WO1995026928A1 - Zeolites et procedes d'utilisation de celles-ci - Google Patents
Zeolites et procedes d'utilisation de celles-ci Download PDFInfo
- Publication number
- WO1995026928A1 WO1995026928A1 PCT/EP1995/001201 EP9501201W WO9526928A1 WO 1995026928 A1 WO1995026928 A1 WO 1995026928A1 EP 9501201 W EP9501201 W EP 9501201W WO 9526928 A1 WO9526928 A1 WO 9526928A1
- Authority
- WO
- WIPO (PCT)
- Prior art keywords
- synthesis mixture
- hydrothermal treatment
- carried out
- zeolite
- source
- Prior art date
Links
Classifications
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07B—GENERAL METHODS OF ORGANIC CHEMISTRY; APPARATUS THEREFOR
- C07B41/00—Formation or introduction of functional groups containing 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
- 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
- B01J29/78—Crystalline aluminosilicate zeolites; Isomorphous compounds thereof of types characterised by their specific structure not provided for in groups B01J29/08 - B01J29/65 containing arsenic, antimony, bismuth, vanadium, niobium, tantalum, polonium, chromium, molybdenum, tungsten, manganese, technetium or rhenium
- B01J29/7815—Zeolite Beta
-
- 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
Definitions
- This invention relates to zeolites, especially those useful as catalysts, their manufacture, and chemical processes using them.
- Zeolite Beta is a large pore high silica zeolite first described in 1967, in U.S. Patent No. 3308069. Its large pore size, based on 12-membered rings, makes it useful in catalysing organic reactions involving relatively large molecules. More recently, a related titanium-containing Beta zeolite has been synthesized and proposed for use as a catalyst, especially for the oxidation of organic molecules - see PCT Application WO 94/02245.
- Redox zeolites are important because they catalyse the oxidation of hydrocarbons, but their synthesis is still at an embryonic stage.
- the present invention provides a Beta zeolite having vanadium in its framework, hereinafter referred to as V-Beta zeolite.
- the invention also provides a process for the manufacture of V-Beta zeolite, wherein a synthesis mixture comprising a source of vanadium, a source of silicon, a source of aluminium, a source of tetraethylammonium ions, and water, is subjected to a hydrothermal treatment.
- the aluminium may be wholly or partly replaced by other cations, especially gallium, boron, or iron.
- the synthesis mixture has a molar composition within the range:
- V-Beta zeolite according to, and produced according to, the invention is advantageously characterized both by a band at about 960cm -1 in its IR spectrum and a band at about 47500cm -1 in its Diffuse Reflectance Spectrum.
- the molar composition is within the range:
- 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. If alkali metal ions, e.g., sodium or potassium ions, are present, they are advantageously present in a molar proportion of SiO 2 :M + of 1: at most 0.5.
- 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 vanadium, vanadyl sulphate; and for aluminium, aluminium powder. If the aluminium is replaced by other cations, suitable sources are, for example; gallium nitrate or oxide; boric acid or an alkoxide thereof, e.g., B(OC H5; or ferric nitrate.
- the tetraethyl ammonium cations are advantageously provided by TEAOH.
- hydrogen peroxide is present in the synthesis mixture, although it may decompose before or during hydrothermal treatment. Preferably it is present in aproportion of 10 to 200 moles per mole of vanadium source.
- hydrogen peroxide is present the oxidation state of the vanadium in the synthesis mixture subjected to hydrothermal treatment may be changed from that of its original source, and/or the oxidation state in the original source may be different from that given above.
- 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 24 hours, followed by elevated temperature ageing, e.g., at 70°C, for from 2 to 6 hours.
- Elevated temperature ageing also causes evaporation of water from the synthesis mixture, if desired reducing the initial volume by as much as 65%, thereby producing a synthesis mixture of a concentration advantageous for hydrothermal treatment.
- the aged mixture 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 SiO 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, 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.
- At least a part of the hydrothermal treatment may be carried out under an atmosphere containing substantial proportions of ethene.
- ethene is present in the reaction vessel from the commencement of the hydrothermal treatment.
- the ethene partial pressure is advantageously 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, HCI, or by bases e.g., ammonium or sodium ions.
- the product may be post-treated, as by steaming.
- the V-Beta zeolite produced by the process of the invention is highly crystalline.
- FIG. 1 the X-ray diffraction spectrum of the uncalcined product
- Fig. 2 the infra-red spectrum of the uncalcined product (trace a) and the calcined product (trace b)
- Fig. 3 the Diffuse Reflectance Spectrum of the uncalcined product.
- the V-Beta zeolite produced according to the invention is useful as a catalyst in all reactions where an acidic catalyst is effective, especially in the production and conversion of organic compounds, for example cracking, hydrocracking, dewaxing, isomerization (including e.g., olefin bond isomerization and skeletal isomerization e.g., of butene), oligomerization, polymerization, alkylation, dealkylation, hydrogenation, dehydrogenation, dehydration, cyclization and aromatization.
- the present invention therefore provides a process for the production or conversion of an organic compound comprising the use of a zeolite catalyst prepared in accordance with the invention.
