CN105439919B - A kind of sulfide oxidation method - Google Patents
A kind of sulfide oxidation method Download PDFInfo
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- CN105439919B CN105439919B CN201410426082.6A CN201410426082A CN105439919B CN 105439919 B CN105439919 B CN 105439919B CN 201410426082 A CN201410426082 A CN 201410426082A CN 105439919 B CN105439919 B CN 105439919B
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- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
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Abstract
The invention discloses a kind of sulfide oxidation method, this method includes being continuously introduced into a kind of liquid mixture into fixed bed reactors, the liquid mixture is set to flow through beds under oxidation reaction condition, to be contacted with the HTS being seated in beds, the liquid mixture contains thioether, at least one oxidant and optional at least one solvent, wherein, this method also includes：When oxidant conversion ratio drops to a certain degree, the temperature of beds is raised until oxidant conversion ratio meets desired value, then stopping heats up and is incubated.This method can effectively extend the single trip use life-span of HTS, reduce the regeneration frequency of HTS, improve the production efficiency of device.
Description
Technical field
The present invention relates to a kind of sulfide oxidation method.
Background technology
Sulfoxides are important sulfur-containing compounds, if dimethyl sulfoxide (DMSO) (DMSO) is a kind of organic compounds containing sulfur,
It is colourless transparent liquid under normal temperature, the characteristic such as have highly polar, high-hygroscopicity, flammable and higher boiling non-proton.Dimethyl sulfoxide (DMSO)
Water, ethanol, acetone, ether and chloroform are dissolved in, is the strong atent solvent of polarity, is widely used as solvent and reaction reagent.Also, two
Methyl sulfoxide has very high selective extraction method ability, can be used as the Extraction solvent that alkane separates with aromatic hydrocarbon, such as：Dimethyl
Sulfoxide can be used for the extracting of aromatic hydrocarbons or butadiene, as process solvent and the solvent that reels off raw silk from cocoons in acrylonitrile polymerization reaction, as poly-
The synthetic of urethane and the solvent that reels off raw silk from cocoons, the synthetic as polyamide, fluoroaluminate glasses, polyimides and polysulfones.Meanwhile
In medical industry, dimethyl sulfoxide (DMSO) not only can be directly as the raw material and carrier of some drugses, and can also play anti-inflammatory and stop
Bitterly, diuresis, calmness etc. act on, therefore are made an addition to frequently as the active component of analgesic drug product in medicine.In addition, dimethyl sulfoxide (DMSO)
Capacitor dielectric, antifreezing agent, brake fluid, rare metal extracting agent etc. can be used as.
At present, sulfoxide is typically made using sulfide oxidation method, and the oxidant that can be used includes nitric acid, peroxide and smelly
Oxygen etc..
When using oxidant (particularly peroxide) by sulfide oxidation, if being used as catalysis using HTS
Agent, it is possible to increase the conversion ratio of oxidant and the selectivity of desirable oxidation product.But with the extension in reaction time, titanium silicon molecule
The catalytic activity of sieve can be on a declining curve, causes oxidant conversion ratio and desirable oxidation selectivity of product substantially to reduce.Work as reaction
When being carried out in fixed bed reactors, because titanium molecular sieve catalysis activity is reduced, it is necessary to by HTS in reactor
Or regenerated outside reactor, cause reactor down-time, so as to influence production efficiency and improve the operating cost of device.
Therefore, for the sulfide oxidation reaction using HTS as catalyst, how to extend as catalyst
HTS the single trip use life-span, it is to improve production efficiency and reduce the key link of operating cost to reduce regeneration frequency
One of.
The content of the invention
It is an object of the invention to solve using HTS as catalyst sulfide oxidation reaction existing for it is above-mentioned not
Foot, there is provided a kind of sulfide oxidation method, this method can effectively extend the single trip use life-span of catalyst, reduce regeneration frequency.
The invention provides a kind of sulfide oxidation method, this method includes being continuously introduced into a kind of liquid into fixed bed reactors
Body mixture, the liquid mixture is set to flow through the beds of the fixed bed reactors under oxidation reaction condition, with
Contacted with the HTS being seated in the beds, the liquid mixture contains thioether, at least one oxidation
Agent and optional at least one solvent, wherein, when this method is additionally included in the condition 1 of satisfaction, raise the temperature of beds
Until when oxidant conversion ratio C ' meets condition 2, stop heating up and being incubated：
Condition 1, sometime the oxidant conversion ratio C under ttWith initial oxidant conversion ratio C0Ratio Ct/C0For 0.8
≤Ct/C0<1；
Condition 2, oxidant conversion ratio C ' and initial oxidant conversion ratio C0Ratio C '/C0For 0.85≤C '/C0≤1。
The method according to the invention, it can effectively extend the single trip use life-span of the HTS as catalyst,
So as to the parallel-adder settle-out time of effectively extension fixture.Method is simple by the present invention, beneficial to industrialized production and application.
Embodiment
The invention provides a kind of sulfide oxidation method, this method includes being continuously introduced into a kind of liquid into fixed bed reactors
Body mixture, the liquid mixture is set to flow through the beds of the fixed bed reactors under oxidation reaction condition, with
Contacted with the HTS being seated in the beds, the liquid mixture contains thioether, at least one oxidation
Agent and optional at least one solvent.
In the present invention, " at least one " represents one or more kinds of, " optional " to represent inessential, it can be understood as to contain
Or be free of.
The method according to the invention, the thioether can be the various compounds containing-S- keys, and preferably described thioether is selected from
Carbon number is 2-18 thioether, more preferably dimethyl sulfide or thioanisole.
The method according to the invention, the oxidant can be it is common it is various can be by the material of sulfide oxidation.This hair
Occasion of the bright method especially suitable for carrying out oxidizing sulfur ether using peroxide as oxidant, can so significantly improve peroxidating
The effective rate of utilization of thing.The peroxide refers to the compound for containing-O-O- keys in molecular structure, can be selected from peroxidating
Hydrogen, organic peroxide and peracid.The organic peroxide refers to one or two hydrogen atom quilt in hydrogen peroxide molecule
Material obtained from organic group substitution.The peracid refers to the organic oxacid for containing-O-O- keys in molecular structure.The present invention
In, the instantiation of the oxidant can include but is not limited to：Hydrogen peroxide, TBHP, dicumyl peroxide,
Cyclohexyl hydroperoxide, Peracetic acid and Perpropionic Acid.Preferably, the oxidant is hydrogen peroxide, so can be further
Reduce separation costs.
The hydrogen peroxide can be hydrogen peroxide existing in a variety of manners commonly used in the art.Root is improved from further
Set out according to the angle of the security of the method for the present invention, the method according to the invention is preferably using existing mistake as an aqueous solution
Hydrogen oxide.The method according to the invention, when the hydrogen peroxide provides as an aqueous solution, the aqueous hydrogen peroxide solution
Concentration can be the normal concentration of this area, such as：20-80 weight %.Concentration meets the water-soluble of the hydrogen peroxide of above-mentioned requirements
Liquid can use conventional method to prepare, and can also be commercially available, such as：It can be the dioxygen for the 30 weight % that can be commercially available
The hydrogen peroxide of water, 50 weight % hydrogen peroxide or 70 weight %.
