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WO1995003249A1 - Procede de fabrication d'un zeolithe - Google Patents

Procede de fabrication d'un zeolithe Download PDF

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Publication number
WO1995003249A1
WO1995003249A1 PCT/EP1994/002457 EP9402457W WO9503249A1 WO 1995003249 A1 WO1995003249 A1 WO 1995003249A1 EP 9402457 W EP9402457 W EP 9402457W WO 9503249 A1 WO9503249 A1 WO 9503249A1
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WO
WIPO (PCT)
Prior art keywords
synthesis mixture
hydrothermal treatment
carried out
ethene
bar
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.)
Ceased
Application number
PCT/EP1994/002457
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English (en)
Inventor
Philip Luc Buskens
Luc Roger Martens
Georges Marie Karel Mathys
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.)
ExxonMobil Chemical Patents Inc
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Exxon Chemical Patents Inc
Priority date (The priority date 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 date listed.)
Filing date
Publication date
Priority claimed from PCT/EP1993/001972 external-priority patent/WO1994002245A1/fr
Priority claimed from GB9406432A external-priority patent/GB9406432D0/en
Application filed by Exxon Chemical Patents Inc filed Critical Exxon Chemical Patents Inc
Priority to BR9407200A priority Critical patent/BR9407200A/pt
Priority to EP94925391A priority patent/EP0710216A1/fr
Priority to JP7504956A priority patent/JPH09500860A/ja
Priority to AU75328/94A priority patent/AU678597B2/en
Publication of WO1995003249A1 publication Critical patent/WO1995003249A1/fr
Anticipated expiration legal-status Critical
Ceased legal-status Critical Current

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Classifications

    • 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
    • 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
    • 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
    • C01B39/46—Other types characterised by their X-ray diffraction pattern and their defined composition
    • C01B39/48—Other types characterised by their X-ray diffraction pattern and their defined composition using at least one organic template directing agent
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07B—GENERAL METHODS OF ORGANIC CHEMISTRY; APPARATUS THEREFOR
    • C07B41/00—Formation or introduction of functional groups containing oxygen
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C51/00—Preparation of carboxylic acids or their salts, halides or anhydrides
    • C07C51/16—Preparation of carboxylic acids or their salts, halides or anhydrides by oxidation
    • C07C51/285—Preparation of carboxylic acids or their salts, halides or anhydrides by oxidation with peroxy-compounds
    • 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
    • C07D301/19—Synthesis of the oxirane ring by oxidation of unsaturated compounds, or of mixtures of unsaturated and saturated compounds with organic hydroperoxides
    • 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
    • B01J2229/00—Aspects of molecular sieve catalysts not covered by B01J29/00
    • B01J2229/10—After treatment, characterised by the effect to be obtained
    • B01J2229/18—After treatment, characterised by the effect to be obtained to introduce other elements into or onto the molecular sieve itself
    • B01J2229/183—After treatment, characterised by the effect to be obtained to introduce other elements into or onto the molecular sieve itself in framework positions
    • 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
    • B01J2229/00—Aspects of molecular sieve catalysts not covered by B01J29/00
    • B01J2229/30—After treatment, characterised by the means used
    • B01J2229/34—Reaction with organic or organometallic compounds
    • 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
    • B01J2229/00—Aspects of molecular sieve catalysts not covered by B01J29/00
    • B01J2229/30—After treatment, characterised by the means used
    • B01J2229/36—Steaming
    • 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
    • B01J29/06—Crystalline aluminosilicate zeolites; Isomorphous compounds thereof
    • B01J29/70—Crystalline aluminosilicate zeolites; Isomorphous compounds thereof of types characterised by their specific structure not provided for in groups B01J29/08 - B01J29/65
    • B01J29/7007—Zeolite Beta

