CN104003914B - A kind of method preparing dimethyl sulfoxide - Google Patents
A kind of method preparing dimethyl sulfoxide Download PDFInfo
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- CN104003914B CN104003914B CN201310060248.2A CN201310060248A CN104003914B CN 104003914 B CN104003914 B CN 104003914B CN 201310060248 A CN201310060248 A CN 201310060248A CN 104003914 B CN104003914 B CN 104003914B
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Abstract
The invention provides a kind of method preparing dimethyl sulfoxide, the method is included under oxidation reaction condition, one liquid mixture is contacted with HTS, obtain the mixture containing dimethyl sulfoxide, described liquid mixture contains dimethyl sulfide and at least one peroxide, and the pH value of described liquid mixture is 59.The method according to the invention, it is possible to be effectively improved the effective rate of utilization of oxidant, the selectivity of dimethyl sulfoxide and dimethyl sulfide conversion ratio.Further, the good stability of the method according to the invention, runs continuously even if long-time, remains able to obtain high oxidant effective rate of utilization, dimethyl sulfoxide selectivity and dimethyl sulfide conversion ratio.
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..
Dimethyl sulfoxide typically uses dimethyl sulfide oxidizing process to prepare, according to the oxidant used and oxygen
The difference of change mode, generally includes nitric acid oxidation method, peroxide oxidation method, Ozonation, anode
Oxidizing process and nitrogen dioxide oxidizing process.
The reaction condition of peroxide oxidation method is gentle, and equipment and process route are simple, and product need not alkali
It is neutralized, and the most pollution-free to environment.But, in peroxide oxidation method, oxidant
Price is high and consumption is big, improves the production cost of dimethyl sulfoxide, limits peroxide oxidation method
Range of application.
Therefore, when using peroxide oxidation method to prepare dimethyl sulfoxide, improve the effective of oxidant
Utilization rate, the conversion ratio of dimethyl sulfide and the selectivity of dimethyl sulfoxide, reduce the life of dimethyl sulfoxide
Producing cost is an important problem.
Summary of the invention
It is an object of the invention to provide a kind of using peroxide as oxidant to prepare dimethyl sulfoxide
Method, the method can be effectively improved the effective rate of utilization of oxidant, dimethyl sulfide conversion ratio and
Dimethyl sulfoxide selectivity.
The invention provides a kind of method preparing dimethyl sulfoxide, the method is included in oxidation reaction condition
Under, one liquid mixture is contacted with HTS, obtains the mixture containing dimethyl sulfoxide,
Described liquid mixture contains dimethyl sulfide and at least one peroxide, described liquid mixture
PH value is 5-9.
The method according to the invention, it is possible to be effectively improved the effective rate of utilization of oxidant, dimethyl sulfoxide
Selectivity and dimethyl sulfide conversion ratio.Further, the good stability of the method according to the invention, even if
Long-time run continuously, remain able to obtain high oxidant effective rate of utilization, dimethyl sulfoxide selectivity
With dimethyl sulfide conversion ratio.
Detailed description of the invention
The invention provides a kind of method preparing dimethyl sulfoxide, the method is included in oxidation reaction condition
Under, one liquid mixture is contacted with HTS, obtains the mixture containing dimethyl sulfoxide,
Described liquid mixture contains dimethyl sulfide and at least one peroxide.
The method according to the invention, the pH value of described liquid mixture is 5-9.It is 5-9's by pH value
Liquid mixture contacts with HTS, it is possible to increase the effective rate of utilization of oxidant, dimethyl sulfide
Conversion ratio and dimethyl sulfoxide selectivity.Further, by by liquid mixture that pH value is 5-9 and titanium
Si molecular sieves contacts, even if running the most continuously, remaining able to obtain high oxidant has
Effect utilization rate, dimethyl sulfide conversion ratio and dimethyl sulfoxide selectivity.From improving oxidant further
The selective angle of effective rate of utilization and the conversion ratio of dimethyl sulfide and dimethyl sulfoxide is set out, institute
The pH value stating liquid mixture is 5.5-8.5.
Method according to the invention it is possible to the pH value of liquid mixture is adjusted by conventional various methods
Joint is for being within the scope of described previously.Specifically, can be by adding in described liquid mixture
At least one alkali compounds regulates the pH value of described liquid mixture.Herein, described basic species
Matter refers to that the pH value of its aqueous solution is the material more than 7.The instantiation of described alkaline matter can wrap
Include but be not limited to: ammonia (that is, NH3), amine, quaternary ammonium base and M1(OH)n(wherein, M1For alkali metal
Or alkaline-earth metal, n is and M1The identical integer of quantivalence).
As described alkaline matter, ammonia can introduce with the form of liquefied ammonia, it is also possible to draws as an aqueous solution
Enter, it is also possible to introduce in gaseous form.Concentration as the ammonia (that is, ammonia) of aqueous solution form does not has
It is particularly limited to, can be conventional selection, such as 1-36 weight %.
As described alkaline matter, amine refers to the hydrogen partial on ammonia or is all replaced the thing formed by alkyl
Matter, including primary amine, secondary amine and tertiary amine.Described amine be specifically as follows the material shown in Formulas I and/
Or C3-C11Heterocyclic amine,
(Formulas I)
In Formulas I, R1、R2And R3Can be each H or C1-C6Alkyl (such as C1-C6Alkyl),
And R1、R2And R3It is asynchronously H.Herein, C1-C6The instantiation of alkyl can include but not
Be limited to: methyl, ethyl, n-pro-pyl, isopropyl, normal-butyl, sec-butyl, isobutyl group, the tert-butyl group,
N-pentyl, isopentyl, tertiary pentyl, neopentyl and n-hexyl.
The instantiation of amine can include but not limited to: methylamine, dimethylamine, trimethylamine, ethamine, two
Ethamine, triethylamine, n-propylamine, di-n-propylamine, Tri-n-Propylamine, 2-aminopropane., diisopropylamine, positive fourth
Base amine, di-n-butyl amine, tri-n-butyl amine, sec-butylamine, diisobutyl amine, triisobutyl amine,
Tert-butylamine, n-amylamine, two n-amylamines, tri-n-amyl amine, neopentyl amine, isobutylcarbylamine, di-iso-amylamine,
Triisoamylamine, tertiary amylamine, n-hexylamine and 1-Aminooctane.
Described heterocyclic amine is the compound having on finger ring and having lone pair electrons on nitrogen-atoms and this nitrogen-atoms.
