CN106964337B - A kind of preparation method of epoxidation catalyst and epoxidation catalyst and its application of preparation - Google Patents
A kind of preparation method of epoxidation catalyst and epoxidation catalyst and its application of preparation Download PDFInfo
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- CN106964337B CN106964337B CN201610021367.0A CN201610021367A CN106964337B CN 106964337 B CN106964337 B CN 106964337B CN 201610021367 A CN201610021367 A CN 201610021367A CN 106964337 B CN106964337 B CN 106964337B
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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
- B01J23/00—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00
- B01J23/002—Mixed oxides other than spinels, e.g. perovskite
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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
- B01J23/00—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00
- B01J23/16—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of arsenic, antimony, bismuth, vanadium, niobium, tantalum, polonium, chromium, molybdenum, tungsten, manganese, technetium or rhenium
- B01J23/24—Chromium, molybdenum or tungsten
- B01J23/28—Molybdenum
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- 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
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- 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
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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
- B01J2523/00—Constitutive chemical elements of heterogeneous catalysts
Abstract
The present invention relates to the epoxidation catalysts and its application of a kind of preparation method of epoxidation catalyst and preparation.Titanium is loaded on silica gel using the method for chemical vapor deposition, after silanization treatment, hydrolysis, molybdenum is loaded to by titanium surface using the compound method of ion exchange in solution, realizes the oriented load of molybdenum.The epoxidation catalyst has excellent molybdenum stability.The epoxidation catalyst prepares corresponding epoxide for olefin oxidation, and catalytic activity is high, and selectivity is high.
Description
Technical field
The present invention relates to a kind of preparation method of epoxidation catalyst and the epoxidation catalyst prepared and its in alkene
Application in epoxidation.
Background technique
The epoxidation reaction of alkene is a kind of important chemical reaction, is on the one hand because epoxidation product itself has weight
The application value wanted, such as can be used for the chiral catalysis synthesis of the modification of organic elastomer, drug；On the other hand it is because of ring
Oxidation product is the raw material for producing polyurethane, surfactant etc..
Since epoxidation product is easy to happen ring-opening reaction even depth oxidation reaction, so the selection of catalyst is very heavy
It wants.The catalyst of common epoxidation reaction of olefines is mainly the compound containing molybdenum, tungsten, titanium or vanadium.
Since molybdenum element has the very strong ability of appraising at the current rate, molybdenum compound has application well in Selective Oxidation,
The molybdenum ion of middle high price is the activated centre in oxidation reaction.The organomolybdenum complexes of high-valence state can be applied to alkene epoxidation
In reaction, and there is good oxidation activity and selective oxidizing.United States Patent (USP) US3362972 discloses the solubilities such as caproic acid molybdenum
Inorganic molybdenum source is efficiently introduced into organic phase by the preparation of molybdenum compound using the effect of oxalic acid.US3351636 compares ring
The substances such as alkanoic acid molybdenum, aphthenic acids titanium, aphthenic acids tantalum and aphthenic acids tungsten produce epoxy in ethylbenzene hydroperoxide (EBHP) propylene oxide
The reactivity worth of propane, wherein the activity and selectivity of molybdenum naphthenate is much higher than other several organo-metallic compounds；Wherein,
The conversion ratio of EBHP is 97.2%, and the selectivity of propylene oxide is 70.8%.EP0193682A1 discloses a kind of propylene glycol oxygen molybdenum
The preparation method of catalyst is prepared for stable homogeneous catalyst solution using ammonium heptamolybdate and propylene glycol as raw material, uses
TBHP prepares propylene oxide, TBHP conversion ratio > 97%, propylene oxide selectivity > 95% as oxidant；EP0264184A1
Disclose a kind of preparation method of ethylene glycol oxygen molybdenum catalyst, TBHP conversion ratio > 98%, propylene oxide selectivity > 96%.
Above-mentioned catalyst is homogeneous catalyst, and catalytic efficiency is higher, but after completion of the reaction, and catalyst and reaction solution need
Separation, the catalyst after reaction can not also reuse, and need complicated removal process, increase plant investment.
