CN103586069A - Preparation method of catalyst for olefin epoxidation reaction and olefin epoxidation method - Google Patents
Preparation method of catalyst for olefin epoxidation reaction and olefin epoxidation method Download PDFInfo
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- CN103586069A CN103586069A CN201310384463.8A CN201310384463A CN103586069A CN 103586069 A CN103586069 A CN 103586069A CN 201310384463 A CN201310384463 A CN 201310384463A CN 103586069 A CN103586069 A CN 103586069A
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Abstract
The invention provides a preparation method of a catalyst for olefin epoxidation reaction. The preparation method comprises the steps of preparing a mixture containing a titanium silicalite molecular sieve, a binder source, an alkaline earth metal oxide and water, molding the mixture to obtain a molded body, and drying and roasting the molded body, wherein the binder source is at least one selected from silica sol, silane with at least two hydrolysable groups and siloxane with at least two hydrolysable groups, and the weight ratio of the titanium silicalite molecular sieve to the binder source measured by SiO2 to the alkaline earth metal oxide to the water in the mixture is (70-98): (1.5-40): (0.05-25): (5-50). The invention also provides an olefin epoxidation method. The catalyst prepared by using the method provided by the invention has high hydrogen peroxide conversion rate and epoxide selectivity in olefin epoxidation reaction.
Description
The application is to be dividing an application of October 11, application number in 2010 are 201010511564.3, denomination of invention is " method of olefin epoxidation catalysts and preparation method thereof and epoxidation of olefins " Chinese patent application the applying date.
Technical field
The present invention relates to a kind of olefin epoxidation catalysts and preparation method thereof and the method for using the epoxidation of olefins of this catalyst.
Background technology
Along with the development of petrochemical industry and fine chemistry industry, oxygen-containing organic compound has become very important intermediate.Take hydrogen peroxide as oxidant, thereby take HTS prepares as catalyst alkene epoxidation the requirement that oxygen-containing organic compound meets Green Chemistry and atom economy idea of development, is a kind of novel environment-friendly process that has development prospect.
Epoxides normally carries out epoxidation reaction by alkene and hydrogen peroxide under catalyst exists to be prepared.At present, HTS is catalyst the most frequently used in epoxidation reaction of olefines.But, when adopting fixed bed reaction technique, the catalyst that contains HTS must moulding and is had enough crushing strengths, otherwise catalyst is easy broken fine grained or the powder of forming in use, this broken catalyst can cause beds pressure drop to increase on the one hand, thereby improve production run cost, has also increased the danger of producing simultaneously; If broken catalyst is taken out of by product on the other hand, will cause catalyst loss and product separation complicated.
And the chemical property of epoxides is active, in reaction system, be easy to further open loop generation side reaction, cause the elective reduction of epoxides.
CN1140348C discloses a kind of composite Ti-Si catalyst of being made by ,Tai source, silicon source, template, alkali, distilled water and inorganic oxide reaction, wherein, the inorganic oxide that this catalyst is 0.1-20mm by MFI structure titanium silicon molecular sieve and the 20.0-99.0 % by weight particle diameter of 1.0-80.0 % by weight forms spherical or irregular particle.Described inorganic oxide is selected from TiO
2, SiO
2, ZrO
2, Al
2o
3, Na
2o, CaO, K
2o, PbO or the compound in them or mixture, inorganic oxide is spherical or irregular particle shape.This patent also discloses the method for preparing above-mentioned catalyst, the method comprises inorganic oxide is incorporated into silicon source: titanium source: template: alkali: the mol ratio of distilled water is in the MFI structure titanium silicon molecular sieve Hydrothermal Synthesis system that forms of 1:0.001-0.2:0.03-0.5:0.1-5:10-200, before normal crystallization, can be at 0-100 ℃ low temperature maturation 1-5 days, make MFI structure titanium silicon molecular sieve separate out nucleus and growth in situ in inorganic oxide surface, again at 120-200 ℃ of normal crystallization 1-10 days, then composite is separated with mother liquor, drying, roasting is made; The composite catalyst making is again through 1-5 formed in situ.This patent further discloses described catalyst can be for take the propylene ring oxidation reaction that hydrogen peroxide is oxidant.But the inorganic oxide in the disclosed catalyst of this patent working example is the mixture of silica or silica and aluminium oxide; And, according to the disclosed data of this patent specification, can find out, the disclosed composite catalyst of this patent is for take the propylene ring oxidation reaction that hydrogen peroxide is oxidant, and the conversion ratio of hydrogen peroxide (for 91.4-94.8%) and expoxy propane selective (for 80.8-89.2%) need further to improve.
CN101203306A discloses a kind of epoxidation catalyst, this catalyst comprises titanium zeolite or vanadium zeolite, adhesive and zinc oxide, and described catalyst is by preparing the aqueous mixture of described zeolite, adhesive source and zinc oxide source and described mixture being produced through rapid draing.Although this application discloses the catalyst obtaining in conjunction with zinc in spray-drying process and has compared with the catalyst that does not contain zinc, the open-loop rate of expoxy propane significantly reduces, but much higher than the open-loop rate of catalyst that does not contain zinc in conjunction with the open-loop rate of the catalyst of zinc again be dried formation particle by spraying after.Therefore, according to the preparation method of the catalyst of this application, processing sequence is had to high dependence; And this application is the concrete conversion ratio of hydrogen peroxide and expoxy propane selective in epoxidation process openly.
