CN101555236A - High-selectivity epoxidation method of olefin catalyzed by nano-SiO* material and H*O* liquid phase - Google Patents
High-selectivity epoxidation method of olefin catalyzed by nano-SiO* material and H*O* liquid phase Download PDFInfo
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Abstract
The invention relates to a chemical reaction process in which multi-phase catalytic oxidation is utilized to prepare an epoxide by using catalyst only without using transition metal-contained catalyst, in particular to a high-selectivity epoxidation method of olefin catalyzed by nano-SiO2 material and H2O liquid phase. The nano-SiO2 material or the surface-modified activated SiO2 material with an organic function group or a zeolite molecular sieve is used as the catalyst for reaction directly together with a reaction substrate and a solvent to form the epoxidation reaction for catalyzing olefin widely in a SiO2-olefin-solvent-H2O2/H2O multi-phase catalytic epoxidation reaction system; the oxidation reagent used for the epoxidation is the H2O2 sold in the market; and the reaction temperature is controlled within 0-100 DEG C and the reaction time is within 0.5-24h. The method has the advantages of using no transition metal-contained catalyst, high conversion ratio of raw materials, good selectivity of target outcome, short reaction time, high efficiency, moderate reaction condition, easily controlled operation, low cost and being friendly to environment in the whole process.
Description
Technical field
The present invention relates to not use and anyly contain the catalyzer of transition metal-type and only use organic catalyst to prepare the chemical reaction process of epoxide, specifically a kind of nanometer SiO by heterogeneous catalytic oxidation
2Catalytic alkene of material and 30%H
2O
2Liquid phase highly selective epoxidizing method.
Background technology
The alkene epoxidation product is extremely wide organic raw material and an intermediate of a class purposes, is widely used in fields such as petrochemical complex, fine chemistry industry and organic synthesis.Yet except that oxyethane, the production method of present industrial most of epoxy compounds such as propylene oxide, Styryl oxide etc. still is traditional environmentally harmful halogenohydrin method and Halcon method (claiming the indirect oxidation method again).
The high-selectivity oxidation of hydro carbons be 21st century one of most important task [(a) C.L.Hill, Nature 1999,401,436; (b) D.E.de Vos; B.F.Sels; P.A.Jacobs, Adv.Catal.2001,46,1], the catalytic epoxidation of olefin(e) compound under mild conditions is the research emphasis in the field of fine chemical always.For the catalysis epoxidation of alkenes compounds, even phase catalytic process has its significant disadvantages, and separation, recovery and the recirculation of Here it is catalyzer is unusual difficulty.Scientist is making great efforts design always and is preparing suitable heterogeneous catalyst, and this is because such catalyst system is easy to overcome typical case's difficulty that even phase system run into [Z.W.Xi etal., Science 2001,292,1139].Heterogeneous catalyst since its have easily isolating characteristics from reaction system and in chemistry and fine chemistry industry process, play an important role.As everyone knows, the more little catalytic activity that they show of the granularity of heterogeneous catalyst is high more, the catalyzer of nanoscale is owing to have bigger specific surface area, surface exposure has a large amount of avtive spots, reactant molecule can be gone up at nearly " molecular level " with the catalyst activity position fully to be contacted, thereby demonstrate the catalytic activity that is superior to corresponding block materials far away, relevant report is also very many.Kai Fa catalysis epoxidation technology is used 30%H in recent years
2O
2As oxygenant is very general, cheap and easy to get comparatively speaking as oxygenant because of it, and the active o content height, reacted by product only is a water, the feature of environmental protection is good, but oxidation activity is low, needs to add high performance catalyst [K.Jahnisch, V.Hessel, H.Lowe, M.Baerns, Angew.Chem.Int.Ed.2004,43,406].For example Chinese patent CN1172922CGO announced a kind of in the presence of titanium-containing molecular sieve catalyst and a kind of salt the epoxidizing method of alkene and hydroperoxidation, and Chinese patent CN1330642C announced in the presence of a kind of zeolite based catalysts and a kind of solvent, reacted the method for preparing epoxide by alkene and superoxide.In addition, it is reported that phosphorus heteropoly tungstic acid catalyzer can be by reaction effective catalyzing propone of control and H under condition of phase transition