Described heterocyclic amine can be such as substituted or unsubstituted pyrroles, substituted or unsubstituted nafoxidine, take
Generation or unsubstituted pyridine, substituted or unsubstituted hexahydropyridine, substituted or unsubstituted imidazoles, replacement
Or unsubstituted pyrazoles, substituted or unsubstituted quinoline, substituted or unsubstituted dihydroquinoline, replacement or
Unsubstituted tetrahydroquinoline, substituted or unsubstituted decahydroquinoline, substituted or unsubstituted isoquinolin and
One or more in substituted or unsubstituted pyrimidine.
As described alkaline matter, quaternary ammonium base is specifically as follows the material shown in Formula II,
(Formula II)
In Formula II, R4、R5、R6And R7Can be each C1-C6Alkyl (such as C1-C6Alkyl).
Described C1-C6The instantiation of alkyl can include but not limited to: methyl, ethyl, n-pro-pyl, different
Propyl group, normal-butyl, sec-butyl, isobutyl group, the tert-butyl group, n-pentyl, neopentyl, isopentyl, uncle
Amyl group, n-hexyl.
The instantiation of described quaternary ammonium base can include but not limited to: Tetramethylammonium hydroxide, tetraethyl hydrogen
Amine-oxides, TPAOH (including four n-pro-pyl ammonium hydroxide and tetra isopropyl ammonium hydroxide),
TBAH (includes 4-n-butyl ammonium hydroxide, four sec-butyl ammonium hydroxide, four isobutyl group hydrogen
Amine-oxides and tetra-tert ammonium hydroxide) and four pentyl ammonium hydroxide.
As described alkaline matter, M1(OH)nFor alkali-metal hydroxide or the hydroxide of alkaline-earth metal
Thing, such as, can be sodium hydroxide, potassium hydroxide, magnesium hydroxide, barium hydroxide and calcium hydroxide.
The method according to the invention, described alkaline matter can be directly appended in described liquid mixture,
Add in described liquid mixture after described alkaline matter can also be configured to solution.
The method according to the invention, described alkaline matter is preferably ammonia.Use ammonia as alkaline matter, one
Aspect can regulate the pH value of described liquid mixture, and on the other hand ammonia is prone to remove, and will not give follow-up
Isolated and purified process increase burden.Meanwhile, ammonia is used can also to obtain higher oxygen as alkaline matter
Agent effective rate of utilization and dimethyl sulfoxide selectivity.
The method according to the invention, HTS plays as the catalyst aoxidized by dimethyl sulfide
Effect, its concrete consumption is as the criterion to be capable of catalysis.Usually, dimethyl sulfide and described titanium
The weight ratio of si molecular sieves can be 0.1-50:1.When reaction is carried out in fixed bed reactors, institute
The weight (hourly) space velocity (WHSV) stating liquid mixture can be according to the catalysis containing HTS of filling in reactor
The amount of agent carries out suitable selection.Usually, the weight (hourly) space velocity (WHSV) of described liquid mixture can be
0.1-500h-1, preferably 5-300h-1。
HTS is that titanium atom replaces the general name of a class zeolite of a part of silicon atom in lattice framework,
Chemical formula xTiO can be used2·SiO2Represent.The present invention does not has for the content of titanium atom in HTS
It is particularly limited to, can be the conventional selection of this area.Specifically, x can be 0.0001-0.04, excellent
Elect 0.01-0.03 as, more preferably 0.015-0.025.
Described HTS can be the common HTS with various topological structure, such as:
Described HTS can be selected from the HTS (such as TS-1) of MFI structure, MEL structure
HTS (such as TS-2), the HTS (such as Ti-Beta) of BEA structure, MWW structure
HTS (such as Ti-MCM-22), 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
Sieve (such as Ti-TUN) and the HTS (such as Ti-ZSM-48) of other structure.
Preferably, described HTS is selected from the HTS of MFI structure, the titanium of MEL structure
Si molecular sieves and the HTS of BEA structure.It is highly preferred that described HTS is MFI knot
The HTS of structure.
Sub-from improving the conversion ratio of dimethyl sulfide, the effective rate of utilization of oxidant and dimethyl further
The selective angle of sulfone is set out, and the crystal grain of described HTS is hollow-core construction, this hollow-core construction
The radical length of chamber portion is 5-300 nanometer, and described HTS is at 25 DEG C, P/P0=0.10、
Adsorption time be the benzene adsorbance recorded under conditions of 1 hour be at least 70 milligrams per gram, this titanium silicon molecule
Hysteresis loop is there is between adsorption isotherm and the desorption isotherm of the nitrogen absorption under low temperature of sieve.Herein, have
The HTS of this structure is referred to as hollow titanium si molecular sieves.Described hollow titanium si molecular sieves can be purchased
To (such as commercially available from the molecule that the trade mark is HTS of Sinopec Hunan Jianchang Petrochemical Co., Ltd
Sieve), it is also possible to prepare according to the method disclosed in CN1132699C.
The method according to the invention, as catalyst HTS according to reaction embodiment not
With, can have different forms.Specifically, the HTS as catalyst can be molecular sieve
Former powder, it is also possible to for the molecular sieve of molding.
In the HTS of described molding, the content of carrier can be the conventional selection of this area.Typically
Ground, on the basis of the total amount of the HTS of described molding, the content of described HTS can be
1-99 weight %, the content of described carrier can be 1-99 weight %.Obtaining higher catalysis activity
Under premise, from the angle of the intensity taking into account catalyst, with the total amount of the HTS of described molding
On the basis of, the content of described HTS is preferably 5-95 weight %, more preferably 10-95 weight %,
More preferably 40-95 weight %；The content of described carrier is preferably 5-95 weight %, more preferably
5-90 weight %, more preferably 5-60 weight %.
When the HTS that described HTS is molding, carrier can be common various heat-resisting
Inorganic oxide.Described heat-resistant inorganic oxide refers to that decomposition temperature is the lowest under oxygen or oxygen-containing atmosphere
Inorganic oxygen-containing compound in 300 DEG C (such as: decomposition temperature is 300-1000 DEG C).Specifically, institute
Stating carrier can be aluminium oxide, silicon oxide, titanium oxide, magnesium oxide, zirconium oxide, thorium oxide, beryllium oxide
With one or more in clay.
Various methods commonly used in the art can be used to prepare the HTS of molding.Such as: permissible
After HTS is mixed with support material, be shaped, and the article shaped obtained is dried with
And optional roasting, thus obtain the HTS of molding.Described support material is selected from heat resistant inorganic oxygen
Compound and the precursor of heat-resistant inorganic oxide.The precursor of described heat-resistant inorganic oxide can be can
Form the material of described heat-resistant inorganic oxide.Such as, when described heat-resistant inorganic oxide is aluminium oxide,
Described precursor can be various hydrated alumina；When described heat-resistant inorganic oxide is silicon oxide, institute
State precursor and can be selected from various Ludox and organosiloxane.