CN1418876A discloses a kind of olefin epoxidation catalysts, and by weight percentage, this catalyst comprises the alumina support of following component: 10-50%; The HTS of 40-80%, HTS general formula is xTiO
2(1-x) SiO
2, x=0.0005-0.04, wherein x is mol ratio, x=Ti/ (Si+Ti); The alkali metal of 5-40% or alkaline earth oxide and composition thereof.Although the catalyst of this application, for take the propylene ring oxidation reaction that hydrogen peroxide is oxidant, can obtain higher expoxy propane selective, hydrogen peroxide low conversion rate, is only 85.1-93.5%.
Therefore, still need a kind of like this catalyst, this catalyst not only has enough hardness and wearability, and has high catalytic activity, can also use the epoxidation reaction of this catalyst to have high epoxidation product selectively and hydrogen peroxide conversion simultaneously.
Summary of the invention
The object of the present invention is to provide a kind of olefin epoxidation catalysts and preparation method thereof, this olefin epoxidation catalysts has high crushing strength and in epoxidation reaction of olefines, demonstrates higher epoxides selectively and hydrogen peroxide conversion; The present invention also aims to provide a kind of method of epoxidation of olefins, the method has the selective and hydrogen peroxide conversion of higher epoxidation product.
The invention provides a kind of olefin epoxidation catalysts, wherein, this catalyst contains HTS, binding agent and alkaline earth oxide, and described binding agent is amorphous silica.
The present invention also provides a kind of method for the preparation of described olefin epoxidation catalysts, wherein, the method comprises: the mixture that preparation contains HTS, binding agent source, alkaline earth oxide and water, this mixture moulding is obtained to formed body, and the dry and roasting by described formed body; Described binding agent source is to select free Ludox, have the silane of at least two hydrolyzable groups and have at least one in the siloxanes of at least two hydrolyzable groups; In described mixture, HTS, with SiO
2the weight ratio of binding agent source, alkaline earth oxide and the water of meter is (70-98): (1.5-40): (0.05-25): (5-50).
The present invention also provides a kind of method of epoxidation of olefins, and the method is included under catalyst existence, and alkene is contacted in solvent with hydrogen peroxide, and wherein, described catalyst is catalyst provided by the invention.
When although the disclosed catalyst of CN1418876A is used for epoxidation reaction, expoxy propane selectively can reach more than 95%, but should be noted that, in the epoxidation reaction condition adopting in documents 1 embodiment, the concentration of hydrogen peroxide is low, is only 0.78 mol/L.That is to say, the high expoxy propane that the disclosed catalyst of CN1418876A demonstrates in propylene ring oxidation reaction condition is to be selectively based upon on the basis of the hydrogen peroxide that uses low concentration, if further improve the concentration of hydrogen peroxide, the disclosed catalyst of CN1418876A is difficult to demonstrate high catalytic activity in propylene ring oxidation reaction, i.e. selective the and hydrogen peroxide conversion of high expoxy propane.The present inventor is through research discovery, and this may be because the acidity of aluminium oxide is stronger, causes the expoxy propane generating, on the acidic site of catalyst, solvolytic reaction occurs, and then makes expoxy propane elective reduction.For this problem, the present invention adopt acid ratio aluminum oxide weak many amorphous silica as the binding agent of olefin epoxidation catalysts, thereby reduced the quantity of acidic site on catalyst.
The present inventor further finds in experiment, although adopt amorphous silica can improve the selective and hydrogen peroxide conversion of the epoxides of epoxidation reaction of olefines, the conversion ratio selective and hydrogen peroxide of epoxides still awaits further raising; If add a certain amount of alkaline earth oxide, can significantly improve the selective and hydrogen peroxide conversion of the epoxides of olefin epoxidation catalysts.Although this may be acidity due to amorphous silica a little less than compared with aluminium oxide many, but still there is acidic site in the surface of amorphous silica, may cause epoxides generation side reaction, in catalyst, add appropriate alkaline earth oxide, this alkaline earth oxide can react with the water in reaction system and generate corresponding alkali, thereby can in and the acidic site on HTS surface, and then it is selective to improve the epoxides of epoxidation catalyst.
In addition, although adopt alkali metal oxide also can realize in and the object of the acidic site on HTS surface, but alkali metal oxide is stronger with the alkalescence of the alkali forming after water in reaction system reacts, be easy to make epoxides generation side reaction, and then make epoxides elective reduction.Olefin epoxidation catalysts therefore of the present invention adopts alkaline earth oxide as metal oxide.
In the epoxidation reaction of propylene, adopt olefin epoxidation catalysts of the present invention as catalyst, and use the aqueous solution of hydrogen peroxide as oxidant, can so that hydrogen peroxide conversion higher than 96%, epoxides is selectively higher than 95%.
According to preparation olefin epoxidation catalysts of the present invention, method is simple, and do not use or substantially not with an organic solvent, so environmental protection.According to the hydrogen peroxide conversion of the method for epoxidation of olefins of the present invention, high and epoxides is selectively good.
The specific embodiment
The invention provides a kind of olefin epoxidation catalysts, wherein, this catalyst contains HTS, binding agent and alkaline earth oxide, and described binding agent is amorphous silica.
According to olefin epoxidation catalysts of the present invention, described catalyst contains alkaline earth oxide.Described alkaline earth oxide can neutralize the acidic site in described catalyst, has reduced the probability of epoxidation product generation side reaction, has improved the selective of epoxidation product.Preferably, described metal oxide is magnesia and/or calcium oxide.