2O
2Epoxidation system oxirane ring propane; SiO
2The metal Schiff-base title complex of load effectively catalyzed ethylene epoxidation generates 1,2-oxyethane; Use cis-MoO
2(L) (solv) composite catalyst epoxidation vinyl benzene under mild conditions of forming of [L=salicyl salicylyl hydrazine] and Y molecular sieve; The Schiff-base title complex of vanadium can effectively styrene catalyzed and tetrahydrobenzene and H
2O
2The epoxidation of oxygenant [(a) S.N.Rao, K.N.Munshi, N.N.Rao, J.Mol.Catal.A:Chem.2000,156,205; (b) D.M.Boghaei; S.Mohebi, J.Mol.Catal.A:Chem.2002,179,41; (c) T.Punniyamurthy; S.Velusamy; J.Iqbal, Chem.Rev.2005,105,2329.].Yet these traditional systems will obtain high catalytic activity, and the reagent that is used for epoxidation reaction of olefines mainly contains peroxy acid, peroxy tert-butyl alcohol, hypochlorite, iodosobenzene, additive+H
2O
2Deng as oxygenant.
Utilizing titanium-silicon molecular sieve catalyst, can the functional quality mark be 30% industrial H
2O
2Make oxygenant, environmentally friendly, so the appearance of titanium containing zeolite catalyst TS-1 and being applied in is described as the milestone of the even phase process heterogenize of tradition at that time; So far this catalyst system has expanded to TS-1, Ti-β, Ti-MWW, Ti-MCM-41, Ti-MCM-48, Ti-SBA-15, embedded type Ti-SiO
2Tsing-Hua University etc. all relates to this class research [(a) B.Notari, Adv.Catal.1996,41,23 in, domestic Guo's news, Wu Peng, Li Can, summer; (b) Q.H.Xia, X.Chen, T.Tatsumi, J.Mol.Catal.A:Chem.2001,176,179; (c) P.Wu, T.Tatsumi, Chem.Commun.2001,1714; (d) X.W.Guo, X.S.Wang, Catal.Today 2002,74, and 65; (e) Q.H.Yang, Can Li, J.Catal.1999,183,128.].Comparable best performance different even phase complex compound and the mimetic enzyme catalysis system of intending of the catalytic activity of this catalyst system; And its advantage also be special obviously because these heterogeneous catalysts can and recycle by repeatedly filtered and recycled, and can use 30%H
2O
2As oxygenant, oxidation efficiency height, few, the pollution-free nothing of by product are corroded and are met requirements of green environmental protection, have higher using value.But for the large-scale technological process of chemical industry, the synthetic cost of titanium-containing zeolite is still than higher, and the zeolite molecular sieve in different apertures has substrate molecule and selects the shape selectivity significantly (for example, the TS-1 molecular sieve bore diameter approximately
To more macromolecular catalytic reaction poor activity), caused correlation technique to be restricted, so that be difficult to industrialization in the application of field of fine chemical.
The catalytic activity of above-mentioned epoxidation catalyst system is all higher, but the porous synthetic materials active centre that has all related to transition metal complex or containing metal Ti, Mg, Al, the Preparation of catalysts cost is higher, recycle difficulty and easily inactivation, easily cause environmental pollution, too not different aspect the explanation of catalytic mechanism: i.e. transition metal ion and H yet
2O
2Effect forms active intermediate.Silicon-dioxide is as the framework ingredient of inert catalyst carrier and molecular sieve, be widely used in the preparation of heterogeneous catalyst and porous zeolite molecular screen material synthetic, but mention that without any research the silicon-dioxide and other porous silicon-base material that do not contain transition metal have catalytic oxidation activity.Now, we find first, at " SiO
2-alkene-solvent-H
2O
2/ H
2O " in the heterogeneous catalytic reaction system formed, do not contain the nanometer SiO of transition metal
2Material is (through SEM-EDX, ICP, AAS analyzes and not to contain transition metal) adding play a part crucial for significantly improving substrate conversion efficiency and epoxidation selectivity, PRELIMINARY RESULTS shows for functional olefin, cycloolefin and linear alpha-olefin function well, can finely overcome the restriction of traditional zeolitic material duct size shape selectivity, and centrifugation repeatedly, washing, dry, reclaim and use, and substrate conversion efficiency, the epoxidation selectivity all can keep, this is one makes us surprised, interesting discovery, this system is simple, cheapness meets present catalysis technique development trend.