The present invention one preferred embodiment in, the preparation method of the HTS of described molding
Including: under the conditions of hydrolysis, at least one can be occurred hydrolysis organo-silicon compound and
At least one water-soluble alkali contacts with water, and mixture contact obtained mixes with HTS, and will
The mixture containing HTS obtained successively is shaped and roasting.Obtain according to this embodiment
The HTS of molding not only there is higher intensity, thus damage relatively more resistant to abrasive wear have higher anti-
Breaking capacity, the bed of the HTS containing this molding has higher anti-ability of caving in；And energy
Enough obtain higher oxidant effective rate of utilization, dimethyl sulfide conversion ratio and dimethyl sulfoxide selectivity.
This preferred embodiment in, described organo-silicon compound, water-soluble alkali and HTS
Consumption is can be as the criterion HTS molding, and the consumption of water is smoothed out to enable to hydrolysis
It is as the criterion.From crushing strength and the dimethyl of the HTS of the molding improving final preparation further
Thioether rate and the selective angle of dimethyl sulfoxide are set out, described HTS, organosilicon compound
The mass ratio of thing, water-soluble alkali and water is preferably 100:10-2000:2-40:50-2000, more preferably
100:100-500:5-40:50-1000, more preferably 100:100-500:5-40:50-500.
Described organo-silicon compound are not particularly limited, and can be that to have hydrolyzable on various silicon atom organic
Group, and the compound of silicon oxide can be formed by hydrolysis-condensation reaction.Specifically, described organosilicon
Compound can be selected from the siloxanes shown in formula III,
In formula III, R8、R9、R10And R11Can be each C1-C4Alkyl.Described C1-C4Alkane
Base includes C1-C4Straight chained alkyl and C3-C4Branched alkyl, its instantiation can include but not limit
In: methyl, ethyl, n-pro-pyl, isopropyl, normal-butyl, sec-butyl, isobutyl group and the tert-butyl group.
Preferably, described organo-silicon compound selected from methyl silicate, tetraethyl orthosilicate, positive n-propyl silicate,
Positive isopropyl silicate and positive silicic acid N-butyl.
Described water-soluble alkali can be the conventional various alkali that can be dissolved in water.Such as: described water solublity
Alkali can be chemical formula M2(OH)mThe compound represented, wherein, M2Can be alkali metal, alkaline earth gold
Genus, NH4 +Or quaternary ammonium group (that is, NH4 +In hydrogen atom by alkyl replace formed group, described alkyl
It is preferably C1-C20Alkyl, C3-C20Cycloalkyl or C6-C20Aryl), m is and M2Change
The integer that conjunction valency is identical；Described water-soluble alkali can also can be dissolved in the organic amine of water (preferably for various
For aliphatic amine) and/or hydramine (preferably aliphatic hydramine), its instantiation can include but not limit
In: ethamine, propylamine and isomer thereof, butylamine and isomer thereof, butanediamine, monoethanolamine, diethanol
Amine and triethanolamine.
Preferably, described water-soluble alkali is synthesis of titanium silicon molecular sieve template, is so obtained in that higher
Dimethyl sulfide conversion ratio, dimethyl sulfoxide selectivity and oxidant effective rate of utilization.Described synthesis titanium
Si molecular sieves template can be the various compounds being used as template when synthesis of titanium silicon molecular sieve, as
Quaternary ammonium base and/or organic amine, preferably quaternary ammonium base.Described quaternary ammonium base can be conventional selection, the most permissible
For the compound shown in formula IV:
In formula IV, R12、R13、R14And R15Can be each C1-C20Alkyl (include C1-C20
Straight chained alkyl and C3-C20Branched alkyl), C3-C20Cycloalkyl or C6-C20Aryl.Excellent
Selection of land, R12、R13、R14And R15It is respectively C1-C10Alkyl (include C1-C10Straight chained alkyl and
C3-C10Branched alkyl) and C3-C10Cycloalkyl.It is further preferred that R12、R13、R14With
R15It is respectively C1-C6Alkyl (include C1-C6Straight chained alkyl and C3-C6Branched alkyl).Described
C1-C20The instantiation of alkyl can include but not limited to: methyl, ethyl, n-pro-pyl, isopropyl,
Normal-butyl, sec-butyl, isobutyl group, the tert-butyl group, n-pentyl, neopentyl, isopentyl, tertiary pentyl,
N-hexyl, n-octyl, n-nonyl, positive decyl, n-undecane base, dodecyl, n-tridecane
In base, n-tetradecane base, Pentadecane base, n-hexadecyl, n-octadecane base and AI3-28404 base
One or more.Described C6-C20The example of aryl can include but not limited to: phenyl, naphthyl,
4-aminomethyl phenyl and 4-ethylphenyl.Described C3-C20The example of cycloalkyl can include but not limited to:
Cyclopropyl, cyclopenta, cyclohexyl, 4-methylcyclohexyl, 4-ethylcyclohexyl, 4-n-pro-pyl cyclohexyl
With 4-normal-butyl cyclohexyl.
The example of described quaternary ammonium base can include but not limited to: TPAOH (includes four n-pro-pyls
Ammonium hydroxide and tetra isopropyl ammonium hydroxide), tetraethyl ammonium hydroxide, Tetramethylammonium hydroxide and four fourths
Base ammonium hydroxide (includes 4-n-butyl ammonium hydroxide, four sec-butyl ammonium hydroxide, four isobutyl group hydroxides
Ammonium and tetra-tert ammonium hydroxide).
Described hydrolysis condition is not particularly limited, and can be conventional selection, with described organosilicon compound
Thing can hydrolyze and be as the criterion completely.Usually, described hydrolysis condition includes: temperature can be 20-100
DEG C, the time can be 0.5-10 hour.
In the present invention, by the mixture forming containing HTS obtained and the article shaped obtained is entered
Row is dried and the condition of roasting is also not particularly limited, and can be the conventional selection of this area.
Specifically, the mode of described molding can be extrusion, spraying, round as a ball, tabletting or combinations thereof.
The catalyst of described molding can have common variously-shaped, can be such as spherical, bar shaped, annular,
Cloverleaf pattern, honeycombed or butterfly etc., preferably spherical.
Under the normal condition of this area, article shaped can be dried, such as can be at 80-250 DEG C
At a temperature of, normal pressure or decompression under conditions of described article shaped is dried.
The condition of described roasting includes: temperature can be 350-600 DEG C, and the time can be 0.5-12 hour.
