CN103586069B - For the preparation method of catalyzer and the method for epoxidation of olefins of epoxidation reaction of olefines - Google Patents
For the preparation method of catalyzer and the method for epoxidation of olefins of epoxidation reaction of olefines Download PDFInfo
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Abstract
The present invention provides the preparation method of a kind of catalyzer for epoxidation reaction of olefines, comprise the mixture of preparation containing HTS, binding agent source, alkaline earth metal oxide and water, this mixture forming is obtained formed body, and by dry for described formed body also roasting; Described binding agent source is be selected from by silicon sol, the silane with at least two hydrolysable group and at least one that has in the siloxanes of at least two hydrolysable group; In described mixture, HTS, with SiO2The weight ratio of binding agent source, alkaline earth metal oxide and the water counted is (70-98): (1.5-40): (0.05-25): (5-50). Present invention also offers a kind of method of epoxidation of olefins. The catalyzer adopting the method for the present invention to prepare demonstrates high hydrogen peroxide conversion and epoxide selectivity in epoxidation reaction of olefines.
Description
Point case application of Chinese patent application that the application to be the applying date be on October 11st, 2010, application number are 201010511564.3, denomination of invention is " method of olefin epoxidation catalysts and its preparation method and epoxidation of olefins ".
Technical field
The present invention relates to the method for the epoxidation of olefins of a kind of olefin epoxidation catalysts and its preparation method and this catalyzer of use.
Background technology
Along with the development of petrochemical complex and fine chemistry industry, oxygen-containing organic compound has become extremely important intermediate. It is oxygenant taking hydrogen peroxide, it is catalyst alkene epoxidation taking HTS thus prepares oxygen-containing organic compound and meet Green Chemistry and the requirement of atom economy idea of development, be a kind of novel environment-friendly process having development prospect.
Epoxide normally carries out epoxidation reaction in the presence of a catalyst by alkene and hydrogen peroxide to be prepared. At present, HTS is catalyzer the most frequently used in epoxidation reaction of olefines. But, when adopting fixed bed reaction technique, catalyzer containing HTS must be shaping and have enough crushing strengths, otherwise catalyzer is in use easily broken forms fine particle or powder, the catalyzer of this fragmentation can cause beds pressure drop to increase on the one hand, thus improves the danger that production run cost too increases production simultaneously; If the catalyzer of fragmentation is taken out of by reaction product on the other hand, then catalyst loss and product separation will be caused complicated.
Further, the chemical property of epoxide is active, is easy to further open loop generation side reaction, causes the selectivity of epoxide to reduce in reaction system.
CN1140348C discloses a kind of composite Ti-Si catalyst being made up of silicon source, titanium source, template, alkali, distilled water and inorganic oxide reaction, wherein, the inorganic oxide that this catalyzer is 0.1-20mm by the MFI structure HTS of 1.0-80.0 weight % and 20.0-99.0 weight % particle diameter forms spherical or irregular particle. Described inorganic oxide is selected from TiO2��SiO2��ZrO2��Al2O3��Na2O��CaO��K2O, PbO or the mixture in them or mixture, inorganic oxide is spherical or irregular particle shape. This patent also discloses the method preparing above-mentioned catalyzer, the method comprises the silicon source that is incorporated into by inorganic oxide: titanium source: template: alkali: the mol ratio of distilled water is in the MFI structure HTS Hydrothermal Synthesis system of 1:0.001-0.2:0.03-0.5:0.1-5:10-200 composition, before normal crystallization, can at 0-100 DEG C low temperature maturation 1-5 days, MFI structure HTS is made to precipitate out nucleus and growth in situ in inorganic oxide surface, again 120-200 DEG C normal crystallization 1-10 days, then matrix material is separated with mother liquor, drying, roasting is made; Obtained composite catalyst is again through 1-5 formed in situ. This patent discloses described catalyzer further and may be used for taking hydrogen peroxide as the propylene ring oxidation reaction of oxygenant. But, the inorganic oxide in catalyzer disclosed in this patent Example is silicon-dioxide or the mixture of silicon-dioxide and aluminum oxide; And, data disclosed in this patent specification can be found out, the composite catalyst of this patent disclosure be used for taking hydrogen peroxide be oxygenant propylene ring oxidation reaction in, the transformation efficiency (for 91.4-94.8%) of hydrogen peroxide and propylene oxide selectivity (for 80.8-89.2%) need to improve further.
CN101203306A discloses a kind of epoxidation catalyst, this catalyzer comprises titanium zeolite or vanadium zeolite, tackiness agent and zinc oxide, and described catalyzer is by preparing the aqueous mixture of described zeolite, adhesive source and zinc oxide source and described mixture is produced through rapid drying. Although that application discloses the catalyzer obtained in spray-drying process in conjunction with zinc compared with the catalyzer not containing zinc, the open-loop rate of propylene oxide significantly reduces, but then much higher than not open-loop rate containing the catalyzer of zinc in the open-loop rate forming after particle again catalyzer in conjunction with zinc by spraying dry. Therefore, according to the preparation method of the catalyzer of this application, processing sequence had extremely high dependency; Further, this application does not specifically disclose the transformation efficiency of hydrogen peroxide and the selectivity of propylene oxide in epoxidation process.
CN1418876A discloses a kind of olefin epoxidation catalysts, and by weight percentage, this catalyzer comprises the alumina supporter of following group of part: 10-50%; The HTS of 40-80%, HTS general formula is xTiO2��(1-x)SiO2, x=0.0005-0.04, wherein x is mol ratio, x=Ti/ (Si+Ti); The basic metal of 5-40% or alkaline earth metal oxide and mixture thereof. Although the propylene ring oxidation reaction of the catalyzer of this application for taking hydrogen peroxide as oxygenant, it is possible to obtain higher propylene oxide selectivity, but hydrogen peroxide low conversion rate, be only 85.1-93.5%.
