CN105439919A - A thioether oxidizing method - Google Patents
A thioether oxidizing method Download PDFInfo
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- CN105439919A CN105439919A CN201410426082.6A CN201410426082A CN105439919A CN 105439919 A CN105439919 A CN 105439919A CN 201410426082 A CN201410426082 A CN 201410426082A CN 105439919 A CN105439919 A CN 105439919A
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Abstract
A thioether oxidizing method is disclosed. The method includes continuously feeding a liquid mixture into a fixed-bed reactor to allow the liquid mixture to flow through a catalyst bed layer under oxidizing reaction conditions and to be in contact with a titanium silicalite molecular sieve in the catalyst bed layer, wherein the liquid mixture comprises thioether, at least one oxidant and at least one optional solvent. The method also includes raising the temperature of the catalyst bed layer when the conversion ratio of the oxidant decreases to a certain degree until the conversion ratio of the oxidant reaches a desired value, and maintaining the temperature. The method effectively prolongs the single-pass service lifetime of the titanium silicalite molecular sieve, reduces the regeneration frequency of the titanium silicalite molecular sieve and increases the production efficiency of devices.
Description
Technical field
The present invention relates to a kind of sulfide oxidation method.
Background technology
Sulfoxides is important sulfocompound, if dimethyl sulfoxide (DMSO) (DMSO) is a kind of organic compounds containing sulfur, is colourless transparent liquid under normal temperature, has the characteristics such as high polarity, high-hygroscopicity, flammable and high boiling point be non-proton.Dimethyl sulfoxide (DMSO) is water-soluble, ethanol, acetone, EC, is the inert solvent that polarity is strong, is widely used as solvent and reaction reagent.And, dimethyl sulfoxide (DMSO) has very high selective extraction method ability, can be used as the Extraction solvent that alkane is separated with aromatic hydrocarbon, such as: dimethyl sulfoxide (DMSO) can be used for the extracting of aromatic hydrocarbons or divinyl, as process solvent and the solvent that reels off raw silk from cocoons in acrylonitrile polymerization reaction, as synthetic and the solvent that reels off raw silk from cocoons of urethane, as the synthetic of polymeric amide, fluoroaluminate glasses, polyimide and polysulfones.Meanwhile, in medicine industry, dimethyl sulfoxide (DMSO) not only directly as raw material and the carrier of some drugs, and can also play the effects such as anti-inflammatory analgetic, diuresis, calmness, and therefore the active ingredient of Chang Zuowei analgesic drug product makes an addition in medicine.In addition, dimethyl sulfoxide (DMSO) also can be used as capacitor dielectric, frostproofer, brake solution, rare metal extracting agent etc.
At present, sulfoxide generally adopts sulfide oxidation method to obtain, and operable oxygenant comprises nitric acid, superoxide and ozone etc.
When adopting oxygenant (particularly superoxide) by sulfide oxidation, if use HTS as catalyzer, the transformation efficiency of oxygenant and the selectivity of desirable oxidation product can be improved.But with the prolongation in reaction times, the catalytic activity of HTS can be on a declining curve, oxygenant transformation efficiency and desirable oxidation selectivity of product is caused obviously to reduce.When react carry out in fixed-bed reactor time, because titanium molecular sieve catalysis activity reduces, need HTS to regenerate in reactor or outside reactor, cause reactor down-time, thus affect production efficiency and improve the running cost of device.
Therefore, for reacting using HTS as the sulfide oxidation of catalyzer, how to extend the one way work-ing life of the HTS as catalyzer, reducing regeneration frequency is enhance productivity and one of key link reducing running cost.
Summary of the invention
The object of the invention is to the sulfide oxidation reaction above shortcomings solved using HTS as catalyzer, provide a kind of sulfide oxidation method, the method can one way work-ing life of extending catalyst effectively, reduces regeneration frequency.
The invention provides a kind of sulfide oxidation method, the method comprises sends into a kind of liquid mixture continuously in fixed-bed reactor, make described liquid mixture under oxidation reaction condition, flow through the beds of described fixed-bed reactor, to contact with the HTS be seated in described beds, described liquid mixture contains thioether, at least one oxygenant and optional at least one solvent, wherein, when the method is also included in and satisfies condition 1, raise beds temperature until oxygenant transformation efficiency C ' satisfy condition 2 time, stop heating up and being incubated:
Oxygenant transformation efficiency C under condition 1, sometime t
twith initial oxidant transformation efficiency C
0ratio C
t/ C
0be 0.8≤C
t/ C
0<1;
Condition 2, oxygenant transformation efficiency C ' and initial oxidant transformation efficiency C
0ratio C '/C
0be 0.85≤C '/C
0≤ 1.
According to method of the present invention, the one way work-ing life of the HTS as catalyzer effectively can be extended, thus the parallel-adder settle-out time of extension fixture effectively.Of the present invention method is simple, is beneficial to suitability for industrialized production application.
Embodiment
The invention provides a kind of sulfide oxidation method, the method comprises sends into a kind of liquid mixture continuously in fixed-bed reactor, make described liquid mixture under oxidation reaction condition, flow through the beds of described fixed-bed reactor, to contact with the HTS be seated in described beds, described liquid mixture contains thioether, at least one oxygenant and optional at least one solvent.
In the present invention, " at least one " represents one or more, and " optionally " represents inessential, can be understood as containing or does not contain.
According to method of the present invention, described thioether can be the various compounds containing-S-key, and preferred described thioether is selected from the thioether that carbonatoms is 2-18, is more preferably dimethyl thioether or thioanisole.
According to method of the present invention, described oxygenant can be common various can by the material of sulfide oxidation.Method of the present invention is specially adapted to the occasion carrying out oxidizing sulfur ether using superoxide as oxygenant, can significantly improve the effective rate of utilization of superoxide like this.Described superoxide refers to the compound containing-O-O-key in molecular structure, can be selected from hydrogen peroxide, organo-peroxide and peracid.Described organo-peroxide refers to that one or two hydrogen atom in hydrogen peroxide molecule is replaced by organic group and the material obtained.Described peracid refers to the organic oxacid containing-O-O-key in molecular structure.In the present invention, the specific examples of described oxygenant can include but not limited to: hydrogen peroxide, tertbutyl peroxide, dicumyl peroxide, cyclohexyl hydroperoxide, Peracetic Acid and Perpropionic Acid.Preferably, described oxygenant is hydrogen peroxide, can reduce separation costs further like this.
The hydrogen peroxide existed in a variety of manners that described hydrogen peroxide can be commonly used for this area.From the angle improved further according to the security of method of the present invention, preferably use the hydrogen peroxide existed as an aqueous solution according to method of the present invention.According to method of the present invention, when described hydrogen peroxide provides as an aqueous solution, the concentration of described aqueous hydrogen peroxide solution can be the normal concentration of this area, such as: 20-80 % by weight.The aqueous solution that concentration meets the hydrogen peroxide of above-mentioned requirements can adopt ordinary method to prepare, and also can be commercially available, such as: can for can be commercially available the hydrogen peroxide of 30 % by weight, the hydrogen peroxide of 50 % by weight or 70 % by weight hydrogen peroxide.
