CN105017108B - A kind of preparation method of dimethyl sulfone - Google Patents
A kind of preparation method of dimethyl sulfone Download PDFInfo
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- CN105017108B CN105017108B CN201410178113.0A CN201410178113A CN105017108B CN 105017108 B CN105017108 B CN 105017108B CN 201410178113 A CN201410178113 A CN 201410178113A CN 105017108 B CN105017108 B CN 105017108B
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Abstract
The invention discloses a kind of preparation method of dimethyl sulfone, it is included under oxidation reaction condition, dimethyl sulfoxide (DMSO) and at least one oxidant is contacted with least one HTS, wherein, at least partly described HTS is non-fresh HTS.With not in the presence of a catalyst by dimethyl sulfoxide (DMSO) compared with oxidant haptoreaction, method of the invention can obtain the dimethyl sulfoxide (DMSO) conversion ratio significantly improved, oxidant effective rate of utilization and dimethyl sulfone selectivity.With by dimethyl sulfoxide (DMSO) and oxidant compared with fresh HTS haptoreaction, the method of the present invention can obtain higher oxidant effective rate of utilization, simultaneously in long period tandem reaction sequence, the conversion ratio of dimethyl sulfoxide (DMSO) and the selectivity of dimethyl sulfone are more stable.In addition, the method reaction condition of the present invention is gentle, and it is easily controllable, suitable for various production-scale devices.
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, accelerate to 60 DEG C of rate of sublimation, thus dimethyl sulfone product drying is preferably carried out 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 has the ability that enhancing human body produces insulin, simultaneously as a kind of organic sulfur compound
Metabolism to carbohydrate also has facilitation, is 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 the skin of human body, hair, nail, bone, muscle and each organ,
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 disease occurs 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 be widely applied using dimethyl sulfone as with vitamin nutriment of equal importance, China
Application study to dimethyl sulfone is not yet carried out very well, and product is mainly used in exporting at present.Therefore, dimethyl sulfone is not only one kind
New high-tech product, and a kind of fine chemical product of high added value.Product is new, market potential is big, and benefit protrudes, and has wide
Wealthy production and application and development prospect.
At present, the product that dimethyl sulfone further aoxidizes as dimethyl sulfoxide (DMSO), for 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 sub- by dimethyl
Sulfone is cooled at 140-145 DEG C with nitric acid oxidation, reaction after terminating, and is filtered, and obtains the crude product of white, needle-shaped crystals.Again through decompression
Distillation, it is finished product to collect 138-145 DEG C of (98.42kPa) cut.
The content of the invention
It is an object of the invention to provide a kind of preparation method of dimethyl sulfone, this method is used as starting using dimethyl sulfoxide (DMSO)
Raw material, dimethyl sulfoxide (DMSO) oxidation is prepared into dimethyl sulfone with oxidant, there is high dimethyl sulfoxide (DMSO) conversion ratio, oxidant to have
Imitate utilization rate and dimethyl sulfone selectivity.
The invention provides a kind of preparation method of dimethyl sulfone, this method is included under oxidation reaction condition, by diformazan
Base sulfoxide and at least one oxidant contact with least one HTS, wherein, at least partly described HTS is
Non-fresh HTS.
The catalyst that the method according to the invention uses is HTS, and at least partly described HTS is non-
Fresh HTS.With not in the presence of catalyst (such as HTS) by dimethyl sulfoxide (DMSO) and oxidant haptoreaction phase
Than method of the invention can obtain the dimethyl sulfoxide (DMSO) conversion ratio significantly improved, oxidant effective rate of utilization and dimethyl sulfone
Selectivity.With with fresh HTS (that is, when oxidation reaction starts, dimethyl sulfoxide (DMSO) and oxidant are used into fresh titanium
Si molecular sieves are as catalyst) haptoreaction compares, and the method according to the invention can obtain higher oxidant and effectively utilize
Rate, while in tandem reaction sequence, the conversion ratio of dimethyl sulfoxide (DMSO) and the selectivity of dimethyl sulfone are more stable.
In addition, the method according to the invention reaction condition is gentle, and it is easily controllable, suitable for various production-scale devices.
Embodiment
Herein, " at least one " represents one or more kinds of.
The invention provides a kind of preparation method of dimethyl sulfone, this method is included under oxidation reaction condition, by diformazan
Base sulfoxide and at least one oxidant contact with least one HTS, wherein, at least partly described HTS is
Non-fresh HTS.
The method according to the invention, at least partly described HTS is non-fresh HTS.With reacting
Stage beginning uses fresh HTS, then in tandem reaction sequence, HTS is separated and passed through optionally
It is exactly non-fresh titanium silicon molecule that different, of the invention methods is recycled after regeneration in the HTS that initial period uses
Sieve.That is, method of the invention, at least part start catalysts are non-fresh HTS.