According to olefin epoxidation catalysts of the present invention, described catalyst contains HTS.Described HTS can be replaced the various molecular sieves that form for the part silicon atom in skeleton structure by titanium atom, be preferably have MFI structure HTS, have MWW structure HTS, there is the HTS of MCM structure and there are one or more in the HTS of BETA structure.More preferably, described HTS is the HTS with MFI structure.Most preferably, described HTS is the hollow HTS with MFI structure.
The crystal grain of the hollow HTS of the described MFI of having structure is hollow-core construction, and the radical length of the cavity part of this hollow crystal grain is 5-300 nanometer, and described HTS is at 25 ℃, P/P
0=0.10, adsorption time is that the benzene adsorbance recording under the condition of 1 hour is at least 70 milligrams/grams, and this has between the adsorption isotherm of nitrogen absorption under low temperature of hollow HTS of MFI structure and desorption isotherm and has hysteresis loop.Described hollow HTS can make with reference to the disclosed method of CN1132699C, the hollow HTS that the trade mark that the hollow HTS using in the embodiment of the present invention is produced for Hunan Jian Chang Co., Ltd is HTS.
While carrying out epoxidation reaction of olefines under the hollow HTS of the described MFI of having structure exists, reaction raw materials contacts with HTS and reacts with the cavity part that solvent can enter described catalyst at an easy rate, thereby further strengthens the activity of catalyst; Oxyalkylene as epoxidation product also can come off from the active site of HTS at an easy rate simultaneously, and then diffuse in the cavity of this HTS, shortened the time of staying of oxyalkylene on the avtive spot of HTS, further reduce the probability of oxyalkylene generation side reaction, thereby further improved the selective of epoxidation reaction.
According to olefin epoxidation catalysts of the present invention, described catalyst also contains binding agent.Described binding agent can be given described HTS with certain shape and intensity.Although amorphous silica and aluminium oxide are all the conventional binding agents in this area, but compare with amorphous silica, aluminium oxide has stronger acidity, and side reaction very easily occurs epoxides under acid condition, and then epoxides is selectively declined.Therefore,, according to olefin epoxidation catalysts of the present invention, described binding agent is amorphous silica.Described amorphous silica is well known to a person skilled in the art, repeats no more herein.
According to olefin epoxidation catalysts of the present invention, the weight ratio of described HTS, amorphous silica and alkaline earth oxide can be (70-98): (1.5-40): (0.05-25).When the too high levels of described alkaline earth oxide, the intensity of catalyst may be not enough; When the content of described alkaline earth oxide is too low, can not improve significantly the conversion ratio of the selective and hydrogen peroxide of epoxidation product.From the angle of the conversion ratio of the selective and hydrogen peroxide of further raising epoxidation product, the weight ratio of described HTS, amorphous silica and alkaline earth oxide is preferably (70-98): (1.5-25): (0.4-2).Under the prerequisite of conversion ratio of selective and hydrogen peroxide of guaranteeing epoxidation product; angle from the intensity of further raising catalyst; the weight ratio of described HTS, amorphous silica and alkaline earth oxide is preferably (80-98): (1.5-20): (0.1-15), and more preferably (80-98): (1.5-18): (0.4-1.6).
HTS is the active component in the catalyst of EPOXIDATION OF ALKENES CATALYZED BY, and in theory, the content of HTS is higher, and the catalytic activity of the catalyst that the HTS of take is active component is just higher.But, while carrying out the epoxidation reaction of alkene due to employing fixed bed reactors technique, require catalyst to there is high crushing strength, thereby avoid that the catalytic bed lamination that causes increases and the problem of catalyst loss because catalyst breaks, thus in olefin epoxidation catalysts the content of binding agent conventionally more than 80 % by weight.The present inventor finds in practice, adopts the HTS with hollow-core construction of the present invention, can significantly reduce the content of binding agent in catalyst, thereby improves the catalytic activity of catalyst.The gross weight of described catalyst of take is benchmark, the content of described HTS is preferably 90-97 % by weight, the total amount of described amorphous silica and metal oxide is preferably 3-10 % by weight, and the weight ratio of described amorphous silica and alkaline earth oxide is preferably 1:(0.05-1).Further preferably, the gross weight of described catalyst of take is benchmark, the content of described HTS is 93-97 % by weight, the total amount of described amorphous silica and metal oxide is preferably 3-7 % by weight, and the weight ratio of described amorphous silica and alkaline earth oxide is preferably 1:(0.1-0.3).So not only can be so that catalyst has high crushing strength, and can obtain high hydrogen peroxide conversion and epoxides selective.
The present invention also provides a kind of preparation method of the catalyst for epoxidation reaction of olefines, wherein, the method comprises: the mixture that preparation contains HTS, binding agent source, alkaline earth oxide and water, this mixture moulding is obtained to formed body, and the dry and roasting by described formed body; Described binding agent source is to select free Ludox, have the silane of at least two hydrolyzable groups and have at least one in the siloxanes of at least two hydrolyzable groups; In described mixture, HTS, with SiO
2the weight ratio of binding agent source, alkaline earth oxide and the water of meter is (70-98): (1.5-40): (0.05-25): (5-50).In the present invention, described " formed body " refers to the effigurate goods of tool, such as: spheric granules, rod-shpaed particle etc.; Described Ludox refers to take the colloidal solution of the silica that water is decentralized photo, and wherein, the content of silica can be 20-40 % by weight.
