CA2342228A1 - Method for producing a titanium silicate with rut structure - Google Patents
Method for producing a titanium silicate with rut structure Download PDFInfo
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- CA2342228A1 CA2342228A1 CA002342228A CA2342228A CA2342228A1 CA 2342228 A1 CA2342228 A1 CA 2342228A1 CA 002342228 A CA002342228 A CA 002342228A CA 2342228 A CA2342228 A CA 2342228A CA 2342228 A1 CA2342228 A1 CA 2342228A1
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- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
- C01B37/00—Compounds having molecular sieve properties but not having base-exchange properties
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- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07D—HETEROCYCLIC COMPOUNDS
- C07D301/00—Preparation of oxiranes
- C07D301/02—Synthesis of the oxirane ring
- C07D301/03—Synthesis of the oxirane ring by oxidation of unsaturated compounds, or of mixtures of unsaturated and saturated compounds
- C07D301/12—Synthesis of the oxirane ring by oxidation of unsaturated compounds, or of mixtures of unsaturated and saturated compounds with hydrogen peroxide or inorganic peroxides or peracids
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J29/00—Catalysts comprising molecular sieves
- B01J29/89—Silicates, aluminosilicates or borosilicates of titanium, zirconium or hafnium
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- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
- C01B39/00—Compounds having molecular sieve and base-exchange properties, e.g. crystalline zeolites; Their preparation; After-treatment, e.g. ion-exchange or dealumination
- C01B39/02—Crystalline aluminosilicate zeolites; Isomorphous compounds thereof; Direct preparation thereof; Preparation thereof starting from a reaction mixture containing a crystalline zeolite of another type, or from preformed reactants; After-treatment thereof
- C01B39/06—Preparation of isomorphous zeolites characterised by measures to replace the aluminium or silicon atoms in the lattice framework by atoms of other elements, i.e. by direct or secondary synthesis
- C01B39/08—Preparation of isomorphous zeolites characterised by measures to replace the aluminium or silicon atoms in the lattice framework by atoms of other elements, i.e. by direct or secondary synthesis the aluminium atoms being wholly replaced
- C01B39/085—Group IVB- metallosilicates
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Abstract
The invention relates to a method for producing a titanium silicate with RUT structure, which consists of the following steps: (i) preparation of a mixtu re of at least one SiO2 source and at least one titanium source; and (ii) crystallization of the mixture prepared in (i) in a pressurized vessel with addition of at least one template compound so that a suspension is obtained. The method is characterized in that amines or ammonium salts suitable for stabilizing cages of the silicate structure [445462] and [44566581] are used as template compound.
Description
Method For Producing a Titanium Silicate with RUT Structure The present invention relates to a process for preparing a titanium silicate having the RUT structure and its use as catalyst and also to a process for reacting organic compounds with the aid of this catalyst.
Silicates as salts of the silicic acids are usually in t0 the form of uniformly structured, spatially limited acyclic or cyclic silicate anions or spatially infinite silicate ions which are joined by means of associated metal cations to form larger complexes. Examples of structures of these spatially infinite silicate anions i5 are chain, band, sheet and framework structures.
An important group of framework silicates are the zeolites. The three-dimensional network of these zeolites is built up of Si04 tetrahedra which are joined 20 to one another via shared oxygen bridges. The zeolites, i.e. aluminosilicates, have ordered channel and cage structures. The pore openings occurring here are in the size range of >0.9 nm. An overview of the various known structures of aluminosilicates may be found, for 25 example, in M.W. Meier, D. H. Olson and C. Baerlocher, ~~Atlas of Zeolite Structure Types", 4th Edition, Elsevier, 1996.
Apart from the aluminosilicates, materials in which 30 titanium is present in place of silicon in the silicate lattice are also known. Among these compounds, particular mention may be made of titanium-containing silicate having the MFI structure type. Such a silicate is disclosed, for example, in US-A-4,410,501.
Silicates as salts of the silicic acids are usually in t0 the form of uniformly structured, spatially limited acyclic or cyclic silicate anions or spatially infinite silicate ions which are joined by means of associated metal cations to form larger complexes. Examples of structures of these spatially infinite silicate anions i5 are chain, band, sheet and framework structures.
An important group of framework silicates are the zeolites. The three-dimensional network of these zeolites is built up of Si04 tetrahedra which are joined 20 to one another via shared oxygen bridges. The zeolites, i.e. aluminosilicates, have ordered channel and cage structures. The pore openings occurring here are in the size range of >0.9 nm. An overview of the various known structures of aluminosilicates may be found, for 25 example, in M.W. Meier, D. H. Olson and C. Baerlocher, ~~Atlas of Zeolite Structure Types", 4th Edition, Elsevier, 1996.
Apart from the aluminosilicates, materials in which 30 titanium is present in place of silicon in the silicate lattice are also known. Among these compounds, particular mention may be made of titanium-containing silicate having the MFI structure type. Such a silicate is disclosed, for example, in US-A-4,410,501.
Titanium silicates having the MFI structure are typically obtained by first preparing an aqueous mixture of an Si02 source and a titanium source. This mixture is then reacted in a pressure vessel in the presence of a template compound. This process is described, for example, in US-A-4,666,692.
The present invention provides a process for preparing a titanium silicate having the RUT structure, which 1o comprises the steps (i) and (ii):
(i) preparation of a mixture comprising at least one Si02 source and at least one titanium source;
(ii) crystallization of the mixture from (i) in a pressure vessel with addition of at least one template compound to give a crystallization product, wherein the template compounds used are amines or ammonium salts which are suitable for stabilizing cages of the silicate structure [445462] and [44566581] .
The present invention likewise provides the titanium silicate having the RUT structure itself, able to be prepared by a process which comprises the steps (i) and (ii) (i) preparation of a mixture comprising at least one Si02 source and at least one titanium source;
(ii) crystallization of the mixture from (i) in a pressure vessel with addition of at least one template compound to give a crystallization product, wherein the template compounds used are amines or ammonium salts which are suitable for stabilizing cages of the silicate structure [445462] and [44566581] .
The present invention provides a process for preparing a titanium silicate having the RUT structure, which 1o comprises the steps (i) and (ii):
(i) preparation of a mixture comprising at least one Si02 source and at least one titanium source;
(ii) crystallization of the mixture from (i) in a pressure vessel with addition of at least one template compound to give a crystallization product, wherein the template compounds used are amines or ammonium salts which are suitable for stabilizing cages of the silicate structure [445462] and [44566581] .
The present invention likewise provides the titanium silicate having the RUT structure itself, able to be prepared by a process which comprises the steps (i) and (ii) (i) preparation of a mixture comprising at least one Si02 source and at least one titanium source;
(ii) crystallization of the mixture from (i) in a pressure vessel with addition of at least one template compound to give a crystallization product, wherein the template compounds used are amines or ammonium salts which are suitable for stabilizing cages of the silicate structure [445462] and [44566581] .
