CN106631936A - Method for producing dimethyl sulfoxide - Google Patents
Method for producing dimethyl sulfoxide Download PDFInfo
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- CN106631936A CN106631936A CN201510726027.3A CN201510726027A CN106631936A CN 106631936 A CN106631936 A CN 106631936A CN 201510726027 A CN201510726027 A CN 201510726027A CN 106631936 A CN106631936 A CN 106631936A
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Abstract
The invention discloses a method for producing dimethyl sulfoxide. The method comprises the following steps: under oxidation reaction condition, the reaction raw materials containing dimethyl thioether, an oxidizing agent and an optional solvent can be contacted with a titanium silicon molecular sieve to obtain a reaction mixture containing dimethyl sulfoxide; the reaction mixture is subjected to gas-liquid separation to obtain a liquid material flow containing dimethyl sulfoxide and a gas material flow; and dimethyl sulfoxide can be separated from the liquid material flow. The method can obtain high dimethyl sulfoxide selectivity and effective utilization rate of the oxidizing agent.
Description
Technical field
The present invention relates to a kind of method for producing dimethyl sulfone.
Background technology
Dimethyl sulfone is white crystalline powder, soluble in water, ethanol, benzene, methyl alcohol and acetone, is slightly soluble in
Ether.Potassium permanganate can not be made under normal temperature to change colour, dimethyl sulfone can be oxidized to methanesulfonic acid by strong oxidizer.Two
The methyl sulfone aqueous solution is in neutrality.In 25 DEG C of microsublimations, accelerate to 60 DEG C of rate of sublimation, thus diformazan
Base sulfone product is preferably dried under cryogenic vacuum.
Dimethyl sulfone is used as in the industry organic synthesis high-temperature solvent and raw material, GC stationary liquid, divides
Analysis reagent, food additives and medicine.Dimethyl sulfone as a kind of organic sulfur compound, with strengthening people
Body produces the ability of insulin, while the metabolism to carbohydrate also has facilitation, it is human collagen albumen
The necessary material of synthesis.Dimethyl sulfone can promote wound healing, also can be to metabolism and neurological health institute
Cobastab, vitamin C, the synthesis of biotin and the activation for needing is worked, and is referred to as " beautifying naturally
Carbonizable substance ".All contain dimethyl in the skin of human body, hair, nail, bone, muscle and each organ
Sulfone, dimethyl sulfone is primarily present in Yu Haiyang and soil in nature, as nutrition in plant growth
Material is absorbed, and the mankind can absorb from the foods such as veterinary antibiotics, fish, meat, egg, milk, once
Shortage will cause health disorders or disease occurs, and be the main thing that human body maintains biological element sulphur balance
Human body diseases are had therapeutic value and health care by matter, are the indispensable medicines of human survival and health care
Thing.External to widely apply dimethyl sulfone as the nutriment of equal importance with vitamin, China is to diformazan
The application study of base sulfone is not yet carried out very well, and current product is mainly used in outlet.Therefore, dimethyl sulfone is not
Only it is a kind of new high-tech product, is also a kind of fine chemical product of high added value.Product is new, market
Potentiality are big, and benefit is projected, with wide production and application and development prospect.
At present, the product that dimethyl sulfone is further aoxidized as dimethyl sulfoxide (DMSO), is dimethyl sulfoxide (DMSO) production
Principal by product.
The content of the invention
It is an object of the invention to provide a kind of method for producing dimethyl sulfone, the method is obtained in that higher
Dimethyl sulfone selectivity.
The invention provides a kind of method for producing dimethyl sulfone, the method is comprised the following steps：
A, under oxidation reaction condition, a kind of reaction raw materials are contacted with least one HTS,
The reactant mixture containing dimethyl sulfone is obtained, the reaction raw materials contain dimethyl sulfide, at least one
Oxidant and optional at least one solvent；
B, the reactant mixture is carried out gas-liquid separation, and to obtain the liquid stream containing dimethyl sulfone gentle
Body logistics；And
C, from the liquid stream isolate dimethyl sulfone.
Dimethyl sulfoxide (DMSO) is produced using the method for the present invention, higher dimethyl sulfone selectivity is obtained in that.
Meanwhile, the method for the present invention can also obtain higher oxidant effective rate of utilization.
Description of the drawings
Accompanying drawing is, for providing a further understanding of the present invention, and to constitute the part of specification, with
Detailed description below is used to explain the present invention together, but is not construed as limiting the invention.
In accompanying drawing：
Fig. 1 is used to illustrate a kind of concrete technology flow process of method of the production dimethyl sulfoxide (DMSO) of the present invention.
Description of reference numerals
1：Dimethyl sulfide basin 2：Oxidant basin
3：Fixed bed reactors 4：Gas-liquid separation unit
5：First distillation unit 6：Cooling unit
7：After-fractionating unit 8：Solvent tanker
Specific embodiment
The invention provides a kind of method for producing dimethyl sulfone, the method comprising the steps of A：It is anti-in oxidation
Under the conditions of answering, a kind of reaction raw materials are contacted with least one HTS, obtained containing dimethyl sulfone
Reactant mixture, the reaction raw materials contain dimethyl sulfide, at least one oxidant and optional
At least one solvent.
In the present invention, " at least one " represents one or more；It is " optional " or " optional
Ground " expression " with or without ", " including or do not include ".
The method according to the invention, is reacted using HTS as dimethyl sulfide and oxidising agent
Catalyst.The HTS is the class boiling that titanium atom replaces a part of silicon atom in lattice framework
The general name of stone, can use chemical formula xTiO2·SiO2Represent.The present invention is for titanium original in HTS
The content of son is not particularly limited, and can be the conventional selection of this area.Specifically, x can be
0.0001-0.05, preferably 0.01-0.03, more preferably 0.015-0.025.
The HTS can be the common HTS with various topological structures, for example：
The HTS can be selected from HTS (such as TS-1), the MEL structures of MFI structure
HTS (such as TS-2), the HTS (such as Ti-Beta) of BEA structures, MWW structures
HTS (such as Ti-MCM-22), the HTS (such as Ti-MOR) of MOR structures,
The HTS (such as Ti-TUN) of TUN structures, the HTS of two dimension hexagonal structure are (such as
Ti-MCM-41, Ti-SBA-15) and other structures HTS (such as Ti-ZSM-48).Institute
State HTS be preferably selected from the HTS of MFI structure, the HTS of MEL structures and
The HTS of the HTS of BEA structures, more preferably MFI structure, such as HTS
TS-1 and/or hollow HTS.The hollow HTS is the HTS of MFI structure,
The crystal grain of the 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 the condition of 1 hour
Under the benzene adsorbance that measures be at least 70 milligrams per grams, absorption of the nitrogen absorption under low temperature of the HTS etc.
There is hysteresis loop between warm line and desorption isotherm.The hollow HTS is commercially available (example
The trade mark such as commercially available from Hunan Jianchang Petrochemical Co., Ltd is the molecular sieve of HTS), it is also possible to according to
Method disclosed in CN1132699C is prepared.
The method according to the invention, at least part of HTS be titanium-silicon molecular sieve TS-1, the titanium silicon
The surface silicon titanium ratio of molecular sieve TS-1 is not less than body phase silicon titanium ratio, and so can further improve oxidant has
Effect utilization rate, and can further extend the single trip use life-span of HTS.Preferably, the table
Face silicon titanium ratio is more than 1.2 with the ratio of the body phase silicon titanium ratio.It is highly preferred that the surface silicon titanium ratio
It is 1.2-5 with the ratio of the body phase silicon titanium ratio.It is further preferred that the surface silicon titanium ratio with it is described
The ratio of body phase silicon titanium ratio is 1.5-4.5 (such as 2.5-4.5).It is further preferred that the surface silicon titanium
Than being 2-3 with the ratio of the body phase silicon titanium ratio.The silicon titanium than refer to silica and titanium oxide mole
Than the surface silicon titanium ratio is determined using X-ray photoelectron spectroscopy, and the body phase silicon titanium ratio adopts X
Ray fluorescence spectrometry is determined.
The method according to the invention, at least part of HTS be titanium-silicon molecular sieve TS-1, the titanium silicon
Molecular sieve TS-1 is prepared using the method for comprising the following steps：
(I) inorganic silicon source is dispersed in the aqueous solution containing titanium source and alkali source template, and alternatively
Water is supplemented, dispersion liquid is obtained, in the dispersion liquid, silicon source：Titanium source：Alkali source template：Water mole
Than for 100：(0.5-8)：(5-30)：(100-2000), the inorganic silicon source is with SiO2Meter, the titanium
Source is with TiO2Meter, the alkali source template is with OH-Or N meters (contain nitrogen unit in the alkali source template
When plain, in terms of N；In the alkali source template not Nitrogen element, with OH-Meter)；
(II) alternatively, the dispersion liquid is stood into 6-24h at 15-60 DEG C；
(III) dispersion liquid that the dispersion liquid or step (II) for obtaining step (I) is obtained is anti-in sealing
Answer and sequentially experience in kettle stage (1), stage (2) and stage (3) to carry out crystallization, the stage (1) exists
80-150 DEG C of crystallization 6-72 hour (h), the stage (2) is cooled to not higher than 70 DEG C and the time of staying at least
After 0.5h, the stage (3) is warming up to 120-200 DEG C of crystallization 6-96h again.