With all using fresh HTS as start catalysts compared with, method of the invention can obtain it is satisfied
While dimethyl sulfoxide (DMSO) conversion ratio and dimethyl sulfone selectivity, additionally it is possible to higher oxidant effective rate of utilization is obtained, and even
In continuous course of reaction, the conversion ratio of dimethyl sulfoxide (DMSO) and the selectivity of dimethyl sulfone are more stable.Meanwhile the non-fresh titanium silicon
Molecular sieve can be some using HTS as catalyst reaction unit (remove prepare dimethyl sulfoxide (DMSO) and/or dimethyl
Reaction unit outside sulfone) draw off agent, these draw off agent through being also used as the non-new of the present invention after optional regeneration treatment
Fresh HTS, now with all using fresh HTS compared with start catalysts, method of the invention can
Obtain significantly reduced operating cost.To draw off agent as the technical scheme and its advantage of the non-fresh HTS of the present invention
It will be described in more detail later.
Herein, it is (logical that the HTS that fresh HTS refers to prepare removes the progress activation process before use
Often to be calcined, to remove the material or group that are remained in the preparation process of HTS) outside, other physics are not lived through
And/or the HTS of chemical treating process.Conversely, in addition to activation process, other physically and/or chemically processes were also subject to
Be then non-fresh HTS, as after catalytic oxidation inactivation or partial inactivation HTS, even include water
The active process such as heat ageing make the HTS that its activity reduces.
The non-fresh HTS can be the non-fresh HTS in various sources, such as can be titanium to be generated
Si molecular sieves, regenerate HTS and fresh HTS is subjected to the titanium as obtained from the active process of hydrothermal aging etc.
One or more in si molecular sieves.Although HTS to be generated can also be directly used in the present invention, if directly made
With HTS to be generated, some impurity may be introduced, the separation for improving the mixture containing dimethyl sulfone finally given is difficult
Degree, therefore, the non-fresh HTS are preferably to regenerate HTS and/or fresh HTS is carried out into such as water
HTS obtained from the active process of heat ageing etc..
The regeneration HTS can be in the common various carded slivers again by the HTS to be generated in various sources
HTS obtained from being regenerated under part.
(remove using various reaction units of the HTS as catalyst and prepare dimethyl sulfoxide (DMSO) and/or dimethyl
Reaction unit outside sulfone) in, in Ammoximation reaction, hydroxylating and epoxidation reaction device, generally in plant running one
After the section time, the catalytic activity of catalyst declines, it is necessary to carry out in device or ex-situ regeneration, even if also being difficult to obtain when carrying out regeneration
, it is necessary to which catalyst is drawn off into (that is, more catalyst changeout) from device during the activity that must be satisfied with, and the catalyst drawn off (that is, is drawn off
Agent or dead catalyst) current processing method is typically to accumulate to bury, and land resource and the stock on the one hand occupying preciousness are empty
Between, another aspect HTS production cost is higher, directly passes into disuse and also result in great waste.The invention of the present invention
People has found in research process, if these are drawn off into agent carries out regeneration treatment, by obtained regenerative agent and dimethyl sulfoxide (DMSO) and
Oxidant contacts under oxidation reaction condition, remains able to obtain high dimethyl sulfoxide (DMSO) conversion ratio and dimethyl sulfone selectivity,
And higher oxidant effective rate of utilization can be obtained, dimethyl sulfoxide (DMSO) conversion ratio and dimethyl sulfone choosing in tandem reaction sequence
The stability of selecting property is more preferable.Therefore, the method according to the invention, the non-fresh HTS are preferably with HTS
Reaction unit as catalyst draws off agent (that is, described HTS to be generated for draw off agent) and/or will draw off agent and carries out
HTS obtained from regeneration, it will more preferably draw off HTS obtained from agent is regenerated.It is described to draw off agent
It can be the agent that draws off drawn off from the various devices using HTS, such as can be to be drawn off from oxidation reaction apparatus
Draw off agent.The oxidation reaction can be various oxidation reactions, such as described to draw off agent can be Ammoximation reaction device
Agent, the one or more drawn off in agent for drawing off agent and epoxidation reaction device of hydroxylating device are drawn off, specifically can be with
For cyclohexanone oxamidinating reaction unit draw off agent, phenol hydroxylation reaction unit draws off agent and propylene ring oxidation reaction device
The one or more drawn off in agent.
The condition that HTS to be generated is regenerated is not particularly limited, can according to HTS to be generated come
Source carries out appropriate selection, such as：High-temperature roasting and/or solvent washing.
Fresh HTS is subjected to the active process such as hydrothermal aging so as to obtain the condition of non-fresh HTS
Also it is not particularly limited, can is conventional selection, such as：Can by fresh HTS under hydrothermal conditions (as from
Under raw pressure, steam treatment 0.5-72 hours are utilized at 200-800 DEG C, such as 500-800 DEG C, such as 3-10 hours), so as to obtain
The non-fresh HTS of hydrothermal aging.
The activity of the non-fresh HTS is different according to its source.Usually, the non-fresh titanium silicon
The activity of molecular sieve can be the 5- of activity (that is, the activity of fresh HTS) of the HTS when fresh
95%.Preferably, the activity of the non-fresh HTS can be active 10- of the HTS when fresh
90%, more preferably active 10-80% of the HTS when fresh.In the non-fresh HTS
During the active 10-80% that activity is the HTS when fresh, gratifying dimethyl sulfoxide (DMSO) can not only be obtained
Conversion ratio and dimethyl sulfone selectivity, and the oxidant effective rate of utilization further improved, tandem reaction sequence can be obtained
Middle dimethyl sulfoxide (DMSO) conversion ratio and dimethyl sulfone selectivity is more stable.From the angle of the further conversion ratio for improving dimethyl sulfoxide (DMSO)
Degree sets out, the active 30-55% that the activity of the non-fresh HTS is the HTS when fresh.It is described new
The activity of fresh HTS is generally more than 95%.