Summary of the invention
The present invention is for overcoming ubiquitous main drawback in the above-mentioned epoxidation systems, and proposes a kind of method of epoxidation of olefins, i.e. nanometer SiO
2Catalytic alkene of material and H
2O
2Liquid phase highly selective epoxidizing method.
Nanometer SiO
2Catalytic alkene and H
2O
2Liquid phase highly selective epoxidizing method, it is to be with nanometer SiO with it
2The activation SiO that has the machine functional group of material or process surface modification
2Material or zeolite molecular sieve directly form " SiO as catalyst for reaction and reaction substrate alkene, solvent
2-alkene-solvent-H
2O
2/ H
2O " EPOXIDATION OF ALKENES CATALYZED BY in the heterogeneous catalyst epoxidation reaction system is H as the epoxidation oxygenant
2O
2Temperature of reaction is controlled at 0～100 ℃, reaction times is 0.5～24h, and described alkene is a kind of in the alkene such as vinylbenzene, tetrahydrobenzene, cyclooctene, norbornylene, α-Pai Xi, beta-pinene, cinnamyl chlorine, methyl acrylate, ethyl propenoate, butyl acrylate, vinylcarbinol, vinyl cyanide, 1-octene.
This method comprises:
(1) different size of particles SiO
2Catalytic alkene and H
2O
2Liquid phase highly selective epoxidizing method;
(2) different sources, different specific surface area, different-grain diameter SiO
2Catalytic alkene and H
2O
2Liquid phase highly selective epoxidizing method;
(3) various SiO
2Handle through the silicate class of different band organic functions base or the suitable modification of other silylating reagent on the powdered material surface, the activation SiO of a series of surfaces band silane functionality group that makes
2Catalytic alkene of material and H
2O
2Liquid phase highly selective epoxidizing method;
(4) the different specific surface areas of various low-cost preparations, the catalytic alkene of zeolite molecular sieve material and the H in different apertures
2O
2Liquid phase highly selective epoxidizing method.
Detailed description of the present invention
In the method for the invention, make nanometer SiO
2Catalytic alkene of material and H
2O
2Liquid phase selective epoxidation reaction, form the epoxidation product of corresponding highly selective.Through a series of catalyzed reactions and relevant characterization research, SiO
2Material catalyzed alkene compound and H
2O
2Epoxidation mechanism may be summarized to be: the promoted bimolecular epoxidation of surface adsorption effect (Surface Adsorption assisted biMolecular Epoxidation (SAME)), promptly these have than higher specific surface area (usually greater than 200m
2/ g) silica-base material surface all has amphipathic (hydrophilic-oleophylic), can be simultaneously with the active oxidizer molecular adsorption of olefin substrate molecule in the organic phase and aqueous phase to together, overcome interfacial tension and made it the initial ring oxidizing reaction.
