CN104557631B - A kind of method preparing dimethyl sulfoxide - Google Patents
A kind of method preparing dimethyl sulfoxide Download PDFInfo
- Publication number
- CN104557631B CN104557631B CN201310520958.9A CN201310520958A CN104557631B CN 104557631 B CN104557631 B CN 104557631B CN 201310520958 A CN201310520958 A CN 201310520958A CN 104557631 B CN104557631 B CN 104557631B
- Authority
- CN
- China
- Prior art keywords
- hts
- catalyst
- dimethyl sulfoxide
- agent
- 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.)
- Active
Links
Abstract
The invention provides a kind of method preparing dimethyl sulfoxide, it is included under oxidation reaction condition, dimethyl sulfide is contacted with HTS with at least one oxidant, wherein, described HTS contains the first HTS and the second HTS, described first HTS contains template, and described second HTS does not contains template.The method of the present invention is obtained in that high dimethyl sulfide conversion ratio, oxidant effective rate of utilization and dimethyl sulfoxide selectivity, can also obtain long catalyst service life simultaneously.
Description
Technical field
The present invention relates to a kind of method preparing dimethyl sulfoxide.
Background technology
Dimethyl sulfoxide (DMSO) is a kind of organic compounds containing sulfur, is colourless transparent liquid under room temperature,
There is the characteristics such as highly polar, high-hygroscopicity, flammable and high boiling point be non-proton.Dimethyl sulfoxide be dissolved in water,
Ethanol, acetone, ether and chloroform, be the atent solvent that polarity is strong, is 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 reacts, the synthesis as polyurethane is molten
Agent and the solvent that reels off raw silk from cocoons, as the synthetic of polyamide, fluoroaluminate glasses, polyimides and polysulfones.Further,
Dimethyl sulfoxide has the highest selective extraction method ability, can be used as the extraction that alkane separates with aromatic hydrocarbon molten
Agent, such as: dimethyl sulfoxide can be used for the extracting of aromatic hydrocarbons or butadiene.Meanwhile, in medical industry,
Dimethyl sulfoxide is possible not only to the raw material directly as some drugs and carrier, and only can also play antiinflammatory
Bitterly, the effect such as diuresis and calmness, therefore the active component frequently as analgesic drug product makes an addition in medicine.Separately
Outward, dimethyl sulfoxide also can be as capacitor dielectric, antifreezing agent, brake fluid and rare metal extracting agent etc..
At present, dimethyl sulfoxide typically uses dimethyl sulfide oxidizing process to prepare, and general employing is following several
Production technology.
1, methanol Carbon bisulfide method: with methanol and Carbon bisulfide as raw material, with γ-Al2O3As catalyst,
First synthesizing dimethyl thioether, then obtain dimethyl sulfoxide with nitrogen dioxide (or nitric acid) oxidation.
2, nitrogen dioxide method: with methanol and hydrogen sulfide as raw material, generates diformazan under gama-alumina effect
Base thioether；Sulphuric acid and sodium nitrite are reacted and prepares nitrogen dioxide；The dimethyl sulfide generated and titanium dioxide
Nitrogen carries out oxidation reaction at 60-80 DEG C and generates thick dimethyl sulfoxide, also has direct oxygen to aoxidize,
Similarly generate thick dimethyl sulfoxide；Thick dimethyl sulfoxide, through decompression distillation, obtains refined dimethyl sulfoxide.
3, dimethyl sulfate ester process: dimethyl sulfate reacted with sodium sulfide, prepares dimethyl sulfide；Sulfur
Acid and sodium nitrite react generation nitrogen dioxide；Dimethyl sulfide and nitrogen dioxide carry out oxidation reaction,
To thick dimethyl sulfoxide, neutralized process, after distillation, obtain refined dimethyl sulfoxide.
Use anodizing can also be produced dimethyl sulfoxide by dimethyl sulphide, but anodizing
Relatively costly, it is unsuitable for large-scale production.
Summary of the invention
It is an object of the invention to provide a kind of method preparing dimethyl sulfoxide, the method is with dimethyl disulfide
Ether, as raw material, obtains dimethyl sulfoxide by using oxidant to be aoxidized by dimethyl sulfide, the method
It is obtained in that high dimethyl sulfide conversion ratio, oxidant effective rate of utilization and dimethyl sulfoxide selectivity.
The present inventor finds in research process, is using HTS as catalyst, is using
When dimethyl sulfide is aoxidized to prepare dimethyl sulfoxide by oxidant, if partial-titanium si molecular sieves is for containing
The HTS of template, and remainder HTS is without template, does not contains with being used alone
The HTS of template is compared as catalyst, it is possible to obtains the dimethyl sulfide improved further and turns
Rate, oxidant effective rate of utilization and dimethyl sulfoxide selectivity；Further, it is possible to obtain longer catalysis
Agent service life.Complete the present invention on this basis.
The invention provides a kind of method preparing dimethyl sulfoxide, the method is included in oxidation reaction condition
Under, dimethyl sulfide is contacted with HTS with at least one oxidant, wherein, described titanium silicon divides
Son sieve includes that the first HTS and the second HTS, described first HTS contain template
Agent, described second HTS does not contains template.
The method according to the invention, with do not use HTS as catalyst, directly with oxidant will
Dimethyl sulfide oxidation is prepared dimethyl sulfoxide and is compared, it is possible to obtains the dimethyl sulfide significantly improved and turns
Rate, oxidant effective rate of utilization and dimethyl sulfoxide selectivity.Although with use HTS conduct
Catalyst, but the HTS that all HTS is without template is compared, it is possible to obtain
Dimethyl sulfide conversion ratio, oxidant effective rate of utilization and the dimethyl sulfoxide selectivity improved further,
Longer catalyst service life can also be obtained simultaneously.Although with use HTS as catalysis
Agent, but the HTS that all HTS is containing template is compared, it is possible to significantly improve
The conversion ratio of dimethyl sulfide, the effective rate of utilization of oxidant and the selectivity of dimethyl sulfoxide.
Detailed description of the invention
The invention provides a kind of method preparing dimethyl sulfoxide, the method is included in oxidation reaction condition
Under, dimethyl sulfide is contacted with HTS with at least one oxidant.