Described roasting is preferably carried out in oxygen-containing atmosphere, and described oxygen-containing atmosphere can be such as air atmosphere or oxygen
Atmosphere.
The granular size of the HTS of molding is also not particularly limited, and can carry out according to concrete shape
Suitable selection.As described in catalyst be spherical time, the mean diameter of described catalyst can be
4-5000 micron, preferably 5-2000 micron, more preferably 40-600 micron.Described mean diameter is
Use the volume average particle size that laser particle analyzer measures.
The method according to the invention, the consumption as the peroxide of oxidant can be according to dimethyl sulfide
Amount carry out suitable selection.Usually, dimethyl sulfide is 1 with the mol ratio of described peroxide:
0.1-4.The method according to the invention, by the pH value of described liquid mixture is adjusted to meet above
Within the scope of described, even if when the large usage quantity of peroxide, remain able to obtain the highest diformazan
The selectivity of base sulfoxide, in the product obtained, the content of dimethyl sulfone is low.Preferably, dimethyl sulfide with
The mol ratio of described peroxide is 1:0.2-2.
Described peroxide refers to the compound in molecular structure containing-O-O-key, can be selected from peroxidating
Hydrogen, hydroperoxides and peracid.Described hydroperoxides refer to a hydrogen atom in hydrogen peroxide molecule
The material replaced by organic group and obtain.Described peracid refers to having containing-O-O-key in molecular structure
Machine oxyacid.The instantiation of described peroxide can include but not limited to: hydrogen peroxide, the tert-butyl group
Hydrogen peroxide, dicumyl peroxide, cyclohexyl hydroperoxide, peracetic acid and Perpropionic Acid.Preferably,
Described oxidant is hydrogen peroxide, so can reduce separation costs further.Described hydrogen peroxide is permissible
For the commonly used in the art hydrogen peroxide existed in a variety of manners.From improving the side according to the present invention further
The angle of the safety of method is set out, and the method according to the invention is preferably used the mistake existed as an aqueous solution
Hydrogen oxide.The method according to the invention, when described hydrogen peroxide provides as an aqueous solution, described mistake
The concentration of hydrogen oxide aqueous solution can be the normal concentration of this area, such as: 20-80 weight %.Concentration
The aqueous solution of the hydrogen peroxide meeting above-mentioned requirements can use conventional method to prepare, it is also possible to is purchased
Arrive, such as: can be the hydrogen peroxide of 30 weight %, the hydrogen peroxide of 50 weight % that can be commercially available
Or 70 hydrogen peroxide of weight %.
The method according to the invention, described liquid mixture can also contain at least one solvent.Described molten
Agent can be various can either dissolve dimethyl sulfide and peroxide or promote the two mixing, can promote again
Enter the liquid substance of dmso solution.Usually, described solvent can be selected from water, C1-C6Alcohol,
C3-C8Ketone and C2-C6Nitrile.The instantiation of described solvent can include but not limited to: water, methanol,
Ethanol, normal propyl alcohol, isopropanol, the tert-butyl alcohol, isobutanol, acetone, butanone and acetonitrile.Preferably, institute
State solvent selected from water and C1-C6Alcohol.It is highly preferred that described solvent is methanol and/or water.As solvent
Water can be the water in various source, be hydrogen peroxide at described oxidant, and hydrogen peroxide be with aqueous solution
When form provides, the water in aqueous hydrogen peroxide solution can use as solvent.
The consumption of solvent can carry out suitable selection according to the consumption of dimethyl sulfide and oxidant.Preferably
Ground, dimethyl sulfide is 1:0.1-20 with the weight ratio of described solvent.It is highly preferred that dimethyl sulfide
It is 1:1-10 with the weight ratio of described solvent.The concrete consumption of solvent and the kind of solvent and the bar of reaction
Parts etc. have certain relation, and those skilled in the art can properly select as the case may be.
The method according to the invention, described oxidation reaction condition can be conventional selection, with can be by diformazan
Base sulfide oxidation becomes dimethyl sulfoxide and is as the criterion.Usually, described oxidation reaction condition includes: temperature can
Think 0-80 DEG C, preferably 20-60 DEG C；Pressure can be 0-3MPa, preferably 0.1-1.5MPa.This
Wen Zhong, pressure is gauge pressure.The method according to the invention, connects described liquid mixture with HTS
The time touched can carry out suitable selection according to the mode of contact.
Method according to the invention it is possible to employing intermittently operated, it would however also be possible to employ continuous operation, there is no spy
Do not limit.Feed way can also be any suitable way well known by persons skilled in the art.Specifically,
When carrying out with andnon-continuous operation manner, can be by dimethyl sulfide, oxidant, catalyst and optional
Solvent adds in reactor, reacts.In a continuous manner time, can be common various solid
Fixed bed reactor or slurry bed reactor are carried out.
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.
The method according to the invention, using HTS as catalyst, will connect with HTS simultaneously
The pH value of the liquid mixture touched is adjusted to 5-9(and is preferably 5.5-8.5), it is possible to increase having of oxidant
Effect utilization rate and the selectivity of dimethyl sulfoxide, can also obtain high dimethyl sulfide simultaneously and convert
Rate.Further, the stability that the method according to the invention has also had, run continuously, still even if long-time
So it is obtained in that high dimethyl sulfide conversion ratio, oxidant effective rate of utilization and dimethyl sulfoxide selects
Property.The one of the method according to the invention preferred embodiment, is using hollow titanium si molecular sieves conduct
During catalyst, it is possible to further enhance the diffusion velocity of reactant and product, reduce side reaction further
Occur such that it is able to obtain higher oxidant effective rate of utilization, dimethyl sulfoxide selectivity and dimethyl
Thioether selectivity.
The present invention is described in detail below in conjunction with embodiment and comparative example.
In following example and comparative example, if not otherwise specified, used reagent is commercially available analysis
Pure reagent.
In following example and comparative example, pressure is all in terms of gauge pressure.
In following example, titanium-silicon molecular sieve TS-1 used is according to Zeolites, the 1992, the 12nd
Rolling up, prepared by the method described in the 943-950 page, its titanium oxide content is 2.5 weight %.
In following example, hollow titanium si molecular sieves used is according in Chinese patent CN1132699C
Prepared by disclosed method, through analyzing, this HTS is MFI structure, this HTS low
There is hysteresis loop between adsorption isotherm and the desorption isotherm of temperature N2 adsorption, crystal grain is hollow crystal grain and sky
The radical length of cavity segment is 15-180 nanometer；This HTS sample at 25 DEG C, P/P0=0.10,
Adsorption time be the benzene adsorbance recorded under conditions of 1 hour be 78 milligrams per gram, its titanium oxide content is
2.5 weight %.