The consumption of described oxygenant can be conventional selection, is not particularly limited.Usually, the mol ratio of thioether and oxygenant can be 0.1-20:1.When desirable oxidation product is sulfoxide (as dimethyl sulfoxide (DMSO)), from the angle improving selectivity of product further, thioether (as dimethyl thioether) can be 0.2-10:1 with the mol ratio of oxygenant, is preferably 0.5-5:1, is more preferably 1-5:1.
According to method of the present invention, using HTS as catalyzer.HTS is the general name that titanium atom replaces a class zeolite of a part of Siliciumatom in lattice framework, can use chemical formula xTiO
2siO
2represent.The present invention is not particularly limited for the content of titanium atom in HTS, can be that the routine of this area is selected.Particularly, x can be 0.0001-0.05, is preferably 0.01-0.03, is more preferably 0.015-0.025.
Described HTS can for the common HTS with various topological framework, such as: described HTS can for being selected from the HTS (as TS-1) of MFI structure, the HTS (as TS-2) of MEL structure, the HTS (as Ti-Beta) of BEA structure, the HTS (as Ti-MCM-22) of MWW structure, the HTS of hexagonal structure is (as Ti-MCM-41, Ti-SBA-15), the HTS (as Ti-MOR) of MOR structure, one or more in the HTS (as Ti-TUN) of TUN structure and the HTS (as Ti-ZSM-48) of other structure.
Preferably, described HTS be selected from the HTS of the HTS of MFI structure, the HTS of MEL structure and BEA structure one or more.More preferably, described HTS is the HTS of MFI structure, as TS-1 molecular sieve.
More preferably, described HTS is the HTS of MFI structure, and the crystal grain of this HTS is hollow structure, and the radical length of the chamber portion of this hollow structure is 5-300 nanometer, and described HTS is at 25 DEG C, P/P
0=0.10, adsorption time is that the benzene adsorptive capacity recorded under the condition of 1 hour is at least 70 milligrams/grams, there is hysteresis loop between the adsorption isothermal line of the nitrogen absorption under low temperature of this HTS and desorption isotherm.Herein, the HTS with this structure is called hollow HTS.Described hollow HTS can be commercially available (be such as purchased from the trade mark of Hunan Jianchang Petrochemical Co., Ltd be the molecular sieve of HTS), also method can prepare disclosed in CN1132699C.
According to method of the present invention, the quantity of described beds can be one or more.When the quantity of beds is multiple, the different zones of fixed-bed reactor can be positioned at, also can be arranged in multiple fixed-bed reactor.
In one embodiment of the invention, described beds contains the first beds and the second beds, with the flow direction of described liquid mixture for benchmark, described first beds is positioned at the upstream of described second beds, namely described liquid mixture first flows through the first beds, then flows through the second beds.Described first beds can, for identical, also can be different with the kind of the HTS of loading in described second beds.Preferably, the HTS of described first beds filling is hollow HTS.More preferably, the HTS of described first beds filling is hollow HTS, and the HTS of described second beds filling is titanium-silicon molecular sieve TS-1, can extend the one way work-ing life of HTS so further.
When described beds contains the first beds and the second beds, the weight ratio of the HTS of loading in the HTS of loading in described first beds and described second beds can be 1-20:1.The HTS of loading at described first beds is hollow HTS, when the HTS of described second beds filling is titanium-silicon molecular sieve TS-1, the weight ratio of the titanium-silicon molecular sieve TS-1 loaded in the hollow HTS of loading in described first beds and described second beds is preferably 2-10:1, can obtain higher desirable oxidation selectivity of product like this.
When described beds contains the first beds and the second beds, described first beds and the second beds can contain one or more beds separately.When the first beds and/or the second beds contain multiple beds, can for being connected in series between multiple beds, also can for being connected in parallel, can also be series connection and combination in parallel, such as: multiple beds is divided into many groups, beds often in group for being connected in series and/or being connected in parallel, for being connected in series and/or being connected in parallel between each group.Described first beds and described second beds can be arranged on the different zones of same reactor, also can be arranged in different reactors.
When described beds contains the first beds and the second beds, it can, for identical, also can be different that described liquid mixture flows through the first beds with the superfacial velocity of the second beds.Preferably, described liquid mixture flows through the superfacial velocity of the first beds is v
1, the superfacial velocity flowing through the second beds is v
2, wherein, v
1<v
2, the one way work-ing life of HTS can be extended so further.More preferably, v
2/ v
1=1.5-10.Further preferably, v
2/ v
1=2-5.
In the present invention, described superfacial velocity (flow velocity) to refer in the unit time by the area of the mass rate (in kg/s) of the liquid mixture of beds whole process and a certain cross section of beds (with m
2meter) ratio.The quality of the liquid mixture of fixed-bed reactor can will be sent into as " by the mass rate of the liquid mixture of whole beds in the unit time " in unit time.In the present invention, particular requirement be there is no for the superfacial velocity of liquid mixture in the first beds, generally can at 0.001-200kg/ (m
2s) in scope.
Various method can be adopted to regulate the superfacial velocity of described liquid mixture in the first beds and the second beds.Such as, the superfacial velocity of regulates liquid mixture can be carried out by the cross-sectional area of selecting catalyst bed.Particularly, the cross-sectional area of described first beds can be made to be greater than the cross-sectional area of described second beds, thus to make v
1< v
2, preferably make v
2/ v
1for 1.5-10, more preferably make v
2/ v
1for 2-5.Superfacial velocity according to expection determines that the method for the cross-sectional area of beds is known in those skilled in the art, no longer describes in detail herein.
When described beds contains the first beds and the second beds, the residence time of described liquid mixture in the first beds is T
1, the total residence time in beds is T, usually, and T
1/ T=0.3-0.96.Preferably, T
1/ T=0.4-0.9 is (as T
1/ T=0.5-0.85), like this in long-time continuous operational process, higher oxygenant transformation efficiency can be obtained, and desirable oxidation selectivity of product is maintained higher level.
According to method of the present invention, when beds contains the first beds and the second beds, material can be supplemented as the case may be between the first beds and the second beds, when the first beds and/or the second beds are multiple beds, fresh material can be supplemented between the first beds and/or between the second beds in described liquid mixture as the case may be.Such as: between the first beds and the second beds, between the first beds and/or between the second beds, supplement thioether, oxygenant and/or solvent.But, it should be noted that, (namely described liquid mixture flows through whole beds of the first beds, the whole process of the first beds) and the second beds whole beds (namely, the whole process of the second beds), described liquid mixture not included in the fresh material introduced between the first beds, between the second beds and between the first beds and the second beds, previously described superfacial velocity is determined by described liquid mixture, is not subject to the impact whether introducing fresh material.
