CA1196903A - Zirconium- and/or hafnium-containing zeolites, process for their manufacture, and their use - Google Patents
Zirconium- and/or hafnium-containing zeolites, process for their manufacture, and their useInfo
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- CA1196903A CA1196903A CA000413530A CA413530A CA1196903A CA 1196903 A CA1196903 A CA 1196903A CA 000413530 A CA000413530 A CA 000413530A CA 413530 A CA413530 A CA 413530A CA 1196903 A CA1196903 A CA 1196903A
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- 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
- C01B39/08—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 the aluminium atoms being wholly replaced
- C01B39/085—Group IVB- metallosilicates
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- 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
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- 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
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- 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
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- 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
- B01J29/40—Crystalline aluminosilicate zeolites; Isomorphous compounds thereof of the pentasil type, e.g. types ZSM-5, ZSM-8 or ZSM-11, as exemplified by patent documents US3702886, GB1334243 and US3709979, respectively
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- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C2529/00—Catalysts comprising molecular sieves
- C07C2529/04—Catalysts comprising molecular sieves having base-exchange properties, e.g. crystalline zeolites, pillared clays
- C07C2529/06—Crystalline aluminosilicate zeolites; Isomorphous compounds thereof
- C07C2529/40—Crystalline aluminosilicate zeolites; Isomorphous compounds thereof of the pentasil type, e.g. types ZSM-5, ZSM-8 or ZSM-11
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- 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
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- 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
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- 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
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- Chemical Kinetics & Catalysis (AREA)
- Materials Engineering (AREA)
- Inorganic Chemistry (AREA)
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- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
- Silicates, Zeolites, And Molecular Sieves (AREA)
Abstract
Abstract of the disclosure:
The invention provides zirconium- and/or hafnium-containing zeolites, a process for their manufacture, and their use.
For their manufacture, a mixture of zirconium and/or hafnium, silicon, sodium, tetrapropylammonium compounds and water, as well as optionally furthermore aluminum compounds, in spe-cific quantitative amounts is for example prepared and hea-ted in a closed vessel. The zeolites are used as catalysts for the manufacture of C2-C4 olefins from methanol.
The invention provides zirconium- and/or hafnium-containing zeolites, a process for their manufacture, and their use.
For their manufacture, a mixture of zirconium and/or hafnium, silicon, sodium, tetrapropylammonium compounds and water, as well as optionally furthermore aluminum compounds, in spe-cific quantitative amounts is for example prepared and hea-ted in a closed vessel. The zeolites are used as catalysts for the manufacture of C2-C4 olefins from methanol.
Description
~ O~ ~ ~F 274 7eoli tes are crystalline alurainosilicate.s, in whieh duc to a three-d..rnensional lin'~a~e of Si0J and .~.lO~ tetrahedra regular structures with cavities and pores are f~rmed. In hydrated state, these pores and ca~ities are fillecl with water, which, on the other hand, ean be easily r-emo~ed withou.t influencing the crystallin2 strueture, or re~laced by other molecules. The negative charges Or tne AlOIl tetrahedra are balanced by cations, whieh ean be replaced by other ions of positive charge. These properties allow the use of the zeolites as ion ~xehangers, adsorbents ar.d catalysts (~.W. ~reck: Zeolite Moleeular Sieves, 1974).
Zeolites of the X, Y, mordenite, erionite or offre-tite type, for example, are of considerable interest in the industrial practice as catalysts for hyclroearbon con~ersion reactions such as cracking, hydrocraeking or isomerization.
7eolites of the pentasil type (for example ~eolite ZSM-~) become increasingly important as catalysts for the conver-sion of methanol to hydroearbons.
Beeause of the numerous applieation possibilities a~
catalysts, there is great interest in novel zeolites having specifie eatalytical properties.
~ 'ery interesting zeolites are for example obtained by incorporating other elements instead o~ 21uminum and/or silicon into the zeolite frame. Thus, zeolites o~ the pentasil series are known which contain boron (German Offenlegungssehrif`t No. 2,746,790), iron (Gerrnan Offenle-gungsschrift No. 2,831,611), arsenic (German Aus]egeschrift No. 2,830,830), antimony (German Offenlenungsschrift No.