According to the present invention, in described mixture, HTS, with SiO
2the consumption of binding agent source, alkaline earth oxide and the water of meter can carry out suitable selection according to the amount of HTS, amorphous silica and alkaline earth oxide in the catalyst of expection, as long as in described mixture, and HTS, with SiO
2the consumption of binding agent source, alkaline earth oxide and the water of meter can guarantee that the amount of HTS, amorphous silica and alkaline earth oxide in final catalyst meets previously described requirement.Preferably, in described mixture, HTS, with SiO
2the weight ratio of binding agent source, alkaline earth oxide and the water of meter is (70-98): (1.5-40): (0.05-25): (5-50).
According to the method for preparing olefin epoxidation catalysts of the present invention, described binding agent source can be for being selected from by Ludox, having the silane of at least two hydrolyzable groups and have at least one in the siloxanes of at least two hydrolyzable groups.Preferably, the silane with at least two hydrolyzable groups and/or the siloxanes with at least two hydrolyzable groups are contained in described binding agent source.By the described hydrolysis-condensation reaction that there is the silane of at least two hydrolyzable groups and/or there is the siloxanes of at least two hydrolyzable groups, can original position generate amorphous silica so on the one hand, give HTS certain shape; The amorphous silica generating at least partly on the other hand can with the silicon hydroxyl generation chemical interaction on HTS surface, thereby strengthen the adhesion strength between amorphous silica and HTS, improve the crushing strength of catalyst of the present invention, and then can reduce the content of binding agent in catalyst.
More preferably, described binding agent source is contained and is had the silane of at least two hydrolyzable groups and have at least one and the Ludox in the siloxanes of at least two hydrolyzable groups.Can guarantee that olefin epoxidation catalysts has under the condition of high intensity like this, reduce the manufacturing cost of catalyst.Described have the silane of at least two hydrolyzable groups, the siloxanes with at least two hydrolyzable groups and the ratio between Ludox and can carry out suitable selection according to the intensity of catalyst of expection, is not particularly limited.Preferably, from olefin epoxidation catalysts is had the prerequisite of enough intensity, reduce the angle of the manufacturing cost of olefin epoxidation catalysts and set out, with SiO
2meter, described Ludox with described in the weight ratio that there is the silane of at least two hydrolyzable groups and/or there is the siloxanes of at least two hydrolyzable groups be 1:(0.02-1).
Described have the silane of at least two hydrolyzable groups and/or have the silane that contains at least two hydrolyzable groups in the molecular structure that the siloxanes of at least two hydrolyzable groups can be known to the skilled person and/or the siloxanes with at least two hydrolyzable groups.
Preferably, the silane that contains at least two hydrolyzable groups described in is with the silane shown in following formula 1:
Formula 1
Wherein, R
1, R
2, R
3and R
4in at least two be-OR independently of one another
11or-OCOR
12, R
1, R
2, R
3and R
4in at the most two be-R independently of one another
13, R
11and R
12be C independently of one another
1-C
5the alkyl of straight or branched, R
13for C
1-C
5the alkyl of straight or branched.
The silane more preferably, with at least two hydrolyzable groups is one or more in tetramethoxy-silicane, tetraethoxysilane, MTMS, ethyl trimethoxy silane, dimethyldimethoxysil,ne, diethyl dimethoxy silane, MTES, dimethyldiethoxysilane, methyl silicate and ethyl orthosilicate.
The siloxanes preferably, with at least two hydrolyzable groups is with the siloxanes shown in following formula 2:
Formula 2
Wherein, R
5, R
6, R
7, R
8, R
9and R
10in at least two be-OR independently of one another
14or-OCOR
15, R
5, R
6, R
7, R
8, R
9and R
10in at the most four be-R independently of one another
16, R
14and R
15be C independently of one another
1-C
5the alkyl of straight or branched, R
16for C
1-C
5the alkyl of straight or branched.
In the present invention, C
1-C
5the alkyl of straight or branched can be for example methyl, ethyl, n-pro-pyl, isopropyl, normal-butyl, isobutyl group, sec-butyl, the tert-butyl group, n-pentyl.
More preferably, described in there are at least two hydrolyzable groups siloxanes be 1,3-dimethoxy-1,1,3,3-tetramethyl disiloxane and/or 1,3-diethoxy-1,1,3,3-tetramethyl disiloxane.
According to the method for preparing olefin epoxidation catalysts of the present invention, in described binding agent source, contain when thering is the silane of at least two hydrolyzable groups and/or thering is the siloxanes of at least two hydrolyzable groups, the method also comprises: described formed body was processed to 1-10 hour with the aqueous solution of alkali before carrying out described roasting at 20-100 ℃, the condensation reaction thereby the siloxanes that has the silane of at least two hydrolyzable groups described in making and/or have at least two hydrolyzable groups is hydrolyzed, forms amorphous silica.
Described alkali can be both also inorganic base for organic base.When described alkali is inorganic base, is preferably and take alkali metal as cationic alkali; When described alkali is organic base, be preferably the alkali that can resolve into gas under hot conditions.Particularly, described alkali can be one or more in NaOH, potassium hydroxide, TMAH and tetraethyl ammonium hydroxide.The consumption of described alkali can be according to having the silane of at least two hydrolyzable groups and/or the amount of siloxanes is selected.Preferably, the concentration of the aqueous solution of described alkali is 0.1-10 % by mole, and the aqueous solution of described alkali and the weight ratio of described formed body are (0.5-5): 1.
Preparation in accordance with the present invention, when Ludox is contained in described binding agent source, the water in described mixture can come from described Ludox on the one hand, when in Ludox, the amount of water can not meet instructions for use on the other hand, can also supplement interpolation water, thereby make the amount of water meet instructions for use.