After heterogeneous catalyst is reacted due to catalyst, reaction solution can be separated simply with catalyst, reduced and urged
The separation costs of agent, and catalyst can be used repeatedly for a long time, reduce catalyst cost, fixed bed reactors more may be used
In the case where realizing that catalyst is motionless, realizes catalysis reaction, the separation of catalyst and reaction solution, enormously simplify process, from
Dynamicization is horizontal high, exactly because it has above-mentioned advantage, most of industrialization reaction is all made of heterogeneous catalyst at present.
The preparation method and its answering in epoxidation of propylene that EP0345856A1 discloses a kind of titanium-based heterogeneous catalyst
With using amorphous silica as carrier, titanium tetrachloride prepares unformed Titanium Dioxide as titanium source, vapor deposition
Agent, and silanization treatment is used, catalyst stability is improved, but Ti-base catalyst reactivity is low, industrially needs multiple urge
Agent series connection, therefore the heterogeneous catalyst for developing high activity has very great help to epoxidation reaction efficiency is improved.
Summary of the invention
The object of the present invention is to provide a kind of preparation methods of epoxidation catalyst, are successfully prepared the ring of high hydrothermal stability
Oxidation catalyst improves molybdenum system heterogeneous catalyst stability.
A kind of application it is another object of the present invention to provide epoxidation catalyst and its in alkene epoxidation uses
The catalyst can effectively improve reactivity, reduce reaction temperature, improve product yield.
To achieve the above objectives, The technical solution adopted by the invention is as follows:
A kind of preparation method of epoxidation catalyst, comprising the following steps:
(1) vapor deposition reaction is carried out using titanium tetrachloride vapors and silica gel；
(2) silanization treatment is carried out to step (1) products therefrom using silylating reagent；
(3) step (2) products therefrom is hydrolyzed；
(4) step (3) products therefrom is reacted with molybdenum source；
(5) step (4) products therefrom is hydrolyzed；
(6) silanization treatment is carried out to step (5) products therefrom using silylating reagent, obtains the epoxida tion catalyst
Agent.
Step (1) of the present invention is to carry out in the presence of an inert gas, the preferred N of inert gas2。
Silica gel of the present invention is fumed silica, rich one of hydroxyl silica gel and chromatographic silica gel or a variety of, preferably
Rich hydroxyl silica gel and/or fumed silica.
The specific surface area of silica gel is 50~1000m in step (1) of the present invention2/ g, preferably 200~800m2/g；It is described
Silica gel is preferably through drying process, and the method for the drying can use any drying means well known in the art, preferably by silicon
Glue is heated to 100~150 DEG C, then uses inert gas such as N2Purge 2~4h.
Titanium tetrachloride vapors use inert gas as carrier gas in step (1) of the present invention, and the inert gas is preferred
N2；The titanium tetrachloride vapors temperature is 100~150 DEG C, preferably 130~140 DEG C.
Titanium tetrachloride is 0.4~12wt%, preferably 2~6% with respect to the dosage of silica gel in step (1) of the present invention.
Vapor deposition reaction temperature is 100-280 DEG C, preferably 150-200 DEG C in step (1) of the present invention.
Step (2) silylating reagent of the present invention uses inert gas as carrier gas, the preferred N of inert gas2。
The dosage of step (2) silylating reagent of the present invention be step (1) in silica gel weight 3~10wt%, preferably 4
~6wt%.
Step (2) silanization treatment temperature of the present invention is 100~250 DEG C, preferably 150~220 DEG C.
Step (2) the silanization treatment time of the present invention is 1~5h, preferably 2~3h.
After step (2) of the present invention, optional blows step (2) products therefrom using inert gas
It sweeps.
Purging temperature of the present invention is 100~250 DEG C, preferably 150~220 DEG C；Purge time be 0.5~4h, preferably 1
~3h.The effect of purging is that removing is only the titanium tetrachloride that physical absorption does not chemically react on a small quantity.