Zeolites of the X, Y, mordenite, erionite or offre-tite type, for example, are of considerable interest in the industrial practice as catalysts for hyclroearbon con~ersion reactions such as cracking, hydrocraeking or isomerization.
7eolites of the pentasil type (for example ~eolite ZSM-~) become increasingly important as catalysts for the conver-sion of methanol to hydroearbons.
Beeause of the numerous applieation possibilities a~
catalysts, there is great interest in novel zeolites having specifie eatalytical properties.
~ 'ery interesting zeolites are for example obtained by incorporating other elements instead o~ 21uminum and/or silicon into the zeolite frame. Thus, zeolites o~ the pentasil series are known which contain boron (German Offenlegungssehrif`t No. 2,746,790), iron (Gerrnan Offenle-gungsschrift No. 2,831,611), arsenic (German Aus]egeschrift No. 2,830,830), antimony (German Offenlenungsschrift No.
2,830,7~7), vanadium ~German ~ffenlegungsschrift No.
2,831,631) chromiurn (German Offenlegun~sschrift No.
2,831,630) or gallium (Bel~ian Patent No. 842,484) in tetrahedral position.
Furtherrnore, titanosilicates (U.S. Patent No. 3,329,l~81) and 7irconosilicat.es ~U.S. Patent No. 3,329,`~80) have been described; where, hwoever, a penta.sil structure can be safely excluded accordirl~ to the X~-ray dlf.fractioll diagram and the chemical composition.
Subjecl: of the ir,~ention are zircono and/or hafno-~luminosilicates havin~ a pentasil structurer _ 3 HOE 81/F 274 K
By pentasils, there are to be understood tho~e defined by Ko-kotailo and Meier ("Pentasil family of high ~ilica crystal-line materials" in: Special Publication No. 33 of the Chemi-cal Society, London 1980). The pentasil family comprise~ for example the ~ynthetic zeolites ZSM-5 (US Patent No. 3,7027886), ZSM-8 (British Patent No 1,334,243), ZSM-11 (US Patent No.
2,831,631) chromiurn (German Offenlegun~sschrift No.
2,831,630) or gallium (Bel~ian Patent No. 842,484) in tetrahedral position.
Furtherrnore, titanosilicates (U.S. Patent No. 3,329,l~81) and 7irconosilicat.es ~U.S. Patent No. 3,329,`~80) have been described; where, hwoever, a penta.sil structure can be safely excluded accordirl~ to the X~-ray dlf.fractioll diagram and the chemical composition.
Subjecl: of the ir,~ention are zircono and/or hafno-~luminosilicates havin~ a pentasil structurer _ 3 HOE 81/F 274 K
By pentasils, there are to be understood tho~e defined by Ko-kotailo and Meier ("Pentasil family of high ~ilica crystal-line materials" in: Special Publication No. 33 of the Chemi-cal Society, London 1980). The pentasil family comprise~ for example the ~ynthetic zeolites ZSM-5 (US Patent No. 3,7027886), ZSM-8 (British Patent No 1,334,243), ZSM-11 (US Patent No.
3,709,979) and ZSM-23 (US Patent No. 4,076,842).
Sub~ect of the invention are especially zircono- and/or ha~no -aluminosilicates having a ZSM-5 structure, preferably those having the following composition, expressed as molar ratio of oxides:
SiO2 : ~p to 0.15) Al203 : (0.002 - 1.0) M02, especially SiO2 : ~p ~o 0.1) Al203 : (0.01 - 0.4) M02, M being zirconium and/or hafnium.
The zirconium and/or hafnium-containing zeolites can be prepared according to the same methods and with the use of the same organic compounds as described for the synthesis of the zirconium- or hafnium-free zeolite ZSM-5, for example with the use of alkylammonium compounds (U.S. Patent No. 3,702~886) alkylamines (U.S. Patent No. 4,151,189) alkyldiamine3 (German Offenlegungsschri~ten Nos. 2,817,576 and 2,831,334) alkylamine3 in the presence of alkylatlon agents (Published European Patent Application No. 11362, German Auslegeschrift No. 2,212,810) aminoalcohol~ (British Patent No. 2,023,562) alcohols (German Of~enlegungsschriften Nos. 2,935,123, 2,643,929, U.S. Patents Nos. 4,199,5567 49175,114, Pub-lished European Patent Application No. 42225) ethers (European Patent Application No. 51741).
