CN105523974B - A kind of preparation method of dimethyl sulfone - Google Patents
A kind of preparation method of dimethyl sulfone Download PDFInfo
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Abstract
The invention provides a kind of preparation method of dimethyl sulfone, this method is included under oxidation reaction condition, in fixed bed reactors, make a kind of liquid mixture by being filled with the beds of at least one HTS, obtain the mixture containing dimethyl sulfone, the liquid mixture contains dimethyl sulfide and at least one peroxide, and the mol ratio of the peroxide and the dimethyl sulfide is more than 2：1.The method of the present invention is using peroxide as oxidant, and low to the extent of corrosion of equipment, the environmental contaminants of release are few, and results in high dimethyl sulfide conversion ratio and dimethyl sulfone selectivity, while also having higher oxidant effective rate of utilization.
Description
Technical field
The present invention relates to a kind of preparation method of dimethyl sulfone.
Background technology
Dimethyl sulfone is white crystalline powder, soluble in water, ethanol, benzene, methanol and acetone, is slightly soluble in ether.Under normal temperature not
Potassium permanganate can be made to change colour, dimethyl sulfone can be oxidized to methanesulfonic acid by strong oxidizer.The dimethyl sulfone aqueous solution is in neutrality.At 25 DEG C
Microsublimation, accelerates to 60 DEG C of rate of sublimation, thus dimethyl sulfone product is preferably dried under cryogenic vacuum.
Dimethyl sulfone is used as organic synthesis high-temperature solvent and raw material, GC stationary liquid, analytical reagent, food in the industry
Product additive and medicine.Dimethyl sulfone produces the ability of insulin with enhancing human body, simultaneously as a kind of organic sulfur compound
Also there is facilitation to the metabolism of carbohydrate, be the necessary material of human collagen albumen synthesis.Dimethyl sulfone can promote wound to be cured
Close, vitamin B, vitamin C, the synthesis of biotin and the activation needed for metabolism and neurological health can also be worked, quilt
Referred to as " beautify carbonizable substance naturally ".All contain dimethyl sulfone in skin, hair, nail, bone, muscle and each organ of human body,
Dimethyl sulfone is primarily present in Yu Haiyang and soil in nature, is absorbed in plant growth as nutriment, the mankind
It can be absorbed from the foods such as veterinary antibiotics, fish, meat, egg, milk, once health disorders will be caused or occur disease by lacking, be
Human body maintains the main matter of biological element sulphur balance, has therapeutic value and healthcare function to human body diseases, is human survival
With the indispensable medicine of health care.It is external to widely apply dimethyl sulfone as with vitamin nutriment of equal importance, China
Application study to dimethyl sulfone is not yet carried out very well, and current product is mainly used in outlet.Therefore, dimethyl sulfone is not only one kind
New high-tech product, is also a kind of fine chemical product of high added value.Product is new, market potential is big, and benefit is protruded, with wide
Wealthy production and application and development prospect.
At present, the product that dimethyl sulfone is further aoxidized as dimethyl sulfoxide (DMSO), is the main pair of dimethyl sulfoxide (DMSO) production
Product.
In addition, dimethyl sulfone can also be obtained directly by dimethyl sulfoxide (DMSO) through nitric acid oxidation.Specifically, can be by dimethyl
Sulfoxide, with nitric acid oxidation, reacts and is cooled to after terminating at 140-145 DEG C, filters, obtains the crude product of white, needle-shaped crystals.Again through subtracting
Pressure distillation, it is finished product to collect 138-145 DEG C of (98.42kPa) cut.But, the dimethyl sulfone yield of this method needs
Further improve；Also, this method, as oxidant, to the seriously corroded of equipment, contains nitrogen dioxide using nitric acid while discharging
Waste gas and acid-bearing wastewater, be unfavorable for environmental protection.
The content of the invention
It is an object of the invention to provide a kind of preparation method of new dimethyl sulfone, this method is used as oxygen using peroxide
Agent, small to the extent of corrosion of equipment, the waste gas waste water of generation is few, and results in high dimethyl sulfide conversion ratio, oxygen
Agent effective rate of utilization and dimethyl sulfone selectivity.
The invention provides a kind of preparation method of dimethyl sulfone, this method is included under oxidation reaction condition, in fixation
In bed reactor, make a kind of liquid mixture by being filled with the beds of at least one HTS, contained
The mixture of dimethyl sulfone, the liquid mixture contains dimethyl sulfide and at least one peroxide, the peroxide
Mol ratio with the dimethyl sulfide is more than 2：1.
The method of the present invention is using peroxide as oxidant, compared with using nitric acid as oxidant, the corruption to equipment
Degree of corrosion is low, and the environmental contaminants discharged are few.Importantly, the method for the present invention results in high dimethyl sulfide
Conversion ratio and dimethyl sulfone selectivity, while also having higher oxidant effective rate of utilization.
Embodiment
The invention provides a kind of preparation method of dimethyl sulfone, this method is included under oxidation reaction condition, in fixation
In bed reactor, make a kind of liquid mixture by being filled with the beds of at least one HTS, contained
The mixture of dimethyl sulfone, the liquid mixture contains dimethyl sulfide and at least one peroxide.
The method according to the invention, the peroxide refers to the compound for containing-O-O- keys in molecular structure, Ke Yiwei
Hydrogen peroxide and/or organic peroxide (such as hydroperoxides and peracid).The instantiation of the peroxide can include
But it is not limited to：Hydrogen peroxide, TBHP, dicumyl peroxide, cyclohexyl hydroperoxide, Peracetic acid and peroxide third
Acid.Preferably, the oxidant is hydrogen peroxide, so can further reduce separation costs.The hydrogen peroxide can be
The hydrogen peroxide existed in a variety of manners commonly used in the art.
