CN106334583A - Preparation method and application of titanium-silicon composite oxide catalyst - Google Patents

Preparation method and application of titanium-silicon composite oxide catalyst Download PDF

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CN106334583A
CN106334583A CN201610601021.8A CN201610601021A CN106334583A CN 106334583 A CN106334583 A CN 106334583A CN 201610601021 A CN201610601021 A CN 201610601021A CN 106334583 A CN106334583 A CN 106334583A
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catalyst
plasma
discharge
titanium
reaction
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CN106334583B (en
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周游
初乃波
王磊
王同济
叶飞
崔娇英
张礼昌
黎源
华卫琦
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Wanhua Chemical Group Co Ltd
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    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J31/00—Catalysts comprising hydrides, coordination complexes or organic compounds
    • B01J31/26—Catalysts comprising hydrides, coordination complexes or organic compounds containing in addition, inorganic metal compounds not provided for in groups B01J31/02 - B01J31/24
    • B01J31/38—Catalysts comprising hydrides, coordination complexes or organic compounds containing in addition, inorganic metal compounds not provided for in groups B01J31/02 - B01J31/24 of titanium, zirconium or hafnium
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J37/00—Processes, in general, for preparing catalysts; Processes, in general, for activation of catalysts
    • B01J37/34—Irradiation by, or application of, electric, magnetic or wave energy, e.g. ultrasonic waves ; Ionic sputtering; Flame or plasma spraying; Particle radiation
    • B01J37/349—Irradiation by, or application of, electric, magnetic or wave energy, e.g. ultrasonic waves ; Ionic sputtering; Flame or plasma spraying; Particle radiation making use of flames, plasmas or lasers
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07D—HETEROCYCLIC COMPOUNDS
    • C07D301/00—Preparation of oxiranes
    • C07D301/02—Synthesis of the oxirane ring
    • C07D301/03—Synthesis of the oxirane ring by oxidation of unsaturated compounds, or of mixtures of unsaturated and saturated compounds
    • C07D301/19—Synthesis of the oxirane ring by oxidation of unsaturated compounds, or of mixtures of unsaturated and saturated compounds with organic hydroperoxides
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07D—HETEROCYCLIC COMPOUNDS
    • C07D303/00—Compounds containing three-membered rings having one oxygen atom as the only ring hetero atom
    • C07D303/02—Compounds containing oxirane rings
    • C07D303/04—Compounds containing oxirane rings containing only hydrogen and carbon atoms in addition to the ring oxygen atoms
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J2231/00—Catalytic reactions performed with catalysts classified in B01J31/00
    • B01J2231/70—Oxidation reactions, e.g. epoxidation, (di)hydroxylation, dehydrogenation and analogues
    • B01J2231/72—Epoxidation

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Abstract

The invention relates to a preparation method of a titanium-silicon composite oxide catalyst. The method comprises the following steps: 1, simultaneously impregnating a silica carrier with a titanium source and a soluble alkaline metal salt; 2, carrying out low temperature plasma treatment; and 3, modifying by using an organosilane reagent. Alkaline oxide is introduced to modify the catalyst when the impregnation process titanium source loading is carried out, and the low temperature plasma treatment is carried out, so the production of a titanium compound outside a framework and the surface acidity of the catalyst are effectively reduced, thereby the catalyst substantially improves the selectivity and the yield of epoxides in the olefin epoxidation reaction.

Description

A kind of preparation method and applications of Ti-Si composite oxide catalyst
Technical field
The present invention relates to a kind of preparation method of epoxidation catalyst, specifically with regard to a kind of Ti-Si composite oxide The preparation method of catalyst and its application in epoxidation reaction of olefines.