Preferably, alkylammonium compound~ 9 alkyl diamines or alkylamine~ are used in the presence o~ alkylat~on a~ents.
Especially preferred alkylammonium compound~ are tetrapro-
Sub~ect of the invention are especially zircono- and/or ha~no -aluminosilicates having a ZSM-5 structure, preferably those having the following composition, expressed as molar ratio of oxides:
SiO2 : ~p to 0.15) Al203 : (0.002 - 1.0) M02, especially SiO2 : ~p ~o 0.1) Al203 : (0.01 - 0.4) M02, M being zirconium and/or hafnium.
The zirconium and/or hafnium-containing zeolites can be prepared according to the same methods and with the use of the same organic compounds as described for the synthesis of the zirconium- or hafnium-free zeolite ZSM-5, for example with the use of alkylammonium compounds (U.S. Patent No. 3,702~886) alkylamines (U.S. Patent No. 4,151,189) alkyldiamine3 (German Offenlegungsschri~ten Nos. 2,817,576 and 2,831,334) alkylamine3 in the presence of alkylatlon agents (Published European Patent Application No. 11362, German Auslegeschrift No. 2,212,810) aminoalcohol~ (British Patent No. 2,023,562) alcohols (German Of~enlegungsschriften Nos. 2,935,123, 2,643,929, U.S. Patents Nos. 4,199,5567 49175,114, Pub-lished European Patent Application No. 42225) ethers (European Patent Application No. 51741).
Preferably, alkylammonium compound~ 9 alkyl diamines or alkylamine~ are used in the presence o~ alkylat~on a~ents.
Especially preferred alkylammonium compound~ are tetrapro-
- 4 - HOE 81/F 274 K
pylammonium compounds, for example the hydroxide or one of the halides. A particularly suitable alkyldiamine is hexa-methylene diamine.
For the synthesis of the zeolites of the invention, one or more compounds ~rom the cited classes are mixed with zirconium and/or hafnium compounds, silicon and sodium compounds and water~ and furthermore aluminum compounds, and the mixture is heated in a closed vessel. Before heating the mixture, preferably, seed crystals of a pentasil are furthermore added. In the case where tetrapropylammonium compounds are used, the starting compounds are generally used in the following ratio, expressed as molar ratio of oxides:
SiO2 : (up to 0.~ Al203 : (0.01 ~ 1.0) M02 :
(0.01 - 0.5) Na20 : (0.02 ~ 1.0) ~2 : (5 ~ 100) H20, preferably in a ratio of SiO2 : (up to 0.1) Al203 : (0.01 - 0.4~ M02 :
(0.02 - 0.3) Na20 : (o.o3 ~ o.6) R20 : (10 ~ 40) H20, M being zirconium and/or hafnium, and R being tetrapropyl-ammonium.
AB silicon, aluminum, zirconium, hafnium or sodium compounds 9 there are used for example silica gel, sodium silicate, alu minum hydroxide, aluminum sulfate, sodium aluminate~ alu-minum halides, aluminum metahydroxide, zirconium halides, zirconium sulfate, zirconyl chloride, hafnium halides hafnium sulfate, sodium hydroxide, sodium sulfate, sodium halides. Other compounds of the four cited elements are also suit~ble for the manufacture of the zeolites according to the invent ion .
The mixture of the compounds chosen and water is ge~
nerally heated for 18 to 360, preferably 2~ to 2llO~ hours at a temperature of ~rom 100 to 200C, peferably 130 to 170C, in a clo~ed vessel.
The zeolites wh~ch are formed are isolated in usual manner, for example by filtration, washed and dried. They can be converted according to known methods to catalytically ,~ ~
pylammonium compounds, for example the hydroxide or one of the halides. A particularly suitable alkyldiamine is hexa-methylene diamine.
