+

WO1998035910A1 - Catalyseurs metalliques a tamis moleculaire - Google Patents

Catalyseurs metalliques a tamis moleculaire Download PDF

Info

Publication number
WO1998035910A1
WO1998035910A1 PCT/EP1998/000765 EP9800765W WO9835910A1 WO 1998035910 A1 WO1998035910 A1 WO 1998035910A1 EP 9800765 W EP9800765 W EP 9800765W WO 9835910 A1 WO9835910 A1 WO 9835910A1
Authority
WO
WIPO (PCT)
Prior art keywords
solution
molecular sieve
titanium
alkali metal
precipitate
Prior art date
Application number
PCT/EP1998/000765
Other languages
English (en)
Inventor
Jihad Dakka
Georges Marie Karel Mathys
Original Assignee
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
Application filed by Exxon Chemical Patents Inc. filed Critical Exxon Chemical Patents Inc.
Publication of WO1998035910A1 publication Critical patent/WO1998035910A1/fr

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

Definitions

  • the present invention relates to metal containing molecular sieve catalysts in particular titanium molecular sieve catalysts and in particular to a method of manufacture of such catalysts
  • Titanium containing molecular sieve catalysts are well known examples of such catalysts are the titanium containing silicalite catalysts based on a crystalline synthetic material comprising silicon and titanium oxides and which are characterised by an infra red absorption band at around 950 cm " ' ' to 960 cm - 1 and typically are of the general formula xTiO2(1 -x)SiO2
  • ⁇ is from 0 0001 to 0 10 preferably 0 1 to 4
  • These catalysts known as TS-1 ana TS-2 are typically prepared in the absence of aluminium from a mixture containing a source of silicon oxide a source of titanium oxide a nitrogenated organic base and water
  • Various specific processes for the preparation of titanium silica te catalysts are described in for example Belgian Patent 886812 EP 0190609 A US 3329481 US4410501 US 4666692 US4701428 EP 031 1983 EP 0376453 M G Cle ⁇ ci et al Journal of Catalysis 129. 159-167 (1991 ), M A Ugina et al Applied Catalysis A General.
  • Typical synthesis mixtures yielding Ti-Beta zeolite after hydrothermal treatment have an initial molar composition within the following ranges
  • 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 H2O2 per mole of TEOT when that is used as the source of titanium
  • a further example of a titanium containing zeolite is Ti MCM-41
  • Various methods for the manufactute of this catalyst are described in for example in A Corma et al , J Chem Soc Chem Commun, page 1635, (1995), A Corma, et al J Chem Soc Chem Commun , page 147 (1994), and T Blasco et al , J Catalysis 156, 65-74, (1995)
  • the present invention provides a method for the synthesis of a metal isomorphous substituted molecular sieve which method comprises
  • the level of alkali metal within the organic structure directing agent is at least 50 ppm
  • the metal may be any metal which may be incorporated in the framework of a molecular sieve and includes for example titanium and chromium
  • the process of the present invention is applicable to any synthesis of a metal containing molecular sieve which is normally sensitive to the presence of alkali metal in the template during syntheses of the molecular sieve
  • the metal is titanium and the metal oxide is si ca/titania
  • the use of an intermediate silica titania co-precipitate or co-gel in the synthesis of zeolite isomorphous substituted molecular sieves enables the use of impure templating agents
  • templating agents which contain relatively high levels of alkali metal species such as Na+ and K+ cations
  • the levels of sodium are 20 ppm or less and the levels of
  • titanium isomorphous substituted molecular sieves may be prepared by this method Which molecular sieve is produced will depend on the templating agent used and the presence of other precursors for the particular zeolite desired It is envisaged that the process will be particularly suitable for the production of titanium isomorphous substituted si calite molecular sieves such as beta and MCM-41 molecular sieves
  • co-precipitate or co-gel may be made by any of the known processes in the art
  • suitable co-precipitates and co-gels may be made according to EP 031 1 983 which describes the synthesis of a co-precipitate, WO95/03249 WO95/03250 and sol-gel methods as disclosed in M A Ugina, et al Applied Catalysis A General 124 391 -408 P Serrano, et al Microporous Materials 4 273-282 and M A Camblor et al Applied Catalysis A General 133 L185- L189 ( 1995)