Background technology
Expoxy propane is a kind of important basic organic chemical raw material, is the third-largest derivative of propylene, is mainly used in giving birth to Produce the chemical products such as PPG, propane diols and nonionic surfactant, its annual requirement increases year by year.At present, industry The technology producing expoxy propane mainly has chlorohydrination and organic peroxide conjugated oxidation, and the latter includes TBHP again Oxidizing process (po/mtbe) and ethylbenzene hydroperoxide oxidizing process (po/sm).The advantage of chlorohydrination is that flow process is short, technical maturity, operation Elasticity is big, little to raw material propylene purity requirement, equipment investment is few.But, chlorohydrination technique often produces 1 ton of expoxy propane can be secondary Produce 40～50 tons and contain 2～3wt%cacl2Waste water with organochlorine.Become increasingly conspicuous in today's society environmental problem, environmental protection pressure is got over Come bigger in the case of, the development space of chlorohydrination is limited.Conjugated oxidation is the Synthesis of Propylene Oxide of current main flow.Its In, ethylbenzene hydroperoxide oxidizing process is well known, mainly includes peroxidating and two steps of epoxidation.In epoxidation step In, ethylbenzene hydroperoxide and propylene react and obtain expoxy propane and 1- phenylethanol, and course of reaction needs to use homogeneous catalyst Or heterogeneous catalysis.(mainly entering the titanium in silicon skeleton) catalyst based on the titanium in silica carrier is commonly used as The heterogeneous catalysis of po/sm technique epoxidation step.
Titaniferous porous oxidation silicon materials generally have good catalysis activity to epoxidation reaction of olefines, are therefore often used as The catalyst of propylene ring oxidation reaction.The species of porous oxidation silicon materials is a lot.1992, the researcher of mobil company became The serial mesoporous silica molecular sieve of the m41s with mcm-41 as representative for the work(synthesis (nature, 1992,359 (6397): 710- 712), this kind of material has broad duct (＞ 2.0nm), uniform pore-size distribution and larger specific surface area (700- 1600m2/g).1998, Zhao Dongyuan et al. successfully synthesize mesoporous silica molecular sieve sba-15 (science, 1998, 279 (5350): 548-552).Sba-15 mesopore molecular sieve is in acid condition, with triblock copolymer p123 (eo20po70eo20) it is template, tetraethyl orthosilicate is silicon source, is obtained by Hydrothermal Synthesiss.Compared with mcm-41, sba- 15 have preferable hydrothermal stability, larger aperture and wider aperture adjustment scope (5-30nm).In addition, macro porous silica gel and Organic mesoporous silicon hms is also commonly used for the carrier of catalyst.For example, United States Patent (USP) us5783167 discloses hydro-thermal method synthesizing titanium-containing The method of mesoporous material ti-mcm-41, SUMITOMO CHEMICAL company (sumitomo) also discloses that a kind of titaniferous with meso-hole structure The synthetic method of catalyst ti-mcm-41.
The method currently preparing Ti-Si composite oxide catalyst, mainly vapour deposition process and sol-gal process.Gas phase Sedimentation is all had the following disadvantages with sol-gal process: preparation process is loaded down with trivial details, complex operation, and condition is harsh and not easily-controllable System, the reaction time is long.Once in addition, condition control is improper, it is (main that gained catalyst easily generates the outer titanium compound of more skeleton It is free state titanium dioxide), catalyst surface acidity is stronger, for effective profit of organic peroxide during propylene ring oxidation reaction Relatively low with rate.
Low temperature plasma is as a kind of effective technological means, more and more closer with contacting of field of catalyst preparation. Plasma technique relates generally to three aspects in the application of field of catalyst preparation: (1) is directly synthesized ultra-fine grain catalyst； (2) prepare loaded catalyst using plasma spray technology；(3) plasmaassisted prepares catalyst.Research report is relatively Many is that plasmaassisted prepares catalyst technology.But it is used for epoxidation catalyst system for using low temperature plasma at present Standby example has no report.
Deficiency for existing Ti-Si composite oxide method for preparing catalyst, it is desirable to provide a kind of new easy and simple to handle Preparation method, and it can be avoided that the generation of the outer titanium compound of skeleton, improve the catalytic performance of catalyst.
Content of the invention
The technical problem to be solved in the present invention is to provide a kind of preparation method of Ti-Si composite oxide catalyst, the method Easy and simple to handle, efficiency high, environmentally friendly, and it is avoided that the generation of the outer titanium compound of skeleton, weaken the surface acidity of catalyst, Improve the catalytic oxidation performance of catalyst.
Further object is that providing the catalyst of methods described preparation in EPOXIDATION OF ALKENES CATALYZED BY Purposes, especially catalysis preparing epoxypropane by epoxidation of propene reaction in, it is possible to increase the utilization rate of organic peroxide, To expoxy propane, there is high selectivity.
