CN1136206C - Catalysts based on organic-inorganic hybrid materials containing titanium, for selective oxidation of hydrocarbons - Google Patents

Catalysts based on organic-inorganic hybrid materials containing titanium, for selective oxidation of hydrocarbons Download PDF

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CN1136206C
CN1136206C CNB008086656A CN00808665A CN1136206C CN 1136206 C CN1136206 C CN 1136206C CN B008086656 A CNB008086656 A CN B008086656A CN 00808665 A CN00808665 A CN 00808665A CN 1136206 C CN1136206 C CN 1136206C
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organic
inorganic hybrid
hybrid materials
titanium
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CN1354687A (en
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M·维斯贝克
H·克劳斯
G·维格纳
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    • BPERFORMING OPERATIONS; TRANSPORTING
    • B01PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01JCHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J31/00Catalysts comprising hydrides, coordination complexes or organic compounds
    • B01J31/02Catalysts comprising hydrides, coordination complexes or organic compounds containing organic compounds or metal hydrides
    • B01J31/12Catalysts comprising hydrides, coordination complexes or organic compounds containing organic compounds or metal hydrides containing organo-metallic compounds or metal hydrides
    • B01J31/122Metal aryl or alkyl compounds
    • CCHEMISTRY; METALLURGY
    • C07ORGANIC CHEMISTRY
    • C07DHETEROCYCLIC COMPOUNDS
    • C07D303/00Compounds containing three-membered rings having one oxygen atom as the only ring hetero atom
    • C07D303/02Compounds containing oxirane rings
    • C07D303/04Compounds containing oxirane rings containing only hydrogen and carbon atoms in addition to the ring oxygen atoms
    • BPERFORMING OPERATIONS; TRANSPORTING
    • B01PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01JCHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J21/00Catalysts comprising the elements, oxides, or hydroxides of magnesium, boron, aluminium, carbon, silicon, titanium, zirconium, or hafnium
    • B01J21/06Silicon, titanium, zirconium or hafnium; Oxides or hydroxides thereof
    • B01J21/063Titanium; Oxides or hydroxides thereof
    • BPERFORMING OPERATIONS; TRANSPORTING
    • B01PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01JCHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J23/00Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00
    • B01J23/38Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of noble metals
    • B01J23/48Silver or gold
    • BPERFORMING OPERATIONS; TRANSPORTING
    • B01PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01JCHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J31/00Catalysts comprising hydrides, coordination complexes or organic compounds
    • B01J31/02Catalysts comprising hydrides, coordination complexes or organic compounds containing organic compounds or metal hydrides
    • B01J31/06Catalysts comprising hydrides, coordination complexes or organic compounds containing organic compounds or metal hydrides containing polymers
    • B01J31/069Hybrid organic-inorganic polymers, e.g. silica derivatized with organic groups
    • BPERFORMING OPERATIONS; TRANSPORTING
    • B01PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01JCHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J31/00Catalysts comprising hydrides, coordination complexes or organic compounds
    • B01J31/02Catalysts comprising hydrides, coordination complexes or organic compounds containing organic compounds or metal hydrides
    • B01J31/12Catalysts comprising hydrides, coordination complexes or organic compounds containing organic compounds or metal hydrides containing organo-metallic compounds or metal hydrides
    • B01J31/123Organometallic polymers, e.g. comprising C-Si bonds in the main chain or in subunits grafted to the main chain
    • B01J31/124Silicones or siloxanes or comprising such units
    • B01J31/125Cyclic siloxanes
    • BPERFORMING OPERATIONS; TRANSPORTING
    • B01PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01JCHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J37/00Processes, in general, for preparing catalysts; Processes, in general, for activation of catalysts
    • B01J37/02Impregnation, coating or precipitation
    • B01J37/03Precipitation; Co-precipitation
    • B01J37/031Precipitation
    • B01J37/033Using Hydrolysis
    • BPERFORMING OPERATIONS; TRANSPORTING
    • B01PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01JCHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J37/00Processes, in general, for preparing catalysts; Processes, in general, for activation of catalysts
    • B01J37/02Impregnation, coating or precipitation
    • B01J37/03Precipitation; Co-precipitation
    • B01J37/036Precipitation; Co-precipitation to form a gel or a cogel
    • BPERFORMING OPERATIONS; TRANSPORTING
    • B01PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01JCHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J37/00Processes, in general, for preparing catalysts; Processes, in general, for activation of catalysts
    • B01J37/04Mixing
    • CCHEMISTRY; METALLURGY
    • C07ORGANIC CHEMISTRY
    • C07DHETEROCYCLIC COMPOUNDS
    • C07D301/00Preparation of oxiranes
    • C07D301/02Synthesis of the oxirane ring
    • C07D301/03Synthesis of the oxirane ring by oxidation of unsaturated compounds, or of mixtures of unsaturated and saturated compounds
    • C07D301/04Synthesis of the oxirane ring by oxidation of unsaturated compounds, or of mixtures of unsaturated and saturated compounds with air or molecular oxygen
    • C07D301/06Synthesis of the oxirane ring by oxidation of unsaturated compounds, or of mixtures of unsaturated and saturated compounds with air or molecular oxygen in the liquid phase
    • CCHEMISTRY; METALLURGY
    • C07ORGANIC CHEMISTRY
    • C07DHETEROCYCLIC COMPOUNDS
    • C07D301/00Preparation of oxiranes
    • C07D301/02Synthesis of the oxirane ring
    • C07D301/03Synthesis of the oxirane ring by oxidation of unsaturated compounds, or of mixtures of unsaturated and saturated compounds
    • C07D301/04Synthesis of the oxirane ring by oxidation of unsaturated compounds, or of mixtures of unsaturated and saturated compounds with air or molecular oxygen
    • C07D301/08Synthesis of the oxirane ring by oxidation of unsaturated compounds, or of mixtures of unsaturated and saturated compounds with air or molecular oxygen in the gaseous phase
    • C07D301/10Synthesis of the oxirane ring by oxidation of unsaturated compounds, or of mixtures of unsaturated and saturated compounds with air or molecular oxygen in the gaseous phase with catalysts containing silver or gold
    • BPERFORMING OPERATIONS; TRANSPORTING
    • B01PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01JCHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J2231/00Catalytic reactions performed with catalysts classified in B01J31/00
    • B01J2231/70Oxidation reactions, e.g. epoxidation, (di)hydroxylation, dehydrogenation and analogues
    • B01J2231/72Epoxidation

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Abstract

The invention relate to supported compositions containing gold and/or silver particles and Ti-containing, organic-inorganic hybrid materials. The invention also relates to a method for producing said compositions and to their use as a catalyst for the selective oxidation of hydrocarbons. The catalytically active compositions present high levels of selectivity and productivity.