The alkali source template can be the various templates that are usually used during synthesis of titanium silicon molecular sieve
Agent, for example：The alkali source template can be the one kind in quaternary ammonium base, aliphatic amine and aliphatic hydramine
Or it is two or more.The quaternary ammonium base can be various organic level Four ammonium alkali, and the aliphatic amine can be each
Plant NH3At least one of hydrogen by aliphatic alkyl (such as alkyl) replacement after formed compound, it is described
Aliphatic hydramine can be various NH3At least one of hydrogen by the aliphatic group of hydroxyl (such as alkane
Base) replace after formed compound.
Specifically, the alkali source template can be the fat that the quaternary ammonium base that represents selected from Formulas I, Formula II are represented
One or more in the aliphatic hydramine that fat race amine and formula III are represented.
(Formulas I)
In Formulas I, R1、R2、R3And R4Respectively C1-C4Alkyl, including C1-C4Straight chained alkyl
And C3-C4Branched alkyl, R1、R2、R3And R4Instantiation can include but is not limited to methyl,
Ethyl, n-propyl, isopropyl, normal-butyl, sec-butyl, isobutyl group or the tert-butyl group.
R5(NH2)n(Formula II)
In Formula II, n is 1 or 2 integer.When n is 1, R5For C1-C6Alkyl, including C1-C6
Straight chained alkyl and C3-C6Branched alkyl, its instantiation can include but is not limited to methyl, ethyl,
N-propyl, isopropyl, normal-butyl, sec-butyl, isobutyl group, the tert-butyl group, n-pentyl, neopentyl,
Isopentyl, tertiary pentyl and n-hexyl.When n is 2, R5For C1-C6Alkylidene, including C1-C6's
Straight-chain alkyl-sub and C3-C6Branched alkylidene, its instantiation can include but is not limited to methylene,
Ethylidene, sub- n-propyl, sub- normal-butyl, sub- n-pentyl or sub- n-hexyl.
(HOR6)mNH(3-m)(formula III)
In formula III, m R6It is identical or different, respectively C1-C4Alkylidene, including C1-C4's
Straight-chain alkyl-sub and C3-C4Branched alkylidene, its instantiation can include but is not limited to methylene,
Ethylidene, sub- n-propyl and sub- normal-butyl；M is 1,2 or 3.
The instantiation of the alkali source template can be including but not limited to：TMAH, tetrem
(including the various isomers of TPAOH, such as four just for base ammonium hydroxide, TPAOH
Propyl group ammonium hydroxide and tetra isopropyl ammonium hydroxide), TBAH is (including tetrabutylammonium hydroxide
The various isomers of ammonium, such as 4-n-butyl ammonium hydroxide and four isobutyl group ammonium hydroxide), ethamine, positive third
Amine, n-butylamine, di-n-propylamine, butanediamine, hexamethylene diamine, MEA, diethanol amine and triethanolamine
In one or more.Preferably, the alkali source template is tetraethyl ammonium hydroxide, tetrapropyl
One or more in ammonium hydroxide and TBAH.It is highly preferred that the alkali source template
Agent is TPAOH.
The titanium source can be inorganic titanium salt and/or organic titanate, preferably organic titanate.The nothing
Machine titanium salt can be TiCl4、Ti(SO4)2And TiOCl2In one or more；Organic metatitanic acid
Ester can be general formula R7 4TiO4The compound of expression, wherein, R7It is the alkyl with 1-6 carbon atom,
Preferably there is the alkyl of 2-4 carbon atom.
The inorganic silicon source can be silica gel and/or Ludox, preferably silica gel.SiO in the Ludox2
Weight/mass percentage composition can be more than 10%, preferably more than 15%, more preferably more than 20%.
When preparing according to the HTS of the preferred embodiment, do not use organic silicon source, such as organosilan and
Organosiloxane.
In the dispersion liquid, silicon source：Titanium source：Alkali source template：The mol ratio of water is preferably 100：(1-6)：
(8-25)：(200-1500), more preferably 100：(2-5)：(10-20)：(400-1000).
The dispersion liquid that step (I) is obtained can be sent directly in step (III) and carry out crystallization.Preferably,
The dispersion liquid that step (I) is obtained is sent in step (II) and 6-24h is stood at a temperature of 15-60 DEG C.
Step (II) is carried out between step (I) and step (III) can significantly improve the titanium silicon point of final preparation
The surface silicon titanium ratio of son sieve TS-1 so that the surface silicon titanium ratio of the final HTS for preparing is not less than
Body phase silicon titanium ratio, can so significantly improve the catalytic performance of the HTS of final preparation, extend its list
Journey service life, and improve oxidant effective rate of utilization.Usually, by step (I) and step
(III) setting steps (II) between, the surface silicon titanium ratio and body phase silicon titanium of the final HTS for preparing
The ratio of ratio can be in the range of 1.2-5, (such as in the model of 2.5-4.5 preferably in the range of 1.5-4.5
In enclosing), more preferably in the range of 2-3.The standing is carried out more preferably at a temperature of 20-50 DEG C,
As carried out at a temperature of 25-45 DEG C.
In step (II), when being stood, dispersion liquid can be placed in sealing container, it is also possible to
It is placed in open container and is stood.Preferably, step (II) is carried out in sealing container, so may be used
To avoid during standing being introduced into foreign matter in dispersion liquid or cause moieties in dispersion liquid to be waved
Send out and be lost in.
After the completion of step (II) standing, the dispersion liquid that directly can be stood Jing is sent in reactor
Carry out crystallization, it is also possible to which sending in reactor after the dispersion liquid Jing standing is carried out into redisperse carries out crystallization,
It is preferred that carry out being sent in reactor after redisperse, so can further improve the dispersion liquid that carries out crystallization point
Scattered uniformity.The method of the redisperse can be conventional method, such as stirring, ultrasonically treated and vibration
In one or more combination.Dispersion liquid of the duration of the redisperse stand can Jing
Form uniform dispersion liquid to be defined, typically can be 0.1-12h, such as 0.5-2h.The redisperse can be
Carry out under environment temperature, carry out at a temperature of such as 15-40 DEG C.
In step (III), the heating rate and rate of temperature fall that temperature is adjusted to each phase temperature can be with root
Selected according to the type of the concrete crystallization device for adopting, be not particularly limited.In general, by temperature
It can be 0.1-20 DEG C/min that degree is increased to the heating rate of stage (1) crystallization temperature, preferably
0.1-10 DEG C/min, more preferably 1-5 DEG C/min.By the drop of stage (1) temperature to stage (2) temperature
Warm speed can be 1-50 DEG C/min, preferably 2-20 DEG C/min, more preferably 5-10 DEG C/min.By rank
Section (2) temperature to stage (3) temperature heating rate can be 1-50 DEG C/min, preferably 2-40 DEG C/min,
More preferably 5-20 DEG C/min.
In step (III), the crystallization temperature in stage (1) is preferably 110-140 DEG C, more preferably 120-140
DEG C, more preferably 130-140 DEG C.The crystallization time in stage (1) is preferably 6-24h, more preferably
For 6-8h.The temperature in stage (2) is preferably not higher than 50 DEG C.The time of staying of (2) in stage is preferred
It is at least 1h, more preferably 1-5h.The crystallization temperature in stage (3) is preferably 140-180 DEG C, more excellent
Elect 160-170 DEG C as.The stage crystallization time of (3) is preferably 12-20h.
In step (III), in a preferred embodiment, the stage crystallization temperature of (1) is less than
The crystallization temperature in stage (3), so can further improve the catalytic performance of the HTS of preparation.
Preferably, the crystallization temperature in stage (1) is lower 10-50 DEG C than the crystallization temperature in stage (3).More preferably
Ground, the crystallization temperature in stage (1) is lower 20-40 DEG C than the crystallization temperature in stage (3).Step (III)
In, in another preferred embodiment, the crystallization time in stage (1) is less than the crystalline substance in stage (3)
The change time, so can further improve the catalytic performance of the HTS of final preparation.Preferably, rank
The crystallization time 5-24h shorter than the crystallization time in stage (3) of section (1).It is highly preferred that the stage (1)
Crystallization time 6-12h shorter than the crystallization time in stage (3), such as short 6-8h.In step (III), this
Two kinds preferred embodiment may be used alone, can also be used in combination, and preferred compositions are used, i.e. rank
The crystallization temperature and crystallization time in section (1) and stage (3) meets both preferred embodiments simultaneously
Require.