The present invention is not particularly limited described dry condition, and usually, described dry temperature can be 60-80 ℃, and the described dry time can be 3-8 hour, and described dry pressure can be normal pressure or decompression.
Described roasting can be carried out well known to a person skilled in the art under condition, is not particularly limited.Preferably, the condition of described roasting comprises: the temperature of roasting is 300-600 ℃, and the time of roasting is 5-15 hour.
Preparation in accordance with the present invention, described mixture can also contain auxiliary agent.The present invention is not particularly limited the kind of described auxiliary agent, can be the conventional various auxiliary agents in this area, is preferably one or more in glycerine, polyvinylpyrrolidone, methylcellulose and polyvinyl alcohol.Can be according to the intensity of the catalyst of the content of HTS, amorphous silica and metal oxide in described catalyst and kind and expection and the consumption that catalytic activity is determined described auxiliary agent.Preferably, the total amount of described mixture of take is benchmark, and the consumption of described auxiliary agent is 0.5-3 % by weight.
Preparation in accordance with the present invention, described mixture also contains surfactant.Described surfactant can significantly reduce the surface tension of water, makes to have certain hydrophobic HTS and is easy to be soaked by water, thereby amorphous silica can be more evenly dispersed on HTS.The various surfactants that described surfactant can be known to the skilled person, are not particularly limited.Various water soluble surfactant actives and/or oil soluble surfactant that described surfactant can be known to the skilled person, be not particularly limited.Described oil soluble surfactant can be for example fatty acid esters of sorbitan (Span series) and/or APES (OP-10).Described oil soluble surfactant is preferably Arlacel-20 (Span20), Arlacel-40 (Span40), Arlacel-60 (Span60), Arlacel-65 (Span65), Arlacel-80 (Span80), sorbitan trioleate (Span85), NPE (TX-10), one or more in OPEO (OPE-10) and dodecyl phenol polyethenoxy ether.Described water soluble surfactant active can be for example one or more in polyoxyethylene sorbitan fatty acid ester (Tween series), polyoxyethylene fatty acid ester, polyoxyethylene aliphatic alcohol ether (AEO series), Pluronic F68 and alkylolamides (Ni Nale, Ninol).Described water soluble surfactant active is preferably one or more in polyoxyethylene sorbitan monolaurate (Tween20), polyethenoxy sorbitan monopalmitate (Tween40), polyethenoxy sorbitan monostearate (Tween60), polyoxyethylene sorbitan monooleate (Tween80) and polyethenoxy sorbitan trioleate (Tween85).The consumption of described surfactant can be determined according to the amount of used HTS, amorphous silica and metal oxide and kind.Preferably, the total amount of described mixture of take is benchmark, and the consumption of described surfactant is 0.001-0.2 % by weight.
The present invention also provides a kind of method of epoxidation of olefins, and the method is included in fixed bed reactors, under catalyst exists, alkene is contacted in solvent with hydrogen peroxide, and wherein, described catalyst is catalyst provided by the invention.
Olefin epoxidation catalysts according to the present invention there is high hydrogen peroxide conversion and epoxides selective, therefore according to the method for epoxidation of olefins of the present invention, also there is high hydrogen peroxide conversion and epoxides selective.
Because making catalyst that the application of the invention provides, the method for epoxidation of olefins of the present invention improves hydrogen peroxide conversion and epoxides optionally, therefore the present invention is not particularly limited for other condition of epoxidation of olefins, can adopt various condition well known to those skilled in the art to carry out the epoxidation reaction of alkene, as long as the catalyst adopting is catalyst provided by the present invention.
Preferably, solvent: alkene: the mol ratio of hydrogen peroxide is (4-15): (0.5-5): 1.Described alkene can for example, for being selected from the alkene that carbon number is 2-8: propylene, butylene and isomers thereof, amylene and isomers thereof, hexene and isomers thereof, heptene and isomers thereof and octene and isomers thereof.Preferably, described alkene is propylene.Described solvent can be selected from the fatty alcohol that water, acetonitrile and carbon number are 1-6.Described carbon number be 1-6 fatty alcohol for example: methyl alcohol, ethanol, propyl alcohol and isomers thereof, butanols and isomers thereof, amylalcohol and isomers thereof and hexanol and isomers thereof.Preferably, described solvent is methyl alcohol.The condition of described contact is well known to a person skilled in the art, for example, the temperature of described contact can be 30-90 ℃, and the pH that can be 0.5-4.5MPa and reaction system at pressure carries out described contact under 5-8, and liquid hourly space velocity (LHSV) can be 0.1-7h
-1.Liquid hourly space velocity (LHSV) in the present invention is liquid volume air speed.
In the present invention, the consumption (weight, weight ratio or weight percentage) of the solid matters such as described HTS, alkaline earth oxide and described formed body calculates with its butt weight, so-called " butt weight " refer to sample through 800 ℃ of roastings the weight after 2 hours.
Below in conjunction with embodiment, the present invention is described in more detail.
In following examples, with reference to the method for stipulating in GB3635-1983, the upper crushing strength of measuring catalyst of the crushing strength analyzer that is QCY-602 in model (manufacture of alkaline research institute of the Ministry of Chemical Industry).
Adopt x-ray fluorescence spectrometry method (XRF) on Philips PW-2400 type x-ray fluorescence spectrometry instrument, to measure the composition of catalyst.
