NZ204155A - Zirconium-and/or hafnium-containing zeolites,their preparation and use - Google Patents

Zirconium-and/or hafnium-containing zeolites,their preparation and use

Info

Publication number
NZ204155A
NZ204155A NZ204155A NZ20415583A NZ204155A NZ 204155 A NZ204155 A NZ 204155A NZ 204155 A NZ204155 A NZ 204155A NZ 20415583 A NZ20415583 A NZ 20415583A NZ 204155 A NZ204155 A NZ 204155A
Authority
NZ
New Zealand
Prior art keywords
zirconium
hafnium
strong
expressed
medium
Prior art date
Application number
NZ204155A
Inventor
H Batters
H Litterer
E I Leupold
F Wunder
Original Assignee
Hoechst Ag
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 Hoechst Ag filed Critical Hoechst Ag
Publication of NZ204155A publication Critical patent/NZ204155A/en

Links

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
    • C01B39/065—Galloaluminosilicates; Group IVB- metalloaluminosilicates; Ferroaluminosilicates
    • 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
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C1/00—Preparation of hydrocarbons from one or more compounds, none of them being a hydrocarbon
    • C07C1/20—Preparation of hydrocarbons from one or more compounds, none of them being a hydrocarbon starting from organic compounds containing only oxygen atoms as heteroatoms
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C2529/00—Catalysts comprising molecular sieves
    • C07C2529/89—Silicates, aluminosilicates or borosilicates of titanium, zirconium or hafnium
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
    • Y02P30/00—Technologies relating to oil refining and petrochemical industry
    • Y02P30/20—Technologies relating to oil refining and petrochemical industry using bio-feedstock
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
    • Y02P30/00—Technologies relating to oil refining and petrochemical industry
    • Y02P30/40—Ethylene production