In step (III), another preferred embodiment in, the temperature in stage (2) is not high
In 50 DEG C, and the time of staying is at least 0.5h, such as 0.5-6h, so can further improve final preparation
The catalytic performance of HTS.Preferably, the time of staying in stage (2) is at least 1h, such as 1-5h.
This preferred embodiment can preferred embodiment be used separately with aforementioned two kinds, it is also possible to which combination makes
With preferred compositions are used, i.e. the crystallization temperature and crystallization time and rank in stage (1) and stage (3)
The temperature of section (2) and the time of staying meet the requirement of above-mentioned three kinds of preferred embodiments simultaneously.
Can adopt in the mixture that obtains from step (III) crystallization of conventional method and reclaim HTS.
Specifically, after the mixture that step (III) crystallization is obtained can alternatively being filtered and washed, will
Solid matter is dried and roasting, so as to obtain HTS.The drying and the roasting can be with
Carry out under normal conditions.Usually, the drying can be in environment temperature (such as 15 DEG C) to 200 DEG C
At a temperature of carry out.The drying can be carried out under environmental pressure (generally 1 standard atmospheric pressure),
Can also carry out at reduced pressure.The duration of the drying can be according to dry temperature and pressure
Power and the mode of drying are selected, and are not particularly limited.For example, the drying is under ambient pressure
When carrying out, temperature is preferably 80-150 DEG C, and more preferably 100-120 DEG C, the dry duration is preferred
For 0.5-5h, more preferably 1-3h.The roasting can be carried out at a temperature of 300-800 DEG C, preferably
Carry out at a temperature of 500-700 DEG C, carry out more preferably at a temperature of 550-650 DEG C, further preferably
Carry out at a temperature of 550-600 DEG C.The duration of the roasting can be according to the temperature for carrying out roasting
Select, typically can be 2-12h, preferably 2-5h.The roasting is carried out preferably in air atmosphere.
The method according to the invention, the HTS and the no spy of the contact form of the reaction raw materials
Do not limit, HTS can be seated in the beds of reactor (such as fixed bed reactors)
In, the reaction raw materials are made by the beds, so as to realize in the presence of HTS,
Dimethyl sulfide and oxidising agent are reacted；The reaction raw materials can also be mixed with HTS
Slurry is formed, so as to realize in the presence of HTS, dimethyl sulfide and oxidising agent being reacted.
When the reaction raw materials and HTS are mixed to form into slurry, can be with after the completion of haptoreaction
Slurry is carried out into solid-liquor separation using various methods, so as to obtain the liquid material containing dimethyl sulfone.Example
Such as：The slurry can be carried out by solid-liquor separation by membrane separation device.
When the HTS is seated in beds, the quantity of the beds can
Think one or more.Can be positioned at a reactor when the quantity of beds is multiple
Zones of different, it is also possible in multiple reactors.
In one embodiment of the invention, the beds contain the first beds and
Two beds, on the basis of the flow direction of the reaction raw materials, the first beds position
In the upstream of second beds, i.e., described reaction raw materials firstly flow through the first beds, then
The second beds are flow through, it is v that the reaction raw materials flow through the superficial velocity of the first beds1,
The superficial velocity for flowing through the second beds is v2, wherein, v1＜ v2, so can further extend
The single trip use life-span of HTS.It is highly preferred that v2/v1=1.5-10.It is further preferred that v2/v1
=2-5.
In the present invention, the superficial velocity refers to former by the whole reaction of beds in the unit interval
The area of the mass flow (in terms of kg/s) of material and a certain cross section of beds is (with m2Meter)
Ratio.Usually, the quality that the reaction raw materials of fixed bed reactors are sent in the unit interval can be made
For " by the mass flow of the reaction raw materials of whole beds in the unit interval ".In the present invention,
For superficial velocity of the reaction raw materials in the first beds does not have particular/special requirement, typically can be
0.001-200kg/(m2S) in the range of.
The reaction raw materials can be adjusted using various methods in the first beds and the second catalysis
Superficial velocity in agent bed.For example, can adjust anti-by the cross-sectional area of selecting catalyst bed
Answer the superficial velocity of raw material.Specifically, the cross-sectional area that can make first beds is more than institute
The cross-sectional area of the second beds is stated, so that v1＜ v2, it is preferable that v2/v1For 1.5-10,
More preferably so that v2/v1For 2-5.The cross-sectional area of beds is determined according to expected superficial velocity
Method be known in those skilled in the art, no longer describe in detail herein.
The kind of the HTS loaded in first beds and second beds
Class can be identical, or it is different.Preferably, the titanium silicon point of the first beds filling
Son sieve is hollow HTS.It is highly preferred that the HTS of the first beds filling
For hollow HTS, the HTS of the second beds filling is HTS
TS-1, so can not only further extend the single trip use life-span of HTS, and can also enter one
Step improves dimethyl sulfone selectivity.
When the beds contain the first beds and the second beds, described first
The titanium silicon molecule loaded in the HTS and second beds that load in beds
The weight ratio of sieve can be 1-20：1, preferably 2-15：1, more preferably 5-10：1.
When the beds contain the first beds and the second beds, described first
Beds and the second beds can each contain one or more beds.First
When beds and/or the second beds contain multiple beds, multiple beds it
Between can be to be connected in series, or be connected in parallel, can also for series connection and combination in parallel, for example：
Multiple beds are divided into it is multigroup, per the beds in group for be connected in series and/or it is in parallel even
Connect, be to be connected in series and/or be connected in parallel between each group.First beds and described second are urged
Agent bed can be arranged on the zones of different of same reactor, it is also possible to be arranged on different reactors
In.
The method according to the invention, in beds the first beds and the second catalyst bed are contained
Layer when, as the case may be can between the first beds and the second beds supplement
Material, when the first beds and/or the second beds are multiple beds, according to concrete
Situation can be between the first beds and/or between the second beds to the reaction raw materials
Middle supplementary fresh material.For example：Between the first beds and the second beds, first urge
Dimethyl sulfide, oxidant and/or solvent are supplemented between agent bed and/or between the second beds.
However, it is desirable to illustrate, the reaction raw materials flow through whole beds of the first beds (i.e.,
The whole process of the first beds) and the second beds whole beds (that is, the second catalyst bed
Layer whole process), the reaction raw materials and not included between the first beds, the second catalyst bed
The fresh material introduced and the first beds and the second beds between layer, it is described previously
Superficial velocity determined by the reaction raw materials, do not affected by whether fresh material is introduced.
The method according to the invention, in the beds the first beds and the second catalysis are contained
During agent bed, the reaction condition of first beds and the second beds can with identical,
Can be difference.From the angle of operation terseness, first beds and the second catalyst
Reaction condition between bed is identical.
The method according to the invention, the HTS can be HTS original powder, or
Shaping HTS, is preferably molded HTS.Shaping HTS is typically contained as work
The HTS and the carrier as binding agent of property composition, wherein, the content of HTS can be
It is conventional to select.Usually, on the basis of the total amount of the shaping HTS, HTS contains
Amount can be 5-95 weight %, preferably 10-95 weight %, more preferably 70-95 weight %, enter one
Step is preferably 75-85 weight %；The content of the carrier can be 5-95 weight %, and preferably 5-90 is heavy
Amount %, more preferably 5-30 weight %, more preferably 15-25 weight %.The shaping titanium silicon point
The carrier of son sieve can be conventional selection, such as aluminum oxide and/or silica.Prepare the shaping titanium silicon molecule
The method of sieve is it is known in the art, no longer describing in detail herein.The particle of the shaping HTS is big
It is little to be also not particularly limited, appropriate selection can be carried out according to concrete shape.Such as in the shaping titanium silicon
When molecular sieve is spherical, the average grain diameter of the shaping HTS can be 4-10000 microns, excellent
Elect 5-5000 microns as, more preferably 40-4000 microns, more preferably 50-2000 microns, such as
500-1000 microns.The average grain diameter is volume average particle size, can be determined using laser particle analyzer.
The method according to the invention, the beds can only load HTS, it is also possible to contain
There are HTS and inactive filler.Loading inactive filler in beds can be to catalyst
The amount of HTS is adjusted in bed, so as to be adjusted to the speed reacted.In the catalysis
When agent bed contains HTS and inactive filler, the content of inactive filler can in beds
Think 5-95 weight %.The inactive filler refers to no to oxidation reaction or substantially no catalysis activity
Filler, its instantiation can including but not limited to：In quartz sand, ceramic ring and potsherd one
Plant or various.