Definitions

  • This invention relates to a process for the manufacture of a zeolite, especially to one suitable for use as a catalyst, to the zeolite produced by the process, and to organic reactions, especially oxidations of hydrocarbons, catalysed thereby.
  • Titanium-containing TS-1 and TS-2 are catalysts for the oxidation of hydrocarbons by hydrogen peroxide.
  • a disadvantage of these catalysts is that because they have MFI and MEL structures, respectively, the rings of which are 10-membered, of diameter of the order of 0.5 nm, the entry of bulky feed molecules is restricted.
  • n-hexane reacts more readily than cyclohexane, and in general reactivity decreases with increasing branching and molecular weight.
  • the activity of the catalysts is high only for hydrogen peroxide; for organic hydroperoxides they are much less efficient.
  • Ti-Beta zeolite capable of efficiently catalysing the oxidation of higher paraffins using hydrogen peroxide.
  • This catalyst Ti-Beta zeolite
  • a process is described for the manufacture of Ti-Beta zeolite which comprises the preparation of a ⁇ synthesis mixture containing a source of titanium (e.g.
  • TEOT tetraethyl orthotitanate
  • a source of aluminium e.g., aluminiu ⁇ powder
  • a source of silicon e.g. colloidal silica
  • an organic nitrogen-containing base especially tetraethylammonium hydroxide, hereinafter TEAOH
  • Typical synthesis mixtures yielding Ti-Beta zeolite after hydrothermal treatment have an initial molar composition within the following ranges: sio 2 (i); ⁇ io 2 (o.oooi to 0.2); AI 2 O 3 (0.005 to 0.100)
  • the Ti plus Si:Al molar ratio is within the range of from 10 to 200:1.
  • Hydrogen peroxide is advantageously present in the synthesis mixture, although it may decompose before or during hydrothermal treatment, preferably in a proportion of 10 to 200 moles H 2 0 2 per mole of TEOT when that is used as the source of titanium.
  • the catalyst formed in accordance with this procedure is active for oxidations using organic peroxides, especially hydroperoxides, thereby enabling the oxidation reaction to take place in a single organic phase, avoiding the aqueous phase also present when H 2 0 2 is employed.
  • the present invention is based on the observation that if ethene is present in contact with a Ti-, V-, or Zr-Beta-forming synthesis mixture during the hydrothermal treatment the corresponding Ti-, V-, or Zr- Beta zeolite is obtained in good yields.
  • the present invention accordingly provides in a first aspect a process for the manufacture of a Ti-, V-, or Zr-Beta zeolite in which at least a part of a hydrothermal treatment of a Ti-, V-, or Zr-Beta forming synthesis mixture is carried out under an ethene- containing atmosphere at a pressure of at least 20 bar and advantageously under an ethene partial pressure of at least 5 bar.
  • the invention provides a process for the manufacture of a Ti-, V-, or Zr-Beta zeolite in which at least a part of a hydrothermal treatment of a Ti-, V-, or Zr-Beta forming synthesis mixture is carried out in the presence of at least 0.1 mole of ethene per mole of tetraethylammonium cations.
  • the mole ratio of ethene:tetraethylammonium is in the range 0.1 to 1:1.
  • the remainder of the description will primarily relate to the aspect of the invention in which the product is Ti-Beta zeolite; it will be understood that mutatis mutandis the same procedure is used for the other products. It will be understood also that it is within the scope of the invention to make products containing mixtures of two or more of Ti, V, and Zr, as well as zeolites containing one or more of Ti, V, or Zr, and small proportions of other cations.
  • Ti-Beta forming synthesis mixture there is typically used a mixture comprising a source of silicon, a source of titanium, a source of aluminium, water, and a source of tetraethylammonium cations.
  • the synthesis mixture is advantageously substantially free from alkali metal cations; by substantially free is meant the absence of more alkali metal than is inevitably present in commercial supplies of the essential components.
  • alkali metal ions e.g., sodium or potassium ions
  • they are advantageously present in a molar proportion of Si0 2 :M + of 1: at most 0.5.
  • the synthesis mixture has a molar composition within the following ranges: Si ⁇ 2 (l); TiO 2 (0.0001 to 0.2); Al 2 O 3 (0.0005 to 0.1); H 2 O(10 to 100) and TEAOH (0.01 to 1) .
  • the Ti plus Si:Al molar ratio is within the range of from 50 to 200:1.
  • Preferred sources of the components are: for silicon, colloidal silica, advantageously a colloidal silica substantially free from alkali metal cations, or a tetraalkylammonium orthosilicate; for aluminium, aluminium powder; and for titanium, a hydrolysable titanium compound, e.g., TiOCl 4 , TiOCl 2 or a tetraalkyl orthotitanate, especially TEOT.
  • a preferred source is vanadyl sulphate and, for zirconium, zirconyl sulphate.
  • the tetraethyl ammonium cations are advantageously provided by TEAOH.
  • hydrogen peroxide is present in the synthesis mixture.
  • it is present in a proportion of from 10 to 200 moles per mole of TEOT, when that is the titanium source.
  • the synthesis mixture is aged between its formation and the hydrothermal treatment.
  • Ageing may be carried out at room temperature or at elevated temperatures, for example at from 60 to 90°C, advantageously about 70°C, the ageing time being from 2 to 24 hours, depending inversely on the temperature.