For the synthesis of the zeolites of the invention, one or more compounds ~rom the cited classes are mixed with zirconium and/or hafnium compounds, silicon and sodium compounds and water~ and furthermore aluminum compounds, and the mixture is heated in a closed vessel. Before heating the mixture, preferably, seed crystals of a pentasil are furthermore added. In the case where tetrapropylammonium compounds are used, the starting compounds are generally used in the following ratio, expressed as molar ratio of oxides:
SiO2 : (up to 0.~ Al203 : (0.01 ~ 1.0) M02 :
(0.01 - 0.5) Na20 : (0.02 ~ 1.0) ~2 : (5 ~ 100) H20, preferably in a ratio of SiO2 : (up to 0.1) Al203 : (0.01 - 0.4~ M02 :
(0.02 - 0.3) Na20 : (o.o3 ~ o.6) R20 : (10 ~ 40) H20, M being zirconium and/or hafnium, and R being tetrapropyl-ammonium.
AB silicon, aluminum, zirconium, hafnium or sodium compounds 9 there are used for example silica gel, sodium silicate, alu minum hydroxide, aluminum sulfate, sodium aluminate~ alu-minum halides, aluminum metahydroxide, zirconium halides, zirconium sulfate, zirconyl chloride, hafnium halides hafnium sulfate, sodium hydroxide, sodium sulfate, sodium halides. Other compounds of the four cited elements are also suit~ble for the manufacture of the zeolites according to the invent ion .
The mixture of the compounds chosen and water is ge~
nerally heated for 18 to 360, preferably 2~ to 2llO~ hours at a temperature of ~rom 100 to 200C, peferably 130 to 170C, in a clo~ed vessel.
The zeolites wh~ch are formed are isolated in usual manner, for example by filtration, washed and dried. They can be converted according to known methods to catalytically ,~ ~
- 5 - HOE ~1/F 274 K
act~ve forms, for example by calcination and/or ion cxchange (D.hT. ~reclc, Zeolite Molecular Sieves, 1974).
After conversion to the catal~Jtically active for.-n, the zeo]ltes OL the inventlon display high selectivitv and a considerably reduced deposition of coke in the conversion of`
;nethanol l;o 10Wer olefin~. This reaction is carried out, L'Ot' example, at ternperature~s between 350 and 430C using methanol with a ~ate~r content of O to 80 p by weiht or~
raw ~.ethanol.
1~ The following Examples illustrate the invention with-out lin~lting it in its scope. All X-ray diffraction data as indicated were obtained by means of a computer-controlled powder diffractometer D--5GO of the Siemens company. The radiation was the K--~ doublet of copper.
Example 1 1.66 g of sodium aluminate (54 weight % A1203, 41 weight ~ Na20) and 1.4~ g of sodiurn hydroxide are dis-solved in 20 g of 20 weight % aqueous tetrapropylammonium hydroxide solution (solution A). A further solution (solu-tion B) is obtained by dissolving 62 g of 110 weight ~ col~
loidal silica gel in 230 g of 20 weight % aqueous tetrapro--pylammoniu~ hydroxide solution and concentrating this solu-tion to a total 220 g in a rotation evaporator. The solu-tions A and B are mixed, and 3.78 g of zirconyl chlorldeZrOC12 8H2o are added to this mixture with thorough stirring. The suspension obtaiend is homogenized and heated for 120 hours at 160C in a closed vessel. The product formed is filt~red off, washed with water and dried at 120C. 27.3 g of zircono~aluminosilicate according to the in~.rention is obtained.
An X--ray diffraction analysis shows a well crystal lized product having a ZSM--5 structure. ~ccording-to a chemica1 analysis of the product calcined f`or 16 hours at 540C, it has the followin6 composition, e~pre3sed as molar ratio o~ oxides:
~i2 : 0.035 ZrO~ : G.026 ~323 : -~3 Na2
act~ve forms, for example by calcination and/or ion cxchange (D.hT. ~reclc, Zeolite Molecular Sieves, 1974).