The method according to the invention, described HTS is that titanium atom replaces a part of silicon in lattice framework
The general name of one class zeolite of atom, can use chemical formula xTiO2·SiO2Represent.The present invention is for titanium silicon
In molecular sieve, the content of titanium atom is not particularly limited, and can be the conventional selection of this area.Specifically,
X can be 0.0001-0.05, preferably 0.01-0.03, more preferably 0.015-0.025.
Described HTS can be the common HTS with various topological structure, such as:
Described HTS can be the HTS (such as TS-1) selected from MFI structure, MEL structure
HTS (such as TS-2), the HTS (such as Ti-Beta) of BEA structure, MWW knot
The HTS (such as Ti-MCM-22) of structure, hexagonal structure HTS (as Ti-MCM-41,
Ti-SBA-15), the titanium silicon molecule of the HTS (such as Ti-MOR) of MOR structure, TUN structure
One or many in the HTS (such as Ti-ZSM-48) of sieve (such as Ti-TUN) and other structure
Kind.
Preferably, described HTS is the HTS selected from MFI structure, MEL structure
One or more in the HTS of HTS and BEA structure.It is highly preferred that described titanium
Si molecular sieves is the HTS of MFI structure, such as TS-1 molecular sieve.
From improving the conversion ratio of dimethyl sulfide, the effective rate of utilization of oxidant and dimethyl sulfone further
Selective angle set out, described HTS is the HTS of MFI structure, and this titanium silicon
The crystal grain of molecular sieve is hollow-core construction, and the radical length of the chamber portion of this hollow-core construction is 5-300 nanometer,
And described HTS is at 25 DEG C, P/P0=0.10, the benzene that adsorption time records under conditions of being 1 hour
Adsorbance is at least 70 milligrams per gram, the adsorption isotherm of the nitrogen absorption under low temperature of this HTS and desorption
Hysteresis loop is there is between isothermal line.Herein, the HTS with this structure is referred to as hollow titanium silicon
Molecular sieve.Described hollow titanium si molecular sieves is commercially available (such as builds length commercially available from Sinopec Hunan
The trade mark of petrochemical industry limited company is the molecular sieve of HTS), it is also possible to according to public in CN1132699C
The method opened prepares.
The method according to the invention, described HTS as the catalyst that dimethyl sulfide is aoxidized,
Its consumption can be the catalytic amount being capable of catalysis.Specifically, dimethyl sulfide and described titanium
The weight ratio of si molecular sieves can be 0.1-50:1, preferably 1-50:1.
The method according to the invention, described HTS can be the former powder of HTS, it is also possible to for
The HTS of molding.
The method according to the invention, described HTS includes that the first HTS and the second titanium silicon divide
Son sieve.
Described first HTS contains template, it is, the first HTS is containing template
The HTS of agent.The described HTS containing template refers to containing residual in building-up process
The HTS of template, namely: HTS does not the most experience removed template method
Process (such as roasting), even if or HTS live through the process of removed template method, but mould
Plate agent is the most all removed.
In described first HTS, the content of template is not particularly limited, and can divide according to titanium silicon
Kind and the concrete hydrolysis condition of son sieve select.Usually, described first titanium silicon molecule
In sieve, the content of template can be 0.1-25 weight %.Preferably, in described first HTS,
The content of template is 1-20 weight %.It is highly preferred that in described first HTS, template
Content is 5-15 weight %.The content of described template can use thermogravimetic analysis (TGA) method to measure, usually,
Can be using percent weight loss containing as template between 200-800 DEG C in thermogravimetic analysis (TGA)
Amount.
Described template can be normally used various template during synthesis of titanium silicon molecular sieve, example
: as described in template can be one or more in quaternary ammonium base, aliphatic amine and aliphatic hydramine.Institute
Stating quaternary ammonium base can be various organic level Four ammonium alkali, and described aliphatic amine can be various NH3In at least
The compound that one hydrogen is formed after being replaced by aliphatic alkyl (such as alkyl), described aliphatic hydramine is permissible
For various NH3In at least one hydrogen by hydroxyl aliphatic group (such as alkyl) replace after formed
Compound.
Specifically, described alkalescence template can be that the quaternary ammonium base that represents selected from formula I, formula II represent
Aliphatic amine and the aliphatic hydramine that represents of general formula III in one or more.
In Formulas I, R1、R2、R3And R4It is respectively C1-C4Alkyl, including C1-C4Straight chained alkyl
And C3-C4Branched alkyl, such as: R1、R2、R3And R4Can be each methyl, ethyl, positive third
Base, isopropyl, normal-butyl, sec-butyl, isobutyl group or the tert-butyl group.
R5(NH2)n(Formula II)
In Formula II, n is the integer of 1 or 2.When n is 1, R5For C1-C6Alkyl, including C1-C6
Straight chained alkyl and C3-C6Branched alkyl, as methyl, ethyl, n-pro-pyl, isopropyl, normal-butyl,
Sec-butyl, isobutyl group, the tert-butyl group, n-pentyl, neopentyl, isopentyl, tertiary pentyl and n-hexyl.
When n is 2, R5For C1-C6Alkylidene, including C1-C6Straight-chain alkyl-sub-and C3-C6Side chain sub-
Alkyl, such as methylene, ethylidene, sub-n-pro-pyl, sub-normal-butyl, sub-n-pentyl or sub-n-hexyl.
(HOR6)mNH(3-m)(formula III)
In formula III, m R6Identical or different, respectively C1-C4Alkylidene, including C1-C4's
Straight-chain alkyl-sub-and C3-C4Branched alkylidene, such as methylene, ethylidene, sub-n-pro-pyl and the positive fourth in Asia
Base；M is 1,2 or 3.
Described template is specifically as follows but is not limited to: Tetramethylammonium hydroxide, tetraethyl ammonium hydroxide,
TPAOH (includes the various isomers of TPAOH, such as four n-pro-pyl ammonium hydroxide
With tetra isopropyl ammonium hydroxide), TBAH (include the various isomeries of TBAH
Body, such as 4-n-butyl ammonium hydroxide and four isobutyl group ammonium hydroxide), ethamine, n-propylamine, n-butylamine,
One or many in di-n-propylamine, butanediamine, hexamethylene diamine, monoethanolamine, diethanolamine and triethanolamine
Kind.Preferably, described template is tetraethyl ammonium hydroxide, TPAOH and tetrabutyl hydrogen-oxygen
Change ammonium.
