EP1131264A1 - Verfahren zur herstellung eines titansilikalits des mel-typs, und dessen verwendungen in der katalyse - Google Patents

Verfahren zur herstellung eines titansilikalits des mel-typs, und dessen verwendungen in der katalyse

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Publication number
EP1131264A1
EP1131264A1 EP99949045A EP99949045A EP1131264A1 EP 1131264 A1 EP1131264 A1 EP 1131264A1 EP 99949045 A EP99949045 A EP 99949045A EP 99949045 A EP99949045 A EP 99949045A EP 1131264 A1 EP1131264 A1 EP 1131264A1
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EP
European Patent Office
Prior art keywords
zeolite
titanium
carbon atoms
xerogel
formula
Prior art date
Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
Withdrawn
Application number
EP99949045A
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English (en)
French (fr)
Inventor
Jean-Louis Grieneisen
Henri Kessler
Eric Fache
Anne-Marie Le Govic
Michel Costantini
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
Rhodia Chimie SAS
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Rhodia Chimie SAS
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Publication date
Application filed by Rhodia Chimie SAS filed Critical Rhodia Chimie SAS
Publication of EP1131264A1 publication Critical patent/EP1131264A1/de
Withdrawn legal-status Critical Current

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Classifications

    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C37/00—Preparation of compounds having hydroxy or O-metal groups bound to a carbon atom of a six-membered aromatic ring
    • C07C37/60—Preparation of compounds having hydroxy or O-metal groups bound to a carbon atom of a six-membered aromatic ring by oxidation reactions introducing directly hydroxy groups on a =CH-group belonging to a six-membered aromatic ring with the aid of other oxidants than molecular oxygen or their mixtures with molecular oxygen
    • 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
    • B01J29/04—Catalysts comprising molecular sieves having base-exchange properties, e.g. crystalline zeolites
    • 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
    • C01B37/005—Silicates, i.e. so-called metallosilicalites or metallozeosilites