Description

Hydrocarbon selective oxidation catalyzer based on organic-inorganic hybrid materials containing titanium
Technical field
The present invention relates to comprise the loading type composition and method of making the same of gold and/or silver-colored particle and organic-inorganic hybrid materials containing titanium and as the purposes of hydrocarbon selective oxidation catalyzer.This catalytic activity composition exhibiting goes out high selectivity and productivity.
Background technology
It is well-known making direct oxidation of ethylene to become the method for ethylene oxide with molecular oxygen, and produces ethylene oxide at the industrial vapor phase process that is used for.Typical catalysts containing metal silver or ionic silver that this method is used also can be with various promotor and activator modifications.Great majority all comprise a kind of inert catalyst carrier of low surface area in this class catalyzer, and for example Alpha-alumina has been coated with silver and promotor on it.People such as Sachtler are in Catalysis Reviews (catalysis comment): scientific and engineering, 23 (1 ﹠amp; 2), collected among the 127-149 (1981) summary of relevant ethene direct oxidation in the presence of loading type silver catalyst.
Also know, these are proved to be and help silver catalyst that ethylene oxide produces and reaction conditions (US 5 at higher alkene such as propylene, 763,630, US 5,703,254 and US 5,760,254) do not produce reasonable result in the direct oxidation, the selectivity of resulting propylene oxide is up to about 50%.Generally speaking, this class higher alkene with the direct oxidation of molecular oxygen in gas phase when being lower than 200 ℃, even in the presence of catalyzer, also can't carry out, therefore, be difficult to optionally prepare the oxidation products of oxidation-sensitive, as epoxide, its reason is that the second order reaction of these products is often carried out soon than the oxidizing reaction of used alkene itself.Another problem is caused to the susceptibility of oxidation by the allyl group that exists in the higher alkene.
For this reason, propylene oxide can only be produced in liquid phase with non-direct method in industry at present.
United States Patent (USP) 5,623,090 has narrated the method that the propylene gas phase is direct oxidation into propylene oxide, its propylene conversion quite low (propylene conversion based on 10% propylene feed concentration is 0.5-1%), but the selectivity of propylene oxide>90%.This be catalytic with gold/titanium dioxide, at 40-80 ℃ of a kind of gas phase oxidation that carries out with molecular oxygen and hydrogen.With the titanium dioxide (anatase octahedrite) of commercially available nano level goldc grains coating as catalyzer.Adopt fiercer reaction conditions, as temperature be increased to>100 ℃, or rising pressure can not make productivity improve.Except propylene conversion was quite low, this method also had a very big shortcoming, and that is exactly that catalyzer is along with the serious inactivation of the process of time.Typical half life is 30-150 minute under 50 ℃ of normal pressures.The rising meeting of described temperature and/or pressure is further shortened half life.
It also is known (WO 9800415A1, WO 9800414A1 and EP 0827779A1) that goldc grains is applied to the supported catalyst that contains the titanium center that is dispersed on the inorganic silicon matrix.All these carry out roasting subsequently by dipping and obtain material and all demonstrate quite low propylene conversion, this catalyzer in time process and inactivation (typical half life is 5-50 hour) thereby can not be used in the large-scale factory.
Know in addition goldc grains is applied to catalyzer on the porous crystalline matrix silicate with definite pore structure, wherein silicon tetrahedron space is replaced (for example TS-1, TS-2 by the titanium similar shape, Ti zeolite such as Ti-β, Ti-ZSM-48, or titaniferous mesoporous molecular sieve, for example Ti-MCM-41 or Ti-HMS) (WO 9800413 A1).Though all these gold-silicate or gold-zeolite structured demonstrate good selectivity, the transformation efficiency of hydro carbons and top all life of catalyst are for being insufficient fully for the use in the chemical industry.
Described method for preparing catalyst is very unsafty with regard to catalyst activity and life-span aspect.For commercial run, need many reactors with the low activity catalyst operation.Short catalyst life means the production route of a kind of tediously long cost costliness of the loss of producing or needs in the regeneration stage.
Known and on the basis of carbon siloxanes, used the component (for example EP-A-743313) of organic-inorganic hybrid materials as coating.
Therefore wish to develop the new catalyst with industrial application value that can reach high reactivity and have both excellent selectivity and life-span.
Summary of the invention
Therefore, an object of the present invention is to provide and have high reactivity and also have optionally new catalyst of excellence simultaneously.
Another purpose is the method for this catalyzer of exploitation preparation.
Another purpose provides and a kind ofly relies on this catalyzer to adopt the oxysome oxygenant to carry out the technical simple vapor phase process of hydrocarbon selective oxidation, and this method obtains high yield and low cost with industrial interested high reactivity, very high selectivity and catalyst life.
Another purpose provides a kind of catalyzer of alternative hydro carbons direct oxidation.
Also having a purpose is to eliminate the shortcoming of known catalysts at least in part.
According to these purposes of the present invention is to reach by comprising the gold and/or the particle of silver and the loading type composition of organic-inorganic hybrid materials.
On meaning of the present invention, organic-inorganic hybrid materials is organically-modified amorphous glass, preferably hydrolysis by low-molecular weight compound normally and condensation reaction form this material in sol-gel process, and contain the bridge joint organic group in network.They contain the structural unit of at least a formula (I)
[R 1] j-SiR 2 k(O 1/2) 4-k-j(I) wherein:
J is 1,2 or 3,
K represents 0,1 or 2,
k+j≤3,
R 1Be the C of bridge joint Si atom 1-C 10Alkylidene group, and
R 2The optional alkyl or aryl that replaces of representative.
This organic-inorganic hybrid materials preferably contains the structural unit of formula (II)
[R 1] j-SiR 2 k(O 1/2) 4-k-j(II) wherein:
J is 1,
K represents 0,1 or 2,
k+j≤3,
R 1Be the C of bridge joint Si atom 1-C 4Alkylidene group, and
R 2Be methyl or ethyl.
General formula (I) and (II) in " O 1/2" part represents the difunctionality oxygen of bridge joint, i.e. for example structural unit Si-O-Si or Si-O-Ti.