For solving above-mentioned technical problem, the present invention employs the following technical solutions:
A kind of preparation method of Ti-Si composite oxide catalyst, this production method comprises the following steps:
A) impregnate: after titanium source and dissolubility alkalinous metal salt are dissolved in organic solvent, then be added thereto to silica Carrier, heats after dipping and obtains catalyst Precursors；
B) Low Temperature Plasma Treating and decomposition: catalyst Precursors are put into the region of discharge of discharge of plasma in low temperature device Carry out discharge process；
C) at least one organosilane reagents will be added in the catalyst Precursors after step b) corona treatment, Reaction obtains Ti-Si composite oxide catalyst.
In the inventive method, in step a), the weight of organic solvent and silica supports than for 0.5～10, preferably 1～ 3；Silica supports are 1～100, preferably 5～20 with the mol ratio of titanium source；Titanium source with the mol ratio of alkalinous metal salt is 0.1～10, preferably 1～5.
In the inventive method, in step a), between temperature is for room temperature to organic solvent boiling point under conditions of impregnate, dipping Time is 1～24 hour.
In the inventive method, in step a), the temperature of heating is 80～120 DEG C, and the time is 1～5 hour.
In the inventive method, in step a), described organic solvent be selected from methyl alcohol, ethanol, isopropanol, toluene, hexane and One or more of heptane.The hydrolysis to titanium source for the moisture can be avoided using organic reagent dissolving titanium source, as far as possible as far as possible Reduce the generation of free titanium.
In the inventive method, in step a), described titanium source is halogenated titanium, such as titanium tetrachloride, titanium tetrabromide, titanium tetra iodide Deng；Or alkoxytitanium, such as tetramethoxy titanate ester, tetraethyl titanate, metatitanic acid orthocarbonate, tetraisopropyl titanate, butyl titanate, metatitanic acid Four isobutyl esters, metatitanic acid four -2- Octyl Nitrite, metatitanic acid four (octadecyl) ester and oxygen pentanedione acid titanium (iv), diisopropyl Epoxide diacetyl acetone acid titanium (iv) etc..
In the inventive method, in step a), described dissolubility alkalinous metal salt is selected from the nitrate of alkalinous metal, chlorine One or more of salt dissolving, carbonate and subcarbonate, preferably magnesium nitrate, magnesium chloride, zinc nitrate, zinc chloride, calcium nitrate One or more of with calcium chloride.Dissolubility alkalinous metal salt is converted into alkalinous metal after Low Temperature Plasma Treating Oxide, thus effectively reducing the surface acidity of catalyst, improves the selectivity of catalyst.
In the inventive method, in step a), described silica supports are silicon oxide pellets, silica gel, mcm are serial, Sba is serial and one or more of organic mesoporous silicon hms, preferably macro porous silica gel, mcm-41, sba-15 and organic mesoporous One or more of silicon hms.
In the inventive method, in step b), described discharge of plasma in low temperature device is put using corona discharge plasma Electrical equipment or dielectric barrier discharge plasma discharger, preferably dielectric barrier discharge plasma discharger, described medium hinders Using single dielectric barrier discharge or double-dielectric barrier discharge, the medium of use is quartzy, ceramic to gear discharge plasma discharger Or lucite.
Preferably, in the inventive method, in step b), catalyst Precursors are laid in flat or coaxial-type dielectric impedance In the region of discharge of discharge plasma discharger, apply high voltage between two electrodes of plasma discharger and carry out at electric discharge Reason, the discharge process time is 0.5～2h, and discharge power is 40～120w.By Low Temperature Plasma Treating it is achieved that Catalyst activity component load on silica supports and alkaline metal oxide synchronously complete to the modification of catalyst, letter Change the preparation process of catalyst, it is to avoid the negative effect to activated centre when alkaline metal oxide is individually modified, such as led Cause active center distribution uneven or cover amount of activated center.And catalysis plasma-treated and that alkalinous metal is modified Agent, that surface is formed is stable Rutile Type tio2, more conventional anatase tio2Acid low, reduce catalyst surface Acidity, improves the epoxidation of catalyst selectively.Secondly, the catalyst Precursors after Low Temperature Plasma Treating and machine silane try More silylation can be generated after agent reaction, remain less silicone hydroxyl, be conducive to improving the hydrophobicity of catalyst, further Improve the selectivity of catalyst.