According to method of the present invention, when described beds contains the first beds and the second beds, described first beds can be identical with the reaction conditions of the second beds, also can be different.From the angle of ease-to-operate, described first beds is identical with the reaction conditions between the second beds.
In the various reactions adopting HTS as catalyzer (referring generally to the reaction of non-sulfide oxidation) device, as Ammoximation reaction, in hydroxylating and epoxidation reaction device, usually after plant running for some time, the catalytic activity of catalyzer declines, need to carry out in device or ex-situ regeneration, even if when carry out regenerating also be difficult to obtain satisfied active time, catalyzer is needed to draw off (namely from device, more catalyst changeout), and the catalyzer drawn off (namely, drawing off agent or spent catalyst) current treatment process normally piles up and buries, occupy valuable land resources and inventory space on the one hand, HTS production cost is higher on the other hand, directly pass into disuse and also result in great waste.
The present inventor finds in research process, regenerates if these are drawn off agent, using the catalyzer that the regenerator obtained uses in the inventive method, still can obtain high catalytic activity.
According to method of the present invention, in a preferred embodiment, at least part of HTS be through regeneration the reaction unit (referring generally to non-sulfide oxidation reaction unit) using HTS as catalyzer draw off agent, draw off such as agent can for Ammoximation reaction device draw off agent, hydroxylating device draw off agent and epoxidation reaction device draw off in agent one or more, what be specifically as follows cyclohexanone oxamidinating reaction unit draws off agent, phenol hydroxylation reaction unit draw off agent and propylene ring oxidation reaction device draw off in agent one or more.
Being not particularly limited drawing off the condition that agent carries out regenerating, appropriate selection can being carried out according to the source drawing off agent, such as: high-temperature roasting and/or solvent wash.
The activity drawing off agent through regeneration is different according to its source.Usually, the activity drawing off agent through regeneration can be the 5-95% of its activity (that is, the activity of fresh dose) when fresh.Preferably, the activity drawing off agent through regeneration can be the 10-90% of its activity when fresh, is more preferably the 10-60% of its activity when fresh.When the activity drawing off agent through regeneration is the 10-60% of its activity when fresh, gratifying oxygenant transformation efficiency and desirable oxidation selectivity of product can not only be obtained, and the oxygenant effective rate of utilization improved further can be obtained, in tandem reaction sequence, the activity of catalyzer is more stable.Further preferably, through the activity drawing off agent of regeneration be the 30-55% of its activity when fresh.The activity of described fresh titanium si molecular sieves is generally more than 95%.
Described activity measures by the following method: will draw off through regeneration the catalyzer that agent and fresh dose are used as cyclohexanone oxamidinating reaction respectively, the condition of this Ammoximation reaction is: catalyzer (in HTS), 36 % by weight ammoniacal liquor (with NH
3meter), the hydrogen peroxide of 30 % by weight is (with H
2o
2meter), the trimethyl carbinol and pimelinketone 1:7.5:10:7.5:10 in mass ratio, at atmosheric pressure in 80 DEG C of reaction 2h.Calculate with the transformation efficiency drawing off pimelinketone when agent and fresh dose are catalyzer through regeneration respectively, and it can be used as the activity drawing off agent and fresh dose through regeneration respectively, wherein, transformation efficiency=[molar weight of the pimelinketone of (molar weight of the molar weight-unreacted pimelinketone of the pimelinketone added)/add] × 100% of pimelinketone.
Be that when drawing off agent through the reaction unit of regeneration, with the total amount of described catalyzer for benchmark, the content that the reaction unit through regeneration draws off agent is preferably more than 5 % by weight, can obtain higher catalytic activity like this at least part of catalyzer.According to method of the present invention, even if all catalyzer is when the reaction unit of regeneration draws off agent, still higher catalytic activity can be obtained.
According to method of the present invention, described HTS can be the former powder of HTS, also can be shaping HTS, is preferably shaping HTS.Shaping HTS is generally containing the HTS as activeconstituents and the carrier as binding agent, and wherein, the content of HTS can be conventional selection.Usually, with the total amount of described shaping HTS for benchmark, the content of HTS can be 5-95 % by weight, is preferably 10-95 % by weight, is more preferably 70-95 % by weight; The content of described carrier can be 5-95 % by weight, is preferably 5-90 % by weight, is more preferably 5-30 % by weight.The carrier of described shaping HTS can be conventional selection, as aluminum oxide and/or silicon oxide.The method preparing described shaping HTS is known in the field, no longer describes in detail herein.The granular size of described shaping HTS is also not particularly limited, and can carry out appropriate selection according to concrete shape.Particularly, the median size of described shaping HTS can be 4-10000 micron, is preferably 5-5000 micron, is more preferably 40-4000 micron, as 50-1000 micron.Described median size is volume average particle size, and laser particle analyzer can be adopted to measure.
According to method of the present invention, described beds only can load HTS, also can contain HTS and inactive filler.In beds, load inactive filler to adjust the amount of HTS in beds, thus the speed of reaction is regulated.When described beds contains HTS and inactive filler, in beds, the content of inactive filler can be 5-95 % by weight.Described inactive filler refers to the filler not having or substantially do not have catalytic activity to oxidizing reaction, and its specific examples can include but not limited to: one or more in quartz sand, ceramic ring and potsherd.
According to method of the present invention, HTS is as catalyzer, and its consumption is as the criterion can realize catalysis.Usually, the weight hourly space velocity of thioether can be 0.1-20h
-1, be preferably 0.1-10h
-1, as 0.5-5h
-1.In the present invention, weight hourly space velocity with the total amount of HTS in whole beds for benchmark.
According to method of the present invention, described liquid mixture contains or not containing solvent, preferably containing solvent, like this by the content of solvent in regulates liquid mixture, can adjust, make reaction more steady to the speed of reaction.Described solvent can either dissolve thioether and oxygenant or mixing both promoting for various, again can the liquid substance of solubilized target oxidation products.Usually, described solvent can be selected from water, C
1-C
6alcohol, C
3-C
8ketone and C
2-C
6nitrile.The specific examples of described solvent can include but not limited to: water, methyl alcohol, ethanol, n-propyl alcohol, Virahol, the trimethyl carbinol, isopropylcarbinol, acetone, butanone and acetonitrile.Preferably, described solvent is selected from water and C
1-C
6alcohol.More preferably, described solvent is methyl alcohol and/or water.
The consumption of described solvent can carry out appropriate selection according to the consumption of thioether and oxygenant.Usually, the weight ratio of described solvent and described thioether can be 0.1-100:1, is preferably 0.2-80:1.