The dosage of the oxidant can be conventional selection, be not particularly limited.Usually, mole of thioether and oxidant
Than that can be 0.1-20：1.When desirable oxidation product is sulfoxide (such as dimethyl sulfoxide (DMSO)), selectivity of product is improved from further
Angle set out, the mol ratio of thioether (such as dimethyl sulfide) and oxidant can be 0.2-10：1, preferably 0.5-5：1, more
Preferably 1-5：1.
The method according to the invention, catalyst is used as using HTS.HTS is titanium atom substitution lattice bone
The general name of a kind of zeolite of a part of silicon atom in frame, chemical formula xTiO can be used2·SiO2Represent.The present invention is for titanium silicon point
The content of titanium atom is not particularly limited in son sieve, 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, such as：The titanium silicon
Molecular sieve can be the HTS (such as TS-1) selected from MFI structure, the HTS (such as TS-2) of MEL structures, BEA knots
The HTS (such as Ti-Beta) of structure, the HTS (such as Ti-MCM-22) of MWW structures, the titanium silicon molecule of hexagonal structure
Sieve (such as Ti-MCM-41, Ti-SBA-15), HTS (such as Ti-MOR), the HTS of TUN structures of MOR structures
It is more than one or both of (such as Ti-TUN) and the HTS of other structures (such as Ti-ZSM-48).
Preferably, the HTS be the HTS selected from MFI structure, MEL structures HTS and
It is more than one or both of HTS of BEA structures.It is highly preferred that the HTS is the titanium silicon of MFI structure
Molecular sieve, such as TS-1 molecular sieves.
It is highly preferred that the HTS is the HTS of MFI structure, the crystal grain of the HTS is hollow
Structure, 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=
0.10th, the benzene adsorbance that adsorption time measures under conditions of being 1 hour is at least 70 milligrams per grams, the low temperature of the HTS
Hysteresis loop be present between the adsorption isotherm and desorption isotherm of N2 adsorption.Herein, the HTS with the structure claims
For hollow HTS.The hollow HTS, which is commercially available, (such as to be built feldspathization share commercially available from Hunan and has
The trade mark of limit company is HTS molecular sieve), it can also be prepared according to the method disclosed in CN1132699C.
The method according to the invention, the quantity of the beds can be one or more.In beds
When quantity is multiple, the different zones of a fixed bed reactors can be located at, can also be located in multiple fixed bed reactors.
In one embodiment of the invention, the beds contain the first beds and the second catalyst
Bed, on the basis of the flow direction of the liquid mixture, first beds are located at second catalyst bed
The upstream of layer, i.e., described liquid mixture firstly flow through the first beds, again pass through the second beds.Described first urges
Agent bed can be identical with the species of the HTS loaded in second beds, or different.
Preferably, the HTS of the first beds filling is hollow HTS.It is highly preferred that described first urges
The HTS of agent bed filling is hollow HTS, and the HTS of the second beds filling is
Titanium-silicon molecular sieve TS-1, it so can further extend the single trip use life-span of HTS.
When the beds contain the first beds and the second beds, first catalyst bed
The weight ratio of HTS of the HTS loaded in layer with being loaded in second beds can be 1-20：
1.It is hollow HTS in the HTS of first beds filling, the second beds filling
HTS when being titanium-silicon molecular sieve TS-1, the hollow HTS loaded in first beds with it is described
The weight of the titanium-silicon molecular sieve TS-1 loaded in second beds is than preferably 2-10：1, it can so obtain higher mesh
Mark oxidation product selectivity.
When the beds contain the first beds and the second beds, first catalyst bed
Layer and the second beds can each contain one or more beds.In the first beds and/or second
Can be to be connected in series when beds contain multiple beds, between multiple beds, or in parallel
Connection, can also be series connection and combination in parallel, such as：Multiple beds are divided into multigroup, the catalyst bed in every group
Layer is to be connected in series and/or be connected in parallel to be connected in series and/or being connected in parallel, between each group.First beds
The different zones of same reactor can be arranged on second beds, different reactors can also be arranged on
In.
When the beds contain the first beds and the second beds, the liquid mixture stream
The superficial velocity for crossing the first beds and the second beds can be identical, or different.Preferably, it is described
The superficial velocity that liquid mixture flows through the first beds is v1, the superficial velocity for flowing through the second beds is v2, its
In, v1<v2, so can further extend single trip use life-span of HTS.It is highly preferred that v2/v1=1.5-10.Enter
One step preferably, v2/v1=2-5.
In the present invention, the superficial velocity (flow velocity) refers to mix by the whole liquid of beds in the unit interval
The area of the mass flow (in terms of kg/s) of thing and a certain cross section of beds is (with m2Meter) ratio.Can be by unit
The quality of the liquid mixture of fixed bed reactors is sent into time as " by the liquid of whole beds in the unit interval
The mass flow of body mixture ".In the present invention, for superficial velocity of the liquid mixture in the first beds without spy
It is different to require, typically can be in 0.001-200kg/ (m2S) in the range of.
The liquid mixture can be adjusted using various methods in the first beds and the second beds
In superficial velocity.For example, the superficial velocity of liquid mixture can be adjusted by the cross-sectional area of selecting catalyst bed.
Specifically, the cross-sectional area of first beds can be made to be more than the cross-sectional area of second beds, from
And cause v1＜ v2, it is preferable that v2/v1For 1.5-10, more preferably cause v2/v1For 2-5.According to expected superficial velocity come really
The method for determining the cross-sectional area of beds is known in those skilled in the art, is no longer described in detail herein.
When the beds contain the first beds and the second beds, the liquid mixture exists
Residence time in first beds is T1, the total residence time in beds is T, usually, T1/ T=0.3-
0.96.Preferably, T1/ T=0.4-0.9 (such as T1/ T=0.5-0.85), so in continuous running for a long time, it can obtain
Get Geng Gao oxidant conversion ratio, and desirable oxidation selectivity of product is maintained to higher level.
The method according to the invention, when beds contain the first beds and the second beds, root
Material can be supplemented between the first beds and the second beds according to concrete condition, in the first beds
And/or second beds when being multiple beds, as the case may be can between the first beds and/
Or second supplement fresh material between beds into the liquid mixture.Such as：In the first beds and
Supplemented between two beds, between the first beds and/or between the second beds thioether, oxidant and/
Or solvent.However, it is desirable to explanation, the liquid mixture flows through whole beds of the first beds, and (that is, first urges
The whole process of agent bed) and the second beds whole beds (that is, the whole process of the second beds), the liquid mixes
Compound is not included between the first beds, is catalyzed between the second beds with the first beds and second
Whether the fresh material introduced between agent bed, previously described superficial velocity are determined do not introduced by the liquid mixture
The influence of fresh material.