Adopt gas chromatography to analyze the composition of epoxidation product: to take methyl tertiary butyl ether(MTBE) as internal standard compound, adopt Agilent-6890 type chromatograph, adopt 30m * 0.25mm FFTP capillary column, sample size is 1.0 μ L, and injector temperature is 180 ℃, and the temperature of capillary column is kept 4 minutes at 60 ℃, then with the speed of 20 ℃/min, be increased to 200 ℃, and keep 4 minutes, adopting flame ionization detector (FID), sensing chamber's temperature is 240 ℃.
Adopt the concentration of Indirect iodimetry analytical reactions front and back hydrogen peroxide, thereby calculate the conversion ratio of hydrogen peroxide.
Embodiment 1
The present embodiment is used for explanation according to the method for olefin epoxidation catalysts of the present invention and preparation method thereof and epoxidation of olefins.
By 100g HTS powder (Hunan Jian Chang Co., Ltd, the trade mark is HTS) mix with 1g magnesia and 10g tetramethoxy-silicane (Qingdao century star chemical reagent Co., Ltd), after mixing, add 5g Ludox (dioxide-containing silica 30 % by weight), 0.2g Span80,2g polyvinyl alcohol (Sanming City Ding Hui Chemical Co., Ltd., the trade mark is polyvinyl alcohol 2099), 1g sesbania powder (Dongming County Zhu Wa sesbania gum factory) and 50g water mixes, then extrusion molding pelletizing, is then dried 4 hours at 70 ℃.The formed body obtaining is of a size of 2 * 2 millimeters.
Get the there-necked flask that above-mentioned formed body 100g puts into 500mL, adding 200g concentration is the sodium hydrate aqueous solution of 10 % by mole, follows to stir said mixture is heated to 90 ℃, and keeps 6 hours.Then filter and obtain solid phase, by deionized water, the solid phase washing obtaining is extremely neutral.Then, the solid phase obtaining is dried to 3 hours at 120 ℃, finally 550 ℃ of roastings 3 hours, thereby obtains catalyst according to the invention.After measured, the intensity of this catalyst is 160N/cm; By XRF analysis, measure, in this catalyst, the content of HTS is 93.2 % by weight, and amorphous silica and magnesian weight ratio are 1:0.2.
14g catalyst is loaded in the isothermal reaction district of fixed-bed tube reactor, catalyst fills porcelain ring filler up and down, and makes whole reaction system seal intact.Make propylene and liquid stream enter reaction zone in the mode to upper reaches, wherein, methyl alcohol in liquid stream: propylene: the mol ratio of hydrogen peroxide is 6:2:1, in liquid stream, add ammoniacal liquor, the pH that makes described liquid stream is 5.3, adds the Span80 of 0.98 % by weight and the Tween80 of 0.06 % by weight in described liquid stream simultaneously.Controlling reaction temperature is 40 ℃, and reaction pressure is 2.5MPa, and liquid hourly space velocity (LHSV) is 1.5h
-1.Sampling analysis product, obtaining hydrogen peroxide conversion is 98.5%, expoxy propane is selectively 97.7%.
Comparative example 1
Adopt the method Kaolinite Preparation of Catalyst identical with embodiment 1, different, do not add magnesia.By XRF analysis, measure, in the catalyst obtaining, the content of HTS is 94.2 % by weight, and the intensity of this catalyst is 60N/cm.
Adopt the method identical with embodiment 1 to carry out epoxidation reaction, different, the catalyst using is the prepared catalyst of comparative example 1.In this epoxidation reaction, hydrogen peroxide conversion is 97.3%, and expoxy propane is selectively 89.1%.
Comparative example 2
Adopt the method Kaolinite Preparation of Catalyst identical with embodiment 1, different, do not add magnesia, but add 1g zinc oxide.The intensity of this catalyst is 65N/cm; By XRF analysis, measure, in this catalyst, the content of HTS is 93.4 % by weight, and the weight ratio of amorphous silica and zinc oxide is 1:0.2.
Adopt the method identical with embodiment 1 to carry out epoxidation reaction, different, the catalyst using is the prepared catalyst of comparative example 2.In this epoxidation reaction, hydrogen peroxide conversion is 97.2%, and expoxy propane is selectively 90.5%.
Embodiment 2
The present embodiment is used for explanation according to the method for olefin epoxidation catalysts of the present invention and preparation method thereof and epoxidation of olefins.
Adopt the method identical with embodiment 1 to prepare olefin epoxidation catalysts, different is, HTS powder (Hunan Jian Chang Co., Ltd, the trade mark is HTS) consumption be 80g, magnesian consumption is 3g, and the consumption of tetraethoxysilane (Qufu morning twilight Chemical Co., Ltd.) is 64g, and the consumption of Ludox (content of silica is 30 % by weight) is 30g, the consumption of Span80 is 2g, and the consumption of water is 20g.After measured, the intensity of this catalyst is 180N/cm; By XRF analysis, measure, in this catalyst, the content of HTS is 70 % by weight, and amorphous silica and magnesian weight ratio are 1:0.11.
Adopt the method identical with embodiment 1 to carry out epoxidation reaction, different, the catalyst using is the prepared catalyst of embodiment 2.Sampling analysis product, obtaining hydrogen peroxide conversion is 94.4%, expoxy propane is selectively 98.5%.
Embodiment 3
The present embodiment is used for explanation according to the method for olefin epoxidation catalysts of the present invention and preparation method thereof and epoxidation of olefins.