Landscapes

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

Description

New Zealand Paient Spedficaiion for Paient Number £04155 2 04155 Priority Date(s): g-S-SQ. i Complete Specification Filsd: .£."rF.'$?>, C! ass: f?/?■?.\.. Cp.y..9.ijzk...
P.O. Journal, No: . ..l?.7rT.
M DRAWIH68 NEW ZEALAND Patents Act 1953 COMPLETE SPECIFICATION "ZIRCONIUM- AND/OR HAFNIUM-CONTAINING ZEOLITES, A PROCESS FOR THEIR PREPARATION AND THEIR USE" We, HOE CHS T AKTIENGESELLSCHAFT, of D-6230 F-rankf urt/Main 80, Federal Republic of Germany, a corporation organized under the laws of the Federal Republic of Germany, do hereby declare the invention, for which we pray that a Patent may be granted to us» and the method by which it is to be performed, to be particularly described in and by the following statement : - 204155 Zeolites are, in particular, crystalline alumino-silicates in which ordered structures containing cavities and pores are formed as a result of three-dimensional linking of SiO^ and AlO^ tetrahedra. In the hydrated 5 state, these pores and cavities are filled with water. This can be removed or replaced by other molecules, without the crystal structure being affected. The negative charges on the AlO^ tetrahedra are compensated by cations. These can, if desired, be exchanged for other cat-10 ions. The properties described make it possible to use the zeolites as ion exchangers, adsorbents and catalysts (D.W. Breck: Zeolite Molecular Sieves, 1974).
Zeolites of the X, Y, mordenite, erionite and . offretite types, for example, are of considerable indus-15 trial interest as catalysts for transformation reactions of hydrocarbons, such as cracking, hydrocracking or iso-merization. Zeolites of the pentasil type (e.g. zeolite ZSM-5) are becoming increasingly important as catalysts for converting methanol to hydrocarbons. 20 Because of the very large number of possible uses as catalysts, there is considerable interest in novel zeo lites having specific catalytic properties. For example, very interesting zeolites are obtained if, instead of / i. aluminum and/or silicon, other elements are incorporated 25 into the zeolite structure. Thus, other zeolites of the pentasil series which contain boron (German Offen legungs-schrift 2,74 6,790^, iron (-German Of f enlegungco eh r i f t- 204155 3 2/831,611), arsenic (Carman Aug logocchrift 2/850/850-3, antimony (Gorman Offon logungoochrift—2,830,787), vanadium (Ccrniow Of f on lo gungoooh r i f t 2/831 /631), chromium (Go rman Offonlogungoochrift—2/831 ,630) or gallium (BoIgi an Patent 5 882,464) in tetrahedral sites have been disclosed. Tit-anosilicates (U.S. Patent 3,329,481 and German—Offonlc gungccchrift 3/047/798) and zirconosilicates (U.S. Patent 3,329,480) having a zeolite structure have also been disclosed.
Furthermore, boron-containing zeolites, gallium- and/or indium-containing zeolites, titanium-containing zeolites and zirconium-and/or hafnium-containing zeolites have already been described (Gorman Potent ■App I i -cat ions P—3^—34—31 6 »3 /—P—3-1—3-4—317 »1 /—P—3-1—3-6—686.4/ containing zeolites which a) in addition to sodium, potassium and choline, contain 20 the elements silicon, aluminum and zirconium and/or hafnium in the following ratio, expressed as molar ratios of the oxi des: where M is zirconium and/or hafnium 25 and b) exhibit the characteristic signals listed in Table 1 in the X-ray diffraction diagram: P 31 36 6 8 A18 / P 31 41 283 .1 and P 31 /. 1 285.8-) The invention relates to zirconium- and/or hafnium- (Si02 + M02) : (0.02 - 0.30) Al203, 2 04155 Table 1 Interplanar spacings d 11.4+ 0.3 5 9.2 + 0.2 7.6 + 0.2 6.6 + 0.1 .7 + 0.1 5.35 + 0.1 4.56 + 0.1 4.32 + 0.1 4.16 + 0.1 3.81 + 0.1 3.75 + 0.1 15 3.59 + 0.1 3.30 + 0.1 3.15 + 0.1 2.86 + 0.1 2.80 + 0.1 Re Lat ive i ntens i ty I/I0 strong to very strong weak weak to medium medium to strong weak to medium weak medium to strong strong weak medi um to st rong strong to very strong strong to very strong medium medi um strong to very strong weak to medium In this table, Ig denotes the intensity of the strongest signal.
The following values apply to the intensity data in Table 1: Relative intensity 100 I/In very strong strong medium weak 80 - 100 50 - 80 20 - 50 0-20 The ratio of silicon to zirconium and/or hafnium, 5 expressed as molar ratios of the oxides, is in general as fo I lows: SiO„ ' ^ = 0.4 - 0.99 , preferably s±o2 + mo2 Si02 sio2 + MO2 = 0.7 - 0.99, where M is zirconium and/or hafnium.