The method according to the invention, contain the first beds and the second beds in the beds
When, the reaction condition of first beds and the second beds can be with identical, or different.From operation letter
Just the angle of property is set out, and first beds are identical with the reaction condition between the second beds.
In (non-sulfide oxidation is referred generally to react) device as the various reactions of catalyst using HTS, such as ammonia
In oximation reaction, hydroxylating and epoxidation reaction device, generally plant running for a period of time after, the catalysis of catalyst
Activity decrease is, it is necessary to carry out in device or ex-situ regeneration, even if when carrying out regeneration and also being difficult to obtain satisfied activity, it is necessary to will urge
Agent draws off (that is, more catalyst changeout) from device, and the processing that the catalyst (that is, drawing off agent or dead catalyst) drawn off is current
Method is typically to accumulate to bury, and on the one hand occupies the land resource and inventory space of preciousness, the life of another aspect HTS
It is higher to produce cost, directly passes into disuse and also result in great waste.
The present inventor has found in research process, is regenerated if these are drawn off into agent, the regeneration that will be obtained
Agent remains able to obtain high catalytic activity as the catalyst used in the inventive method.
The method according to the invention, in a preferred embodiment, at least part HTS are through regeneration
Reaction unit (referring generally to non-sulfide oxidation reaction unit) using HTS as catalyst draws off agent, such as described unloads
Go out agent can be Ammoximation reaction device draw off agent, hydroxylating device draws off drawing off for agent and epoxidation reaction device
More than one or both of agent, be specifically as follows cyclohexanone oxamidinating reaction unit draws off agent, phenol hydroxylation reaction dress
That puts draws off the drawing off more than one or both of agent of agent and propylene ring oxidation reaction device.
The condition that agent regenerated will be drawn off to be not particularly limited, appropriate choosing can be carried out according to the source for drawing off agent
Select, such as：High-temperature roasting and/or solvent washing.
The activity for drawing off agent through regeneration is different according to its source.Usually, the activity for drawing off agent through regeneration
Can be the 5-95% of its activity (that is, fresh dose of activity) when fresh.Preferably, the activity for drawing off agent through regeneration can
Think its active 10-90% when fresh, more preferably its active 10-60% when fresh.In unloading through regeneration
When going out the active 10-60% that the activity of agent is it when fresh, can not only obtain gratifying oxidant conversion ratio and
Desirable oxidation selectivity of product, and the oxidant effective rate of utilization further improved can be obtained, urged in tandem reaction sequence
The activity of agent is more stable.It is further preferred that the active 30- that the activity for drawing off agent through regeneration is it when fresh
55%.The activity of the fresh HTS is generally more than 95%.
The activity determines by the following method：Respectively by through regeneration draw off agent and fresh dose is used as cyclohexanone oxamidinating
The catalyst of reaction, the condition of the Ammoximation reaction are：Catalyst (in terms of 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
Under power 2h is reacted in 80 DEG C.Calculate respectively with through regeneration draw off agent and when fresh dose is catalyst cyclohexanone conversion ratio, and
Agent and fresh dose of activity are drawn off as through regeneration respectively, wherein, conversion ratio=[(cyclohexanone of addition of cyclohexanone
Mole-unreacted cyclohexanone mole)/add cyclohexanone mole] × 100%.
When at least part catalyst is that the reaction unit through regeneration draws off agent, on the basis of the total amount of the catalyst,
The content that reaction unit through regeneration draws off agent is preferably more than 5 weight %, can so obtain higher catalytic activity.According to
The method of the present invention, even if whole catalyst draw off agent for the reaction unit through regeneration, remain able to obtain higher catalysis
Activity.
The method according to the invention, the HTS can be HTS original powder, or shaping titanium silicon
Molecular sieve, preferably it is molded HTS.Shaping HTS typically contain as active component HTS and
As the carrier of binding agent, wherein, the content of HTS can be conventional selection.Usually, with the shaping titanium silicon point
On the basis of the total amount of son sieve, the content of HTS can be 5-95 weight %, preferably 10-95 weight %, be more preferably
70-95 weight %；The content of the carrier can be 5-95 weight %, and preferably 5-90 weight %, more preferably 5-30 are heavy
Measure %.The carrier of the shaping HTS can be conventional selection, such as aluminum oxide and/or silica.Prepare the shaping
The method of HTS is it is known in the art, being no longer described in detail herein.The granular size of the shaping HTS
It is not particularly limited, appropriate selection can be carried out according to concrete shape.Specifically, the average grain of the shaping HTS
Footpath can be 4-10000 microns, preferably 5-5000 microns, more preferably 40-4000 microns, such as 50-1000 microns.It is described flat
Equal particle diameter is volume average particle size, laser particle analyzer can be used to determine.
The method according to the invention, the beds can only load HTS, can also contain titanium silicon point
Son sieve and inactive filler.Loading inactive filler in beds can be to the amount of HTS in beds
It is adjusted, so as to which the speed of reaction be adjusted.Contain HTS and inactive filler in the beds
When, the content of inactive filler can be 5-95 weight % in beds.The inactive filler refers to oxidation reaction
Without or the basic filler without catalytic activity, its instantiation can include but is not limited to：Quartz sand, ceramic ring and ceramics are broken
One or more in piece.
The method according to the invention, HTS is as catalyst, and its dosage is can realize that catalysis is defined.One
As, the weight (hourly) space velocity (WHSV) of thioether can be 0.1-20h-1, preferably 0.1-10h-1, such as 0.5-5h-1.In the present invention, weight (hourly) space velocity (WHSV)
On the basis of the total amount of HTS in whole beds.
The method according to the invention, the liquid mixture preferably comprise solvent, so pass through regulation with or without solvent
The content of solvent in liquid mixture, the speed of reaction can be adjusted, make reaction more steady.The solvent can be
It is various to dissolve thioether and oxidant or promote the two to mix, the liquid substance of the enough solubilized target oxidation products of and can.One
As, the solvent can be selected from water, C1-C6Alcohol, C3-C8Ketone and C2-C6Nitrile.The instantiation of the solvent can wrap
Include but be not limited to：Water, methanol, ethanol, normal propyl alcohol, isopropanol, the tert-butyl alcohol, isobutanol, acetone, butanone and acetonitrile.Preferably, institute
State solvent and be selected from water and C1-C6Alcohol.It is highly preferred that the solvent is methanol and/or water.
The dosage of the solvent can carry out appropriate selection according to the dosage of thioether and oxidant.Usually, it is described molten
Agent and the weight ratio of the thioether can be 0.1-100：1, preferably 0.2-80：1.
The method according to the invention, desirable oxidation product be sulfoxide (such as：Dimethyl sulfoxide (DMSO)) when, preferably also include to
At least one alkaline matter is sent into the liquid mixture, the addition of the alkaline matter causes the liquid mixture pH value
In the range of 6.5-9, more preferable reaction effect can be so obtained.It is highly preferred that the addition of the alkaline matter makes
The pH value for obtaining the liquid mixture is in the range of 7-8.5.In the pH value of the liquid mixture contacted with HTS
More than 6.5 when (or being more than 7), if using alkali, the pH value of the liquid mixture is further improved, remains able to obtain
The effect above.The pH value of the liquid mixture refers in 25 DEG C and the pressure of 1 normal atmosphere, the pH of the liquid charging stock of measure
Value.