In the inventive method, in step c), the catalyst Precursors after step b) corona treatment are tried with machine silane The reaction of agent is carried out preferably in nitrogen atmosphere, and reaction temperature is 100～450 DEG C, and the reaction time is 0.5～10 hour.Nitrogen Atmosphere is to prevent the silylation introducing to be oxidized by oxygen；Reaction temperature can introduce the efficiency of silylation with modulation, including introduce Trimethoxyllsilyl content and speed.
In the inventive method, in step c), the weight of organosilan and catalyst Precursors is than for 0.01～0.2
In the inventive method, in step c), described organosilane reagents are selected from HMDS, hexamethyl chlorine silicon Azane, seven methyl chloride silazane, trim,ethylchlorosilane, dimethylchlorosilane, tetramethyl-disilazane, dimethyl diethoxy silicon One or more of alkane, trimethylmethoxysilane, dimethyldimethoxysil,ne and trimethylethoxysilane.Preferably six Methyl disilazane.
The epoxidation that the catalyst that preparation method of the present invention obtains can be used for the alkene that catalyzed alkene is mainly c2～c12 is anti- Should, especially propylene liquid phase epoxidation prepares expoxy propane, that is, pass through propylene and organic peroxide (such as ethylbenzene peroxidating Hydrogen, TBHP, isopropyl benzene hydroperoxide etc.) react in the liquid phase.
The propylene ring oxidation reaction performance of above-mentioned catalyst can be carried out on reactor or fixed bed reaction evaluating apparatus Investigate.The appreciation condition of reactor is as follows: ethylbenzene hydroperoxide selected by organic peroxide, and concentration is the ethylbenzene of 20～40wt% Hydrogenperoxide steam generator is 10～30 with the mass ratio of catalyst；Propylene is 1～20 with the mol ratio of ethylbenzene hydroperoxide, preferably rubs That ratio 6～10；Nitrogen is pressurized to 2.0～4.0mpa, 60～100 DEG C of reaction temperature, 1～5 hour reaction time.The commenting of fixed bed Valency condition is: Catalyst packing quality is 4～12g, and concentration is the mass space velocity of the ethylbenzene hydroperoxide solution of 20～40wt% For 1～10h-1, propylene is 1～20 with the mol ratio of ethylbenzene hydroperoxide, preferred molar ratio 6～10.Reaction temperature 60～100 DEG C, reaction pressure 3.0～5.0mpa.
The positive effect of the present invention is:
1st, provide a kind of new, efficiently and rapidly prepare the side of epoxidation catalyst with lower temperature plasma technology Method；Titanium source is resolved into active titanium component and alkalinous metal salt is resolved into it by the low temperature plasma being related in the method The isolation of corresponding oxide, compared with the usual roasting method adopting, has the spies such as low temperature, low energy consumption, decomposable process be fast Point, and easy and simple to handle, environmentally friendly, it is to carry out at room temperature avoiding high-temperature roasting additionally, due to Low Temperature Plasma Treating Lead to framework titania to separate out, form oarse-grained free state tio2.
2nd, the load of catalyst activity component and basic anhydride modification one step are completed by the present invention, at plasma Reason achieves synchronous dispersed.Because treatment temperature is relatively low and the presence of high energy electron, with the metal of plasma preparation Oxide catalyst have particle uniformly, complete crystal form, active component granularity are easily controlled, catalysis activity is good, unique properties The advantages of.
3rd, the inventive method prepares Ti-Si composite oxide catalyst, greatly reduces outer titanium species (the i.e. free state of skeleton Titanium dioxide) generation, strengthen the interaction of basic anhydride and carrier, thus effectively reducing the surface acid of catalyst Property, this catalyst is used in the reaction of propylene liquid phase method preparing epoxypropane by epoxidation, organic peroxy can be significantly improved The effective rate of utilization of thing, shows as catalyst and has high selectivity to expoxy propane, selectively can reach 86%～95%.