According to method of the present invention, when desirable oxidation product is sulfoxide (such as: dimethyl sulfoxide (DMSO)), preferably also comprise and send at least one alkaline matter in described liquid mixture, the addition of described alkaline matter makes this liquid mixture pH value be in the scope of 6.5-9, can obtain better reaction effect like this.More preferably, the addition of described alkaline matter makes the pH value of described liquid mixture be in the scope of 7-8.5., if use alkali, improve the pH value of this liquid mixture further, still can obtain above-mentioned effect time (or being more than 7) in the pH value of the liquid mixture contacted with HTS more than 6.5.The pH value of described liquid mixture refers at 25 DEG C and 1 standard atmosphere pressure, the pH value of this liquid starting material of mensuration.
Herein, described alkaline matter refer to the pH value of its aqueous solution be greater than 7 material.The specific examples of described alkaline matter can include but not limited to: ammonia (that is, NH
3), amine, quaternary ammonium hydroxide and M
1(OH)
n(wherein, M
1for basic metal or alkaline-earth metal, n is and M
1the identical integer of valency).
As described alkaline matter, ammonia can be introduced with the form of liquefied ammonia, also can introduce as an aqueous solution, can also introduce with the form of gas.Concentration as the ammonia (that is, ammoniacal liquor) of aqueous solution form is not particularly limited, and can be conventional selection, such as 1-36 % by weight.
As described alkaline matter, amine refers to hydrogen partial on ammonia or is all replaced the material formed by alkyl, comprises primary amine, secondary amine and tertiary amine.Described amine is specifically as follows the material shown in formula I and/or C
3-C
11heterocyclic amine,
In formula I, R
1, R
2and R
3can be H or C separately
1-C
6alkyl (as C
1-C
6alkyl), and R
1, R
2and R
3be asynchronously H.Herein, C
1-C
6alkyl comprise C
1-C
6straight chained alkyl and C
3-C
6branched-chain alkyl, its specific examples can include but not limited to: methyl, ethyl, n-propyl, sec.-propyl, normal-butyl, sec-butyl, isobutyl-, the tertiary butyl, n-pentyl, isopentyl, tert-pentyl, neo-pentyl and n-hexyl.
The specific examples of amine can include but not limited to: methylamine, dimethylamine, Trimethylamine 99, ethamine, diethylamine, triethylamine, Tri N-Propyl Amine, di-n-propylamine, Tri-n-Propylamine, Isopropylamine, Diisopropylamine, n-butylamine, di-n-butyl amine, tri-n-butyl amine, sec-butylamine, diisobutyl amine, triisobutyl amine, tert-butylamine, n-amylamine, two n-amylamines, tri-n-amyl amine, neopentyl amine, isobutylcarbylamine, di-iso-amylamine, tri-isoamylamine, tertiary amylamine, normal hexyl Amine and n-octyl amine.
Described heterocyclic amine is compound finger ring having nitrogen-atoms and this nitrogen-atoms has lone-pair electron.Described heterocyclic amine can be such as one or more in substituted or unsubstituted pyrroles, substituted or unsubstituted Pyrrolidine, substituted or unsubstituted pyridine, substituted or unsubstituted hexahydropyridine, substituted or unsubstituted imidazoles, substituted or unsubstituted pyrazoles, substituted or unsubstituted quinoline, substituted or unsubstituted dihydroquinoline, substituted or unsubstituted tetrahydroquinoline, substituted or unsubstituted decahydroquinoline, substituted or unsubstituted isoquinoline 99.9 and substituted or unsubstituted pyrimidine.
As described alkaline matter, quaternary ammonium hydroxide is specifically as follows the material shown in formula II,
In formula II, R
4, R
5, R
6and R
7can be C separately
1-C
6alkyl (as C
1-C
6alkyl).Described C
1-C
6alkyl comprise C
1-C
6straight chained alkyl and C
3-C
6branched-chain alkyl, its specific examples can include but not limited to: methyl, ethyl, n-propyl, sec.-propyl, normal-butyl, sec-butyl, isobutyl-, the tertiary butyl, n-pentyl, neo-pentyl, isopentyl, tert-pentyl and n-hexyl.
The specific examples of described quaternary ammonium hydroxide can include but not limited to: Tetramethylammonium hydroxide, tetraethyl ammonium hydroxide, TPAOH (comprising four n-propyl ammonium hydroxide and tetra isopropyl ammonium hydroxide), TBAH (comprising 4-n-butyl ammonium hydroxide, four sec-butyl ammonium hydroxide, four isobutyl-ammonium hydroxide and tetra-tert ammonium hydroxide) and four pentyl ammonium hydroxide.
As described alkaline matter, M
1(OH)
nfor the oxyhydroxide of alkali-metal oxyhydroxide or alkaline-earth metal, such as, can be sodium hydroxide, potassium hydroxide, magnesium hydroxide, hydrated barta and calcium hydroxide.
According to method of the present invention, described alkaline matter can directly use, and uses after also described alkaline matter can being mixed with solution.Can send in fixed-bed reactor after solvent by alkaline matter and oxygenant and optionally, described mixing can be carried out outside reactor, also can carry out in reactor, be not particularly limited.
According to method of the present invention, satisfy condition 1 time, raise beds temperature until oxygenant transformation efficiency C ' satisfy condition 2 time, stop heat up and be incubated:
Oxygenant transformation efficiency C under condition 1, sometime t
twith initial oxidant transformation efficiency C
0ratio C
t/ C
0be 0.8≤C
t/ C
0<1;
Condition 2, oxygenant transformation efficiency C ' and initial oxidant transformation efficiency C
0ratio C '/C
0be 0.85≤C '/C
0≤ 1.
According to method of the present invention, when oxygenant transformation efficiency declines, improve the temperature of beds, the oxygenant transformation efficiency originally presenting downtrending can be made to go up, and oxygenant transformation efficiency go up to satisfy condition 2 time, keep the temperature of beds, namely stop heating up.The oxygenant transformation efficiency long period can be maintained higher level like this, extend the one way work-ing life of HTS.
In condition 1, preferably, 0.85≤C
t/ C
0.When condition 1 meets above-mentioned requirements, more effectively can extend the one way work-ing life of HTS.
From the angle of the complicacy of reduction operation, in condition 1, C
t/ C
0<0.9.
From the angle improving oxygenant transformation efficiency further, in condition 2,0.9≤C '/C
0.
In the present invention, oxygenant transformation efficiency=(participating in the mole number of the oxygenant of the mole number/add of the oxygenant of reaction) × 100%;
Wherein, the mole number of remaining oxygenant in the reaction mixture of the mole number of the oxygenant of the mole number=add of the oxygenant of reaction-obtain is participated in.
Oxygenant transformation efficiency C can be determined by the composition of monitoring the reaction mixture exported from fixed-bed reactor in reaction process continuously
0, C
tand C '.When fixed-bed reactor are multiple fixed-bed reactor, by with the flow direction of liquid mixture for benchmark, by be positioned at logistics end fixed-bed reactor export reaction mixture to determine oxygenant transformation efficiency C
0, C
tand C '.