The method according to the invention, used as catalyst, its consumption is can realize urging for the HTS
Change function to be defined, be not particularly limited.Typically can connecing according to HTS and the reaction raw materials
Tactile form is selected.For example, when HTS is mixed to form into slurry with the reaction raw materials,
Dimethyl sulfide can be 0.1-50 with the weight ratio of HTS：1, preferably 1-50：1, such as 1-25：
1；When HTS is seated in the beds of reactor, the reaction raw materials it is heavy when
Air speed can be 0.05-100h-1, preferably 0.1-50h-1, more preferably 10-40h-1.In the present invention,
Weight (hourly) space velocity (WHSV) is on the basis of the total amount of HTS in whole beds in HTS
During type HTS, on the basis of the total amount for being molded HTS.
The method according to the invention, the oxidant can be it is common it is various can be by dimethyl sulfide oxygen
The material of change.Method of the invention is particularly suitable for carrying out cacodyl oxide base sulphur as oxidant using peroxide
The occasion of ether, can so significantly improve the effective rate of utilization of peroxide.The peroxide is referred to point
The compound containing-O-O- keys, can be selected from hydrogen peroxide, organic peroxide and peracid in minor structure.
The organic peroxide refers to that one or two hydrogen atom in hydrogen peroxide molecule is taken by organic group
Material obtained from generation.The peracid refers to the organic oxacid containing-O-O- keys in molecular structure.This
In invention, the instantiation of the oxidant can be including but not limited to：Hydrogen peroxide, t-butyl peroxy
Change hydrogen, cumyl hydroperoxide, cyclohexyl hydroperoxide, ethylbenzene hydroperoxide, Peracetic acid and peroxide
Propionic acid.Preferably, the oxidant is hydrogen peroxide, so can further reduce separation costs.
The hydrogen peroxide can be the hydrogen peroxide for existing in a variety of manners commonly used in the art.From entering one
Step improves the angle of the security of the method according to the invention and sets out, and the method according to the invention is preferably used
The hydrogen peroxide for existing as an aqueous solution.The method according to the invention, in the hydrogen peroxide with water-soluble
When liquid form is provided, the concentration of the aqueous hydrogen peroxide solution can be the normal concentration of this area, for example：
20-80 weight %.Concentration meets the aqueous solution of the hydrogen peroxide of above-mentioned requirements can be matched somebody with somebody using conventional method
System, it is also possible to be commercially available, for example：The hydrogen peroxide of 30 weight % that can be to be commercially available,
The hydrogen peroxide of the hydrogen peroxide of 50 weight % or 70 weight %.
The consumption of the oxidant can be conventional selection, be not particularly limited.Usually, the oxidation
Agent can be 2 with the mol ratio of the dimethyl sulfide：More than 1.The oxidant and the dimethyl
The mol ratio of thioether can be 20：Less than 1, such as 10：Less than 1, preferably 5：Less than 1, it is more excellent
Elect 3 as：Less than 1, more preferably 2.5：Less than 1.Preferably, the oxidant and dimethyl
The mol ratio of thioether is 2-2.5：1.
The method according to the invention, the liquid material preferably comprises solvent, so with or without solvent
The content of solvent in by adjusting reaction raw materials, can be adjusted to the speed reacted, and make reaction more
Steadily.The solvent can either dissolve dimethyl sulfide and oxidant or promote the two mixed for various
Close, the liquid substance of solubilized target oxidation product is capable of again.Usually, the solvent can selected from water,
C1-C6Alcohol, C3-C8Ketone and C2-C6Nitrile.The instantiation of the solvent can include but not limit
In：Water, methyl alcohol, ethanol, normal propyl alcohol, isopropanol, the tert-butyl alcohol, isobutanol, acetone, butanone and second
Nitrile.Preferably, the solvent is selected from water and C1-C6Alcohol.It is highly preferred that the solvent be methyl alcohol and/
Or water.
The consumption of the solvent can carry out appropriate selection according to the consumption of dimethyl sulfide and oxidant.
Usually, the solvent and the mol ratio of the dimethyl sulfide can be 0.1-100：1, preferably
0.2-80：1, more preferably 2-50：1.
The method according to the invention, the oxidation reaction condition is sent out be enough to make dimethyl sulfide with oxidant
Raw reaction is defined, and is not particularly limited.Usually, the oxidation reaction condition includes：Temperature can be
20-160 DEG C, preferably 30-140 DEG C, more preferably 40-120 DEG C, more preferably 40-80 DEG C；
In terms of gauge pressure, pressure can be 0-3MPa, preferably 0.1-2.5MPa.
The method according to the invention also includes step B：The reactant mixture is carried out into gas-liquid separation to obtain
Liquid stream containing dimethyl sulfone and gas stream.
The present invention is not particularly limited for the method that the reactant mixture is carried out gas-liquid separation, can be with
Using conventional gas-liquid separating method, for example：Can by the way that the reactant mixture is carried out into flash distillation, from
And realize gas-liquid separation.The condition of the flash distillation can be selected according to the concrete composition of reactant mixture
Select, be not particularly limited.The method for determining the condition of flash distillation according to the composition of gas-liquid mixture is ability
Well known to field technique personnel, no longer describe in detail herein.
The gas stream may also contain other gases, such as oxidant in addition to containing dimethyl sulfide
(such as hydrogen peroxide) decomposes the gas (such as oxygen) for producing, and preferably further enters the gas stream
Row is separated, to isolate dimethyl sulfide.The gas stream can be separated using various methods,
So as to isolate dimethyl sulfide, for example, the gas stream can be cooled down, be made dimethyl sulfide
Condensation, so as to isolate dimethyl sulfide.The dimethyl sulfide isolated can circulate described for preparing
Reaction raw materials, so as to further reduce the operating cost of the inventive method.
The method according to the invention also includes step C：Dimethyl sulfone is isolated from the liquid stream.
The liquid stream is in addition to containing dimethyl sulfone, it is also possible to containing solvent.Can be each by what is commonly used
Plant Liquid liquid Separation method and isolate dimethyl sulfone from the liquid stream.For example, can be by the liquid
Logistics carries out separated and goes out dimethyl sulfone therein and solvent.The dimethyl sulfone isolated can be directly defeated
Go out, the solvent isolated then can be recycled.Solvent in addition to water is being used, while using with dioxygen
Water form provide hydrogen peroxide as oxidant when, the liquid stream contain dimethyl sulfone, solvent and
Water, as the case may be, first can isolate dimethyl sulfone, remaining logistics from the liquid stream
Can again be separated, solvent is separated from water；Can also be separated by a step, from the liquid
Solvent, water and dimethyl sulfone are isolated in logistics.
Fig. 1 shows a kind of specific technological process of the method for production dimethyl sulfone of the invention,
The technological process is used using the hydrogen peroxide of hydrogen peroxide form offer as oxidant, and preferably hydrogen peroxide
It is more than 2 and not higher than 2.5 with the mol ratio of dimethyl sulfide.Below in conjunction with Fig. 1 to the technological process
It is described in detail.
By the dimethyl sulfide being stored in dimethyl sulfide basin 1, it is stored in oxidant basin 2
Hydrogen peroxide and the optional solvent being stored in solvent tanker 8 are mixed to form reaction raw materials, and are fixing
In bed reactor 3, contact with the HTS being seated in the beds of fixed bed reactors 3
Reaction.The mixing can be carried out outside fixed bed reactors 3, for example：Will be anti-by pipe-line mixer
The each component in raw material is answered to mix.The mixing can also be carried out in fixed bed reactors 3.
Gas-liquid point is carried out in gas-liquid separation unit 4 from the reactant mixture of the output of fixed bed reactors 3
From obtaining gas stream and liquid stream.The gas-liquid separation unit 4 can contain flash column, pass through
The reactant mixture is carried out into flash distillation, so as to be isolated gas stream and liquid stream are become, wherein,
The gas stream contains unreacted dimethyl sulfide, and the liquid stream contains dimethyl sulfone.
The liquid stream is subsequently entered and further separated in the first distillation unit 5, obtains dimethyl
Sulfone simultaneously outputs it, and raffinate can contain solvent (in addition to water with direct reuse in the raffinate
Solvent) and during water, can the raffinate send into be separated in after-fractionating unit 7 solvent and
After water, solvent is recycled in solvent tanker 8 to be used to prepare the reaction raw materials, by the outer discharger of water
Or be recycled in oxidant basin 2 and be used to prepare the hydrogen peroxide of variable concentrations.
The gas stream is entered in cooling unit 6, by cooling so that two in the gas stream
Dimethyl sulfide is condensed, so as to separate from the gas stream.The dimethyl sulfide isolated can be with
Used in direct cycling to dimethyl sulfide basin 1, it is also possible to be further recycled to diformazan after purification
Used in base thioether basin 1.Remaining gas stream (predominantly oxygen) can directly give off device.