The activity determines by the following method：Non-fresh HTS and fresh HTS are used as ring respectively
The catalyst of hexanone Ammoximation reaction, the condition of the Ammoximation reaction are：HTS, 36 weight % ammoniacal liquor are (with NH3
Meter), 30 weight % hydrogen peroxide is (with H2O2Meter), the tert-butyl alcohol and cyclohexanone in mass ratio 1：7.5：10：7.5：10, in atmospheric pressure
Reacted 2 hours in 80 DEG C under power.Hexamethylene during using non-fresh HTS and fresh HTS as catalyst is calculated respectively
The conversion ratio of ketone, so that it is determined that the activity of non-fresh HTS and fresh HTS, wherein, the conversion ratio of cyclohexanone
=[(mole of the mole of the cyclohexanone of addition-unreacted cyclohexanone)/mole of the cyclohexanone added] ×
100%.
The method according to the invention, although as long as containing non-fresh HTS in HTS, with
On the basis of the total amount of the HTS, the content of non-fresh HTS is preferably more than 5 weight % such as 30 weight %
More than, the effect for preferably improving oxidant effective rate of utilization can not only be so obtained, and course of reaction is more steady easy
Control, while can also obtain gratifying dimethyl sulfoxide (DMSO) conversion ratio and dimethyl sulfone selectivity.The method according to the invention,
Even if whole HTSs are non-fresh HTS (that is, the content of non-fresh HTS is 100 weight %),
Remain able to obtain gratifying dimethyl sulfoxide (DMSO) conversion ratio, oxidant effective rate of utilization and dimethyl sulfone selectivity.Obtaining
On the premise of obtaining high oxidant effective rate of utilization, from the selection of the further conversion ratio and dimethyl sulfone for improving dimethyl sulfoxide (DMSO)
The angle of property is set out, and on the basis of the total amount of the HTS, the content of non-fresh HTS is more preferably 50-80
Weight %, more preferably 60-75 weight %.
In a kind of preferred embodiment of the present invention, the HTS is being contacted with the liquid mixture
Before, the method according to the invention preferably contacts at least partly described HTS with least one acid.So further
Improve dimethyl sulfoxide (DMSO) conversion ratio and dimethyl sulfone selectivity while, additionally it is possible to further extend catalyst use the longevity
Life, further reduce the operating cost of the inventive method.For purposes of clarity, hereinafter, the titanium silicon point that will be contacted with acid
Son sieve is referred to as modified HTS.
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 can be more than 10 weight % (such as 10-100 weights
Measure %), preferably more than 50 weight %, it is specifically as follows 50-90 weight %.
The acid is general acid, can be inorganic acid (such as hydrochloric acid, sulfuric acid, phosphoric acid, nitric acid, perchloric acid and hydrobromic acid), have
One or more in machine 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-C6Aliphatic sulfonic and C6-C12Aromatic sulphonic acid.The acid is preferably with the shape of the aqueous solution
Formula is provided, and the concentration of sour aqueous acid medium can be selected according to the species of acid, be not particularly limited, usually, sour
The concentration of aqueous acid medium can be 0.01-50 weight %.
The condition handled with acid HTS with cause contact after HTS ultraviolet-visible (UV-
Vis) in spectrum, the peak height of the absworption peak between 240-300nm reduces by more than 2% (generally 2-20%, such as 3-5%), uses
The pore volume of static determination of nitrogen adsorption reduces by more than 1% (generally 1-10%, such as 1-3%).
Usually, for HTS in terms of silica, the HTS can be 1 with the sour mol ratio：
0.01-10, preferably 1：0.05-5 (such as 1：0.1-1).The contact can 0-200 DEG C, preferably 20-180 DEG C, more preferably
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.One
As, the time of the contact can be 0.1-72 hours, preferably 0.5-24 hours, more preferably 4-8 hours.
The method according to the invention, for the HTS as the catalyst for aoxidizing dimethyl sulfoxide (DMSO), its dosage can
The catalytic amount of catalysis can be realized by thinking.Specifically, the mass ratio of dimethyl sulfoxide (DMSO) and the HTS is
0.1-60：1, preferably 5-50：1.
The method according to the invention, the HTS can be HTS original powder, or the titanium of shaping
Si molecular sieves.
The method according to the invention, the oxidant can be it is commonly used in the art it is various can be by dimethyl sulfoxide (DMSO) oxygen
Change, form the material of dimethyl sulfone.Method of the invention is particularly suitable for carry out cacodyl oxide base using peroxide as oxidant
Sulfoxide, so as to prepare the occasion of dimethyl sulfone, the effective rate of utilization of peroxide can be so significantly improved, reduces dimethyl sulfone
Production cost.The peroxide refer in molecular structure contain-O-O- keys compound, can be hydrogen peroxide and/or
Organic peroxide (including organic hydroperoxide and peracid), its instantiation can include but is not limited to：Hydrogen peroxide, uncle
Butylhydroperoxide, dicumyl peroxide, cyclohexyl hydroperoxide, Peracetic acid and Perpropionic Acid.Preferably, the oxidant
For hydrogen peroxide, separation costs so can be further reduced.The hydrogen peroxide can be commonly used in the art with various shapes
Hydrogen peroxide existing for formula.