- the zeolite can also be used (either as initially prepared or in a modified form) in a selective adsorption process e.g. a separation or purification.
- 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.
- organic hydroperoxides avoids the two phase system necessarily associated with aqueous hydrogen peroxide.
- V-Beta zeolite is more effective in the oxidation of larger molecules, e.g., cycloparaffins and cycloolefins.
- 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 alkylaromatic hydrocarbons.
- saturated hydrocarbons e.g., paraffins and cycloparaffins
- alkyl substituents in alkylaromatic 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 O 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 production 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, oxygen, 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, tertamyl 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 dissolving 1.00 g of vanadyl sulphate in 63 ml H 2 O and cooling the resulting blue solution to 5°C before adding 39 ml H O 2 (35% in H 2 O). The resulting orange solution is stirred for 3 hours at 5°C, giving a clear yellow-orange solution.
- Mixture B was produced by adding 0.0316 g Al powder to 29.42 g of TEAOH (40% in H O) and dissolving it by heating at 90°C for 2 hours. Then, 32.72 g of distilled H 2 O were added. This mixture was cooled to 5°C.
- the autoclave was put in an oven and crystallization proceeded without agitation at 140°C for 10 days. After this time the autoclave was cooled and the solids separated from the clear mother liquor by centrifugation at 13,000 rpm.
- the organic template was then removed from the zeolite pores by calcination in a U-tube, initially under nitrogen for 8 hours at 500°C then, after allowing the tube to cool to 400°C, under oxygen for 2 hours at 500°C. The yield was 50% of theory.
- FIG. 1 shows that the product is all Beta zeolite phase.
- Figure 2 shows the band around 960cm -1 shows the vanadium as part of the zeolite framework.
- the band at 47500 -1 in Figure 3 is absent in vanadium-free Beta zeolite.
- V-Beta zeolite produced as described in Example 1 was used as a catalyst for the oxidation of cyclohexane using tert.butyl hydroperoxide (TBHP).
- TBHP tert.butyl hydroperoxide
- 8.42 g (100 mmole)of cyclohexane were treated with 28.32 (246 mmole) of TBHP, in the form of an 80% THBP solution in tert.butyl peroxide, in the presence of 0.15 g of V-Beta, for 7 hours at 100°C, the reaction mixture being subsequently stored at 5 to 10°C for 3 weeks.
- the results are shown in the Table below.
- esters that are cleaved to adipic acid by the zeolite catalyst while standing at low temperatures for 21 days.
- adipic acid already formed may have diffused slowly out of the zeolite during the standing period.
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- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Life Sciences & Earth Sciences (AREA)
- Geology (AREA)
- General Life Sciences & Earth Sciences (AREA)
- Materials Engineering (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Engineering & Computer Science (AREA)
- Inorganic Chemistry (AREA)
- Crystallography & Structural Chemistry (AREA)
- Catalysts (AREA)
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
- Silicates, Zeolites, And Molecular Sieves (AREA)
Abstract
Priority Applications (7)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
PL95316570A PL316570A1 (en) | 1994-03-31 | 1995-03-31 | Zeolites and processes employing them |
EP95913891A EP0752975A1 (fr) | 1994-03-31 | 1995-03-31 | Zeolites et procedes d'utilisation de celles-ci |
BR9507209A BR9507209A (pt) | 1994-03-31 | 1995-03-31 | Zeólito processo para a sua fabricaç o e uso do mesmo |
JP7525412A JPH09512246A (ja) | 1994-03-31 | 1995-03-31 | ゼオライト及び該ゼオライトを使用したプロセス |
AU21113/95A AU2111395A (en) | 1994-03-31 | 1995-03-31 | Zeolites and processes employing them |
CZ962741A CZ274196A3 (en) | 1994-03-31 | 1995-03-31 | Beta-zeolite process of its preparation and use |
KR1019960705384A KR970702213A (ko) | 1994-03-31 | 1995-03-31 | 제올라이트 및 이들을 사용하는 방법(zeolites and processes employing them) |
Applications Claiming Priority (2)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
GB9406434A GB9406434D0 (en) | 1994-03-31 | 1994-03-31 | Zeolites and processes employing them |
GB9406434.2 | 1994-03-31 |
Publications (1)
Publication Number | Publication Date |
---|---|
WO1995026928A1 true WO1995026928A1 (fr) | 1995-10-12 |