  • a preferred ageing treatment comprises initial room temperature ageing for from 12 to 18 hours, followed by elevated temperature ageing, e.g. , at 70°C, for from 2 to 4 hours.
  • Elevated temperature ageing also causes evaporation of water from the synthesis mixture, thereby producing a synthesis gel of a concentration advantageous for hydrothermal treatment.
  • the aged gel may be diluted before treatment, e.g. , with ethanol. If ethanol is added, it is advantageously present in the synthesis mixture subjected to hydro ⁇ thermal treatment in a proportion of at most 2 moles per mole of Sip 2 .
  • the synthesis mixture preferably aged, is advantageously subjected to hydrothermal treatment at a temperature within the range of from 120°C to 200°C, preferably from 130°C to 150°C, under the pressure regime as indicated above, advantageously for a time in the range of from 1 hour to 30 days, preferably from 6 days to 15 days, until crystals are formed.
  • Hydrothermal treatment is advantageously effected in an autoclave.
  • a higher zeolite yield may be obtained or a lower proportion of tetraethylammonium ions may be included in the synthesis mixture.
  • ethene is present in the reaction vessel from the commencement of the hydrothermal treatment.
  • the ethene partial pressure is at least 5 bar, preferably at least 20 bar, and most preferably at least 30 bar, for at least a part of the period of hydrothermal treatment.
  • the total pressure is at least 30 bar, and preferably at least 40 bar.
  • the ethene partial pressure is at least 80%, preferably at least 90%, of the total pressure.
  • the synthesis mixture is cooled, and the crystals are separated from the mother liquor, washed and dried.
  • the resulting calcined product may either be used as such or subjected to further treatment e.g., by acid, for example, HCl, or by bases e.g., ammonium or sodium ions.
  • the product may be post-treated, as by steaming.
  • the Ti-Beta zeolite produced by the process of the invention may be highly crystalline and is characterized by an IR absorption at ⁇ 960 cm -1 and by an absorption band in Diffuse Reflectance Spectroscopy at the wave number 47,500 cm -1 .
  • Diffuse Reflectance Spectroscopy is described in chapter 4 of "Characterisation of Heterogeneous Catalysts" by Chemical Industries, Volume 15, published by Manel Dekker Inc. of New York in 1984. The system used was as shown in Figure 3 of that chapter using a Cary 5 spectrometer.
  • the zeolite produced by the process of the invention is an active oxidation catalyst, especially for reactions employing a peroxide as oxidant, including organic peroxides, including hydroperoxides, as well as hydrogen peroxide.
  • a peroxide as oxidant including organic peroxides, including hydroperoxides, as well as hydrogen peroxide.
  • Ti-Beta zeolite is more effective in the oxidation of larger molecules, e.g., cycloparaffins and cycloolefins.
  • organic hydroperoxides avoids the two phase system necessarily associated with aqueous hydrogen peroxide.
  • the present invention accordingly also provides the use of the product of the process of the invention as a catalyst in the oxidation of an organic compound, especially in single phase oxidation by an organic peroxide.
  • the catalyst of the invention is effective in oxidizing saturated hydrocarbons, e.g., paraffins and cycloparaffins, and the alkyl substituents in alkyl- aromatic hydrocarbons.
  • saturated hydrocarbons e.g., paraffins and cycloparaffins
  • alkyl substituents in alkyl- aromatic hydrocarbons e.g., paraffins and cycloparaffins
  • ring-opening and acid formation may take place, for example, in the oxidation of cyclohexane by tertiary butyl peroxide or H 2 0 2 adipic acid is produced, and in the oxidation of cyclopentane glutaric acid is produced.
  • the catalyst is also effective in the epoxidation of unsaturated hydrocarbons, e.g,. olefins and dienes, and the produc ⁇ tion of ether glycols, diols, the oxidation of alcohols, ketones or aldehydes to acids, and the hydroxylation of aromatic hydrocarbons.
  • unsaturated hydrocarbons e.g,. olefins and dienes
  • the oxidizing agent may be, for example, ozone, nitrous oxide, or preferably hydrogen peroxide or an organic peroxide including a hydroperoxide.
  • suitable organic hydroperoxides include di-isopropyl benzene monohydroperoxide, cumene hydroperoxide, tert.butyl hydroperoxide, cyclohexyl hydroperoxide, ethylbenzene hydroperoxide, tert.amyl hydroperoxide, and tetralin hydroperoxide.
  • the compound to be oxidized is liquid or in the dense phase under the conditions used for the reaction.
  • the reaction is carried out in the presence of a suitable solvent.
  • the use of a tertiary butyl hydroperoxide is particularly beneficial since the tertiary butyl alcohol produced can readily be converted to the valuable isobutylene molecule.
  • the oxidation reaction may be carried out under batch conditions or in a fixed bed, and the use of the heterogeneous catalyst facilitates a continuous reaction in a monophase or biphase system.
  • the catalyst is stable under the reaction conditions, and may be totally recovered and reused.
  • Mixture A was prepared by adding dropwise 3.4 ml TEOT to 63.39 ml distilled H 2 0. The mixture is cooled to 5°C, and 39 ml H 2 0 2 (35% in H 2 0) added. The resulting mixture was stirred for 2 hours at 5°C, resulting in a clear yellow-orange liquid.