Brief description
Fig. 1 is the xrd spectrogram contrast of the catalyst that embodiment 1 and comparative example 1-2 method prepare；Xrd spectrogram reacts The type of catalyst surface free state titanium species, as seen from Figure 1, embodiment 1 is plasma-treated and alkalinous metal is modified Catalyst b, that surface is formed is stable Rutile Type tio2；And the conventional preparation of comparative example 2 or comparative example 1 are without alkalescence gold Belong to the catalyst that modification obtains, that surface is formed is acid stronger anatase tio2.
The infrared spectrum contrast of the catalyst that Fig. 2 is prepared with comparative example 3 method for embodiment 1；Infrared spectrum proves Skeleton titanium species (963cm is generated in catalyst-1Place peak), and the catalyst that the visible embodiment 1 of contrast obtains must compared with comparative example 3 Few (the 3410cm of catalyst silicone hydroxyl arriving-1Silicone hydroxyl vibration peak), illustrate that its hydrophobicity is more preferable.
Fig. 3 is the thermogravimetric curve of the catalyst that comparative example 1 and embodiment 1-2 method prepare.Thermogravimetric curve reaction It is weightless feature after silanization treatment for the catalyst, the weightless step after 400 DEG C is mainly derived from the silylation of introducing.Logical Cross contrast and can illustrate that the catalyst of embodiment 1-2 is weightless more compared with the catalyst of comparative example 1, silane in catalyst is described Quito, further illustrates its hydrophobicity good.
Specific embodiment
The present invention is described in further detail by following examples, but the technology contents described in the present embodiment are illustrative , rather than determinate, should not limit to protection scope of the present invention according to this.
Flat type dielectric barrier discharge plasma discharger: Nanjing Su Man Electronics Co., Ltd., model ctp- 2000k；Single medium, quartz.
The analysis method of conversion ratio:
Iodimetric titration concrete steps:
(1) add 20ml acetic acid in conical flask, in n2After emptying, add 5g about ki；
(2) take 1g about analysis sample add thing mixed above, simultaneously prepare blank sample to compare；
(3) after water seal, magnetic agitation in the dark, react 30min；
(4) add pure water 50ml, using the na preparing concentration2s2o3Solution is titrated, software supervision titration end-point.
(5) according to na2s2o3The usage amount of solution calculates the content of organic peroxide, and then calculates its conversion ratio.(note:For the na consuming2s2o3Solution Volume,It is the na using2s2o3The concentration of solution.)
Chromatographiccondition is as shown in the table:
Table 1 operation condition of chromatogram
[comparative example 1]
Under agitation, by 5g ticl4It is dissolved in 80ml isopropanol.25g macropore c type silica gel is added in above solution (Qingdao Gui Chuan Fine Chemical Co., Ltd is 100% calculating according to dioxide-containing silica, similarly hereinafter), at 40 DEG C, dipping 12 is little When.Then thing mixed above is processed 3 hours by 100 DEG C of oil bath.By the catalyst Precursors obtaining (in terms of oxide).Make There is power supply with the plasma that power is 50w, with air as discharge medium, put in flat type dielectric barrier discharge plasma Process 1 hour in electrical equipment.Afterwards at 250 DEG C, with high pure nitrogen as carrier gas, it is passed through 3g HMDS and reacts 1 hour, Obtain catalyst a.It is respectively used to reactor and fixed bed propylene ring oxidation reaction, evaluated its reactivity worth.The results are shown in Table 2.The appreciation condition of reactor is as follows: catalyst amount is 3.0g, the ethylbenzene solution 45g of 30% ethylbenzene hydroperoxide, propylene 50g, nitrogen is pressurized to 4.0mpa, 60 DEG C of reaction temperature, 2 hours reaction time.The appreciation condition of fixed bed is: Catalyst packing Measure as 6.0g, propylene flow 15g/ hour, the flow 20g/ hour of the ethylbenzene solution of 30% ethylbenzene hydroperoxide (ebhp), reaction Temperature 60 C, reaction pressure 4.0mpa.
[comparative example 2]
Method according to comparative example 1 prepares catalyst synthesizing epoxypropane, except for the difference that, by plasma treatment procedure Change following steps into: (1) 500 DEG C of roastings 3 hours in nitrogen atmosphere；(2) it is passed through steam treatment at 300 DEG C 2 hours.System The standby catalyst obtaining is denoted as catalyst a, and reaction evaluating the results are shown in Table 2.