The high-specific surface area that the present invention uses, the SiO of nanometer particle size
2Material can obtain from following approach: the commodity of the different sizes such as aerosil-200, aerosil-300 of specialized companies such as external Aldrich, the Degussa that (1) is directly bought, Alfa, the specific surface area of these materials is between 200～350m
2/ g, particle diameter is between 10～20nm; (2) directly buy the like product of domestic manufacturer, be commonly called as white carbon black or fumed silica (burn and get), be used for starting material usually as the heteroatoms zeolite molecular sieve of hydro-thermal synthesis of high purity by organic silicon high-temperature; (3) laboratory utilizes ultrasonic, high speed shear, microemulsified environment technology for hydrolyzing from organosilicon, through low temperature hydrolysis, spraying drying, the homemade nanometer SiO of roasting
2Material (granularity is less than 20nm); (4) SiO of surface modification
2Material: the silicate class or other silylating reagent that have the organic functions base below the use (have (EtO)
3Si-C
3H
6NH
2, (MeO)
3Si-C
3H
6NH
2, CH
3(EtO)
2Si-C
3H
6NH
2, (EtO)
3Si-(CH
2)
3-NHC
2H
4NH
2, CH
3Si (OCH
3)
3, (CH
3)
3Si-Cl, HMDS, CH
3(MeO)
2Si-C
3H
6NHC
2H
4NH
2Deng) direct and powder nanometer SiO
2Thereby the material reaction makes its surface carry out suitable modification and handles, and makes the activation SiO that a series of surfaces have the machine functional group
2Material; (5) with the different specific surface areas of the low-cost preparation of simple method, the molecular screen material in different apertures, as materials such as 4A, ZSM-5, mordenite, beta, SBA-15 series, Y, MCM-41 series, MCM-22, SAPOs series, AlPOs series; (6) various types of silicon glue material is as (100-300 orders) such as silica gel for chromatography, the drier gels that dewaters.
In the method for the invention, catalyzed alkene and H
2O
2The reaction solvent of liquid phase selective epoxidation reaction selects all is common solvent, cheap, and easily-controlled reaction conditions.Wherein solvent is one of following: CH
3OH, EtOH, Bu
tOH, MeCOMe, MeCOEt, pimelinketone, CH
3CN, DMF, DMA, CHCl
3, CH
2Cl
2, DMSO, hexanaphthene, THF, Ether etc.In addition, cooperate with reaction solvent jointly as epoxidation reaction system additive be that use always, cheap various salts, the mass concentration scope by obtained aqueous solution provides a reaction medium that is more suitable for alkene epoxidation for salts solution and the reaction solvent acting in conjunction of 0.01～1mol/L.Wherein salt is one of following: K
2CO
3, Na
2CO
3, KHCO
3, NaHCO
3, CH
3COONa, CH
3COOK, NaH
2PO
4, Na
2HPO
4, Na
3PO
4, soluble tartrate, soluble tartrate, tartrate receive, microsolubility CaSO
4And MgSO
4Etc. single alkali metal/alkaline-earth metal or mixing salt.
Described H
2O
2With the mol ratio of alkene be 0.5～5.
The volume ratio of the aqueous solution of described solvent and salt is: 3～1/3.
A kind of with among 4A, ZSM-5, mordenite, beta, SBA-15 series, Y, MCM-41 series, MCM-22, SAPOs series and the AlPOs of described catalyst zeolite molecular screening.
Described temperature of reaction is 0～80 ℃
The described reaction times is 0.5～6h.
In the method for the invention, reaction process is very simple, and the epoxidation of the various alkene highly selectivies of catalysis expeditiously, the suitable alkene of selecting the end alkene of straight or branched, interior alkene, the interior alkene of ring-type and band functional group of alkene, patent of the present invention has mainly been chosen alkene such as styrenic, cyclenes hydro carbons, esters of acrylic acid, ketene, linear alpha-olefin class.
The present invention has following advantage:
(1) do not use the catalyzer of any transition metal-type.The present invention only uses commercialization or the homemade nanometer SiO of simple method
2The activation SiO that has the machine functional group of material or process surface modification
2Material or common cheaply zeolite molecular sieve are directly as catalyst for reaction, can bring significant effect, avoid expensive Ti-Si zeolite, the synthetic and last handling process of hydro-thermal of hydrotalcite catalyst, avoided loaded down with trivial details organic synthesis and purifying, the waste of avoiding the transition metal resource and the pollution etc. of organic complex catalyzer.These SiO
2After continue to be used to EPOXIDATION OF ALKENES CATALYZED BY after the simple aftertreatment, activation, recycling is good, saves cost greatly in reaction for material.