The effect of step (2) of the present invention is carried out at silanization to hydroxyl remaining in products therefrom in step (1)
Reason.
Step (3) hydrolysis temperature of the present invention is 300-380 DEG C, preferably 320-350 DEG C.
Step (3) 1~5h of hydrolysis time, preferably 2~3h of the present invention.
It is preferable to use water vapours to be hydrolyzed for step (3) of the present invention.
It is 0.1~0.5g/ (hgcat), preferably 0.2~0.4g/ that step (3) water vapour of the present invention, which is passed through rate,
(h·gcat)。
The effect of step (3) of the present invention is to convert hydroxyl for the chlorine on titanium.
Step (4) of the present invention can carry out under conditions of containing or without solvent, preferably contain solvent
Under the conditions of carry out, it is preferred that the mass ratio 1 of silica gel described in solvent usage and step (1) in step (4) of the present invention~
10:1, preferably 3~5:1.
Solvent includes in paracide, o-dichlorohenzene, diphenyl ether and N-Methyl pyrrolidone in step (4) of the present invention
One or more, preferred paracide.
Step (4) reaction temperature of the present invention is 170~230 DEG C, preferably 180~200 DEG C.
Step (4) reaction time of the present invention is 1~6h, preferably 3~4h.
Molybdenum source in step (4) of the present invention includes dichloro dioxy molybdenum and/or molybdenum pentachloride, preferably dichloro dioxy molybdenum.
The mass ratio of molybdenum source and silica gel described in step (1) is 1:10~60, preferably 1:20 in step (4) of the present invention
~50.
The effect of step (4) of the present invention is that molybdenum source reacts with the hydroxyl on titanium, and molybdenum loads to titanium surface, is realized
The oriented load of molybdenum.
Preferably, step (4) of the present invention after the reaction was completed, is filtered, and then uses ethyl alcohol and/or acetone washing
To solvent-free remnants, then it is dried, continues step (5).
Step (5) hydrolysis temperature of the present invention is 300~380 DEG C, preferably 320~350 DEG C.
Step (5) 1~5h of hydrolysis time, preferably 2~3h of the present invention.
It is preferable to use water vapours to be hydrolyzed for step (5) of the present invention.
It is 0.1~0.5g/ (hgcat), preferably 0.2~0.4g/ that water vapour, which is passed through rate, in step (5) of the present invention
(h·gcat)。
The effect of step (5) of the present invention is to convert the chlorine not reacted with the hydroxyl on titanium remaining on molybdenum to
Hydroxyl.
Step (6) silylating reagent of the present invention uses inert gas as carrier gas, the preferred N of inert gas2。
Step (6) silanization treatment temperature of the present invention is 100-250 DEG C, preferably 150-220 DEG C.
The dosage of step (6) silylating reagent of the present invention is 0.1~7wt% of silica gel weight in step (1), preferably
1~5wt%.
Step (6) the silanization treatment time of the present invention is 1~5h, preferably 2~3h.
The effect of step (6) of the present invention is that hydroxyl remaining in step (5) products therefrom is carried out silanization treatment.
Step (6) silanization of the present invention can be improved catalyst surface hydrophobicity, obtain the titanium molybdenum of silanization treatment
Complex loop oxidation catalyst.
Alkylating reagent of the present invention includes hmds, trimethylsilyl diethylamine and trimethyl silane miaow
One or more, the preferred hmds of azoles.
In epoxidation catalyst of the present invention, Ti content is 0.1~3wt%, and preferably 0.5~1.5%, Mo content is
0.2~5wt%, preferably 1~1.5% are calculated on the basis of epoxidation catalyst gross weight.
The present invention also provides the sides that a kind of epoxidation catalyst prepared using the method for the invention prepares epoxides
Method, comprising the following steps: alkene is reacted under the catalysis of the epoxidation catalyst with oxidant, obtains epoxidation
Object.