Definitions

  • the present invention relates to a new process for preparing a titanium silicalite of MEL type, the product obtained and its various applications in the field of catalysis.
  • Titanium silicalites are known products and widely described in the literature, in particular in “Atlas of zeolites structure types by WM Meier and DH Oison published by the Structure Commission of the International Zeolite Association (1992), p 132. "
  • One of the first processes for preparing TS-2 consists in carrying out the crystallization of a product resulting from the reaction of a source of silicon, in particular of o-silicate tetraethyl, a source of titanium oxide, in particular a titanium tetraalkoxide, a mobilizing agent consisting of OH- ions and a structuring agent, preferably tetrabutylammonium hydroxide.
  • TS-2 prepared according to this synthetic route does not really have an MEL type structure, but is formed of MEL / MFI intergrowths, resulting from poor stacking of "pentasil" sheets. These numerous defects can be harmful in catalysis.
  • the process described consists in preparing a reaction mixture comprising both a source of titanium oxide, a source of silicon oxide and a structuring agent comprising at least one compound of the 3,5-di ⁇ methylpiperidinium type; maintaining the aqueous solution under conditions sufficient to form zeolite crystals, then recovering the latter.
  • the objective of the present invention is to provide a more industrial process for the preparation of pure TS-2 which involves a lesser amount of structuring agent and a much shorter crystallization step.
  • a process has now been found, and this is the subject of the present invention, for the preparation of a titanium silicalite which consists:
  • amorphous xerogel (Ti ⁇ 2-Si ⁇ 2) comprising at least the silicon and titanium elements with a solution comprising at least one structuring agent and at least one mobilizing agent OH "> the impregnation solution comprising at least one effective amount of a compound of the 3,5-dimethylpiperidinium type used as a structuring agent,
  • the titanium silicalite obtained according to this impregnation technique has a MEL type structure. It is based on silicon oxide and titanium oxide and its chemical composition, after calcination corresponds to the following formula:
  • the titanium silicalite obtained according to the process of the invention has a quadratic crystal system and an X-ray diffraction diagram defined in table (I).
  • titanium silicalite can in particular and advantageously be carried out by establishing their X-ray diffraction diagram.
  • This diffraction diagram can be obtained using a diffractometer using the conventional method of powders with K radiation from copper.
  • ) is calculated, as a function of the absolute error (2), by the Bragg relation.
  • the relative intensity l / l 0 assigned to each value of dhki is estimated from the height of the corresponding diffraction peak.
  • the crystals are in the form of the following medium-sized parallelepipeds:
  • the zeolite is prepared according to a process which consists of:
  • an amorphous xerogel (Ti ⁇ 2-Si ⁇ ) comprising at least ' the silicon and titanium elements with a solution comprising at least one structuring agent and at least one mobilizing agent OH " ' > the impregnation solution comprising at least one effective amount a compound of the 3,5-dimethylpiperidinium type used as a structuring agent,
  • xerogel a dry, amorphous gel composed of a mixed oxide Ti ⁇ 2
  • a preferred method of preparation consists in hydrolyzing in an acid medium a source of silicon and then adding a source of titanium.
  • the soil thus prepared is gelled by adding a base or by heating.
  • the gel is dried at an appropriate temperature.
  • silicon element with oxidation state +4 can be used.
  • hydrolyzable tetravalent silicon compounds such as silicon halides or the like.
  • the source of silicon is preferably chosen from alkylsilicates, tetraethylsilicate being that which is most preferred.
  • titanium oxides and hydroxides crystallized or amorphous, tetravalent titanium compounds which can be hydrolysed such as halides (TiCL,), organic derivatives titanium, such as, for example, alkyl o-titanates, preferably tetraethyl o-titanate or tetrabutyl o-titanate, soluble titanium salts such as TiOS0 4 , TiOCI 2 , (NH ⁇ TiO ⁇ O ⁇ . It is also possible to use as sources of silica or titanium oxide, compounds comprising the elements Si and Ti such as, for example, glasses or gels based on the oxides of these two elements.