(2) conversion of raw material height, good selectivity of target products.The prior art conversion of raw material generally about 60-80%, exists to transform not exclusively, and other byproducts is arranged, and brings difficulty to separation.The present invention under mild conditions, when the broad variety olefin catalytic oxidation is generated epoxide, conversion of raw material height, even can transform fully, and product is the target epoxidation product only, do not have other byproducts, the selectivity of reaction is good, the yield height.
(3) reaction times weak point, the efficient height.Under condition of the present invention, the reaction times that the catalyzed oxidation functional olefines generates epoxide is 0.5～24h, and the preferable reaction times is 0.5～6h, and the method for preparing epoxide with other catalyzed oxidations is compared, has the reaction times weak point, the advantage that reaction efficiency is high.
(4) reaction conditions gentleness, operation is easy to control.The present invention is reflected in the organic solvent and carries out, temperature of reaction is controlled at 0～100 ℃, and temperature is to influence reaction times and important factor optionally, in this catalytic oxidation system, 10 ℃ of the every risings of temperature, speed of reaction just increases by 0.5～2 times, but temperature is too high, can increase energy expenditure, also can cause the selectivity variation that generates target product, make products distribution complicated, by product increases, and therefore must select suitable temperature.
(5) cost is low.Prior art mainly adopts clorox, peroxy acid and alkyl peroxide as oxygenant, and production cost is higher; In the process of reaction, the by product that they generate can cause certain harm and pollution to environment; And they are all unstable, easily decompose, and have transportation, the uneasy congruent shortcoming that stores and use.It is commercially available 30%H that the present invention is used as the epoxidation oxidising agent
2O
2, raw material is cheap and easy to get.Compare as epoxidation reagent with a series of organo-peroxides or clorox etc., have safe in utilizationly, be convenient to advantage such as transportation storage etc.Utilize this invention to provide to such an extent that epoxidizing method does not need specific installation when preparing epoxide, have the reaction conditions gentleness, easy to operate, the characteristics that cost is relatively low have better industrial application prospects.
(6) whole process is environmentally friendly, and reacted organic solvent can pass through the recycling of distillatory method, is a kind of green chemical synthesis method.The raw material that this method consumed is alkene, H
2O
2, product is single epoxide, and flow process is simple, and the oxidant consumption amount is very low, is a new way that is suitable for industrial scale operation.
Embodiment
Below by several specific embodiments technical scheme of the present invention is further described.Following examples do not constitute limitation of the invention.
Embodiment 1:
In the round-bottomed flask of 25ml, successively add solvent acetonitrile, the 5ml 0.2mol/L K of 5ml
2CO
3The aqueous solution, 20mg nanometer SiO
2, 0.21g vinylbenzene (2.0mmol), 0.34g H
2O
2(the n hydrogen peroxide: n vinylbenzene=1.5: 1), reactor is warming up to 60 ℃ of reaction 6h (round-bottomed flask is joined prolong) under quick magnetic agitation then, and SiO is reclaimed in the extraction back for 3.0mmol, 30% aqueous solution
2, washing, vacuum-drying.Solution carries out quantitative analysis with chromatogram.Styrene conversion rate 95.0mol%, epoxide selectivity 99.8%.
Embodiment 2:
In the round-bottomed flask of 50ml, successively add solvent butyl alcohol-tert, the 10ml0.1mol/L NaHCO of 10ml
3The aqueous solution, 50mg nanometer SiO
2, 1.36g norbornylene (10mmol), 1.36g H
2O
2(the n hydrogen peroxide: n vinylbenzene=1.2: 1), reactor is warming up to 60 ℃ of reaction 6h (round-bottomed flask is joined prolong) under quick magnetic agitation then, and SiO is reclaimed in centrifugal back for 12mmol, 30% aqueous solution
2, washing, vacuum-drying.Solution carries out quantitative analysis with chromatogram.Norbornylene transformation efficiency 97.2mol%, epoxide selectivity 100%.