[embodiment 1]
Under agitation, by 5g ticl4With 3g mg (no3)2It is dissolved in 80ml isopropanol.25g is added in above solution Macropore c type silica gel, impregnates 12 hours at 40 DEG C.Then thing mixed above is processed 3 hours by 100 DEG C of oil bath.Will The catalyst Precursors arriving use the plasma that power is 50w that power supply occurs, with air as discharge medium, in the resistance of flat medium Process 1 hour in gear discharge plasma discharger.Afterwards at 250 DEG C, with high pure nitrogen as carrier gas, it is passed through 3g hexamethyl two Silicon amine alkane reacts 1 hour, obtains catalyst b.It is respectively used to reactor and fixed bed propylene ring oxidation reaction, evaluated it anti- Answer performance.The results are shown in Table 2.
[comparative example 3]
Method according to embodiment 1 prepares catalyst synthesizing epoxypropane, except for the difference that, by plasma treatment procedure Change following steps into: (1) 500 DEG C of roastings 3 hours in nitrogen atmosphere；(2) it is passed through steam treatment at 300 DEG C 2 hours.System The standby catalyst obtaining is denoted as catalyst b, and reaction evaluating the results are shown in Table 2.
[embodiment 2]
Under agitation, by 10g ticl4With 4g zn (no3)2It is dissolved in 100ml ethanol.60g is added in above solution Sba-15 (Catalyst Factory, Nankai Univ is 100% calculating according to dioxide-containing silica), impregnates 2 hours at 20 DEG C.Then will Thing mixed above is processed 2 hours by 80 DEG C of oil bath.The catalyst Precursors obtaining are sent out using the plasma that power is 40w Raw power supply, with air as discharge medium, is processed 0.5 hour in flat type dielectric barrier discharge plasma discharger.Afterwards At 120 DEG C, with high pure nitrogen as carrier gas, it is passed through 1g HMDS and reacts 0.5 hour, obtain catalyst c.By its point Not Yong Yu reactor and fixed bed propylene ring oxidation reaction, evaluate its reactivity worth.The results are shown in Table 2.
[embodiment 3]
Under agitation, by 18g butyl titanate and 3g zncl2It is dissolved in 80ml ethanol.Add in above solution 40g hms (Catalyst Factory, Nankai Univ is 100% calculating according to dioxide-containing silica), impregnates 20 hours at 20 DEG C.Then Thing mixed above is processed 1 hour by 80 DEG C of oil bath.The catalyst Precursors obtaining are used the plasma that power is 80w There is power supply, with air as discharge medium, process 1.5 hours in flat type dielectric barrier discharge plasma discharger.It Afterwards at 300 DEG C, with high pure nitrogen as carrier gas, it is passed through 8g HMDS and reacts 8 hours, obtain catalyst d.By its point Not Yong Yu reactor and fixed bed propylene ring oxidation reaction, evaluate its reactivity worth.The results are shown in Table 2.
[embodiment 4]
Under agitation, by 28g tetraisopropyl titanate and 4g mgcl2It is dissolved in 60ml isopropanol.Add in above solution Enter 40g mcm-41 (Catalyst Factory, Nankai Univ is 100% calculating according to dioxide-containing silica), dipping 24 is little at 40 DEG C When.Then thing mixed above is processed 5 hours by 80 DEG C of oil bath.It is 80w's that the catalyst Precursors obtaining are used power There is power supply in plasma, with air as discharge medium, process 1.5 in flat type dielectric barrier discharge plasma discharger Hour.Afterwards at 400 DEG C, with high pure nitrogen as carrier gas, it is passed through 5g HMDS and reacts 2 hours, obtain catalyst e.It is respectively used to reactor and fixed bed propylene ring oxidation reaction, evaluated its reactivity worth.The results are shown in Table 2.