  • the sources of silica and titanium oxide can be used in the soluble form or in powdery solids but also in the form of agglomerates such as, for example, extruded pellets which can be transformed into titanozeosilite of desired structure without modification of shape.
  • the molar ratio Ti ⁇ 2 Si ⁇ 2 in this xerogel is preferably between 25 and 200, more preferably between 35 and 100.
  • a source of silicon is hydrolyzed in an acid solution (for example, dilute HCl), then a source of titanium in the same solution, in order to obtain a clear solution.
  • the hydrolysis of the silicon source is preferably started with a dilute acid having a concentration advantageously between 0.01 and 2 N.
  • the amount of acid involved is such that the H2 ⁇ / Si ratio is between 2 and 10 and preferably between 3 and 5.
  • the source of titanium is added.
  • a preferred variant consists in diluting the source of titanium by adding an organic solvent, for example an alcohol with low carbon condensation, for example from 1 to 5 carbon atoms, and preferably isopropanol is used.
  • an organic solvent for example an alcohol with low carbon condensation, for example from 1 to 5 carbon atoms, and preferably isopropanol is used.
  • the amount of solvent represents from 50% to 85% of the volume represented by the source of titanium and of the organic solvent.
  • the hydrolysis operation can be carried out from 0 ° C to room temperature (generally 15 ° C - 25 ° C). It is also possible to exceed this temperature.
  • a base which can be of mineral origin, for example NH OH or of organic origin.
  • an organic compound which also has the role of structuring agent and preferably, a compound of the 3,5-dimethylpiperidinium type.
  • the basic solution used generally has a high concentration preferably between 10 and 40% by weight.
  • the amount of base added is such that the pH of the solution obtained is between approximately 5 and approximately 7.
  • the operation is carried out at a temperature advantageously between 0 and 25 ° C.
  • the gel obtained is subjected to drying at a temperature advantageously chosen between 50 and 120 ° C., under atmospheric pressure or under reduced pressure chosen between 1 mm of mercury and atmospheric pressure.
  • a xerogel is obtained which has a large specific surface area varying most often between 400 m 2 / g and 700 m 2 / g. Its pore volume is most often between 0.25 and 0.5 cm 3 / g.
  • the pore size varies widely between 5 and 100 ⁇ but the xerogel has a large microporous volume since almost 80% of the volume is constituted by micropores having from 3 to 20 ⁇ .
  • the xerogel obtained is impregnated using a solution comprising an organic compound used as a structuring agent and a mobilizing agent, of the OH " type.
  • the mobilizing agent OH " is introduced in the form of weak and / or strong base (s) preferably containing no alkaline cations. Mention may be made of amines and quaternary ammonium hydroxides. Examples are given below.
  • the structuring agent it directs and stabilizes the formation of the zeolite.
  • structuring agents suitable for the invention mention may be made of those which correspond to the following formula:
  • R a and Rb identical or different, represent an alkyl group, linear or branched, having from 1 to 7 carbon atoms; the groups R a and Rb, can together form a ring system which includes the nitrogen atom, comprising from 4 to 7 carbon atoms, said system being able to be substituted or not by alkyl, linear or branched groups having from 1 to 3 carbon atoms,
  • 3,5-DMP compounds there may be mentioned 3,5-dimethyl-N, N-diethylpiperidinium, 3,5-dimethyl-N-methyl-N-ethylpiperidinium.
  • spiro-3,5-dimethyipiperidinium compounds mention may be made of the compounds 1-azonia-3,5,7-trimethyl-spiro [5.4] decane.
  • the anion can be essentially a halide or hydroxide anion.
  • halide we consider fluoride, chloride, bromide , iodide or combinations thereof.
  • the illustrative anions are: hydroxide, acetate, sulfate, carboxylate, tetrafluoroborate, halides such as fluoride, chloride, bromide, iodide. Iodides and hydroxides are the preferred anions. of the process of the invention consists in associating 3,5-
  • HTA tetraikylammonium hydroxide
  • tetraikylammonium hydroxides mention may in particular be made of tetraethylammonium, tetrapropylammonium and tetrabutylammonium hydroxides.
  • the amount of HTA used is such that the HTA / 3.5-DMP molar ratio varies between 0.5 and 2.10 -3 and, preferably, between 0.1 and 0.01
  • the second HTA structuring agent is added in any way to the
  • the reaction mixture is crystallized at an appropriate temperature, with stirring.