  • the desired titanium isomorphous substituted molecular sieve may be derived from the co-precipitate or the co-gel using organic templating agents containing high levels of alkali metal cations via either the hydrothermal crystallization of a liquid gel produced by the complete dissolution of either a co-precipitate or a co- gel, by the formation of a liquid gel with incomplete dissolution of the co-gel or co- precipitate or by incipient wetness impregnation of the co-precipitate or co-gel as described in M A Camblor et al Applied Catalysis A General, 133 L185-L189 (1995) and US5474754
  • TS-1 may be made by the following process
  • the silica titania co-precipitate may be formed by mixing any suitable silica source together with a source of titanium to form a co-solution which may then be subject to the appropriate conditions for co- precipitation
  • the silica source such as for example tetra ethyl ortho silicate (TEOS) is hydrolysed in an acid environment preferably a nitric acid environment followed by addition of a solution of a titanate such as for example tetrapropyl ortho titanate (TPOTi) in a suitable solvent such as for example isopropanoi
  • TPOTi tetrapropyl ortho titanate
  • the titanate is not hydroiysed before mixing with the silica source
  • the silica titania may be co-precipitated by removal of water and the solvent used to prepare the co-solution
  • heating to a temperature in the range of room temperature to 200°C is particularly suitable preferably it is in the range 80 to 120°C
  • the silica titania co-precipitate may then be used for the production of titanium isomorpnous substituted molecular sieves such as s ⁇ l ⁇ cal ⁇ te-1 by dissolution in an appropriate templating agent e g tetra propyl ammonium hydroxide (TPAOH)
  • TPAOH tetra propyl ammonium hydroxide
  • the resultant solution may then optionally be seeded with colloidal molecular sieve such as colloidal silicalite which may be prepared according to the procedure described in for example WO93/08125 the disclosure of which is incorporated by reference
  • the titanium containing molecular sieve e g s ⁇ l ⁇ cal ⁇ te-1 may be obtained by crystallisation whilst stirring at an appropriate temperature and over an appropriate period of time
  • 1 to 30 days preferably 1 to 10 days and most preferably is at least 3 days at 50 to 200 C preferably 130 to 180"C to be particularly suitable for the formation of isomorphous titanium s ⁇ l ⁇ ca t
  • the crystallised product obtained may be removed from the crystallisation medium by filtration and the washed
  • Temporalat'ng agent may be used in the formation of the co-precipitate or co-gel In this aspect the templating agent will need to be substantially free of alkali metal cations
  • Typical templating agents include for example TEAOH TPAOH TMAOH and dibenzyldimethyl ammonium hydroxide
  • the titanium containing catalysts of the present invention are useful catalysts particularly for hydrocarbon oxidation
  • the direct oxidation of saturates to introduce functional groups such as keto ⁇ es and alcohols using a heterogeneous catalyst system would be extremely attractive especially if there is high conversions and selectivity for either alcohol or ketone or even if conversion is low there is relatively high selectivity for one of the products
  • titanium isomorphous substituted molecular sieve catalysts of the present invention and in particular titanium s ⁇ l ⁇ cal ⁇ te-1 have been found to be an active oxidation catalyst especially for reactions involving hydrogen peroxide as oxidant
  • the new catalysts may also be effective with organic hydroperoxide oxidants
  • the solution contains from 10-100 preferably 10 to 70 wt % hydrogen peroxide for example diluted hydrogen peroxide (30 to 40% by weight in water) It is also preferred that a polar solvent be present when aqueous hydrogen peroxide is used to increase the solubility of the organic compound in the H202 aqueous phase
  • suitable solvents include acetone and methanol
  • the oxidising agent may be an organic hydroperoxide
  • suitable organic hydroperoxides include di-isopropyl benzene monohydroperoxide, cumene hydroperoxide tert butyl hydroperoxide cyclohexylhydroperoxide ethylbenzene hydroperoxide tert amyl hydroperoxide tetra ne hydroperoxide and the compound containing the saturated organic group is liquid or in the dense phase at the conditions used for the reaction