Alkene of the present invention includes substitution and unsubstituted aliphatic and alicyclic olefin, they can be hydrocarbon or ester
Or alcohol or ketone or ether etc..Preferably with the compound of 2-30 carbon atom in these substances, preferably 2-15 carbon atom
Compound, the compound of more preferable 3-12 carbon atom.Typical alkene is ethylene, propylene, n-butene, isobutene, amylene, first
Base amylene, n-hexylene, octene, laurylene, cyclohexene, cyclo-octene, cyclododecene, methylcyclohexene, butadiene, styrene, first
Base styrene, vinyltoluene, vinylcyclohexene, phenyl cyclohexene etc..Also it can be used former with halogen, oxygen atom, sulphur
Sons etc. and the alkene containing substituent group, these alkene replaced can be allyl alcohol, methallyl alcohol, allyl ether, acrylic acid
Methyl esters, methyl oleate, methyl vinyl ketone, allyl chloride etc..In general, all can use the epoxidised alkene object of pervious method
Matter can the method according to the invention epoxidation.Olefinic material includes containing up to thousands of a carbon atom ethylenic unsaturation polymerized hydrocarbons
Object.Representative alkene includes Linseed oil, olive oil, soya-bean oil, cotton seed oil, tall oil glyceride, castor oil, corn
Oil, the butyl macrogol ester of unsaturated fatty acid, the polybutadiene of liquid or solid, polyisobutylene, ethylene and propylene are not
Saturated copolymer and the trimer of ethylene, propylene and cyclopentadiene etc..Wherein propylene is preferred alkene.
It is ROOH that structural formula, which can be used, in oxidant of the present invention, and wherein R is the organic hydroperoxide of organic group
Come carry out.R can be substituted or unsubstituted alkyl, naphthenic base, aralkyl, arylalkenyl, hydroxyl virtue in a preferred embodiment
Alkyl, cycloalkenyl, hydroxycycloalkyl and the similar group containing 3-20 carbon atom.R is also possible to heterocycle.
Representative hydrogen peroxide can be cumene hydroperoxide, ethylbenzene hydroperoxide, tert-butyl hydroperoxide, ring
Hexyl hydrogen peroxide, Cyclohexanone peroxides, tetrahydronaphthalene hydrogen peroxide, methyl ethyl ketone peroxide, methylcyclohexene peroxidating
Hydrogen and toluene, to ethyltoluene, isopropylbenzene, isobutylbenzene, diisopropylbenzene (DIPB), cymene, ortho-xylene, meta-xylene,
The hydrogen peroxide of paraxylene, cyclohexylbenzene etc..It is preferred that tert-butyl hydroperoxide and/or isopropyl benzene hydroperoxide.
Reaction condition used in epoxidation of the present invention can change within a fairly wide range.
The molar ratio of alkene and oxidant of the present invention is 1-20:1, preferably 5-10:1.
Epoxidation reaction temperature of the present invention is 0~200 DEG C, preferably 50~150 DEG C.
Epoxidation reaction oxidant feed mass space velocity of the present invention is 0.5~10h-1, preferably 1~5h-1。
Epoxidation reaction pressure requirements of the present invention are not stringent, and predominantly ensuring to react is that liquid-solid two-phase reacts, root
Different pressure is selected according to different olefin substrates, the reaction pressure is absolute pressure 0.1-10MPa.
Epoxidation reaction of the present invention can be such as fixed bed, anti-to carry out in any reactor known in the art
Answer kettle etc., preferably fixed bed.
It is of the present invention " optional " to be meant that " use " or " not using ".
The invention has the advantages that compared with prior art
(1) completely new catalyst preparation route is used, the epoxidation catalyst of high hydrothermal stability is successfully prepared, is improved
Molybdenum system heterogeneous catalyst stability.
(2) by substep silanization treatment, molybdenum is mainly linked on titanium surface, to form titanium-oxygen-molybdenum bridged bond, is improved
Molybdenum stability.