In following example and comparative example, the hydrogen peroxide of use is the hydrogen peroxide of 30 weight %.
In following example and comparative example, gas chromatogram is used to analyze each composition in the reactant liquor obtained
Content, is 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.
XThioether=[(mo Thioether-mThioether)/mo Thioether] × 100% (V)
In Formula V, XThioetherRepresent the conversion ratio of dimethyl sulfide；
mo ThioetherRepresent the quality of the dimethyl sulfide added；
mThioetherRepresent the quality of unreacted dimethyl sulfide.
SSulfoxide=[nSulfoxide/(no Thioether-nThioether)] × 100% (VI)
In Formula IV, SSulfoxideRepresent the selectivity of dimethyl sulfoxide；
no ThioetherRepresent the mole of the dimethyl sulfide added；
nThioetherRepresent the mole of unreacted dimethyl sulfide；
nSulfoxideRepresent the mole of the dimethyl sulfoxide obtained.
UOxidant=[nSulfoxide/(no Oxidant-nOxidant)] × 100% (VII)
In Formula VII, UOxidantRepresent the effective rate of utilization of oxidant；
no OxidantRepresent the mole of the oxidant added；
nOxidantRepresent the mole of unreacted oxidant；
nSulfoxideRepresent the mole of the dimethyl sulfoxide obtained.
Embodiment 1-20 is used for the method according to the invention is described.
Embodiment 1
(1) by titanium-silicon molecular sieve TS-1 and Ludox (dioxide-containing silica is 30 weight %) and water
Mix homogeneously, wherein, the weight ratio of titanium-silicon molecular sieve TS-1, Ludox in terms of silicon dioxide and water is
1:0.2:1.5.By the mixture that obtains through spin pelletize, and by the wet grain that obtains 550 DEG C of roastings 5
Hour, thus obtain the catalyst that mean diameter is 200 μm.Wherein, in catalyst, titanium silicon molecule
The content of sieve is 80 weight %.
(2) Catalyst packing step (1) prepared is in fixed bed reactors, forms catalyst bed
Layer, wherein, the quantity of beds is 1 layer.
By dimethyl sulfide, hydrogen peroxide and methanol mixed, form liquid mixture.To liquid mixture
Middle interpolation ammonia (concentration is 25 weight %), is adjusted to 6.5 by the pH value of liquid mixture.Then,
Described liquid mixture is sent in fixed bed reactors and connects with the beds containing HTS
Touch reaction.Wherein, in liquid mixture, dimethyl sulfide is 1:1 with the mol ratio of hydrogen peroxide, two
Dimethyl sulfide is 1:5 with the weight ratio of methanol, and the weight (hourly) space velocity (WHSV) of liquid mixture is 100h-1.Catalyst
Temperature in bed is 30 DEG C, and the pressure in fixed bed reactors is 0.5MPa.
Reactant mixture reaction started latter 0.5 hour and obtain for 150 hours carries out gas chromatographic analysis,
And calculate the conversion ratio of dimethyl sulfide, the effective rate of utilization of oxidant and the selectivity of dimethyl sulfoxide.
Result is listed in Table 1.
Embodiment 2
Method same as in Example 1 is used to prepare dimethyl sulfoxide, except for the difference that, hollow by equivalent
HTS replaces the titanium-silicon molecular sieve TS-1 in embodiment 1.Turning of calculated dimethyl sulfide
The selectivity of rate, the effective rate of utilization of oxidant and dimethyl sulfoxide is listed in Table 1.
Comparative example 1
Using method same as in Example 1 to prepare dimethyl sulfoxide, except for the difference that, omission ammonia is adjusted
The step of the pH value of joint liquid mixture.The conversion ratio of calculated dimethyl sulfide, oxidant
The selectivity of effective rate of utilization and dimethyl sulfoxide is listed in Table 1.
Embodiment 3
Use method same as in Example 2 to prepare dimethyl sulfoxide, except for the difference that, use following methods
Prepare catalyst: under conditions of normal pressure (1 normal atmosphere) and 40 DEG C, tetraethyl orthosilicate is added
In TPAOH aqueous solution, add hollow titanium si molecular sieves after stirring 2 hours and continue stirring 1
Hour, wherein, hollow titanium si molecular sieves, tetraethyl orthosilicate, TPAOH and the mass ratio of water
For 100:200:20:250.By the mixture that obtains after spin pelletize, little 550 DEG C of roastings 5
Time, obtain the catalyst that mean diameter is 200 μm.Wherein, in catalyst, containing of HTS
Amount is 60 weight %.
The conversion ratio of calculated dimethyl sulfide, the effective rate of utilization of oxidant and dimethyl sulfoxide
Selectivity is listed in Table 1.
Table 1
Embodiment 4
(1) hollow titanium si molecular sieves is mixed with Ludox (dioxide-containing silica is 30 weight %) and water
Closing uniformly, wherein, the weight ratio of hollow titanium si molecular sieves, Ludox in terms of silicon dioxide and water is 1:
0.1:1.By the mixture that obtains through spin pelletize, and by the wet grain that obtains 580 DEG C of roastings 4 hours,
Thus obtain the catalyst that mean diameter is 300 μm.Wherein, in catalyst, containing of HTS
Amount is 70 weight %.
(2) Catalyst packing step (1) prepared is in fixed bed reactors, forms catalyst bed
Layer, wherein, the quantity of beds is 1 layer.
Dimethyl sulfide, hydrogen peroxide and acetone are mixed, forms liquid mixture.To liquid mixture
Middle interpolation ammonia (concentration is 25 weight %), is adjusted to 7.0 by the pH value of liquid mixture.Then,
Described liquid mixture is sent in fixed bed reactors and connects with the beds containing HTS
Touch reaction.Wherein, in liquid mixture, dimethyl sulfide is 1:1 with the mol ratio of hydrogen peroxide, two
Dimethyl sulfide is 1:10 with the weight ratio of acetone, and the weight (hourly) space velocity (WHSV) of liquid mixture is 200h-1.Catalysis
Temperature in agent bed is 50 DEG C, and the pressure in fixed bed reactors is 0.1MPa.
Reactant mixture reaction started latter 0.5 hour and obtain for 150 hours carries out gas chromatographic analysis,
And calculate the conversion ratio of dimethyl sulfide, the effective rate of utilization of oxidant and the selectivity of dimethyl sulfoxide.
Result is listed in table 2.