In the present invention, initial oxidant transformation efficiency C
0after fixed-bed reactor steady running, determine from the composition of the first batch of reaction mixture of fixed-bed reactor output.Such as, the reaction mixture that fixed-bed reactor steady running can be obtained within 0.5-10 hour is as first batch of reaction mixture.
Ordinary method can be adopted to measure the composition of the reaction mixture exported from fixed-bed reactor, such as vapor-phase chromatography.
According to method of the present invention, although satisfy condition 1 time, raise the temperature of beds until oxygenant transformation efficiency C ' satisfies condition 2, but the temperature of beds is preferably raised with the amplitude of 0.01-2 DEG C/day, such one side can obtain longer HTS one way work-ing life, desirable oxidation selectivity of product can also be maintained higher level for a long time on the other hand.More preferably, the temperature of beds is raised with the amplitude of 0.02-1 DEG C/day.According to method of the present invention, in tandem reaction sequence, the temperature elevation amplitude of beds can be different, can raise the temperature of beds early stage in the reaction with lower amplitude, and the phase can raise the temperature of beds with higher amplitude after the reaction.
According to method of the present invention, the method improving the temperature of beds or the temperature of maintenance beds can be selected according to concrete plant running mode.Such as: regulating for the operational conditions to the heating unit that beds heats, regulating for carrying out heat exchange to beds with the operational conditions of the heat transferring medium shifted out by reaction heat, the temperature regulating described liquid mixture and combination thereof.
According to method of the present invention, the initial temperature of beds is fixed with the requirements for starting construction of device.Preferably, the initial temperature of beds is 20-50 DEG C, is more conducive to actually operating so on the one hand, can also obtain longer HTS one way work-ing life on the other hand.The initial temperature of beds is the temperature of finger device beds when realizing steady running.
According to method of the present invention, when adjusting the temperature of beds, remaining reaction condition, as pressure, Feed space velocities, proportioning raw materials can remain unchanged.
According to method of the present invention, the pressure in fixed-bed reactor can be selected according to concrete device and concrete operational conditions, is not particularly limited.Usually, in gauge pressure, the pressure in fixed-bed reactor can be 0-3MPa, is preferably 0.1-3MPa, as 0.5-2.5MPa.
Can also comprise according to method of the present invention and the reaction mixture exported from fixed-bed reactor is separated, to obtain desirable oxidation product (as sulfoxide) and unreacted reactant.The method being carried out being separated by reaction mixture can be selected for the routine of this area, is not particularly limited.Isolated unreacted reactant can recycle.
Below in conjunction with embodiment, the present invention is further described, but does not therefore limit content of the present invention.
In following examples and comparative example, agents useful for same is commercially available chemical pure or analytical reagent; Pressure is all in gauge pressure.
In following examples and comparative example, titanium-silicon molecular sieve TS-1 used according to Zeolites, the method preparation described in 1992, Vol.12:943-950, its titanium oxide content is 2.5 % by weight; Hollow HTS used is be the hollow HTS of HTS purchased from the trade mark of Hunan Jianchang Petrochemical Co., Ltd, and its titanium oxide content is 2.5 % by weight.
In following comparative example and embodiment, adopt gas-chromatography to analyze the content of each composition in the reaction solution obtained, adopt following formula to calculate oxygenant transformation efficiency, oxygenant effective rate of utilization and sulfoxide selectivity on this basis respectively:
Oxygenant transformation efficiency=(participating in the mole number of the oxygenant of the mole number/add of the oxygenant of reaction) × 100%;
Oxygenant effective rate of utilization=the mole number of the oxygenant of the mole number/participation reaction of sulfoxide (in the reaction mixture obtained) × 100%;
Sulfoxide selectivity=the mole number of the thioether of the mole number/participation reaction of sulfoxide (in the reaction mixture obtained) × 100%,
Wherein, participate in the mole number of remaining oxygenant in the reaction mixture of the mole number of the oxygenant of the mole number=add of the oxygenant of reaction-obtain,
Participate in the mole number of remaining thioether in the reaction mixture of the mole number of the thioether of the mole number=add of the thioether of reaction-obtain.
Following examples 4,10-13 and 17 adopt following methods to measure the activity of catalyzer:
By catalyzer, 36 % by weight ammoniacal liquor (with NH
3meter), the hydrogen peroxide of 30 % by weight is (with H
2o
2meter), the trimethyl carbinol and pimelinketone in mass ratio=1:7.5:10:7.5:10 mixing after at atmosheric pressure after 80 DEG C of stirring reaction 2h, reactant is filtered, analyze with the composition of vapor-phase chromatography to the liquid phase obtained, adopt the transformation efficiency of following formulae discovery pimelinketone and it can be used as the activity of this catalyzer
The transformation efficiency (%) of pimelinketone=[molar weight of the pimelinketone of (molar weight of the molar weight-unreacted pimelinketone of the pimelinketone added)/add] × 100%.
Embodiment 1-17 is for illustration of method of the present invention.
Embodiment 1
By catalyzer, (for volume average particle size is the spherical catalyst of 500 μm, in catalyzer, the content of titanium-silicon molecular sieve TS-1 is 85 % by weight, and the content of silicon oxide is 15 % by weight, and density is 0.76g/cm
3) be seated in miniature isometrical fixed-bed reactor, form beds, wherein, the quantity of beds is 1 layer, and the aspect ratio of beds is 10.By the thermopair of landfill in beds, observing and controlling operation is carried out to the heating of beds and insulation.
Dimethyl thioether, hydrogen peroxide (providing with the form of the hydrogen peroxide of 30 % by weight) and acetone are mixed to form liquid mixture, the bottom of liquid mixture fixed-bed reactor are sent into and flows through beds.In liquid mixture, the mol ratio of dimethyl thioether and hydrogen peroxide is 2:1, and the weight ratio of dimethyl thioether and acetone is 1:10, and the weight hourly space velocity of dimethyl thioether is 0.5h
-1.Initial temperature in beds is 40 DEG C, is 1MPa by the pressure-controlling in fixed-bed reactor in reaction process.
The composition of the reaction mixture exported from reactor is monitored continuously, at oxygenant transformation efficiency C in reaction process
twith initial (reaction proceeds to 2 little sampling and measuring constantly) oxygenant transformation efficiency C
0ratio C
t/ C
0be 0.8≤C
t/ C
0during <0.9, raise the temperature of beds until oxygenant transformation efficiency C ' and initial oxidant transformation efficiency C with the amplitude of 0.02-1 DEG C/day
0ratio C '/C
0be 0.9≤C '/C
0when≤1, stop heating up and being incubated.