As Si02 source in the abovementioned process, use is made, in particular, of esters of orthosilicic acid.
Preference is given to using tetraesters. Tetraethyl orthosilicate is particularly preferably used in the process of the present invention.
As titanium source in the process of the present invention, it is possible to use, for example, titanium dioxide. However, preference is given to using titanates, particularly preferably orthotitanates and in particular tetraisopropyl orthotitanate.
It is of course possible to use two or more suitable Si02 sources and/or two or more suitable titanium sources in the process of the present invention.
In the process of the present invention, a mixture is prepared from the Si02 source or sources and the titanium source or sources. Particular preference is given to using an aqueous mixture of these components.
The order in which the components are mixed is not critical. The way in which the components are mixed with one another is likewise not critical. All methods and apparatuses known from the prior art, e.g. blade stirrers, can be used for this purpose.
In the process of the present invention, a template compound as described above is added to the above-described mixture. This template compound is preferably added in an aqueous solution to the above-described mixture. In general, the concentration of this solution of template compound can be chosen freely. However, it preferably has a content of template compound in the range from 1 to 25o by weight, particularly preferably in the range from 2 to 15% by weight and in particular in the range from 3 to 8o by weight.
Preference is given to using tetraesters. Tetraethyl orthosilicate is particularly preferably used in the process of the present invention.
As titanium source in the process of the present invention, it is possible to use, for example, titanium dioxide. However, preference is given to using titanates, particularly preferably orthotitanates and in particular tetraisopropyl orthotitanate.
It is of course possible to use two or more suitable Si02 sources and/or two or more suitable titanium sources in the process of the present invention.
In the process of the present invention, a mixture is prepared from the Si02 source or sources and the titanium source or sources. Particular preference is given to using an aqueous mixture of these components.
The order in which the components are mixed is not critical. The way in which the components are mixed with one another is likewise not critical. All methods and apparatuses known from the prior art, e.g. blade stirrers, can be used for this purpose.
In the process of the present invention, a template compound as described above is added to the above-described mixture. This template compound is preferably added in an aqueous solution to the above-described mixture. In general, the concentration of this solution of template compound can be chosen freely. However, it preferably has a content of template compound in the range from 1 to 25o by weight, particularly preferably in the range from 2 to 15% by weight and in particular in the range from 3 to 8o by weight.
Examples of such template compounds are tetramethylammonium hydroxide or pyrrolidine.
In addition to the template compound, one or more further basic compounds, e.g. hydroxides of ammonium salts, can be added to the abovementioned mixture of the Si02 source or sources and the titanium source or sources in the process of the present invention.
l0 The alkali metal or alkaline earth metal content of the suspension obtained from step (ii) in the process of the present invention is generally < 1000 ppm, preferably < 500 ppm and particularly preferably c 200 ppm.
Depending on the Si02 and/or titanium sources, the preparation of the mixture as described above may result in formation of an alcohol by hydrolysis. This is generally distilled from the mixture at from 90 to 100°C, but can also remain in the mixture. The residue is transferred to a pressure vessel. If the starting materials are chosen so that no distillation is necessary, the mixture comprising the SiOz source or sources and the titanium source or sources can be transferred immediately to the pressure vessel.
The mixture is reacted in the pressure vessel at a reaction temperature which is generally in the range from 80 to 300°C, preferably from 120 to 250°C, particularly preferably from 150 to 220°C. The reaction time here is generally in the range from 3 to 15 days, preferably in the range from 6 to 13 days, particularly preferably in the range from 8 to 11 days.
After the reaction is complete, the crystalline product resulting from the reaction can be separated from the liquid phase by all customary methods of the prior art.
Depending on the application for which the product is intended, it may be necessary to wash it one or more times with water. The solid obtained is dried in the process of the present invention. Here too, use can be made of all customary methods of the prior art. For example, the solid obtained can be dried in an oven suitable for this purpose at temperatures in the range from 105 to 115°C. The drying time is generally from 5 to 20 hours, preferably from 7 to 15 hours.
Naturally, spray drying the crystalline product as described above, which is present in suspension in the liquid phase, in at least one spray-drying step is also conceivable.
To remove the template compound added in step (ii) and any further basic compounds, the crystalline product is calcined at least once subsequent to drying.
The temperatures selected in the calcination or calcinations are generally in the range from 120 to 850°C, preferably from 180 to 700°C, particularly preferably from 250 to 550°C. Calcination is generally carried out in an oxygen-containing atmosphere in which the oxygen content is from 0.1 to 90o by volume, preferably from 0.2 to 22o by volume, particularly preferably from 0.2 to loo by volume. The pressure selected for the calcination is generally in the range from 0.01 to 5 bar, preferably from 0.05 to 1.5 bar.
Accordingly, the present invention also provides a process for preparing a titanium silicate having the RUT structure which comprises, in addition to the steps (i) and (ii) as described above, the steps (iii) and (iv) (iii) drying of the crystallization product resulting from (ii) ;
In addition to the template compound, one or more further basic compounds, e.g. hydroxides of ammonium salts, can be added to the abovementioned mixture of the Si02 source or sources and the titanium source or sources in the process of the present invention.
l0 The alkali metal or alkaline earth metal content of the suspension obtained from step (ii) in the process of the present invention is generally < 1000 ppm, preferably < 500 ppm and particularly preferably c 200 ppm.
Depending on the Si02 and/or titanium sources, the preparation of the mixture as described above may result in formation of an alcohol by hydrolysis. This is generally distilled from the mixture at from 90 to 100°C, but can also remain in the mixture. The residue is transferred to a pressure vessel. If the starting materials are chosen so that no distillation is necessary, the mixture comprising the SiOz source or sources and the titanium source or sources can be transferred immediately to the pressure vessel.
The mixture is reacted in the pressure vessel at a reaction temperature which is generally in the range from 80 to 300°C, preferably from 120 to 250°C, particularly preferably from 150 to 220°C. The reaction time here is generally in the range from 3 to 15 days, preferably in the range from 6 to 13 days, particularly preferably in the range from 8 to 11 days.
After the reaction is complete, the crystalline product resulting from the reaction can be separated from the liquid phase by all customary methods of the prior art.
Depending on the application for which the product is intended, it may be necessary to wash it one or more times with water. The solid obtained is dried in the process of the present invention. Here too, use can be made of all customary methods of the prior art. For example, the solid obtained can be dried in an oven suitable for this purpose at temperatures in the range from 105 to 115°C. The drying time is generally from 5 to 20 hours, preferably from 7 to 15 hours.
Naturally, spray drying the crystalline product as described above, which is present in suspension in the liquid phase, in at least one spray-drying step is also conceivable.
To remove the template compound added in step (ii) and any further basic compounds, the crystalline product is calcined at least once subsequent to drying.