Embodiment 5
(1) by titanium-silicon molecular sieve TS-1 and Ludox (dioxide-containing silica is 30 weight %) and water
Mix homogeneously, wherein, the weight ratio of titanium-silicon molecular sieve TS-1, Ludox in terms of silicon dioxide and water is
1:0.5:5.By the mixture that obtains through mist projection granulating, and by little 550 DEG C of roastings 5 for the wet grain that obtains
Time, thus obtain the catalyst that mean diameter is 80 μm.Wherein, in catalyst, HTS
Content is 60 weight %.
(2) Catalyst packing step (1) prepared is in fixed bed reactors, forms catalyst bed
Layer, wherein, the quantity of beds is 1 layer.
Dimethyl sulfide, hydrogen peroxide and water are mixed, forms liquid mixture.In liquid mixture
Add ammonia (concentration is 25 weight %), the pH value of liquid mixture is adjusted to 8.0.Then, will
Described liquid mixture is sent in fixed bed reactors and is contacted with the beds containing HTS
Reaction.Wherein, in liquid mixture, dimethyl sulfide is 1:2 with the mol ratio of hydrogen peroxide, diformazan
Base thioether is 1:2 with the weight ratio of water, and the weight (hourly) space velocity (WHSV) of liquid mixture is 10h-1.Beds
In temperature be 40 DEG C, the pressure in fixed bed reactors is 0.2MPa.
Reactant mixture reaction started latter 0.5 hour and obtain for 150 hours carries out gas chromatographic analysis,
And calculate the conversion ratio of dimethyl sulfide, the effective rate of utilization of oxidant and the selectivity of dimethyl sulfoxide.
Result is listed in table 2.
Table 2
Embodiment 6
(1) hollow titanium si molecular sieves is mixed with Ludox (dioxide-containing silica is 30 weight %) and water
Closing uniformly, wherein, the weight ratio of hollow titanium si molecular sieves, Ludox in terms of silicon dioxide and water is 1:
0.05:0.5.By the mixture that obtains through spin pelletize, and by little 550 DEG C of roastings 5 for the wet grain that obtains
Time, thus obtain the catalyst that mean diameter is 600 μm.Wherein, in catalyst, HTS
Content be 95 weight %.
(2) Catalyst packing step (1) prepared is in fixed bed reactors, forms catalyst bed
Layer, wherein, the quantity of beds is 1 layer.
By dimethyl sulfide, peracetic acid and methanol mixed, form liquid mixture.To liquid mixture
Middle interpolation ammonia (concentration is 25 weight %), is adjusted to 7.5 by the pH value of liquid mixture.Then,
Described liquid mixture is sent in fixed bed reactors and connects with the beds containing HTS
Touch reaction.Wherein, in liquid mixture, dimethyl sulfide is 1:0.5 with the mol ratio of peracetic acid,
Dimethyl sulfide is 1:5 with the weight ratio of methanol, and the weight (hourly) space velocity (WHSV) of liquid mixture is 10h-1.Catalysis
Temperature in agent bed is 30 DEG C, and the pressure in fixed bed reactors is 1.5MPa.
Reactant mixture reaction started latter 0.5 hour and obtain for 150 hours carries out gas chromatographic analysis,
And calculate the conversion ratio of dimethyl sulfide, the effective rate of utilization of oxidant and the selectivity of dimethyl sulfoxide.
Result is listed in table 3.
Embodiment 7
Method same as in Example 6 is used to prepare dimethyl sulfoxide, except for the difference that, by liquid mixture
PH value be adjusted to 6.5.The conversion ratio of calculated dimethyl sulfide, the effective rate of utilization of oxidant
List in table 3 with the selectivity of dimethyl sulfoxide.
Embodiment 8
Use method same as in Example 6 to prepare dimethyl sulfoxide, except for the difference that, be not to use ammonia
The pH value of regulation liquid mixture, but use the aqueous solution (concentration is 25 weight %) of NaOH to adjust
The pH value of joint liquid mixture.The conversion ratio of calculated dimethyl sulfide, effective profit of oxidant
List in table 3 with the selectivity of rate and dimethyl sulfoxide.
Embodiment 9
Method same as in Example 6 is used to prepare dimethyl sulfoxide, except for the difference that, by liquid mixture
PH value be adjusted to 8.5.The conversion ratio of calculated dimethyl sulfide, the effective rate of utilization of oxidant
List in table 3 with the selectivity of dimethyl sulfoxide.
Embodiment 10
Method same as in Example 6 is used to prepare dimethyl sulfoxide, except for the difference that, by liquid mixture
PH value be adjusted to 5.5.The conversion ratio of calculated dimethyl sulfide, the effective rate of utilization of oxidant
List in table 3 with the selectivity of dimethyl sulfoxide.
Comparative example 2
Using method same as in Example 6 to prepare dimethyl sulfoxide, except for the difference that, omission ammonia is adjusted
The step of the pH value of joint liquid mixture.The conversion ratio of calculated dimethyl sulfide, oxidant
The selectivity of effective rate of utilization and dimethyl sulfoxide is listed in table 3.
Table 3
Embodiment 11
(1) hollow titanium si molecular sieves is mixed with Ludox (dioxide-containing silica is 30 weight %) and water
Closing uniformly, wherein, the weight ratio of hollow titanium si molecular sieves, Ludox in terms of silicon dioxide and water is 1:
0.1:5.By the mixture that obtains through mist projection granulating, and by the wet grain that obtains 550 DEG C of roastings 5 hours,
Thus obtain the catalyst that mean diameter is 80 μm.Wherein, in catalyst, the content of HTS
It is 90 weight %.
(2) Catalyst packing step (1) prepared is in fixed bed reactors, forms catalyst bed
Layer, wherein, the quantity of beds is 1 layer.
Dimethyl sulfide, tert-butyl hydroperoxide and acetonitrile are mixed, forms liquid mixture.To liquid
Mixture adds ammonia (concentration is 25 weight %), the pH value of liquid mixture is adjusted to 7.5.
Then, described liquid mixture is sent into the catalyst bed in fixed bed reactors and containing HTS
Layer haptoreaction.Wherein, in liquid mixture, dimethyl sulfide and the mol ratio of tert-butyl hydroperoxide
For 1:0.2, dimethyl sulfide is 1:2 with the weight ratio of acetonitrile, and the weight (hourly) space velocity (WHSV) of liquid mixture is
10h-1.Temperature in beds is 20 DEG C, and the pressure in fixed bed reactors is 0.1MPa.
Reactant mixture reaction started latter 0.5 hour and obtain for 150 hours carries out gas chromatographic analysis,
And calculate the conversion ratio of dimethyl sulfide, the effective rate of utilization of oxidant and the selectivity of dimethyl sulfoxide.
