[go: up one dir, main page]

WO1997029991A1 - PROCEDE DE PREPARATION D'UNE ZEOLITE BETA CONTENANT Ti ET SANS Al - Google Patents

PROCEDE DE PREPARATION D'UNE ZEOLITE BETA CONTENANT Ti ET SANS Al Download PDF

Info

Publication number
WO1997029991A1
WO1997029991A1 PCT/ES1997/000032 ES9700032W WO9729991A1 WO 1997029991 A1 WO1997029991 A1 WO 1997029991A1 ES 9700032 W ES9700032 W ES 9700032W WO 9729991 A1 WO9729991 A1 WO 9729991A1
Authority
WO
WIPO (PCT)
Prior art keywords
process according
solution
range
beta
impregnated
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/ES1997/000032
Other languages
English (en)
Spanish (es)
Inventor
Avelino Corma Canos
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.)
Consejo Superior de Investigaciones Cientificas CSIC
Universidad Politecnica de Valencia
Original Assignee
Consejo Superior de Investigaciones Cientificas CSIC
Universidad Politecnica de Valencia
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
Application filed by Consejo Superior de Investigaciones Cientificas CSIC, Universidad Politecnica de Valencia filed Critical Consejo Superior de Investigaciones Cientificas CSIC
Publication of WO1997029991A1 publication Critical patent/WO1997029991A1/fr
Anticipated expiration legal-status Critical
Ceased legal-status Critical Current

Links

Classifications

    • 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
    • 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
    • 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
    • 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
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C45/00—Preparation of compounds having >C = O groups bound only to carbon or hydrogen atoms; Preparation of chelates of such compounds
    • C07C45/27—Preparation of compounds having >C = O groups bound only to carbon or hydrogen atoms; Preparation of chelates of such compounds by oxidation
    • C07C45/28—Preparation of compounds having >C = O groups bound only to carbon or hydrogen atoms; Preparation of chelates of such compounds by oxidation of CHx-moieties