Described second HTS does not contains template, it is, the second HTS is without mould
The HTS of plate agent.In the present invention, " not containing template " refers to containing of template in molecular sieve
Amount is for less than 0.1 weight %.If the HTS synthesized lives through such as roasting process, the most generally
No longer contain template.Described second HTS can be the common various titaniums being stripped of template
Si molecular sieves.
At employing HTS as in the various commercial plants of catalyst, such as Ammoximation reaction, hydroxyl
Change in reaction and epoxidation reaction device, generally after plant running a period of time, the catalysis of catalyst
Activity decrease, in needing to carry out device or ex-situ regeneration, even if also being difficult to obtain satisfied work when carrying out regenerating
During property, need catalyst draws off from device (i.e., more catalyst changeout), and the catalyst drawn off is (i.e.,
Drawing off agent or dead catalyst) current processing method typically accumulation buries, and on the one hand occupies preciousness
Land resource and inventory space, on the other hand HTS production cost is higher, directly passes into disuse also
Cause waste greatly.The present inventor finds in research process, if these are drawn off agent
Carry out regenerating as at least part of second HTS, remain able to obtain high dimethyl sulfide and convert
Rate and dimethyl sulfoxide selectivity, and it is obtained in that higher oxidant effective rate of utilization, successive reaction
During dimethyl sulfide conversion ratio and the selective stability of dimethyl sulfoxide more preferable.
Therefore, the present invention one preferred embodiment in, the most described second titanium silicon molecule
Sieve draws off agent for the reaction unit using HTS as catalyst through regenerating.Preferred according to this
Embodiment, is being obtained in that high dimethyl sulfide conversion ratio, oxidant effective rate of utilization and dimethyl
The while that sulfoxide being selective, additionally it is possible to realize the recycling of discarded HTS, reduce this further
The cost of bright method.
It is described that to draw off agent can be as drawing off the device of catalyst from various use HTSs
Draw off agent, can be such as draw off from oxidation reaction apparatus draw off agent.Described oxidation reaction can be
Each kinds of oxidation reaction, such as described in draw off agent can be Ammoximation reaction device to draw off agent, hydroxylating anti-
Answer device draw off agent and epoxidation reaction device draw off in agent one or more, be specifically as follows ring
Hexanone Ammoximation reaction device draw off agent, phenol hydroxylation reaction unit draw off agent and epoxidation of propylene
Reaction unit draw off in agent one or more.
It is not particularly limited drawing off the condition that agent carries out regenerating, can fit according to the source drawing off agent
When selection, such as: high-temperature roasting and/or solvent washing.
Different according to its source through the activity drawing off agent of regeneration.Usually, drawing off through regeneration
The activity of agent can be the 5-95% of this HTS activity (that is, the activity of fresh dose) when fresh.
Preferably, the activity drawing off agent through regeneration can be this HTS activity when fresh
10-90%, the more preferably 10-50% of the activity when fresh.In the work drawing off agent through regeneration
Property when being the 10-50% of this HTS activity when fresh, can not only obtain gratifying
Dimethyl sulfide conversion ratio and dimethyl sulfoxide selectivity, and it is obtained in that the oxidant of raising further
Effective rate of utilization.The activity of described fresh titanium si molecular sieves is generally more than 90%, and usually more than 95%.
Described activity measures by the following method: respectively draw off agent and fresh dose through regeneration is used as hexamethylene
The catalyst of ketone oxamidinating reaction, the condition of this Ammoximation reaction is: HTS, 36 weight %
Ammonia is (with NH3Meter), the hydrogen peroxide of 30 weight % is (with H2O2Meter), the tert-butyl alcohol and Ketohexamethylene be by weight
Amount ratio 1:7.5:10:7.5:10, reacts 2h in 80 DEG C at atmosheric pressure.Calculate respectively with through again
Raw draw off agent and fresh dose of sieve is the conversion ratio of Ketohexamethylene during catalyst, and as unloading through regeneration
Go out agent and the activity of fresh dose, wherein, the conversion ratio of Ketohexamethylene=[(mole of the Ketohexamethylene of addition-not
The mole of Ketohexamethylene of reaction)/the mole of Ketohexamethylene that adds] × 100%.
When at least part of second HTS is to draw off agent through the reaction unit of regeneration, with described second
On the basis of the total amount of HTS, the reaction unit through regenerating draws off the content of agent and is preferably 5 weight %
Above, so can not only obtain the effect preferably improving oxidant effective rate of utilization, and react
Cheng Gengwei is the most easy to control, also can obtain higher dimethyl sulfide conversion ratio and dimethyl sulfoxide choosing simultaneously
Selecting property.The method according to the invention, unloads even if whole second HTS is the reaction unit through regenerating
When going out agent, remain able to obtain gratifying dimethyl sulfide conversion ratio, oxidant effective rate of utilization and
Dimethyl sulfoxide selectivity.On the premise of obtaining high oxidant effective rate of utilization, from improving further
The conversion ratio of dimethyl sulfide and the selective angle of dimethyl sulfoxide are set out, and divide with described second titanium silicon
On the basis of the total amount of son sieve, the reaction unit through regenerating draws off the content of agent and is more preferably 50-80 weight %.
The method according to the invention, the ratio between described first HTS and the second HTS
Can select according to concrete reaction condition, be not particularly limited.Usually, divide with described titanium silicon
On the basis of the total amount of son sieve, the content of described first HTS can be 5-95 weight %, is preferably
10-90 weight %, more preferably 15-50 weight %；The content of described second HTS can be
5-95 weight %, preferably 10-90 weight %, more preferably 80-85 weight %.
Described oxidant can be commonly used in the art various can be aoxidized by dimethyl sulfide, forms diformazan
The material of base sulfoxide.Method of the invention is particularly suitable for carrying out cacodyl oxide using peroxide as oxidant
Base thioether, thus prepare the occasion of dimethyl sulfoxide, so can significantly improve effective profit of peroxide
By rate, reduce the production cost of dimethyl sulfoxide.Described peroxide refers in molecular structure containing-O-O-
The compound of key, can be hydrogen peroxide and/or organic peroxide, its instantiation can include but not
It is limited to: hydrogen peroxide, tert-butyl hydroperoxide, dicumyl peroxide, cyclohexyl hydroperoxide, peroxide
Acetic acid and Perpropionic Acid.Preferably, described oxidant is hydrogen peroxide, so can reduce further point
From cost.Described hydrogen peroxide can be the commonly used in the art hydrogen peroxide existed in a variety of manners.