  • Mixture B was prepared by adding 0.0312 g Al powder to 28.71 g of TEAOH (40% in H 2 0) and dissolving it by heating to 90°C. After cooling 31 ml of distilled H 2 0 were added. This mixture was cooled to 5°C and added to mixture A. The resulting mixture was stirred for another hour, then 12.23 g colloidal silica (Ludox HS40, 40% in water, stabilized by Na + ) added. The synthesis mixture was stirred overnight at room temperature, followed by heating for 4 hours at 70°C. The resulting concentrated gel was diluted with 10 ml of ethanol, transferred to a stainless steel autoclave and made up to 100 ml with water.
  • the contents of the autoclave were a milk white suspension. This was centrifuged at 4000 rpm for 20 minutes to separate the solids. After drying at 60°C, the solids were calcined at 550°C in air for 12 hours to yield a Ti-Beta zeolite. More details of synthesis conditions for this and the remaining Examples are given in Table 1, while characteristics of the zeolites produced are given in Table 2.
  • Mixture A was obtained by adding dropwise 0.5 ml TEOT to 63 ml distilled H 2 0. This mixture was cooled to 5°C. Subsequently, 39 ml H 2 0 (35% in H 2 0) were added. The resulting mixture was stirred for 3 hours at 5°C, resulting in a clear yellow-orange liquid.
  • Mixture B was produced by adding 0.0312 g Al powder to 29.43 g of TEAOH (40% in H 2 0) and dissolving it by heating at 90°C. Then, 31 ml of distilled H 2 0 were added. This mixture was cooled to 5°C.
  • the autoclave was put in an oven and crystallization proceeded without agitation at 125°C for 6 days. After this time the autoclave was quickly cooled to room temperature and the solids separated from the liquid by centrifugation at 13,000 rpm. The organic template was then removed from the zeolite pores by calcination at 550°C in air for 12 hours.
  • the autoclave was kept in an oven at 135°C in static conditions. After 6 days the crystals were separated 13,000 rpm. Finally, the solids obtained were dried overnight at 60°C. The organic template was removed from the zeolite pores by calcination at 550°C in air for 12 hours.
  • Mixture B was produced by adding 0.910 g Al powder to 29.43 g of TEAOH (40% in H 2 0) and dissolving it by heating at 90°C. Then, 31.08 g of distilled H 2 0 were added. This mixture was cooled to 5°C.
  • the autoclave was put in an oven and the crystallization proceeded without agitation at 135°C for 10 days. After this time the autoclave was quickly cooled to room temperature and the solid material separated from the liquid by centrifugation at 13,000 rpm. After drying at 60°C, the organic template was removed from the zeolite pores by calcination at 550°C in air for 12 hours.
  • the aluminium source 0.3859 g Al powder and 366 g of TEAOH (40% in H 2 0) were combined in a beaker, covered to prevent evaporation, and heated at 80°C for 2 hours. After dissolution of aluminium, 183 ml of distilled water were added. The resulting solution was cooled to 5°C.
  • the autoclave was kept at 140°C without agitation. After 11 days, pressure had risen to 50 bar. The crystals were separated from the mother liquor and washed by centrifugation at 13,000 rpm. After drying at 60°C, the organic template was removed from the zeolite pores by calcination at 550°C in air for 12 hours.
  • Example 5 The same procedure as described for Example 5 was used to compose the synthesis gel, but all reagent quantities were halved.
  • the gel was transferred to a 1000 ml, ptfe-lined, stainless steel autoclave, and occupied about 50% of the volume.
  • ethene was introduced to give an ethene pressure of 7 bar.
  • the autoclave was heated to 140°C. After 18 hours the pressure had risen to 14 bar. It was increased to 34 bar by introducing further ethene into the autoclave. Finally, after 3 days, the pressure which had risen to 36 bar was increased to 44 bar by adding further ethene.
  • the molar ratio of ethene:TEAOH was about 0.4:1.
  • Camblor method 10 Camblor- ⁇ yes(vw) yes(s) yes(s) yes(w) yes(s) no
  • Tables 1 and 2 show, with reference to Comparison Example 1 and Example 1, the importance of ageing the synthesis mixture before the hydrothermal treatment.
  • XRD x-ray diffraction
  • Example 2 In contrast in Example 1, carried out with ageing, all the above-mentioned IR bands were present, although the 960 cm -1 was weak, and while the above- mentioned DRS bands were present, they were weak, and were accompanied by a strong band at 47,500 cm -1 , assigned to titanium in the framework of the zeolite.
  • the yield, at 4% was, however, very low, yield being calculated as follows:
  • Yield % 100 (weight of calcined zeolite obtained) weight of Si0 2 and A1 2 0 3 in gel
  • Example 2 an NH 4 + stabilized silica source is used; a much higher yield, 20%, is obtained, and the DRS bands attributable to the Ti0 phase are absent.
  • Example 3 With a higher titanium content and higher temperature and longer time of crystallization, an improved yield (35%) is obtained. In Example 4, a higher yield (75%) results from a higher aluminium content, but a strong band at 34,000 cm -1 indicates Ti0 2 present, possibly indicating co-formation of Al- ⁇ , Al-Rich Ti- ⁇ and Ti0 2 .
  • Example 5 a high ethene pressure is maintained, in Example 5, by a small head-space and in Example 6 by ethene addition during crystallization. High yields are obtained with no indication of Ti0 2 contamination.
  • the results show that the optimum synthesis has the following characteristics: a high ethene pressure; synthesis gel ageing; peroxide presence; absence of alkali metal cations; and low aluminium content.