Result is listed in table 4.
Embodiment 12
(1) by titanium-silicon molecular sieve TS-1 and Ludox (dioxide-containing silica is 30 weight %) and water
Mix homogeneously, wherein, the weight ratio of titanium-silicon molecular sieve TS-1, Ludox in terms of silicon dioxide and water is
1:0.08:0.8.By the mixture that obtains through spin pelletize, and by the wet grain that obtains 550 DEG C of roastings 5
Hour, thus obtain the catalyst that mean diameter is 400 μm.Wherein, in catalyst, titanium silicon molecule
The content of sieve is 92 weight %.
(2) Catalyst packing step (1) prepared is in fixed bed reactors, forms catalyst bed
Layer, wherein, the quantity of beds is 1 layer.
By dimethyl sulfide, Perpropionic Acid and methanol mixed, form liquid mixture.To liquid mixture
Middle interpolation ammonia (concentration is 25 weight %), is adjusted to 7.5 by the pH value of liquid mixture.Then,
Described liquid mixture is sent in fixed bed reactors and connects with the beds containing HTS
Touch reaction.Wherein, in liquid mixture, dimethyl sulfide is 1:2 with the mol ratio of Perpropionic Acid, two
Dimethyl sulfide is 1:10 with the weight ratio of methanol, and the weight (hourly) space velocity (WHSV) of liquid mixture is 10h-1.Catalyst
Temperature in bed is 30 DEG C, and the pressure in fixed bed reactors is 2.5MPa.
Reactant mixture reaction started latter 0.5 hour and obtain for 150 hours carries out gas chromatographic analysis,
And calculate the conversion ratio of dimethyl sulfide, the effective rate of utilization of oxidant and the selectivity of dimethyl sulfoxide.
Result is listed in Table 1.
Comparative example 3
The method identical with embodiment 12 is used to prepare dimethyl sulfoxide, except for the difference that, omission ammonia
The step of the pH value of regulation liquid mixture.The conversion ratio of calculated dimethyl sulfide, oxidant
Effective rate of utilization and the selectivity of dimethyl sulfoxide list in table 4.
Embodiment 13
Use the method identical with embodiment 12 to prepare dimethyl sulfoxide, except for the difference that, use equivalent
Hollow titanium si molecular sieves replaces the titanium-silicon molecular sieve TS-1 in embodiment 12.Calculated dimethyl disulfide
The selectivity of the conversion ratio of ether, the effective rate of utilization of oxidant and dimethyl sulfoxide is listed in table 4.
Table 4
Embodiment 14
(1) hollow titanium si molecular sieves is mixed with Ludox (dioxide-containing silica is 30 weight %) and water
Closing uniformly, wherein, the weight ratio of hollow titanium si molecular sieves, Ludox in terms of silicon dioxide and water is 1:
0.5:5.By the mixture that obtains through mist projection granulating, and by the wet grain that obtains 550 DEG C of roastings 5 hours,
Thus obtain the catalyst that mean diameter is 100 μm.Wherein, in catalyst, containing of HTS
Amount is 45 weight %.
(2) Catalyst packing step (1) prepared is in fixed bed reactors, forms catalyst bed
Layer, wherein, the quantity of beds is 1 layer.
By dimethyl sulfide, hydrogen peroxide and methanol mixed, form liquid mixture.To liquid mixture
Middle interpolation ammonia (concentration is 25 weight %), is adjusted to 8.5 by the pH value of liquid mixture.Then,
Described liquid mixture is sent in fixed bed reactors and connects with the beds containing HTS
Touch reaction.Wherein, in liquid mixture, dimethyl sulfide is 1:1 with the mol ratio of hydrogen peroxide, two
Dimethyl sulfide is 1:4 with the weight ratio of methanol, and the weight (hourly) space velocity (WHSV) of liquid mixture is 250h-1.Catalyst
Temperature in bed is 40 DEG C, and the pressure in fixed bed reactors is 0.8MPa.
Reactant mixture reaction started latter 0.5 hour and obtain for 150 hours carries out gas chromatographic analysis,
And calculate the conversion ratio of dimethyl sulfide, the effective rate of utilization of oxidant and the selectivity of dimethyl sulfoxide.
Result is listed in table 5.
Embodiment 15
The method identical with embodiment 14 is used to prepare dimethyl sulfoxide, except for the difference that, dimethyl sulfide
It is 1:2 with the mol ratio of oxidant.The conversion ratio of calculated dimethyl sulfide, oxidant effective
The selectivity of utilization rate and dimethyl sulfoxide is listed in table 5.
Embodiment 16
The method identical with embodiment 14 is used to prepare dimethyl sulfoxide, except for the difference that, dimethyl sulfide
It is 1:4 with the mol ratio of oxidant.The conversion ratio of calculated dimethyl sulfide, oxidant effective
The selectivity of utilization rate and dimethyl sulfoxide is listed in table 5.
Comparative example 4
The method identical with embodiment 14 is used to prepare dimethyl sulfoxide, except for the difference that, omission ammonia
The step of the pH value of regulation liquid mixture.The conversion ratio of calculated dimethyl sulfide, oxidant
Effective rate of utilization and the selectivity of dimethyl sulfoxide list in table 5.
Comparative example 5
The method identical with embodiment 15 is used to prepare dimethyl sulfoxide, except for the difference that, omission ammonia
The step of the pH value of regulation liquid mixture.The conversion ratio of calculated dimethyl sulfide, oxidant
Effective rate of utilization and the selectivity of dimethyl sulfoxide list in table 5.
Comparative example 6
The method identical with embodiment 16 is used to prepare dimethyl sulfoxide, except for the difference that, omission ammonia
The step of the pH value of regulation liquid mixture.The conversion ratio of calculated dimethyl sulfide, oxidant
Effective rate of utilization and the selectivity of dimethyl sulfoxide list in table 5.
Embodiment 17
Use the method identical with embodiment 14 to prepare dimethyl sulfoxide, except for the difference that, use with lower section
Method prepares catalyst:
Under conditions of normal pressure (1 normal atmosphere) and 40 DEG C, tetraethyl orthosilicate is joined tetrapropyl
In ammonium hydroxide aqueous solution, add hollow titanium si molecular sieves after stirring 2 hours and continue stirring 1 hour, its
In, hollow titanium si molecular sieves, tetraethyl orthosilicate, TPAOH are 100 with the mass ratio of water:
400:30:200.By the mixture that obtains after spin pelletize, 550 DEG C of roastings 5 hours, obtain
Mean diameter is the catalyst of 60 μm.Wherein, in catalyst, the content of HTS is 30 weights
Amount %.