[embodiment 5]
Under agitation, by 20g metatitanic acid orthocarbonate and 4g mgcl2It is dissolved in 60ml hexane.Add in above solution 30g silicon oxide pellets (Qingdao wave silica-gel desiccant Co., Ltd), impregnate 16 hours at 60 DEG C.Then will be mixed above Thing is processed 4 hours by 120 DEG C of oil bath.The catalyst Precursors obtaining are used the plasma that power is 100w that electricity occurs Source, with air as discharge medium, is processed 2 hours in flat type dielectric barrier discharge plasma discharger.Afterwards at 300 DEG C Under, with high pure nitrogen as carrier gas, it is passed through 5g HMDS and reacts 2 hours, obtain catalyst f.It is respectively used to anti- Answer kettle and fixed bed propylene ring oxidation reaction, evaluate its reactivity worth.The results are shown in Table 2.
[embodiment 6]
Under agitation, by 30g tetrabutyl titanate and 8g ca (no3)2It is dissolved in 80ml toluene.Add in above solution Enter 60g macropore c type silica gel (Qingdao Gui Chuan Fine Chemical Co., Ltd), impregnate 12 hours at 20 DEG C.Then will be mixed above Thing is processed 4 hours by 120 DEG C of oil bath.The catalyst Precursors obtaining are used the plasma that power is 120w that electricity occurs Source, with air as discharge medium, is processed 2 hours in flat type dielectric barrier discharge plasma discharger.Afterwards at 200 DEG C Under, with high pure nitrogen as carrier gas, it is passed through 6g HMDS and reacts 3 hours, obtain catalyst g.It is respectively used to anti- Answer kettle and fixed bed propylene ring oxidation reaction, evaluate its reactivity worth.The results are shown in Table 2.
Table 2 catalyst performance contrasts

Claims (10)

1. a kind of preparation method of Ti-Si composite oxide catalyst is it is characterised in that comprise the following steps:
A) impregnate: after titanium source and dissolubility alkalinous metal salt are dissolved in organic solvent, then it is added thereto to silica supports, Heat after dipping and obtain catalyst Precursors；
B) Low Temperature Plasma Treating and decomposition: the region of discharge that catalyst Precursors are put into discharge of plasma in low temperature device is carried out Discharge process；
C) at least one organosilane reagents will be added in the catalyst Precursors after step b) corona treatment, react Obtain Ti-Si composite oxide catalyst.
2. method according to claim 1 is it is characterised in that the weight of organic solvent and silica supports is than for 0.5 ～10, silica supports are 10～100 with the mol ratio of titanium source, and titanium source is 0.1～1 with the mol ratio of alkalinous metal salt.
3. method according to claim 1 is it is characterised in that in step a), in temperature for room temperature to organic solvent boiling point Between under conditions of impregnate, dip time be 1～24 hour.
4. it is characterised in that in step a), the temperature of heating is 80～120 DEG C to method according to claim 1, Time is 1～5 hour.
5. method according to claim 1 is it is characterised in that in step a), described organic solvent is selected from methyl alcohol, second One or more of alcohol, isopropanol, toluene, hexane and heptane.
6. the method according to any one of claim 1-5 is it is characterised in that described soluble alkali metallic salt is One or more of the nitrate of alkalinous metal, chlorate, carbonate and subcarbonate, preferably magnesium nitrate, magnesium chloride, nitre One or more of sour zinc, zinc chloride, calcium nitrate and calcium chloride.
7. the method according to any one of claim 1-6 is it is characterised in that in step b), the discharge process time is 0.5 ～2h, discharge power is 40～120w.
8. the method according to any one of claim 1-7 is it is characterised in that in step b), described low-temperature plasma Body discharger adopts corona discharge plasma discharger or dielectric barrier discharge plasma discharger, and preferably dielectric impedance is put Electro-plasma discharger, dielectric barrier discharge plasma discharger is put using single dielectric barrier discharge or bi-medium to block Electricity, the medium of use is quartz, ceramic or lucite.
9. method according to claim 1 is it is characterised in that in step c), after step b) corona treatment Catalyst Precursors are carried out in nitrogen atmosphere with the reaction of organosilane reagents, and reaction temperature is 100～450 DEG C, the reaction time For 0.5～10 hour, the weight of organosilan and catalyst Precursors was than for 0.01～0.2.
10. purposes in EPOXIDATION OF ALKENES CATALYZED BY for the catalyst of method preparation, institute according to any one of right 1-9 The preferred propylene of alkene stated, epoxidation reaction is preferably the liquid phase epoxidation reaction of alkene and organic peroxide.
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