General formula (I) and (II) in alkylidene group R 1Preferably with a chain, star (branching), cage shape, or preferred especially cyclic structural unit connects.The ring texture unit can be [O-Si (CH for example 3)-] 3Or [O-Si (CH 3)-] 4
Embodiment
Alkylidene group is interpreted as representing all alkylidene groups, arylidene or the alkarylene that contain 1-10 carbon atom known to the those skilled in the art, for example methylene radical, ethylidene, positive propylidene, isopropylidene, positive butylidene, isobutylene, positive pentylidene, isopentylidene, new pentylidene, positive hexylidene, cyclohexylidene, isohexylidene, inferior heptyl, octylene, nonamethylene, inferior decyl and phenylene, these groups also can be cyclic or be branching or non-branching chain form, and can be optional the replacements.Possible substituting group is all group that adverse effect does not take place with catalyst component such as titanium or promotor, for example alkyl, aryl or alkoxyl groups.
In a particularly preferred specific embodiments of the present invention, this organic-inorganic hybrid materials contains one or more following structural units:
a)Si[(C 2H 4)Si(CH 3) 2(O 1/2)] 4
B) ring-{ OSi (CH 3) [(C 2H 4) Si (CH 3) 2(O 1/2)] 4
C) ring-{ OSi (CH 3) [(C 2H 4) Si (CH 3) (O 1/2) 2] 4
D) ring-{ OSi (CH 3) [(C 2H 4) Si (O 1/2) 3] 4
With regard to meaning of the present invention, organic-inorganic hybrid materials comprises 0.1-6% weight, preferred 0.8-5% weight, the titanium of preferred especially 1.0-4% weight.Titanium exists with oxide form, and preferably in conjunction with or be bonded in the organic-inorganic hybrid materials with chemical mode by the Si-O-Ti key.
The catalytic activity of this class material shows the non-linear increase with total titanium content when titanium content is higher.This shows not to be that all titanium centers all have identical catalytic activity.We suppose that titanium is bonded on the silicon by the different silicones key in active catalyst.
Except titanium, also can comprise external oxide compound according to organic-inorganic hybrid materials of the present invention, promptly so-called promotor, they are from the 5th family in IUPAC (1985) periodictable, as vanadium, niobium and tantalum, preferred especially tantalum, the 8th family, preferred especially Fe, the metal of the 15th family such as arsenic, antimony and bismuth, preferred especially antimony, and the metal of the 13rd family such as boron, aluminium, gallium, indium and thallium, preferred especially aluminium and boron.
These promotor major parts exist with the homogeneous phase form, promptly form the farmland hardly." " form with high dispersing is present in the organic-inorganic hybrid materials M bonded promotor, and major part is by element-O-Si key bonding.The chemical constitution of this class material can change in wide region.The scope of promoter component is 0-10%.Can certainly use several different promotor.Promotor is preferably used with the form of the promotor precursor compound that is dissolved in specific solvent, as promoter salts or organic promoter compound.
This class promotor can be improved the active of composition and be prolonged the life-span of composition in the hydrocarbon catalyticing oxidation reaction process.
The organic-inorganic hybrid materials of high-specific surface area is preferred.Specific surface area should be at least 1m 2/ g is preferably 25-700m 2/ g.
The organic-inorganic hybrid materials of surface modification also is preferred.With regard to meaning of the present invention, surface modification is meant by being selected from silicon-alkyl, silicon-aryl, containing fluoroalkyl and/or containing the covalent attachment of group of fluoro aryl or the content of coordination mating surface silanol reducing.
According to loading type composition of the present invention comprise be coated on as on the organic-inorganic hybrid materials of solid support material the gold and/or silver-colored.Under the catalytic activity state, mainly there be (by the spectroscopic analysis of X-gamma absorption) in gold and/or silver with the metal element form.Small portion gold and/or silver-colored oxidation state that also can be higher exist.Take a picture judgement, overwhelming majority gold and/or silver-colored being present on the surface of solid support material by TEM.It is nanometer scale bunch form the gold and/or silver-colored.The diameter of goldc grains is preferably 0.5-50nm, and more preferably 0.5-15nm is preferably 0.5-10nm especially.The diameter of silver granuel is preferably 0.5-100nm, and more preferably 0.5-40nm is preferably 0.5-20nm especially.
The content of gold should be 0.001-4% weight, is preferably 0.001-2% weight, is preferably 0.005-1.5% weight especially.
The content of silver should be 0.005-20% weight, is preferably 0.01-15% weight, is preferably 0.1-10% weight especially.
Golden and/or silver-colored content does not have the effect that improves catalytic activity when higher than described scope.For economic reasons, bullion content should be to reach the active required minimum content of maximum catalyst.
Described purpose also comprises the gold and/or the particle of silver and the loading type method for compositions of organic-inorganic hybrid materials containing titanium by preparation and reaches.
Organic-inorganic hybrid materials containing titanium prepares by sol-gel method.This preparation example is as realizing by following method: suitable normally low-molecular weight compound is blended in a kind of solvent, adds entry then and randomly add catalyzer (for example acid, alkali and/or organometallic compound) to cause hydrolysis and/or condensation reaction.Such sol-gel method program is known in principle concerning the personnel that are proficient in present technique.
The low-molecular weight compound that is suitable for is the precursor of organic and inorganic tackiness agent and silicon, titanium and promotor for example.On meaning of the present invention, lower molecular weight is meant monomer or oligopolymer.
This sol-gel method forms a kind of unbodied three-dimensional network (gel) based on the polycondensation with colloidal form dissolved metal component mixture (colloidal sol) of hydrolysis.Following reaction formula can be used to illustrate this process:
The parent material that is suitable for is the soluble titanium known to organic and inorganic tackiness agent and the personnel that are proficient in present technique and the compound of silicon, these compounds can be used as the precursor of corresponding oxide or oxyhydroxide, for example corresponding alkoxide, soluble salt and organic titanium or silicoorganic compound.
Though all salt for example halogenide, nitrate and oxyhydroxide can use, preferably the alkoxide of these metals such as ethylate, propylate etc.
On meaning of the present invention, the organic and inorganic tackiness agent is a polyfunctional organosilane, for example contains at least 2 by alkylene-bridged multifunctional silanol and/or the alkoxide of C1-C10.
The preferred organic and inorganic tackiness agent that can mention is:
a)Si[(C 2H 4)Si(OH)(CH 3) 2] 4
B) ring-{ OSi (CH 3) [(C 2H 4) Si (OH) (CH 3) 2] 4
C) ring-{ OSi (CH 3) [(C 2H 4) Si (OC 2H 5) 2(CH 3)] 4
D) ring-{ OSi (CH 3) [(C 2H 4) Si (OCH 3) (CH 3) 2] 4
E) ring-{ OSi (CH 3) [(C 2H 4) Si (OC 2H 5) 3] 4
Organic and inorganic tackiness agent synthetic and for example be described among EP 0743313, the EP 0787734 and WO 98/52992 with the technology of this compounds enforcement sol-gel method.