From the angle of the further security for improving the method according to the invention, the method according to the invention preferably makes
With existing hydrogen peroxide as an aqueous solution.The method according to the invention, 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, such as：20-80 weight %.On concentration meets
Stating the aqueous solution of the hydrogen peroxide of requirement can use conventional method to prepare, and can also be commercially available, such as：Can be being capable of business
The hydrogen peroxide of the 30 weight % bought hydrogen peroxide, 50 weight % hydrogen peroxide or 70 weight %.
The dosage of the oxidant can be conventional selection, be not particularly limited.Usually, the oxidant and described two
The mol ratio of methyl sulfoxide is 0.1-10：1, preferably 0.5-5：1.
The method according to the invention, from the further mixability improved in reaction system between each reactant, strengthen and expand
The angle for dissipating and more easily the severe degree of reaction being adjusted is set out, and the contact can be at least one solvent
In the presence of carry out.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 include but is not limited to：Water, methanol, ethanol, normal propyl alcohol, isopropyl
Alcohol, the tert-butyl alcohol, isobutanol, acetone, butanone and acetonitrile.Preferably, the solvent is selected from water and C1-C6Alcohol.It is highly preferred that institute
It is methanol and/or water to state solvent.Water as solvent can be the water in various sources, such as：The water of addition；Oxidant be with
Existing for hydrogen peroxide form during hydrogen peroxide, the water that is present in hydrogen peroxide.
The dosage of the solvent is not particularly limited, and can be conventional selection.Usually, the matter of solvent and dimethyl sulfoxide (DMSO)
It can be 1-100 to measure ratio：1.Furthermore it is also possible to according to the shape for being contacted dimethyl sulfoxide (DMSO) and oxidant with HTS
The difference of formula, appropriate adjustment is carried out to the dosage of solvent.
The method according to the invention, the oxidation reaction condition are not particularly limited, to be enough to aoxidize dimethyl sulfoxide (DMSO)
Dimethyl sulfone is formed to be defined.Usually, the oxidation reaction condition includes：Temperature can be 0-200 DEG C, preferably 20-180 DEG C
(such as 20-100 DEG C)；In terms of gauge pressure, pressure can be 0-3MPa, preferably 0-1.5MPa.
Method according to the invention it is possible to using intermittently operated, continuous operation can also be used.
The method according to the invention can also include being separated in the mixture containing dimethyl sulfone that contact obtains, with
Isolate dimethyl sulfone therein.The method of dimethyl sulfone in the mixture that the present invention obtains for isolating contact is without spy
Do not limit, can be the conventional selection of this area.Such as can be fractionated by the way that obtained mixture will be contacted, so as to obtain
Dimethyl sulfone.
The invention will be further described for following embodiment, but and is not so limited present disclosure.
In following examples and comparative example, if not otherwise specified, for pressure in terms of gauge pressure, used reagent is commercially available
AR, hydrogen peroxide be 30 weight % hydrogen peroxide.
In following examples and comparative example, fresh titanium-silicon molecular sieve TS-1 used is according to Zeolites, and the 1992, the 12nd
Prepared by volume, the method described in the 943-950 pages, TiO2Content is 2.5 weight %.
In following examples, fresh hollow HTS HTS used is according to the method system disclosed in CN1132699C
Standby, through analysis, the HTS is MFI structure, is existed between the nitrogen absorption under low temperature and desorption isotherm of the HTS
Hysteresis loop, crystal grain are that the radical length of hollow crystal grain and chamber portion is 15-180 nanometers；The HTS sample at 25 DEG C,
P/P0=0.10, the benzene adsorbance that adsorption time measures under conditions of being 1 hour is 78 milligrams per grams, TiO2Content is 2.5 weights
Measure %.
In following examples and comparative example, static nitrogen adsorption method and solid ultraviolet-visible is respectively adopted and diffuses spectrometry
To acid, the pore volume of rear HTS and ultraviolet absorption peak characterize before modified.Wherein, solid ultraviolet-visible diffusing reflection spectrum
(UV-Vis) measured on SHIMADZU UV-3100 type ultraviolet-visible spectrometers；Pore volume is in Micromeritics companies
Determined on ASAP2405 type static state n2 absorption apparatus.
In following examples and comparative example, the content of each composition in the reaction solution obtained using gas chromatography analysis,
Below equation is respectively adopted on the basis of this to calculate dimethyl sulfoxide (DMSO) conversion ratio, oxidant effective rate of utilization and dimethyl sulfone choosing
Selecting property：
Dimethyl sulfoxide (DMSO) conversion ratio (the %)=[(mole of the dimethyl sulfoxide (DMSO) of addition-unreacted dimethyl sulfoxide (DMSO)
Mole)/add dimethyl sulfoxide (DMSO) mole] × 100%；
Oxidant effective rate of utilization (%)=[mole/(mole of the oxidant of addition of the dimethyl sulfone of reaction generation
The mole of amount-unreacted oxidant)] × 100%；
Dimethyl sulfone selectivity (%)=[mole of the dimethyl sulfone of reaction generation/(dimethyl sulfoxide (DMSO) of addition rubs
That amount-unreacted dimethyl sulfoxide (DMSO) mole)] × 100%.