The novel zeolites according to the invention possess a structure similar to that of the T (U.S. Patent 2,950,952) or ZSM-34 (German Of fen legungsschrift 10 2,749,024) zeolites, but differ from these in composition, in particular as a result of the zirconium and/or hafnium content.
The zeolites according to the invention differ from the zirconosilicates according to U.S. Patent 15 3,329,480 in structure.
The zeolites according to the invention can be prepared by mixing zirconium and/or hafnium compounds with aluminum compounds, silicon compounds, sodium compounds, potassium compounds, choline compounds and water, 20 and heating the mixture in a sealed vessel. It is also possible to add seed crystals to this mixture before it is heated.
The starting compounds are employed in general in the following ratio, expressed as molar ratios of the 25 oxides: (S i 0 2 + M02) : (0.02 - 0.30)Al203 : (0.05 - 0.70)Na20 : (0.02 - 0.30)K20 : (0.02 - 0.5)R20 : (10 - 90)H20, 2 ; ^i 5 5 preferably in the ratio (Si02 + M02) : (0.02 - 0.18)Al203 : (0.10 - 0„60)Na20 : (0.04 - 0.20)K20 : (0.10 - 0.40)r20 : (10 - 40)h20, where R is choline and M is zirconium and/or hafnium. 5 The ratio of silicon to zirconium and/or hafnium in the mixture of the starting compounds, expressed as molar ratios of the oxides, is in general as follows: SiO„ Si02 + mo2 = 0.4 - 0.99, preferab ly Si02 Si00 + MO~ 10 2 2 = 0.6 - 0,99, where M is zirconium and/or hafnium.
Examples of compounds which can be employed are: silica gel, potassium silicate, sodium silicate, aluminum hydroxide, aluminum sulfate, potassium aluminate, alumi-15 num halides, aluminum metahydroxide, zirconium halides, zirconium nitrate, zirconium sulfate, zirconyl halides, hafnium halides, hafnium oxychloride, sodium hydroxide, sodium sulfate, sodium halides, potassium hydroxide, potassium sulfate, potassium halides, choline hydroxide 20 and choline chloride. However, other silicon, aluminum, zirconium, hafnium, potassium, sodium and choline compounds are also suitable for the preparation of the zeolites according to the invention.
A mixture of the particular selected compounds 25 with water is heated in general for 48 to 2,000 hours, preferably 48 to 1,000 hours, at a temperature between 80 and 160°C, preferably between 90 and 150°C, in a sealed f •• „ 1 55 vesseI.
The zeolites formed are isolated in a customary manner, for example by filtration, and are washed and dried. They can be converted to the catalytica I ly active 5 forms by known methods, e.g. by calcination and/or ion exchange (D.W. Breck, Zeolite Molecular Sieves, 1974).
After they have been converted to the catalytic-ally active forms, the zeolites according to the invention are distinguished in particular by high selectivity and 10 by a low level of coking in the conversion of methanol to lower olefins. It is surprising that it is at all possible to obtain zeolites having the features according to the invention with the aid of the stated method.
The examples which follow are intended to illus trate the invention, but are not intended to restrict it in any way. All X-ray diffraction data given were recorded using a computei— controlled D-500 powder dif-fractometer from Siemens. Copper Kocradiation was used. 20 Example 1 1.5 g of sodium aluminate (54% by weight of AI2O3 and 41% by weight of Na20), 5.9 g of sodium hydroxide, 1.6 g of potassium hydroxide and 12.7 g of choline chloride are dissolved in 43 g of water. Fi rst 7.0 g of zir-25 conyl chloride (ZrOCl2 x 8H20) and then 29.4 g of 40% strength by weight colloidal silica gel are introduced into this solution, while stirring thoroughly. The resulting mixture is homogenized, and heated for 8 days at 150°C in a sealed vessel. The product formed is filtered off, L *r J washed with water and dried at 120°C.
The product contains silicon, aluminum and zirconium in the following amounts, expressed as molar ratios of the oxides: Si02 : 0.066 Al203 : 0.197 Zr02 The result of the X-ray diffraction analysis is reproduced in Table 2.
Tab le 2 Relative intensity 100 I/I0 Interplanar spacings 10 deft: 11 .48 9.18 7.58 6.65 6.36 .77 5.35 4.57 4.35 4.16 3.81 3.78 3.60 3.32 3.17 2.93 2.87 2.82 100 5 18 44 8 22 8 45 61 13 58 92 65 38 31 7 95 7 2.67