From the angle of the further security for improving the method according to the invention, the method according to the invention preferably makes
With the hydrogen peroxide existed as an aqueous solution.The method according to the invention, is provided as an aqueous solution in the hydrogen peroxide
When, the concentration of the aqueous hydrogen peroxide solution can be the normal concentration of this area, for example：20-80 weight %.On concentration is met
Stating the aqueous solution of the hydrogen peroxide of requirement can be prepared using conventional method, can also be commercially available, for example：Can be being capable of business
The hydrogen peroxide of the 30 weight % bought hydrogen peroxide, 50 weight % hydrogen peroxide or 70 weight %.
The consumption of the peroxide is defined by that dimethyl sulfide can be oxidized into dimethyl sulfone.Usually, it is described
The mol ratio of peroxide and the dimethyl sulfide is more than 2：1.Preferably 2.5：More than 1.The peroxide with it is described
The mol ratio of dimethyl sulfide can be 20：Less than 1, such as 10：Less than 1, preferably 5：Less than 1.Preferably, the peroxide
Mol ratio with dimethyl sulfide is 2.5-5：1.
The method according to the invention, the liquid mixture can contain solvent, can also be free of solvent.From further carrying
Mixability, enhanced dispersion in high reaction system between each reactant and more easily the severe degree to reaction is adjusted
The angle of section is set out, and the liquid mixture is preferably also containing at least one solvent.The species of the solvent is not particularly limited.
Usually, the solvent can be selected from water, C1-C6Alcohol, C3-C8Ketone and C2-C6Nitrile.The instantiation of the solvent can be with
Including but not limited to：Water, methanol, ethanol, normal propyl alcohol, isopropanol, the tert-butyl alcohol, isobutanol, acetone, butanone and acetonitrile.Preferably,
The solvent is selected from water and C1-C6Alcohol.It is highly preferred that the solvent is methanol and/or water.
The content of the solvent can be conventional selection.Preferably, the weight ratio of dimethyl sulfide and the solvent is 1：
0.1-20.It is highly preferred that the weight ratio of dimethyl sulfide and the solvent is 1：1-10.The specific consumption and the kind of solvent of solvent
Class and the condition of reaction etc. have certain relation, and those skilled in the art can be properly selected as the case may be.
Before the liquid mixture and the HTS haptoreaction is made, the method according to the invention is preferably also wrapped
Include and at least one acid is added into the liquid mixture as pH value regulator, the sour addition causes the liquid to mix
The pH value of thing is preferably 0.5-5.5, more preferably 1-5 (such as 2-5), so can further improve the selection for dimethyl sulfone
Property, while higher dimethyl sulfide conversion ratio and oxidant effective rate of utilization can also be obtained.Although the peroxide was
When sour, the pH value of the liquid mixture is general between 3.5-4, but if adding acid into the liquid mixture, will
The pH value of the liquid mixture is adjusted to less than 3.5 to being not less than 1, remains able to obtain the effect above.The liquid mixture
PH value refer to 25 DEG C and 1 normal atmosphere pressure determine liquid mixture pH value.
As pH value regulator, the sour species can be conventional selection.Usually, for adjusting the liquid mixing
The acid of the pH value of thing can be inorganic acid and/or organic acid, and the organic acid can be carboxylic acid and/or sulfonic acid, such as C1-C6Fat
Aliphatic carboxylic acid, C6-C12Aromatic carboxylic acid, C1-C6Aliphatic sulfonic and C6-C12Aromatic sulphonic acid.The acid-specific can be with
For the one or more in hydrochloric acid, sulfuric acid, nitric acid, phosphoric acid, formic acid and acetic acid, preferably hydrochloric acid and/or sulfuric acid.It can use pure
Acid, can also use the aqueous solution of acid.Acid is (such as molten with other components in dimethyl sulfide and oxidant and liquid mixture
Agent) mixing can be carried out in reactor, can also be carried out outside reactor.
The sour consumption is defined by enabling to the pH value of liquid mixture to meet previously described requirement.
The method according to the invention, the HTS can be the common titanium silicon molecule with various topological structures
Sieve, for example：The HTS can be selected from HTS (such as TS-1), the HTS of MEL structures of MFI structure
The HTS (such as Ti-Beta) of (such as TS-2), BEA structures, the HTS (such as Ti-MCM-22) of MWW structures, two dimension
The HTS (such as Ti-MCM-41, Ti-SBA-15) of hexagonal structure, HTS (such as Ti-MOR), the TUN of MOR structures
The HTS (such as Ti-TUN) of structure and the HTS (such as Ti-ZSM-48) of other structures.Preferably, the titanium silicon
Molecular sieve be selected from the HTS of MFI structure, the HTS of MEL structures, the HTS of two-dimentional hexagonal structure and
The HTS of BEA structures.It is highly preferred that the HTS is the HTS of MFI structure, such as TS-1 molecules
Sieve.
The present invention it is a kind of preferred embodiment in, at least partly the HTS is the titanium silicon of MFI structure
Molecular sieve, and the crystal grain of the HTS is hollow-core construction, the radical length of the chamber portion of the hollow-core construction is received for 5-300
Rice, and the HTS is in 25 DEG C, P/P0=0.10, adsorption time is that the benzene adsorbance measured under conditions of 1 hour is
, there is hysteresis loop between the adsorption isotherm and desorption isotherm of the nitrogen absorption under low temperature of the HTS at least 70 milligrams per grams.
The dimethyl sulfide conversion ratio further improved, oxidant effective rate of utilization and dimethyl are resulted according to the embodiment
Sulfone selectivity.Herein, the HTS with the structure is referred to as hollow HTS.The hollow HTS can
To be commercially available (for example commercially available from Hunan Jianchang Petrochemical Co., Ltd the trade mark as HTS molecular sieve), can also basis
Method disclosed in CN1132699C is prepared.