Embodiment 3
In the round-bottomed flask of 500ml, successively add solvent methanol, the 100ml 0.2mol/L Na of 100ml
3PO
4The aqueous solution, 100mg nanometer SiO
2, 11.0g cyclooctene (100mmol), 17.0g H
2O
2(the n hydrogen peroxide: n vinylbenzene=1.5: 1), reactor is warming up to 60 ℃ of reaction 6h (round-bottomed flask is joined prolong) under quick magnetic agitation then, filters the back and reclaims SiO for 150mmol, 30% aqueous solution
2, washing, vacuum-drying.Solution carries out quantitative analysis with chromatogram.Cyclooctene transformation efficiency 95.3mol%, epoxide selectivity 100%.
Embodiment 4
In the round-bottomed flask of 100ml, successively add solvent acetonitrile, the 20ml0.2mol/L CH of 20ml
3The COOK aqueous solution, 150mg ZSM-5 (SiO
2/ Al
2O
3=25), 1.04g vinylbenzene (10mmol), 1.36g H
2O
2(the n hydrogen peroxide: n vinylbenzene=1.2: 1), reactor is warming up to 60 ℃ of reaction 6h (round-bottomed flask is joined prolong) under quick magnetic agitation then, and ZSM-5, washing, vacuum-drying are reclaimed in centrifugal back for 12mmol, 30% aqueous solution.Solution carries out quantitative analysis with chromatogram.Styrene conversion rate 92.5mol%, epoxide selectivity 99.6%.
Embodiment 5
In the round-bottomed flask of 100ml, successively add solvent acetonitrile, the 20ml0.2mol/L MgSO of 20ml
4The aqueous solution, 150mg SBA-15,1.10g cyclooctene (10mmol), 1.36g H
2O
2(the n hydrogen peroxide: n vinylbenzene=1.2: 1), reactor is warming up to 60 ℃ of reaction 6h (round-bottomed flask is joined prolong) under quick magnetic agitation then, and SBA-15, washing, vacuum-drying are reclaimed in centrifugal back for 12mmol, 30% aqueous solution.Solution carries out quantitative analysis with chromatogram.Cyclooctene transformation efficiency 98.3mol%, epoxide selectivity 100%.
Embodiment 6～22
Form with form provides representational embodiment below, preferred commercialization of catalyzer or the homemade nanometer SiO of simple method
2The activation SiO that has the machine functional group of material or process surface modification
2Material or common cheaply zeolite molecular sieve, alkene such as alkene optimization styrene, tetrahydrobenzene, cyclooctene, norbornylene, α-Pai Xi, beta-pinene, cinnamyl chlorine, methyl acrylate, ethyl propenoate, butyl acrylate, vinylcarbinol, vinyl cyanide, 1-octene.Embodiment 6 is blank reaction experiment example, does not promptly add catalyst S iO
2, its experimental technique and step are followed embodiment 1-5; The experimental technique of embodiment 7～22 and step are followed embodiment 1-5 equally, 100mg SiO
2Or zeolite molecular sieve, the solvent acetonitrile of 50ml, 50ml salts solution (concentration range is 0.05～1mol/L), these as a result example do not constitute limitation of the invention.