In following examples, HTS (including fresh HTS and non-fresh titanium are determined using following methods
Si molecular sieves) activity：
By HTS, 36 weight % ammoniacal liquor (with NH3Meter), 30 weight % hydrogen peroxide is (with H2O2Meter), the tert-butyl alcohol
With cyclohexanone in mass ratio=1：7.5：10：7.5：, will be anti-after 10 mixing at atmosheric pressure after 80 DEG C of stirring reactions 2 hours
Answer thing to filter, the composition of liquid phase is analyzed with gas chromatography, the conversion ratio of cyclohexanone is calculated using below equation and incited somebody to action
Its activity as HTS,
The conversion ratio of cyclohexanone=[(mole of the cyclohexanone of addition-unreacted cyclohexanone mole)/add
The mole of cyclohexanone] × 100%.
Embodiment 1-12 is used for the method for illustrating the present invention.
Embodiment 1
The HTS SH-1 as catalyst used in the present embodiment is will be from cyclohexanone oxamidinating course of reaction
Obtained from the titanium-silicon molecular sieve TS-1 drawn off is regenerated, wherein, regeneration condition is：Roasted at 550 DEG C in air atmosphere
Burn 4h.HTS SH-1 activity is 50%, and the activity of fresh titanium-silicon molecular sieve TS-1 is 95%.
Dimethyl sulfoxide (DMSO), the SH-1 as catalyst, the hydrogen peroxide as oxidant and the methanol as solvent are sent
Enter and oxidation reaction is carried out in small-sized slurry bed reactor, catalysis is isolated from the reactant mixture of slurry bed reactor output
Agent, the liquid phase mixture containing dimethyl sulfone is obtained, the catalyst isolated recycles.Wherein, dimethyl sulfoxide (DMSO) and oxidation
The mol ratio of agent is 1：0.5, the mass ratio of dimethyl sulfoxide (DMSO) and catalyst is 25：1, the mass ratio of methanol and dimethyl sulfoxide (DMSO) is
100：1, reaction temperature is 35 DEG C, and the pressure in reactor is 0.5MPa, and the combined feed speed of reaction mass is 20mL/min.
The obtained liquid phase mixture containing dimethyl sulfone is analyzed with gas chromatography, and calculates dimethyl sulfoxide (DMSO)
Conversion ratio, oxidant effective rate of utilization and dimethyl sulfone selectivity, wherein, obtained when proceeding to 0.5 hour and 80 hours to reaction
To liquid phase mixture analyzed respectively, obtained result is listed in table 1.
Comparative example 1
Dimethyl sulfone is prepared using method same as Example 1, unlike, without using catalyst.
The obtained liquid phase mixture containing dimethyl sulfone is analyzed with gas chromatography, and calculates dimethyl sulfoxide (DMSO)
Conversion ratio, oxidant effective rate of utilization and dimethyl sulfone selectivity, wherein, obtained when proceeding to 0.5 hour and 80 hours to reaction
To liquid phase mixture analyzed respectively, obtained result is listed in table 1.
Comparative example 2
Dimethyl sulfone is prepared using method same as Example 1, unlike：
The catalyst used is that (the fresh titanium-silicon molecular sieve TS-1 is to form HTS to fresh titanium-silicon molecular sieve TS-1
SH-1 raw material).
The obtained liquid phase mixture containing dimethyl sulfone is analyzed with gas chromatography, and calculates dimethyl sulfoxide (DMSO)
Conversion ratio, oxidant effective rate of utilization and dimethyl sulfone selectivity, wherein, obtained when proceeding to 0.5 hour and 80 hours to reaction
To liquid phase mixture analyzed respectively, obtained result is listed in table 1.
Embodiment 2
Dimethyl sulfone is prepared using method same as Example 1, unlike：
The catalyst used is HTS SH-2, is the hollow titanium silicon that will be drawn off from cyclohexanone oxamidinating course of reaction
Obtained from molecular sieve is regenerated, wherein, regeneration condition is：4h is calcined in air atmosphere at 550 DEG C.The titanium silicon molecule
The activity for sieving SH-2 is 47%, and the activity of fresh hollow HTS is 96%.
The obtained liquid phase mixture containing dimethyl sulfone is analyzed with gas chromatography, and calculates dimethyl sulfoxide (DMSO)
Conversion ratio, oxidant effective rate of utilization and dimethyl sulfone selectivity, wherein, obtained when proceeding to 0.5 hour and 80 hours to reaction
To liquid phase mixture analyzed respectively, obtained result is listed in table 1.
Table 1
The result of table 1 shows, makees even if drawing off agent using the very low regeneration of the catalytic activity in other catalytic oxidations
For the catalyst of dimethyl sulfoxide (DMSO) oxidation reaction, higher dimethyl sulfoxide (DMSO) conversion ratio and dimethyl sulfone selectivity can be also obtained；
And with using fresh HTS compared with catalyst, moreover it is possible to obtain higher oxidant effective rate of utilization, long week
More preferable catalytic activity conservation rate can be obtained in phase tandem reaction sequence.