  • the oxidant is a an organic hydroperoxide then tertiary butyl hydroperoxide is particularly beneficial since the tertiary butyl alcohol produced can readily be converted to the valuable isobutylene molecule
  • the preferred oxidising agent is hydrogen peroxide
  • the saturated groups which may be oxidised by the process of this invention include long or short branched or linear alkanes containing 3 or more, preferably 3 to 30 more preferably 3 to 12 carbon atoms cyclic alkanes and mono- and poly- alkyl aromatics in which at least one of the alkyl groups contain at least two preferably at least three more preferably 3 to 18 most preferably 3 to 12 carbon atoms and mono- and poly-alkyl cyclic alkanes
  • the process of the invention is equally applicable to the epoxidation of olefins dienes, the production of ether glycols diols the oxidation of alcohols or ketones, aldehydes to acids and the hydroxylation of aromatics
  • saturated groups may be oxidised with high selectivity to alcohols and ketones under relatively mild conditions
  • the reactivity sequence for the aliphatic compounds slows down from tertiary to secondary and to primary compounds
  • the process uses mild temperature and pressure conditions and the conversion and yield are high and by-product formation is small
  • the oxidant conversion is high
  • the optimum reaction temperature is between 50 and 150°C preferably about 100°C when using hydrogen peroxide
  • the oxidation reaction may be in the liquid or dense phase or in the gaseous phase preferably the reactions are in the liquid phase
  • the reaction can be carried out at room temperature but higher reaction rates may be involved at higher temperatures, for example under reflux conditions
  • Increase of the pressure either due to the autogeneous pressure created by the heated reactants or by use of a pressurised reactor still higher temperatures can be reached
  • Use of higher pressures in the range of 1 to 100 bars (105 to 107Pa) can increase the conversion and selectivity of the reaction
  • the oxidation reaction can be carried out under batch conditions or in a fixed bed and the use of the heterogeneous catalyst enables a continuous reaction in system
  • the catalyst is stable under the reaction conditions and can be totally recovered and reused
  • the oxidation process of the present invention is preferably carried out in the presence of a solvent Choice of solvent is important since it should dissolve the organic phase and the aqueous phase when hydrogen peroxide is used which is generally present due to the use of aqueous hydrogen peroxide as the oxidising agent where organic hydroperoxides are used suitable organic solvents should be used
  • Polar compounds are preferred which are inert under reaction conditions and examples of preferred solvents are alcohols, ketones and ethers, with a number of carbon atoms which is not too high, preferably less than or equal to 6 Methanol or tertiary butanol is the most preferred of the alcohols, acetone and butanone are the most preferred of the ketones
  • the amount of solvent may influence the reaction product and the conversion, the choice of solvent and the amount
  • the catalyst was characterized by XRD UV-Vis, IR ICP and its catalytic performance in n-heptane oxidation with 30% H2O2
  • the catalytic test results are summarized in Table 1
  • TEOS Tetra Ethyl ortho Silicate
  • TPAOH Tetra Propylammonium Hydroxide
  • the catalytic test shows the following results (Table 1 )
  • TS-1 was synthesized using a freshly prepared silica -titania coprecipitate
  • the silica-titania coprecipitate was made by hydrolizing TEOS and TEOT in a 0 05M HNO3 solution
  • the resulting clear solution was heated at 100°C under stirring until a white solid material formed This material was then dried overnight at 120°C to remove the remaining water and alcohol
  • the coprecipetate was found to be amorphous by X-ray powder diffraction Typical procedure is as follows 300g TEOS ( 1 44 mol) was added slowly to 1460 g 0 05M HNO3 (7 26 g HNO3 65%) 16.22g TEOT(0 048 mol) was disolved in 162g isopropanol and was added dropwise to the silicen solution (addition time 5h) Si Ti ratio 30 1
  • the catalytic test shows the following results (table 1 )
  • the catalyst were tested in n-heptane oxidation with aqueous H2O2 30 %
  • the reaction conditions are 20 4 g n-heptane (0 204 mol) 44 4 g H2O2 30 % (0 39 mole), 1 g catalyst 71 1 g acetone 100° C, under magnetic stirring
  • the results are summarized in the following table