Herein, the alkaline matter refers to that the pH value of its aqueous solution is the material more than 7.The alkaline matter it is specific
Example can include but is not limited to：Ammonia (that is, NH3), amine, quaternary ammonium base and M1(OH)n(wherein, M1For alkali metal or alkaline-earth metal, n
For with M1Chemical valence identical integer).
As the alkaline matter, ammonia can be introduced in the form of liquefied ammonia, can also be introduced as an aqueous solution, can be with
Introduce in gaseous form.Concentration as the ammonia (that is, ammoniacal liquor) of aqueous solution form is not particularly limited, and can be conventional choosing
Select, such as 1-36 weight %.
As the alkaline matter, amine refers to hydrogen partial on ammonia or is all substituted the material to be formed by alkyl, including one
Level amine, secondary amine and tertiary amine.The amine is specifically as follows material and/or C shown in Formulas I3-C11Heterocyclic amine,
In Formulas I, R1、R2And R3Can be each H or C1-C6Alkyl (such as C1-C6Alkyl), and R1、R2And R3When different
For H.Herein, C1-C6Alkyl include C1-C6Straight chained alkyl and C3-C6Branched alkyl, its instantiation can include but
It is not limited to：Methyl, ethyl, n-propyl, isopropyl, normal-butyl, sec-butyl, isobutyl group, the tert-butyl group, n-pentyl, isopentyl, uncle penta
Base, neopentyl and n-hexyl.
The instantiation of amine can include but is not limited to：Methylamine, dimethylamine, trimethylamine, ethamine, diethylamine, triethylamine, just
Propylamine, di-n-propylamine, Tri-n-Propylamine, isopropylamine, diisopropylamine, n-butylamine, di-n-butyl amine, tri-n-butyl amine, sec-butyl
It is amine, diisobutyl amine, triisobutyl amine, tert-butylamine, n-amylamine, two n-amylamines, tri-n-amyl amine, neopentyl amine, iso-amylamine, two different
Amylamine, triisoamylamine, tertiary amylamine, n-hexylamine and n-octyl amine.
The heterocyclic amine is with the compound with lone pair electrons on nitrogen-atoms and the nitrogen-atoms on finger ring.The heterocycle
Amine for example can be substituted or unsubstituted pyrroles, substituted or unsubstituted nafoxidine, substituted or unsubstituted pyridine, substitution
Or unsubstituted hexahydropyridine, substituted or unsubstituted imidazoles, substituted or unsubstituted pyrazoles, substituted or unsubstituted quinoline,
Substituted or unsubstituted EEDQ, substituted or unsubstituted tetrahydroquinoline, substituted or unsubstituted decahydroquinoline, substitution or not
One or more in substituted isoquinolin and substituted or unsubstituted pyrimidine.
As the alkaline matter, quaternary ammonium base is specifically as follows the material shown in Formula II,
In Formula II, R4、R5、R6And R7Can be each C1-C6Alkyl (such as C1-C6Alkyl).The C1-C6Alkyl
Including C1-C6Straight chained alkyl and C3-C6Branched alkyl, its instantiation can include but is not limited to：Methyl, ethyl, positive third
Base, isopropyl, normal-butyl, sec-butyl, isobutyl group, the tert-butyl group, n-pentyl, neopentyl, isopentyl, tertiary pentyl and n-hexyl.
The instantiation of the quaternary ammonium base can include but is not limited to：TMAH, tetraethyl ammonium hydroxide, four
Propyl group ammonium hydroxide (including four n-propyl ammonium hydroxide and tetra isopropyl ammonium hydroxide), TBAH are (including four just
Butyl ammonium hydroxide, four sec-butyl ammonium hydroxide, four isobutyl group ammonium hydroxide and tetra-tert ammonium hydroxide) and four pentyl hydrogen-oxygen
Change ammonium.
As the alkaline matter, M1(OH)nThe hydroxide of hydroxide or alkaline-earth metal for alkali metal, such as can
Think sodium hydroxide, potassium hydroxide, magnesium hydroxide, barium hydroxide and calcium hydroxide.
The method according to the invention, the alkaline matter can be used directly, can also be configured to the alkaline matter
Used after solution.It is sent into after can alkaline matter be mixed with oxidant and optionally solvent in fixed bed reactors, it is described
Mixing can be carried out outside reactor, can also be carried out, be not particularly limited in reactor.
The method according to the invention, in the condition 1 of satisfaction, the temperature of beds is raised until oxidant conversion ratio C '
During the condition 2 of satisfaction, stop heating up and being incubated：
Condition 1, sometime the oxidant conversion ratio C under ttWith initial oxidant conversion ratio C0Ratio Ct/C0For 0.8
≤Ct/C0<1；
Condition 2, oxidant conversion ratio C ' and initial oxidant conversion ratio C0Ratio C '/C0For 0.85≤C '/C0≤1。
The method according to the invention, when oxidant conversion ratio declines, the temperature of beds is improved, enables to original
The oxidant conversion ratio of this presentation downward trend gos up, and when oxidant conversion ratio gos up to the condition 2 of satisfaction, keeps catalyst
The temperature of bed, that is, stop heating.The oxidant conversion ratio long period can so be maintained to higher level, extend titanium silicon point
The single trip use life-span of son sieve.
In condition 1, it is preferable that 0.85≤Ct/C0.When condition 1 meets above-mentioned requirements, it can more effectively extend titanium silicon
The single trip use life-span of molecular sieve.
From the angle for the complexity for reducing operation, condition 1, Ct/C0<0.9。
From the further angle for improving oxidant conversion ratio, condition 2,0.9≤C '/C0。
In the present invention, oxidant conversion ratio=(participate in mole of the oxidant of molal quantity/addition of the oxidant of reaction
Number) × 100%；
Wherein, molal quantity=molal quantity of the oxidant of addition-obtained reactant mixture of the oxidant of reaction is participated in
In remaining oxidant molal quantity.
The composition for the reactant mixture that can be exported by continuous monitoring during the course of the reaction from fixed bed reactors come
Determine oxidant conversion ratio C0、CtAnd C '.When fixed bed reactors are multiple fixed bed reactors, by with liquid mixture
On the basis of flow direction, oxidant conversion ratio is determined by the reactant mixture of the fixed bed reactors output positioned at logistics end
C0、CtAnd C '.
In the present invention, initial oxidant conversion ratio C0It is defeated from fixed bed reactors after fixed bed reactors stable operation
The composition of the first batch of reactant mixture gone out determines.For example, it will can be obtained within fixed bed reactors stable operation 0.5-10 hours
The reactant mixture arrived is as first batch of reactant mixture.
Conventional method can be used to determine the composition of the reactant mixture exported from fixed bed reactors, such as gas phase color
Spectrometry.