According to this preferred embodiment, the HTS can be with all hollow HTSs, or
The combination of hollow HTS and the HTS of other species, such as by hollow HTS and other MFI structures
HTS (such as titanium-silicon molecular sieve TS-1), the HTS and the titanium silicon molecule of BEA structures of two-dimentional hexagonal structure
Sieve is applied in combination.When the HTS of hollow HTS and other species is applied in combination, preferably with the liquid
On the basis of the flow direction of mixture, the upstream that the hollow HTS is located at other HTSs is (that is, described hollow
HTS and other HTSs the filling order in the reaction zone cause the liquid mixture successively with it is described
Hollow HTS and the contact of other HTSs), so result in higher oxidant effective rate of utilization and target
Oxidation product selectivity.The mass ratio of the hollow HTS and other HTSs can be 1-10：1, be preferably
2-5：1., can be anti-by the way that hollow HTS and the layering of other HTSs are seated in into fixed bed in practical operation
Answer in device, and hollow HTS is located at the upstream of other HTSs and is realized.
When the HTS is hollow HTS and the HTS of other species is applied in combination, preferably
Ground, the HTS is hollow HTS and titanium-silicon molecular sieve TS-1, with the flow direction of the liquid mixture
On the basis of, the hollow HTS be located at the titanium-silicon molecular sieve TS-1 upstream (that is, described hollow HTS and
Titanium-silicon molecular sieve TS-1 in the reaction zone filling order cause dimethyl sulfide successively with the hollow HTS and
Titanium-silicon molecular sieve TS-1 is contacted).So it can not only further extend the catalyst stabilization duration of runs, while can also be further
Improve the selectivity and oxidant effective rate of utilization of dimethyl sulfone.
In using various commercial plants of the HTS as catalyst, such as Ammoximation reaction, hydroxylating and
In epoxidation reaction device, generally plant running for a period of time after, the catalytic activity of catalyst declines, it is necessary to carry out in device
Or ex-situ regeneration, even if when carrying out regeneration and also being difficult to obtain satisfied activity, it is necessary to which catalyst is drawn off (i.e., from device
More catalyst changeout), and catalyst (that is, drawing off agent or dead catalyst) the current processing method drawn off is typically accumulation burial,
On the one hand the land resource and inventory space of preciousness are occupied, another aspect HTS production cost is higher, directly discards
Without also result in great waste.The present inventor has found in research process, (that is, is unloaded if these are drawn off into agent
The HTS gone out) regenerated after contacted with dimethyl sulfide and oxidant under oxidation reaction condition, remain able to obtain
Higher dimethyl sulfide conversion ratio and dimethyl sulfone selectivity, and result in higher oxidant effective rate of utilization,
Dimethyl sulfide conversion ratio and dimethyl sulfone selectivity are more stable in tandem reaction sequence.Therefore, the method according to the invention,
At least partly described HTS is preferably to draw off agent using HTS as the reaction unit of catalyst through regeneration.
It is described draw off agent can be to use HTS as the reaction unit of catalyst (generally except thioether oxidation unit from various
Outer reaction unit) in draw off draw off agent, for example can draw off agent for what is drawn off from oxidation reaction apparatus.Specifically, institute
State and draw off agent and draw off drawing off for agent and epoxidation reaction device for the draw off agent, hydroxylating device of Ammoximation reaction device
One or more in agent.Draw off agent more specifically, described and can draw off agent, phenol hydroxyl for cyclohexanone oxamidinating reaction unit
The one or more drawn off in agent for drawing off agent and propylene ring oxidation reaction device of glycosylation reaction device.
The condition that agent regenerated will be drawn off to be not particularly limited, appropriate choosing can be carried out according to the source for drawing off agent
Select, for example：High-temperature roasting and/or solvent washing.
The activity for drawing off agent through regeneration is different according to its source.Usually, the activity for drawing off agent through regeneration
The 5-95% for the activity (that is, the activity of fresh HTS) that can be the HTS when fresh.Preferably, through again
The active 10-90% that the raw activity for drawing off agent can be the HTS when fresh, more preferably the titanium silicon
Active 30-50% of the molecular sieve when fresh.It is the HTS when fresh in the activity for drawing off agent through regeneration
During the 30-50% of activity, gratifying dimethyl sulfide conversion ratio and dimethyl sulfone selectivity, Er Qieneng can not only be obtained
Enough obtain the oxidant effective rate of utilization further improved.The activity of the fresh HTS is generally more than 90%, leads to
It is often more than 95%.
The activity is determined by the following method：Respectively agent and fresh HTS will be drawn off as hexamethylene through regeneration
The catalyst of ketone oxamidinating reaction, the condition of the Ammoximation reaction is：HTS, 36 weight % ammoniacal liquor are (with NH3Meter),
30 weight % hydrogen peroxide is (with H2O2Meter), the tert-butyl alcohol and cyclohexanone be by weight 1：7.5：10：7.5：10, at atmosheric pressure
2h is reacted in 80 DEG C.Calculate respectively to draw off agent and fresh HTS as the conversion ratio of cyclohexanone during catalyst, and will
Its respectively as the activity for drawing off agent and fresh HTS, wherein, the conversion ratio of cyclohexanone=[(cyclohexanone of addition
The mole of mole-unreacted cyclohexanone)/add cyclohexanone mole] × 100%.