The silicon precursor that is suitable for for example is, the alcoxylates of silicon such as Si (OC 2H 5) 4, Si (OCH 3) 4, (H 3C) Si (OC 2H 5) 3, (C 6H 5) Si (OC 2H 5) 3Also can use its condensation product to replace the monomer alcoxylates.Si (OC for example 2H 5) 4Condenses commercially available product is arranged.In addition, can also use its polymkeric substance, for example poly-diethoxy silane.
The titanium precursor compound that is suitable for as the catalytic titanium compound is known in the prior art, for example solubility titanium salt (as halogenated titanium, nitrate and vitriol), mineral acid or organic acid titanium salt and titanic acid ester.
Preferably titanium derivative for example contains C 1-C 6Alkyl is as tetraalkyl titanate or other organic titanic compound of methyl, ethyl, n-propyl, normal-butyl, isobutyl-, the tertiary butyl etc., as methyl ethyl diketone oxygen titanium and titanocene dichloride.Preferred titanium precursor compound is titanic hydroxide four positive butyl esters, titanium acetylacetone, titanocene dichloride and titanium tetrachloride.Under the situation of the existence that plural components such as methyl ethyl diketone or ethanoyl ethyl acetate are arranged, also can use the titanium precursor compound.
The promotor precursor compound that is suitable for is the alcoxylates of mixture, organic promoter compound or promotor of salt, the promotor of for example promotor.The preferred alcoxylates that uses.
The preferred solvent that sol-gel method is used is an alcohols, for example methyl alcohol, ethanol, Virahol or butanols; Ketone, for example acetone; Ethers, for example THF or methyl tertiary butyl ether.
Say that in principle any program of being proficient in known to the personnel of present technique that is used for sol-gel method all can be used to synthetic organic-inorganic hybrid materials containing titanium of the present invention.-Si-O-Ti-group for example can produce by following method: hydrolysis and/or condensation reaction in the time of by Si precursor and Ti precursor, by organic and inorganic tackiness agent and Ti precursors reaction, randomly add the Si precursor subsequently, reaction in the time of perhaps by organic and inorganic tackiness agent, Ti precursor and Si precursor.
In a preferred specific embodiments, earlier the Si precursor is incorporated in the solvent, carry out partial hydrolysis with the water that is less than theoretical aequum, and adding catalyzer, add Ti compound and remaining water then, randomly add, add the organic and inorganic tackiness agent at last with catalyzer.
The consumption and the temperature that depend on composition, catalyzer, water may form gel through several minutes after several days.Behind the gel formation, can be immediately or through carrying out drying after the slaking in 30 days at the most.For hydrolysis and condensation reaction are carried out fully, can be randomly with excessive water or water vapour to wet and/or the exsiccant gel carry out one or many and handle.Preferably, carry out drying particularly preferably in 100-180 ℃ at 50-250 ℃.
This material can randomly be ground into powder (for example by grinding) before or after drying, or as molding.
Precious metal can be with the form of precursor compound, and as salt or organic coordination compound, or compound adds in sol-gel process, perhaps by known method, for example by dipping or precipitation, applies after preparing gel.The surface modification of said composition also can be carried out according to this step.
Surface modification can be carried out before or after the coating precious metal.
On meaning of the present invention, modification is interpreted as referring in particular to the lip-deep process that the group that will be selected from silicon-alkyl, silicon-aryl, contain fluoroalkyl or contain fluoro aryl is applied to this loading type composition, and these groups are bonded on the lip-deep functional group (as the OH yl) by covalent linkage or coordinate bond.But any other surface treatment method also obviously comprises within the scope of the invention.
Preferably carry out modification, wherein preferably have organic silicon compound with organosilicon and/or fluorine-containing organosilicon or organic compound.
Possible silicoorganic compound are all silylating agents of being proficient in known to the people of present technique, for example organosilane, Organosilyl amine, Organosilyl acid amides and derivative thereof, organosilazanes, organo-siloxane and other silicoorganic compound, certainly, these compounds can be used in combination.Also obviously belong to silicoorganic compound by silicon and compound partially fluorinated or that the perfluorination organic group is formed.
The object lesson of organosilane is a trimethylchlorosilane, dichlorodimethylsilane, chlorine bromine dimethylsilane, the nitrotrimethylolmethane methyl-monosilane, one chlorine trimethyl silane, iodine dimethyl butyrate base silane, the Chlorodimethyl phenyl silane, Chlorodimethyl silane, dimethyl n propyl chloride silane, dimethyl isopropyl chloride silane, tertiary butyl dimethyl nitrogen silane, the tripropyl chlorosilane, dimethyl octyl group chlorosilane, the tributyl chlorosilane, three hexyl chloride silane, the dimethyl ethyl chlorosilane, the dimethyl stearyl chlorosilane, the normal-butyl dimethylchlorosilane, the brooethyl dimethylchlorosilane, CMDMCS chloromethyl dimethyl chlorosilane, 3-chloropropyl dimethylchlorosilane, the dimethoxy-methyl chlorosilane, the aminomethyl phenyl chlorosilane, the triethoxy chlorosilane, the 3,5-dimethylphenyl chlorosilane, the methyl phenyl vinyl chlorosilane, the benzyl dimethyl chlorosilane, diphenyl chlorosilane, diphenyl methyl chloro silane, the diphenylacetylene chlorosilane, tribenzyl chlorosilane and 3-cyano group propyl-dimethyl chlorosilane.
The object lesson of Organosilyl amine is N-trimethyl silyl diethylamide and pentafluorophenyl group dimetylsilyl amine, and comprises N-trimethyl-silyl-imidazole, N-t-butyldimethylsilyl imidazoles, N-dimethylethylsilyl imidazoles, N-dimethyl-n-propyl silyl imidazoles, N-dimethyl sec.-propyl silyl imidazoles, N-trimethyl silyl dimethyl amine, N-trimethyl silyl pyrroles, N-trimethyl silyl tetramethyleneimine, N-trimethyl silyl piperidines and 1-cyano ethyl (diethylin) dimethylsilane.
The object lesson of Organosilyl acid amides and derivative thereof is N, the two trimethyl silyl ethanamides of O-, N, the two trimethyl silyl trifluoroacetamides of O-, N-trimethyl silyl ethanamide, N-methyl-N-trimethyl silyl ethanamide, N-methyl-N-trimethyl silyl trifluoroacetamide, N-methyl-N-trimethyl silyl seven fluorine butyramides, N-(t-butyldimethylsilyl)-N-TFA amine and N, two (the diethyl hydrogen silyl) trifluoroacetamides of O-.