Adopt the method identical with embodiment 1 to prepare olefin epoxidation catalysts, different is, HTS powder (Hunan Jian Chang Co., Ltd, the trade mark is HTS) consumption be 120g, the consumption of calcium oxide is 0.5g, the consumption of MTES (Qufu morning twilight Chemical Co., Ltd.) is 7g, and the consumption of Ludox (content of silica is 30 % by weight) is 2g, and the consumption of Tween20 is 0.15g.After measured, the intensity of this catalyst is 120N/cm; By XRF analysis, measure, in this catalyst, the content of HTS is 97 % by weight, and amorphous silica and magnesian weight ratio are 1:0.2.
Adopt the method identical with embodiment 1 to carry out epoxidation reaction, different, the catalyst using is the prepared catalyst of embodiment 2.Sampling analysis product, obtaining hydrogen peroxide conversion is 99.8%, expoxy propane is selectively 98.2%.
Embodiment 4
The present embodiment is used for explanation according to the method for olefin epoxidation catalysts of the present invention and preparation method thereof and epoxidation of olefins.
By 100g HTS powder (Hunan Jian Chang Co., Ltd, the trade mark is HTS), with 2g magnesia, 70g Ludox (mass fraction is 30 % by weight), 0.2g Span80,2g polyvinyl alcohol (Sanming City Ding Hui Chemical Co., Ltd., the trade mark is polyvinyl alcohol 2099), 1g sesbania powder (Dongming County Zhu Wa sesbania gum factory) and 20g water mixes, mix rear extrusion molding, catalyst size is 2 * 2 millimeters, 70 ℃ dry after 4 hours 550 ℃ of roastings 3 hours, thereby obtain catalyst according to the invention.After measured, the intensity of this catalyst is 165N/cm; By XRF analysis, measure, in this catalyst, the content of HTS is 81 % by weight, and amorphous silica and magnesian weight ratio are 1:0.08.
Adopt the method identical with embodiment 1 to carry out epoxidation reaction, different, the catalyst using is the catalyst of embodiment 4 preparations.Sampling analysis product, obtaining hydrogen peroxide conversion is 96.4%, expoxy propane is selectively 95.2%.
Comparative example 3
Adopt the method Kaolinite Preparation of Catalyst identical with embodiment 4, different, with aluminium oxide, replace Ludox.The intensity of this catalyst is 90N/cm; By XRF analysis, measure, in this catalyst, the content of HTS is 82 % by weight, and aluminium oxide and magnesian weight ratio are 1:0.09.
Adopt the method identical with embodiment 1 to carry out epoxidation reaction, different, the catalyst using is the prepared catalyst of comparative example 3.In this epoxidation reaction, hydrogen peroxide conversion is 93.6%, and expoxy propane is selectively 90.5%.
Comparative example 4
Adopt hollow HTS powder (Hunan Jian Chang Co., Ltd, the trade mark is HTS), according to the method Kaolinite Preparation of Catalyst of CN1132200 embodiment 2.The intensity of this catalyst is 100N/cm; By XRF analysis, measure, in this catalyst, the content of HTS is 79 % by weight, and aluminium oxide and magnesian weight ratio are 1:0.27.
Adopt the method identical with embodiment 1 to carry out epoxidation reaction, different, the catalyst using is the prepared catalyst of comparative example 4.In this epoxidation reaction, hydrogen peroxide conversion is 90.4%, and expoxy propane is selectively 90.3%.
Embodiment 5
The present embodiment is used for explanation according to the method for olefin epoxidation catalysts of the present invention and preparation method thereof and epoxidation of olefins.
By 100g HTS powder (Hunan Jian Chang Co., Ltd, the trade mark is HTS), mix with 2g magnesia, 70g tetramethoxy-silicane (Qingdao century star chemical reagent Co., Ltd), after mixing, add 0.2g Span80,2g polyvinyl alcohol (Sanming City Ding Hui Chemical Co., Ltd., the trade mark is polyvinyl alcohol 2099), 1g sesbania powder (Dongming County Zhu Wa sesbania gum factory) and 50g water mixes, then extrusion molding pelletizing, is then dried 4 hours at 70 ℃.The formed body obtaining is of a size of 2 * 2 millimeters.
Get the there-necked flask that above-mentioned formed body 100g puts into 500mL, adding 200mL concentration is the sodium hydrate aqueous solution of 20 % by weight, follows to stir said mixture is heated to 90 ℃, and keeps 6 hours.Then filter and obtain solid phase, by deionized water, the solid phase washing obtaining is extremely neutral.Then, the solid phase obtaining is dried to 3 hours at 120 ℃, finally 550 ℃ of roastings 3 hours, thereby obtains catalyst according to the invention.After measured, the intensity of this catalyst is 200N/cm; By XRF analysis, measure, in this catalyst, the content of HTS is 75 % by weight, and amorphous silica and magnesian weight ratio are 1:0.07.
Adopt the method identical with embodiment 1 to carry out epoxidation reaction, different, the catalyst using is the catalyst of embodiment 5 preparations.Sampling analysis product, obtaining hydrogen peroxide conversion is 95.8%, expoxy propane is selectively 95.3%.
Above embodiment shows, catalyst according to the invention in the epoxidation reaction of alkene, demonstrate high hydrogen peroxide conversion and epoxides selective.
Claims (17)
1. the preparation method for the catalyst of epoxidation reaction of olefines, it is characterized in that, the method comprises: the mixture that preparation contains HTS, binding agent source, alkaline earth oxide and water, this mixture moulding is obtained to formed body, and the dry and roasting by described formed body; Described binding agent source is to select free Ludox, have the silane of at least two hydrolyzable groups and have at least one in the siloxanes of at least two hydrolyzable groups; In described mixture, HTS, with SiO
2the weight ratio of binding agent source, alkaline earth oxide and the water of meter is (70-98): (1.5-40): (0.05-25): (5-50).