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  • Chemical & Material Sciences (AREA)
  • Organic Chemistry (AREA)
  • Life Sciences & Earth Sciences (AREA)
  • General Life Sciences & Earth Sciences (AREA)
  • Geology (AREA)
  • Engineering & Computer Science (AREA)
  • Materials Engineering (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Inorganic Chemistry (AREA)
  • Oil, Petroleum & Natural Gas (AREA)
  • Silicates, Zeolites, And Molecular Sieves (AREA)
  • Catalysts (AREA)
  • Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)

Abstract

La fabrication d'un zéolithe Bêta substitué s'effectue sous forte pression d'éthène, qu'on aura avantage à accompagner d'un vieillissement du gel de synthèse et d'une faible teneur en aluminium.
PCT/EP1994/002457 1993-07-23 1994-07-23 Procede de fabrication d'un zeolithe Ceased WO1995003249A1 (fr)

Priority Applications (4)

Application Number Priority Date Filing Date Title
BR9407200A BR9407200A (pt) 1993-07-23 1994-07-23 Processo para a fabricação de um TI-,V-ou ZR-Beta-Zeólito e Ti-,V-ou ZR-Beta-Zeólitos obtidos
EP94925391A EP0710216A1 (fr) 1993-07-23 1994-07-23 Procede de fabrication d'un zeolithe
JP7504956A JPH09500860A (ja) 1993-07-23 1994-07-23 ゼオライトの製造法
AU75328/94A AU678597B2 (en) 1993-07-23 1994-07-23 Process for the manufacture of a zeolite

Applications Claiming Priority (4)