The object lesson of organosilazanes is hexamethyldisilazane, heptamethyldisilazane, 1,1,3,3-tetramethyl-disilazane, 1, two (chloromethyl) tetramethyl-disilazanes, 1 of 3-, 3-divinyl-1,1,3,3-tetramethyl-disilazane and 1,3-phenylbenzene tetramethyl-disilazane.
The example of other silicoorganic compound is N-methoxyl group-N, the two trimethyl silyl trifluoroacetamides of O-, N-methoxyl group-N, the two trimethyl silyl carbamates of O-, N, the two trimethyl silyl sulfamates of O-, trimethylsilyl triflate and N, N '-two trimethyl silyl ureas.
Preferred silylating agent is hexamethyldisilazane, hexamethyldisiloxane, N-methyl-N-(trimethyl silyl)-2,2,2-trifluoroacetamide (MSTFA) and trimethylchlorosilane.
What comprise the particle of gold and/or silver and organic-inorganic hybrid materials containing titanium can be approx describes (not considering the group that forms on the modification rear surface and the group of any not complete reaction here) with following empirical formula according to the dry state form of loading type composition of the present invention:
Hyb×SiO x×TiO y×MO z×E (III)
The component that Hyb representative in the formula (III) is formed by the organic and inorganic tackiness agent in sol-gel method, M is a kind of promotor, preferred Ta, Fe, Sb, Al or its combination, x, y, z are the required number of the valency that effectively satisfies Si, Ta and M, and E is a precious metal.
With the silicon oxide is benchmark, and the content of the Hyb that represents with molecular fraction is 0.05-200%, is preferably 10-120%, more preferably 30-100%.With the silicon oxide is benchmark, and the content of titanium oxide is the 0.1-10% mole, is preferably 0.5-8.0%, more preferably 1.0-7.0%.With the silicon oxide is benchmark, MO zContent be the 0-12% mole.With the composition that does not comprise precious metal is benchmark, and the content of E is 0.001-15% weight.Preferred 0.001-2% weight in the situation of gold, and in the situation of silver preferred 0.01-15% weight.
Surprisingly, we find, compare with the catalyst system of paraffinic hydrocarbons catalytic oxidation use with present known alkene, go out the catalytic activity of high several number magnitude and good catalyst life according to loading type composition exhibiting of the present invention.
Therefore described purpose is used for hydrocarbon oxidation by loading type composition of the present invention and further reaches, thereby the present invention also provides this purposes.
Can be by heating (being up to 250 ℃) and with appropriate solvent such as alcohols through the catalyzer of long-time rear section inactivation, or with Dilute Hydrogen Peroxide Solution (8%H for example 2O 2-methanol solution) washing is regenerated.
According to composition of the present invention, can be applicable to all hydro carbons in principle.The term hydro carbons is interpreted as representing unsaturated or saturated hydrocarbons, for example alkene and alkane, and these hydro carbons also can contain heteroatoms, as N, O, P, S or halogen.Wanting oxidized organic composition can be acyclic, monocyclic, dicyclo or polycyclic, and can be monoolefine, diolefine or polyene hydrocarbon.Under the situation of the organic composition with 2 or more a plurality of pairs of keys, two keys can exist with conjugation and non-conjugated form.Preferred oxidized hydro carbons is can form to have enough low dividing potential drop is convenient to shift out consistently product from catalyzer oxidation products person.Preferably contain 2-20, unsaturated and the saturated hydrocarbons of preferred 2-10 carbon atom, particularly ethene, ethane, propylene, propane, Trimethylmethane, iso-butylene, 1-butylene, 2-butylene, cis-2-butene, trans-2-butene, 1,3-butadiene, amylene, pentane, 1-hexene, 1-hexane, hexadiene, tetrahydrobenzene and benzene.
This organic-inorganic hybrid materials allow a class " Catalyst Design ", promptly to material property, for example hydrophobicity (polarity) and/or porous comprehensive and simultaneously controlled influence.Surprisingly, this has caused the catalyzer of remarkable improvement.Surface polarity has direct influence to activity of such catalysts and selectivity.The hydrophobicity of this class material is determined by the number and the character of the Si-C key of end group and above-mentioned all bridge joints fully.With other switch is arranged, for example the Si-O-C key is compared, and this key has extra advantage, and promptly they have very big unreactiveness, that is to say, and is insensitive to hydrolysis and oxidizing reaction.
In contrast, the common feature of all catalyzer known in the past is that gold grain is applied on the pure inorganic carrier material.Though adopt these to pass through subsequently modification to the surface, be conceivable to surperficial polar influence for example by using silicon-alkyl end group measure, it is possible that but this only is only on extremely limited degree, particularly depends on the upward number of reactive group (as Si-OH) of surface.
This loading type composition can be used for oxidizing reaction as abrasive flour, spheroidal particle, pill, extrudate, particle etc. with any desired physical form.
A kind of preferred purposes is to be used for hydro carbons, the particularly gaseous oxidation of alkene in the presence of oxygen and hydrogen and loading type composition of the present invention.In the method, from olefine selective obtain epoxide, from saturated secondary hydrocarbon-selective obtain ketone, and optionally obtain alcohols from saturated tertiary hydrocarbon.Depend on used educt, catalyst life is a couple of days, several months or longer.
Hydrocarbon, oxygen, hydrogen can change in wide region with the relative molar ratio of diluent gas randomly.
For the total mole number of hydrocarbon, oxygen, hydrogen and diluent gas, the mole number of used hydrocarbon can change in wide region.Based on used oxygen (by mole), preferably use excessive hydrocarbon.The content of hydrocarbon is typically greater than 1% (mole), less than 60% (mole).Hydrocarbon content is preferably 5-35% (mole), is preferably 10-30% (mole) especially.Along with the increase of hydrocarbon content, productivity also increases, and the burning of hydrogen then reduces.
Oxygen can use with multiple multi-form form as molecular oxygen, air and nitrogen oxide.Preferred molecular oxygen.For the total mole number of hydrocarbon, oxygen, hydrogen and diluent gas, the molar content of oxygen can change in wide region.For hydrocarbon, preferably use the insufficient oxygen of mole number.The consumption of oxygen is preferably 1-12% (mole), is preferably 6-12% (mole) especially.Along with the increase of oxygen level, productivity also increases.For the purpose of fully, oxygen level should be chosen in below 20% (mole).