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, agents useful for same is commercially available reagent, and pressure is in terms of gauge pressure.
In following examples and comparative example, each composition in the reactant liquor for obtaining is analyzed using gas chromatography
Content, below equation is respectively adopted on this basis to be had calculating dimethyl sulfide conversion ratio, oxidant
Effect utilization rate and dimethyl sulfone selectivity：
Dimethyl sulfide conversion ratio (the %)=[(mole of the dimethyl sulfide of addition-unreacted two
The mole of Dimethyl sulfide)/add dimethyl sulfide mole] × 100%；
Oxidant effective rate of utilization (%)=[mole of the dimethyl sulfone that 2 × reaction is generated/(addition
The mole of the mole of oxidant-unreacted oxidant)] × 100%；
Dimethyl sulfone selective (%)=[mole/(diformazan of addition of the dimethyl sulfone that reaction is generated
The mole of base thioether-unreacted dimethyl sulfide mole)] × 100%.
In embodiment and comparative example the step of prepare HTS included below, X-ray diffraction analysis
Carry out on Siemens D5005 type X-ray diffractometers, be in 2 θ with authentic specimen with sample
The ratio of diffracted intensity (peak height) sum at the five fingers diffractive features peak is representing sample between 22.5 ° -25.0 °
Relative to the degree of crystallinity of authentic specimen；Fourier turn infrared is in the type Fouriers of Nicolet 8210
Carry out on leaf infrared spectrometer；Silicon titanium than referring to the mol ratio of silica and titanium oxide, adopt by surface silicon titanium ratio
Determined with the ESCALab250 types x-ray photoelectron spectroscopy of Thermo Scientific companies, body phase
Silicon titanium ratio is determined using Rigaku Electric Co., Ltd 3271E types Xray fluorescence spectrometer.
Embodiment 1-16 is used to illustrate the method for the present invention.
Embodiment 1
Catalyst used in the present embodiment is shaping titanium-silicon molecular sieve TS-1, is that volume average particle size is
500 μm of spheric catalyst, in catalyst, the content of titanium-silicon molecular sieve TS-1 is 80 weight %, oxygen
The content of SiClx is 20 weight %.Wherein, titanium-silicon molecular sieve TS-1 reference Zeolites, 1992, Vol.12
Prepared by the method described in the 943-950 page, concrete grammar is as follows.
At room temperature (20 DEG C), using 22.5 grams of tetraethyl orthosilicates and 7.0 grams as the 4 third of template
Base ammonium hydroxide mixes, and adds 59.8 grams of distilled water, and stirring mixing is after normal pressure and 60 DEG C of hydrolysis 1.0
Hour, obtain the hydrating solution of tetraethyl orthosilicate.With vigorous stirring, delay in the hydrating solution
The solution being made up of 1.1 grams of butyl titanates and 5.0 grams of anhydrous isopropyl alcohols is slowly added, gained is mixed
Compound is stirred 3 hours at 75 DEG C, obtains clear colloid.This colloid is placed in into stainless steel sealing reaction
In kettle, constant temperature is placed 36 hours at a temperature of 170 DEG C, obtains the mixture of crystallization product.To obtain
Mixture filter, after collecting the solid matter water used wash that obtains, in 110 DEG C of dryings 60 minutes, connect
In 500 DEG C of roastings 6 hours, obtain titanium-silicon molecular sieve TS-1, its titanium oxide content is 2.8 weight %.
By Catalyst packing in isometrical fixed bed reactors, beds are formed, wherein, catalyst
The quantity of bed is 1 layer.Using dimethyl sulfide, as oxidant hydrogen peroxide (with 30 weight %
The form of hydrogen peroxide provide) and be mixed to form reaction raw materials as the methyl alcohol of solvent, by reaction raw materials from
Bottom is sent in fixed bed reactors and flows through beds, with HTS haptoreaction.Its
In, dimethyl sulfide is 1 with the mol ratio of hydrogen peroxide：2.2, the mol ratio of dimethyl sulfide and methyl alcohol
For 1：2.Temperature in reactor is 80 DEG C, by the pressure control in fixed bed reactors in course of reaction
2.5MPa is made as, the weight (hourly) space velocity (WHSV) of dimethyl sulfide is 10h-1。
The reactant mixture exported from reactor is carried out into flash distillation, gas stream and liquids are separated into
Stream.Wherein, gas stream condenses dimethyl sulfide by cooling, to reclaim dimethyl sulfide and circulate
Use；Liquid stream is distilled, and methyl alcohol, water and dimethyl sulfone are collected respectively, and dimethyl sulfone is exported,
Methanol loop is used, and water is used to produce hydrogen peroxide after being further purified.
The composition of the reactant mixture exported from reactor using gas-chromatography monitoring in course of reaction, and
Dimethyl sulfide conversion ratio, oxidant effective rate of utilization and dimethyl sulfone selectivity are calculated, is listed by table 1
Reaction time under reactor output reactant mixture determine result list in table 1.
Embodiment 2
Using method production dimethyl sulfone same as Example 1, except for the difference that, HTS is molded
Titanium-silicon molecular sieve TS-1 in TS-1 is prepared using following methods.
First butyl titanate is dissolved in the alkali source template TPAOH aqueous solution, silicon is subsequently adding
Glue (is purchased from Qingdao silica gel factory), obtains dispersion liquid, in the dispersion liquid, silicon source：Titanium source：Alkali source template
Agent：The mol ratio of water is 100：4：12：400, silicon source is with SiO2Meter, titanium source is with TiO2Meter, alkali
Source template is in terms of N.In room temperature (for 25 after above-mentioned dispersion liquid is sealed in beaker using sealed membrane
DEG C, similarly hereinafter) 24h is stood, it is stirred at 35 DEG C 2 hours followed by magnetic agitation, it is allowed to again
Dispersion.Again the dispersion liquid after disperseing is transferred in sealed reactor, at 140 DEG C the first stage is experienced
Crystallization 6h, is then cooled to mixture 30 DEG C of experience second stage and stops after 2h, continues anti-in sealing
Answer in kettle and experience phase III crystallization 12h (wherein, by room temperature to first at a temperature of 170 DEG C
The heating rate of stage crystallization temperature is 2 DEG C/min, by first paragraph crystallization temperature to second segment treatment temperature
Rate of temperature fall be 5 DEG C/min, be to the heating rate of the 3rd section of crystallization temperature by second segment treatment temperature
10 DEG C/min), without filtration and washing step after gained crystallization product is taken out, directly in 110 DEG C of drying
2h, then the roasting 3h at 550 DEG C, obtains molecular sieve.The XRD crystalline phases figure of gained sample and enforcement
Titanium-silicon molecular sieve TS-1 prepared by the step of example 1 (1) is consistent, and illustrate to obtain is with MFI structure
Titanium-silicon molecular sieve TS-1；In FFIR figure, in 960cm-1Nearby there is absworption peak,
Show that titanium has been enter into framework of molecular sieve, in the HTS, titanium oxide content be 3.5 weight %, table
Face silicon titanium ratio/body phase silicon titanium ratio be 2.58 (in HTS prepared by embodiment 1, surface silicon titanium than/
Body phase silicon titanium ratio is for 1.05).The reactant mixture of reactor output is true under the reaction time listed by table 1
Fixed result is listed in table 1.
Embodiment 3
Dimethyl sulfone is prepared using method same as Example 2, except for the difference that, HTS is prepared
During TS-1, the crystallization temperature of phase III is also 140 DEG C.The XRD crystalline phases figure of gained sample and enforcement
Titanium-silicon molecular sieve TS-1 prepared by example 1 is consistent, and illustrate to obtain is the TS-1 molecules with MFI structure
Sieve；In 960cm in fourier-transform infrared spectrogram-1Nearby there is absworption peak, show that titanium has been enter into molecule
Sieve skeleton frame, in the HTS, surface silicon titanium ratio/body phase silicon titanium ratio is 4.21, and titanium oxide content is
3.1 weight %.The result that the reactant mixture of reactor output determines under the reaction time listed by table 1
List in table 1.
Embodiment 4
Dimethyl sulfone is prepared using method same as Example 2, except for the difference that, HTS is prepared
During TS-1, the crystallization temperature of first stage is 110 DEG C.The XRD crystalline phases figure and embodiment of gained sample
1 titanium-silicon molecular sieve TS-1 for preparing is consistent, and illustrate to obtain is the TS-1 molecular sieves with MFI structure；
In 960cm in fourier-transform infrared spectrogram-1Nearby there is absworption peak, show that titanium has been enter into molecule sieve skeleton
Frame, in the HTS, surface silicon titanium ratio/body phase silicon titanium ratio is 2.37, and titanium oxide content is 3.2 weights
Amount %.The result that the reactant mixture of reactor output determines under the reaction time listed by table 1 is in table 1
In list.