Therefore, still a kind of like this catalyzer is needed, this catalyzer not only has enough hardness and wear resistance, and has high catalytic activity, simultaneously the epoxidation reaction of this catalyzer of use can also have high epoxidation product selectivity and hydrogen peroxide conversion.
Summary of the invention
It is an object of the invention to provide a kind of olefin epoxidation catalysts and its preparation method, this olefin epoxidation catalysts has high crushing strength and demonstrates higher epoxide selectivity and hydrogen peroxide conversion in epoxidation reaction of olefines; The present invention also aims to provide a kind of method of epoxidation of olefins, the method has selectivity and the hydrogen peroxide conversion of higher epoxidation product.
The present invention provides a kind of olefin epoxidation catalysts, and wherein, this catalyzer contains HTS, binding agent and alkaline earth metal oxide, and described binding agent is soft silica.
Present invention also offers a kind of method for the preparation of described olefin epoxidation catalysts, wherein, the method comprises: the mixture of preparation containing HTS, binding agent source, alkaline earth metal oxide and water, obtains formed body by this mixture forming, and by dry for described formed body also roasting; Described binding agent source is be selected from by silicon sol, the silane with at least two hydrolysable group and at least one that has in the siloxanes of at least two hydrolysable group; In described mixture, HTS, with SiO2The weight ratio of binding agent source, alkaline earth metal oxide and the water counted is (70-98): (1.5-40): (0.05-25): (5-50).
Present invention also offers a kind of method of epoxidation of olefins, the method comprises in the presence of a catalyst, is contacted in a solvent with hydrogen peroxide by alkene, and wherein, described catalyzer is catalyzer provided by the invention.
Although when catalyzer disclosed in CN1418876A is used for epoxidation reaction, propylene oxide selectivity can reach more than 95%, but it is to be noted that, in the epoxidation reaction condition adopted in documents 1 embodiment, the concentration of hydrogen peroxide is low, is only 0.78 mol/L. That is, the high propylene oxide selectivity that catalyzer disclosed in CN1418876A demonstrates in propylene ring oxidation reaction condition is based upon on the basis of the hydrogen peroxide using lower concentration, if improving the concentration of hydrogen peroxide further, catalyzer disclosed in CN1418876A is difficult to demonstrate high catalytic activity in propylene ring oxidation reaction, namely high propylene oxide selectivity and hydrogen peroxide conversion. The present inventor finds through research, and this may be owing to the acidity of aluminum oxide is relatively strong, causes the propylene oxide generated, on the acidic site of catalyzer, solvolytic reaction occurs, and then propylene oxide selectivity is reduced. For this problem, the present invention adopts acid much more weak than aluminum oxide soft silica as the binding agent of olefin epoxidation catalysts, thus decreases the quantity of acidic site on catalyzer.
The present inventor finds in an experiment further, although adopting soft silica can improve epoxide selectivity and the hydrogen peroxide conversion of epoxidation reaction of olefines, but the transformation efficiency of the selectivity of epoxide and hydrogen peroxide still awaits further raising; If adding a certain amount of alkaline earth metal oxide, then can significantly improve epoxide selectivity and the hydrogen peroxide conversion of olefin epoxidation catalysts. Although this may be owing to the acidity of soft silica is much weak compared with aluminum oxide, but still there is acidic site in the surface of soft silica, epoxide generation side reaction may be caused, add appropriate alkaline earth metal oxide in the catalyst, this alkaline earth metal oxide can carry out to the water in reaction system reacting the corresponding alkali of generation, such that it is able to the acidic site on neutralization HTS surface, and then improve the epoxide selectivity of epoxidation catalyst.
In addition, although adopting alkalimetal oxide can also realize the object neutralizing the acidic site on HTS surface, but the alkalescence of the alkali that the water in alkalimetal oxide and reaction system is formed after reacting is stronger, it is easy to make epoxide generation side reaction, and then epoxide selectivity is reduced. Therefore the olefin epoxidation catalysts of the present invention adopts alkaline earth metal oxide as metal oxide.
In the epoxidation reaction of propylene, adopt the olefin epoxidation catalysts of the present invention as catalyzer, and use the aqueous solution of hydrogen peroxide as oxygenant, it is possible to making hydrogen peroxide conversion higher than 96%, epoxide selectivity is higher than 95%.
Method is simple for preparation olefin epoxidation catalysts according to the present invention, and do not use or substantially do not use organic solvent, therefore environmental protection. The hydrogen peroxide conversion height of the method for the epoxidation of olefins according to the present invention and the selectivity of epoxide are good.
Embodiment
The present invention provides a kind of olefin epoxidation catalysts, and wherein, this catalyzer contains HTS, binding agent and alkaline earth metal oxide, and described binding agent is soft silica.
Olefin epoxidation catalysts according to the present invention, described catalyzer contains alkaline earth metal oxide. Described alkaline earth metal oxide can neutralize the acidic site in described catalyzer, decrease the probability of epoxidation product generation side reaction, it is to increase the selectivity of epoxidation product. Preferably, described metal oxide is magnesium oxide and/or calcium oxide.
Olefin epoxidation catalysts according to the present invention, described catalyzer contains HTS. The various molecular sieves that described HTS can be replaced by titanium atom and formed for the part Siliciumatom in skeleton structure, it is preferable to the HTS with MFI structure, the HTS with MWW structure, the HTS with MCM structure and have in the HTS of BETA structure one or more. More preferably, described HTS is the HTS with MFI structure. Most preferably, described HTS is the hollow titanium si molecular sieves with MFI structure.