When at least part HTS is that the reaction unit through regeneration draws off agent, with the total amount of the HTS
On the basis of, the content that the reaction unit through regeneration draws off agent is preferably that more than 5 weight %, can not only so obtain and preferably carry
The effect of hyperoxia agent effective rate of utilization, and course of reaction is more steady easy to control, while can also obtain higher dimethyl
Thioether rate and dimethyl sulfone selectivity.The method according to the invention, even if whole HTSs are the reaction through regeneration
When device draws off agent (that is, the content for drawing off agent is 100 weight %), remain able to obtain gratifying dimethyl sulfide conversion
Rate, oxidant effective rate of utilization and dimethyl sulfone selectivity.
The method according to the invention, preferably will at least before the HTS is contacted with the liquid mixture
The part HTS is contacted with as at least one acid of modifying agent.So further improving the selection of dimethyl sulfone
Property while, additionally it is possible to further extension catalyst service life, further reduction the inventive method operating cost.For
Clear purpose, hereinafter, is referred to as modified HTS by the HTS contacted with acid.
The content of the HTS of the modification can be selected according to specific use occasion.The titanium silicon molecule
Sieve can also partly can be modified HTS with the HTS of all modifications.Usually, with the titanium silicon point
On the basis of the total amount of son sieve, the content of the HTS of the modification is preferably more than 10 weight %.
As modifying agent, the acid is general acid, can be the one or more in inorganic acid, organic acid and ackd salt.
The organic acid can be carboxylic acid and/or sulfonic acid, such as C1-C6Aliphatic carboxylic acid, C6-C12Aromatic carboxylic acid, C1-C6Fat
Fat race sulfonic acid and C6-C12Aromatic sulphonic acid.Preferably, it is described acid for acetic acid, hydrochloric acid, sulfuric acid, phosphoric acid, nitric acid, perchloric acid and
It is more than one or both of hydrobromic acid.The acid is preferably provided in form of an aqueous solutions, and the concentration of sour aqueous acid medium can
To be selected according to the species of acid, it is not particularly limited, usually, the concentration of sour aqueous acid medium can be 0.01-50
Weight %, preferably 10-35 weight %.
Compared with the HTS before with acid treatment, the condition handled with acid HTS with cause contact
In ultraviolet-visible (UV-Vis) spectrum of HTS afterwards, the peak height of the absworption peak between 240-300nm reduces 2%
More than (generally 2-20%, such as 3-8%), reduce more than 1% with the pore volume of static determination of nitrogen adsorption (generally 1-10%,
Such as 1.5-3%).
Usually, HTS is in terms of silica, and the HTS can be 1 with the sour mol ratio：
0.01-10, preferably 1：0.05-8, more preferably 1：0.1-5.The contact can 0-200 DEG C, preferably 20-180 DEG C, more
It is preferred that being carried out at a temperature of 50-100 DEG C.The time of the contact can be selected according to the temperature of contact and the species of acid
Select.Usually, the time of the contact can be 0.1-72 hours, preferably 0.5-24 hours (such as 5-24 hours).
The method according to the invention, the HTS can be the former powder of HTS, or the titanium of shaping
Si molecular sieves, the HTS being preferably molded.The HTS of shaping contains carrier (namely binding agent) and titanium silicon
Molecular sieve, wherein, the content of carrier using HTS can be bonded together to be formed the formed body with some strength as
It is accurate.Usually, on the basis of the total amount of the HTS of the shaping, the content of HTS can be 5-95 weights
Measure %, preferably 10-95 weight %, more preferably 40-95 weight %, more preferably 60-95 weight % (such as 70-90 weights
Measure %)；The content of the carrier can be 5-95 weight %, more preferably preferably 5-90 weight %, 5-60 weight %, enter one
Step is preferably 5-40 weight % (such as 10-30 weight %).The carrier of the HTS of the shaping can be conventional selection, such as
Aluminum oxide and/or silica.The method for preparing the HTS of the shaping is it is known in the art, no longer detailed herein
State.The granular size of the HTS of the shaping is also not particularly limited, and appropriate choosing can be carried out according to concrete shape
Select.Usually, the average grain diameter of the HTS of the shaping can be 4-5000 microns, preferably 5-2000 microns, more
Preferably 100-1000 microns.The average grain diameter is for volume average particle size, can be determined using laser particle analyzer.
The method according to the invention, HTS is as catalyst, and its consumption is can realize that catalysis is defined.
In actual mechanical process, the consumption of HTS can be represented with the weight (hourly) space velocity (WHSV) of liquid mixture.Usually, the liquid
The weight (hourly) space velocity (WHSV) of body mixture can be 0.1-500h-1, preferably 5-300h-1(such as 100-200h-1).The weight (hourly) space velocity (WHSV) with
On the basis of the whole HTSs loaded in fixed bed reactors.
Filler can also be further loaded in the method according to the invention, fixed bed reactors, filling filler can be to urging
The amount of catalyst is adjusted in agent bed, so that the treating capacity to reaction speed and reactor is adjusted.The filler
Content appropriate selection can be carried out according to expected reaction speed and the treating capacity of reactor, specifically made with disclosure satisfy that
With requiring to be defined.Usually, the content of filler can be 5-70 weight %, preferably 30-70 weights in the beds
Measure %, more preferably 30-50 weight %.
The present invention is not particularly limited for the species of the filler, can be conventional various fillers, for example, can select
From Raschig ring, Pall ring, cascade ring, arc saddle, square saddle and becket intalox saddle.The instantiation of the filler can be θ rings
And/or β rings.
, can be by the filler and the catalyst with the mixing of the two when the beds are also filled with filler
The form of thing is seated in fixed bed reactors；Can also be by the beds formed by catalyst and by filling out that filler is formed
Bed of material interval is seated in fixed bed reactors；The combination of above two mode can also be used.
The method according to the invention, the oxidation reaction condition can be conventional selection, with can be by dimethyl sulfide oxygen
It is melted into and is defined for dimethyl sulfone.Usually, the oxidation reaction condition includes：Temperature can be 0-160 DEG C, preferably 20-120
DEG C (such as 30-80 DEG C)；Pressure can be 0-3MPa, preferably 0.1-1.5MPa.Herein, pressure is gauge pressure.