Claims (9)

  1. - 9 -
    X iJ-J' 1
    Table 2 cont i nued
    Interplanar spacings dCfill
    Relative intensity 100 I/I0
  2. 2.49
  3. 8
  4. 5 Example 2
  5. 5.0 g of sodium aluminate, 16.6 g of sodium hydroxide, 4.4 g of potassium hydroxide and 42 g of choline chloride are dissolved in 135 g of water. First 102 g of
    40% strength by weight of colloidal silica gel and then
    /
    10 11.6 g of zirconyl chloride (ZrOCl2 x 8H20> are introduced into this solution while stirring thoroughly. The resulting mixture is heated for 30 days at 105°C in a sealed vessel. The product is filtered off, washed with water and dried at 120°C.
    15 The product contains silicon, aluminum and zii—
    conium in the following amounts, expressed as molar ratios oftheoxides:
    Si02 : 0.081 Al203 : 0.118 Zr02.
    The X-ray signals correspond to those shown in
    20 Table 1.
    -10 - 3. - ■*.' 1;WHAT WE CLAIM IS:;I. A zirconium- and/or hafnium-containing zeolite whi ch a) in addition to sodium, potassium and choline, contains the elements silicon, aluminum and zirconium and/or hafnium in the following ratio, expressed as molar ratios of the oxides:;(Si02 + M02) : (0.02 - 0.30)Al203,;t where M is zirconium and/or hafnium,;and b) exhibits the following characteristic signals in the X-ray diffraction diagram:;Interplanar spacings Relative intensity dCAD I/I0;II.4 _+ 0.3 strong to very strong 9.2 +_ 0.2 weak;7.6 + 0.2 weak to medium;6.6 +_ 0.1 medium to strong;5.7 +_ 0.1 weak to medium 5.35 + 0.1 weak;4.56 _+ 0.1 medium to strong;4.32+^0.1 strong;4.16 +_ 0.1 weak;3.81 +_ 0.1 medium to strong;3.75 +_ 0.1 strong to very strong;3.59 hh 0.1 strong to very strong;3.30 _+ 0.1 medium;3 .15 +_ 0 .1 medium;2.86 0.1 strong to very strong;- 11 -;Z04ISS;cont inue d;Interplanar spacings Relative intensity dtfa I/I0;2.80 +_ 0.1 weak to medium where Ig denotes the intensity of the strongest signal.;2. A zirconium- and/or hafnium-containing zeolite as claimed in claim 1, wherein the ratio of silicon to zirconium and/or hafnium, expressed as molar ratios of the oxides, is as follows:;Si00;±— = 0,4 - 0.99,;Si02 + M02;where M is zirconium and/or hafnium.;3. A zirconium- and/or hafnium-containing zeolite as claimed in claim 1, wherein the ratio of silicon to zirconium and/or hafnium, expressed as molar ratios of the oxides, is as follows:;SiO_;■ = 0.7 - 0.99/;Si02 + M02;where M is zirconium and/or hafnium.;4. A process for the preparation of a zirconium-and/or hafnium-containing zeolite as claimed in any one of claims 1 to 3, wherein a mixture of a silicon compound, an aluminum compound, a sodium compound, a potassium compound, a choline compound and water and a zirconium compound and/or hafnium compound is prepared, which has the following composition, expressed as molar ratios of the oxides:;<Si02 + M02) : (0.02 - 0.30)Al203 : (0.05 - 0.70)Na20 : (0.02 - 0.30)K20 : (0.02 - 0.5)R20 : (10-90)H20,;- 12 -;ao4iss where R is choline and M is zirconium and/or hafnium, and this mixture is heated in a sealed vessel.;5. The process as claimed in claim 4 , wherein the mixture to be heated has the following composition, expressed as molar ratios of the oxides:;O/O 0-6o;<Si02 + M02> : (0.02 - 0.18)Al203 : («&r&5 - -e-r*G)Na20
    O-Oif 0-20 O to
    : (.Mi - G-?3€)K20 : (€tG€ - &rl>R20 : (10 - -96>H20,
    where R is choline and M is zirconium and/or hafnium.
  6. 6. The process as claimed in claim 4 or 5, wherein the ratio of silicon to zirconium and/or hafnium in the mixture of the starting compounds, expressed as molar ratios of the oxides, is as follows:
    SiO„
    Si02 + M02
    = 0.4 - 0,99/
    where M is zirconium and/or hafnium.
  7. 7. The process as claimed in claim 4 or 5, wherein the ratio of silicon to zirconium and/or titanium in the mix-ture of the starting compounds, expressed as molar ratios c£ ^pf the oxides, is as follows:
    \\
    Si00
    = = 0.6 - 0,99,
    Si02 + M02
    where M is zirconium and/or hafnium.
  8. 8. The use of a zirconium- and/or hafnium-containing zeolite as claimed in any one of claims 1 to 3, as a catalyst in the preparation of C2~ to C^-olefins from methanol.
  9. 9. A zirconium-and /or hafnium-containing zeolite according to claim 1 substantially as hereinbefore described.
    HOECHST AKTIENGESELLSCHAFT By Their Attorneys ,
    HENRY HUGHES
NZ204155A 1982-05-08 1983-05-06 Zirconium-and/or hafnium-containing zeolites,their preparation and use NZ204155A (en)

Applications Claiming Priority (1)

Application Number Priority Date Filing Date Title
DE19823217323 DE3217323A1 (en) 1982-05-08 1982-05-08 ZIRCON AND / OR HAFNIUM-CONTAINING ZEOLITES AND METHOD FOR THE PRODUCTION THEREOF AND THEIR USE

Publications (1)

Publication Number Publication Date
NZ204155A true NZ204155A (en) 1985-10-11

Family

ID=6163073

Family Applications (1)

Application Number Title Priority Date Filing Date
NZ204155A NZ204155A (en) 1982-05-08 1983-05-06 Zirconium-and/or hafnium-containing zeolites,their preparation and use