Landscapes

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

Abstract

La présente invention concerne des catalyseurs métalliques et plus particulièrement des catalyseurs à tamis moléculaire substitué, isomorphe et contenant du titane, et leur procédé de fabrication. Ledit procédé de fabrication présente une caractéristique importante en ce qu'on peut utiliser des agents matriciels relativement impurs par rapport à des cations de métaux alcalins.
PCT/EP1998/000765 1997-02-14 1998-02-11 Catalyseurs metalliques a tamis moleculaire WO1998035910A1 (fr)

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
GB9703093.6 1997-02-14
GBGB9703093.6A GB9703093D0 (en) 1997-02-14 1997-02-14 Metal molecular sieve catalysts

Publications (1)

Publication Number Publication Date
WO1998035910A1 true WO1998035910A1 (fr) 1998-08-20

Family

ID=10807665

Family Applications (1)

Application Number Title Priority Date Filing Date
PCT/EP1998/000765 WO1998035910A1 (fr) 1997-02-14 1998-02-11 Catalyseurs metalliques a tamis moleculaire

Country Status (2)

Country Link
GB (1) GB9703093D0 (fr)
WO (1) WO1998035910A1 (fr)

Cited By (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
FR2784672A1 (fr) * 1998-10-19 2000-04-21 Rhodia Chimie Sa Procede de preparation d'une silicalite de titane de type mel, produit obtenu et ses applications en catalyse
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
WO2003042101A3 (fr) * 2001-11-15 2003-09-12 Pq Holding Inc Tamis moleculaires ts-pq au titano-silicate ; procedes de synthese et utilisation
CN110054199A (zh) * 2019-06-11 2019-07-26 兰州理工大学 一种绿色节能合成Fe-ZSM-5分子筛的方法
CN115286008A (zh) * 2022-07-21 2022-11-04 武汉理工大学 一种表面只含骨架内六配位Ti的Ti-MCM-41分子筛及其制备方法、深度脱硫应用

Citations (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
EP0292363A2 (fr) * 1987-05-22 1988-11-23 Rhone-Poulenc Chimie Zéolites de structures MFI à base de silice et d'oxyde de titane et procédé de synthèse de celles-ci
EP0311983A2 (fr) * 1987-10-12 1989-04-19 Enichem Anic S.r.l. Procédé de préparation de silicalite de titane
EP0543247A1 (fr) * 1991-11-21 1993-05-26 BASF Aktiengesellschaft Procédé de préparation de cristaux de silicate de titane à structure zéolite essentiellement exempts de métaux alcalins
EP0659685A1 (fr) * 1993-12-23 1995-06-28 ARCO Chemical Technology, L.P. Procédé d'époxydation et catalyseur à cet effet

Patent Citations (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
EP0292363A2 (fr) * 1987-05-22 1988-11-23 Rhone-Poulenc Chimie Zéolites de structures MFI à base de silice et d'oxyde de titane et procédé de synthèse de celles-ci
EP0311983A2 (fr) * 1987-10-12 1989-04-19 Enichem Anic S.r.l. Procédé de préparation de silicalite de titane
EP0543247A1 (fr) * 1991-11-21 1993-05-26 BASF Aktiengesellschaft Procédé de préparation de cristaux de silicate de titane à structure zéolite essentiellement exempts de métaux alcalins
EP0659685A1 (fr) * 1993-12-23 1995-06-28 ARCO Chemical Technology, L.P. Procédé d'époxydation et catalyseur à cet effet