Definitions

  • the present invention relates to a crystalline material of a microporous nature to its preparation process, and its use as a catalyst for the selective oxidation of organic compounds
  • This material hereinafter referred to as Ti-Beta, contains Si and Ti in network positions
  • the material prepared by our procedure is also structurally and compositionally related to a Ti-Beta zeolite developed in patent ES-2037596, whose empirical formula in its calcined and anhydrous state can be represented by M 2 / nX0 2 bT ⁇ 0 2 aY0 2 (in where M is a vation cation n, Y corresponds to one or several elements with an oxidation state + 4, such as for example Si, Ge, V, X corresponds to one or several cations with a formal oxidation state of + 3, 10 ⁇ a ⁇ 100, and O b / a ⁇ 0 1
  • This material can be used as a catalyst for the selective oxidation of organic compounds using organic or inorganic peroxides and hydroperoxides as oxidizing agents
  • the preparation process for Beta-Ti disclosed in ES-2037596 involves the crystallization of a reaction mixture prepared by consecutive hydrolysis of a source of Ti and a source of Si, in a basic solution followed by the addition
  • the solid containing T ⁇ 0 S ⁇ 0 2 and 2 can be prepared by coprecipitation •? Or both as a cogel, followed by drying at a temperature adequate and atmospheric pressure or under vacuum conditions
  • a source of sili ⁇ cio hydrolyses in an acid solution (for example diluted HCL) and then, and in the same solution, a source of Ti is hydrolyzed in order to obtain a clear solution.
  • H 2 0 2 can be added to this solution.
  • the pH of the resulting solution is increased to a value such that coprecipitation of Ti0 2 -Si0 2 cogel (optionally including X 2 0 3 ) takes place.
  • the source of Ti may be halides of Ti, and organic derivatives of Ti such as, for example, alkyltitanates. Among the latter, tetareis or tetrabutyl titanate is preferred.
  • the source of Si is preferably selected from alkylsilicates among which tetraethyl is preferred.
  • the molar Ti0 2 / Si0 2 ratio in this cogel is greater than zero and preferably in the range from 0.2 to 0001, and more preferably in the range 0.1 -0025.
  • the reaction mixture After impregnation of the dried solid, with the solution containing the structure directing agent and the mineralizer (and optionally H 2 0 2 ), the reaction mixture crystallizes at the appropriate temperature, either under static conditions or with stirring Suitable temperatures are in the range 373-453K, and preferably in the range 393-443K, and more preferably at 400-420k.
  • the composition of the reaction mixture is characterized by its low H 2 0 content, with a molar ratio H 2 0 / SiO 2 preferably below 10, and more preferably in the range 4-6.
  • the molar ratio Q / Si0 2 (where Q represents the structure manager) is in the range 0.15-0.80, and preferably in the range 0.20-0.50, and more preferably 0.30-0.45.
  • Example 1 This example illustrates the preparation of a cogel T ⁇ 0 2 .S ⁇ 0 2 to be usa ⁇ do in crystallization of Ti-Beta zeolite
  • An acid solution is prepared by mixing 10 g of deionized H 2 0 and 10 g of a 0 1 N solution of HCI Then 24 90 g of tetraethylorthosilicate (TEOS) are hydrolyzed in this solution at room temperature, under a solution prepared by mixing 55g of Isopropanol and 1 36 g of tetrabutyl titanate (TBT) are added, stirring, to the previous solution, obtaining a clear solution. At this time, 1.88 g of 40% aqueous tetrapropylammonium hydroxide is added under stirring. The PH increases from ⁇ 2 to ⁇ 6 This causes the abrupt precipitation of a gel that is kept under stirring for 2.5 hours in a closed container. After this the container is moved to an oven and dried at 373K for 20 hours.
  • TEOS tetraethylorthosilicate
  • This example illustrates the preparation of Al-free Ti-Beta zeolite or other trivalent cation.
  • This example illustrates the catalytic activity of the free Ti-Beta of Al and with 2.8% of T00 2 by weight, in the oxidation of 1-hexene 14 2 g of 1-hexene (165 mmol), 4 0 g of H 2 0 2 35wt% (41 3 mmol), and 100 g of catalyst were placed in a glass reactor, using methanol (118g) as solvent The reaction temperature was 50 ° C After 2h of reaction the olefin conversion was 30% With an epoxide selectivity of 70%, and 30 of the methyl glycoleter
  • This example illustrates the catalytic activity of Ti-Beta, described in example 3, for the hydroxylation of phenol 47.2 g of phenol, 92 4 of water, 2 6 g of
  • H 2 0 2 (35% wt) and 2 25g of catalyst, were reacted at 80 ° C After 3 hours, the conversion of H 2 0 2 was 95%, the selectivity to catechol plus hydroquinone being 63% with a catechol / hydroquinone ratio of 1 1

Landscapes

  • Chemical & Material Sciences (AREA)
  • Organic Chemistry (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Inorganic Chemistry (AREA)
  • Engineering & Computer Science (AREA)
  • Materials Engineering (AREA)
  • Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
  • Catalysts (AREA)

Abstract

L'invention concerne un procédé de synthèse de zéolite bêta avec Si et Ti comme uniques composants de réseau. Le procédé de préparation implique la cristallisation d'un cogel de TiO2-SiO2 imprégné d'une solution qui contient une base organique. Dans sa forme calcinée et anhydre, le matériau microporeux possède une composition chimique qui correspond à la formule empirique: a TiO2: SiO2. Dans cette formule, a a une valeur supérieure à zéro et inférieure à 0,07. Ce matériau joue le rôle d'un catalysateur pour l'oxydation sélective de composés organiques utilisant du peroxyde d'hydrogène et des peroxydes ou hydroperoxydes organiques en tant qu'agents d'oxydation.
PCT/ES1997/000032 1996-02-16 1997-02-14 PROCEDE DE PREPARATION D'UNE ZEOLITE BETA CONTENANT Ti ET SANS Al Ceased WO1997029991A1 (fr)