(3) compared to homogeneous catalyst technique, the fixed-bed process that this patent uses is easy to operate, without complicated catalysis
Agent post-processes link.
(4) catalyst activity is high, and selectivity is high, high by 10% or more compared to simple titanium system heterogeneous catalyst activity.
(5) catalyst cellular structure 10-20nm is suitble to a variety of olefin epoxidation process, the ring including various macrocycloalkenes
Oxidation process.
Detailed description of the invention
Fig. 1 is the embodiment of the present invention 17 as a result, XTBHP/ % indicates TBHP conversion ratio, SPO/ % indicates PO selectivity.
Specific embodiment
Illustrate a kind of preparation method of high activity epoxidation heterogeneous catalyst provided by the present invention in detail further below
And its application in alkene epoxidation, but the present invention is not therefore subject to any restriction.
Embodiment 1
Step (1): by 100g silica gel (U.S. high chemical industry SG08-1, specific surface area 300m2/ g, average pore size 11nm) it is packed into stone
In English fixed bed reactors, heating bed is to 120 DEG C, N2Flow 0.5L/min purges dry 2h, 5g titanium tetrachloride is added to
In 100ml three-necked flask, 140 DEG C are heated to, using 0.5L/min N2As carrier gas, titanium tetrachloride vapors are passed through, are stopped after 2h
It is passed through titanium tetrachloride vapors.
Step (2): heating bed temperature is to 190 DEG C, using 0.5L/min N2As carrier gas, it is passed through two silicon of 5g hexamethyl
Amine gas is passed through time 2h.
Step (3): 190 DEG C of bed temperature are maintained, N2Purge 2h.
Step (4): bed temperature is improved to 340 DEG C, it is 0.3g/ (hgcat) that water vapour, which is passed through rate, is passed through water vapour
2h。
Step (5): it by step (4) products therefrom, molybdenum dioxydichloride 3g, is added in 400g paracide, is heated to
180 DEG C of condensing reflux 3h, filtering are washed to paracide washing using excess ethyl alcohol solvent and are finished.
Step (6): step (5) products therefrom is added in quartz fixed bed reactor, improves bed temperature to 340
DEG C, it is 0.3g/ (hgcat) that water vapour, which is passed through rate, is passed through water vapour 2h.
Step (7): catalyst bed is cooled to 190 DEG C, using 0.5L/min N2As carrier gas, continues up and state bed
Layer is passed through 5g hmds gas, is passed through time 2h, is cooled to room temperature after being disposed, obtains 1# epoxidation catalyst,
XRF (AXIOS Xray fluorescence spectrometer, Panaco) analyzes Ti content 1.2wt%, molybdenum content 1.4wt%, with epoxida tion catalyst
It is calculated on the basis of agent gross weight.
Embodiment 2
In addition to the dosage of step (1) titanium tetrachloride is 2g, in step (5) other than molybdenum dioxydichloride 2.1g, remaining condition
With embodiment 1.Obtain 2# epoxidation catalyst, Ti content 0.5wt%, molybdenum content 1wt%.
Embodiment 3
In addition to the dosage of step (1) titanium tetrachloride is 6g, in step (5) other than molybdenum dioxydichloride 2.1g, remaining condition
With embodiment 1.Obtain 3# epoxidation catalyst, Ti content 1.5wt%, molybdenum content 1wt%.
Embodiment 4
In addition to the dosage of step (1) titanium tetrachloride is 4g, in step (5) other than molybdenum dioxydichloride 3.2g, remaining condition
With embodiment 1.Obtain 4# epoxidation catalyst, Ti content 1wt%, molybdenum content 1.5wt%.
Embodiment 5
In addition to the dosage of step (1) titanium tetrachloride is 4g, in step (5) other than molybdenum dioxydichloride 2.1g, remaining condition
With embodiment 1.Obtain 5# epoxidation catalyst, Ti content 1wt%, molybdenum content 1wt%.