From the angle of the safety improving the method according to the invention further, according to the side of the present invention
Method is preferably used the hydrogen peroxide existed as an aqueous solution.The method according to the invention, at described peroxide
When change hydrogen provides as an aqueous solution, the concentration of described aqueous hydrogen peroxide solution can be the routine of this area
Concentration, such as: 20-80 weight %.Concentration meets the aqueous solution of the hydrogen peroxide of above-mentioned requirements and can adopt
Prepare by conventional method, it is also possible to be commercially available, such as: can be 30 weight that can be commercially available
The hydrogen peroxide of %, the hydrogen peroxide of 50 weight % or the hydrogen peroxide of 70 weight %.
The consumption of described oxidant can be conventional selection, is not particularly limited.Usually, dimethyl disulfide
Ether can be 1:0.1-2, preferably 1:0.5-1.5 with the mol ratio of oxidant.
The method according to the invention, from the mixing journey improved further reaction system between each reactant
Degree, enhanced dispersion and more easily the angle that is adjusted of severe degree of reaction is set out, described in connect
Touch and carry out the most in the presence of at least one solvent.The kind of described solvent is not particularly limited.Typically
Ground, described solvent can be selected from water, C1-C6Alcohol, C3-C8Ketone and C2-C6Nitrile.Described solvent
Instantiation can include but not limited to: water, methanol, ethanol, normal propyl alcohol, isopropanol, the tert-butyl alcohol,
Isobutanol, acetone, butanone and acetonitrile.Preferably, described solvent is selected from water and C1-C6Alcohol.More excellent
Selection of land, described solvent is methanol and/or water.Can be the water in various source as the water of solvent, described
Oxidant is hydrogen peroxide, and when hydrogen peroxide provides as an aqueous solution, in aqueous hydrogen peroxide solution
Water can use as solvent.
The consumption of described solvent is not particularly limited, and can be conventional selection.Usually, solvent and diformazan
The weight ratio of base thioether can be with 0.1-1000:1, preferably 1-800:1, more preferably 5-200:1.
Furthermore it is also possible to according to dimethyl sulfide and oxidant being carried out the form that contacts not with HTS
With, the consumption of solvent is carried out suitable adjustment.
The method according to the invention, described oxidation reaction condition is not particularly limited, and can be this area
Conventional selection.Usually, described oxidation reaction condition includes: temperature can be 0-100 DEG C, is preferably
20-80℃；In terms of gauge pressure, pressure can be 0-3MPa, preferably 0.1-2.5MPa.
Method according to the invention it is possible to employing intermittently operated, it would however also be possible to employ continuous operation.
The method according to the invention can also include the mixture containing dimethyl sulfoxide contact obtained
Separate, to isolate dimethyl sulfoxide therein.The present invention is for isolating the mixing that contact obtains
The method of the dimethyl sulfoxide in thing is not particularly limited, and can be the conventional selection of this area.Such as may be used
Carry out fractional distillation with the mixture by contact being obtained, thus obtain dimethyl sulfoxide.
Below with reference to embodiment, the invention will be further described, but and is not so limited the interior of the present invention
Hold.
In following example and comparative example, if not otherwise specified, used reagent is commercially available reagent.
In following example and comparative example, the hydrogen peroxide of use is the hydrogen peroxide of 30 weight %.
In following example and comparative example, pressure is all in terms of gauge pressure.
In following example and comparative example, DTG is used to measure in the HTS containing template
The content of template, concrete method of testing is: in the heat that model is TA951 commercially available from E.I.Du Pont Company
HTS rate of weight loss between 200-800 DEG C, this rate of weight loss is measured on weight analysis instrument
Corresponding to the content of template, wherein, heating rate is 10 DEG C/min, tests in air atmosphere.
In following example and comparative example, gas chromatography is used to analyze each composition in the reactant liquor obtained
Content, be respectively adopted below equation on this basis to calculate the conversion ratio of dimethyl sulfide, oxidant
Effective rate of utilization and the selectivity of dimethyl sulfoxide:
The dimethyl sulfide conversion ratio=[(mole of the dimethyl sulfide of addition-unreacted dimethyl disulfide
Ether mole)/the mole of dimethyl sulfide that adds] × 100%；
Oxidant effective rate of utilization=[mole/(oxidant of addition of the dimethyl sulfoxide that reaction generates
The mole of mole-unreacted oxidant)] × 100%；
Dimethyl sulfoxide selectivity=[mole/(dimethyl of addition of the dimethyl sulfoxide that reaction generates
The mole of thioether-unreacted dimethyl sulfide mole)] × 100%.
Embodiment 1-10 is for the method that the present invention is described.
Embodiment 1
(1) catalyst is provided
The second HTS used in the present embodiment is titanium-silicon molecular sieve TS-1, with reference to Zeolites,
Prepared by 1992, the Vol.12 methods described in the 943-950 page, concrete grammar is as follows.
At room temperature (20 DEG C), using 22.5 grams of tetraethyl orthosilicates and 7.0 grams as the 4 third of template
Base ammonium hydroxide mixes, and adds 59.8 grams of distilled water, in normal pressure and 60 DEG C of hydrolysis 1.0 after stirring mixing
Hour, obtain the hydrating solution of tetraethyl orthosilicate.With vigorous stirring, slow in described hydrating solution
Slowly add the solution being made up of 1.1 grams of butyl titanates and 5.0 grams of anhydrous isopropyl alcohols, gained is mixed
Compound stirs 3 hours at 75 DEG C, obtains clear colloid.This colloid is placed in rustless steel and seals reaction
In still, at a temperature of 170 DEG C, constant temperature is placed 36 hours, obtains the mixture of crystallization product.To obtain
Mixture filter, after collecting the solid matter water used wash that obtains, be dried 60 minutes in 110 DEG C, connect
500 DEG C of roastings 6 hours, thus obtain the second HTS, its titanium oxide content is 2.5 weights
Amount %.
The method identical with the second HTS is used to prepare the first HTS, except for the difference that, no
Roasting is carried out at 500 DEG C, but by 110 DEG C of titanium silicon containing template obtained after being dried 60 minutes
Molecular sieve TS-1 is as the first HTS, and its titanium oxide content is 2.5 weight %, containing of template
Amount is 14.2 weight %.