Embodiment 3
Dimethyl sulfone is prepared using method same as Example 1, unlike：
(1) catalyst used is HTS SH-3, be will be drawn off from cyclohexanone oxamidinating course of reaction it is hollow
Obtained from HTS is regenerated, wherein, regeneration condition is that 4h is calcined in air atmosphere at 550 DEG C.The titanium silicon
Molecular sieve SH-3 activity is 30%, and the activity of fresh hollow HTS is 95%；
(2) mol ratio of all water of solvent, dimethyl sulfoxide (DMSO) and oxidant is 1：5, dimethyl sulfoxide (DMSO) and catalyst
Mass ratio is 10：1, the mass ratio of water (not including the water in hydrogen peroxide) and dimethyl sulfoxide (DMSO) is 5：1, reaction temperature is 45 DEG C,
Pressure in reactor is 0.5MPa, and the combined feed speed of reaction mass is 100mL/min.
The obtained liquid phase mixture containing dimethyl sulfone is analyzed with gas chromatography, and calculates dimethyl sulfoxide (DMSO)
Conversion ratio, oxidant effective rate of utilization and dimethyl sulfone selectivity, wherein, obtained when proceeding to 0.5 hour and 80 hours to reaction
To liquid phase mixture analyzed respectively, obtained result is listed in table 2.
Embodiment 4
Dimethyl sulfone is prepared using method same as Example 1, unlike：
(1) catalyst used is HTS SH-4, is the titanium silicon point that will be drawn off from phenol hydroxylation course of reaction
Obtained from son sieve TS-1 is regenerated, wherein, regeneration condition is that 4h is calcined in air atmosphere at 550 DEG C.The titanium silicon point
Son sieve SH-4 activity is 76%, and the activity of fresh titanium-silicon molecular sieve TS-1 is 95%；
(2) acetone as solvent is used, the mol ratio of dimethyl sulfoxide (DMSO) and oxidant is 1：4, dimethyl sulfoxide (DMSO) is with urging
The mass ratio of agent is 15：1, the mass ratio of acetone and dimethyl sulfoxide (DMSO) is 10：1, reaction temperature is 60 DEG C, the pressure in reactor
Power is 1.0MPa, and in terms of dimethyl sulfoxide (DMSO), the combined feed speed of reaction mass is 50mL/min.
The obtained liquid phase mixture containing dimethyl sulfone is analyzed with gas chromatography, and calculates dimethyl sulfoxide (DMSO)
Conversion ratio, oxidant effective rate of utilization and dimethyl sulfone selectivity, wherein, obtained when proceeding to 0.5 hour and 80 hours to reaction
To liquid phase mixture analyzed respectively, obtained result is listed in table 2.
Table 2
Embodiment 5
The catalyst used in the present embodiment is HTS SH-5, is that will be drawn off from cyclohexanone oxamidinating course of reaction
Hollow HTS regenerated obtained from, wherein, regeneration condition is is calcined 4h at 550 DEG C in air atmosphere.
HTS SH-5 activity is 9.5%, and the activity of fresh hollow HTS is 95%.
Using dimethyl sulfoxide (DMSO), the SH-5 as catalyst, the TBHP as oxidant and as solvent
Acetonitrile is sent into small-sized slurry bed reactor and carries out oxidation reaction, is isolated from the reactant mixture of slurry bed reactor output
Catalyst, the liquid phase mixture containing dimethyl sulfone is obtained, the catalyst isolated recycles.Wherein, dimethyl sulfoxide (DMSO) with
The mol ratio of oxidant is 1：2.2, the mass ratio of dimethyl sulfoxide (DMSO) and catalyst is 50：1, the quality of acetonitrile and dimethyl sulfoxide (DMSO)
Than for 80：1, reaction temperature is 20 DEG C, and the pressure in reactor is 0.5MPa, and the combined feed speed of reaction mass is 20mL/
min。
The obtained liquid phase mixture containing dimethyl sulfone is analyzed with gas chromatography, and calculates dimethyl sulfoxide (DMSO)
Conversion ratio, oxidant effective rate of utilization and dimethyl sulfone selectivity, wherein, it is small that 0.5 hour, 2 hours and 100 are proceeded to reaction
The liquid phase mixture constantly obtained is analyzed respectively, and obtained result is listed in table 3.
Embodiment 6
Dimethyl sulfone is prepared using method same as Example 5, unlike：
The catalyst used is HTS SH-5 and fresh hollow HTS in mass ratio 1：1 is mixed to get
Mixture, the activity of fresh hollow HTS is 95%.
The obtained liquid phase mixture containing dimethyl sulfone is analyzed with gas chromatography, and calculates dimethyl sulfoxide (DMSO)
Conversion ratio, oxidant effective rate of utilization and dimethyl sulfone selectivity, wherein, it is small that 0.5 hour, 2 hours and 100 are proceeded to reaction
The liquid phase mixture constantly obtained is analyzed respectively, and obtained result is listed in table 3.
Embodiment 7
Dimethyl sulfone is prepared using method same as Example 5, unlike：
The catalyst used is HTS SH-5 and fresh hollow HTS in mass ratio 2：1 is mixed to get
Mixture, the activity of fresh hollow HTS is 95%.