Family
ID=10752840
Family Applications (1)
Application Number | Title | Priority Date | Filing Date |
---|---|---|---|
PCT/EP1995/001201 WO1995026928A1 (fr) | 1994-03-31 | 1995-03-31 | Zeolites et procedes d'utilisation de celles-ci |
Country Status (10)
Country | Link |
---|---|
EP (1) | EP0752975A1 (fr) |
JP (1) | JPH09512246A (fr) |
KR (1) | KR970702213A (fr) |
AU (1) | AU2111395A (fr) |
BR (1) | BR9507209A (fr) |
CA (1) | CA2183597A1 (fr) |
CZ (1) | CZ274196A3 (fr) |
GB (1) | GB9406434D0 (fr) |
PL (1) | PL316570A1 (fr) |
WO (1) | WO1995026928A1 (fr) |
Cited By (5)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
EP0967014A1 (fr) * | 1998-06-25 | 1999-12-29 | Institut Français du Pétrole | Catalyseur d'hydrocraquage comprenant une zéolite beta et un élément du groupe VB |
FR2780309A1 (fr) * | 1998-06-25 | 1999-12-31 | Inst Francais Du Petrole | Catalyseur d'hydrocraquage comprenant une zeolithe beta, un element du groupe vb, et un element promoteur choisi dans le groupe forme par le bore, le phosphore et le silicium |
CN1052453C (zh) * | 1996-06-05 | 2000-05-17 | 中国石油化工总公司 | 一种钒硅分子筛(vs-1)的制备方法 |
CN1052452C (zh) * | 1996-06-05 | 2000-05-17 | 中国石油化工总公司 | 一种钒硅分子筛(vs-2)的制备方法 |
US6524470B1 (en) | 1998-05-06 | 2003-02-25 | Institut Francais du Pétrole | Catalyst comprising beta zeolite and promoter element for hydrocracking |
Citations (2)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
WO1993008125A1 (fr) * | 1991-10-23 | 1993-04-29 | Exxon Chemical Patents Inc. | Cristaux ou agglomeres de tamisage moleculaire de dimensions nanometriques et leurs procedes de fabrication |
WO1995003249A1 (fr) * | 1993-07-23 | 1995-02-02 | Exxon Chemical Patents Inc. | Procede de fabrication d'un zeolithe |
-
1994
- 1994-03-31 GB GB9406434A patent/GB9406434D0/en active Pending
-
1995
- 1995-03-31 KR KR1019960705384A patent/KR970702213A/ko not_active Application Discontinuation
- 1995-03-31 CZ CZ962741A patent/CZ274196A3/cs unknown
- 1995-03-31 JP JP7525412A patent/JPH09512246A/ja active Pending
- 1995-03-31 BR BR9507209A patent/BR9507209A/pt unknown
- 1995-03-31 EP EP95913891A patent/EP0752975A1/fr not_active Withdrawn
- 1995-03-31 AU AU21113/95A patent/AU2111395A/en not_active Abandoned
- 1995-03-31 WO PCT/EP1995/001201 patent/WO1995026928A1/fr not_active Application Discontinuation
- 1995-03-31 PL PL95316570A patent/PL316570A1/xx unknown
- 1995-03-31 CA CA002183597A patent/CA2183597A1/fr not_active Abandoned
Patent Citations (2)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
WO1993008125A1 (fr) * | 1991-10-23 | 1993-04-29 | Exxon Chemical Patents Inc. | Cristaux ou agglomeres de tamisage moleculaire de dimensions nanometriques et leurs procedes de fabrication |
WO1995003249A1 (fr) * | 1993-07-23 | 1995-02-02 | Exxon Chemical Patents Inc. | Procede de fabrication d'un zeolithe |
Non-Patent Citations (1)
Title |
---|
TAPAS SEN & AL.: "Novel large-pore vanadium alumino- and boro-silicates with bea structure", JOURNAL OF THE CHEMICAL SOCIETY, CHEMICAL COMMUNICATIONS, no. 2, 21 January 1995 (1995-01-21), LETCHWORTH GB, pages 207 - 208 * |
Cited By (6)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
CN1052453C (zh) * | 1996-06-05 | 2000-05-17 | 中国石油化工总公司 | 一种钒硅分子筛(vs-1)的制备方法 |
CN1052452C (zh) * | 1996-06-05 | 2000-05-17 | 中国石油化工总公司 | 一种钒硅分子筛(vs-2)的制备方法 |
US6524470B1 (en) | 1998-05-06 | 2003-02-25 | Institut Francais du Pétrole | Catalyst comprising beta zeolite and promoter element for hydrocracking |
EP0967014A1 (fr) * | 1998-06-25 | 1999-12-29 | Institut Français du Pétrole | Catalyseur d'hydrocraquage comprenant une zéolite beta et un élément du groupe VB |
FR2780309A1 (fr) * | 1998-06-25 | 1999-12-31 | Inst Francais Du Petrole | Catalyseur d'hydrocraquage comprenant une zeolithe beta, un element du groupe vb, et un element promoteur choisi dans le groupe forme par le bore, le phosphore et le silicium |
US6231750B1 (en) | 1998-06-25 | 2001-05-15 | Institut Francais Du Petrole | Hydrocracking catalyst comprising a beta zeolite and a group VB element |
Also Published As
Publication number | Publication date |
---|---|
GB9406434D0 (en) | 1994-05-25 |
JPH09512246A (ja) | 1997-12-09 |
CZ274196A3 (en) | 1997-11-12 |
BR9507209A (pt) | 1997-09-09 |
AU2111395A (en) | 1995-10-23 |
EP0752975A1 (fr) | 1997-01-15 |
CA2183597A1 (fr) | 1995-10-12 |
KR970702213A (ko) | 1997-05-13 |
PL316570A1 (en) | 1997-01-20 |
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