2. method according to claim 1, wherein, HTS in described mixture, with SiO
2in the catalyst that the consumption of binding agent source, alkaline earth oxide and the water of meter makes finally to obtain, the weight ratio of HTS, amorphous silica and alkaline earth oxide is (80-98): (1.5-20): (0.1-15).
3. method according to claim 1, wherein, HTS in described mixture, with SiO
2in the catalyst that the consumption of binding agent source, alkaline earth oxide and the water of meter makes finally to obtain, the weight ratio of HTS, amorphous silica and alkaline earth oxide is (80-98): (1.5-18): (0.4-1.6).
4. method according to claim 3, wherein, HTS in described mixture, with SiO
2the gross weight of the catalyst that the consumption of binding agent source, alkaline earth oxide and the water of meter makes finally to obtain is benchmark, the content of HTS is 90-97 % by weight, the total amount of amorphous silica and alkaline earth oxide is 3-10 % by weight, and the weight ratio of described amorphous silica and described alkaline earth oxide is 1:(0.05-1).
5. according to the method described in any one in claim 1-4, wherein, described alkaline earth oxide is magnesia and/or calcium oxide.
6. according to the method described in any one in claim 1-4, wherein, described HTS is HTS, the HTS with MWW structure with MFI structure, has the HTS of MCM structure and have one or more in the HTS of BETA structure.
7. method according to claim 6, wherein, described in there is the HTS of MFI structure crystal grain be hollow-core construction, the radical length of the cavity part of this hollow-core construction is 5-300 nanometer, described in there is MFI structure HTS at 25 ℃, P/P
0=0.10, adsorption time is that the benzene adsorbance recording under the condition of 1 hour is at least 70 milligrams/grams, and this has between the adsorption isotherm of nitrogen absorption under low temperature of HTS of MFI structure and desorption isotherm and has hysteresis loop.
8. method according to claim 1, wherein, the silane with at least two hydrolyzable groups and/or the siloxanes with at least two hydrolyzable groups are contained in described binding agent source.
9. method according to claim 8, wherein, Ludox is also contained in described binding agent source, with SiO
2meter, described Ludox with described in the weight ratio that there is the silane of at least two hydrolyzable groups and/or there is the siloxanes of at least two hydrolyzable groups be 1:(0.02-1).
10. method according to claim 8 or claim 9, wherein, the method also comprises: described formed body was processed to 1-10 hour with the aqueous solution of alkali before carrying out described roasting at 20-100 ℃.
11. methods according to claim 10, wherein, described alkali is one or more in NaOH, potassium hydroxide, TMAH and tetraethyl ammonium hydroxide, the concentration of the aqueous solution of described alkali is 0.1-10 % by mole, and the aqueous solution of described alkali and the weight ratio of described formed body are (0.5-5): 1.
12. according to the method described in claim 1 or 8, wherein, described in there are at least two hydrolyzable groups silane be the silane shown in formula 1,
Formula 1
Wherein, R
1, R
2, R
3and R
4in at least two be-OR independently of one another
11or-OCOR
12, R
1, R
2, R
3and R
4in at the most two be-R independently of one another
13, R
11and R
12be C independently of one another
1-C
5the alkyl of straight or branched, R
13for C
1-C
5the alkyl of straight or branched;
The described siloxanes with at least two hydrolyzable groups is the siloxanes shown in formula 2,
Formula 2
Wherein, R
5, R
6, R
7, R
8, R
9and R
10in at least two be-OR independently of one another
14or-OCOR
15, R
5, R
6, R
7, R
8, R
9and R
10in at the most four be-R independently of one another
16, R
14and R
15be C independently of one another
1-C
5the alkyl of straight or branched, R
16for C
1-C
5the alkyl of straight or branched.
13. methods according to claim 12, the silane wherein, with at least two hydrolyzable groups is one or more in tetramethoxy-silicane, tetraethoxysilane, MTMS, ethyl trimethoxy silane, dimethyldimethoxysil,ne, diethyl dimethoxy silane, MTES, dimethyldiethoxysilane, methyl silicate, ethyl orthosilicate; The described siloxanes with at least two hydrolyzable groups is 1,3-dimethoxy-1,1,3,3-tetramethyl disiloxane and/or 1,3-diethoxy-1,1,3,3-tetramethyl disiloxane.
14. methods according to claim 1, wherein, the condition of described roasting comprises: sintering temperature is 300-600 ℃, roasting time is 5-15 hour.
The method of 15. 1 kinds of epoxidation of olefins, the method is included in fixed bed reactors, under catalyst exists, alkene is contacted in solvent with hydrogen peroxide, it is characterized in that, described catalyst is the catalyst that in claim 1-14 prepared by the method described in any one.
16. methods according to claim 15, wherein, described alkene is propylene.
17. methods according to claim 15, wherein, the condition of described contact comprises: solvent: alkene: the mol ratio of hydrogen peroxide is (4-15): (0.5-5): 1, temperature is 30-90 ℃, and pressure is 0.5-4.5MPa, and liquid hourly space velocity (LHSV) is 0.1-7h
-1, the pH of reaction system is 5-8.
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| TWI585080B (en) * | 2014-07-29 | 2017-06-01 | 贏創德固賽有限責任公司 | Process for the epoxidation of an olefin |
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| CN114426549B (en) * | 2020-10-15 | 2024-02-09 | 中国石油化工股份有限公司 | Method for preparing dicyclopentadiene dioxide DCPDPO and 2-phenyl-2-propanol |
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