Embodiment 5
Dimethyl sulfone is prepared using method same as Example 2, except for the difference that, HTS is prepared
During TS-1, the crystallization time of first stage is 12h.The XRD crystalline phases figure and embodiment 1 of gained sample
The titanium-silicon molecular sieve TS-1 of preparation is consistent, and illustrate to obtain is the TS-1 molecular sieves with MFI structure；
In 960cm in fourier-transform infrared spectrogram-1Nearby there is absworption peak, show that titanium has been enter into molecule sieve skeleton
Frame, in the HTS, surface silicon titanium ratio/body phase silicon titanium ratio is 3.78, and titanium oxide content is 3.4 weights
Amount %.The result that the reactant mixture of reactor output determines under the reaction time listed by table 1 is in table 1
In list.
Embodiment 6
Dimethyl sulfone is prepared using method same as Example 2, except for the difference that, HTS is prepared
During TS-1, second stage is to be cooled to 70 DEG C of stop 2h.The XRD crystalline phases figure of gained sample and enforcement
Titanium-silicon molecular sieve TS-1 prepared by example 1 is consistent, and illustrate to obtain is the TS-1 molecules with MFI structure
Sieve；In 960cm in fourier-transform infrared spectrogram-1Nearby there is absworption peak, show that titanium has been enter into molecule
Sieve skeleton frame, in the HTS, surface silicon titanium ratio/body phase silicon titanium ratio is 2.75, and titanium oxide content is
3.1 weight %.The result that the reactant mixture of reactor output determines under the reaction time listed by table 1
List in table 1.
Embodiment 7
Dimethyl sulfone is prepared using method same as Example 2, except for the difference that, HTS is prepared
During TS-1, second stage is to be cooled to 30 DEG C of stop 0.2h.The XRD crystalline phases figure of gained sample and enforcement
Titanium-silicon molecular sieve TS-1 prepared by example 1 is consistent, and illustrate to obtain is the TS-1 molecules with MFI structure
Sieve；In 960cm in fourier-transform infrared spectrogram-1Nearby there is absworption peak, show that titanium has been enter into molecule
Sieve skeleton frame, in the HTS, surface silicon titanium ratio/body phase silicon titanium ratio is 1.14, and titanium oxide content is
3.1 weight %.The result that the reactant mixture of reactor output determines under the reaction time listed by table 1
List in table 1.
Embodiment 8
Dimethyl sulfone is prepared using method same as Example 2, except for the difference that, HTS is prepared
During TS-1, without second stage.The titanium silicon that the XRD crystalline phases figure of gained sample is prepared with embodiment 1
Molecular sieve TS-1 is consistent, and illustrate to obtain is the TS-1 molecular sieves with MFI structure；Fourier transform
In 960cm in infrared spectrum-1Nearby there is absworption peak, show that titanium has been enter into framework of molecular sieve, the titanium silicon
In molecular sieve, surface silicon titanium ratio/body phase silicon titanium ratio is 1.08, and titanium oxide content is 2.5 weight %.By table
The result that the reactant mixture of reactor output determines under 1 reaction time listed is listed in table 1.
Embodiment 9
Dimethyl sulfone is prepared using method same as Example 2, except for the difference that, HTS is prepared
During TS-1, aqueous dispersions do not stand at room temperature 12h, but being sent directly in reactor carries out crystallization.
The XRD crystalline phases figure of gained sample is consistent with titanium-silicon molecular sieve TS-1 prepared by embodiment 1, and explanation is obtained
Be the TS-1 molecular sieves with MFI structure；In 960cm in fourier-transform infrared spectrogram-1Near
There is absworption peak, show that titanium has been enter into framework of molecular sieve, in the HTS, titanium oxide content is 3.5
Weight %, surface silicon titanium ratio/body phase silicon titanium ratio is 1.18.Reactor is defeated under the reaction time listed by table 1
The result that the reactant mixture for going out determines is listed in table 1.
Embodiment 10
Dimethyl sulfone is prepared using method same as Example 1, except for the difference that, is filled in beds
What is filled out is the mixture of the catalyst that embodiment 1 is used and the catalyst that embodiment 2 is used, with the mixing
On the basis of the total amount of thing, the content of the catalyst that embodiment 2 is used is 60 weight %.Listed by table 1
Reaction time under reactor output reactant mixture determine result list in table 1.
Table 1
Embodiment 11
Respectively loading catalyst C1 (is for volume average particle size in the fixed bed reactors of two series connection
500 μm of spheric catalyst, the catalyst contains the hollow HTS of 75 weight %, 25 weight
The silica of %, hollow HTS is to be purchased from the trade mark of Hunan Jianchang Petrochemical Co., Ltd
The hollow HTS of HTS) beds are formed, wherein, each catalyst reactor bed
Quantity be 1 layer.On the basis of reaction raw materials flow direction in the reactor, by positioned at upstream
Beds in fixed bed reactors are referred to as the first beds, positioned at the fixed bed reaction in downstream
Beds in device are referred to as the second beds, the loaded catalyst in the first beds
It is 5 with the weight ratio of the loaded catalyst in the second beds：1, the first beds it is interior
Footpath is 2 with the ratio of the internal diameter of the second beds：1.
By dimethyl sulfide, hydrogen peroxide (providing in the hydrogen peroxide form of 40 weight %) and as molten
The methyl alcohol of agent is mixed to form reaction raw materials, by reaction raw materials from the bottom of the fixed bed reactors positioned at upstream
The first beds are sent into and flow through, the reactant mixture of output subsequently enters next fixed bed reaction
In device and flow through the second beds.Wherein, dimethyl sulfide and the mol ratio of hydrogen peroxide are 1：
2.5, dimethyl sulfide is 1 with the mol ratio of methyl alcohol：5.Temperature in two fixed bed reactors is
40 DEG C, the Stress control in two fixed bed reactors is into 1.0MPa, dimethyl in course of reaction
The weight (hourly) space velocity (WHSV) of thioether is 20h-1。
The reactant mixture exported from reactor is carried out into flash distillation, gas stream and liquids are separated into
Stream.Wherein, gas stream condenses dimethyl sulfide by cooling, to reclaim dimethyl sulfide and circulate
Use；Liquid stream is distilled, and methyl alcohol, water and dimethyl sulfone are collected respectively, and dimethyl sulfone is exported,
Methanol loop is used, and water is used to produce hydrogen peroxide after being further purified.
The composition of the reactant mixture exported from reactor using gas-chromatography monitoring in course of reaction, and
Dimethyl sulfide conversion ratio, oxidant effective rate of utilization and dimethyl sulfone selectivity are calculated, is listed by table 2
Reaction time under reactor output reactant mixture determine result list in table 2.
Embodiment 12
Dimethyl sulfone, except for the difference that, the second catalyst bed are produced using with the identical method of embodiment 11
Layer in catalyst C1 by etc. weight catalyst C2 (shaping titanium-silicon molecular sieve TS-1, be volume put down
Particle diameter is 500 μm of spheric catalyst, and the catalyst contains the titanium-silicon molecular sieve TS-1 of 75 weight %,
The silica of 25 weight %, titanium-silicon molecular sieve TS-1 is prepared using method same as Example 2) generation
Replace.The result that the reactant mixture of reactor output determines under the reaction time listed by table 2 is in table 2
List.
Embodiment 13
Dimethyl sulfone, except for the difference that, the first catalyst bed are produced using with the identical method of embodiment 12
Under conditions of catalyst type and loadings in layer and the second beds keeps constant, second is made
The internal diameter of beds is identical with the internal diameter of the first beds, i.e. the first beds and second
The ratio of the internal diameter of beds is 1：1.Reactor output is anti-under the reaction time listed by table 2
The result that mixture determines is answered to list in table 2.
Embodiment 14
Dimethyl sulfone, except for the difference that, the first catalyst bed are produced using with the identical method of embodiment 12
Catalyst type in layer and the second beds and under conditions of loadings keep constant, reduces the
The internal diameter of one beds, makes the internal diameter of the first beds and the internal diameter of the second beds
Ratio is 1：2.The result that the reactant mixture of reactor output determines under the reaction time listed by table 2
List in table 2.
Embodiment 15
Catalyst C3 used in the present embodiment is shaping titanium-silicon molecular sieve TS-1, is volume average particle size
For 500 μm of spheric catalyst, the catalyst contains the titanium-silicon molecular sieve TS-1 of 75 weight %, 25 weights
The silica of amount %, titanium-silicon molecular sieve TS-1 is prepared using following methods.