The temperatures selected in the calcination or calcinations are generally in the range from 120 to 850°C, preferably from 180 to 700°C, particularly preferably from 250 to 550°C. Calcination is generally carried out in an oxygen-containing atmosphere in which the oxygen content is from 0.1 to 90o by volume, preferably from 0.2 to 22o by volume, particularly preferably from 0.2 to loo by volume. The pressure selected for the calcination is generally in the range from 0.01 to 5 bar, preferably from 0.05 to 1.5 bar.
Accordingly, the present invention also provides a process for preparing a titanium silicate having the RUT structure which comprises, in addition to the steps (i) and (ii) as described above, the steps (iii) and (iv) (iii) drying of the crystallization product resulting from (ii) ;
(iv) calcination of the dried product from (iii).
To prepare the titanium silicate having the RUT
structure by the process of the present invention, as described above, the concentrations of the SiOz source or sources and the titanium source or sources for preparing the mixture as described in step (i) are selected so that the crystalline product resulting from step (ii) or (iv) has a titanium concentration which is generally in the range from 0.001 to 5o by weight.
However, the titanium concentrations in the titanium silicate having the RUT structure are preferably selected so as to be in the range from 0.002 to 1% by weight, particularly preferably from 0.003 to 0.5o by IS weight, more particularly preferably from 0.004 to 0.1%
by weight, very particularly preferably from 0.005 to 0.05% by weight and most preferably about 0.01% by weight.
Accordingly, the present invention also provides a titanium silicate having the RUT structure whose titanium content is in the range from 0.001 to 5o by weight.
Here, these figures for the titanium content are based on results obtained from wet chemical analysis.
The present invention also provides a titanium silicate having the RUT structure which displays at least the following reflections in the X-ray diffraction pattern:
To prepare the titanium silicate having the RUT
structure by the process of the present invention, as described above, the concentrations of the SiOz source or sources and the titanium source or sources for preparing the mixture as described in step (i) are selected so that the crystalline product resulting from step (ii) or (iv) has a titanium concentration which is generally in the range from 0.001 to 5o by weight.
However, the titanium concentrations in the titanium silicate having the RUT structure are preferably selected so as to be in the range from 0.002 to 1% by weight, particularly preferably from 0.003 to 0.5o by IS weight, more particularly preferably from 0.004 to 0.1%
by weight, very particularly preferably from 0.005 to 0.05% by weight and most preferably about 0.01% by weight.
Accordingly, the present invention also provides a titanium silicate having the RUT structure whose titanium content is in the range from 0.001 to 5o by weight.
Here, these figures for the titanium content are based on results obtained from wet chemical analysis.
The present invention also provides a titanium silicate having the RUT structure which displays at least the following reflections in the X-ray diffraction pattern:
Diffraction angle 2A Lattice plane spacing d (0.1 nm) 10.79 8.19 13.69 6.45 14.48 6.10 20.19 4.49 22.16 4.00 23.26 3.82 27.45 3.24 A further characteristic which distinguishes titanium-containing zeolites from zeolites which do not contain titanium is a specific lattice vibration band in the IR
spectrum (DE 3047798). Accordingly, the present invention also provides a titanium silicate having the RUT structure which displays a band in the range from 955 to 970 cm-1 in the IR spectrum.
Titanium zeolites having the MFI structure are known to be suitable as catalysts for the reaction of organic compounds. This is disclosed, for example, in B. Notari, Stud. Surf. Sci. Catal., Vol. 37, Amsterdam, pages 413 to 425 (1987). The titanium silicates of the present invention having the RUT structure have also been found to be suitable as catalysts.
The present invention therefore also provides for the use of a titanium silicate as defined herein as catalyst.
For use of the titanium silicate of the present invention having the RUT structure as catalyst, particularly mention may be made of processes in which _ g _ organic compounds are reacted. The present invention therefore also provides a process for the reaction of an organic compound in which the organic compound is brought into contact with a catalyst according to the present invention, as described above, during the reaction.
In particular, the present invention also relates to a process in which the organic compound is oxidized during the reaction.
Examples of reactions are:
the epoxidation of olefins, e.g. the preparation of IS propene oxide from propene and Hz02 or from propene and mixtures which provide H202 in situ;
hydroxylations, e.g. the hydroxylation of monocyclic, bicyclic or polycyclic aromatics to form monosubstituted, disubstituted or higher-substituted hydroxyaromatics, for example the reaction of phenol and H202 or of phenol and mixtures which provide H202 in situ to form hydroquinone;
the conversion of alkanes into alcohols, aldehydes and acids;
oxime formation from ketones in the presence of H20z or mixtures which provide H202 in situ and ammonia (ammonoximation), for example the preparation of cyclohexanone oxime from cyclohexanone;
isomerization reactions, e.g. the conversion of epoxides into aldehydes;
and also further reactions described in the literature, as are described, for example, by W. Holderich in "Zeolites: Catalysts for the Synthesis of Organic Compounds", Elsevier, Stud. Surf. Sci. Catal., 49, Amsterdam (1989), p. 69 to 93 and particularly for possible oxidation reactions by B. Notari in Stud.
Surf. Sci. Catal., 37 (1987), pp. 413 to 425, or in Advances in Catalysis, Vol. 41, Academic Press (1996), pp. 253 to 334.
The term "mixture which provides H202 in situ" as used for the purposes of the present invention means that this mixture, which can consist of two or more different compounds, is combined in a single-vessel reaction with at least one compound which is to be reacted with H202 and the H202 formed from the mixture reacts either at the time it is formed or at a later point in time with the compound or compounds to be reacted.
Depending on the type of process in which the titanium silicate of the present invention having the RUT
structure is used as catalyst, the silicate is used either as powder or as shaped bodies.
When the catalyst is used as powder, recourse can be made directly to the crystalline product which results from the process of the present invention, as described above .
If the crystalline product is shaped to form a shaped body, it is possible to employ, for example, the dried crystalline product from the above-described step (iii) .
The product obtained, for example, from a spray-drying step is compacted to produce the shaped body in a further step of the process of the present invention.
This processing step can be carried out in all apparatuses known for this purpose, but preference is given to kneaders, pan mills or extruders. For industrial implementation of the process of the present invention, particular preference is given to using a pan mill.
In this shaping step, one or more viscosity-increasing substances can be additionally added as pasting agents.
All suitable substances known from the prior art can be used for this purpose. In the process of the present invention, preference is given to using water or mixtures of water with one or more organic substances which are miscible with water as pasting agents. The pasting agent can be removed again during the later calcination of the shaped body.
Preference is given to using organic, in particular hydrophilic organic, polymers such as cellulose, cellulose derivatives such as methylcellulose, polyvinylpyrrolidone, ammonium (meth)acrylates, Tylose, particularly preferably methylcellulose.
As further additives, it is possible to add ammonium, amines or amine-like compounds such as tetraalkylammonium compounds or aminoalkoxides. Such further additives are described in EP-A 0389041, EP-A
02002660 and WO 95/19222, the full scope of which is incorporated by reference into the present application.