The crystal grain of the described hollow titanium si molecular sieves with MFI structure is hollow structure, and the radical length of the cavity part of this hollow crystal grain is 5-300 nanometer, and described HTS is at 25 DEG C, P/P0=0.10, the benzene adsorptive capacity recorded when adsorption time is 1 hour is at least 70 milligrams/grams, and this has and there is hysteresis loop between the adsorption isothermal line of the nitrogen absorption under low temperature of the hollow titanium si molecular sieves of MFI structure and desorption isotherm. Described hollow titanium si molecular sieves can obtain with reference to method disclosed in CN1132699C, the hollow titanium si molecular sieves that the hollow titanium si molecular sieves used in the embodiment of the present invention is HTS for the trade mark that Hunan Jian Chang company limited produces.
When carrying out epoxidation reaction of olefines under the described hollow titanium si molecular sieves with MFI structure exists, the cavity part that reaction raw materials can enter described catalyzer easily with solvent contacts with HTS and reacts, thus strengthens the activity of catalyzer further; Simultaneously olefin oxide as epoxidation product can also come off from the reactive site of HTS easily, and then diffuse in the cavity of this HTS, shorten the residence time of olefin oxide on the avtive spot of HTS, further reduce the probability of olefin oxide generation side reaction, thus further increase the selectivity of epoxidation reaction.
Olefin epoxidation catalysts according to the present invention, described catalyzer is also containing binding agent. Described binding agent can give described HTS with certain shape and intensity. Although soft silica and aluminum oxide are all the binding agents that this area is commonly used, but compared with soft silica, aluminum oxide has stronger acidity, and side reaction very easily occurs epoxide in acid condition, and then epoxide selectivity is declined. Therefore, according to the olefin epoxidation catalysts of the present invention, described binding agent is soft silica. Described soft silica well known to a person skilled in the art, repeats no more herein.
Olefin epoxidation catalysts according to the present invention, the weight ratio of described HTS, soft silica and alkaline earth metal oxide can be (70-98): (1.5-40): (0.05-25). When the too high levels of described alkaline earth metal oxide, the intensity of catalyzer may be not enough; When the content of described alkaline earth metal oxide is too low, the selectivity of epoxidation product and the transformation efficiency of hydrogen peroxide can not be improved significantly. From the angle improving the selectivity of epoxidation product and the transformation efficiency of hydrogen peroxide further, the weight ratio of described HTS, soft silica and alkaline earth metal oxide is preferably (70-98): (1.5-25): (0.4-2). Under the prerequisite of the transformation efficiency of the selectivity and hydrogen peroxide of guaranteeing epoxidation product; from the angle of the intensity improving catalyzer further; the weight ratio of described HTS, soft silica and alkaline earth metal oxide is preferably (80-98): (1.5-20): (0.1-15), it is more preferable to be (80-98): (1.5-18): (0.4-1.6).
HTS is the active ingredient in the catalyzer of EPOXIDATION OF ALKENES CATALYZED BY, and in theory, the content of HTS is more high, is that the catalytic activity of the catalyzer of active component is more high taking HTS. But, when carrying out the epoxidation reaction of alkene due to employing fixed-bed reactor technique, require that catalyzer has high crushing strength, thus the catalytic bed pressure avoiding causing owing to catalyzer breaks increases and the problem of catalyst loss, therefore in olefin epoxidation catalysts the content of binding agent usually at more than 80 weight %. The present inventor finds in practice, adopts the HTS with hollow structure of the present invention, it is possible to significantly reduces the content of binding agent in catalyzer, thus improves the catalytic activity of catalyzer. Taking the gross weight of described catalyzer as benchmark, the content of described HTS is preferably 90-97 weight %, the total amount of described soft silica and metal oxide is preferably 3-10 weight %, and the weight ratio of described soft silica and alkaline earth metal oxide is preferably 1:(0.05-1). Further preferably, taking the gross weight of described catalyzer as benchmark, the content of described HTS is 93-97 weight %, the total amount of described soft silica and metal oxide is preferably 3-7 weight %, and the weight ratio of described soft silica and alkaline earth metal oxide is preferably 1:(0.1-0.3). It is possible not only to make catalyzer to have high crushing strength like this, and high hydrogen peroxide conversion and epoxide selectivity can be obtained.
Present invention also offers the preparation method of a kind of catalyzer for epoxidation reaction of olefines, wherein, the method comprises: the mixture of preparation containing HTS, binding agent source, alkaline earth metal oxide and water, this mixture forming is obtained formed body, and by dry for described formed body also roasting; Described binding agent source is be selected from by silicon sol, the silane with at least two hydrolysable group and at least one that has in the siloxanes of at least two hydrolysable group; In described mixture, HTS, with SiO2The weight ratio of binding agent source, alkaline earth metal oxide and the water counted is (70-98): (1.5-40): (0.05-25): (5-50). In the present invention, described " formed body " refers to the goods with a shaped, such as: spheroidal particle, rod-shpaed particle etc.; Described silicon sol refers to the colloidal solution of the silicon-dioxide taking water as disperse phase, and wherein, the content of silicon-dioxide can be 20-40 weight %.
According to the present invention, in described mixture, HTS, with SiO2The binding agent source of meter, the consumption of alkaline earth metal oxide and water can carry out appropriate selection according to the amount of the HTS in the catalyzer of expection, soft silica and alkaline earth metal oxide, as long as in described mixture, and HTS, with SiO2The consumption of binding agent source, alkaline earth metal oxide and the water counted can guarantee that the amount of HTS, soft silica and alkaline earth metal oxide in final catalyzer meets previously described requirement. Preferably, in described mixture, HTS, with SiO2The weight ratio of binding agent source, alkaline earth metal oxide and the water counted is (70-98): (1.5-40): (0.05-25): (5-50).