First butyl titanate is dissolved in the alkali source template TPAOH aqueous solution, silicon is subsequently adding
Glue (is purchased from Qingdao silica gel factory), obtains dispersion liquid, in the dispersion liquid, silicon source：Titanium source：Alkali source template
Agent：The mol ratio of water is 100：2：10：600, silicon source is with SiO2Meter, titanium source is with TiO2Meter, alkali
Source template is in terms of N.10h are stood at 40 DEG C after above-mentioned dispersion liquid is sealed in beaker using sealed membrane,
It is stirred at 25 DEG C 0.5 hour followed by magnetic agitation, is allowed to disperse again.After disperseing again
Dispersion liquid be transferred in sealed reactor, 130 DEG C experience first stage crystallization 8h, then will mixing
Thing is cooled to 50 DEG C of experience second stage and stops after 5h, continues in sealed reactor in 170 DEG C of temperature
Degree experience phase III crystallization 16h is (wherein, by the intensification speed of room temperature to first stage crystallization temperature
Rate is 1 DEG C/min, is to the rate of temperature fall of second stage treatment temperature by first stage crystallization temperature
10 DEG C/min, it is to the heating rate of phase III crystallization temperature by second stage treatment temperature
20 DEG C/min), without filtration and washing step after gained crystallization product is taken out, directly in 120 DEG C of drying
3h, then the roasting 2h at 580 DEG C, obtains molecular sieve.The XRD crystalline phases figure of gained sample and enforcement
Titanium-silicon molecular sieve TS-1 prepared by example 1 is consistent, and illustrate to obtain is the titanium silicon molecule with MFI structure
Sieve TS-1；In FFIR figure, in 960cm-1Nearby there is absworption peak, show titanium
Into framework of molecular sieve, in the HTS, surface silicon titanium ratio/body phase silicon titanium ratio is 2.25, titanium oxide
Content is 2.6 weight %.
Dimethyl sulfone, except for the difference that, the first catalyst bed are produced using with the identical device of embodiment 11
Loading catalyst C1, loading catalyst C3 in the second beds, in the first beds in layer
Loaded catalyst and the second beds in loaded catalyst weight ratio be 10：1, the
The ratio of the internal diameter of the internal diameter of one beds and the second beds is 4：1.
Dimethyl sulfide, dicumyl peroxide and acetone as solvent are mixed to form into reaction raw materials, will
The first beds are sent into and flow through to reaction raw materials from the bottom of the fixed bed reactors positioned at upstream, defeated
The reactant mixture for going out subsequently enters in next fixed bed reactors and flows through the second beds.Its
In, dimethyl sulfide is 1 with the mol ratio of dicumyl peroxide：2, dimethyl sulfide and acetone mole
Than for 1：10.Temperature in two fixed bed reactors is 80 DEG C, by two fixations in course of reaction
Stress control in bed reactor is 1.8MPa, and the weight (hourly) space velocity (WHSV) of dimethyl sulfide is 15h-1。
The reactant mixture exported from reactor is carried out into flash distillation, gas stream and liquids are separated into
Stream.Wherein, gas stream condenses dimethyl sulfide by cooling, to reclaim dimethyl sulfide and circulate
Use；Liquid stream is distilled, and acetone and dimethyl sulfone are collected respectively, dimethyl sulfone is exported, third
Ketone is recycled.
The composition of the reactant mixture exported from reactor using gas-chromatography monitoring in course of reaction, and
Dimethyl sulfide conversion ratio, oxidant effective rate of utilization and dimethyl sulfone selectivity are calculated, is listed by table 2
Reaction time under reactor output reactant mixture determine list in table 2.
Table 2
Embodiment 11-14 is compared as can be seen that making reaction raw materials priority and hollow HTS
With titanium-silicon molecular sieve TS-1 haptoreaction, and reaction raw materials are made by being filled with hollow HTS
When superficial velocity during beds is less than the beds by being filled with titanium-silicon molecular sieve TS-1
Superficial velocity, being obtained in that more preferable reaction effect, and further extend the one way of HTS makes
Use the life-span.
Embodiment 16
Catalyst used in the present embodiment is shaping titanium-silicon molecular sieve TS-1, and its volume average particle size is
850 μm of spheric catalyst, on the basis of the total amount of the catalyst, the content of titanium-silicon molecular sieve TS-1
For 85 weight %, the content of silica is 15 weight %.Wherein, titanium-silicon molecular sieve TS-1 is using following
It is prepared by method.
First butyl titanate is dissolved in the alkali source template TPAOH aqueous solution, silicon is subsequently adding
Glue (is purchased from Qingdao silica gel factory), obtains dispersion liquid, in the dispersion liquid, silicon source：Titanium source：Alkali source template
Agent：The mol ratio of water is 100：5：18：1000, silicon source is with SiO2Meter, titanium source is with TiO2Meter, alkali
Source template is in terms of N.In 45 DEG C of standings after above-mentioned dispersion liquid is sealed in beaker using sealed membrane
8h；The dispersion liquid that Jing stands is transferred in sealed reactor, at 140 DEG C first stage crystallization 6h is experienced,
Then by mixture be cooled to 40 DEG C experience second stage stop 1h after, continue in sealed reactor in
Phase III crystallization 12h is experienced at a temperature of 160 DEG C (wherein, by room temperature to first stage crystallization temperature
The heating rate of degree is 5 DEG C/min, by the cooling of first stage crystallization temperature to second stage treatment temperature
Speed is 5 DEG C/min, is to the heating rate of phase III crystallization temperature by second stage treatment temperature
5 DEG C/min), without filtration and washing step after gained crystallization product is taken out, directly in 110 DEG C of drying
2h, then the roasting 3h at 550 DEG C, obtains molecular sieve.The XRD crystalline phases figure of gained sample and enforcement
Titanium-silicon molecular sieve TS-1 prepared by example 1 is consistent, and illustrate to obtain is the titanium silicon molecule with MFI structure
Sieve TS-1；In FFIR figure, in 960cm-1Nearby there is absworption peak, show titanium
Into framework of molecular sieve, in the HTS, surface silicon titanium ratio/body phase silicon titanium ratio is 2.71, titanium oxide
Content is 4.3 weight %.
By Catalyst packing in isometrical fixed bed reactors, beds are formed, wherein, catalyst
The quantity of bed is 1 layer.
Dimethyl sulfide, the TBHP as oxidant and the acetonitrile as solvent are mixed into shape
Into reaction raw materials, beds are sent in fixed bed reactors and flow through to reaction raw materials.Wherein, two
Dimethyl sulfide is 1 with the mol ratio of TBHP：2, dimethyl sulfide is with the mol ratio of acetonitrile
1：8.Temperature in reactor is 65 DEG C, remains the pressure in fixed bed reactors in course of reaction
2.5MPa, the weight (hourly) space velocity (WHSV) of dimethyl sulfide is 40h-1。
The reactant mixture exported from reactor is carried out into flash distillation, gas stream and liquids are separated into
Stream.Wherein, gas stream condenses dimethyl sulfide by cooling, to reclaim dimethyl sulfide and circulate
Use；Liquid stream is distilled, and acetonitrile and dimethyl sulfone are collected respectively, dimethyl sulfone is exported, second
Nitrile is recycled.
The composition of the reactant mixture exported from reactor using gas-chromatography monitoring in course of reaction, and
Dimethyl sulfide conversion ratio, oxidant effective rate of utilization and dimethyl sulfone selectivity are calculated, is listed by table 3
Reaction time under reactor output reactant mixture determine list in table 3.
Table 3
The preferred embodiment of the present invention described in detail above, but, the present invention is not limited to above-mentioned reality
The detail in mode is applied, in the range of the technology design of the present invention, can be to the technical side of the present invention
Case carries out various simple variants, and these simple variants belong to protection scope of the present invention.
It is further to note that each particular technique described in above-mentioned specific embodiment is special
Levy, in the case of reconcilable, can be combined by any suitable means, in order to avoid need not
The repetition wanted, the present invention is no longer separately illustrated to various possible combinations.
Additionally, can also be combined between a variety of embodiments of the present invention, as long as its
Without prejudice to the thought of the present invention, it should equally be considered as content disclosed in this invention.
Claims (14)
1. a kind of method for producing dimethyl sulfone, the method is comprised the following steps：
A, under oxidation reaction condition, a kind of reaction raw materials are contacted with least one HTS,
The reactant mixture containing dimethyl sulfone is obtained, the reaction raw materials contain dimethyl sulfide, at least one
Oxidant and optional at least one solvent；
B, the reactant mixture is carried out gas-liquid separation, and to obtain the liquid stream containing dimethyl sulfone gentle
Body logistics；And
C, from the liquid stream isolate dimethyl sulfone.