The method of the present invention is not particularly limited for the type of the fixed bed reactors, can be common various shapes
The fixed bed reactors of formula.Filling form of the method for the present invention for HTS in fixed bed reactors is also no special
Do not limit, can be conventional selection.
The method according to the invention can also include being separated in the mixture containing dimethyl sulfone that contact is obtained, with
Isolate dimethyl sulfone therein.The present invention is for isolating the method for the dimethyl sulfone in the mixture that contact is obtained without spy
Do not limit, can be the conventional selection of this area.It can be for example fractionated by the way that obtained mixture will be contacted, so as to obtain
Dimethyl sulfone.
Describe the present invention in detail with reference to embodiments, but and be not so limited the scope of the present invention.
In following examples and comparative example, if not otherwise specified, used reagent is commercially available reagent, titanium used
Si molecular sieves are fresh HTS, and pressure is in terms of gauge pressure.
In following examples, titanium-silicon molecular sieve TS-1 used is according to Zeolites, 1992, Vol.12：Retouched in 943-950
Prepared by the method stated, its titanium oxide content is 2.5 weight %；Hollow HTS used is to build feldspathization stock purchased from Hunan
The hollow HTS that the trade mark of part Co., Ltd is HTS, its titanium oxide content is 2.5 weight %；Titanium silicon molecule used
Sieve Ti-MCM-41 be according to Corma etc. in Chem.Commun., prepared by the method described in 1994,147-148, its oxygen
Change Ti content is 3 weight %；HTS Ti-Beta used is to exist according to Takashi Tatsumi etc.
J.Chem.Soc.Chem.Commun., prepared by the method described in 1997,677-678, and its titanium oxide content is 2.6 weights
Measure %.
In embodiment 3 and 17, static nitrogen adsorption method is respectively adopted and solid ultraviolet-visible diffuses spectrometry to before modified
The pore volume and ultraviolet absorption peak of HTS afterwards are characterized.Wherein, solid ultraviolet-visible diffusing reflection spectrum (UV-Vis)
Measured on SHIMADZU UV-3100 type ultraviolet-visible spectrometers；ASAP 2405 of the pore volume in Micromeritics companies
Determined on type static state n2 absorption apparatus.
In following examples, using the type Laser particle-size distributions of Mastersizer 2000 commercially available from Malvern company of Britain
Instrument determines average grain diameter, wherein, average grain diameter is volume average particle size.
In following examples, the content of each composition in obtained reaction solution is analyzed using gas chromatography, it is basic herein
On below equation is respectively adopted to calculate the choosing of the conversion ratio of dimethyl sulfide, the effective rate of utilization of oxidant and dimethyl sulfone
Selecting property：
Dimethyl sulfide conversion ratio (the %)=[(mole of the dimethyl sulfide of addition-unreacted dimethyl sulfide
Mole)/add dimethyl sulfide mole] × 100%；
Oxidant effective rate of utilization (%)=[mole of the dimethyl sulfone of 2 × reaction generation/(oxidant of addition
The mole of mole-unreacted oxidant)] × 100%；
Dimethyl sulfone selectivity (%)=[mole of the dimethyl sulfone of reaction generation/(dimethyl sulfide of addition rubs
That amount-unreacted dimethyl sulfide mole)] × 100%.
Embodiment 13,14 and 16-18 determine the activity of catalyst using following methods：
By catalyst, 36 weight % ammoniacal liquor (with NH3Meter), 30 weight % hydrogen peroxide is (with H2O2Meter), the tert-butyl alcohol and ring
Hexanone is in mass ratio=1：7.5：10：7.5：At atmosheric pressure in after 80 DEG C of stirring reaction 2h after 10 mixing, by reactant mistake
Filter, the composition of the liquid phase with gas chromatography to obtaining is analyzed, and is calculated the conversion ratio of cyclohexanone using below equation and is incited somebody to action
Its as the catalyst activity,
The conversion ratio (%) of cyclohexanone=[(mole of the mole of the cyclohexanone of addition-unreacted cyclohexanone)/
The mole of the cyclohexanone of addition] × 100%.
Embodiment 1-18 is used for the method for illustrating the present invention.
Embodiment 1
(1) titanium-silicon molecular sieve TS-1 is well mixed with Ludox (silica content is 30 weight %) and water, wherein, titanium
The weight ratio of silicalite TS-1, the Ludox counted using silica and water is 1：0.2：1.5.Obtained mixture is made through spin
Grain, and obtained wet grain is calcined 5 hours at 550 DEG C, (it is designated as so as to obtain the catalyst that volume average particle size is 200 μm
C1).Wherein, in catalyst, the content of titanium-silicon molecular sieve TS-1 is 80 weight %.
(2) Catalyst packing for preparing step (1) forms beds in isometrical fixed bed reactors.By two
Dimethyl sulfide, hydrogen peroxide (being 30 weight % hydrogen peroxide) and methanol mixing, form liquid mixture.Then, by the liquid
Body mixture is sent into fixed bed reactors and flows through beds.Wherein, in liquid mixture, dimethyl sulfide and peroxide
The mol ratio for changing hydrogen is 1：3, the weight ratio of dimethyl sulfide and methanol is 1：5, the weight (hourly) space velocity (WHSV) of liquid mixture is 100h-1。
Temperature in beds is 30 DEG C, and the pressure in fixed bed reactors is 0.5MPa.
The reactant mixture for reacting 0.5 hour and obtaining for 100 hours is subjected to gas chromatographic analysis, and calculates dimethyl disulfide
Ether conversion ratio, oxidant effective rate of utilization and dimethyl sulfone selectivity.As a result listed in table 1.