  • the composition of the reaction mixture is characterized by a low water content.
  • the amount of water is determined so that it allows wetting of the xerogel.
  • the H2 ⁇ / Si ⁇ 2 ratio is less than 10, preferably between 3 and 10, and more preferably between 4 and 6.
  • the OH7Si ⁇ 2 molar ratio advantageously varies between 0.05 and 1.0, preferably between 0.05 and 0.5.
  • the quantity of structuring agent expressed by the molar ratio Q / Si0 2 (in which Q represents the 3,5-DMP) must be at most equal to 0.13, preferably between 0.05 and 0.125, and even more preferably between 0.075 and 0.125.
  • the molar ratio Q / Si ⁇ 2 is between 0.125 and 1.0, preferably between 0.15 and 0.20.
  • the crystallization of the zeolite can be obtained by heating the xerogel for the time necessary for crystallization, according to the standard procedure for the synthesis of zeolite well known to those skilled in the art.
  • Appropriate temperatures are between 90 and 210 ° C, preferably between 120 and 190 ° C and more preferably between 150 and 170 ° C.
  • the duration of heating can be between 6 hours and
  • This heating and this crystallization are preferably carried out in a container or autoclave coated with a layer such as for example polytetrafluoroethane.
  • a variant of the process of the invention consists in adding crystallized seeds of determined structure, MEL, in a proportion which does not exceed a few weight percentages (generally ⁇ 5%) relative to the weight of SiO + TiO engaged, facilitates crystallization zeolite. As seeds of crystallization, one can use any zeolite having the MEL structure, whatever its chemical composition.
  • silicalite which is a zeolite equivalent to titanium silicalite, but containing only silicon in its framework. It is also possible to use seeds of titanium silicalite MEL originating from a previous manufacture. It should be noted that when only 3,5-DMP is used as a structuring agent, it is particularly advantageous to add seeds of crystallization.
  • the material obtained is separated according to conventional solid / liquid separation techniques, preferably by filtration. It may be advantageous to carry out a washing operation, preferably with deionized water.
  • the material obtained is subjected to drying at a temperature preferably chosen between 50 and 120 ° C., under atmospheric pressure or under reduced pressure chosen between 1 mm of mercury and atmospheric pressure. Finally, it is calcined preferably in air, at a temperature of at least
  • the duration of the calcination, given below for information, is most often between 2 and 12 hours.
  • the zeolites obtained according to the process of the invention have catalytic properties which allow their use as catalysts or catalyst supports for reactions of transformation of various organic compounds.
  • a preferred application of the zeolites of the invention is their use for the hydroxylation reactions of phenolic compounds.
  • the process of the invention advantageously applies to phenolic compounds which are soluble in the medium, under the reaction conditions.
  • the phenolic compound is soluble in an amount of at least 90% by weight.
  • R2 R3 and R4, identical or different, represent a hydrogen atom or any substituent
  • R - R ' represents a hydrogen atom or a hydrocarbon radical having from 1 to 24 carbon atoms, which can be a saturated or unsaturated, linear or branched acyclic aliphatic radical; a saturated or unsaturated, monocyclic or polycyclic cycloaliphatic radical; a saturated or unsaturated, linear or branched aliphatic radical, carrying a cyclic substituent.
  • cyclic substituent is meant a saturated, unsaturated or aromatic carbocycle having, generally, from 4 to 7 carbon atoms, and preferably 6 carbon atoms.
  • the process of the invention applies to any phenolic compound corresponding to the general formula (III) and, more particularly, to the phenolic compounds of formula (III) in which R 'represents: a hydrogen atom. a linear or branched alkyl radical having from 1 to 6 carbon atoms, preferably from 1 to 4 carbon atoms, and more particularly a methyl or ethyl radical,. a cyclohexyl radical,. a benzyl radical.
  • the phenolic compound of formula (III) may carry one or more substituents R-
  • substituents are given below, but this list is in no way limiting. Any substituent can be present on the cycle as long as it does not interfere with the desired product.
  • the process of the invention applies more preferably to phenolic compounds of formula (III) in which:
  • R 0 one of the following groups:
  • a hydrogen atom a hydrogen atom,. an alkyl radical, linear or branched, having from 1 to 6 carbon atoms, preferably from 1 to 4 carbon atoms, such as methyl, ethyl, propyl, isopropyl, butyl, sec-butyl, tert-butyl,
  • a linear or branched alkenyl radical having from 2 to 6 carbon atoms, preferably from 2 to 4 carbon atoms, such as vinyl, allyl,.
  • a linear or branched alkoxy radical having from 1 to 6 carbon atoms, preferably from 1 to 4 carbon atoms such as the methoxy, ethoxy, propoxy, isopropoxy, butoxy, radicals.
  • an acyl group having from 2 to 6 carbon atoms,. a radical of formula: -R5-OH
  • R5 represents a valence bond or a divalent, linear or branched, saturated or unsaturated hydrocarbon radical, having from 1 to
  • R ⁇ represents a hydrogen atom or a linear or branched alkyl radical having from 1 to 6 carbon atoms
  • X symbolizes a halogen atom, preferably a chlorine, bromine or fluorine atom.
  • R 2 , R3 and R 4 identical or different, represent R 7 , one of the following more complex radicals:. a saturated or unsaturated carbocyclic radical having from 4 to 7 carbon atoms, preferably a cyclohexyl radical,. a radical of formula
  • R5 represents a valential bond or a divalent, linear or branched, saturated or unsaturated hydrocarbon radical having from 1 to 6 carbon atoms such as, for example, methylene, ethylene, propylene, isopropylene, isopropylidene and R 0 having the meaning given above and m is an integer from 0 to 4,.
  • R 5 represents a radical - R 5 - A - R 8 in which R 5 has the meaning given above, R 8 represents a linear or branched alkyl radical having from 1 to 6 carbon atoms or a radical of formula
  • Rg represents a hydrogen atom or an alkyl radical having from 1 to 4 carbon atoms, a cyclohexyl or phenyl radical.
  • R - R ' represents a hydrogen atom - R- j , R2, R3 and R 4 , identical or different, represent one of the following groups:
  • an alkyl radical linear or branched having from 1 to 4 carbon atoms ,.
  • a linear or branched alkoxy radical having from 1 to 4 carbon atoms,. a hydroxyl group, . a halogen atom,
  • a phenyl radical - two groups R 1 and R 2 and / or R 3 and R 4 placed on two vicinal carbon atoms can form together and with the carbon atoms which carry them a benzene ring.
  • the compounds of formula (III) are chosen in which R ′ represents a hydrogen atom and one of the radicals R ⁇ R2, R3 and R 4 represents a hydroxyl group, a methyl radical or a methoxy radical and the other 3 represent a hydrogen atom.
  • R ⁇ represents a radical of type R 7 , such as 2-phenoxyphenol, 3-phenoxyphenol.
  • R ⁇ represents a radical of type R 7 , such as 2-phenoxyphenol, 3-phenoxyphenol.
  • R ⁇ represents a radical of type R 7 , such as 2-phenoxyphenol, 3-phenoxyphenol.
  • phenol o-cresol, m-cresol, p-cresol.
  • the phenolic compound of formula (III), the hydrogen peroxide and the zeolitic catalyst are used during the hydroxylation process.
  • the hydrogen peroxide used according to the invention can be in the form of an aqueous solution or an organic solution.
  • aqueous solutions being commercially more readily available are used.
  • the concentration of the aqueous hydrogen peroxide solution is not critical.
  • a dilute solution of hydrogen peroxide its concentration can advantageously be between 20% and 40% by weight.
  • the amount of hydrogen peroxide can range up to 1 mole of H2O2 for 1 mole of phenolic compound of formula (III).
  • reaction is carried out in an aqueous medium.
  • the total weight content of water expressed relative to the phenolic compound of formula (III) can vary between 30% and 100%, preferably between 40% and 70%.
  • the amount of zeolitic catalyst which is used in the process of the invention can vary within wide limits.
  • the catalyst can represent, by weight relative to the phenolic compound of formula (III) used, from 0.1 to 25%, preferably from 3 to 10%.
  • the process is carried out continuously, for example by reacting a mixture of phenolic compound (III), of hydrogen peroxide solution on a fixed bed of catalyst, these catalyst / phenolic compound ratios of formula (III) do not make sense and at a given time, there may be an excess weight of catalyst compared to the phenolic compound of formula (III).
  • a solvent for said compound which is preferably miscible or partially miscible with water.
  • solvents such solvents, mention may be made of water, alcohols such as methanol, ethanol, isopropanol, tert-butanol; ketones such as acetone or methyl isobutyl ketone; nitriles such as acetonitrile; carboxylic acids such as acetic acid; esters of carboxylic acids such as propyl acetate; ethers such as methyltertiobutylether; polar aprotic solvents such as tetrahydrothiophene dioxide (sulfolane), ethylene glycol carbonate, propylene glycol carbonate, N-methylpyrrolidone.