The conversion ratio of calculated dimethyl sulfide, the effective rate of utilization of oxidant and dimethyl sulfoxide
Selectivity is listed in table 5.
Embodiment 18
Use the method identical with embodiment 16 to prepare dimethyl sulfoxide, except for the difference that, use and implement
The method that example 17 is identical prepares catalyst.The conversion ratio of calculated dimethyl sulfide, oxidant
The selectivity of effective rate of utilization and dimethyl sulfoxide is listed in table 5.
Embodiment 19
Use the method identical with embodiment 16 to prepare dimethyl sulfoxide, except for the difference that, use titanium silicon to divide
Son sieve TS-1 replaces hollow titanium si molecular sieves.The conversion ratio of calculated dimethyl sulfide, oxidant
Effective rate of utilization and the selectivity of dimethyl sulfoxide list in table 5.
Table 5
Embodiment 20
Dimethyl sulfide, hydrogen peroxide and methanol mixed is uniform, and with ammonia by the pH value of mixture
It is adjusted to 7.5.Said mixture and hollow titanium si molecular sieves are sent in reactor, with stirring, instead
Answer 2 hours.The mixture obtained is filtered, the hollow titanium si molecular sieves that is recycled and containing two
The liquid phase of methyl sulfoxide.Wherein, reaction condition includes: dimethyl sulfide with the mol ratio of hydrogen peroxide is
1:2, dimethyl sulfide is 1:1 with the mass ratio of hollow titanium si molecular sieves, dimethyl sulfide and methanol
Mass ratio is 1:5；Temperature in reactor is 60 DEG C, and pressure is 0.8MPa.
By reclaim hollow titanium si molecular sieves the most again with dimethyl sulfide, hydrogen peroxide and
Send in reactor after methanol mixed and proceed to react next time.Wherein, HTS recycles
100 times.
In course of reaction, the detection composition of the mixture of output from reactor every time, and calculate dimethyl
Thioether rate, oxidant effective rate of utilization and dimethyl sulfoxide selectivity.Wherein, the 1st time and the 100th
Secondary result is listed in table 6.
Comparative example 7
The method identical with embodiment 20 is used to prepare dimethyl sulfoxide, except for the difference that, omission ammonia
The step of the pH value of regulation mixture.The dimethyl sulfide of calculated 1st time and the 100th time
The selectivity of conversion ratio, the effective rate of utilization of oxidant and dimethyl sulfoxide is listed in table 6.
Table 6
Claims (12)
1. the method preparing dimethyl sulfoxide, the method is included in and can be aoxidized by dimethyl sulfide
Become under the oxidation reaction condition of dimethyl sulfoxide, by one liquid mixture and at least one titanium silicon molecule
Sieve contact, obtain the mixture containing dimethyl sulfoxide, described liquid mixture contain dimethyl sulfide and
At least one peroxide, the pH value of described liquid mixture is 5-9, by described liquid mixing
Thing adds at least one alkali compounds to regulate the pH value of described liquid mixture, described peroxidating
Thing is selected from ammonia, amine, quaternary ammonium base selected from hydrogen peroxide, hydroperoxides and peracid, described alkali compounds
And M1(OH)n, M1For alkali metal or alkaline-earth metal, n is and M1The identical integer of quantivalence.
Method the most according to claim 1, wherein, the pH value of described liquid mixture is 5.5-8.5.
Method the most according to claim 1, wherein, described alkali compounds is ammonia.
Method the most according to claim 1, wherein, described amine be the material shown in Formulas I and/or
C3-C11Heterocyclic amine,
In Formulas I, R1、R2And R3It is respectively H or C1-C6Alkyl, and R1、R2And R3Time different
For H.
Method the most according to claim 1, wherein, described quaternary ammonium base is the material shown in Formula II,
In Formula II, R4、R5、R6And R7It is respectively C1-C6Alkyl.
Method the most according to claim 1, wherein, M1(OH)nSelected from sodium hydroxide, hydrogen-oxygen
Change potassium, magnesium hydroxide, barium hydroxide and calcium hydroxide.
Method the most according to claim 1, wherein, described HTS is for having MFI knot
The HTS of structure.
Method the most according to claim 7, wherein, the crystal grain of described HTS is hollow
Structure, the radical length of the chamber portion of this hollow-core construction is 5-300 nanometer, and described HTS
At 25 DEG C, P/P0=0.10, the benzene adsorbance that adsorption time records under conditions of being 1 hour is at least 70
Milligrams per gram, exists stagnant between adsorption isotherm and the desorption isotherm of the nitrogen absorption under low temperature of this HTS
Rear ring.
Method the most according to claim 1, wherein, described peroxide selected from hydrogen peroxide,
Tert-butyl hydroperoxide, isopropyl benzene hydroperoxide, cyclohexyl hydroperoxide, peracetic acid and Perpropionic Acid.
Method the most according to claim 1, wherein, described liquid mixture is possibly together with at least one
Planting solvent, dimethyl sulfide is 1:0.1-20 with the weight ratio of described solvent.
11. methods according to claim 10, wherein, described solvent is selected from water, C1-C10Alcohol,
C3-C10Ketone and C2-C10Nitrile.
12. methods according to claim 1, wherein, dimethyl sulfide and described HTS
Weight ratio be 0.1-50:1；Dimethyl sulfide is 1:0.1-4 with the mol ratio of described peroxide；Institute
State oxidation reaction condition to include: temperature is 0-80 DEG C；In terms of gauge pressure, pressure is 0-3MPa.
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| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US3996295A (en) * | 1974-07-04 | 1976-12-07 | Produits Chimiques Ugine Kuhlmann | Preparation of dimethylsulfoxide by liquid phase reaction of dimethysulfide and hydrogen peroxide |
| JPS55131396A (en) * | 1979-03-31 | 1980-10-13 | Oji Paper Co Ltd | Preparation of dimethyl sulfoxide and dimethyl sulfone |
| 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 |
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| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US3996295A (en) * | 1974-07-04 | 1976-12-07 | Produits Chimiques Ugine Kuhlmann | Preparation of dimethylsulfoxide by liquid phase reaction of dimethysulfide and hydrogen peroxide |
| JPS55131396A (en) * | 1979-03-31 | 1980-10-13 | Oji Paper Co Ltd | Preparation of dimethyl sulfoxide and dimethyl sulfone |
| 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 |
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| Sulfoxidation of Thioethers using Titanium Silicate Molecular Sieve Catalysts;Ravinder S. Reddy等;《J . CHEM. SOC., CHEM. COMMUN.》;19921231(第2期);第84-85页 * |
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