Carry out the reaction of 660 hours, the temperature at the end of reaction in beds is 80 DEG C.In reaction process, sampling analysis is carried out to the liquid mixture exported from reactor, and calculate oxygenant transformation efficiency, oxygenant effective rate of utilization and dimethyl sulfoxide (DMSO) selectivity, wherein to react 2 hours and the result that obtains for 660 hours is listed in Table 1.
Comparative example 1
Adopt the method cacodyl oxide base thioether identical with embodiment 1, unlike, do not change the temperature of beds in reaction process.
The result of reacting 2 hours and obtain for 360 hours is listed in Table 1.
Embodiment 2
Adopt the method cacodyl oxide base thioether identical with embodiment 1, unlike, in fixed-bed reactor, also send into ammoniacal liquor (concentration is 25 % by weight), so that the pH value of the liquid mixture formed by dimethyl thioether, hydrogen peroxide and acetone is adjusted to 7.5 by 5.2.
Carry out the reaction of 700 hours, the temperature at the end of reaction in beds is 75 DEG C.The result of reacting 2 hours and obtain for 700 hours is listed in Table 1.
Embodiment 3
Adopt the method cacodyl oxide base thioether identical with embodiment 1, unlike, (density of catalyzer is 0.69g/cm in the hollow HTS replacement of the titanium-silicon molecular sieve TS-1 equivalent in catalyzer
3).
Carry out the reaction of 690 hours, the temperature at the end of reaction in beds is 75 DEG C.The result of reacting 2 hours and obtain for 690 hours is listed in Table 1.
Embodiment 4
Adopt the method cacodyl oxide base thioether identical with embodiment 1, unlike, catalyzer is that the preformed catalyst (forming this live catalyst drawing off agent identical with embodiment 1) drawn off from cyclohexanone oxamidinating reaction process carries out regenerating obtaining, and regeneration condition is: at 550 DEG C in air atmosphere roasting 4h.The activity of regenerated catalyst is 50%, and its activity when fresh is 95%.
Carry out the reaction of 700 hours, the temperature at the end of reaction in beds is 72 DEG C.The result of reacting 2 hours and obtain for 700 hours is listed in Table 1.
Embodiment 5
Adopt the method cacodyl oxide base thioether identical with embodiment 1, unlike, under the condition that catalyzer total filling amount is in the reactor constant, the catalyzer C1 that first filling is in the reactor identical with embodiment 3, then the catalyzer C2 (that is, liquid mixture first flows through hollow HTS, then flows through titanium-silicon molecular sieve TS-1) that filling is identical with embodiment 1, wherein, the weight ratio of C1 and C2 is 2:1.
Carry out the reaction of 720 hours, the temperature at the end of reaction in beds is 68 DEG C.The result of reacting 2 hours and obtain for 720 hours is listed in Table 1.
Embodiment 6
Adopt the method cacodyl oxide base thioether identical with embodiment 5, unlike, under the condition that the loadings of C1 and C2 is constant, first load C2 in the reactor, recharge C1 (that is, liquid mixture first flows through titanium-silicon molecular sieve TS-1, then flows through hollow HTS).
Carry out the reaction of 660 hours, the temperature at the end of reaction in beds is 79 DEG C.The result of reacting 2 hours and obtain for 660 hours is listed in Table 1.
Embodiment 7
Adopt the method cacodyl oxide base thioether identical with embodiment 5, unlike, under the condition that the total filling amount of catalyzer is constant, make the weight ratio of C1 and C2 be 1:1.
Carry out the reaction of 680 hours, the temperature at the end of reaction in beds is 76 DEG C.The result of reacting 2 hours and obtain for 680 hours is listed in Table 1.
Embodiment 8
Adopt the method cacodyl oxide base thioether identical with embodiment 5, unlike, under the condition that the total filling amount of catalyzer is constant, make the weight ratio of C1 and C2 be 8:1.
Carry out the reaction of 720 hours, the temperature at the end of reaction in beds is 66 DEG C.The result of reacting 2 hours and obtain for 720 hours is listed in Table 1.
Embodiment 9
Adopt the method cacodyl oxide base thioether identical with embodiment 8, unlike, under the condition that the total filling amount of catalyzer is constant, make the weight ratio of C1 and C2 be 20:1.
Carry out the reaction of 690 hours, the temperature at the end of reaction in beds is 79 DEG C.The result of reacting 2 hours and obtain for 690 hours is listed in Table 1.
Table 1
Embodiment 1 and comparative example 1 are compared and can find out, adopts method of the present invention effectively can extend the one way work-ing life of the HTS as catalyzer.
Embodiment 1 and embodiment 2 are compared and can find out, be in the scope of 6.5-9 by the pH value of the liquid mixture contacted with HTS is adjusted to, better reaction effect can be obtained, and extend the one way work-ing life of HTS further.
The result of embodiment 5-9 confirms, hollow HTS and titanium-silicon molecular sieve TS-1 are combinationally used, and with the flow direction of liquid mixture for benchmark, hollow HTS is made to be positioned at the upstream of titanium-silicon molecular sieve TS-1, the HTS one way extended further can be obtained use, and reduce the elevation amplitude of reaction bed temperature.
Embodiment 10-16 relates to following six kinds of catalyzer.
C3: (for volume average particle size is the spherical catalyst of 200 μm, density is 0.67g/cm to the shaping hollow HTS drawn off from propylene ring oxidation reaction process
3) carry out regenerating obtaining, this catalyzer contains the hollow HTS of 85 % by weight, the silicon oxide of 15 % by weight, and regeneration condition is: at 570 DEG C in air atmosphere roasting 4h.The activity of regenerated catalyst be 30% (its activity be 96%) when fresh.
C4: (for volume average particle size is the spherical catalyst of 200 μm, density is 0.75g/cm to the shaping titanium-silicon molecular sieve TS-1 drawn off from propylene ring oxidation reaction process
3) carry out regenerating obtaining, this catalyzer contains the titanium-silicon molecular sieve TS-1 of 85 % by weight, the silicon oxide of 15 % by weight, and regeneration condition is: at 570 DEG C in air atmosphere roasting 4h.The activity of regenerated catalyst be 30% (its activity be 95%) when fresh.
C5: the fresh shaping hollow HTS forming C1.
C6: the fresh shaping titanium-silicon molecular sieve TS-1 forming C2.
C7: fresh shaping hollow HTS, for volume average particle size is the spherical catalyst of 500 μm, this catalyzer contains the hollow HTS of 75 % by weight, the silicon oxide of 25 % by weight, and density is 0.68g/cm
3.
C8: fresh shaping titanium-silicon molecular sieve TS-1, for volume average particle size is the spherical catalyst of 500 μm, this catalyzer contains the titanium-silicon molecular sieve TS-1 of 75 % by weight, the silicon oxide of 25 % by weight, and density is 0.71g/cm
3.