The method according to the invention, although in the condition 1 of satisfaction, the temperature of beds is raised until oxidant converts
Rate C ' meets condition 2, it is preferred that raising the temperature of beds with 0.01-2 DEG C/day of amplitude, so on the one hand
The longer HTS single trip use life-span can be obtained, on the other hand desirable oxidation selectivity of product can also be tieed up for a long time
Hold in higher level.It is highly preferred that the temperature of beds is raised with 0.02-1 DEG C/day of amplitude.According to the side of the present invention
Method, in tandem reaction sequence, the temperature elevation amplitude of beds can be different, and early stage can be with relatively low width in the reaction
The temperature of degree rise beds, the phase can be with the temperature of higher amplitude rise beds after the reaction.
The method of the method according to the invention, the temperature for improving beds or the temperature for maintaining beds can
Selected in a manner of according to specific plant running.Such as：Adjust the heater for being heated to beds
Service condition, adjust for being exchanged heat with the service condition of the heat transferring medium that removes reaction heat, being adjusted to beds
Save temperature of the liquid mixture and combinations thereof.
The method according to the invention, depending on the initial temperatures of beds is with the requirements for starting construction of device.Preferably, it is catalyzed
The initial temperature of agent bed is 20-50 DEG C, is so on the one hand more beneficial for practical operation, on the other hand can also obtain longer titanium
The si molecular sieves single trip use life-span.The initial temperature of beds refers to the temperature of beds when device realizes stable operation
Degree.
The method according to the invention, when the temperature to beds is adjusted, remaining reaction condition, as pressure,
Feed space velocities, raw material proportioning can keep constant.
The method according to the invention, the pressure in fixed bed reactors can be according to specific device and specific operation
Condition is selected, and is not particularly limited.Usually, in terms of gauge pressure, the pressure in fixed bed reactors can be 0-3MPa, excellent
Elect 0.1-3MPa, such as 0.5-2.5MPa as.
The method according to the invention can also include being separated the reactant mixture exported from fixed bed reactors,
To obtain desirable oxidation product (such as sulfoxide) and unreacted reactant.The method that reactant mixture is separated can be
The conventional selection of this area, is not particularly limited.The unreacted reactant isolated can recycle.
The present invention is further described with reference to embodiments, but and is not so limited present disclosure.
In following examples and comparative example, agents useful for same is commercially available chemical pure or AR；Pressure is with table
Pressure meter.
In following examples and comparative example, titanium-silicon molecular sieve TS-1 used is according to Zeolites, and 1992, Vol.12：
Prepared by the method described in 943-950, its titanium oxide content is 2.5 weight %；Hollow HTS used is purchased from lake
The trade mark of Nan Jian feldspathizations limited company is HTS hollow HTS, and its titanium oxide content is 2.5 weight %.
In following comparative example and embodiment, the content of each composition in obtained reaction solution is analyzed using gas-chromatography,
Below equation is respectively adopted on the basis of this to calculate oxidant conversion ratio, oxidant effective rate of utilization and sulfoxide selectivity：
Oxidant conversion ratio=(molal quantity for participating in the oxidant of molal quantity/addition of the oxidant of reaction) × 100%；
Oxidant effective rate of utilization=(oxidant that the molal quantity of sulfoxide/participation is reacted in obtained reactant mixture
Molal quantity) × 100%；
Sulfoxide selectivity=(molal quantity of the thioether of the molal quantity of sulfoxide/participation reaction in obtained reactant mixture) ×
100%,
Wherein, molal quantity=molal quantity of the oxidant of addition-obtained reactant mixture of the oxidant of reaction is participated in
In remaining oxidant molal quantity,
The molal quantity=molal quantity of the thioether of addition-for participating in the thioether of reaction is remaining in obtained reactant mixture
The molal quantity of thioether.
Example 4 below, 10-13 and 17 determine the activity of catalyst using following methods：
By catalyst, 36 weight % ammoniacal liquor (with NH3Meter), 30 weight % hydrogen peroxide is (with H2O2Meter), the tert-butyl alcohol and ring
Hexanone is in mass ratio=1：7.5：10：7.5：After 10 mixing at atmosheric pressure after 80 DEG C of stirring reaction 2h, by reactant mistake
Filter, is analyzed with the composition of liquid phase of the gas chromatography to obtaining, and is calculated the conversion ratio of cyclohexanone using below equation and is incited somebody to action
Its activity as the catalyst,
The conversion ratio (%) of cyclohexanone=[(mole of the mole of the cyclohexanone of addition-unreacted cyclohexanone)/
The mole of the cyclohexanone of addition] × 100%.
Embodiment 1-17 is used for the method for illustrating the present invention.
Embodiment 1
By catalyst, (for the spheric catalyst that volume average particle size is 500 μm, titanium-silicon molecular sieve TS-1 contains in catalyst
Measure as 85 weight %, the content of silica is 15 weight %, density 0.76g/cm3) it is seated in miniature isometrical fixed bed reaction
In device, beds are formed, wherein, the quantity of beds is 1 layer, and the ratio of height to diameter of beds is 10.By filling out
It is embedded in heating and insulation of the thermocouple in beds to beds and carries out observing and controlling operation.
Dimethyl sulfide, hydrogen peroxide (offer in the form of 30 weight % hydrogen peroxide) and acetone are mixed to form liquid
Mixture, the bottom of liquid mixture fixed bed reactors is sent into and flows through beds.In liquid mixture, dimethyl
The mol ratio of thioether and hydrogen peroxide is 2：1, the weight ratio of dimethyl sulfide and acetone is 1：10, the heavy space-time of dimethyl sulfide
Speed is 0.5h-1.Initial temperature in beds is 40 DEG C, is by the Stress control in fixed bed reactors in course of reaction
1MPa。
The composition for the reactant mixture that continuous monitoring exports from reactor in course of reaction, in oxidant conversion ratio CtWith
Initially (reaction is measured by sampling when proceeding to 2 hours) oxidant conversion ratio C0Ratio Ct/C0For 0.8≤Ct/C0<When 0.9, with
The temperature of 0.02-1 DEG C/day of amplitude rise beds is until oxidant conversion ratio C ' and initial oxidant conversion ratio C0's
Ratio C '/C0For 0.9≤C '/C0When≤1, stop heating up and being incubated.
The reaction of 660 hours is carried out, the temperature at the end of reaction in beds is 80 DEG C.To from anti-in course of reaction
Answer the liquid mixture exported in device to be sampled analysis, and calculate oxidant conversion ratio, oxidant effective rate of utilization and diformazan
Base sulfoxide selectivity, wherein reaction 2 hours and 660 hours obtained results listed in table 1.
Comparative example 1
Using method cacodyl oxide base thioether same as Example 1, the difference is that, do not change catalyst in course of reaction
The temperature of bed.
React 2 hours and 360 hours obtained results are listed in table 1.
Embodiment 2
Using method cacodyl oxide base thioether same as Example 1, the difference is that, also it is sent into fixed bed reactors
Ammoniacal liquor (concentration is 25 weight %), by the pH value of the liquid mixture formed by dimethyl sulfide, hydrogen peroxide and acetone by
5.2 are adjusted to 7.5.