Second HTS and the first HTS are mixed by weight for 2:1, thus obtains
Catalyst C1.
(2) dimethyl sulfoxide is prepared
Using dimethyl sulfide, the hydrogen peroxide as oxidant, the methanol as solvent and catalyst C1
Send into equipped with the slurry bed reactor of membrane separator carries out oxidation reaction, obtain containing dimethyl sulfoxide
Mixture.Wherein, dimethyl sulfide is 1:1, dimethyl sulfide and catalysis with the mol ratio of oxidant
The weight ratio of agent C1 is 5:1, and solvent is 50:1 with the weight ratio of catalyst C1, and reaction temperature is
30 DEG C, the pressure in reactor is 0.5MPa, and the volume space velocity of reaction mass is 20h-1.
The mixture that reaction obtains is separated into the liquid-phase mixing containing dimethyl sulfoxide in membrane separator
Thing and the residue containing catalyst, the residue containing catalyst is sent in reactor and is recycled.
Liquid phase mixture gas chromatography containing dimethyl sulfoxide is analyzed, and calculates dimethyl disulfide
Ether conversion ratio, oxidant effective rate of utilization and dimethyl sulfoxide selectivity.Wherein, reaction is proceeded to 0.5
Hour and 6 little constantly from reactor the mixture of output be analyzed the result that obtains respectively in Table 1
List.
Comparative example 1
(1) use method same as in Example 1 to provide catalyst, except for the difference that, do not use second
HTS, but using the first HTS as catalyst D1.
(2) method same as in Example 1 is used to prepare dimethyl sulfoxide, except for the difference that, catalyst
The catalyst D1 of C1 equivalent replaces.
Wherein, reaction is proceeded to 0.5 hour and the 6 little mixture difference of output from reactor constantly
The result being analyzed obtaining is listed in Table 1.
Comparative example 2
(1) use method same as in Example 1 to provide catalyst, except for the difference that, do not use first
HTS, but using the second HTS as catalyst D2.
(2) method same as in Example 1 is used to prepare dimethyl sulfoxide, except for the difference that, catalyst
The catalyst D2 of C1 equivalent replaces.
Wherein, reaction is proceeded to 0.5 hour and the 6 little mixture difference of output from reactor constantly
The result being analyzed obtaining is listed in Table 1.
Embodiment 2
(1) method same as in Example 1 is used to provide catalyst, except for the difference that, by the second titanium silicon
Molecular sieve and the first HTS obtain catalyst C2 by weight mixing for 5:1.
(2) method same as in Example 1 is used to prepare dimethyl sulfoxide, except for the difference that, dimethyl
Thioether is 2:3 with the mol ratio of oxidant, and dimethyl sulfide is 2:1 with the weight ratio of catalyst C2,
Solvent is 200:1 with the weight ratio of catalyst C2, and reaction temperature is 40 DEG C, and the pressure in reactor is
0.2MPa, the volume space velocity of reaction mass is 10h-1。
Wherein, reaction is proceeded to 0.5 hour and the 6 little mixture difference of output from reactor constantly
The result being analyzed obtaining is listed in Table 1.
Table 1
Embodiment 3
(1) catalyst is provided
With reference to the method disclosed in Chinese patent CN1132699C, following methods is used to prepare hollow titanium silicon
Molecular sieve, and as the second HTS:
The second HTS embodiment 1 obtained is according to molecular sieve (in gram): sulphuric acid is (to rub
You count): the ratio mix homogeneously of water (in mol)=100:0.15:150, in 90 DEG C of reactions
5.0 hour.Then, the mixture obtained is filtered, after the solid matter collected is washed,
It is dried 2 hours at 120 DEG C, obtains the TS-1 molecular sieve of acid treatment.The TS-1 of acid treatment that will obtain
Molecular sieve is according to molecular sieve (in gram): triethanolamine (in mol): TPAOH (with
Mole meter): the ratio mix homogeneously of water (in mol)=100:0.20:0.15:180, put into
Rustless steel sealed reactor, at the temperature of 190 DEG C and self-generated pressure, constant temperature is placed 12 hours, and cooling is unloaded
After pressure, the mixture obtained is filtered, after collecting solid matter and washing, be dried 2 at 120 DEG C
Hour, then 550 DEG C of roastings 5 hours, thus obtain the second HTS, its titanium oxide content
It is 2.5 weight %.
The method identical with the second HTS is used to prepare the first HTS, except for the difference that, no
Roasting is carried out at 500 DEG C, but hollow containing template that will obtain after being dried 2 hours at 120 DEG C
HTS is as the first HTS, and its titanium oxide content is 2.4 weight %, containing of template
Amount is 7.3 weight %.
Second HTS and the first HTS are mixed by weight for 5:1, thus obtains
Catalyst C3.
(2) method same as in Example 1 is used to prepare dimethyl sulfoxide, except for the difference that, dimethyl
Thioether is 1:0.5 with the mol ratio of oxidant, and dimethyl sulfide is 50 with the weight ratio of catalyst C3:
1, solvent is 80:1 with the weight ratio of catalyst C3, and reaction temperature is 20 DEG C, the pressure in reactor
For 0.5MPa, the volume space velocity of reaction mass is 2.0h-1。
The liquid phase mixture gas chromatography containing dimethyl sulfoxide obtained is analyzed, and calculates
Dimethyl sulfide conversion ratio, oxidant effective rate of utilization and dimethyl sulfoxide selectivity.Wherein, to reaction
Proceed to 0.5 hour, 6 hours and 110 little constantly from reactor the mixture of output carry out respectively point
The result that analysis obtains is listed in table 2.
Embodiment 4
(1) method same as in Example 3 is used to provide catalyst, except for the difference that, by the second titanium silicon
Molecular sieve and the first HTS mix by weight 2:1, thus obtain catalyst C4.
(2) method same as in Example 3 is used to prepare dimethyl sulfoxide, except for the difference that, catalyst
The catalyst C4 of C3 equivalent replaces.
Wherein, reaction is proceeded to the little output from reactor constantly in 0.5 hour, 6 hours and 110
The result that mixture is analyzed obtaining respectively is listed in table 2.