Embodiment 10
Carry out in the reducing fixed-bed reactor with two beds.With liquid starting material flow direction in the reactor for benchmark, the beds being positioned at upstream is called the first beds, the beds being positioned at downstream is called the second beds, is the internal diameter zone of transition of taper between two beds, wherein not loading catalyst.First beds and the equal loading catalyst C3 of the second beds, the weight ratio of the loaded catalyst in the loaded catalyst in the first beds and the second beds is 5:1, and the ratio of the internal diameter of the first beds and the internal diameter of the second beds is 2:1.First beds and the second beds adopt the thermopair of landfill in beds to carry out observing and controlling operation to the heating of beds and insulation respectively, and the temperature of two beds controls as identical.
Dimethyl thioether, hydrogen peroxide (providing with the form of the hydrogen peroxide of 30 % by weight), ammoniacal liquor (concentration is 24 % by weight) and methanol mixed are formed liquid mixture, this liquid mixture is sent into fixed-bed reactor from bottom and also flows through the first beds and the second beds successively.Wherein, the mol ratio of dimethyl thioether and hydrogen peroxide is 3:1, the weight ratio of dimethyl thioether and methyl alcohol is 1:10, and the pH value of the liquid mixture by dimethyl thioether, hydrogen peroxide and the formation of methanol is adjusted to 8.5 by 5.8 by the consumption of ammoniacal liquor, and the weight hourly space velocity of dimethyl thioether is 2.0h
-1.Initial temperature in first beds and the second beds is 45 DEG C, is 2.0MPa by the pressure-controlling in fixed-bed reactor in reaction process.
The composition of the reaction mixture exported from reactor is monitored continuously, at oxygenant transformation efficiency C in reaction process
twith initial (reaction proceeds to 2 little sampling and measuring constantly) oxygenant transformation efficiency C
0ratio C
t/ C
0be 0.85≤C
t/ C
0during <0.9, raise the temperature of beds until oxygenant transformation efficiency C ' and initial oxidant transformation efficiency C with the amplitude of 0.01-2 DEG C/day
0ratio C '/C
0be 0.9≤C '/C
0≤ 1.
Carry out the reaction of 750 hours, the temperature at the end of reaction in beds is 72 DEG C.React the oxygenant transformation efficiency, oxygenant effective rate of utilization and the dimethyl sulfoxide (DMSO) selectivity that within 2 hours and 750 hours, obtain to list in table 2.
Embodiment 11
Adopt the method cacodyl oxide base thioether identical with embodiment 10, unlike, the catalyzer C3 in the second beds is replaced by the catalyzer C4 of equivalent.Carry out the reaction of 900 hours, the temperature at the end of reaction in beds is 68 DEG C.React the oxygenant transformation efficiency, oxygenant effective rate of utilization and the dimethyl sulfoxide (DMSO) selectivity that within 2 hours and 900 hours, obtain to list in table 2.
Embodiment 12
Adopt the method cacodyl oxide base thioether identical with embodiment 11, unlike, under the condition that the loadings of the catalyzer C4 in the second beds is constant, make the internal diameter of the second beds identical with the internal diameter of the first beds, namely the ratio of the internal diameter of the first beds and the second beds is 1:1.Carry out the reaction of 800 hours, the temperature at the end of reaction in beds is 74 DEG C.React the oxygenant transformation efficiency, oxygenant effective rate of utilization and the dimethyl sulfoxide (DMSO) selectivity that within 2 hours and 800 hours, obtain to list in table 2.
Embodiment 13
Adopt the method production dimethyl sulfoxide (DMSO) identical with embodiment 11, unlike, under the condition that catalyst type in first beds and the second beds and loadings all remain unchanged, improve the internal diameter of the second beds, make the ratio of the internal diameter of the first beds and the internal diameter of the second beds be 1:2.Carry out the reaction of 780 hours, the temperature at the end of reaction in beds is 70 DEG C.React the oxygenant transformation efficiency, oxygenant effective rate of utilization and the dimethyl sulfoxide (DMSO) selectivity that within 2 hours and 780 hours, obtain to list in table 2.
Embodiment 14
Adopt the method production dimethyl sulfoxide (DMSO) identical with embodiment 11, unlike, the catalyzer C5 of the catalyzer C3 equivalent in the first beds replaces, and the catalyzer C6 of the catalyzer C4 equivalent in the second beds replaces.Carry out the reaction of 880 hours, the temperature at the end of reaction in beds is 71 DEG C.React the oxygenant transformation efficiency, oxygenant effective rate of utilization and the dimethyl sulfoxide (DMSO) selectivity that within 2 hours and 880 hours, obtain to list in table 2.
Embodiment 15
Adopt the method production dimethyl sulfoxide (DMSO) identical with embodiment 9, unlike, loading catalyst C7 in first beds, loading catalyst C8 in second beds, the weight ratio of the loaded catalyst in the loaded catalyst in the first beds and the second beds is 10:1, and the ratio of the internal diameter of the first beds and the internal diameter of the second beds is 4:1.
Dimethyl thioether, dicumyl peroxide, pyridine and acetonitrile are mixed to form liquid mixture, this liquid mixture are sent into fixed-bed reactor from bottom and also flows through the first beds and the second beds successively.Wherein, the mol ratio of dimethyl thioether and dicumyl peroxide is 1:1, the weight ratio of dimethyl thioether and acetonitrile is 1:50, the pH value of the liquid mixture formed by dimethyl thioether, dicumyl peroxide and acetonitrile is adjusted to 8.0 by 5.9 by the consumption of pyridine, and the weight hourly space velocity of dimethyl thioether is 1.0h
-1.Initial temperature in first beds and the second beds is 45 DEG C, is 1.8MPa by the pressure-controlling in fixed-bed reactor in reaction process.
The composition of the reaction mixture exported from reactor is monitored continuously, at oxygenant transformation efficiency C in reaction process
twith initial (reaction proceeds to 2 little sampling and measuring constantly) oxygenant transformation efficiency C
0ratio C
t/ C
0be 0.85≤C
t/ C
0during <0.9, raise the temperature of beds until oxygenant transformation efficiency C ' and initial oxidant transformation efficiency C with the amplitude of 0.01-2 DEG C/day
0ratio C '/C
0be 0.9≤C '/C
0≤ 1.
Carry out the reaction of 800 hours, the temperature at the end of reaction in beds is 76 DEG C.React the oxygenant transformation efficiency, oxygenant effective rate of utilization and the dimethyl sulfoxide (DMSO) selectivity that within 2 hours and 800 hours, obtain to list in table 2.
Embodiment 16
Adopt the method production dimethyl sulfoxide (DMSO) identical with embodiment 15, unlike, improve the internal diameter of the first beds, make the ratio of the internal diameter of the first beds and the internal diameter of the second beds be 6:1.Carry out the reaction of 760 hours, the temperature at the end of reaction in beds is 75 DEG C.React the oxygenant transformation efficiency, oxygenant effective rate of utilization and the dimethyl sulfoxide (DMSO) selectivity that within 2 hours and 760 hours, obtain to list in table 2.