The reaction of 700 hours is carried out, the temperature at the end of reaction in beds is 75 DEG C.Reaction 2 hours and 700 small
When obtained result listed in table 1.
Embodiment 3
Using method cacodyl oxide base thioether same as Example 1, the difference is that, the HTS in catalyst
TS-1 replaces that (density of catalyst is 0.69g/cm with the hollow HTS of equivalent3)。
The reaction of 690 hours is carried out, the temperature at the end of reaction in beds is 75 DEG C.Reaction 2 hours and 690 small
When obtained result listed in table 1.
Embodiment 4
Using method cacodyl oxide base thioether same as Example 1, the difference is that, catalyst is from cyclohexanone oxamidinating
The preformed catalyst (it is same as Example 1 to form the fresh catalyst that this draws off agent) that course of reaction is drawn off is regenerated and obtained
, regeneration condition is：4h is calcined in air atmosphere at 550 DEG C.The activity of regenerated catalyst is 50%, and it is when fresh
Activity be 95%.
The reaction of 700 hours is carried out, the temperature at the end of reaction in beds is 72 DEG C.Reaction 2 hours and 700 small
When obtained result listed in table 1.
Embodiment 5
Using method cacodyl oxide base thioether same as Example 1, the difference is that, catalyst general assembly in the reactor
Under conditions of the amount of filling out is constant, first filling in the reactor catalyst C1 same as Example 3, then load and embodiment 1
Identical catalyst C2 (that is, liquid mixture firstly flows through hollow HTS, again passes through titanium-silicon molecular sieve TS-1), wherein,
C1 and C2 weight ratio is 2：1.
The reaction of 720 hours is carried out, the temperature at the end of reaction in beds is 68 DEG C.Reaction 2 hours and 720 small
When obtained result listed in table 1.
Embodiment 6
Using method cacodyl oxide base thioether same as Example 5, the difference is that, it is constant in C1 and C2 loadings
Under the conditions of, C2 is first loaded in the reactor, and (that is, liquid mixture firstly flows through titanium-silicon molecular sieve TS-1 to reloading C1, again passes through sky
Heart HTS).
The reaction of 660 hours is carried out, the temperature at the end of reaction in beds is 79 DEG C.Reaction 2 hours and 660 small
When obtained result listed in table 1.
Embodiment 7
Using method cacodyl oxide base thioether same as Example 5, the difference is that, it is constant in the total filling amount of catalyst
Under conditions of, the weight ratio for making C1 and C2 is 1：1.
The reaction of 680 hours is carried out, the temperature at the end of reaction in beds is 76 DEG C.Reaction 2 hours and 680 small
When obtained result listed in table 1.
Embodiment 8
Using method cacodyl oxide base thioether same as Example 5, the difference is that, it is constant in the total filling amount of catalyst
Under conditions of, the weight ratio for making C1 and C2 is 8：1.
The reaction of 720 hours is carried out, the temperature at the end of reaction in beds is 66 DEG C.Reaction 2 hours and 720 small
When obtained result listed in table 1.
Embodiment 9
Using method cacodyl oxide base thioether same as Example 8, the difference is that, it is constant in the total filling amount of catalyst
Under conditions of, the weight ratio for making C1 and C2 is 20：1.
The reaction of 690 hours is carried out, the temperature at the end of reaction in beds is 79 DEG C.Reaction 2 hours and 690 small
When obtained result listed in table 1.
Table 1
Using embodiment 1 compared with comparative example 1 as can be seen that using the present invention method can effectively extend as
The single trip use life-span of the HTS of catalyst.
By embodiment 1 as can be seen that passing through the liquid mixture that will be contacted with HTS compared with embodiment 2
PH value be adjusted to be in the range of 6.5-9, more preferable reaction effect can be obtained, and further extend HTS
The single trip use life-span.
Embodiment 5-9's as a result, it was confirmed that hollow HTS is applied in combination with titanium-silicon molecular sieve TS-1, and with liquid
On the basis of the flow direction of mixture, hollow HTS is located at the upstream of titanium-silicon molecular sieve TS-1, can obtain into one
The HTS single trip use extended is walked, and reduces the elevation amplitude of reaction bed temperature.
Embodiment 10-16 is related to following six kinds of catalyst.
C3：The hollow HTS of shaping drawn off from propylene ring oxidation reaction process (is 200 μm for volume average particle size
Spheric catalyst, density 0.67g/cm3) regenerated obtained from, the catalyst contains 85 weight % hollow titanium silicon
Molecular sieve, 15 weight % silica, regeneration condition are：4h is calcined in air atmosphere at 570 DEG C.Regenerated catalyst
Activity be 30% (its activity when fresh is 96%).
C4：The shaping titanium-silicon molecular sieve TS-1 drawn off from propylene ring oxidation reaction process (is 200 μm for volume average particle size
Spheric catalyst, density 0.75g/cm3) regenerated obtained from, the catalyst contains 85 weight % titanium silicon molecule
TS-1,15 weight % silica are sieved, regeneration condition is：4h is calcined in air atmosphere at 570 DEG C.Regenerated catalyst
Activity be 30% (its activity when fresh is 95%).
C5：Form the C1 hollow HTS of fresh shaping.
C6：Form C2 fresh shaping titanium-silicon molecular sieve TS-1.
C7：The hollow HTS of fresh shaping, is the spheric catalyst that volume average particle size is 500 μm, the catalyst
Hollow HTS containing 75 weight %, 25 weight % silica, density 0.68g/cm3。
C8：Fresh shaping titanium-silicon molecular sieve TS-1, is the spheric catalyst that volume average particle size is 500 μm, the catalyst
Titanium-silicon molecular sieve TS-1 containing 75 weight %, 25 weight % silica, density 0.71g/cm3。
Embodiment 10
Carried out in the reducing fixed bed reactors with two beds.With the stream of liquid charging stock in the reactor
On the basis of dynamic direction, the beds positioned at upstream are referred to as the first beds, the beds positioned at downstream claim
It is the internal diameter transition region of taper for the second beds, between two beds, wherein not loading catalyst.First urges
Agent bed and the equal loading catalyst C3 of the second beds, the loaded catalyst in the first beds are urged with second
The weight ratio of loaded catalyst in agent bed is 5：1, the internal diameter of the first beds and the second beds
The ratio of internal diameter is 2：1.Heat of the landfill in beds is respectively adopted in first beds and the second beds
Heating and insulation of the galvanic couple to beds carry out observing and controlling operation, and the temperature control of two beds is identical.
By dimethyl sulfide, hydrogen peroxide (offer in the form of 30 weight % hydrogen peroxide), (concentration is 24 weights to ammoniacal liquor
Amount %) and methanol be mixed to form liquid mixture, by the liquid mixture from bottom feeding fixed bed reactors in and flow successively
Cross the first beds and the second beds.Wherein, the mol ratio of dimethyl sulfide and hydrogen peroxide is 3：1, diformazan
The weight of base thioether and methanol ratio is 1：10, the dosage of ammoniacal liquor mixes the liquid formed by dimethyl sulfide, hydrogen peroxide and methanol
The pH value of compound is adjusted to 8.5 by 5.8, and the weight (hourly) space velocity (WHSV) of dimethyl sulfide is 2.0h-1.First beds and the second catalysis
Initial temperature in agent bed is 45 DEG C, by the Stress control in fixed bed reactors is 2.0MPa in course of reaction.