Instead of basic additives, it is also possible to use acidic additives. Preference is given to acidic organic compounds which can be burnt out by calcination after the shaping step. Particular preference is given to carboxylic acids.
To influence properties of the shaped body, it is possible to add further substances, preferably organic compounds, in particular organic polymers, as further additives which can also influence the formability of the composition. Such additives are, inter alia, alginates, polyvinylpyrrolidones, starch, cellulose, l0 polyethers, polyesters, polyamides, polyacrylates, polymethacrylates, polyethylenimines or polyetherols.
Of course, it is also possible for mixtures of two or more of the abovementioned additives to be incorporated.
The order in which the additives are added is not critical.
If desired, the generally still pulverulent mixture can be homogenized for from 10 to 180 minutes in a kneader or extruder prior to compaction. This is generally carried out at temperatures in the range from about 10°C to the boiling point of the pasting agent and at atmospheric pressure or slightly superatmospheric pressure. The mixture is kneaded until an extrudable composition has been formed.
In principle, kneading and shaping can be carried out using all conventional kneading and shaping apparatuses or processes as are well known from the prior art and are suitable, for example, for the production of shaped catalyst bodies.
Preference is given to using processes in which shaping occurs in customary extruders to form, for example, extrudates having a diameter of usually from about 1 to about 10 mm, in particular from about 1.5 to about mm. Such extrusion apparatuses are described, for example, in "Ullmanns Enzyklopadie der Technischen 5 Chemie", 4th Edition, Volume 2 (1972), p. 295 ff. Apart from the use of an extruder, the use of a ram extruder is also preferred. In the case of industrial application of the process, preference is given to using extruders.
The extrudates are either rods or honeycombs. The honeycombs can be of any shape. The extrudates can be, for example, round rods, tubes or star-shaped profiles.
The honeycombs can also have any diameter. The external shape and the diameters are generally decided by the process engineering requirements which are determined by the process in which the shaped body is to be used.
Before, during or after the shaping step, noble metals in the form of suitable noble metal components, for example in the form of water-soluble salts, can be applied to the material. This preferably gives catalysts containing from 0.01 to 30o by weight of one or more noble metals selected from the group consisting of ruthenium, rhodium, palladium, osmium, iridium, platinum, rhenium, gold and silver.
However, in many cases it is most useful to apply the noble metal components to the shaped bodies after the shaping step, particularly when high-temperature treatment of the noble metal-containing catalyst is undesirable. The noble metal components can be applied to the shaped body by, in particular, ion exchange, impregnation or spraying. They can be applied by means of organic solvents, aqueous ammoniacal solutions or supercritical phases such as carbon dioxide.
The use of the abovementioned methods enables a wide variety of types of noble metal catalysts to be produced. Thus, one type of coated catalyst can be produced by spraying the noble metal solution onto the shaped bodies. The thickness of this noble metal-containing shell can be significantly increased by impregnation, while ion exchange results in virtually uniform distribution of noble metal across the cross section of the catalyst particles.
l0 After extrusion has been carried out, the shaped bodies obtained are dried at generally from 50 to 250°C, preferably from 80 to 250°C, at pressures of generally from 0.01 to 5 bar, preferably from 0.05 to 1.5 bar, for from about 1 to 20 hours.
The subsequent calcination is carried out at from 250 to 800°C, preferably from 350 to 600°C, particularly preferably from 400 to 500°C. The pressure range is similar to that for drying. In general, calcination is carried out in an oxygen-containing atmosphere in which the oxygen content is from 0.1 to 90% by volume, preferably from 0.2 to 22o by volume, particularly preferably from 0.2 to loo by volume.
The titanium silicate of the present invention having the RUT structure is preferably used as powder when employed as catalyst.
The titanium silicate having the RUT structure which has been discussed comprehensively above is particularly suitable for the epoxidation of alkenes.
Accordingly, the present invention also provides a process in which an alkene is reacted to form an alkene oxide .
Alkenes which are suitable for such a functionalization are, for example:
ethylene, propylene, but-1-ene, but-2-ene, isobutene, butadiene, pentenes, isoamylene, piperylene, hexenes, hexadienes, heptenes, octenes, diisobutene, trimethylpentene, nonenes, dodecene, tridecene, tetradecanes to eicosenes, tripropylene and tetraproylene, polybutadienes, polyisobutenes, isoprenes, terpenes, geraniol, linalol, linalyl acetate, methylenecyclopropane, cyclopentene, cyclohexene, norbornene, cycloheptene, vinylcyclohexane, vinyloxirane, vinylcyclohexene, styrene, cyclooctene, cyclooctadiene, vinylnorbornene, indene, tetrahydroindene, methylstyrene, dicyclopentadiene, divinylbenzene, cyclododecene, cyclododecatriene, stilbene, diphenylbutadiene, vitamin A, beta-carotene, vinylidene fluoride, allyl halides, crotyl chloride, methallyl chloride, dichlorobutenes, ?0 allyl alcohol, methallyl alcohol, butenols, butenediols, cyclopentenediols, pentenols, octadienols, tridecenols, unsaturated steroids, ethoxyethylene, isoeugenol, anethole, isoallesafrol, unsaturated carboxylic acids such as acrylic acid, methacrylic acid, crotonic acid, malefic acid, vinylacetic acid, unsaturated fatty acids such as oleic acid, linoleic acid, palmitic acid, and also naturally occurring fats and oils.
An advantage of the titanium silicate having the RUT
structure prepared according to the present invention is that the crystalline product as described above resulting from the process of the present invention has a large specific external surface area. This is generally in the range from 10 to 200 m2/g, preferably in the range from 80 to 120 m2/g.
These values for the specific external surface area are based on results obtained by nitrogen adsorption in accordance with DIN 66131.
Furthermore, the titanium silicate of the present invention having the RUT structure has a particular internal structure in which essentially no pores having a width of > 5.5 A are present.
It is thus possible, without restricting the pore system as in the case of zeolites having a structure other than the RUT structure, for sterically very bulky molecules and/or mixtures of natural materials to be reacted catalytically on the external surface. Since catalysis over the titanium silicate of the present invention having the RUT structure takes place at the external surface, relatively high molecular weight compounds can be reacted in polymer-analogous reactions of all the abovementioned reaction classes.
When using the titanium silicate of the present invention having the RUT structure as catalyst in the conversion of an alkene to an alkene oxide, it is possible to employ all oxidants which are suitable for this purpose. Examples which may be mentioned are hydrogen peroxide, compositions which can generate hydrogen peroxide in situ, or organic hydroperoxides.
An advantage of the titanium silicate of the present invention having the RUT structure when used as catalyst is that, in contrast to titanium-containing zeolite catalysts of the prior art, it is possible to use, for example, hydrogen peroxide solutions which have a very low concentration of H202.