Non-Patent Citations (4)

* Cited by examiner, † Cited by third party
Title
CAMBLOR M A ET AL: "A NEW HIGHLY EFFICIENT METHOD FOR THE SYNTHESIS OF TI-BETA ZEOLITE OXIDATION CATALYST", APPLIED CATALYSIS A: GENERAL, vol. 133, no. 2, 1995, pages L185 - L189, XP002032291 *
MIGUEL A. CAMBLOR: "Large pore Ti-Beta zeolite with very low aluminium content: an active and selective catalyst for oxidations using hydrogen peroxide", INDUSTRIAL CHEMISTRY LIBRARY, vol. 8, 1996, pages 391 - 404, XP002067432 *
SERRANO D. P. ET AL.: "Evidence of solid-solid transformations during the TS-1 crystallzation from amorphous wetness impregnated SiO2-TiO2 xerogels", MICROPOROUS MATERIALS, vol. 7, no. 6, December 1996 (1996-12-01), pages 309 - 321, XP002067617 *
ZHANG G ET AL: "PREPARATION OF COLLOIDAL SUSPENSIONS OF DISCRETE TS-1 CRYSTALS", CHEMISTRY OF MATERIALS, vol. 9, no. 1, January 1997 (1997-01-01), pages 210 - 217, XP000683976 *

Cited By (7)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
FR2784672A1 (fr) * 1998-10-19 2000-04-21 Rhodia Chimie Sa Procede de preparation d'une silicalite de titane de type mel, produit obtenu et ses applications en catalyse
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
WO2000023377A1 (fr) * 1998-10-19 2000-04-27 Rhodia Chimie Procede de preparation d'une silicalite de titane de type mel, produit obtenu et ses applications en catalyse
WO2003042101A3 (fr) * 2001-11-15 2003-09-12 Pq Holding Inc Tamis moleculaires ts-pq au titano-silicate ; procedes de synthese et utilisation
CN110054199A (zh) * 2019-06-11 2019-07-26 兰州理工大学 一种绿色节能合成Fe-ZSM-5分子筛的方法
CN115286008A (zh) * 2022-07-21 2022-11-04 武汉理工大学 一种表面只含骨架内六配位Ti的Ti-MCM-41分子筛及其制备方法、深度脱硫应用

Also Published As

Publication number Publication date
GB9703093D0 (en) 1997-04-02

Similar Documents

Publication Publication Date Title
EP0659685B1 (fr) Procédé d'époxydation et catalyseur à cet effet
US6042807A (en) Tellurium-containing molecular sieves
US5977009A (en) Catalyst compositions derived from titanium-containing molecule sieves
US6710193B2 (en) Process for preparing crystalline microporous and mesoporous metal silicates, products obtainable by said process and their use
US5637715A (en) Process for preparing an oxime a structured catalyst including microporous oxides of silicon, aluminum and titanium
JP3049086B2 (ja) 飽和炭化水素鎖の酸化
US5739076A (en) Catalysts and their use in oxidation of saturated hydrocarbons
CA2399192C (fr) Procede servant a produire une zeolithe contenant du titane
JP2001278619A (ja) 結晶質固体の製造方法
WO1998035910A1 (fr) Catalyseurs metalliques a tamis moleculaire
US5618512A (en) Niobium-containing zeolites
AU678597B2 (en) Process for the manufacture of a zeolite
JPH09512246A (ja) ゼオライト及び該ゼオライトを使用したプロセス
US5406002A (en) Zeolite catalyst and catalysed reactions
GB2322364A (en) Zirconium molecular sieve catalysts
WO1993015035A1 (fr) Oxydation amelioree de chaines d'hydrocarbures satures

Legal Events

Date Code Title Description
AK Designated states

Kind code of ref document: A1

Designated state(s): CA 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

DFPE Request for preliminary examination filed prior to expiration of 19th month from priority date (pct application filed before 20040101)
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
点击 这是indexloc提供的php浏览器服务，不要输入任何密码和下载