| Embodiment | Alkene | N hydrogen peroxide: n alkene | Olefin conversion (mol%) | Epoxy selectivity (%) |
| 6 | Vinylbenzene | 1.5 | 17.1 | 76.4 |
| 7 | Vinylbenzene | 1.0 | 85.2 | 99.8 |
| 8 | Vinylbenzene | 1.5 | 100 | 100 |
| 9 | Tetrahydrobenzene | 1.0 | 82.3 | 100 |
| 10 | Tetrahydrobenzene | 1.5 | 95.4 | 100 |
| 11 | Cyclooctene | 1.0 | 90.0 | 100 |
| 12 | Cyclooctene | 1.5 | 99.2 | 100 |
| 13 | Norbornylene | 1.0 | 97.2 | 100 |
| 14 | α-Pai Xi | 1.5 | 81.5 | 95.2 |
| 15 | Beta-pinene | 1.5 | 80.2 | 90.1 |
| 16 | β-cinnamyl chlorine | 1.5 | 85.3 | 91.5 |
| 17 | Methyl acrylate | 1.5 | 91.5 | 100 |
| 18 | Ethyl propenoate | 1.5 | 95.6 | 100 |
| 19 | Butyl acrylate | 1.0 | 92.3 | 100 |
| 20 | Vinylcarbinol | 1.5 | 73.2 | 80.4 |
| 21 | Vinyl cyanide | 1.5 | 76.5 | 96.5 |
| 22 | The 1-octene | 1.5 | 99.7 | 100 |
Show by above-mentioned example as a result, according to reaction conditions provided by the present invention, can be optionally substrate widely be oxidized to epoxide, this method has the reaction conditions gentleness, operation is easy to control, the feed stock conversion height, good selectivity of target products, the reaction times is short, the efficient height, cost is low, and the characteristics of whole process environment-friendly and green have application promise in clinical practice.
Claims (9)
1, a kind of nanometer SiO
2Material catalyzed alkene and H
2O
2Liquid phase highly selective epoxidizing method, it is with nanometer SiO
2The activation SiO that has the machine functional group of material or process surface modification
2Material or zeolite molecular sieve directly form SiO as catalyst for reaction and reaction substrate alkene, solvent
2-alkene-solvent-H
2O
2/ H
2EPOXIDATION OF ALKENES CATALYZED BY in the O heterogeneous catalyst epoxidation reaction system is H as the epoxidation oxygenant
2O
2Temperature of reaction is controlled at 0～100 ℃, reaction times is 0.5～24h, and described alkene is a kind of in the alkene such as vinylbenzene, tetrahydrobenzene, cyclooctene, norbornylene, α-Pai Xi, beta-pinene, cinnamyl chlorine, methyl acrylate, ethyl propenoate, butyl acrylate, vinylcarbinol, vinyl cyanide, 1-octene.
2, nanometer SiO according to claim 1
2Material catalyzed alkene and H
2O
2Liquid phase highly selective epoxidizing method is characterized in that a kind of with among 4A, ZSM-5, mordenite, beta, SBA-15 series, Y, MCM-41 series, MCM-22, SAPOs series and the AlPOs of described catalyst zeolite molecular screening.
3, nanometer SiO according to claim 1
2Catalytic alkene of material and H
2O
2Liquid phase highly selective epoxidizing method is characterized in that: described organic solvent is CH
3OH, EtOH, Bu
tOH, MeCOMe, MeCOEt, pimelinketone, CH
3CN, DMF, DMA, CHCl
3, CH
2Cl
2, a kind of among DMSO, hexanaphthene, THF and the Ether.
4, nanometer SiO according to claim 1
2Material catalyzed alkene and H
2O
2Liquid phase highly selective epoxidizing method is characterized in that: cooperate with reaction solvent in reaction system jointly as also being added with additive salt in the epoxidation reaction system, wherein additive is selected K
2CO
3, Na
2CO
3, KHCO
3, NaHCO
3, CH
3COONa, CH
3COOK, NaH
2PO
4, Na
2HPO
4, Na
3PO
4, soluble tartrate, soluble tartrate, tartrate receive, microsolubility CaSO
4And MgSO
4In single alkali metal or alkaline-earth metal or mix salt.
5, nanometer SiO according to claim 1
2Material catalyzed alkene and H
2O
2Liquid phase highly selective epoxidizing method is characterized in that: described temperature of reaction is 0～80 ℃.
6, nanometer SiO according to claim 1
2Material catalyzed alkene and H
2O
2Liquid phase highly selective epoxidizing method is characterized in that: the described reaction times is 0.5～6h.
7, nanometer SiO according to claim 1
2Material catalyzed alkene and H
2O
2Liquid phase highly selective epoxidizing method is characterized in that: described additive salt is the aqueous solution of salt, and the mass concentration scope of the aqueous solution is 0.01～1mol/L.