Country Status (7)

Country Link
EP (1) EP0094023A1 (en)
JP (1) JPS58208128A (en)
AU (1) AU1434583A (en)
CA (1) CA1195674A (en)
DE (1) DE3217323A1 (en)
NZ (1) NZ204155A (en)
ZA (1) ZA833241B (en)

Families Citing this family (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
DE3240869A1 (en) * 1982-11-05 1984-05-10 Hoechst Ag, 6230 Frankfurt ZEOLITES CONTAINING TITANIUM, ZIRCONIUM AND / OR HAFNIUM AND METHOD FOR THE PRODUCTION THEREOF AND THEIR USE
DE3240870A1 (en) * 1982-11-05 1984-05-10 Hoechst Ag, 6230 Frankfurt ZEOLITES CONTAINING TITANIUM, ZIRCONIUM AND / OR HAFNIUM AND METHOD FOR THE PRODUCTION THEREOF AND THEIR USE

Family Cites Families (7)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
DD40952A (en) *
NL238953A (en) * 1958-05-08
US3329482A (en) * 1963-10-18 1967-07-04 Union Oil Co Methods for the manufacture of group iv-b metallo-silicate zeolites
US3329480A (en) * 1963-10-18 1967-07-04 Union Oil Co Crystalline zircono-silicate zeolites
DE2017807A1 (en) * 1969-05-01 1970-11-12 W.R. Grace & Co., New York, N.Y. (V.St.A.) Synthetic aluminosilicate zeolite and process for its production
NZ185397A (en) * 1976-11-04 1979-12-11 Mobil Oil Corp Crystalline aluminosilicate zeolites and use as catalysts
EP0077523B1 (en) * 1981-10-17 1985-05-29 Hoechst Aktiengesellschaft Zeolites containing zirconium and/or hafnium, process for producing them and their use

Also Published As

Publication number Publication date
DE3217323A1 (en) 1983-11-10
JPS58208128A (en) 1983-12-03
ZA833241B (en) 1984-01-25
CA1195674A (en) 1985-10-22
EP0094023A1 (en) 1983-11-16
AU1434583A (en) 1983-11-10

Similar Documents

Publication Publication Date Title
CA1040187A (en) Method of preparing a crystalline aluminosilicate zeolite
CA1173017A (en) Nu-5 zeolites
CA1064890A (en) Crystalline zeolite, synthesis and use thereof
JPH0214286B2 (en)
GB2062603A (en) Crystalline borosilicate compositions
JPS63162521A (en) Novel synthesis of ferric silicate type zeolites, obtained substances and their uses
CA1185224A (en) Titanium-containing zeolites, process for their manufacture, and their use
US5328675A (en) Transition-metal-aluminosilicate hydrocarbon conversion catalysts having an L type structure, ECR-22-D
NZ201908A (en) Gallium and/or indium-containing zeolites and use as olefin producing catalysts
JPH0341408B2 (en)
US4623526A (en) Process for the preparation of a crystalline titanoborosilicate
US4519998A (en) Process for the preparation of a crystalline titanoborosilicate
CA1182096A (en) Gallium- and/or indium-containing zeolites, process for their manufacture, and their use
CA2447448C (en) Porous crystalline material (zeolite itq-21), the preparation method thereof and use of same in the catalytic conversion of organic compounds
NZ202185A (en) Zircono-and/or hafno-aluminosilicates having a pentasil structure,their preparation and use as olefin producing catalysts
JPS5874521A (en) Titanium-containing zeolites, manufacture and use
NZ204156A (en) A crystalline aluminosilicate zeolite
NZ204154A (en) Titanium-containing zeolites,their preparation and use
NZ204155A (en) Zirconium-and/or hafnium-containing zeolites,their preparation and use
CA1196902A (en) Zeolite lz-133
NZ206145A (en) Titanium,zirconium and/or hafnium containing zeolites
US5219813A (en) Process for the preparation of novel molecular sieves
NZ201754A (en) Zeolitic boro-aluminosilicates and use as olefin producing catalysts
NZ206144A (en) Titanium,zirconium and/or hafnium containing zeolites
CA1182098A (en) Boro-aluminosilicates having zeolite structure, process for their manufacture, and their use