Embodiment 6
Heating bed is to other than 150 DEG C in the step (1), remaining condition is the same as embodiment 1.Obtain 6# epoxida tion catalyst
Agent, Ti content 0.8wt%, molybdenum content 1.4wt%.
Embodiment 7
Heating bed is to other than 170 DEG C in the step (1), remaining condition is the same as embodiment 1.Obtain 7# epoxida tion catalyst
Agent, Ti content 1wt%, molybdenum content 1.4wt%.
Embodiment 8
Heating bed is to other than 220 DEG C in the step (1), remaining condition is the same as embodiment 1.Obtain 8# epoxida tion catalyst
Agent, Ti content 1.2wt%, molybdenum content 1.4wt%.
Embodiment 9
Other than being heated to 170 DEG C in step (5), remaining condition is the same as embodiment 1.9# epoxidation catalyst is obtained,
Ti content 1.2wt%, molybdenum content 1.3wt%.
Embodiment 10
Other than being heated to 190 DEG C in step (5), remaining condition is the same as embodiment 1.10# epoxidation catalyst is obtained,
Ti content 1.2wt%, molybdenum content 1.4wt%.
Embodiment 11
Other than being heated to 200 DEG C in step (5), remaining condition is the same as embodiment 1.11# epoxidation catalyst is obtained,
Ti content 1.2wt%, molybdenum content 1.4wt%.
Embodiment 12
Other than bed temperature is 320 DEG C in step (4), step (6), remaining condition is the same as embodiment 1.Obtain 12# ring
Oxidation catalyst, Ti content 1.2wt%, molybdenum content 1.4wt%.
Embodiment 13
Other than bed temperature is 330 DEG C in step (4), step (6), remaining condition is the same as embodiment 1.Obtain 13# ring
Oxidation catalyst, Ti content 1.2wt%, molybdenum content 1.4wt%.
Embodiment 14
Other than bed temperature is 350 DEG C in step (4), step (6), remaining condition is the same as embodiment 1.Obtain 14# ring
Oxidation catalyst, Ti content 1.2wt%, molybdenum content 1.4wt%.
Comparative example 1
100g silica gel (U.S. high chemical industry SG08-1) is fitted into quartz fixed bed reactor, heats bed to 180 DEG C, N2Stream
0.5L/min is measured, dry 2h is purged, 10g titanium tetrachloride is added in 100ml three-necked flask, be heated to 180 DEG C, use
0.5L/min N2As carrier gas, titanium tetrachloride vapors are passed through, have led to titanium tetrachloride vapors in 1.5h, nitrogen continues after having led to
Purge 0.5h.
Bed temperature is increased to 600 DEG C, N2Purge 4h.
Bed temperature is improved to 300 DEG C, it is 0.3g/ (hgcat) that water vapour, which is passed through rate, is passed through water vapour 2h.
Catalyst bed is cooled to 190 DEG C, using 0.5L/min N2As carrier gas, continues up and state bed and be passed through 5g
Hmds gas is passed through time 2h, is cooled to room temperature after being disposed, and obtains 15# epoxidation catalyst, catalyst Ti
Content is 2.5wt%.
15 epoxidation catalyst performance evaluation of embodiment
Epoxidation catalyst performance is evaluated using fixed bed reactors, using tert-butyl hydroperoxide containing 55wt% (TBHP)
T-butanol solution as oxidant, the catalytic performance of different epoxidation catalysts, epoxy are had rated as raw material using propylene
Change Catalyst packing 10g, 60 DEG C of reaction temperature, propylene: TBHP=10 (mol), TBHP mass space velocity 2.5h-1, evaluate 10h and make even
Mean value, the TBHP conversion ratio and propylene oxide (PO) of different epoxidation catalysts selectively the results are shown in Table 1.