Comparative example 3
(1) use method same as in Example 3 to provide catalyst, except for the difference that, do not use first
HTS, but using the second HTS as catalyst D3.
(2) method same as in Example 3 is used to prepare dimethyl sulfoxide, except for the difference that, catalyst
The catalyst D3 of C3 equivalent replaces.
Wherein, reaction is proceeded to the little output from reactor constantly in 0.5 hour, 6 hours and 110
The result that mixture is analyzed obtaining respectively is listed in table 2.
Comparative example 4
(1) use method same as in Example 3 to provide catalyst, except for the difference that, do not use second
HTS, but using the first HTS as catalyst D4.
(2) method same as in Example 3 is used to prepare dimethyl sulfoxide, except for the difference that, catalyst
The catalyst D4 of C3 equivalent replaces.
Wherein, reaction is proceeded to the little output from reactor constantly in 0.5 hour, 6 hours and 110
The result that mixture is analyzed obtaining respectively is listed in table 2.
Comparative example 5
Use method same as in Example 3 to prepare dimethyl sulfoxide, except for the difference that, do not use catalyst.
Wherein, reaction proceeds to the 0.5 little mixture exported from reactor constantly be analyzed respectively
The result obtained is listed in table 2.
Table 2
Embodiment 5
(1) catalyst is provided
With reference to Zeolites, 1992, the Vol.12 methods described in the 943-950 page prepare titanium silicon molecule
Sieving TS-1 and as the second HTS, concrete grammar is as follows.
At room temperature (20 DEG C), using 22.5 grams of tetraethyl orthosilicates and 10.0 grams of three second as template
Hydramine mixes, and adds 59.8 grams of distilled water, hydrolyzes 1.0 hours in normal pressure and 60 DEG C after stirring mixing,
Obtain the hydrating solution of tetraethyl orthosilicate.With vigorous stirring, add lentamente in described hydrating solution
Enter the solution being made up of 1.0 grams of butyl titanates and 5.0 grams of anhydrous isopropyl alcohols, gained mixture is existed
75 DEG C are stirred 3 hours, obtain clear colloid.This colloid is placed in rustless steel sealed reactor,
At a temperature of 170 DEG C, constant temperature is placed 36 hours, obtains the mixture of crystallization product.The mixture that will obtain
Filter, after collecting the solid matter water used wash obtained, be dried 60 minutes in 110 DEG C, then 550
DEG C roasting 4 hours, thus obtain the second HTS.
The method identical with the second HTS is used to prepare the first HTS, except for the difference that, no
Roasting is carried out at 500 DEG C, but by 110 DEG C of titanium silicon containing template obtained after being dried 60 minutes
Molecular sieve TS-1 is as the first HTS, and its titanium oxide content is 2.1 weight %, template content
It is 13.2 weight %.
Second HTS and the first HTS are mixed by weight 1:1, thus is urged
Agent C5.
(2) dimethyl sulfoxide is prepared
Dimethyl sulfide, the hydrogen peroxide as oxidant, the water as solvent and catalyst C5 are sent
Enter equipped with the slurry bed reactor of membrane separator carries out oxidation reaction, obtain containing dimethyl sulfoxide
Mixture.Wherein, dimethyl sulfide is 1:1.5, dimethyl sulfide and catalysis with the mol ratio of oxidant
The weight ratio of agent C5 is 10:1, and solvent is 5:1 with the weight ratio of catalyst C5, and reaction temperature is
40 DEG C, the pressure in reactor is 0.5MPa, and the volume space velocity of reaction mass is 25.0h-1。
The mixture that reaction obtains is separated into the liquid-phase mixing containing dimethyl sulfoxide in membrane separator
Thing and the residue containing catalyst, the residue containing catalyst is sent in reactor and is recycled.
Liquid phase mixture gas chromatography containing dimethyl sulfoxide is analyzed, and calculates dimethyl disulfide
Ether conversion ratio, oxidant effective rate of utilization and dimethyl sulfoxide selectivity.Wherein, reaction is proceeded to 0.5
Hour and 6 little constantly from reactor the mixture of output be analyzed the result that obtains respectively in table 3
List.
Embodiment 6
(1) catalyst is provided
With reference to Zeolites, 1992, the Vol.12 methods described in the 943-950 page prepare titanium silicon molecule
Sieving TS-1 and as the second HTS, concrete grammar is as follows.
At room temperature (20 DEG C), using 25.5 grams of tetraethyl orthosilicates and 15.0 grams of positive fourths as template
Amine mixes, and adds 40.8 grams of distilled water, hydrolyzes 1.0 hours after stirring mixing at normal pressure and 60 DEG C,
Obtain the hydrating solution of tetraethyl orthosilicate.With vigorous stirring, add lentamente in described hydrating solution
Enter the solution being made up of 1.0 grams of butyl titanates and 5.0 grams of anhydrous isopropyl alcohols, gained mixture is existed
75 DEG C are stirred 3 hours, obtain clear colloid.This colloid is placed in rustless steel sealed reactor,
At a temperature of 170 DEG C, constant temperature is placed 36 hours, obtains the mixture of crystallization product.The mixing that will obtain
Thing filters, and after collecting the solid matter water used wash obtained, is dried 60 minutes in 110 DEG C, then exists
550 DEG C of roastings 5 hours, thus obtain the second HTS.
The method identical with the second HTS is used to prepare the first HTS, except for the difference that, no
Roasting is carried out at 500 DEG C, but by 110 DEG C of titanium silicon containing template obtained after being dried 60 minutes
Molecular sieve TS-1 is as the first HTS, and its titanium oxide content is 2.0 weight %, template content
It is 12.7 weight %.
Second HTS and the first HTS are mixed by weight 3:1, thus is urged
Agent C6.
(2) dimethyl sulfoxide is prepared
Using dimethyl sulfide, the hydrogen peroxide as oxidant, the methanol as solvent and catalyst C6
Send into equipped with the slurry bed reactor of membrane separator carries out oxidation reaction, obtain containing dimethyl sulfoxide
Mixture.Wherein, the mol ratio of dimethyl sulfide and oxidant is 1:0.5, dimethyl sulfide with urge
The weight ratio of agent C6 is 2:1, and solvent is 10:1 with the weight ratio of catalyst C6, reaction temperature
Being 50 DEG C, the pressure in reactor is 1.5MPa, and the volume space velocity of reaction mass is 15.0h-1。
The mixture that reaction obtains is separated into the liquid-phase mixing containing dimethyl sulfoxide in membrane separator
Thing and the residue containing catalyst, the residue containing catalyst is sent in reactor and is recycled.