Embodiment 2
Dimethyl sulfone is prepared using method same as Example 1, unlike, in step (1), titanium-silicon molecular sieve TS-1
Replaced with the hollow HTS of equivalent, so as to obtain the catalyst (being designated as C2) that volume average particle size is 200 μm.Wherein,
In catalyst, the content of HTS is 80 weight %.
Reaction 0.5 hour and the result obtained for 100 hours are listed in table 1.
Embodiment 3
Dimethyl sulfone is prepared using method same as Example 1, unlike, the titanium-silicon molecular sieve TS-1 of step (1)
The titanium-silicon molecular sieve TS-1 being modified with equivalent is replaced, wherein, modified titanium-silicon molecular sieve TS-1 is prepared using following methods：
Titanium-silicon molecular sieve TS-1 is mixed with hydrochloric acid (mass concentration is the 36 weight % aqueous solution), by obtained mixture
In 90 DEG C of stirring reactions 5 hours, the temperature of obtained reactant mixture, which is down to after room temperature, to be filtered, by obtained solid matter
Dried at 120 DEG C to constant weight, obtain modified HTS.Wherein, titanium-silicon molecular sieve TS-1 is with SiO2Meter, HTS
Mol ratio with HCl is 1：0.2.Through characterizing, compared with raw material HTS, the UV- of the HTS of obtained modification
The peak height of absworption peak in Vis spectrum between 240-300nm reduces 3.1%, is reduced by the pore volume of static determination of nitrogen adsorption
1.6%.
Reaction 0.5 hour and the result obtained for 150 hours are listed in table 1.
Embodiment 4
Dimethyl sulfone is prepared using method same as Example 1, unlike, in step (2), also to liquid mixture
Middle addition hydrochloric acid, 5.0 are adjusted to by the pH value of liquid mixture from 5.7.
Reaction 0.5 hour and the result obtained for 120 hours are listed in table 1.
Embodiment 5
Dimethyl sulfone is prepared using method same as Example 1, unlike, in step (2), in the general assembly of catalyst
Under conditions of the amount of filling out is constant, in fixed bed reactors formed two beds, be designated as respectively the first beds and
Second beds, the upper surface of the first beds connects with the lower surface of the second beds, is mixed with liquid
On the basis of flow direction of the thing in fixed bed reactors, the first beds are located at the upstream of the second beds (i.e.,
Liquid mixture firstly flows through the first beds, again passes through the second beds), the first beds filling is urged
Agent C2, the second beds loading catalyst C1, and catalyst C2 and catalyst C1 weight ratio are 2：1.
Reaction 0.5 hour and the result obtained for 200 hours are listed in table 1.
Embodiment 6
Dimethyl sulfone is prepared using method same as Example 5, unlike, it is constant in the total filling amount of catalyst
Under the conditions of, make in step (2), catalyst C2 and catalyst C1 weight ratio is 5：1.
Reaction 0.5 hour and the result obtained for 200 hours are listed in table 1.
Embodiment 7
Dimethyl sulfone is prepared using method same as Example 5, unlike, in catalyst C1 and catalyst C2 dress
Under conditions of the amount of filling out is constant, the loading catalyst C1 in the first beds, the loading catalyst in the second beds
C2。
Reaction 0.5 hour and the result obtained for 80 hours are listed in table 1.
Embodiment 8
Dimethyl sulfone is prepared using method same as Example 5, unlike, it is constant in the total filling amount of catalyst
Under the conditions of, the weight ratio for making catalyst C2 and catalyst C1 is 1：1.
Reaction 0.5 hour and the result obtained for 120 hours are listed in table 1.
Embodiment 9
Dimethyl sulfone is prepared using method same as Example 5, unlike, it is constant in the total filling amount of catalyst
Under the conditions of, the weight ratio for making catalyst C2 and catalyst C1 is 10：1.
Reaction 0.5 hour and the result obtained for 140 hours are listed in table 1.
Embodiment 10
Dimethyl sulfone is prepared using method same as Example 6, unlike, the catalyst C3 of catalyst C1 equivalent
Instead of catalyst C3 preparation method is as follows：
HTS Ti-Beta is well mixed with Ludox (silica content is 30 weight %) and water, wherein, titanium
Si molecular sieves Ti-Beta, the Ludox counted using silica and water weight ratio is 1：0.2：1.5.By obtained mixture through rolling
Ball is granulated, and obtained wet grain is calcined 5 hours at 550 DEG C, so as to obtain the catalyst C3 that average grain diameter is 200 μm.Wherein,
In catalyst C3, HTS Ti-Beta content is 80 weight %.
Reaction 0.5 hour and the result obtained for 130 hours are listed in table 1.
Embodiment 11
Dimethyl sulfone is prepared using method same as Example 6, unlike, the catalyst C4 of catalyst C1 equivalent
Instead of catalyst C4 preparation method is as follows：
HTS Ti-MCM-41 is well mixed with Ludox (silica content is 30 weight %) and water, wherein,
HTS Ti-MCM-41, the Ludox counted using silica and water weight ratio is 1：0.2：1.5.By obtained mixture
Granulated through spin, and obtained wet grain is calcined 5 hours at 550 DEG C, so as to obtain the catalyst C4 that average grain diameter is 200 μm.
Wherein, in catalyst C4, HTS Ti-MCM-41 content is 80 weight %.
Reaction 0.5 hour and the result obtained for 120 hours are listed in table 1.
Table 1
The result of table 1 shows, dimethyl sulfone is prepared using the method for the present invention, results in high dimethyl sulfide and turns
Rate, oxidant effective rate of utilization and dimethyl sulfone selectivity.