1 epoxidation catalyst evaluation result of table
| Catalyst number | TBHP conversion ratio % | PO selectivity/% |
| 1# | 98.1 | 95.6 |
| 2# | 93.5 | 96.8 |
| 3# | 96.2 | 96.1 |
| 4# | 98.5 | 93.6 |
| 5# | 95.3 | 96.2 |
| 6# | 93.1 | 96.3 |
| 7# | 95.6 | 96.0 |
| 8# | 96.5 | 94.7 |
| 9# | 96.1 | 96.2 |
| 10# | 98.2 | 95.7 |
| 11# | 98.5 | 95.2 |
| 12# | 98.2 | 93.2 |
| 13# | 98.1 | 94.3 |
| 14# | 98.0 | 95.7 |
| 15# | 85 | 93.1 |
Note: PO is selectively the selectivity that TBHP is converted into PO
The other olefin catalytic performance evaluations of embodiment 16
1# epoxidation catalyst is investigated to the catalytic performance of other epoxidation reaction of olefines.Remaining condition and 15 phase of embodiment
Together, 2 be the results are shown in Table.
The other alkene evaluation results of table 2
| Substrate | TBHP conversion ratio/% | Epoxide selectivities/% |
| Butylene | 97.5 | 96.2 |
| Isobutene | 98.3 | 97.0 |
| Styrene | 65.2 | 81.2 |
| Cyclohexene | 99.5 | 97.2 |
| Cyclo-octene | 99.3 | 97.1 |
| Cyclododecene | 98.5 | 96.9 |
Note: epoxide selectivities are the selectivity that TBHP is converted into epoxides
The evaluation of 17 catalyst life of embodiment
1# epoxidation catalyst 10g is loaded in fixed bed reactors, using tert-butyl hydroperoxide containing 55wt% (TBHP)
T-butanol solution as oxidant, using propylene as raw material, 60 DEG C of reaction temperature, propylene: TBHP=10 (mol), TBHP
Mass space velocity 2.5h-1, device continuously runs 600h, TBHP conversion ratio (XTBHP/ % indicates TBHP conversion ratio) and PO selectivity
(SPO/ % indicates PO selectivity) the result is shown in Figure 1, TBHP conversion ratio and PO selectively have no and are decreased obviously.
Claims (21)
1. a kind of preparation method of epoxidation catalyst, comprising the following steps:
(1) vapor deposition reaction is carried out using titanium tetrachloride vapors and silica gel；
(2) silanization treatment is carried out to step (1) products therefrom using silylating reagent；
(3) step (2) products therefrom is hydrolyzed；
(4) step (3) products therefrom is reacted with molybdenum source；
(5) step (4) products therefrom is hydrolyzed；
(6) silanization treatment is carried out to step (5) products therefrom using silylating reagent, obtains the epoxidation catalyst；
The molybdenum source of the step (4) includes dichloro dioxy molybdenum and/or molybdenum pentachloride.
2. the method according to claim 1, wherein silica gel is fumed silica, rich hydroxyl in the step (1)
One of base silica gel and chromatographic silica gel are a variety of；The specific surface area of silica gel is 50~1000m in the step (1)2/g。
3. the method according to claim 1, wherein silica gel is rich hydroxyl silica gel and/or gas in the step (1)
Aerosil；The specific surface area of silica gel is 200~800m in the step (1)2/g。
4. the method according to claim 1, wherein in the step (1) titanium tetrachloride vapors temperature be 100~
150℃；Step (1) the vapor deposition reaction temperature is 100-280 DEG C.
5. the method according to claim 1, wherein in the step (1) titanium tetrachloride vapors temperature be 130~
140℃；Step (1) the vapor deposition reaction temperature is 150-200 DEG C.
6. the method according to claim 1, wherein the step (3) hydrolysis temperature is 300-380 DEG C.
7. the method according to claim 1, wherein the step (3) hydrolysis temperature is 320-350 DEG C.
8. the method according to claim 1, wherein molybdenum source and silica gel described in step (1) in the step (4)
Mass ratio be 1:10~60；Step (4) reaction temperature is 170~230 DEG C.