Preference is given to using H202 solutions whose HZOZ
concentration is in the range from 0.05 to 40% by weight, particularly preferably from 0.1 to 20% by weight, in particular from 0.5 to loo by weight.
Particularly when the oxidant used is a mixture of hydrogen and oxygen, the titanium silicate of the invention having the RUT structure can further comprise one or more elements selected from the group consisting of ruthenium, rhodium, palladium, osmium, iridium, platinum, iron, cobalt, nickel, rhenium, silver and l0 gold in addition to titanium, silicon and oxygen.
Naturally, it is also possible in the process of the present invention for the titanium silicate having the RUT structure used as catalyst to be regenerated after t5 it has become exhausted.
If the catalyst has been used in powder form, it can be regenerated by, for example, washing it with oxidizing mineral acids such as nitric acid and then refluxing it 20 with hydrogen peroxide.
If the titanium silicate of the present invention having the RUT structure has been used as catalyst in the form of a shaped body, the shaped body can be 25 regenerated in or outside the reaction arrangement employed, e.g. a reactor, by treating it with gases which comprise or provide oxygen, e.g. air, synthetic air, nitrogen oxides or molecular oxygen. Here, the catalyst is preferably heated from room temperature to 30 a temperature in the range from 120 to 850°C, preferably from 180 to 700°C and particularly preferably from 250 to 550°C, and air or oxygen is added to an inert gas flowing over the catalyst in concentrations of generally from 0.1 to 90o by volume, 35 preferably from 0.2 to 22o by volume and particularly preferably from 0.2 to 10% by volume, based on the total gas stream. A pressure of generally from 0.01 to bar, preferably from 0.05 to 1.5 bar, is generally employed.
The following examples illustrate the process of the 5 present invention without restricting it in any way.
EXAMPLES
Example 1 455 g of tetraethyl orthosilicate were placed in a four-necked flask (2 1 capacity) and, while stirring (250 rpm, blade stirrer), 15 g of tetraisopropyl orthotitanate were added from a dropping funnel over a period of 30 minutes. A colorless, clear mixture was formed. Finally, 800 g of a 20% strength by weight tetramethylammonium hydroxide solution (alkali metal contents < 10 ppm) was added and the mixture was stirred for another one hour. The alcohol mixture (about 450 g) formed by hydrolysis was distilled off at 90 - 100°C. 1.5 1 of deionized water were added and the now slightly opaque sol was transferred to a 2.5 1 stirring autoclave (stainless steel 1.4571).
At a heating rate of 3°C/min, the closed autoclave (anchor stirrer, 200 rpm) was brought to a reaction temperature of 175°C. The reaction was ended after 10 days. The cooled reaction mixture was centrifuged and the solid was washed a number of times with water until neutral. The solid obtained was dried at 100°C for 24 hours (weight: 149 g).
Finally, the template remaining in the product was burnt off in air at 550°C for 5 hours (calcination loss: 14o by weight).
The calcined product had a Ti content of 1.5s by weight and a residual alkali metal content of less then 100 ppm according to wet chemical analysis. The yield based on Si02 used was 870. The crystallites had a size of from 0.05 to 0.25 ~m and the product displayed a typical band at about 960 cm-1 in the IR.
The product displays the X-ray diffraction pattern reproduced in Figure 1. In Figure 1, the intensity I is plotted on the ordinate.
Example 2 A 250 ml glass autoclave was charged with 36 g of methanol and 0.5 g of titanium silicate powder from Example 1 and the suspension was stirred by means of a magnetic stirrer. The closed glass autoclave was then cooled to -30°C and 10 g of propene were injected.
Subsequently, the glass autoclave was warmed to 0°C and 17 g of a 300 strength hydrogen peroxide solution were metered in. The reaction mixture was stirred at 0°C for 5 hours under the autogenous pressure. The catalysts was then centrifuged off and the propylene oxide content was determined by gas chromatography. The .
propylene oxide content was 0.3% by weight.
Example 3 A 250 ml glass autoclave was charged with 36 g of methanol and 0.5 g of titanium silicate from Example l and the suspension was stirred by means of a magnetic stirrer. The closed glass autoclave was then cooled to -30°C and 20.2 g of propene were injected.
Subsequently, the glass autoclave was warmed to 0°C and 23 g of 0.5% strength hydrogen peroxide solution were metered in. The reaction mixture was stirred at 0°C for 30 minutes under the autogenous pressure. The catalyst was then centrifuged off and the propylene oxide content was determined by gas chromatography. The propylene oxide content was 0.0980 by weight.
spectrum (DE 3047798). Accordingly, the present invention also provides a titanium silicate having the RUT structure which displays a band in the range from 955 to 970 cm-1 in the IR spectrum.
Titanium zeolites having the MFI structure are known to be suitable as catalysts for the reaction of organic compounds. This is disclosed, for example, in B. Notari, Stud. Surf. Sci. Catal., Vol. 37, Amsterdam, pages 413 to 425 (1987). The titanium silicates of the present invention having the RUT structure have also been found to be suitable as catalysts.
The present invention therefore also provides for the use of a titanium silicate as defined herein as catalyst.
For use of the titanium silicate of the present invention having the RUT structure as catalyst, particularly mention may be made of processes in which _ g _ organic compounds are reacted. The present invention therefore also provides a process for the reaction of an organic compound in which the organic compound is brought into contact with a catalyst according to the present invention, as described above, during the reaction.
In particular, the present invention also relates to a process in which the organic compound is oxidized during the reaction.
Examples of reactions are:
the epoxidation of olefins, e.g. the preparation of IS propene oxide from propene and Hz02 or from propene and mixtures which provide H202 in situ;
hydroxylations, e.g. the hydroxylation of monocyclic, bicyclic or polycyclic aromatics to form monosubstituted, disubstituted or higher-substituted hydroxyaromatics, for example the reaction of phenol and H202 or of phenol and mixtures which provide H202 in situ to form hydroquinone;
the conversion of alkanes into alcohols, aldehydes and acids;
oxime formation from ketones in the presence of H20z or mixtures which provide H202 in situ and ammonia (ammonoximation), for example the preparation of cyclohexanone oxime from cyclohexanone;
isomerization reactions, e.g. the conversion of epoxides into aldehydes;
and also further reactions described in the literature, as are described, for example, by W. Holderich in "Zeolites: Catalysts for the Synthesis of Organic Compounds", Elsevier, Stud. Surf. Sci. Catal., 49, Amsterdam (1989), p. 69 to 93 and particularly for possible oxidation reactions by B. Notari in Stud.
Surf. Sci. Catal., 37 (1987), pp. 413 to 425, or in Advances in Catalysis, Vol. 41, Academic Press (1996), pp. 253 to 334.