  • alcohols such as methanol, ethanol, isopropanol, tert-butanol
  • ketones such as acetone or methyl isobutyl ketone
  • nitriles such as acetonitrile
  • the hydroxylation of the phenolic compound of formula (III) is carried out at a temperature which can be between 45 ° C. and 150 ° C.
  • a preferred variant of the process of the invention consists in choosing the temperature between 50 ° C and 120 ° C, and even more preferably around 80 ° C.
  • the reaction is advantageously carried out at atmospheric pressure.
  • the method according to the invention is simple to implement continuously or discontinuously.
  • the following different reagents are introduced in any order, phenolic compound of formula (III), and catalyst.
  • the reaction medium is brought to the desired temperature and then the hydrogen peroxide solution is added gradually.
  • the zeolitic catalyst is separated according to conventional solid / liquid separation techniques, preferably by filtration and then the untransformed phenolic compound, are separated from the hydroxylation products by the usual means, in particular by distillation and are returned to the reaction zone.
  • TPABr tetrapropyiammonium bromide.
  • 3,5-DMDEPI 3,5-dimethyl-NN-diethylpiperidinium iodide
  • 3,5-DMDEPI is characterized by proton nuclear magnetic resonance
  • N.N-diethylpiperidinium (3,5-DMDEPOH) is produced from silver oxide according to the following procedure: a solution containing 50 g of
  • the solution is stirred for 1 hour at room temperature and then 2 hours at 70 ° C. in order to remove the alcohols (alcohols released by hydrolysis + isopropanol).
  • the clear soil thus obtained is gelled by adding 2.25 g of a 25% solution of 3,5-DMDEPOH.
  • the gel is then dried overnight in an oven at 110 ° C.
  • the Si ⁇ 2-TiO 2 xerogel thus prepared is finely ground in a mortar before use.
  • the mixture is stirred for approximately 10 minutes.
  • the molar composition reduced to one mole of silica of the reaction mixture is as follows:
  • reaction mixture is then crystallized in an autoclave coated internally with polytetrafluoroethane, by heating at 170 ° C for 9 days with stirring (rotary oven). After crystallization, the solid phase is separated by filtration, washed with water and dried at 80 ° C.
  • Titanium silicalite (TS-2) is in the form of parallelepipedic crystals of size 150 x 150 x 400 nm approximately.
  • the infrared spectrum of the solid comprises a band at 960 cm " characteristic of titanium silicalites.
  • UV-Visible spectrum is devoid of the bands characteristic of the presence of extra-reticular Ti ⁇ 2.
  • the impregnated xerogel is stirred for approximately 10 minutes.
  • the molar composition reduced to one mole of silica of the reaction mixture is as follows:
  • reaction mixture is then crystallized in an autoclave coated internally with polytetrafluoroethane, by heating at 170 ° C for 7 days with stirring (rotary oven). After crystallization, the solid phase is separated by filtration, washed with water and dried at 80 ° C.
  • the solid After calcination at 560 ° C for 8 hours, the solid is characterized by X-ray diffraction.
  • Titanium silicalite (TS-2) is in the form of spherical particles of 0.5 ⁇ m polycrystalline.
  • Example 2 Preparation of titanium silicalite (TS-2) Example 2 is repeated, but with 6.25 g of 3.5-DMDEPOH at 25% instead of 5.0 g.
  • the molar composition reduced to one mole of silica of the reaction mixture is as follows:
  • reaction mixture 1 Si ⁇ 2; 0.0222 TiO 2 ; 0.125 3.5-DMDEPOH; 2% of germs.
  • the reaction mixture is then crystallized in an autoclave coated internally with polytetrafluoroethane, by heating at 170 ° C for 8 days with stirring (rotary oven).
  • the solid phase is separated by filtration, washed with water and dried at 80 ° C. After calcination at 560 ° C for 8 hours, the solid is characterized by X-ray diffraction and by scanning electron microscopy.
  • Example 3 is repeated but the hydrothermal synthesis is carried out statically and for 3 days (instead of 8 days in Example 3). After crystallization, the solid phase is separated by filtration, washed with water and dried at 80 ° C.
  • Titanium silicalite (TS-2) is in the form of spherical particles of 0.5 ⁇ m polycrystalline.
  • Example 6 is repeated but the titanium silicalite (TS-2) of Example 3 is replaced by that of Example 4. About 30 minutes after the end of the pouring, the hydrogen peroxide has been completely consumed .