9. the method according to claim 1, wherein the molybdenum source of the step (4) includes dichloro dioxy molybdenum；It is described
The mass ratio of molybdenum source and silica gel described in step (1) is 1:20~50 in step (4)；Step (4) reaction temperature be 180~
200℃。
10. the method according to claim 1, wherein the step (4) carries out in the presence of a solvent,
The solvent includes one of paracide, o-dichlorohenzene, diphenyl ether and N-Methyl pyrrolidone or a variety of；The step
(4) mass ratio of solvent usage and silica gel described in step (1) is 1~10:1 in.
11. according to the method described in claim 10, it is characterized in that, the solvent of the step (4) includes paracide；It is described
The mass ratio of solvent usage and silica gel described in step (1) is 3~5:1 in step (4).
12. the method according to claim 1, wherein the step (5) hydrolysis temperature is 300~380 DEG C.
13. the method according to claim 1, wherein the step (5) hydrolysis temperature is 320~350 DEG C.
14. the method according to claim 1, wherein the step (6) silanization treatment temperature is 100-250
℃。
15. the method according to claim 1, wherein the step (6) silanization treatment temperature is 150-220
℃。
16. a kind of epoxidation catalyst of -15 described in any item method preparations according to claim 1, which is characterized in that described
Epoxidation catalyst Ti content is 0.1~3wt%, and Mo content is 0.2~5wt%, is counted on the basis of epoxidation catalyst gross weight
It calculates.
17. epoxidation catalyst according to claim 16, which is characterized in that the epoxidation catalyst Ti content is
0.5~1.5%, Mo content are 1~1.5%, are calculated on the basis of epoxidation catalyst gross weight.
18. epoxidation catalyst described in a kind of claim 16 prepares the purposes of epoxide for catalyzed alkene, described
Olefinic carbon number is 2-30.
19. purposes according to claim 18, which is characterized in that the olefinic carbon number is 2-15.
20. purposes according to claim 19, which is characterized in that the olefinic carbon number is 3-12.
21. purposes according to claim 20, which is characterized in that the alkene is selected from ethylene, propylene, n-butene, isobutyl
Alkene, amylene, methylpentene, n-hexylene, octene, laurylene, cyclohexene, cyclo-octene, cyclododecene, methylcyclohexene, butadiene,
One of styrene, methyl styrene, vinyltoluene, vinylcyclohexene and phenyl cyclohexene are a variety of.
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| CN107930610B (en) * | 2017-11-29 | 2019-09-20 | 万华化学集团股份有限公司 | A kind of preparation method of olefin epoxidation catalysts and the catalyst thus prepared |
| CN110270382B (en) * | 2018-03-13 | 2021-09-21 | 中国石油化工股份有限公司 | Hydrophobically modified hydrogenation catalyst, and preparation method and application thereof |
| CN109364980A (en) * | 2018-11-13 | 2019-02-22 | 湘潭大学 | A kind of preparation method and application preparing mesoporous catalyst by chemical vapour deposition technique carried metal titanium |
| CN111377951B (en) * | 2018-12-28 | 2022-09-20 | 万华化学集团股份有限公司 | Rare earth metal compound, preparation method, composition and method for catalyzing olefin epoxidation |
| CN110947375B (en) * | 2019-11-26 | 2021-07-09 | 红宝丽集团股份有限公司 | Catalyst for preparing propylene oxide and preparation method thereof |
| CN111018809B (en) * | 2019-12-24 | 2022-08-05 | 万华化学集团股份有限公司 | Load system and method for treating styrene epoxidation reaction liquid |
| CN113181961B (en) * | 2020-01-14 | 2022-09-20 | 万华化学集团股份有限公司 | Preparation method and application of propylene epoxidation catalyst |
| JP7280948B2 (en) * | 2020-01-14 | 2023-05-24 | 万華化学集団股▲分▼有限公司 | Method for preparing propylene epoxidation catalyst and use thereof |
| CN117186416A (en) * | 2023-09-08 | 2023-12-08 | 海南思瑞新能源科技有限公司 | Silicon-carbon copolymer, preparation method thereof and application thereof in battery anode material |
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