Liquid phase mixture gas chromatography containing dimethyl sulfoxide is analyzed, and calculates dimethyl disulfide
Ether conversion ratio, oxidant effective rate of utilization and dimethyl sulfoxide selectivity.Wherein, reaction is proceeded to 0.5
Hour and 6 little constantly from reactor the mixture of output be analyzed the result that obtains respectively in table 3
List.
Table 3
Embodiment 7-10 uses following methods to measure the activity of HTS.
By HTS, 36 weight % ammonia (with NH3Meter), the hydrogen peroxide of 30 weight % (with
H2O2Meter), the tert-butyl alcohol and Ketohexamethylene by weight after=1:7.5:10:7.5:10 mixing at atmospheric pressure
Under power after 80 DEG C of stirring reaction 2h, reactant is filtered, with gas chromatography, the composition of liquid phase is entered
Row is analyzed, and uses below equation to calculate the conversion ratio of Ketohexamethylene and as the activity of HTS,
The conversion ratio (%) of the Ketohexamethylene=[(mole of the Ketohexamethylene of addition-unreacted Ketohexamethylene
Mole)/the mole of Ketohexamethylene that adds] × 100%.
Embodiment 7
(1) using method same as in Example 1 to provide catalyst, except for the difference that, the second titanium silicon divides
Son sieve is the temperature of 550 DEG C by the titanium-silicon molecular sieve TS-1 that draws off from cyclohexanone oxamidinating course of reaction
Under in air atmosphere roasting 4 hours and obtain, wherein, activity is 40%, the activity when fresh
It is 95%.By this second HTS according to ratio same as in Example 1 and the first HTS
Mixing, thus obtain catalyst C7.
(2) method same as in Example 1 is used to prepare dimethyl sulfoxide, except for the difference that, catalyst
The catalyst C7 of C1 equivalent replaces.
Liquid phase mixture gas chromatography containing dimethyl sulfoxide is analyzed, and calculates dimethyl disulfide
Ether conversion ratio, oxidant effective rate of utilization and dimethyl sulfoxide selectivity.Wherein, reaction is proceeded to 0.5
Hour, 6 hours and 110 little constantly from reactor the mixture of output be analyzed the knot that obtains respectively
Fruit is listed in table 4.
Embodiment 8
(1) using method same as in Example 3 to provide catalyst, except for the difference that, the second titanium silicon divides
Son sieves the hollow titanium si molecular sieves for drawing off from phenol hydroxylation reaction unit at a temperature of 570 DEG C
Roasting 4 hours in air atmosphere and obtain, its activity is 30%, and the activity when fresh is 96%.
This second HTS is mixed with the first HTS according to ratio same as in Example 3, from
And obtain catalyst C8.
(2) method same as in Example 3 is used to prepare dimethyl sulfoxide, except for the difference that, catalyst
The catalyst C8 of C3 equivalent replaces.
Liquid phase mixture gas chromatography containing dimethyl sulfoxide is analyzed, and calculates dimethyl disulfide
Ether conversion ratio, oxidant effective rate of utilization and dimethyl sulfoxide selectivity.Wherein, reaction is proceeded to 0.5
Hour, 6 hours and 110 little constantly from reactor the mixture of output be analyzed the knot that obtains respectively
Fruit is listed in table 4.
Embodiment 9
(1) using method same as in Example 6 to provide catalyst, except for the difference that, the second titanium silicon divides
Son sieves the hollow titanium si molecular sieves for drawing off from propylene ring oxidation reaction device at a temperature of 570 DEG C
Roasting 4 hours in air atmosphere and obtain, its activity is 12%, and the activity when fresh is 96%.
This second HTS is mixed with the first HTS according to ratio same as in Example 6, from
And obtain catalyst C9.
(2) method same as in Example 6 is used to prepare dimethyl sulfoxide, except for the difference that, catalyst
The catalyst C9 of C6 equivalent replaces.
Liquid phase mixture gas chromatography containing dimethyl sulfoxide is analyzed, and calculates dimethyl disulfide
Ether conversion ratio, oxidant effective rate of utilization and dimethyl sulfoxide selectivity.Wherein, reaction is proceeded to 0.5
Hour, 6 hours and 110 constantly from reactor the mixture of output be analyzed the result that obtains respectively
List in table 4.
Embodiment 10
(1) using method same as in Example 3 to provide catalyst, except for the difference that, the second titanium silicon divides
Son sieve by (A) by the hollow titanium si molecular sieves that draws off from propylene ring oxidation reaction device at 570 DEG C
At a temperature of in air atmosphere roasting 4 hours and the regenerative agent that obtains, its activity is 48%, when fresh
Activity be 96%；And the hollow titanium silicon molecule that (B) is prepared according to method same as in Example 3
Screen banks becomes, and wherein, the weight ratio of HTS prepared by regenerative agent method same as in Example 3 is
1:1.This second HTS is mixed with the first HTS according to ratio same as in Example 3
Close, thus obtain catalyst C10.
(2) method same as in Example 3 is used to prepare dimethyl sulfoxide, except for the difference that, catalyst
The catalyst C10 of C3 equivalent replaces.
Liquid phase mixture gas chromatography containing dimethyl sulfoxide is analyzed, and calculates dimethyl disulfide
Ether conversion ratio, oxidant effective rate of utilization and dimethyl sulfoxide selectivity.Wherein, reaction is proceeded to 0.5
Hour, 6 hours and 110 little constantly from reactor the mixture of output be analyzed the knot that obtains respectively
Fruit is listed in table 4.
Table 4
Claims (12)
1. the method preparing dimethyl sulfoxide, the method is included under oxidation reaction condition, by two
Dimethyl sulfide contacts with HTS with at least one oxidant, and wherein, described HTS contains
First HTS and the second HTS, described first HTS contains template, described
Second HTS does not contains template, on the basis of the total amount of described HTS, described first titanium
The content of si molecular sieves is 15-50 weight %, and the content of described second HTS is 50-85 weight
%, in described first HTS, the content of template is 5-15 weight %.