The composition for the reactant mixture that continuous monitoring exports from reactor in course of reaction, in oxidant conversion ratio CtWith
Initially (reaction is measured by sampling when proceeding to 2 hours) oxidant conversion ratio C0Ratio Ct/C0For 0.85≤Ct/C0<When 0.9, with
The temperature of 0.01-2 DEG C/day of amplitude rise beds is until oxidant conversion ratio C ' and initial oxidant conversion ratio C0's
Ratio C '/C0For 0.9≤C '/C0≤1。
The reaction of 750 hours is carried out, the temperature at the end of reaction in beds is 72 DEG C.Reaction 2 hours and 750 small
When obtained oxidant conversion ratio, oxidant effective rate of utilization and dimethyl sulfoxide (DMSO) selectively listed in table 2.
Embodiment 11
Using method cacodyl oxide base thioether same as in Example 10, the difference is that, urging in the second beds
Agent C3 is replaced by the catalyst C4 of equivalent.The reaction of 900 hours is carried out, the temperature at the end of reaction in beds is 68
℃.2 hours and 900 hours obtained oxidant conversion ratios, oxidant effective rate of utilization and dimethyl sulfoxide (DMSO) selectivity is reacted to exist
Listed in table 2.
Embodiment 12
Using with the identical method cacodyl oxide base thioether of embodiment 11, unlike, urging in the second beds
Under conditions of agent C4 loadings are constant, make the internal diameter of the second beds identical with the internal diameter of the first beds,
I.e. the ratio of the internal diameter of the first beds and the second beds is 1：1.The reaction of 800 hours is carried out, reaction terminates
When beds in temperature be 74 DEG C.It is effectively sharp to react oxidant conversion ratio, the oxidant obtained for 2 hours and 800 hours
Listed with rate and dimethyl sulfoxide (DMSO) selectivity in table 2.
Embodiment 13
Dimethyl sulfoxide (DMSO) is produced using with the identical method of embodiment 11, unlike, the first beds and second
Under conditions of catalyst type and loadings in beds keep constant, the internal diameter of the second beds is improved,
It is 1 to make the ratio of the internal diameter of the first beds and the internal diameter of the second beds：2.The reaction of 780 hours is carried out, instead
Temperature at the end of answering in beds is 70 DEG C.React 2 hours and 780 hours obtained oxidant conversion ratio, oxidants
Effective rate of utilization and dimethyl sulfoxide (DMSO) are selectively listed in table 2.
Embodiment 14
Dimethyl sulfoxide (DMSO) is produced using with the identical method of embodiment 11, unlike, urging in the first beds
Agent C3 is replaced with the catalyst C5 of equivalent, and the catalyst C4 in the second beds is replaced with the catalyst C6 of equivalent.Enter
The row reaction of 880 hours, the temperature at the end of reaction in beds are 71 DEG C.React 2 hours and 880 hours obtained oxygen
Agent conversion ratio, oxidant effective rate of utilization and dimethyl sulfoxide (DMSO) are selectively listed in table 2.
Embodiment 15
Dimethyl sulfoxide (DMSO) is produced using method same as Example 9, unlike, load and urge in the first beds
Agent C7, loading catalyst C8 in the second beds, loaded catalyst and the second catalysis in the first beds
The weight ratio of loaded catalyst in agent bed is 10：1, the internal diameter of the first beds is interior with the second beds
The ratio in footpath is 4：1.
Dimethyl sulfide, dicumyl peroxide, pyridine and acetonitrile are mixed to form liquid mixture, by the liquid mixture
It is sent into from bottom in fixed bed reactors and flows successively through the first beds and the second beds.Wherein, dimethyl
The mol ratio of thioether and dicumyl peroxide is 1：1, the weight ratio of dimethyl sulfide and acetonitrile is 1：50, the dosage of pyridine will be by
The pH value for the liquid mixture that dimethyl sulfide, dicumyl peroxide and acetonitrile are formed is adjusted to 8.0 by 5.9, dimethyl sulfide
Weight (hourly) space velocity (WHSV) be 1.0h-1.Initial temperature in first beds and the second beds is 45 DEG C, in course of reaction
It is 1.8MPa by the Stress control in fixed bed reactors.
The composition for the reactant mixture that continuous monitoring exports from reactor in course of reaction, in oxidant conversion ratio CtWith
Initially (reaction is measured by sampling when proceeding to 2 hours) oxidant conversion ratio C0Ratio Ct/C0For 0.85≤Ct/C0<When 0.9, with
The temperature of 0.01-2 DEG C/day of amplitude rise beds is until oxidant conversion ratio C ' and initial oxidant conversion ratio C0's
Ratio C '/C0For 0.9≤C '/C0≤1。
The reaction of 800 hours is carried out, the temperature at the end of reaction in beds is 76 DEG C.Reaction 2 hours and 800 small
When obtained oxidant conversion ratio, oxidant effective rate of utilization and dimethyl sulfoxide (DMSO) selectively listed in table 2.
Embodiment 16
Dimethyl sulfoxide (DMSO) is produced using with the identical method of embodiment 15, unlike, improve the first beds
Internal diameter, it is 6 to make the ratio of the internal diameter of the first beds and the internal diameter of the second beds：1.Carry out 760 hours anti-
Should, the temperature at the end of reaction in beds is 75 DEG C.React 2 hours and 760 hours obtained oxidant conversion ratio, oxygen
Agent effective rate of utilization and dimethyl sulfoxide (DMSO) are selectively listed in table 2.
Table 2
Table 2 as a result, it was confirmed that make liquid mixture successively contacted instead with hollow HTS and titanium-silicon molecular sieve TS-1
At once, liquid mixture is made to be less than the apparent speed by titanium-silicon molecular sieve TS-1 by the superficial velocity in hollow HTS
Degree, it can further extend the single trip use life-span of HTS.
Embodiment 17
The catalyst used in the present embodiment is the shaping HTS TS- that will be drawn off from phenol hydroxylation course of reaction
Obtained from 1 is regenerated (for the spheric catalyst that volume average particle size is 850 μm), the catalyst contains 80 weight % titanium
The silica of silicalite TS-1 and 20 weight %, regeneration condition are：4h is calcined in air atmosphere at 570 DEG C.After regeneration
The activity of catalyst be 40% (its activity when fresh is 95%).
By Catalyst packing in fixed bed reactors, beds are formed, wherein, the quantity of beds is 1
Layer, the ratio of height to diameter of beds is 20.By fill heating of the thermocouple to beds in beds and
Insulation carries out observing and controlling operation.