Table 2
The result of table 2 confirms, when making liquid mixture successively with hollow HTS and titanium-silicon molecular sieve TS-1 contact reacts, make liquid mixture be less than the superfacial velocity by titanium-silicon molecular sieve TS-1 by the superfacial velocity in hollow HTS, the one way work-ing life of HTS can be extended further.
Embodiment 17
The catalyzer used in the present embodiment is for being undertaken regenerating by the shaping titanium-silicon molecular sieve TS-1 drawn off from phenol hydroxylation reaction process (for volume average particle size is the spherical catalyst of 850 μm) and obtain, this catalyzer contains the titanium-silicon molecular sieve TS-1 of 80 % by weight and the silicon oxide of 20 % by weight, and regeneration condition is: at 570 DEG C in air atmosphere roasting 4h.The activity of regenerated catalyst be 40% (its activity be 95%) when fresh.
By catalyst loading in fixed-bed reactor, form beds, wherein, the quantity of beds is 1 layer, and the aspect ratio of beds is 20.By the thermopair of landfill in beds, observing and controlling operation is carried out to the heating of beds and insulation.
Thioanisole, tertbutyl peroxide, methyl alcohol and pyridine are mixed and sends into afterwards in fixed-bed reactor and flow through beds.Wherein, the mol ratio of thioanisole and tertbutyl peroxide is 2:1, the weight ratio of thioanisole and methyl alcohol is 1:10, and the pH value of the liquid mixture by thioanisole, tertbutyl peroxide and the formation of methanol is adjusted to 8.0 by 6.4 by the consumption of pyridine, and the weight hourly space velocity of thioanisole is 2.0h
-1.Initial temperature in beds is 50 DEG C, in reaction process, the pressure in fixed-bed reactor is remained 2.5MPa.
The composition of the reaction mixture exported from reactor is monitored continuously, at oxygenant transformation efficiency C in reaction process
twith initial (reaction proceeds to 2 little sampling and measuring constantly) oxygenant transformation efficiency C
0ratio C
t/ C
0be 0.8≤C
t/ C
0during <0.9, raise the temperature of beds until oxygenant transformation efficiency C ' and initial oxidant transformation efficiency C with the amplitude of 0.02-1 DEG C/day
0ratio C '/C
0be 0.9≤C '/C
0when≤1, stop heating up and being incubated.
Carry out the reaction of 800 hours, the temperature at the end of reaction in beds is 82 DEG C.React the oxygenant transformation efficiency, oxygenant effective rate of utilization and the sulfoxide selectivity that within 2 hours and 800 hours, obtain to list in table 3.
Table 3
The result of embodiment 4,10-13 and 17 confirms, draw off agent as catalyzer even if use, method of the present invention also can obtain good reaction effect, and can obtain higher oxygenant effective rate of utilization, achieves effective recycling of waste catalyst.
Claims (13)
1. a sulfide oxidation method, the method comprises sends into a kind of liquid mixture continuously in fixed-bed reactor, make described liquid mixture under oxidation reaction condition, flow through the beds of described fixed-bed reactor, to contact with the HTS be seated in described beds, described liquid mixture contains thioether, at least one oxygenant and optional at least one solvent, wherein, when the method is also included in and satisfies condition 1, raise beds temperature until oxygenant transformation efficiency C ' satisfy condition 2 time, stop heat up and be incubated:
Oxygenant transformation efficiency C under condition 1, sometime t
twith initial oxidant transformation efficiency C
0ratio C
t/ C
0be 0.8≤C
t/ C
0<1;
Condition 2, oxygenant transformation efficiency C ' and initial oxidant transformation efficiency C
0ratio C '/C
0be 0.85≤C '/C
0≤ 1.
2. method according to claim 1, wherein, in condition 1,0.85≤C
t/ C
0<0.9.
3. method according to claim 1 and 2, wherein, in condition 2,0.9≤C '/C
0.
4. method according to claim 1, wherein, described beds contains the first beds and the second beds, with the flow direction of described liquid mixture for benchmark, described first beds is positioned at the upstream of described second beds, the HTS of described first beds filling is hollow HTS, described hollow HTS is the HTS of MFI structure, the crystal grain of this HTS is hollow structure, the radical length of the chamber portion of this hollow structure is 5-300 nanometer, and this HTS is at 25 DEG C, P/P
0=0.10, adsorption time is that the benzene adsorptive capacity recorded under the condition of 1 hour is at least 70 milligrams/grams, there is hysteresis loop between the adsorption isothermal line of the nitrogen absorption under low temperature of this HTS and desorption isotherm,
The HTS of described second beds filling is titanium-silicon molecular sieve TS-1.
5. method according to claim 4, the weight ratio of the titanium-silicon molecular sieve TS-1 that the hollow HTS of described first beds filling and described second beds load is 1-20:1, is preferably 2-10:1.
6. the method according to claim 4 or 5, wherein, the superfacial velocity that described liquid mixture flows through the first beds is v
1, the superfacial velocity flowing through the second beds is v
2, v
1< v
2; Preferably, v
2/ v
1=1.5-10, more preferably, v
2/ v
1=2-5.
7. according to the method in claim 4-6 described in any one, wherein, the residence time of described liquid mixture in described beds is T, and the residence time in described first beds is T
1, T
1/ T=0.4-0.9.
8. according to the method in claim 1 and 4-7 described in any one, wherein, at least part of HTS be through regeneration the reaction unit using HTS as catalyzer draw off agent, described in draw off agent be Ammoximation reaction device draw off agent, hydroxylating device draw off agent and epoxidation reaction device draw off in agent one or more.
9. according to the method in claim 1,2,4 and 5 described in any one, wherein, the initial temperature of beds is 20-50 DEG C, raises the temperature of beds with the amplitude of 0.01-2 DEG C/day.
10. method according to claim 1, wherein, the mol ratio of described thioether and described oxygenant is 0.1-20:1, and the weight hourly space velocity of thioether is 0.1-20h
-1; In gauge pressure, pressure is 0-3MPa.
11. according to the method in claim 1,2,4,5 and 10 described in any one, and wherein, described thioether is dimethyl thioether or thioanisole.
12. according to the method in claim 1,2,4,5 and 10 described in any one, and wherein, described oxygenant is superoxide.
13. according to the method in claim 1-12 described in any one, and wherein, the method also comprises sends at least one alkali in described liquid mixture, and the feeding amount of described alkali makes to be in the scope of 6.5-9 with the pH value of described liquid mixture.
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| WO2014067235A1 (en) * | 2012-10-29 | 2014-05-08 | 中国石油化工股份有限公司 | Dimethylsulfoxide preparation method |
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