) | A kind of sulfide oxidation method | |
| CN105017105B (en) | A kind of preparation method of dimethyl sulfone | |
| CN105439924A (en) | Preparation method of dimethyl sulfoxide | |
| CN105523973B (en) | A kind of method for preparing dimethyl sulfone | |
| CN105985268B (en) | A kind of preparation method of dimethyl sulfone | |
| CN105367463A (en) | Method for simultaneously producing dimethyl sulfone and dimethyl sulfoxide | |
| CN105017107A (en) | Dimethyl sulfone preparation method | |
| CN105985271A (en) | Dimethyl sulfone preparation method | |
| CN108794361A (en) | A method of dimethyl sulfone is produced by hydrogen sulfide | |
| CN109721514A (en) | A kind of preparation method of sulfone | |
| CN106631935A (en) | Method for simultaneous production of dimethyl sulfone and acetone |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| C06 | Publication | ||
| PB01 | Publication | ||
| C10 | Entry into substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| GR01 | Patent grant | ||
| GR01 | Patent grant |