Application Number Priority Date Filing Date Title
USPCT/EP93/01972 1993-07-23
PCT/EP1993/001972 WO1994002245A1 (fr) 1992-07-24 1993-07-23 Catalyseurs et leur emploi dans l'oxydation d'hydrocarbures satures
GB9406432.6 1994-03-31
GB9406432A GB9406432D0 (en) 1993-07-23 1994-03-31 Process for the manufacture of a zeolite

Publications (1)

Publication Number Publication Date
WO1995003249A1 true WO1995003249A1 (fr) 1995-02-02

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PCT/EP1994/002457 Ceased WO1995003249A1 (fr) 1993-07-23 1994-07-23 Procede de fabrication d'un zeolithe

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EP (1) EP0710216A1 (fr)
JP (1) JPH09500860A (fr)
AU (1) AU678597B2 (fr)
BR (1) BR9407200A (fr)
CA (1) CA2167279A1 (fr)
CZ (1) CZ18596A3 (fr)
PL (1) PL312687A1 (fr)
WO (1) WO1995003249A1 (fr)

Cited By (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO1995026928A1 (fr) * 1994-03-31 1995-10-12 Exxon Chemical Patents Inc. Zeolites et procedes d'utilisation de celles-ci
FR2730723A1 (fr) * 1995-02-17 1996-08-23 Rhone Poulenc Chimie Zeolithe ti-beta, son procede de preparation et son utilisation comme catalyseur d'oxydation
FR2869894A1 (fr) * 2004-05-10 2005-11-11 Inst Francais Du Petrole Methode de synthese de metalloaluminosilicate cristallise par synthese directe

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HUE063679T2 (hu) 2019-06-12 2024-01-28 Nouryon Chemicals Int Bv Eljárás diacil-peroxidok elõállítására
WO2020249692A1 (fr) * 2019-06-12 2020-12-17 Nouryon Chemicals International B.V. Procédé d'isolement d'acide carboxylique à partir d'un flux latéral aqueux
ES2961184T3 (es) 2019-06-12 2024-03-08 Nouryon Chemicals Int Bv Proceso para la producción de peróxidos de diacilo
WO2020249689A1 (fr) 2019-06-12 2020-12-17 Nouryon Chemicals International B.V. Procédé de production de peroxyesters
EP3983370B1 (fr) 2019-06-12 2023-08-02 Nouryon Chemicals International B.V. Procédé de production de péroxydes de diacyle

Citations (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
EP0158491A2 (fr) * 1984-04-10 1985-10-16 Imperial Chemical Industries Plc Synthèse de produits zéolitiques
ES2037596A1 (es) * 1991-07-31 1993-06-16 Univ Politecnica De Valencia E Sintesis de un silicoaluminotitanato isomorfo a la zeolita beta, activo para la oxidacion selectiva de compuestos organicos.

Patent Citations (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
EP0158491A2 (fr) * 1984-04-10 1985-10-16 Imperial Chemical Industries Plc Synthèse de produits zéolitiques
ES2037596A1 (es) * 1991-07-31 1993-06-16 Univ Politecnica De Valencia E Sintesis de un silicoaluminotitanato isomorfo a la zeolita beta, activo para la oxidacion selectiva de compuestos organicos.

Non-Patent Citations (2)

* Cited by examiner, † Cited by third party
Title
DATABASE WPI Week 9327, Derwent World Patents Index; AN 93-215789 *
M.A. CAMBLOR ET AL., JOURNAL OF THE CHEMICAL SOCIETY, CHEMICAL COMMUNICATIONS, no. 8, 1992, LETCHWORTH GB, pages 589 - 590 *

Cited By (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO1995026928A1 (fr) * 1994-03-31 1995-10-12 Exxon Chemical Patents Inc. Zeolites et procedes d'utilisation de celles-ci
FR2730723A1 (fr) * 1995-02-17 1996-08-23 Rhone Poulenc Chimie Zeolithe ti-beta, son procede de preparation et son utilisation comme catalyseur d'oxydation
FR2869894A1 (fr) * 2004-05-10 2005-11-11 Inst Francais Du Petrole Methode de synthese de metalloaluminosilicate cristallise par synthese directe

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EP0710216A1 (fr) 1996-05-08
CA2167279A1 (fr) 1995-02-02
AU7532894A (en) 1995-02-20
PL312687A1 (en) 1996-05-13
AU678597B2 (en) 1997-06-05
BR9407200A (pt) 1996-09-17
CZ18596A3 (en) 1996-07-17
JPH09500860A (ja) 1997-01-28

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