Do not having under the situation of hydrogen, loading type composition exhibiting of the present invention goes out to have only low-down activity and selectivity.Do not having under the situation of hydrogen, during up to 180 ℃, productivity is still very low, when temperature is higher than 200 ℃, has also formed a large amount of carbonic acid gas except partial oxidation products.Can use any known hydrogen source, for example from hydro carbons and dehydrogenating alcohol and the molecular hydrogen that produces.In another specific embodiments of the present invention, hydrogen also can reactor in front in for example by propane or Trimethylmethane or alcohols, for example isopropylcarbinol dehydrogenation and producing on the spot.Hydrogen also can be incorporated in the reaction system with the form that is combined in the chemical seed in complex compound such as the catalyzer-hydride-complex.For the total mole number of hydrocarbon, oxygen, hydrogen and diluent gas, the molar content of hydrogen can change in wide region.Typical hydrogen richness is preferably 5-80% (mole) greater than 0.1% (mole), is preferably 10-65% (mole) especially.Along with the increase of hydrogen richness, productivity also increases.
Except above-mentioned essential substantially educt gas, also can randomly use diluent gas, as nitrogen, helium, argon, methane, carbonic acid gas or similar rare gas element.Also can use the mixture of above-mentioned inert component.The inert component additive all is favourable for the conduction and the secure context of the heat that is discharged by this exothermic oxidation reaction.If method of the present invention is carried out in gas phase, then preferred using gas dilution component, for example nitrogen, helium, argon, methane and possible water vapour and carbonic acid gas.Though water vapour and carbonic acid gas are not complete inert, they have positive influence when very low concentration (<2% volume).
If method of the present invention is carried out, then can select a kind of oxidation-stabilized and heat-staple inert liq (for example alcohols, many alcohols, polyethers and halogenated hydrocarbon) easily in liquid phase.Also be applicable to according to loading type composition of the present invention and in liquid phase, carry out hydrocarbon oxidation.Alkene relies on described catalyzer highly selective to change into epoxide in liquid phase both can to carry out in the presence of organic hydroperoxide (R-OOH), and also can carry out in the presence of oxygen and hydrogen.
We have found that above-mentioned selective oxidation reaction has the high susceptibility to catalyst structure.When having golden and/or silver-colored nano-dispersed particle in this loading type composition, the productivity of observing the selective oxidation product increases
The gold on this organic and inorganic carrier and/or the space of silver and titanium oxide (peripheral interface) closely interact and carry out effectively especially, promptly obtain excellent epoxidation catalyst in the presence of oxygen and hydrogen.Activity of such catalysts and life-span can particularly further improve by adding tantalum and/or iron and/or antimony and/or aluminium by adding a spot of promotor such as external metal.According to composition of the present invention can be with technical scale, do not have any Technology problem and prepare with low cost.
React the characteristic that catalyzer of the present invention is described by Preparation of catalysts and catalytic test among the following embodiment.
Self-evident, the present invention is not limited to the following example.
Embodiment
Catalyst test explanation (testing sequence)
Use the metal tube reactor of internal diameter 10mm, long 20cm, this reactor carries out temperature control with oily thermostatic bath.Infeed educt gas with one group of four logistics setter (hydrocarbon, oxygen, hydrogen, nitrogen) to reactor.For reaction is carried out, under 150 ℃ and 1 pressure that cling to, begin to introduce the 0.5g powdered catalyst.Educt is metered into the reactor from the top.Standard catalyst load be 4 liters/gram catalyzer/hour.For example select propylene as " the standard hydrocarbon ".In order to carry out oxidizing reaction, select nitrogen-rich stream: N 2/ H 2/ O 2/ C 3H 6=15/65/10/10%, hereinafter referred to as standard gas composition.Reactant gases carries out quantitative analysis with vapor-phase chromatography.Each reaction product is separated with vapor-phase chromatography, adopts the FID/WLD method of associating in this vapor-phase chromatography, and wherein product flows through placed in-line 3 capillary chromatographic columns:
FID:HP-Innowax, internal diameter 0.32mm, long 60m, coat-thickness 0.25 μ.
WLD:HP-Plot Q, internal diameter 0.32mm, long 30m, coat-thickness 20 μ,
HP-Plot Molsieve 5A, internal diameter 0.32mm, long 30m, thick coating
Spend 12 μ.
Embodiment 1
Present embodiment is described the surface is coated with goldc grains then through modification the Preparation of catalysts that comprises organic-inorganic hybrid materials containing titanium.Binder content is 40%, and titanium oxide content is 4.5%.
Toward the 40.7g tetraethoxysilane (195.4mmol) and the middle tosic acid aqueous solution that adds 3.5g 0.1N of 21.1g ethanol (analytical pure), this mixture was stirred 1 hour.Slowly add 4.0g four titanium butoxide (11.75mmol) then, again this mixture was stirred 30 minutes.Add 8.44g ring-{ OSi (CH 3) [(C 2H 4) Si (OH) (CH 3) 2] 4(13mmol) solution in 20.0g ethanol (analytical pure), mixture restir 30 minutes.Under agitation add the tosic acid aqueous solution of 3.9g 0.1N and the mixture of 3.9g ethanol (analytical pure), relief mixture leaves standstill.After about 24 hours, mixture reaches gelation point.Through in gel, adding water till no longer forming bubble and can detecting streak after about 14 days curing time.Exchange several times water.Then with product reheat 1 hour in 60 ℃ of water.Decant goes out supernatant liquor, and residue was 150 ℃ of dryings 8 hours.
The theory of resulting catalyzer consists of 40% ring-{ OSi (CH 3) [(C 2H 4) Si (CH 3) 2(O 1/2)] 4, 55.6%SiO 2And 4.5%TiO 2
In order to carry out surface modification, under protection of inert gas, earlier the 20g powder is joined and contain 20g1,1; 1; 3,3, in the reactor of 3-hexamethyldisilazane and 200g anhydrous n-hexane; under agitation mixture heating up was refluxed 2 hours; decant goes out supernatant liquor, and residue washs 2 times with normal hexane, each 300ml; under vacuum, remove volatile component, then 150 ℃ of dryings 4 hours.
The BET surface-area is 345m 2/ g.
Earlier 2.5g is contained titanium carrier and join in the 20ml methyl alcohol (Merck company, analytical pure), add 40mg HAuCl 4* 3H 2O (0.1mmol, Merck company) is dissolved in the solution in the 5ml methyl alcohol, with 0.8ml 2N K 2CO 3With pH regulator to 8, this mixture was stirred 30 minutes, add the 2ml sodium citrate solution, check pH once more, mixture was stirred 120 minutes, isolate solids, use methanol wash 3 times, each 20ml, under 120 ℃ and normal pressure dry 10 hours, then 200 ℃ of roastings 5 hours.Gold content in this gold-titanium-Si catalyst is 0.58% weight (icp analysis).