Embodiment 1 and embodiment 3 are compared and can be seen that the HTS for using acid modified as catalyst,
With directly by HTS as catalyst compared with, higher dimethyl sulfone selectivity is resulted in, while can also be further
Extend the parallel-adder settle-out time of the HTS as catalyst.
Embodiment 1 and embodiment 4 are compared and be can be seen that with the sour liquid mixture for adjusting and being contacted with catalyst
PH value, results in more preferable reaction effect.
Embodiment 12
(1) titanium-silicon molecular sieve TS-1 is well mixed with Ludox (silica content is 30 weight %) and water, wherein, titanium
The weight ratio of silicalite TS-1, the Ludox counted using silica and water is 1：0.15：5.Obtained mixture is made through spin
Grain, and obtained wet grain is calcined 5 hours at 550 DEG C, so as to obtain the catalyst that average grain diameter is 500 μm.Wherein, catalyst
In, the content of HTS is 85 weight %.
(2) Catalyst packing for preparing step (1) forms beds in isometrical fixed bed reactors, wherein,
The quantity of beds is 1 layer.
Dimethyl sulfide, hydrogen peroxide (being 30 weight % hydrogen peroxide) and acetone are mixed, liquid mixture is formed.So
Afterwards, the liquid mixture is sent into fixed bed reactors and flows through beds.Wherein, in liquid mixture, diformazan
The mol ratio of base thioether and hydrogen peroxide is 1：4, the weight ratio of dimethyl sulfide and acetone is 1：2, liquid mixture it is heavy when
Air speed is 150h-1.Temperature in beds is 80 DEG C, and the pressure in fixed bed reactors is 1.5MPa.
The reactant mixture for reacting 1 hour and obtaining for 100 hours is subjected to gas chromatographic analysis, and calculates dimethyl sulfide
Conversion ratio, oxidant effective rate of utilization and dimethyl sulfone selectivity.As a result listed in table 2.
Embodiment 13
Dimethyl sulfone is prepared using with the identical method of embodiment 12, unlike, it is seated in fixed bed reactors
Catalyst is preformed catalyst (fresh dose of use and the step of embodiment 12 (1) that will be drawn off from cyclohexanone oxamidinating course of reaction
Identical method is prepared) regenerated obtained from, regeneration condition is：4h is calcined in air atmosphere at 550 DEG C.Again
The activity of raw rear catalyst is 45%, and its activity when fresh is 95%.
Reaction 1 hour and the result obtained for 180 hours are listed in table 2.
Embodiment 14
Dimethyl sulfone is prepared using with the identical method of embodiment 13, unlike, in step (2), also mixed to liquid
Phosphoric acid is added in thing, the pH value of liquid mixture is adjusted to 2 from 5.6.
Reaction 1 hour and the result obtained for 200 hours are listed in table 2.
Table 2
Embodiment 15
(1) hollow HTS is well mixed with Ludox (silica content is 30 weight %) and water, wherein, it is empty
The weight ratio of heart HTS, the Ludox counted using silica and water is 1：0.1：8.Obtained mixture is made through spin
Grain, and obtained wet grain is calcined 5 hours at 550 DEG C, so as to obtain the catalyst that average grain diameter is 100 μm.Wherein, catalyst
In, the content of hollow HTS is 90 weight %.
(2) Catalyst packing for preparing step (1) forms beds in fixed bed reactors, wherein, catalysis
The quantity of agent bed is 1 layer.
By dimethyl sulfide, hydrogen peroxide (being 40 weight % hydrogen peroxide), acetonitrile and hydrochloric acid (concentration is 20 weight %)
Mixing, forms liquid mixture, and the pH value of liquid mixture is adjusted to 3.0 by the consumption of hydrochloric acid from 5.8.Then, by the liquid
Body mixture is sent into fixed bed reactors and flows through beds.Wherein, in liquid mixture, dimethyl sulfide and peroxide
The mol ratio for changing hydrogen is 1：2.5, the weight ratio of dimethyl sulfide and acetonitrile is 1：10, the weight (hourly) space velocity (WHSV) of liquid mixture is
200h-1.Temperature in beds is 20 DEG C, and the pressure in fixed bed reactors is 0.5MPa.
The reactant mixture for reacting 1 hour and obtaining for 120 hours is subjected to gas chromatographic analysis, and calculates dimethyl sulfide
Conversion ratio, oxidant effective rate of utilization and dimethyl sulfone selectivity.As a result listed in table 3.
Embodiment 16
Dimethyl sulfone is prepared using with the identical method of embodiment 15, unlike, in step (2), it is seated in fixed bed
Catalyst in reactor is the hollow HTS of shaping (the fresh dose of use that will be drawn off from phenol hydroxylation reaction unit
Prepared with the step of embodiment 15 (1) identical method) regenerated obtained from, its activity is 30%, the activity when fresh
For 96%, regeneration condition is：4h is calcined in air atmosphere at 570 DEG C.
Reaction 1 hour and the result obtained for 200 hours are listed in table 3.
Embodiment 17
Dimethyl sulfone is prepared using with the identical method of embodiment 16, unlike, will be from phenol hydroxylation reaction unit
In carry out acid treatment after the hollow HTS regeneration of the shaping that draws off, be then packed into fixed bed reactors and form catalyst
The method of bed, wherein acid treatment is as follows：
The agent that draws off after regeneration is mixed with acetic acid (mass concentration is the 32 weight % aqueous solution), by obtained mixture
In 60 DEG C of stirring reactions 24 hours, the temperature of obtained reactant mixture, which is down to after room temperature, to be filtered, by obtained solid formation
Matter is dried to constant weight at 120 DEG C, obtains modified HTS.Wherein, HTS is with SiO2Meter, HTS with
CH3COOH mol ratio is 1：5.Through characterizing, with after regeneration draw off agent compared with, the UV-Vis spectrum of modified HTS
In absworption peak peak height between 240-300nm reduce 5.5%, reduce 2.2% by the pore volume of static determination of nitrogen adsorption.