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
ESP9600370 1996-02-16
ES9600370 1996-02-16

Publications (1)

Publication Number Publication Date
WO1997029991A1 true WO1997029991A1 (fr) 1997-08-21

Family

ID=8293836

Family Applications (1)

Application Number Title Priority Date Filing Date
PCT/ES1997/000032 Ceased WO1997029991A1 (fr) 1996-02-16 1997-02-14 PROCEDE DE PREPARATION D'UNE ZEOLITE BETA CONTENANT Ti ET SANS Al

Country Status (1)

Country Link
WO (1) WO1997029991A1 (fr)

Cited By (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
FR2784671A1 (fr) * 1998-10-19 2000-04-21 Rhodia Chimie Sa Procede de preparation d'une titanozeosilite de type mfi, produit obtenu et ses applications en catalyse
EP1167332A1 (fr) * 2000-06-22 2002-01-02 Ube Industries, Ltd. Procédé pour la préparation de phénols dihydriques
CN113443635A (zh) * 2020-03-26 2021-09-28 中国石油天然气股份有限公司 一种含钛Beta分子筛及其合成方法

Citations (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO1994002245A1 (fr) * 1992-07-24 1994-02-03 Exxon Chemical Patents Inc. Catalyseurs et leur emploi dans l'oxydation d'hydrocarbures satures
US5374747A (en) * 1993-12-23 1994-12-20 Arco Chemical Technology, L.P. Epoxidation process and catalyst therefore
EP0659685A1 (fr) * 1993-12-23 1995-06-28 ARCO Chemical Technology, L.P. Procédé d'époxydation et catalyseur à cet effet
US5474754A (en) * 1994-08-15 1995-12-12 Arco Chemical Technology, L.P. Preparation of an aluminosilicotitanate isomorphous with zeolite beta
EP0747324A1 (fr) * 1995-06-07 1996-12-11 ARCO Chemical Technology, L.P. Procédé de préparation de zéolithe bêta essentiellement silicique

Patent Citations (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO1994002245A1 (fr) * 1992-07-24 1994-02-03 Exxon Chemical Patents Inc. Catalyseurs et leur emploi dans l'oxydation d'hydrocarbures satures
US5374747A (en) * 1993-12-23 1994-12-20 Arco Chemical Technology, L.P. Epoxidation process and catalyst therefore
EP0659685A1 (fr) * 1993-12-23 1995-06-28 ARCO Chemical Technology, L.P. Procédé d'époxydation et catalyseur à cet effet
US5474754A (en) * 1994-08-15 1995-12-12 Arco Chemical Technology, L.P. Preparation of an aluminosilicotitanate isomorphous with zeolite beta
EP0747324A1 (fr) * 1995-06-07 1996-12-11 ARCO Chemical Technology, L.P. Procédé de préparation de zéolithe bêta essentiellement silicique

Non-Patent Citations (2)

* Cited by examiner, † Cited by third party
Title
CAMBLOR M A ET AL: "SYNTHESIS OF A TITANIUMSILICOALUMINATE ISOMORPHOUS TO ZEOLITE BETA AND ITS APPLICATION AS A CATALYST FOR THE SELECTIVE OXIDATION OF LARGE ORGANIC MOLECULES", JOURNAL OF THE CHEMICAL SOCIETY, CHEMICAL COMMUNICATIONS, no. 8, 15 April 1992 (1992-04-15), pages 589 - 590, XP000384413 *
CAMBLOR MIGUEL A. ET AL.: "A new efficient method for the synthesis of Ti-Beta zeolite oxidation catalyst", APPLIED CATALYSIS, vol. 133, no. 2, 1995, pages L185 - L189, XP002032291 *