The term "mixture which provides H202 in situ" as used for the purposes of the present invention means that this mixture, which can consist of two or more different compounds, is combined in a single-vessel reaction with at least one compound which is to be reacted with H202 and the H202 formed from the mixture reacts either at the time it is formed or at a later point in time with the compound or compounds to be reacted.
Depending on the type of process in which the titanium silicate of the present invention having the RUT
structure is used as catalyst, the silicate is used either as powder or as shaped bodies.
When the catalyst is used as powder, recourse can be made directly to the crystalline product which results from the process of the present invention, as described above .
If the crystalline product is shaped to form a shaped body, it is possible to employ, for example, the dried crystalline product from the above-described step (iii) .
The product obtained, for example, from a spray-drying step is compacted to produce the shaped body in a further step of the process of the present invention.
This processing step can be carried out in all apparatuses known for this purpose, but preference is given to kneaders, pan mills or extruders. For industrial implementation of the process of the present invention, particular preference is given to using a pan mill.
In this shaping step, one or more viscosity-increasing substances can be additionally added as pasting agents.
All suitable substances known from the prior art can be used for this purpose. In the process of the present invention, preference is given to using water or mixtures of water with one or more organic substances which are miscible with water as pasting agents. The pasting agent can be removed again during the later calcination of the shaped body.
Preference is given to using organic, in particular hydrophilic organic, polymers such as cellulose, cellulose derivatives such as methylcellulose, polyvinylpyrrolidone, ammonium (meth)acrylates, Tylose, particularly preferably methylcellulose.
As further additives, it is possible to add ammonium, amines or amine-like compounds such as tetraalkylammonium compounds or aminoalkoxides. Such further additives are described in EP-A 0389041, EP-A
02002660 and WO 95/19222, the full scope of which is incorporated by reference into the present application.
Instead of basic additives, it is also possible to use acidic additives. Preference is given to acidic organic compounds which can be burnt out by calcination after the shaping step. Particular preference is given to carboxylic acids.
To influence properties of the shaped body, it is possible to add further substances, preferably organic compounds, in particular organic polymers, as further additives which can also influence the formability of the composition. Such additives are, inter alia, alginates, polyvinylpyrrolidones, starch, cellulose, l0 polyethers, polyesters, polyamides, polyacrylates, polymethacrylates, polyethylenimines or polyetherols.
Of course, it is also possible for mixtures of two or more of the abovementioned additives to be incorporated.
The order in which the additives are added is not critical.
If desired, the generally still pulverulent mixture can be homogenized for from 10 to 180 minutes in a kneader or extruder prior to compaction. This is generally carried out at temperatures in the range from about 10°C to the boiling point of the pasting agent and at atmospheric pressure or slightly superatmospheric pressure. The mixture is kneaded until an extrudable composition has been formed.
In principle, kneading and shaping can be carried out using all conventional kneading and shaping apparatuses or processes as are well known from the prior art and are suitable, for example, for the production of shaped catalyst bodies.
Preference is given to using processes in which shaping occurs in customary extruders to form, for example, extrudates having a diameter of usually from about 1 to about 10 mm, in particular from about 1.5 to about mm. Such extrusion apparatuses are described, for example, in "Ullmanns Enzyklopadie der Technischen 5 Chemie", 4th Edition, Volume 2 (1972), p. 295 ff. Apart from the use of an extruder, the use of a ram extruder is also preferred. In the case of industrial application of the process, preference is given to using extruders.
The extrudates are either rods or honeycombs. The honeycombs can be of any shape. The extrudates can be, for example, round rods, tubes or star-shaped profiles.
The honeycombs can also have any diameter. The external shape and the diameters are generally decided by the process engineering requirements which are determined by the process in which the shaped body is to be used.
Before, during or after the shaping step, noble metals in the form of suitable noble metal components, for example in the form of water-soluble salts, can be applied to the material. This preferably gives catalysts containing from 0.01 to 30o by weight of one or more noble metals selected from the group consisting of ruthenium, rhodium, palladium, osmium, iridium, platinum, rhenium, gold and silver.
However, in many cases it is most useful to apply the noble metal components to the shaped bodies after the shaping step, particularly when high-temperature treatment of the noble metal-containing catalyst is undesirable. The noble metal components can be applied to the shaped body by, in particular, ion exchange, impregnation or spraying. They can be applied by means of organic solvents, aqueous ammoniacal solutions or supercritical phases such as carbon dioxide.
The use of the abovementioned methods enables a wide variety of types of noble metal catalysts to be produced. Thus, one type of coated catalyst can be produced by spraying the noble metal solution onto the shaped bodies. The thickness of this noble metal-containing shell can be significantly increased by impregnation, while ion exchange results in virtually uniform distribution of noble metal across the cross section of the catalyst particles.
l0 After extrusion has been carried out, the shaped bodies obtained are dried at generally from 50 to 250°C, preferably from 80 to 250°C, at pressures of generally from 0.01 to 5 bar, preferably from 0.05 to 1.5 bar, for from about 1 to 20 hours.
The subsequent calcination is carried out at from 250 to 800°C, preferably from 350 to 600°C, particularly preferably from 400 to 500°C. The pressure range is similar to that for drying. In general, calcination is carried out in an oxygen-containing atmosphere in which the oxygen content is from 0.1 to 90% by volume, preferably from 0.2 to 22o by volume, particularly preferably from 0.2 to loo by volume.
The titanium silicate of the present invention having the RUT structure is preferably used as powder when employed as catalyst.
The titanium silicate having the RUT structure which has been discussed comprehensively above is particularly suitable for the epoxidation of alkenes.
Accordingly, the present invention also provides a process in which an alkene is reacted to form an alkene oxide .
Alkenes which are suitable for such a functionalization are, for example:
ethylene, propylene, but-1-ene, but-2-ene, isobutene, butadiene, pentenes, isoamylene, piperylene, hexenes, hexadienes, heptenes, octenes, diisobutene, trimethylpentene, nonenes, dodecene, tridecene, tetradecanes to eicosenes, tripropylene and tetraproylene, polybutadienes, polyisobutenes, isoprenes, terpenes, geraniol, linalol, linalyl acetate, methylenecyclopropane, cyclopentene, cyclohexene, norbornene, cycloheptene, vinylcyclohexane, vinyloxirane, vinylcyclohexene, styrene, cyclooctene, cyclooctadiene, vinylnorbornene, indene, tetrahydroindene, methylstyrene, dicyclopentadiene, divinylbenzene, cyclododecene, cyclododecatriene, stilbene, diphenylbutadiene, vitamin A, beta-carotene, vinylidene fluoride, allyl halides, crotyl chloride, methallyl chloride, dichlorobutenes, ?0 allyl alcohol, methallyl alcohol, butenols, butenediols, cyclopentenediols, pentenols, octadienols, tridecenols, unsaturated steroids, ethoxyethylene, isoeugenol, anethole, isoallesafrol, unsaturated carboxylic acids such as acrylic acid, methacrylic acid, crotonic acid, malefic acid, vinylacetic acid, unsaturated fatty acids such as oleic acid, linoleic acid, palmitic acid, and also naturally occurring fats and oils.