It is sent into fixed bed reactors and flows through after thioanisole, TBHP, methanol and pyridine are mixed and urges
Agent bed.Wherein, the mol ratio of thioanisole and TBHP is 2：1, the weight ratio of thioanisole and methanol is
1：10, the dosage of pyridine adjusts the pH value of the liquid mixture formed by thioanisole, TBHP and methanol by 6.4
Save as 8.0, the weight (hourly) space velocity (WHSV) of thioanisole is 2.0h-1.Initial temperature in beds is 50 DEG C, will be solid in course of reaction
Pressure in fixed bed reactor remains 2.5MPa.
The composition for the reactant mixture that continuous monitoring exports from reactor in course of reaction, in oxidant conversion ratio CtWith
Initially (reaction is measured by sampling when proceeding to 2 hours) oxidant conversion ratio C0Ratio Ct/C0For 0.8≤Ct/C0<When 0.9, with
The temperature of 0.02-1 DEG C/day of amplitude rise beds is until oxidant conversion ratio C ' and initial oxidant conversion ratio C0's
Ratio C '/C0For 0.9≤C '/C0When≤1, stop heating up and being incubated.
The reaction of 800 hours is carried out, the temperature at the end of reaction in beds is 82 DEG C.Reaction 2 hours and 800 small
When obtained oxidant conversion ratio, oxidant effective rate of utilization and sulfoxide selectively listed in table 3.
Table 3
Embodiment 4,10-13's and 17 using agent is drawn off as catalyst, method of the invention as a result, it was confirmed that even if also can
Preferable reaction effect is enough obtained, and higher oxidant effective rate of utilization can be obtained, realize waste catalyst has
Effect recycles.
Claims (21)
1. a kind of sulfide oxidation method, this method includes being continuously introduced into a kind of liquid mixture into fixed bed reactors, makes institute
The beds that liquid mixture flows through the fixed bed reactors under oxidation reaction condition are stated, with being seated in described urge
HTS contact in agent bed, the liquid mixture contain thioether, at least one oxidant and it is optional extremely
A kind of few solvent, the thioether is dimethyl sulfide or thioanisole, and the oxidant is peroxide, wherein, this method is also
When being included in the condition 1 of satisfaction, the temperature of beds is raised until when oxidant conversion ratio C ' meets condition 2, stops heating
And it is incubated：
Condition 1, sometime the oxidant conversion ratio C under ttWith initial oxidant conversion ratio C0Ratio Ct/C0For 0.8≤Ct/
C0<1；
Condition 2, oxidant conversion ratio C ' and initial oxidant conversion ratio C0Ratio C '/C0For 0.85≤C '/C0≤1。
2. the method according to claim 11, wherein, in condition 1,0.85≤Ct/C0<0.9。
3. method according to claim 1 or 2, wherein, in condition 2,0.9≤C '/C0。
4. according to the method for claim 1, wherein, the beds contain the first beds and the second catalysis
Agent bed, on the basis of the flow direction of the liquid mixture, first beds are located at second catalyst
The upstream of bed, the HTS of the first beds filling is hollow HTS, and the hollow titanium silicon divides
Son sieve is the HTS of MFI structure, and the crystal grain of the HTS is hollow-core construction, the chamber portion of the hollow-core construction
Radical length is 5-300 nanometers, and the HTS is in 25 DEG C, P/P0=0.10, adsorption time is to be surveyed under conditions of 1 hour
Benzene adsorbance be at least 70 milligrams per grams, the adsorption isotherm and desorption isotherm of the nitrogen absorption under low temperature of the HTS
Between hysteresis loop be present；
The HTS of the second beds filling is titanium-silicon molecular sieve TS-1.
5. according to the method for claim 4, the hollow HTS of first beds filling and described the
The weight ratio of the titanium-silicon molecular sieve TS-1 of two beds filling is 1-20：1.
6. the method according to claim 11, wherein, the hollow HTS of the first beds filling and institute
The weight ratio for stating the titanium-silicon molecular sieve TS-1 of the second beds filling is 2-10：1.
7. according to the method described in any one in claim 4-6, wherein, the liquid mixture flows through the first catalyst bed
The superficial velocity of layer is v1, the superficial velocity for flowing through the second beds is v2, v1＜ v2。
8. the method according to claim 11, wherein, v2/v1=1.5-10.
9. the method according to claim 11, wherein, v2/v1=2-5.
10. according to the method described in any one in claim 4-6, wherein, the liquid mixture is in the catalyst bed
Residence time in layer is T, and the residence time in first beds is T1, T1/ T=0.4-0.9.
11. according to the method for claim 7, wherein, during stop of the liquid mixture in the beds
Between be T, the residence time in first beds is T1, T1/ T=0.4-0.9.
12. according to the method described in any one in claim 1 and 4-6, wherein, at least part HTS is through regeneration
The agent that draws off using HTS as the reaction unit of catalyst, it is described to draw off agent and being drawn off for Ammoximation reaction device
Agent, the one or more drawn off in agent for drawing off agent and epoxidation reaction device of hydroxylating device.
13. according to the method for claim 7, wherein, at least part HTS is with HTS through regeneration
Reaction unit as catalyst draws off agent, described to draw off agent and draw off agent, hydroxylating dress for Ammoximation reaction device
That puts draws off the one or more drawn off in agent of agent and epoxidation reaction device.
14. according to the method for claim 10, wherein, at least part HTS is with HTS through regeneration
Reaction unit as catalyst draws off agent, described to draw off agent and draw off agent, hydroxylating dress for Ammoximation reaction device
That puts draws off the one or more drawn off in agent of agent and epoxidation reaction device.
15. according to the method described in any one in claim 1,2 and 4-6, wherein, the initial temperature of beds is
20-50 DEG C, the temperature of beds is raised with 0.01-2 DEG C/day of amplitude.
16. according to the method for claim 1, wherein, the mol ratio of the thioether and the oxidant is 0.1-20：1, sulphur
The weight (hourly) space velocity (WHSV) of ether is 0.1-20h-1；In terms of gauge pressure, pressure 0-3MPa.
17. according to the method described in any one in claim 1,2,4-6 and 10, wherein, the oxidant be hydrogen peroxide,
One or both of TBHP, dicumyl peroxide, cyclohexyl hydroperoxide, Peracetic acid and Perpropionic Acid with
On.
18. according to the method described in any one in claim 1,2,4-6 and 10, wherein, this method is also included to the liquid
At least one alkali is sent into body mixture, the feeding amount of the alkali to be in 6.5-9's with the pH value of the liquid mixture
In the range of.
19. according to the method for claim 7, wherein, this method also includes being sent at least one into the liquid mixture
Kind alkali, the feeding amount of the alkali to be in the range of 6.5-9 with the pH value of the liquid mixture.
20. according to the method for claim 10, wherein, this method also includes being sent at least one into the liquid mixture
Kind alkali, the feeding amount of the alkali to be in the range of 6.5-9 with the pH value of the liquid mixture.
21. according to the method for claim 12, wherein, this method also includes being sent at least one into the liquid mixture
Kind alkali, the feeding amount of the alkali to be in the range of 6.5-9 with the pH value of the liquid mixture.
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