After conversion to the catal~Jtically active for.-n, the zeo]ltes OL the inventlon display high selectivitv and a considerably reduced deposition of coke in the conversion of`
;nethanol l;o 10Wer olefin~. This reaction is carried out, L'Ot' example, at ternperature~s between 350 and 430C using methanol with a ~ate~r content of O to 80 p by weiht or~
raw ~.ethanol.
1~ The following Examples illustrate the invention with-out lin~lting it in its scope. All X-ray diffraction data as indicated were obtained by means of a computer-controlled powder diffractometer D--5GO of the Siemens company. The radiation was the K--~ doublet of copper.
Example 1 1.66 g of sodium aluminate (54 weight % A1203, 41 weight ~ Na20) and 1.4~ g of sodiurn hydroxide are dis-solved in 20 g of 20 weight % aqueous tetrapropylammonium hydroxide solution (solution A). A further solution (solu-tion B) is obtained by dissolving 62 g of 110 weight ~ col~
loidal silica gel in 230 g of 20 weight % aqueous tetrapro--pylammoniu~ hydroxide solution and concentrating this solu-tion to a total 220 g in a rotation evaporator. The solu-tions A and B are mixed, and 3.78 g of zirconyl chlorldeZrOC12 8H2o are added to this mixture with thorough stirring. The suspension obtaiend is homogenized and heated for 120 hours at 160C in a closed vessel. The product formed is filt~red off, washed with water and dried at 120C. 27.3 g of zircono~aluminosilicate according to the in~.rention is obtained.
An X--ray diffraction analysis shows a well crystal lized product having a ZSM--5 structure. ~ccording-to a chemica1 analysis of the product calcined f`or 16 hours at 540C, it has the followin6 composition, e~pre3sed as molar ratio o~ oxides:
~i2 : 0.035 ZrO~ : G.026 ~323 : -~3 Na2
- 6 ~ E ~1~F 271l K
_xample 2 0.77 g of sodium hydroxide ar~ dissolved in 5 K of 20 weight ~ aqueous tetrapropylamr,lonium hydroxide solutlon (solution A). A second solutio~ clution B~ 1~ prepare~ by dissolving 12.4 g of 40 w.eight ~.co;loidal si.lica ~el in l~5 g of 20 weight % tetrapropylammonlum hy~roxide solution, and concentrati.ng thi.s solution to a total 45 K in a rotation evaporator. Solutions A and ~ are mixed. 1.~J8 g of` zi.rconyl chloride ~rOC12 ~8 H20 in 5 ml of H20, and 0.1 g of seed crystals (product 1) are added with thorov.gh stirring to this mixture. The suspension forlrled is homogenized and heated for 160 hours at 150C in a closed vessel. The product obtained is filtered off, washed ~ith ~ater and dried at 120C. 4.2 g of zirconosilicate of the invention are obtained. According to X-ray di~fracti.on analysis, the product has a ZSM-5 structure. The chç¢ical analvsis of t~.e product calcined for 16 hours at 540C yields the following composition:
SiO2 : 0.210 ZrO2 : 0.121 Na20 Example 3 The zircono-alumirlosilicate havirlO a ZSM--5 stlSuc~ul~e prepared according to Exa.mple 1 (calcined form) s exchan-ged with ammonium nitrate solution, and together t~ith abinder (Boehmit) extruded (zeolit e content 65 ~eight %), and calcined again as indicated in Example 1.
520 ml/h of 33 ~eight % aqueous methanol are dosed a~
a temperature of 350C under normal pressure to a verti-cally positioned, electrically heated tube reactor having alenght of 1 rn and ~acked with ~50 ml of thi.s catalyst. The reaction mixture which forrns is cooledS and after separa-tion of the condensable portions the gaseous phase is ana--lyzed. The C2 C4 olefin sel.ectivity is 65 %, and the se-lectivity to hydrocarbons ha~ri.n~ more thcln l~ carbon ctomsis 14 ~.
~ 7 -. HOE ~1JF 274 K
Co~.parative Example Operatic~ns are a9 in Example 3; ho~ever, instead Or the zircono-a].uminosilicate a cc,mm~rcial aluminosilicate catalyst havin~ 2 ~S~ 5 Q,truc'Gurc is used~
The C2-CI~ ole~in selectit~ity i;-, 56 'h, and the se-lectivity to h~drocarbon~ havin~ more than ~ carboll atoms i.s 23 %.