The obtained liquid phase mixture containing dimethyl sulfone is analyzed with gas chromatography, and calculates dimethyl sulfoxide (DMSO)
Conversion ratio, oxidant effective rate of utilization and dimethyl sulfone selectivity, wherein, it is small that 0.5 hour, 2 hours and 100 are proceeded to reaction
The liquid phase mixture constantly obtained is analyzed respectively, and obtained result is listed in table 3.
Embodiment 8
Dimethyl sulfone is prepared using method same as Example 5, unlike：
HTS SH-5 is handled with acid.Wherein, the acid used is hydrochloric acid (concentration is 12 weight %), titanium silicon
Molecular sieve SH-5 is (with SiO2Meter) with HCl mol ratio it is 1：1；Concrete operations are：HTS SH-5 is mixed with acid, will
It is 6h to obtain the stirring reaction time under conditions of mixture is 80 DEG C in temperature, after the temperature of obtained mixture is down to room temperature,
Filtered, collect solid matter and dried at 120 DEG C to constant weight, obtain modified HTS.Through characterizing, with titanium silicon point
Son sieve SH-5 is compared, and the peak height of the absworption peak in the UV-Vis spectrums of modified HTS between 240-300nm is reduced
4.8%, the pore volume of static determination of nitrogen adsorption reduces 2.1%.
The obtained liquid phase mixture containing dimethyl sulfone is analyzed with gas chromatography, and calculates dimethyl sulfoxide (DMSO)
Conversion ratio, oxidant effective rate of utilization and dimethyl sulfone selectivity, wherein, it is small that 0.5 hour, 2 hours and 100 are proceeded to reaction
The liquid phase mixture constantly obtained is analyzed respectively, and obtained result is listed in table 3.
Comparative example 3
Dimethyl sulfone is prepared using method same as Example 5, unlike：The catalyst used is fresh hollow titanium
Si molecular sieves.
The obtained liquid phase mixture containing dimethyl sulfone is analyzed with gas chromatography, and calculates dimethyl sulfoxide (DMSO)
Conversion ratio, oxidant effective rate of utilization and dimethyl sulfone selectivity, wherein, it is small that 0.5 hour, 2 hours and 100 are proceeded to reaction
The liquid phase mixture constantly obtained is analyzed respectively, and obtained result is listed in table 3.
Table 3
Embodiment 9
The catalyst used in the present embodiment is HTS SH-6, will be drawn off from propylene ring oxidation reaction process
Obtained from hollow HTS is regenerated, wherein, regeneration condition is：4h is calcined in air atmosphere at 570 DEG C.It is non-
Fresh HTS SH-6 activity is 48%, and the activity of fresh hollow HTS is 96%.
Dimethyl sulfoxide (DMSO), the SH-6 as catalyst, the Perpropionic Acid as oxidant and the water as solvent are sent into
Oxidation reaction is carried out in small-sized slurry bed reactor, catalyst is isolated from the reactant mixture of slurry bed reactor output,
The liquid phase mixture containing dimethyl sulfone is obtained, the catalyst isolated recycles.Wherein, dimethyl sulfoxide (DMSO) and oxidant
Mol ratio is 1：10, the mass ratio of dimethyl sulfoxide (DMSO) and catalyst is 5：1, the mass ratio of water and dimethyl sulfoxide (DMSO) is 5：1, reaction
Temperature is 80 DEG C, and the pressure in reactor is 1.2MPa, and the combined feed speed of reaction mass is 40mL/min.
The obtained liquid phase mixture containing dimethyl sulfone is analyzed with gas chromatography, and calculates dimethyl sulfoxide (DMSO)
Conversion ratio, oxidant effective rate of utilization and dimethyl sulfone selectivity, wherein, it is small that 0.5 hour, 2 hours and 100 are proceeded to reaction
The liquid phase mixture constantly obtained is analyzed respectively, and obtained result is listed in table 4.
Embodiment 10
Dimethyl sulfone is prepared using method same as Example 9, unlike：
HTS SH-6 is handled with acid.Wherein, the acid used is nitric acid, is comprised the concrete steps that titanium silicon molecule
Sieve SH-6 and nitric acid (mass concentration for 20% aqueous solution) mix, by obtained mixture in 60 DEG C of stirring reactions 8 hours, instead
Answer the temperature of mixture to be filtered after being down to room temperature, collect obtained solid matter and dried at 120 DEG C to constant weight, changed
The HTS of property.Wherein, HTS SH-6 is (with SiO2Meter) and HNO3Mol ratio be 2：1.Through characterizing, with titanium silicon
Molecular sieve SH-6 is compared, the peak of the absworption peak in the UV-Vis spectrums of the HTS of obtained modification between 240-300nm
Height reduces 3.6%, and the pore volume of static determination of nitrogen adsorption reduces 1.8%.
The obtained liquid phase mixture containing dimethyl sulfone is analyzed with gas chromatography, and calculates dimethyl sulfoxide (DMSO)
Conversion ratio, oxidant effective rate of utilization and dimethyl sulfone selectivity, wherein, it is small that 0.5 hour, 2 hours and 100 are proceeded to reaction
The liquid phase mixture constantly obtained is analyzed respectively, and obtained result is listed in table 4.