Cited By (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
FR2784671A1 (fr) * 1998-10-19 2000-04-21 Rhodia Chimie Sa Procede de preparation d'une titanozeosilite de type mfi, produit obtenu et ses applications en catalyse
WO2000023185A1 (fr) * 1998-10-19 2000-04-27 Rhodia Chimie Procede de preparation d'une titanozeosilite de type mfi, produit obtenu et ses applications en catalyse
EP1167332A1 (fr) * 2000-06-22 2002-01-02 Ube Industries, Ltd. Procédé pour la préparation de phénols dihydriques
CN113443635A (zh) * 2020-03-26 2021-09-28 中国石油天然气股份有限公司 一种含钛Beta分子筛及其合成方法
CN113443635B (zh) * 2020-03-26 2023-02-10 中国石油天然气股份有限公司 一种含钛Beta分子筛及其合成方法

Similar Documents

Publication Publication Date Title
CA2142336C (fr) Atiere de type zeolite, avec de tres grands pores et un reseau constitue de silicone et d'oxydes de titane; sa preparation par synthese et son utilisation pour l'oxydation selective de produits organiques
CA1196925A (fr) Methode d'epoxydation de composes olefiniques
CN101229510B (zh) 一种含铋的硅酸盐的合成和应用
JP3049086B2 (ja) 飽和炭化水素鎖の酸化
EP1110910B1 (fr) Tamis moléculaire de silicalite de titane et procédé pour sa préparation
EP1731515B1 (fr) Procédé de fabrication d'oxyde de propylène
DK157361B (da) Fremgangsmaade til fremstilling af titanmodificeret poroest, krystallinsk siliciumoxid og anvendelse af dette.
US20010001656A1 (en) Crystalline microporous and mesoporous metal silicates and use thereof
JP2022506869A (ja) 階層的細孔を有するｔｓ－１分子篩の製造方法
ES2236000T3 (es) Materiales microporosos de alta superficie activos en reacciones de oxidacion tiq-6 y metiq-6.
KR102575606B1 (ko) 계층적 다공성 ts-1 분자체의 제조 방법
JP2001517147A (ja) Ｔｉ含有分子ふるいから誘導される触媒組成物
JPH1095610A (ja) 微孔性および中孔性の金属珪酸塩の製造法、結合剤不含の成形体および該化合物からなる酸化触媒
US5474754A (en) Preparation of an aluminosilicotitanate isomorphous with zeolite beta
CA2399192C (fr) Procede servant a produire une zeolithe contenant du titane
WO2002030821A1 (fr) Zeolite itq-16
US5656252A (en) Process for obtaining zeolites containing titanium
WO1997029991A1 (fr) PROCEDE DE PREPARATION D'UNE ZEOLITE BETA CONTENANT Ti ET SANS Al
JPS62162614A (ja) 合成ゼオライト物質及びその製造法
EP1386885A1 (fr) Procédé de préparation d'un silicate de titane cristallin microporeux
JP2002527346A (ja) Ｍｆｉタイプのチタノゼオシライトの製造方法、それによって得られる生成物およびその触媒への使用
WO2000023377A1 (fr) Procede de preparation d'une silicalite de titane de type mel, produit obtenu et ses applications en catalyse
JP2004523457A (ja) アルカリ性媒体中でのゼオライトｉｔｑ−１６の合成
JPH09208511A (ja) 芳香族ヒドロキシ化合物の製造方法
US6074624A (en) Titanostannosilicates and preparation thereof

Legal Events

Date Code Title Description
AK Designated states

Kind code of ref document: A1

Designated state(s): CA JP US

AL Designated countries for regional patents

Kind code of ref document: A1

Designated state(s): AT BE CH DE DK ES FI FR GB GR IE IT LU MC NL PT SE

121 Ep: the epo has been informed by wipo that ep was designated in this application
122 Ep: pct application non-entry in european phase
NENP Non-entry into the national phase

Ref country code: JP

Ref document number: 97529021

Format of ref document f/p: F

NENP Non-entry into the national phase

Ref country code: CA