_xample 2 0.77 g of sodium hydroxide ar~ dissolved in 5 K of 20 weight ~ aqueous tetrapropylamr,lonium hydroxide solutlon (solution A). A second solutio~ clution B~ 1~ prepare~ by dissolving 12.4 g of 40 w.eight ~.co;loidal si.lica ~el in l~5 g of 20 weight % tetrapropylammonlum hy~roxide solution, and concentrati.ng thi.s solution to a total 45 K in a rotation evaporator. Solutions A and ~ are mixed. 1.~J8 g of` zi.rconyl chloride ~rOC12 ~8 H20 in 5 ml of H20, and 0.1 g of seed crystals (product 1) are added with thorov.gh stirring to this mixture. The suspension forlrled is homogenized and heated for 160 hours at 150C in a closed vessel. The product obtained is filtered off, washed ~ith ~ater and dried at 120C. 4.2 g of zirconosilicate of the invention are obtained. According to X-ray di~fracti.on analysis, the product has a ZSM-5 structure. The chç¢ical analvsis of t~.e product calcined for 16 hours at 540C yields the following composition:
SiO2 : 0.210 ZrO2 : 0.121 Na20 Example 3 The zircono-alumirlosilicate havirlO a ZSM--5 stlSuc~ul~e prepared according to Exa.mple 1 (calcined form) s exchan-ged with ammonium nitrate solution, and together t~ith abinder (Boehmit) extruded (zeolit e content 65 ~eight %), and calcined again as indicated in Example 1.
520 ml/h of 33 ~eight % aqueous methanol are dosed a~
a temperature of 350C under normal pressure to a verti-cally positioned, electrically heated tube reactor having alenght of 1 rn and ~acked with ~50 ml of thi.s catalyst. The reaction mixture which forrns is cooledS and after separa-tion of the condensable portions the gaseous phase is ana--lyzed. The C2 C4 olefin sel.ectivity is 65 %, and the se-lectivity to hydrocarbons ha~ri.n~ more thcln l~ carbon ctomsis 14 ~.
~ 7 -. HOE ~1JF 274 K
Co~.parative Example Operatic~ns are a9 in Example 3; ho~ever, instead Or the zircono-a].uminosilicate a cc,mm~rcial aluminosilicate catalyst havin~ 2 ~S~ 5 Q,truc'Gurc is used~
The C2-CI~ ole~in selectit~ity i;-, 56 'h, and the se-lectivity to h~drocarbon~ havin~ more than ~ carboll atoms i.s 23 %.
Claims (13)
OR PRIVILEGE IS CLAIMED ARE DEFINED AS FOLLOWS:
1. A compound selected from the group of zircono-aluminosilicates, hafno-aluminosilicates and zircono-hafnium-aluminosilicates having a pentasil structure.
2. A compound as claimed in claim 1 having a ZSM-5 structure.
3. A compound as claimed in claim 1 having the following composition, expressed as molar ratio of oxides:
SiO2: (up to 0.15) Al2O3 : (0.002 - 1.0) MO2, M being zirconium, hafnium, or zirconium and hafnium.
SiO2: (up to 0.15) Al2O3 : (0.002 - 1.0) MO2, M being zirconium, hafnium, or zirconium and hafnium.
4. A compound as claimed in claim 1 or claim 2 having the following composition, expressed as molar ratio of oxides:
SiO2 : (up to 0.1) Al2O3 : (0.01 - 0.4) MO2, being zirconium, hafnium or zirconium and hafnium.
SiO2 : (up to 0.1) Al2O3 : (0.01 - 0.4) MO2, being zirconium, hafnium or zirconium and hafnium.
5. A process for the preparation of a compound as claimed in claim 1 in which zirconium and/or hafnium, silicon and sodium compounds, water and aluminum compounds are mixed with one or more organic compounds selected from the group consisting of alkylammonium compounds, alkylamines, alkyldiamines, amino-alcohols, alcohols and ethers, and this mixture is heated in a closed vessel.