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  • Chemical & Material Sciences (AREA)
  • Organic Chemistry (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Crystallography & Structural Chemistry (AREA)
  • Engineering & Computer Science (AREA)
  • Materials Engineering (AREA)
  • Inorganic Chemistry (AREA)
  • Silicates, Zeolites, And Molecular Sieves (AREA)
  • Low-Molecular Organic Synthesis Reactions Using Catalysts (AREA)
  • Catalysts (AREA)
  • Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
EP99949045A 1998-10-19 1999-10-13 Verfahren zur herstellung eines titansilikalits des mel-typs, und dessen verwendungen in der katalyse Withdrawn EP1131264A1 (de)

Applications Claiming Priority (3)

Application Number Priority Date Filing Date Title
FR9813078 1998-10-19
FR9813078A FR2784672B1 (fr) 1998-10-19 1998-10-19 Procede de preparation d'une silicalite de titane de type mel, produit obtenu et ses applications en catalyse
PCT/FR1999/002478 WO2000023377A1 (fr) 1998-10-19 1999-10-13 Procede de preparation d'une silicalite de titane de type mel, produit obtenu et ses applications en catalyse

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EP1131264A1 true EP1131264A1 (de) 2001-09-12

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EP (1) EP1131264A1 (de)
JP (1) JP2002527347A (de)
CN (1) CN1324325A (de)
AU (1) AU6206799A (de)
FR (1) FR2784672B1 (de)
NO (1) NO20011920L (de)
WO (1) WO2000023377A1 (de)

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WO2018229033A1 (fr) 2017-06-13 2018-12-20 Rhodia Operations Compositions comprenant de l'hydroquinone et du catechol, procede de preparation de ces compositions
WO2019106142A1 (fr) 2017-11-30 2019-06-06 Rhodia Operations Compositions comprenant du 4-alkoxyphénol et du 2-alkoxyphénol, et leur procede de preparation
WO2019115760A1 (fr) 2017-12-15 2019-06-20 Rhodia Operations Procédé d'hydroxylation d'un composé aromatique

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FR2987046B1 (fr) * 2012-02-17 2014-03-21 Rhodia Operations Procede d'hydroxylation de composes aromatiques, catalyseur d'hydroxylation et son procede de preparation
JP5972694B2 (ja) * 2012-07-18 2016-08-17 ユニゼオ株式会社 Ｆｅ（ＩＩ）置換ＭＥＬ型ゼオライト、それを含むガス吸着剤及びその製造方法、並びに一酸化窒素及びハイドロカーボンの除去方法
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CN111484031B (zh) * 2019-01-28 2023-03-10 中国石油化工股份有限公司 改性钛硅分子筛及其制备方法和应用以及硫醚氧化方法

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Cited By (3)

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Publication number Priority date Publication date Assignee Title
WO2018229033A1 (fr) 2017-06-13 2018-12-20 Rhodia Operations Compositions comprenant de l'hydroquinone et du catechol, procede de preparation de ces compositions
WO2019106142A1 (fr) 2017-11-30 2019-06-06 Rhodia Operations Compositions comprenant du 4-alkoxyphénol et du 2-alkoxyphénol, et leur procede de preparation
WO2019115760A1 (fr) 2017-12-15 2019-06-20 Rhodia Operations Procédé d'hydroxylation d'un composé aromatique

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NO20011920D0 (no) 2001-04-18
CN1324325A (zh) 2001-11-28
FR2784672A1 (fr) 2000-04-21
JP2002527347A (ja) 2002-08-27
AU6206799A (en) 2000-05-08
FR2784672B1 (fr) 2000-12-29
WO2000023377A1 (fr) 2000-04-27

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