In the test of carrying out according to testing sequence, propylene conversion reaches 1.5% under 95% constant PO selective conditions in 50 hours.
Embodiment 2
Present embodiment is described the surface is coated with goldc grains then through modification the Preparation of catalysts that comprises organic-inorganic hybrid materials containing titanium that is similar to embodiment 1.This support of the catalyst was ground earlier before the coating precious metal.
In order to grind, this titanium-containing materials is suspended in the Virahol, in ball mill, grind then, on rotatory evaporator, remove solvent, 150 ℃ in gained powder under normal pressure dry 4 hours carries out surface modification subsequently and is coated with precious metal.
In the test of carrying out according to testing sequence (140 ℃), propylene conversion reaches 2.5% under 95% constant PO selective conditions in 50 hours.According to testing sequence in 150 ℃ of tests of carrying out, propylene conversion reaches 3.4% under 95% constant PO selective conditions in 50 hours.
Embodiment 3
Present embodiment is described the surface is coated with goldc grains then through modification the Preparation of catalysts that comprises organic-inorganic hybrid materials containing titanium.This preparation is undertaken by the method that is similar to embodiment 2, but binder content is 20%, and content of titanium dioxide is 3%.
Toward the 55.6g tetraethoxysilane (266.9mmol) and the middle tosic acid aqueous solution that adds 4.8g 0.1N of 16.9g ethanol (analytical pure), this mixture was stirred 1 hour.Slowly add 2.65g four titanium butoxide (7.78mmol) then, again this mixture was stirred 30 minutes.Add 4.16g ring-{ OSi (CH 3[(C 2H 4) Si (OH) (CH 3) 2] 4(6.4mmol) solution in 10.0g ethanol (analytical pure), mixture restir 30 minutes.Under agitation add the tosic acid aqueous solution of 5.1g 0.1N and the mixture of 5.1g ethanol (analytical pure), relief mixture leaves standstill.After about 24 hours, mixture reaches gelation point.Through in gel, adding water till no longer forming bubble and can detecting streak after about 18 days curing time.Exchange several times water.Then with product reheat 1 hour in 60 ℃ of water.Decant goes out supernatant liquor, and residue was 150 ℃ of dryings 8 hours.Obtain 21.9g output.
The BET surface-area is 118m 2/ g.
The theory of resulting catalyzer consists of 20% ring-{ OSi (CH 3) [(C 2H 4) Si (CH 3) 2(O 1/2)] 4, 77%SiO 2And 3%TiO 2
Then resulting support of the catalyst is carried out surface modification.Under protection of inert gas, earlier the 10g product is joined for this reason and contain 10g 1; 1,1,3; 3; in the reactor of 3-hexamethyldisilazane and 100g anhydrous n-hexane, under agitation mixture heating up was refluxed 2 hours, decant goes out supernatant liquor; residue washs 2 times with normal hexane; each 150ml removes volatile component under vacuum, then 150 ℃ of dryings 4 hours.
Earlier 2.5g is contained titanium carrier and join in the 20ml methyl alcohol (Merck company, analytical pure), add 40mg HAuCl 4* 3H 2O (0.1mmol, Merck company) is dissolved in the solution in the 5ml methyl alcohol, with 0.8ml 2N K 2CO 3With pH regulator to 8, this mixture was stirred 30 minutes, add the 2ml sodium citrate solution, check pH once more, mixture was stirred 120 minutes, isolate solids, use methanol wash 3 times, each 20ml, under 120 ℃ and normal pressure dry 10 hours, then 200 ℃ of roastings 5 hours.Gold content in this gold-titanium-Si catalyst is 0.55% weight (icp analysis).
In the test of carrying out according to testing sequence, propylene conversion reaches 0.5% under 95% constant PO selective conditions in 50 hours.
Embodiment 4
Present embodiment is described the surface is coated with goldc grains then through modification the Preparation of catalysts that comprises organic-inorganic hybrid materials containing titanium.This preparation is undertaken by the method that is similar to embodiment 2, but titanium oxide content is 3%.
Toward the 123.3g tetraethoxysilane (591.8mmol) and the middle tosic acid aqueous solution that adds 10.8g 0.1N of 62.1g ethanol (analytical pure), this mixture was stirred 1 hour.Slowly add 7.95g four titanium butoxide (23.3mmol) then, again this mixture was stirred 30 minutes.Add 24.93g ring-{ OSi (CH 3[(C 2H 4) Si (OH) (CH 3) 2] 4(38.5mmol) solution in 60.0g ethanol (analytical pure), mixture restir 30 minutes.Under agitation add the tosic acid aqueous solution of 11.4g 0.1N and the mixture of 11.4g ethanol (analytical pure), relief mixture leaves standstill.After about 24 hours, mixture reaches gelation point.Through in gel, adding water till no longer forming bubble and can detecting streak after about 10 days curing time.Exchange several times water.Then with product reheat 1 hour in 60 ℃ of water.Decant goes out supernatant liquor, and residue was 150 ℃ of dryings 8 hours.Obtain 63.4g output.
The theory of resulting catalyzer consists of 40% ring-{ OSi (CH 3) [(C 2H 4) Si (CH 3) 2(O 1/2)] 4, 57%SiO 2And 3%TiO 2
Then resulting support of the catalyst is carried out surface modification.Under protection of inert gas, earlier the 25g product is joined for this reason and contain 25g 1; 1,1,3; 3; in the reactor of 3-hexamethyldisilazane and 250g anhydrous n-hexane, under agitation mixture heating up was refluxed 2 hours, decant goes out supernatant liquor; residue washs 2 times with normal hexane; each 400ml removes volatile component under vacuum, then 150 ℃ of dryings 4 hours.
The BET surface-area is 264m 2/ g.
Earlier 2.5g is contained titanium carrier and join in the 20ml methyl alcohol (Merck company, analytical pure), add 40mg HAuCl 4* 3H 2O (0.1mmol, Merck company) is dissolved in the solution in the 5ml methyl alcohol, with 0.8ml 2N K 2CO 3With pH regulator to 8, this mixture was stirred 30 minutes, add the 2ml sodium citrate solution, check pH once more, mixture was stirred 120 minutes, isolate solids, use methanol wash 3 times, each 20ml, under 120 ℃ and normal pressure dry 10 hours, then 200 ℃ of roastings 5 hours.Gold content in this gold-titanium-Si catalyst is 0.58% weight (icp analysis).
In the test of carrying out according to testing sequence, propylene conversion reaches 1.5% under 95% constant PO selective conditions in 50 hours.
Embodiment 5
Present embodiment is described the surface is coated with the oxide compound that comprises organic-inorganic hybrid materials and silicon, titanium and tantalum of goldc grains then through modification the preparation of amorphous catalytic agent carrier.