8, nanometer SiO according to claim 1
2Material catalyzed alkene and H
2O
2Liquid phase highly selective epoxidizing method is characterized in that: described H
2O
2With the mol ratio of alkene be 0.5～5.
9, as nanometer SiO as described in the claim 6
2Material catalyzed alkene and H
2O
2Liquid phase highly selective epoxidizing method is characterized in that: the volume ratio of the aqueous solution of described solvent and salt is: 3～1/3.
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Cited By (6)
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| CN102755908A (en) * | 2011-04-28 | 2012-10-31 | 中国科学院大连化学物理研究所 | Alkene epoxidation method |
| CN103539761A (en) * | 2012-07-18 | 2014-01-29 | 湖北大学 | Method for preparing monocyclic oxide through catalyzing diolefin liquid epoxidation reaction with SBA-15 |
| CN106699694A (en) * | 2015-11-18 | 2017-05-24 | 浙江新化化工股份有限公司 | Method for preparing 2,3-epoxypinane by epoxidation of alpha-pinene |
| CN106699693A (en) * | 2016-12-05 | 2017-05-24 | 扬州大学 | Method for synthesizing epoxy phenyl ethane through styrene epoxidation |
| CN107879898A (en) * | 2016-09-29 | 2018-04-06 | 中国石油化工股份有限公司 | A kind of method that vicinal diamines class compound is synthesized using difunctional characteristic catalyst |
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| US6114552A (en) * | 1999-09-28 | 2000-09-05 | Arco Chemical Technology, L.P. | Heterogeneous epoxidation catalyst |
| US6960671B2 (en) * | 2002-09-20 | 2005-11-01 | Arco Chemical Technology, L.P. | Process for direct oxidation of propylene to propylene oxide and large particle size titanium silicalite catalysts for use therein |
| CN101279262B (en) * | 2008-05-29 | 2011-01-26 | 湖北大学 | Preparation of highly selective epoxidized nano composite oxides for catalyzing olefin hydrocarbon and air |
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Cited By (10)
| Publication number | Priority date | Publication date | Assignee | Title |
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| CN102755908A (en) * | 2011-04-28 | 2012-10-31 | 中国科学院大连化学物理研究所 | Alkene epoxidation method |
| CN102755908B (en) * | 2011-04-28 | 2014-05-14 | 中国科学院大连化学物理研究所 | Alkene epoxidation method |
| CN103539761A (en) * | 2012-07-18 | 2014-01-29 | 湖北大学 | Method for preparing monocyclic oxide through catalyzing diolefin liquid epoxidation reaction with SBA-15 |
| CN106699694A (en) * | 2015-11-18 | 2017-05-24 | 浙江新化化工股份有限公司 | Method for preparing 2,3-epoxypinane by epoxidation of alpha-pinene |
| CN106699694B (en) * | 2015-11-18 | 2019-07-30 | 浙江新化化工股份有限公司 | A kind of method that australene epoxidation prepares 2,3- epoxypinane |
| CN107879898A (en) * | 2016-09-29 | 2018-04-06 | 中国石油化工股份有限公司 | A kind of method that vicinal diamines class compound is synthesized using difunctional characteristic catalyst |
| CN107879898B (en) * | 2016-09-29 | 2022-11-22 | 中国石油化工股份有限公司 | Method for synthesizing o-diol compound by using bifunctional catalyst |
| CN106699693A (en) * | 2016-12-05 | 2017-05-24 | 扬州大学 | Method for synthesizing epoxy phenyl ethane through styrene epoxidation |
| CN111318299A (en) * | 2018-12-14 | 2020-06-23 | 万华化学集团股份有限公司 | Modified molecular sieve catalyst and preparation method thereof, and preparation method of styrene oxide |
| CN111318299B (en) * | 2018-12-14 | 2022-07-12 | 万华化学集团股份有限公司 | Modified molecular sieve catalyst and preparation method thereof, and preparation method of styrene oxide |
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