Reaction 1 hour and the result obtained for 250 hours are listed in table 3.
Embodiment 18
Dimethyl sulfone is prepared using with the identical method of embodiment 15, unlike, in step (2), it is seated in fixed bed
Catalyst in reactor is the hollow HTS of shaping (the fresh dose of use that will be drawn off from propylene ring oxidation reaction device
Prepared with the step of embodiment 15 (1) identical method) regenerated obtained from, its activity is 40%, the activity when fresh
For 96%, regeneration condition is：4h is calcined in air atmosphere at 570 DEG C.
Reaction 1 hour and the result obtained for 200 hours are listed in table 3.
Table 3
Embodiment 13,14 and 16-18 result show, though at least part catalyst source in using HTS as
The reaction unit of catalyst draws off agent, and it is effective that method of the invention can also obtain high dimethyl sulfide conversion ratio, oxidant
Utilization rate and dimethyl sulfone selectivity；Moreover, in tandem reaction sequence, the activity of catalyst is more stable.
Claims (15)
1. a kind of preparation method of dimethyl sulfone, this method is included under oxidation reaction condition, in fixed bed reactors, makes one
Kind of liquid mixture obtains the mixing containing dimethyl sulfone by being filled with the beds of at least one HTS
Thing, the mixture containing dimethyl sulfone is fractionated, and obtains dimethyl sulfone, the liquid mixture contain dimethyl sulfide and
The mol ratio of at least one peroxide, the peroxide and the dimethyl sulfide is more than 2：1, at least partly described titanium
Si molecular sieves are the agent that draws off using HTS as the reaction unit of catalyst through regeneration, described to draw off agent to be oximes
Reaction unit draws off agent, one kind drawn off in agent or many for drawing off agent and epoxidation reaction device of hydroxylating device
Kind, the active 30-50% that the activity for drawing off agent through regeneration is it when fresh.
2. according to the method described in claim 1, wherein, will at least partly titanium silicon before being contacted with the liquid mixture
Molecular sieve is contacted 0.1-72 hours with least one acid at a temperature of 0-200 DEG C.
3. method according to claim 2, wherein, HTS is in terms of silica, the HTS and institute
The mol ratio for stating acid is 1：0.01-10.
4. according to the method in claim 2 or 3, wherein, it is described acid be selected from acetic acid, hydrochloric acid, sulfuric acid, phosphoric acid, nitric acid, high chlorine
Acid and hydrobromic acid.
5. the method according to any one in claim 1-3, wherein, it is described to draw off agent and react dress for cyclohexanone oxamidinating
That puts draws off agent, one kind drawn off in agent or many for drawing off agent and propylene ring oxidation reaction device of phenol hydroxylation reaction unit
Kind.
6. the method according to any one in claim 1-3, wherein, the HTS is with MFI structure
HTS.
7. method according to claim 6, wherein, at least partly described HTS is hollow HTS, institute
The crystal grain for stating hollow HTS is hollow-core construction, and the radical length of the chamber portion of the hollow-core construction is 5-300 nanometers, and
The HTS is in 25 DEG C, P/P0=0.10, adsorption time is that the benzene adsorbance measured under conditions of 1 hour is at least 70
, there is hysteresis loop between the adsorption isotherm and desorption isotherm of the nitrogen absorption under low temperature of the HTS in milligrams per gram.
8. method according to claim 7, wherein, the HTS is hollow HTS and HTS
TS-1, on the basis of the flow direction of the liquid mixture, the hollow HTS is located at the HTS TS-
1 upstream.
9. method according to claim 8, wherein, the weight of the hollow HTS and the titanium-silicon molecular sieve TS-1
Amount is than being 1-10：1.
10. according to the method described in claim 1, wherein, the liquid mixture is also containing at least one solvent, dimethyl disulfide
The weight ratio of ether and the solvent is 1：0.1-20.
11. method according to claim 10, wherein, the solvent is selected from water, C1-C10Alcohol, C3-C10Ketone and C2-
C10Nitrile.
12. the method according to any one in claim 1,2,10 and 11, wherein, this method is also included to the liquid
At least one acid is added in mixture, the sour addition causes the pH value of the liquid mixture to be 0.5-5.5.
13. according to the method described in claim 1, wherein, the mol ratio of the peroxide and dimethyl sulfide is 2.5-5：
1。
14. the method according to claim 1 or 13, wherein, the peroxide is selected from hydrogen peroxide, tert-butyl hydroperoxide
Hydrogen, dicumyl peroxide, cyclohexyl hydroperoxide, Peracetic acid and Perpropionic Acid.
15. the method according to any one in claim 1,2,10 and 13, wherein, the heavy space-time of the liquid mixture
Speed is 0.1-500h-1；The oxidation reaction condition includes：Temperature is 0-160 DEG C；In terms of gauge pressure, pressure is 0-3MPa.
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| JP2003128660A (en) * | 2001-10-22 | 2003-05-08 | Showa Denko Kk | Oxidation method of carbon-carbon double bond and production method of oxidized compound using the same |
| CN1657168A (en) * | 2004-12-09 | 2005-08-24 | 华东师范大学 | Preparation method of acid modified titanium-containing molecular sieve |
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| WO2004058737A1 (en) * | 2002-12-24 | 2004-07-15 | Showa Denko K.K. | Method of oxidizing carbon-carbon double bond and process for producing oxidized compound |
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| CN1657168A (en) * | 2004-12-09 | 2005-08-24 | 华东师范大学 | Preparation method of acid modified titanium-containing molecular sieve |
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