6. A process as claimed in claim 5 in which the organic compound is an alkylammonium compound.
7. A process as claimed in claim 5 in which the organic compound is a tetrapropylammonium compound.
8. A process as claimed in claim 5 in which the organic compound is an alkylamine and it is used in the presence of an alkylating agent.
9. A process as claimed in claim 5 in which the organic compound is an alkyldiamine.
10. A process as claimed in claim 5, claim 6 or claim 7 in which seed crystals of a pentasil are added to the mixture before heating.
11. A process as claimed in claim 5 in which the mixture has the following composition, expressed as molar ratio of oxides:
SiO2 : (up to 0.2) Al2O3 : (0.01 - 1.0) MO2 : (0.01 - 0.5) Na2O :
(0.02 - 1.0) R2O : (5 - 100) H2O, M being zirconium, hafnium or zirconium and hafnium, and R being tetrapropylammonium.
SiO2 : (up to 0.2) Al2O3 : (0.01 - 1.0) MO2 : (0.01 - 0.5) Na2O :
(0.02 - 1.0) R2O : (5 - 100) H2O, M being zirconium, hafnium or zirconium and hafnium, and R being tetrapropylammonium.
12. A process as claimed in claim 11 in which the mixture has the following composition, expressed as molar ratio of oxides:
SiO2 : (up to 0.1) Al2O3 : (0.01 - 0-4) MO2 : (0.02 - 0.3) Na2O :
(0.03 - 0.6) R2O : (10 - 40) H2O, M being zirconium, hafnium, or zirconium and hafnium and R being tetrapropylammonium.
SiO2 : (up to 0.1) Al2O3 : (0.01 - 0-4) MO2 : (0.02 - 0.3) Na2O :
(0.03 - 0.6) R2O : (10 - 40) H2O, M being zirconium, hafnium, or zirconium and hafnium and R being tetrapropylammonium.
13. A process for the preparation of a C2-C4 olefin in which methanol is reacted in the presence of a compound as claimed in claim 1, claim 2 or claim 3.
Applications Claiming Priority (6)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| DE19813141285 DE3141285A1 (en) | 1981-10-17 | 1981-10-17 | Zirconium- and/or hafnium-containing zeolites and a process for their preparation, and their use |
| DEP3141285.8 | 1981-10-17 | ||
| DEP3219494.3 | 1982-05-25 | ||
| DE19823219494 DE3219494A1 (en) | 1982-05-25 | 1982-05-25 | Zirconium- and/or hafnium-containing zeolites, process for their preparation and their use |
| DE19823231467 DE3231467A1 (en) | 1982-08-25 | 1982-08-25 | Zirconium- and/or hafnium-containing zeolites, process for their preparation, and their use |
| DE3231467.1 | 1982-08-25 |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| CA1196903A true CA1196903A (en) | 1985-11-19 |
Family
ID=27189627
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CA000413530A Expired CA1196903A (en) | 1981-10-17 | 1982-10-15 | Zirconium- and/or hafnium-containing zeolites, process for their manufacture, and their use |
Country Status (5)
| Country | Link |
|---|---|
| EP (1) | EP0077523B1 (en) |
| AU (1) | AU550136B2 (en) |
| CA (1) | CA1196903A (en) |
| DE (1) | DE3263914D1 (en) |
| NZ (1) | NZ202185A (en) |
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US5246688A (en) * | 1990-08-29 | 1993-09-21 | Rhone-Poulenc Chimie | Production of silica-based mfi zeolites |
| US5399336A (en) * | 1990-06-29 | 1995-03-21 | Rhone-Poulenc Chimie | Stannozeosilite/zirconozeosilite zeolites and catalytic hydroxylation of phenolics therewith |