The method preparing olefin epoxidation catalysts according to the present invention, described binding agent source can for being selected from by silicon sol, the silane with at least two hydrolysable group and at least one that has in the siloxanes of at least two hydrolysable group. Preferably, the silane with at least two hydrolysable group and/or the siloxanes with at least two hydrolysable group are contained in described binding agent source. So on the one hand by the described silane with at least two hydrolysable group and/or the hydrolysis-condensation reaction with the siloxanes of at least two hydrolysable group can in-situ preparation soft silica, give the shape that HTS is certain; The soft silica generated on the other hand at least partly can with the silicone hydroxyl generation chemical interaction on HTS surface, thus strengthen the cohesive strength between soft silica and HTS, improve the crushing strength of the catalyzer of the present invention, and then the content of binding agent in catalyzer can be reduced.
More preferably, the silane with at least two hydrolysable group and at least one having in the siloxanes of at least two hydrolysable group and silicon sol are contained in described binding agent source. When guaranteeing that olefin epoxidation catalysts has high intensity, the manufacturing cost of catalyzer can be reduced like this. The described silane with at least two hydrolysable group, the ratio that has between the siloxanes of at least two hydrolysable group and silicon sol can carry out appropriate selection according to the intensity of catalyzer of expection, it does not have be particularly limited to. Preferably, from, under the prerequisite making olefin epoxidation catalysts have enough intensity, the angle of the manufacturing cost reducing olefin epoxidation catalysts is set out, with SiO2Meter, described silicon sol and the described silane with at least two hydrolysable group and/or the weight ratio with the siloxanes of at least two hydrolysable group are 1:(0.02-1).
Silane containing at least two hydrolysable group and/or there is the siloxanes of at least two hydrolysable group in the molecular structure that the described silane with at least two hydrolysable group and/or the siloxanes with at least two hydrolysable group can be known to the skilled person.
Preferably, the described silane containing at least two hydrolysable group is with the silane shown in following formula 1:
Formula 1
Wherein, R1��R2��R3And R4In at least two be-OR independently of one another11Or-OCOR12, R1��R2��R3And R4In at the most two be-R independently of one another13, R11And R12It is C independently of one another1-C5The alkyl of straight or branched, R13For C1-C5The alkyl of straight or branched.
More preferably, the silane described in at least two hydrolysable group is one or more in tetramethoxy-silicane, tetraethoxysilane, methyltrimethoxy silane, ethyl trimethoxy silane, dimethyldimethoxysil,ne, diethyl dimethoxy silane, Union carbide A-162, dimethyldiethoxysilane, methyl silicate and tetraethoxy.
Preferably, the siloxanes described in at least two hydrolysable group is with the siloxanes shown in following formula 2:
Formula 2
Wherein, R5��R6��R7��R8��R9And R10In at least two be-OR independently of one another14Or-OCOR15, R5��R6��R7��R8��R9And R10In at the most four be-R independently of one another16, R14And R15It is C independently of one another1-C5The alkyl of straight or branched, R16For C1-C5The alkyl of straight or branched.
In the present invention, C1-C5The alkyl of straight or branched can be such as methyl, ethyl, n-propyl, sec.-propyl, normal-butyl, isobutyl-, sec-butyl, the tertiary butyl, n-pentyl.
More preferably, the siloxanes described in at least two hydrolysable group is 1,3-dimethoxy-1,1,3,3-tetramethyl disiloxane and/or 1,3-diethoxy-1,1,3,3-tetramethyl disiloxane.
The method preparing olefin epoxidation catalysts according to the present invention, when the silane with at least two hydrolysable group is contained in described binding agent source and/or has the siloxanes of at least two hydrolysable group, the method also comprises: at 20-100 DEG C, described formed body was processed 1-10 hour with the aqueous solution of alkali before carrying out described roasting, thus there is described in making the silane of at least two hydrolysable group and/or the siloxanes with at least two hydrolysable group is hydrolyzed condensation reaction, form soft silica.
Described alkali can also be able to be both mineral alkali for organic bases. When described alkali is mineral alkali, it is preferable to taking basic metal as cationic alkali; When described alkali is organic bases, it is preferable to the alkali of gas can be resolved under the high temperature conditions. Specifically, described alkali can be one or more in sodium hydroxide, potassium hydroxide, Tetramethylammonium hydroxide and tetraethyl ammonium hydroxide. The consumption of described alkali can be selected according to the amount of the silane and/or siloxanes with at least two hydrolysable group. Preferably, the concentration of the aqueous solution of described alkali is 0.1-10 mole of %, 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 silicon sol is contained in described binding agent source, the water in described mixture can come from described silicon sol on the one hand, on the other hand when the amount of water in silicon sol can not meet service requirements, interpolation water can also be supplemented, thus the amount making water meets service requirements.
The condition of described drying is not particularly limited by the present invention, and generally, the temperature of described drying can be 60-80 DEG C, and the time of described drying can be 3-8 hour, and the pressure of described drying can be normal pressure or decompression.
Described roasting can carry out under condition well known to a person skilled in the art, it does not have is particularly limited to. Preferably, the condition of described roasting comprises: the temperature of roasting is 300-600 DEG C, and the time of roasting is 5-15 hour.
Preparation in accordance with the present invention, described mixture can also contain auxiliary agent. The kind of described auxiliary agent is not particularly limited by the present invention, it is possible to be the conventional various auxiliary agents in this area, it is preferable to one or more in glycerine, polyvinylpyrrolidone, methylcellulose gum and polyvinyl alcohol. The consumption of described auxiliary agent can be determined according to the intensity of the content of HTS, soft silica and metal oxide in described catalyzer and kind and the catalyzer of expection and catalytic activity. Preferably, taking the total amount of described mixture as benchmark, the consumption of described auxiliary agent is 0.5-3 weight %.