Embodiment 11
Dimethyl sulfone is prepared using method same as Example 9, unlike：
Catalyst is HTS SH-7, is that fresh hollow HTS is placed in autoclave, spontaneous
Under pressure, obtained from 800 DEG C carry out 5 hours handling with vapor.Non-fresh HTS SH-7 activity is 50%,
The activity of fresh hollow HTS is 95%.
The obtained liquid phase mixture containing dimethyl sulfone is analyzed with gas chromatography, and calculates dimethyl sulfoxide (DMSO)
Conversion ratio, oxidant effective rate of utilization and dimethyl sulfone selectivity, wherein, it is small that 0.5 hour, 2 hours and 100 are proceeded to reaction
The liquid phase mixture constantly obtained is analyzed respectively, and obtained result is listed in table 4.
Embodiment 12
Dimethyl sulfone is prepared using with the identical method of embodiment 11, unlike：Catalyst is by HTS SH-
7 with fresh hollow HTS in mass ratio 3：1 mixture being mixed to get.
The obtained liquid phase mixture containing dimethyl sulfone is analyzed with gas chromatography, and calculates dimethyl sulfoxide (DMSO)
Conversion ratio, oxidant effective rate of utilization and dimethyl sulfone selectivity, wherein, it is small that 0.5 hour, 2 hours and 100 are proceeded to reaction
The liquid phase mixture constantly obtained is analyzed respectively, and obtained result is listed in table 4.
Table 4
By embodiment 5 and embodiment 8, embodiment 9 as can be seen that by by least part titanium compared with embodiment 10
Si molecular sieves are handled with acid, can further improve the conversion ratio of dimethyl sulfoxide (DMSO) and the selectivity of dimethyl sulfone；Also,
In long period tandem reaction sequence, the active conservation rate of catalyst is more preferable, so as to further extend the use longevity of catalyst
Life.
Claims (13)
1. a kind of preparation method of dimethyl sulfone, this method are included under oxidation reaction condition, by dimethyl sulfoxide (DMSO) and at least one
Kind oxidant contacts with least one HTS, wherein, at least partly described HTS is non-fresh titanium silicon molecule
Sieve, the active 10-80% that the activity of the non-fresh HTS is the HTS when fresh, the oxidant
For peroxide, the HTS is the HTS with MFI structure, and the non-fresh HTS is to unload
Go out HTS obtained from agent is regenerated, the agent that draws off for drawing off agent as cyclohexanone oxamidinating reaction unit is described
It is regenerated as high-temperature roasting.
2. the method according to claim 11, wherein, on the basis of the total amount of the HTS, the non-fresh titanium
The content of si molecular sieves is 5-100 weight %.
3. according to the method for claim 1, wherein, the activity of the non-fresh HTS exists for the HTS
Active 30-55% when fresh.
4. the method according to claim 11, wherein, before being contacted with dimethyl sulfoxide (DMSO) and oxidant, by least part titanium silicon
Molecular sieve contacts with least one acid.
5. the method according to claim 11, wherein, on the basis of the total amount of the HTS, with the sour titanium contacted
The content of si molecular sieves is more than 10 weight %.
6. according to the method for claim 4, wherein, the acid is selected from hydrochloric acid, sulfuric acid, phosphoric acid, nitric acid, perchloric acid and hydrogen bromine
Acid.
7. according to the method described in any one in claim 4-6, wherein, the condition of the contact includes：Temperature is 0-200
DEG C, the time is 0.1-72 hours.
8. according to the method for claim 1, wherein, the mass ratio of dimethyl sulfoxide (DMSO) and the HTS is 0.1-
60：1.
9. according to the method for claim 1, wherein, the contact is carried out in the presence of at least one solvent, the solvent
Mass ratio with dimethyl sulfoxide (DMSO) is 1-100：1.
10. according to the method for claim 1, wherein, the mol ratio of the oxidant and the dimethyl sulfoxide (DMSO) is 0.1-
10：1.
11. the method according to claim 1 or 10, wherein, the oxidant is selected from hydrogen peroxide, organic hydroperoxide
And peracid.
12. according to the method for claim 11, wherein, the oxidant is selected from hydrogen peroxide.
13. according to the method described in any one in claim 1-6,8,9 and 10, wherein, the oxidation reaction condition includes：
Temperature is 0-200 DEG C；In terms of gauge pressure, pressure 0-3MPa.
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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 |
| CN103288692A (en) * | 2012-02-29 | 2013-09-11 | 中国石油化工股份有限公司 | Method for preparing dimethyl sulfone from dimethyl sulfoxide |
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| Publication number | Priority date | Publication date | Assignee | Title |
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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 |
| CN103288692A (en) * | 2012-02-29 | 2013-09-11 | 中国石油化工股份有限公司 | Method for preparing dimethyl sulfone from dimethyl sulfoxide |
Non-Patent Citations (1)
| Title |
|---|
| Vapor phase oxidation of dimethyl sulfide with ozone over V2O5/TiO2 catalyst;Endalkachew Sahle-Demessie et al.;《Applied Catalysis B: Environmental》;20080503;第84卷;408-419 * |
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