Method the most according to claim 1, wherein, described template is quaternary ammonium base, aliphatic
One or more in amine and aliphatic hydramine.
Method the most according to claim 1, wherein, the most described second HTS
For through regeneration the reaction unit using HTS as catalyst draw off agent.
Method the most according to claim 3, wherein, described in draw off agent be Ammoximation reaction device
Draw off agent, hydroxylating device draw off agent and the one drawing off in agent of epoxidation reaction device or
Multiple.
Method the most according to claim 3, wherein, in described second HTS, through again
The content drawing off agent of the raw reaction unit using HTS as catalyst is for 5-100 weight %.
Method the most according to claim 1, wherein, dimethyl sulfide and described HTS
Weight ratio be 0.1-50:1.
Method the most according to claim 1, wherein, described contact exists at least one solvent
Under carry out, the weight ratio of described solvent and dimethyl sulfide is 0.1-1000:1.
Method the most according to claim 7, wherein, described solvent is selected from water, C1-C6Alcohol,
C3-C8Ketone and C2-C6Nitrile.
Method the most according to claim 1, wherein, dimethyl sulfide and the mol ratio of oxidant
For 1:0.1-2.
10. according to the method described in claim 1 or 9, wherein, described oxidant is peroxide.
11. methods according to claim 10, wherein, described oxidant selected from hydrogen peroxide,
Tert-butyl hydroperoxide, dicumyl peroxide, cyclohexyl hydroperoxide, peracetic acid and Perpropionic Acid.
12. methods according to claim 1, wherein, described oxidation reaction condition includes: temperature
For 0-100 DEG C；And in terms of gauge pressure, pressure is 0-3MPa.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201310520958.9A CN104557631B (en) | 2013-10-29 | 2013-10-29 | A kind of method preparing dimethyl sulfoxide |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201310520958.9A CN104557631B (en) | 2013-10-29 | 2013-10-29 | A kind of method preparing dimethyl sulfoxide |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN104557631A CN104557631A (en) | 2015-04-29 |
| CN104557631B true CN104557631B (en) | 2016-08-17 |
Family
ID=53074810
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN201310520958.9A Active CN104557631B (en) | 2013-10-29 | 2013-10-29 | A kind of method preparing dimethyl sulfoxide |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN104557631B (en) |
Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1301599A (en) * | 1999-12-24 | 2001-07-04 | 中国石油化工集团公司 | Titanium-silicon molecular sieve and its preparing method |
| 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 |
| CN103288691A (en) * | 2012-02-29 | 2013-09-11 | 中国石油化工股份有限公司 | Method for oxidizing dimethyl sulfide |
| CN103289727A (en) * | 2012-02-29 | 2013-09-11 | 中国石油化工股份有限公司 | Method for oxidizing sulphur-containing compound |
-
2013
- 2013-10-29 CN CN201310520958.9A patent/CN104557631B/en active Active
Patent Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1301599A (en) * | 1999-12-24 | 2001-07-04 | 中国石油化工集团公司 | Titanium-silicon molecular sieve and its preparing method |
| CN103288691A (en) * | 2012-02-29 | 2013-09-11 | 中国石油化工股份有限公司 | Method for oxidizing dimethyl sulfide |
| CN103289727A (en) * | 2012-02-29 | 2013-09-11 | 中国石油化工股份有限公司 | Method for oxidizing sulphur-containing compound |
| 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 |
Non-Patent Citations (3)
| Title |
|---|
| Sulfoxidation of Thioethers using Titanium Silicate Molecular Sieve Catalysts;Ravinder S. Reddy等;《J . CHEM. SOC., CHEM. COMMUN.》;19921231(第2期);第84页左栏第2段，右栏表1 * |
| TS-1分子筛与模板剂结构相容性的分子模拟;周涵 等;《石油学报(石油加工)》;20040108;第16卷(第4期);第43-48页 * |
| 钛硅分子筛的合成及改性研究;李海龙;《大连理工大学硕士学位论文》;20130815;第1-79页 * |
Also Published As
| Publication number | Publication date |
|---|---|
| CN104557631A (en) | 2015-04-29 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN105439815B (en) | A kind of method for preparing propane diols | |
| CN104557630B (en) | A kind of preparation method of dimethyl sulfoxide | |
| CN103182323B (en) | Regeneration method of deactivated titanium-silicon molecular sieve catalyst | |
| CN103182322B (en) | A kind of method processing deactivated titanium silicon molecular sieve | |
| CN105085201B (en) | A kind of method for preparing propylene glycol monomethyl ether | |
| CN104557479B (en) | A kind of method preparing propylene glycol monomethyl ether | |
| CN102309983A (en) | Method for regenerating inactivated titanium silicon molecular sieve | |
| CN105399609A (en) | Propylene glycol monomethyl ether preparation method | |
| CN104876907B (en) | Propylene carbonate preparation method | |
| CN104556109B (en) | Method for preparing titanosilicate molecular sieve and phenol oxidation method | |
| CN106967012B (en) | A kind of styrene oxidation method | |
| CN106966862A (en) | It is a kind of while preparing the method for propane diols and propene carbonate | |
| CN107235868B (en) | A kind of sulfide oxidation method | |
| CN102311128B (en) | Method for treating titanium-silicon molecular sieve | |
| CN104557631B (en) | A kind of method preparing dimethyl sulfoxide | |
| CN105367457B (en) | A kind of sulfide oxidation method | |
| CN104557632B (en) | Method for preparing dimethyl sulfoxide | |
| CN103508845A (en) | Method for oxidizing cyclohexane | |
| CN104557624B (en) | Method for preparing dimethyl sulfone | |
| CN106631930B (en) | A kind of sulfide oxidation method | |
| CN107721973A (en) | A kind of method for preparing single thiocarbonic acid propylene | |
| CN105439920B (en) | Method that is a kind of while producing dimethyl sulfoxide (DMSO) and acetone | |
| CN109593033A (en) | A kind of method of oxidizing cyclohexanone | |
| CN105367540A (en) | Method for simultaneously preparing propylene glycol monomethyl ether and propylene carbonate | |
| CN104418777B (en) | Preparation method of dimethyl sulfoxide |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| C06 | Publication | ||
| PB01 | Publication | ||
| C10 | Entry into substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| C14 | Grant of patent or utility model | ||
| GR01 | Patent grant |