Preparation in accordance with the present invention, described mixture is also containing tensio-active agent. described tensio-active agent can significantly reduce the surface tension of water so that has certain hydrophobic HTS and is easy to be soaked by water, so that soft silica can more uniformly be dispersed in HTS. the various tensio-active agents that described tensio-active agent can be known to the skilled person, it does not have be particularly limited to. the various water soluble surfactant active that described tensio-active agent can be known to the skilled person and/or oil soluble surfactant, it does not have be particularly limited to. described oil soluble surfactant can be such as fatty acid esters of sorbitan (Span series) and/or alkylphenol polyoxyethylene (OP-10). described oil soluble surfactant is preferably sorbitan monolaurate ester (Span20), anhydro sorbitol list cetylate (Span40), Arlacel-60 (Span60), anhydro sorbitol tristearate (Span65), polyoxyethylene-sorbitan mono-oleate (Span80), sorbitan trioleate (Span85), polyoxyethylene nonylphenol ether (TX-10), one or more in polyoxyethylene octylphenol ether (OPE-10) and dodecyl phenol polyethenoxy ether. described water soluble surfactant active can be such as one or more in Vykamol Sorbitol 8B (Tween series), polyoxyethylene fatty acid ester, polyoxyethylene aliphatic alcohol ether (AEO series), Pluronic F68 and alkylol amide (Ni Nale, Ninol). described water soluble surfactant active be preferably in polyoxyethylene sorbitan monolaurate (Tween20), polyethenoxy sorbitan list cetylate (Tween40), polyethenoxy sorbitan monostearate (Tween60), polyoxyethylene sorbitan monooleate (Tween80) and polyethenoxy sorbitan trioleate (Tween85) one or more. the consumption of described tensio-active agent can be determined according to the amount of the HTS used, soft silica and metal oxide and kind. preferably, taking the total amount of described mixture as benchmark, the consumption of described tensio-active agent is 0.001-0.2 weight %.
Present invention also offers a kind of method of epoxidation of olefins, the method is included in fixed-bed reactor, in the presence of a catalyst, is contacted in a solvent with hydrogen peroxide by alkene, and wherein, described catalyzer is catalyzer provided by the invention.
Olefin epoxidation catalysts according to the present invention has high hydrogen peroxide conversion and epoxide selectivity, and therefore method according to the epoxidation of olefins of the present invention also has high hydrogen peroxide conversion and epoxide selectivity.
Owing to the method for the epoxidation of olefins of the present invention makes catalyzer that the application of the invention provides to improve hydrogen peroxide conversion and epoxide optionally, therefore the present invention is not particularly limited for other condition of epoxidation of olefins, various condition well known to those skilled in the art can be adopted to carry out the epoxidation reaction of alkene, as long as the catalyzer adopted is catalyzer 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 being selected from the alkene that carbonatoms is 2-8, such as: propylene, butylene and isomer, amylene and isomer, own alkene and isomer, heptene and isomer thereof and octene and isomer thereof. Preferably, described alkene is propylene. Described solvent can be selected from the fatty alcohol that water, acetonitrile and carbonatoms are 1-6. Described carbonatoms is that the aliphatic alcohols of 1-6 is such as methyl alcohol, ethanol, propyl alcohol and isomer, butanols and isomer, amylalcohol and isomer thereof and own alcohol and isomer thereof. Preferably, described solvent is methyl alcohol. The condition of described contact well known to a person skilled in the art, such as, the temperature of described contact can be 30-90 DEG C, it is possible to pressure be 0.5-4.5MPa and reaction system pH be 5-8 under carry out described contact, liquid hourly space velocity can be 0.1-7h-1. Liquid hourly space velocity 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 metal oxide and described formed body calculates with its dry base weight, and so-called " dry base weight " refers to that sample is through the weight of 800 DEG C of roastings 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 regulation in GB3635-1983, it is the upper crushing strength measuring catalyzer of crushing strength determinator (manufacture of alkaline institute of the Ministry of Chemical Industry) of QCY-602 in model.
X-ray fluorescence spectrometry method (XRF) is adopted to measure the composition of catalyzer on PhilipsPW-2400 type x-ray fluorescence spectrometry instrument.
Vapor-phase chromatography is adopted to analyze the composition of epoxidation product: to take methyl tertiary butyl ether as internal standard substance, adopt Agilent-6890 type chromatographic instrument, adopt 30m �� 0.25mmFFTP capillary column, sample size is 1.0 �� L, and injector temperature is 180 DEG C, the temperature of capillary column is kept 4 minutes at 60 DEG C, then it is increased to 200 DEG C with the speed of 20 DEG C/min, and keep 4 minutes, and adopting flame ionization detector (FID), sensing chamber's temperature is 240 DEG C.
Adopt the concentration of hydrogen peroxide before and after Indirect iodimetry analytical reaction, thus calculate the transformation efficiency of hydrogen peroxide.
Embodiment 1
The present embodiment is used for illustrating according to the olefin epoxidation catalysts of the present invention and the method for its preparation method and epoxidation of olefins.
By 100g HTS powder (Hunan Jian Chang company limited, the trade mark is HTS) mix with 1g magnesium oxide and 10g tetramethoxy-silicane (Qingdao century star chemical reagent company limited), 5g silicon sol (dioxide-containing silica 30 weight %), 0.2gSpan80,2g polyvinyl alcohol (Sanming City Ding Hui Chemical Co., Ltd. is added after mixing, the trade mark is polyvinyl alcohol 2099), 1g sesbania powder (Dongming County Zhu Wa sesbania gum factory) and 50g water mixes, then extrusion moulding pelletizing, then 70 DEG C of dryings 4 hours. The formed body obtained is of a size of 2 �� 2 millimeters.