An advantage of the titanium silicate having the RUT
structure prepared according to the present invention is that the crystalline product as described above resulting from the process of the present invention has a large specific external surface area. This is generally in the range from 10 to 200 m2/g, preferably in the range from 80 to 120 m2/g.
These values for the specific external surface area are based on results obtained by nitrogen adsorption in accordance with DIN 66131.
Furthermore, the titanium silicate of the present invention having the RUT structure has a particular internal structure in which essentially no pores having a width of > 5.5 A are present.
It is thus possible, without restricting the pore system as in the case of zeolites having a structure other than the RUT structure, for sterically very bulky molecules and/or mixtures of natural materials to be reacted catalytically on the external surface. Since catalysis over the titanium silicate of the present invention having the RUT structure takes place at the external surface, relatively high molecular weight compounds can be reacted in polymer-analogous reactions of all the abovementioned reaction classes.
When using the titanium silicate of the present invention having the RUT structure as catalyst in the conversion of an alkene to an alkene oxide, it is possible to employ all oxidants which are suitable for this purpose. Examples which may be mentioned are hydrogen peroxide, compositions which can generate hydrogen peroxide in situ, or organic hydroperoxides.
An advantage of the titanium silicate of the present invention having the RUT structure when used as catalyst is that, in contrast to titanium-containing zeolite catalysts of the prior art, it is possible to use, for example, hydrogen peroxide solutions which have a very low concentration of H202.
Preference is given to using H202 solutions whose HZOZ
concentration is in the range from 0.05 to 40% by weight, particularly preferably from 0.1 to 20% by weight, in particular from 0.5 to loo by weight.
Particularly when the oxidant used is a mixture of hydrogen and oxygen, the titanium silicate of the invention having the RUT structure can further comprise one or more elements selected from the group consisting of ruthenium, rhodium, palladium, osmium, iridium, platinum, iron, cobalt, nickel, rhenium, silver and l0 gold in addition to titanium, silicon and oxygen.
Naturally, it is also possible in the process of the present invention for the titanium silicate having the RUT structure used as catalyst to be regenerated after t5 it has become exhausted.
If the catalyst has been used in powder form, it can be regenerated by, for example, washing it with oxidizing mineral acids such as nitric acid and then refluxing it 20 with hydrogen peroxide.
If the titanium silicate of the present invention having the RUT structure has been used as catalyst in the form of a shaped body, the shaped body can be 25 regenerated in or outside the reaction arrangement employed, e.g. a reactor, by treating it with gases which comprise or provide oxygen, e.g. air, synthetic air, nitrogen oxides or molecular oxygen. Here, the catalyst is preferably heated from room temperature to 30 a temperature in the range from 120 to 850°C, preferably from 180 to 700°C and particularly preferably from 250 to 550°C, and air or oxygen is added to an inert gas flowing over the catalyst in concentrations of generally from 0.1 to 90o by volume, 35 preferably from 0.2 to 22o by volume and particularly preferably from 0.2 to 10% by volume, based on the total gas stream. A pressure of generally from 0.01 to bar, preferably from 0.05 to 1.5 bar, is generally employed.
The following examples illustrate the process of the 5 present invention without restricting it in any way.
EXAMPLES
Example 1 455 g of tetraethyl orthosilicate were placed in a four-necked flask (2 1 capacity) and, while stirring (250 rpm, blade stirrer), 15 g of tetraisopropyl orthotitanate were added from a dropping funnel over a period of 30 minutes. A colorless, clear mixture was formed. Finally, 800 g of a 20% strength by weight tetramethylammonium hydroxide solution (alkali metal contents < 10 ppm) was added and the mixture was stirred for another one hour. The alcohol mixture (about 450 g) formed by hydrolysis was distilled off at 90 - 100°C. 1.5 1 of deionized water were added and the now slightly opaque sol was transferred to a 2.5 1 stirring autoclave (stainless steel 1.4571).
At a heating rate of 3°C/min, the closed autoclave (anchor stirrer, 200 rpm) was brought to a reaction temperature of 175°C. The reaction was ended after 10 days. The cooled reaction mixture was centrifuged and the solid was washed a number of times with water until neutral. The solid obtained was dried at 100°C for 24 hours (weight: 149 g).
Finally, the template remaining in the product was burnt off in air at 550°C for 5 hours (calcination loss: 14o by weight).
The calcined product had a Ti content of 1.5s by weight and a residual alkali metal content of less then 100 ppm according to wet chemical analysis. The yield based on Si02 used was 870. The crystallites had a size of from 0.05 to 0.25 ~m and the product displayed a typical band at about 960 cm-1 in the IR.
The product displays the X-ray diffraction pattern reproduced in Figure 1. In Figure 1, the intensity I is plotted on the ordinate.
Example 2 A 250 ml glass autoclave was charged with 36 g of methanol and 0.5 g of titanium silicate powder from Example 1 and the suspension was stirred by means of a magnetic stirrer. The closed glass autoclave was then cooled to -30°C and 10 g of propene were injected.
Subsequently, the glass autoclave was warmed to 0°C and 17 g of a 300 strength hydrogen peroxide solution were metered in. The reaction mixture was stirred at 0°C for 5 hours under the autogenous pressure. The catalysts was then centrifuged off and the propylene oxide content was determined by gas chromatography. The .
propylene oxide content was 0.3% by weight.
Example 3 A 250 ml glass autoclave was charged with 36 g of methanol and 0.5 g of titanium silicate from Example l and the suspension was stirred by means of a magnetic stirrer. The closed glass autoclave was then cooled to -30°C and 20.2 g of propene were injected.
Subsequently, the glass autoclave was warmed to 0°C and 23 g of 0.5% strength hydrogen peroxide solution were metered in. The reaction mixture was stirred at 0°C for 30 minutes under the autogenous pressure. The catalyst was then centrifuged off and the propylene oxide content was determined by gas chromatography. The propylene oxide content was 0.0980 by weight.
Claims (10)
1. A process for preparing a titanium silicate having the RUT structure, which comprises the steps (i) and (ii) (i) preparation of a mixture comprising at least one SiO2 source and at least one titanium source;
(ii) crystallization of the mixture from (i) in a pressure vessel with addition of at least one template compound to give a crystallization product, wherein the template compounds used are amines or ammonium salts which are suitable for stabilizing cages of the silicate structure [445962] and [44566581].
(ii) crystallization of the mixture from (i) in a pressure vessel with addition of at least one template compound to give a crystallization product, wherein the template compounds used are amines or ammonium salts which are suitable for stabilizing cages of the silicate structure [445962] and [44566581].
2. A process as claimed in claim 1 which additionally comprises the steps (iii) and (iv):
(iii)drying of the crystallization product resulting from (ii);
(iv) calcination of the dried product from (iii).