2. method according to claim 1, wherein, at least part of HTS is titanium silicon point
Son sieve TS-1, the surface silicon titanium ratio of the titanium-silicon molecular sieve TS-1 is not less than body phase silicon titanium ratio, the silicon
Than referring to the mol ratio of silica and titanium oxide, the surface silicon titanium ratio adopts x-ray photoelectron power spectrum to titanium
Method is determined, and the body phase silicon titanium ratio adopts x-ray fluorescence spectrometry；
Preferably, the surface silicon titanium ratio and the ratio of the body phase silicon titanium ratio are more than 1.2；
It is highly preferred that the surface silicon titanium ratio is 1.2-5 with the ratio of the body phase silicon titanium ratio；
It is further preferred that the surface silicon titanium ratio is 1.5-4.5 with the ratio of the body phase silicon titanium ratio.
3. method according to claim 1 and 2, wherein, at least part of HTS is titanium
Silicalite TS-1, the titanium-silicon molecular sieve TS-1 is prepared using the method for comprising the following steps：
(I) inorganic silicon source is dispersed in the aqueous solution containing titanium source and alkali source template, and alternatively
Water is supplemented, dispersion liquid is obtained, in the dispersion liquid, silicon source：Titanium source：Alkali source template：Water mole
Than for 100：(0.5-8)：(5-30)：(100-2000), the inorganic silicon source is with SiO2Meter, the titanium
Source is with TiO2Meter, the alkali source template is with N or OH-Meter；
(II) alternatively, the dispersion liquid is stood into 6-24 hours at 15-60 DEG C；
(III) dispersion liquid that the dispersion liquid or step (II) for obtaining step (I) is obtained is anti-in sealing
Answer and sequentially experience in kettle stage (1), stage (2) and stage (3) to carry out crystallization, stage (1)
At 80-150 DEG C, preferably at 110-140 DEG C, more preferably at 120-140 DEG C, further preferably at 130-140 DEG C
Crystallization 6-72 hour, preferred 6-8 hours；Stage (2) is cooled to not higher than 70 DEG C and the time of staying extremely
It is less 0.5 hour, preferably 1-5 hours；Stage (3) be warming up to 120-200 DEG C, preferred 140-180 DEG C,
More preferably 160-170 DEG C, then crystallization 6-96 hour, preferred 12-20 hours.
4. method according to claim 3, wherein, stage (1) and stage (3) meet with
One of lower condition or both：
Condition 1：Crystallization temperature of the crystallization temperature in stage (1) less than the stage (3), it is preferable that rank
The crystallization temperature of section (1) is lower 10-50 DEG C than the crystallization temperature in stage (3), preferably low 20-40 DEG C；
Condition 2：Crystallization time of the crystallization time in stage (1) less than the stage (3), it is preferable that rank
The crystallization time 5-24 hours shorter than the crystallization time in stage (3) of section (1), preferably short 6-12 hours.
5. the method according to claim 3 or 4, wherein, the stage (2) is cooled to not higher than 50
DEG C, and the time of staying be at least 1 hour.
6. the method according to any one in claim 3-5, wherein, the titanium source is inorganic
Titanium salt and/or organic titanate；The alkali source template is in quaternary ammonium base, aliphatic amine and aliphatic hydramine
One or more, preferably quaternary ammonium base, more preferably TPAOH；The inorganic silicon
Source is silica gel and/or Ludox；
Preferably, the inorganic titanium salt is TiCl4、Ti(SO4)2And TiOCl2In one or more；
The organic titanate is selected from general formula R7 4TiO4The compound of expression, R7Selected from 2-4 carbon atom
Alkyl.
7. the method according to any one in claim 1-6, wherein, the HTS
In being seated in beds, the beds contain the first beds and the second catalyst bed
Layer, on the basis of the flow direction of the reaction raw materials, first beds are located at described second
The upstream of beds, HTS and described second catalysis of the first beds filling
The HTS of agent bed filling is identical or different, and the reaction raw materials flow through the first beds
Superficial velocity is v1, the superficial velocity for flowing through the second beds is v2, v1＜ v2；Preferably, v2/v1
=1.5-10；It is highly preferred that v2/v1=2-5.
8. method according to claim 7, wherein, the titanium of the first beds filling
Si molecular sieves are hollow HTS, and the hollow HTS is the titanium silicon molecule of MFI structure
Sieve, the crystal grain of the 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 the condition of 1 hour
Under the benzene adsorbance that measures be at least 70 milligrams per grams, absorption of the nitrogen absorption under low temperature of the HTS etc.
There is hysteresis loop between warm line and desorption isotherm；
The HTS of the second beds filling is titanium-silicon molecular sieve TS-1.
9. the method according to claim 7 or 8, wherein, the first beds filling
The weight ratio of HTS that loads with second beds of HTS be 1-20：1,
Preferably 2-15：1, more preferably 5-10：1.
10. the method according to any one in claim 1-9, wherein, the oxidant and institute
The mol ratio for stating dimethyl sulfide is 2：More than 1；
Preferably, the oxidant and the mol ratio of dimethyl sulfide are 2-3：1；
It is highly preferred that the oxidant is 2-2.5 with the mol ratio of dimethyl sulfide：1.
11. methods according to any one in claim 1-10, wherein, the oxidant is
Peroxide；
Preferably, the oxidant is selected from hydrogen peroxide, organic hydroperoxide and peracid.
12. methods according to any one in claim 1-11, wherein, the solvent is selected from
The solvent is selected from water, C1-C10Alcohol, C3-C10Ketone and C2-C10Nitrile.
13. methods according to any one in claim 1-12, wherein, the reaction raw materials
It is 20-160 DEG C, is preferably 30-140 DEG C, is more preferably 40-120 in temperature with the HTS
DEG C, and pressure is to contact under conditions of 0-3MPa, preferred 0.1-2.5MPa, the pressure is gauge pressure；
When the contact is carried out in fixed bed reactors, the weight (hourly) space velocity (WHSV) of the reaction raw materials is 0.05-100h-1,
Preferably 0.1-50h-1, more preferably 10-40h-1。
14. methods according to any one in claim 1-13, wherein, the gas-liquid separation
Condition unreacted dimethyl sulfide is contained in the gas stream, the method also include it is following
Step：Isolate unreacted dimethyl sulfide from the gas stream, and by the unreacted isolated
Dimethyl sulfide circulate for preparing the reaction raw materials.
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| CN109721515A (en) * | 2017-10-31 | 2019-05-07 | 中国石油化工股份有限公司 | A kind of preparation method of sulfone |
| CN109721514A (en) * | 2017-10-31 | 2019-05-07 | 中国石油化工股份有限公司 | A kind of preparation method of sulfone |
| CN109721516A (en) * | 2017-10-31 | 2019-05-07 | 中国石油化工股份有限公司 | A kind of sulfide oxidation method |
| WO2022133768A1 (en) * | 2020-12-23 | 2022-06-30 | Solvay Sa | Desulfurization process |
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| CN104557633A (en) * | 2013-10-29 | 2015-04-29 | 中国石油化工股份有限公司 | Method for preparing dimethyl sulfone |
| CN104557634A (en) * | 2013-10-29 | 2015-04-29 | 中国石油化工股份有限公司 | Method for producing dimethyl sulfone |
| CN104944441A (en) * | 2014-03-31 | 2015-09-30 | 中国石油化工股份有限公司 | Method for synthesizing titanium-silicon molecular sieve |
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| CN104557633A (en) * | 2013-10-29 | 2015-04-29 | 中国石油化工股份有限公司 | Method for preparing dimethyl sulfone |
| CN104557634A (en) * | 2013-10-29 | 2015-04-29 | 中国石油化工股份有限公司 | Method for producing dimethyl sulfone |
| CN104944441A (en) * | 2014-03-31 | 2015-09-30 | 中国石油化工股份有限公司 | Method for synthesizing titanium-silicon molecular sieve |
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| CN109721515A (en) * | 2017-10-31 | 2019-05-07 | 中国石油化工股份有限公司 | A kind of preparation method of sulfone |
| CN109721514A (en) * | 2017-10-31 | 2019-05-07 | 中国石油化工股份有限公司 | A kind of preparation method of sulfone |
| CN109721516A (en) * | 2017-10-31 | 2019-05-07 | 中国石油化工股份有限公司 | A kind of sulfide oxidation method |
| CN109721516B (en) * | 2017-10-31 | 2020-12-04 | 中国石油化工股份有限公司 | Thioether oxidation method |
| CN109721515B (en) * | 2017-10-31 | 2020-12-04 | 中国石油化工股份有限公司 | Preparation method of sulfone |
| CN109721514B (en) * | 2017-10-31 | 2020-12-04 | 中国石油化工股份有限公司 | Preparation method of sulfone |
| WO2022133768A1 (en) * | 2020-12-23 | 2022-06-30 | Solvay Sa | Desulfurization process |
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