Get the there-necked flask that above-mentioned formed body 100g puts into 500mL, add the aqueous sodium hydroxide solution that 200g concentration is 10 moles of %, with stirring, said mixture is heated to 90 DEG C, and keeps 6 hours. Then carry out filtration and obtain solid phase, with deionized water by extremely neutral for the solid phase washing obtained. Then, solid phase drying 3 hours at 120 DEG C that will obtain, finally 550 DEG C of roastings 3 hours, thus obtain catalyst according to the invention. After measured, the intensity of this catalyzer is 160N/cm; Being measured by XRF analysis, in this catalyzer, the content of HTS is the weight ratio of 93.2 weight %, soft silica and magnesium oxide is 1:0.2.
Being loaded in the isothermal reaction district of fixed-bed tube reactor by 14g catalyzer, catalyzer fills porcelain ring filler up and down, and makes whole reaction system stopping property intact. Make propylene and liquid stream to enter reaction zone in the way of upper reaches, wherein, methyl alcohol in liquid stream: propylene: the mol ratio of hydrogen peroxide is 6:2:1, liquid stream adds ammoniacal liquor, the pH making described liquid stream is 5.3, adds the Tween80 of the Span80 and 0.06 weight % of 0.98 weight % in described liquid stream simultaneously. Control temperature of reaction is 40 DEG C, and reaction pressure is 2.5MPa, and liquid hourly space velocity is 1.5h-1. Sampling analysis reaction product, obtaining hydrogen peroxide conversion is 98.5%, and propylene oxide selectivity is 97.7%.
Comparative example 1
The method identical with embodiment 1 is adopted to prepare catalyzer, the difference is that, do not add magnesium oxide. Being measured by XRF analysis, in the catalyzer obtained, the content of HTS is 94.2 weight %, and the intensity of this catalyzer is 60N/cm.
The method identical with embodiment 1 is adopted to carry out epoxidation reaction, the difference is that, the catalyzer of the catalyzer used prepared by comparative example 1. In this epoxidation reaction, hydrogen peroxide conversion is 97.3%, and propylene oxide selectivity is 89.1%.
Comparative example 2
The method identical with embodiment 1 is adopted to prepare catalyzer, the difference is that, do not add magnesium oxide, but add 1g zinc oxide. The intensity of this catalyzer is 65N/cm; Being measured by XRF analysis, in this catalyzer, the content of HTS is the weight ratio of 93.4 weight %, soft silica and zinc oxide is 1:0.2.
The method identical with embodiment 1 is adopted to carry out epoxidation reaction, the difference is that, the catalyzer of the catalyzer used prepared by comparative example 2. In this epoxidation reaction, hydrogen peroxide conversion is 97.2%, and propylene oxide selectivity is 90.5%.
Embodiment 2
The present embodiment is used for illustrating according to the olefin epoxidation catalysts of the present invention and the method for its preparation method and epoxidation of olefins.
The method identical with embodiment 1 is adopted to prepare olefin epoxidation catalysts, the difference is that, HTS powder (Hunan Jian Chang company limited, the trade mark is HTS) consumption be 80g, the consumption of magnesium oxide is 3g, and the consumption of tetraethoxysilane (Qufu morning twilight Chemical Co., Ltd.) is 64g, and the consumption of silicon sol (content of silicon-dioxide is 30 weight %) is 30g, the consumption of Span80 is 2g, and the consumption of water is 20g. After measured, the intensity of this catalyzer is 180N/cm; Being measured by XRF analysis, in this catalyzer, the content of HTS is the weight ratio of 70 weight %, soft silica and magnesium oxide is 1:0.11.
The method identical with embodiment 1 is adopted to carry out epoxidation reaction, the difference is that, the catalyzer of the catalyzer used prepared by embodiment 2. Sampling analysis reaction product, obtaining hydrogen peroxide conversion is 94.4%, and propylene oxide selectivity is 98.5%.
Embodiment 3
The present embodiment is used for illustrating according to the olefin epoxidation catalysts of the present invention and the method for its preparation method and epoxidation of olefins.
The method identical with embodiment 1 is adopted to prepare olefin epoxidation catalysts, the difference is that, HTS powder (Hunan Jian Chang company limited, the trade mark is HTS) consumption be 120g, the consumption of calcium oxide is 0.5g, the consumption of Union carbide A-162 (Qufu morning twilight Chemical Co., Ltd.) is 7g, and the consumption that the consumption of silicon sol (content of silicon-dioxide is 30 weight %) is 2g, Tween20 is 0.15g. After measured, the intensity of this catalyzer is 120N/cm; Being measured by XRF analysis, in this catalyzer, the content of HTS is the weight ratio of 97 weight %, soft silica and magnesium oxide is 1:0.2.
The method identical with embodiment 1 is adopted to carry out epoxidation reaction, the difference is that, the catalyzer of the catalyzer used prepared by embodiment 2. Sampling analysis reaction product, obtaining hydrogen peroxide conversion is 99.8%, and propylene oxide selectivity is 98.2%.
Embodiment 4
The present embodiment is used for illustrating according to the olefin epoxidation catalysts of the present invention and the method for its preparation method and epoxidation of olefins.
By 100g HTS powder (Hunan Jian Chang company limited, the trade mark is HTS), with 2g magnesium oxide, 70g silicon sol (massfraction is 30 weight %), 0.2gSpan80,2g 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 mixing, mix rear extrusion moulding, catalyst size is 2 �� 2 millimeters, 70 DEG C of dryings 550 DEG C of roastings 3 hours, thus obtained catalyst according to the invention after 4 hours. After measured, the intensity of this catalyzer is 165N/cm; Being measured by XRF analysis, in this catalyzer, the content of HTS is the weight ratio of 81 weight %, soft silica and magnesium oxide is 1:0.08.