Families Citing this family (11)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| AU542052B2 (en) * | 1980-06-12 | 1985-02-07 | Imperial Chemical Industries Ltd. | Zeoliteeuz and its use as a catalyst |
| DE3217323A1 (en) * | 1982-05-08 | 1983-11-10 | Hoechst Ag, 6230 Frankfurt | ZIRCON AND / OR HAFNIUM-CONTAINING ZEOLITES AND METHOD FOR THE PRODUCTION THEREOF AND THEIR USE |
| DE3402020A1 (en) * | 1984-01-21 | 1985-07-25 | Hoechst Ag, 6230 Frankfurt | METHOD FOR PRODUCING OLEFINS FROM METHANOL |
| DE3420707A1 (en) * | 1984-06-02 | 1985-12-05 | Hoechst Ag, 6230 Frankfurt | METHOD FOR ISOMERIZING O-, M-, AND / OR P-TOLUIDINE |
| EP0164045B1 (en) * | 1984-06-02 | 1989-04-05 | Hoechst Aktiengesellschaft | Process for the isomerisation of mono- or dichlorotoluene |
| DE3880369T2 (en) * | 1987-05-22 | 1993-08-05 | Rhone Poulenc Chimie | ZEOLITE WITH MFI STRUCTURE BASED ON SILICONE AND TITANIUM OXIDE AND METHOD FOR THE SYNTHESIS THEREOF. |
| FR2663919B1 (en) * | 1990-06-29 | 1993-07-02 | Rhone Poulenc Chimie | SILICA AND ZIRCONIUM OXIDE ZEOLITHS AND THEIR SYNTHESIS PROCESS. |
| FR2674517B1 (en) * | 1991-03-27 | 1993-07-02 | Rhone Poulenc Chimie | PROCESS FOR THE PREPARATION OF SILICA-BASED ZEOLITHS AND OXIDES OF TETRAVALENT ELEMENTS. |
| FR2666321B1 (en) * | 1990-08-29 | 1992-12-11 | Rhone Poulenc Chimie | PROCESS FOR THE PREPARATION OF SILICA-BASED ZEOLITHS AND TETRAVALENT ELEMENT OXIDES. |
| GB2322364A (en) * | 1997-02-14 | 1998-08-26 | Exxon Chemical Patents Inc | Zirconium molecular sieve catalysts |
| US6759360B2 (en) | 2002-03-29 | 2004-07-06 | Exxonmobil Chemical Patent Inc. | Interior surface modifications of molecular sieves with organometallic reagents and the use thereof for the conversion of oxygenates to olefins |
Family Cites Families (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| DD40952A (en) * | ||||
| US3013987A (en) * | 1958-09-24 | 1961-12-19 | Union Carbide Corp | Metal loading of molecular sieves |
| 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 |
| US3702886A (en) * | 1969-10-10 | 1972-11-14 | Mobil Oil Corp | Crystalline zeolite zsm-5 and method of preparing the same |
| DE2831631A1 (en) * | 1978-07-19 | 1980-02-07 | Basf Ag | Synthetic crystalline vanadium silicate - with zeolite structure, useful as catalyst in (hydro)cracking processes |
-
1982
- 1982-10-13 DE DE8282109452T patent/DE3263914D1/en not_active Expired
- 1982-10-13 EP EP82109452A patent/EP0077523B1/en not_active Expired
- 1982-10-15 CA CA000413530A patent/CA1196903A/en not_active Expired
- 1982-10-15 NZ NZ202185A patent/NZ202185A/en unknown
- 1982-10-15 AU AU89400/82A patent/AU550136B2/en not_active Ceased
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US5399336A (en) * | 1990-06-29 | 1995-03-21 | Rhone-Poulenc Chimie | Stannozeosilite/zirconozeosilite zeolites and catalytic hydroxylation of phenolics therewith |
| US5246688A (en) * | 1990-08-29 | 1993-09-21 | Rhone-Poulenc Chimie | Production of silica-based mfi zeolites |
Also Published As
| Publication number | Publication date |
|---|---|
| AU550136B2 (en) | 1986-03-06 |
| EP0077523B1 (en) | 1985-05-29 |
| AU8940082A (en) | 1983-04-28 |
| EP0077523A3 (en) | 1983-09-14 |
| DE3263914D1 (en) | 1985-07-04 |
| NZ202185A (en) | 1985-10-11 |
| EP0077523A2 (en) | 1983-04-27 |
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