This Preparation of catalysts is undertaken by the method that is similar to embodiment 2, but adds 2.4g Ta (OEt) in adding four titanium butoxide after 60 minutes in this uniform mixture 5(6mmol, Chempur company, 99.9%) stirs mixture 15 minutes, by the method that is similar to embodiment 2, adds silicon-carbon alkane linking agent, makes the mixture gel, carries out aftertreatment, with the product modification and be coated with goldc grains.
In the test of carrying out according to testing sequence, propylene conversion reaches 2.7% under 94% constant PO selective conditions in 50 hours.
Embodiment 6
Present embodiment is described the surface is coated with silver granuel then through modification the Preparation of catalysts that comprises organic-inorganic hybrid materials containing titanium.This Preparation of catalysts is undertaken by the method that is similar to embodiment 2.This support of the catalyst coating silver granuel rather than goldc grains.
At room temperature while stirring the 2.5g titanium-containing catalyst carrier is joined 150mg Silver Nitrate (0.97mmol, Merck company) in the solution of 25ml methyl alcohol.This suspension at room temperature stirred 1 hour, isolated solids, used 20ml methanol wash 1 time.White solid that should be wet is 120 ℃ of dryings 3 hours, then in air 150 ℃ of roastings 2 hours, watered 5 hours 200 ℃ of roastings.
In the test of carrying out according to testing sequence, propylene conversion reaches 0.3% under 94% constant PO selective conditions in 50 hours.
Embodiment 7
Replace propylene as unsaturated hydrocarbons with suitable-2-butylene.Carry out the partial oxidation of suitable-2-butylene with the catalyzer that comprises organic-inorganic hybrid materials and silicon and titanyl compound and metallic gold.This Preparation of catalysts is undertaken by the method that is similar to embodiment 2.
In the test of carrying out according to testing sequence, in 50 hours 91% constant 2, the transformation efficiency of suitable-2-butylene reaches 2.0% under the 3-butylene oxide ring selective conditions.
Embodiment 8
Select tetrahydrobenzene to replace propylene as unsaturated hydrocarbons.Carry out the partial oxidation of tetrahydrobenzene with the catalyzer that comprises organic-inorganic hybrid materials and silicon and titanyl compound and metallic gold.This Preparation of catalysts is undertaken by the method that is similar to embodiment 2.
By means of vaporizer tetrahydrobenzene is converted into gas phase.
In the test of carrying out according to testing sequence, the transformation efficiency of tetrahydrobenzene reaches 1.8% under 90% cyclohexene oxide selective conditions in 50 hours.
Embodiment 9
Replace propylene as unsaturated hydrocarbons with 1,3-butadiene.Carry out the partial oxidation of 1,3-butadiene with the catalyzer that comprises organic-inorganic hybrid materials and silicon and titanyl compound and metallic gold.This Preparation of catalysts is undertaken by the method that is similar to embodiment 2.
In the test of carrying out according to testing sequence, butadiene conversion reaches 0.6% under 85% oxybutylene selective conditions in 40 hours.
Embodiment 10
Replace propylene as unsaturated hydrocarbons with propane.Carry out the partial oxidation of propane with the catalyzer that comprises organic-inorganic hybrid materials and silicon and titanyl compound and metallic gold.This Preparation of catalysts is undertaken by the method that is similar to embodiment 2.
In the test of carrying out according to testing sequence, conversion of propane reaches 0.4% under 80% acetone selective conditions in 40 hours.

Claims (13)

1. loading type composition, said composition comprise the particle and the organic-inorganic hybrid materials containing titanium of gold and/or silver, it is characterized in that this organic-inorganic hybrid materials contains the structural unit of at least a formula (I)
[R 1] j-SiR 2 k(O 1/2) 4-k-j (I)
Wherein:
J is 1,2 or 3,
K represents 0,1 or 2,
k+j≤3,
R 1Be the C of bridge joint Si atom 1-C 10Alkylidene group, and
R 2The optional alkyl or aryl that replaces of representative.
2. according to the loading type composition of claim 1, it is characterized in that this organic-inorganic hybrid materials contains the structural unit of at least a formula (II)
[R 1] j-SiR 2 k(O 1/2) 4-k-j (II)
Wherein:
J is 1,
K represents 0,1 or 2,
k+j≤3,
R 1Be the C of bridge joint Si atom 1-C 4Alkylidene group, and
R 2Represent methylidene or ethyl.
3. according to the loading type composition of claim 1 or 2, it is characterized in that this organic-inorganic hybrid materials contains at least a following structural unit:
a)Si[(C 2H 4)Si(CH 3) 2(O 1/2)] 4
B) ring-{ OSi (CH 3) [(C 2H 4) Si (CH 3) 2(O 1/2)] 4
C) ring-{ OSi (CH 3) [(C 2H 4) Si (CH 3) (O 1/2) 2] 4
D) ring-{ OSi (CH 3) [(C 2H 4) Si (O 1/2) 3] 4
4. according to the loading type composition of claim 1 or 2, it is characterized in that this organic-inorganic hybrid materials comprises the titanium of 0.1-6% weight and randomly is called other external oxide compound of so-called promotor.
5. according to the loading type composition of claim 1 or 2, it is characterized in that said composition comprises gold or the silver of 0.01-8% weight or the mixture of Jin Heyin of 0.001-4% weight.
6. according to the loading type composition of claim 1 or 2, it is characterized in that its surface carried out modification.
7. according to the loading type preparation of compositions method of claim 1, it is characterized in that described organic-inorganic hybrid materials containing titanium prepares by sol-gel method.
8. according to the method for claim 7, it is characterized in that with organic and inorganic tackiness agent and silicon precursor, titanium precursor and randomly the promotor precursor mix.
9. according to the method for claim 8, it is characterized in that this organic and inorganic tackiness agent is at least 2 and passes through C 1-C 10The polyfunctional organosilane of alkylene-bridged Siliciumatom.
10. according to each method among the claim 7-9, it is characterized in that this organic-inorganic hybrid materials is carried out surface modification and/or coating gold and/or silver-colored particle, described precious metal exists with nanometer scale.
11. according to the composition of claim 1 purposes as the hydrocarbon selective oxidation catalyzer.
12., it is characterized in that propylene oxidation is become propylene oxide according to the purposes of claim 11.
13. the hydrocarbon selective oxidation method of carrying out in the presence of according to the composition of claim 1 and molecular oxygen and hydrogen.
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PL356206A1 (en) 2004-06-14
CN1354687A (en) 2002-06-19
CZ20014376A3 (en) 2002-03-13

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