The method identical with embodiment 1 is adopted to carry out epoxidation reaction, the difference is that, the catalyzer that the catalyzer used is prepared for embodiment 4. Sampling analysis reaction product, obtaining hydrogen peroxide conversion is 96.4%, and propylene oxide selectivity is 95.2%.
Comparative example 3
The method identical with embodiment 4 is adopted to prepare catalyzer, the difference is that, replace silicon sol with aluminum oxide. The intensity of this catalyzer is 90N/cm; Being measured by XRF analysis, in this catalyzer, the content of HTS is the weight ratio of 82 weight %, aluminum oxide and magnesium oxide is 1:0.09.
The method identical with embodiment 1 is adopted to carry out epoxidation reaction, the difference is that, the catalyzer of the catalyzer used prepared by comparative example 3. In this epoxidation reaction, hydrogen peroxide conversion is 93.6%, and propylene oxide selectivity is 90.5%.
Comparative example 4
Adopt hollow titanium si molecular sieves powder (Hunan Jian Chang company limited, the trade mark is HTS), prepare catalyzer according to the method for CN1132200 embodiment 2. The intensity of this catalyzer is 100N/cm; Being measured by XRF analysis, in this catalyzer, the content of HTS is the weight ratio of 79 weight %, aluminum oxide and magnesium oxide is 1:0.27.
The method identical with embodiment 1 is adopted to carry out epoxidation reaction, the difference is that, the catalyzer of the catalyzer used prepared by comparative example 4. In this epoxidation reaction, hydrogen peroxide conversion is 90.4%, and propylene oxide selectivity is 90.3%.
Embodiment 5
The present embodiment is used for illustrating according to the olefin epoxidation catalysts of the present invention and the method for its preparation method and epoxidation of olefins.
By 100g HTS powder (Hunan Jian Chang company limited, the trade mark is HTS) mix with 2g magnesium oxide, 70g tetramethoxy-silicane (Qingdao century star chemical reagent company limited), 0.2gSpan80,2g polyvinyl alcohol (Sanming City Ding Hui Chemical Co., Ltd. is added after mixing, the trade mark is polyvinyl alcohol 2099), 1g sesbania powder (Dongming County Zhu Wa sesbania gum factory) and 50g water mixes, then extrusion moulding pelletizing, then 70 DEG C of dryings 4 hours. The formed body obtained is of a size of 2 �� 2 millimeters.
Get the there-necked flask that above-mentioned formed body 100g puts into 500mL, add the aqueous sodium hydroxide solution that 200mL concentration is 20 weight %, with stirring, said mixture is heated to 90 DEG C, and keeps 6 hours. Then carry out filtration and obtain solid phase, with deionized water by extremely neutral for the solid phase washing obtained. Then, solid phase drying 3 hours at 120 DEG C that will obtain, finally 550 DEG C of roastings 3 hours, thus obtain catalyst according to the invention. After measured, the intensity of this catalyzer is 200N/cm; Being measured by XRF analysis, in this catalyzer, the content of HTS is the weight ratio of 75 weight %, soft silica and magnesium oxide is 1:0.07.
The method identical with embodiment 1 is adopted to carry out epoxidation reaction, the difference is that, the catalyzer that the catalyzer used is prepared for embodiment 5. Sampling analysis reaction product, obtaining hydrogen peroxide conversion is 95.8%, and propylene oxide selectivity is 95.3%.
Above embodiment shows, catalyst according to the invention demonstrates high hydrogen peroxide conversion and epoxide selectivity in the epoxidation reaction of alkene.
Claims (15)
1. the preparation method for the catalyzer of epoxidation reaction of olefines, it is characterized in that, the method comprises: the mixture of preparation containing HTS, binding agent source, alkaline earth metal oxide and water, this mixture forming is obtained formed body, and by dry for described formed body also roasting, wherein, described formed body was processed 1-10 hour with the aqueous solution of alkali before carrying out described roasting at 20-100 DEG C; Described binding agent source is have the silane of at least two hydrolysable group and/or have the siloxanes of at least two hydrolysable group; Or described binding agent source is the silane with at least two hydrolysable group and at least one having in the siloxanes of at least two hydrolysable group and silicon sol; In described mixture, HTS, with SiO2The weight ratio of binding agent source, alkaline earth metal oxide and the water counted is (70-98): (1.5-40): (0.05-25): (5-50).
2. method according to claim 1, wherein, HTS in described mixture, with SiO2The consumption of binding agent source, alkaline earth metal oxide and the water counted makes in the catalyzer finally obtained, and the weight ratio of HTS, soft silica and alkaline earth metal oxide is (80-98): (1.5-20): (0.1-15).
3. method according to claim 1, wherein, HTS in described mixture, with SiO2The consumption of binding agent source, alkaline earth metal oxide and the water counted makes in the catalyzer finally obtained, and the weight ratio of HTS, soft silica and alkaline earth metal oxide is (80-98): (1.5-18): (0.4-1.6).
4. method according to claim 3, wherein, HTS in described mixture, with SiO2The consumption of binding agent source, alkaline earth metal oxide and the water counted makes the gross weight of the catalyzer finally to obtain as benchmark, the content of HTS is 90-97 weight %, the total amount of soft silica and alkaline earth metal oxide is 3-10 weight %, and the weight ratio of described soft silica and described alkaline earth metal oxide is 1:(0.05-1).
5., according to method described in any one in claim 1-4, wherein, described alkaline earth metal oxide is magnesium oxide and/or calcium oxide.