(iii)drying of the crystallization product resulting from (ii);
(iv) calcination of the dried product from (iii).
3. A titanium silicate having the RUT structure, able to be prepared by a process comprising the steps (i) and (ii):
(i) preparation of a mixture comprising at least one SiO2 source and at least one titanium source;
(ii) crystallization of the mixture from (i) in a pressure vessel with addition of at least one template compound to give a crystallization product, wherein the template compounds used are amines or ammonium salts which are suitable for stabilizing cages of the silicate structure [445462] and [44566581).
(i) preparation of a mixture comprising at least one SiO2 source and at least one titanium source;
(ii) crystallization of the mixture from (i) in a pressure vessel with addition of at least one template compound to give a crystallization product, wherein the template compounds used are amines or ammonium salts which are suitable for stabilizing cages of the silicate structure [445462] and [44566581).
4. A titanium silicate having the RUT structure as claimed in claim 3 whose titanium content is in the range from 0.001 to 5% by weight.
5. A titanium silicate having the RUT structure as claimed in claim 3 or 4 which has at least the following reflections in the X-ray diffraction pattern:
Diffraction angle 2.theta. Lattice plane spacing d (0.1 nm) 10.79 8.19 13.69 6.45 14.48 6.10 20.19 4.49 22.16 4.00 23.26 3.82 27.45 3.24
Diffraction angle 2.theta. Lattice plane spacing d (0.1 nm) 10.79 8.19 13.69 6.45 14.48 6.10 20.19 4.49 22.16 4.00 23.26 3.82 27.45 3.24
6. A titanium silicate having the RUT structure as claimed in any of claims 3 to 5 which has a band in the range from 955 to 970 cm-1 in the IR
spectrum.
spectrum.
7. The use of a titanium silicate having the RUT
structure prepared as claimed in claim 1 or 2 or a titanium silicate having the RUT structure as claimed in any of claims 3 to 6 as catalyst.
structure prepared as claimed in claim 1 or 2 or a titanium silicate having the RUT structure as claimed in any of claims 3 to 6 as catalyst.
8. A process for the reaction of an organic compound, which comprises bringing the organic compound into contact with a titanium silicate as claimed in any of claims 3 to 6 during the reaction.
9. A process as claimed in claim 8, wherein the organic compound is oxidized during the reaction.
10. A process as claimed in claim 8 or 9, wherein an alkene is reacted to form an alkene oxide.
Applications Claiming Priority (3)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| DE19839792.5 | 1998-09-01 | ||
| DE19839792A DE19839792A1 (en) | 1998-09-01 | 1998-09-01 | Process for the production of a titanium silicate with a RUT structure |
| PCT/EP1999/006434 WO2000012432A1 (en) | 1998-09-01 | 1999-09-01 | Method for producing a titanium silicate with rut structure |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| CA2342228A1 true CA2342228A1 (en) | 2000-03-09 |
Family
ID=7879420
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CA002342228A Abandoned CA2342228A1 (en) | 1998-09-01 | 1999-09-01 | Method for producing a titanium silicate with rut structure |
Country Status (10)
| Country | Link |
|---|---|
| EP (1) | EP1107931B1 (en) |
| JP (1) | JP2002525259A (en) |
| KR (1) | KR20010079727A (en) |
| CN (1) | CN1324326A (en) |
| AT (1) | ATE218510T1 (en) |
| AU (1) | AU5857999A (en) |
| BR (1) | BR9913362A (en) |
| CA (1) | CA2342228A1 (en) |
| DE (2) | DE19839792A1 (en) |
| WO (1) | WO2000012432A1 (en) |
Families Citing this family (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| DE19939416A1 (en) * | 1999-08-20 | 2001-02-22 | Basf Ag | Production of zeolite, e.g. titanium zeolite, useful as catalyst (support), sorbent, pigment or filler for plastics, involves crystallizing solid from precursor(s) and direct drying of reaction mixture |
| EP1129992A1 (en) | 2000-03-02 | 2001-09-05 | Degussa AG | Process for the preparation of a titanium-containing zeolite |
| EP1138387A1 (en) * | 2000-03-29 | 2001-10-04 | Degussa AG | Process for the preparation of titanium silicalite shaped body |
| EP1138386A1 (en) | 2000-03-29 | 2001-10-04 | Degussa AG | Process for the preparation of titanium silicalite shaped body |
| US7288237B2 (en) * | 2005-11-17 | 2007-10-30 | Lyondell Chemical Technology, L.P. | Epoxidation catalyst |
| JP2012158511A (en) * | 2011-01-14 | 2012-08-23 | Sumitomo Chemical Co Ltd | Method for producing titanosilicate, and method for producing olefin oxide |
Family Cites Families (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US5262550A (en) * | 1992-04-30 | 1993-11-16 | Arco Chemical Technology, L.P. | Epoxidation process using titanium-rich silicalite catalysts |
| DE4424816A1 (en) * | 1994-07-14 | 1996-01-18 | Basf Ag | Crystalline solids with RUB-17 structure |
-
1998
- 1998-09-01 DE DE19839792A patent/DE19839792A1/en not_active Withdrawn
-
1999
- 1999-09-01 BR BR9913362-8A patent/BR9913362A/en not_active Application Discontinuation
- 1999-09-01 DE DE59901658T patent/DE59901658D1/en not_active Expired - Lifetime
- 1999-09-01 AT AT99946088T patent/ATE218510T1/en not_active IP Right Cessation
- 1999-09-01 AU AU58579/99A patent/AU5857999A/en not_active Abandoned
- 1999-09-01 WO PCT/EP1999/006434 patent/WO2000012432A1/en not_active Application Discontinuation
- 1999-09-01 KR KR1020017002761A patent/KR20010079727A/en not_active Application Discontinuation
- 1999-09-01 JP JP2000571045A patent/JP2002525259A/en not_active Withdrawn
- 1999-09-01 CA CA002342228A patent/CA2342228A1/en not_active Abandoned
- 1999-09-01 EP EP99946088A patent/EP1107931B1/en not_active Expired - Lifetime
- 1999-09-01 CN CN99812597A patent/CN1324326A/en active Pending
Also Published As
| Publication number | Publication date |
|---|---|
| CN1324326A (en) | 2001-11-28 |
| DE59901658D1 (en) | 2002-07-11 |
| EP1107931A1 (en) | 2001-06-20 |
| JP2002525259A (en) | 2002-08-13 |
| EP1107931B1 (en) | 2002-06-05 |
| ATE218510T1 (en) | 2002-06-15 |
| AU5857999A (en) | 2000-03-21 |
| BR9913362A (en) | 2001-06-05 |
| DE19839792A1 (en) | 2000-03-02 |
| WO2000012432A1 (en) | 2000-03-09 |
| KR20010079727A (en) | 2001-08-22 |
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