6. according to method described in any one in claim 1-4, wherein, described HTS be have the HTS of MFI structure, the HTS with MWW structure, the HTS with MCM structure and have in the HTS of BETA structure one or more.
7. method according to claim 6, wherein, described in there is MFI structure the crystal grain of HTS be hollow structure, the radical length of the cavity part of this hollow structure is 5-300 nanometer, described in there is MFI structure HTS at 25 DEG C, P/P0=0.10, the benzene adsorptive capacity recorded when adsorption time is 1 hour is at least 70 milligrams/grams, and this has and there is hysteresis loop between the adsorption isothermal line of the nitrogen absorption under low temperature of the HTS of MFI structure and desorption isotherm.
8. method according to claim 1, wherein, described binding agent source is the silane with at least two hydrolysable group and at least one having in the siloxanes of at least two hydrolysable group and silicon sol, with SiO2Meter, described silicon sol and the described silane with at least two hydrolysable group and/or the weight ratio with the siloxanes of at least two hydrolysable group are 1:(0.02-1).
9. method according to claim 1, wherein, described alkali is one or more in sodium hydroxide, potassium hydroxide, Tetramethylammonium hydroxide and tetraethyl ammonium hydroxide, the concentration of the aqueous solution of described alkali is 0.1-10 mole of %, and the aqueous solution of described alkali and the weight ratio of described formed body are (0.5-5): 1.
10. method according to claim 1 or 8, wherein, described in there are at least two hydrolysable group silane be the silane shown in formula 1,
Wherein, R1��R2��R3And R4In at least two be-OR independently of one another11Or-OCOR12, R1��R2��R3And R4In at the most two be-R independently of one another13, R11And R12It is C independently of one another1-C5The alkyl of straight or branched, R13For C1-C5The alkyl of straight or branched;
The described siloxanes with at least two hydrolysable group is the siloxanes shown in formula 2,
Wherein, R5��R6��R7��R8��R9And R10In at least two be-OR independently of one another14Or-OCOR15, R5��R6��R7��R8��R9And R10In at the most four be-R independently of one another16, R14And R15It is C independently of one another1-C5The alkyl of straight or branched, R16For C1-C5The alkyl of straight or branched.
11. methods according to claim 10, wherein, the silane described in at least two hydrolysable group is one or more in tetramethoxy-silicane, tetraethoxysilane, methyltrimethoxy silane, ethyl trimethoxy silane, dimethyldimethoxysil,ne, diethyl dimethoxy silane, Union carbide A-162, dimethyldiethoxysilane, methyl silicate, tetraethoxy; The described siloxanes with at least two hydrolysable group is 1,3-dimethoxy-1,1,3,3-tetramethyl disiloxane and/or 1,3-diethoxy-1,1,3,3-tetramethyl disiloxane.
12. methods according to claim 1, wherein, the condition of described roasting comprises: maturing temperature is 300-600 DEG C, and roasting time is 5-15 hour.
The method of 13. 1 kinds of epoxidation of olefins, the method is included in fixed-bed reactor, in the presence of a catalyst, is contacted in a solvent with hydrogen peroxide by alkene, it is characterized in that, described catalyzer is the catalyzer that in claim 1-12 prepared by method described in any one.
14. methods according to claim 13, wherein, described alkene is propylene.
15. methods according to claim 13, wherein, the condition of described contact comprises: solvent: alkene: the mol ratio of hydrogen peroxide is (4-15): (0.5-5): 1, and temperature is 30-90 DEG C, pressure is 0.5-4.5MPa, and liquid hourly space velocity is 0.1-7h-1, the pH of reaction system is 5-8.
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| CN104340988B (en) * | 2013-07-31 | 2016-03-16 | 中国石油化工股份有限公司 | The forming method of HTS and the shaping HTS obtained by the method and application |
| CN103785465A (en) * | 2013-12-26 | 2014-05-14 | 大连理工大学 | Modification method for titanium silicalite molecular sieves |
| CN106795126B (en) * | 2014-07-29 | 2018-10-26 | 赢创德固赛有限公司 | The epoxidizing method of alkene |
| EP3202764B1 (en) * | 2014-09-29 | 2022-08-24 | China Petroleum & Chemical Corporation | Olefin oxidation method, and reaction apparatus and system |
| CN105329909A (en) * | 2015-11-30 | 2016-02-17 | 湖北大学 | Method for synthesizing Ti-MWW molecular sieve hollow sphere with high external specific surface area |
| CN107715868B (en) | 2017-10-27 | 2019-07-23 | 万华化学集团股份有限公司 | A kind of preparation method and its usage of oxidation catalyst of cyclopropene |
| 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 |
| CN108530393A (en) * | 2018-03-19 | 2018-09-14 | 华东师范大学 | A kind of synthetic method of epoxides |
| CN109513455B (en) * | 2018-12-04 | 2021-09-24 | 红宝丽集团股份有限公司 | Epoxidation catalyst, method of making and method of using the same |
| CN110694676A (en) * | 2019-11-08 | 2020-01-17 | 湘潭大学 | Chemical vapor deposition preparation method of mesoporous catalyst and application of mesoporous catalyst in olefin epoxidation reaction |
| CN111992245A (en) * | 2020-05-31 | 2020-11-27 | 南京克米斯璀新能源科技有限公司 | Catalyst for removing hydroxyl from Fischer-Tropsch oil |
| 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 |
| CN112661686B (en) * | 2020-12-25 | 2023-03-24 | 淄博正华助剂股份有限公司 | Method for producing peroxycarboxylic acid alkyl ester based on titanium silicalite molecular sieve composite catalyst |
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| CN1173961C (en) * | 2001-11-14 | 2004-11-03 | 中国石油化工股份有限公司 | Catalyst for olefine epoxidation |
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