CA1185224A - Titanium-containing zeolites, process for their manufacture, and their use - Google Patents
Titanium-containing zeolites, process for their manufacture, and their useInfo
- Publication number
- CA1185224A CA1185224A CA000413523A CA413523A CA1185224A CA 1185224 A CA1185224 A CA 1185224A CA 000413523 A CA000413523 A CA 000413523A CA 413523 A CA413523 A CA 413523A CA 1185224 A CA1185224 A CA 1185224A
- Authority
- CA
- Canada
- Prior art keywords
- titanium
- titano
- aluminosilicate
- tio2
- sio2
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Expired
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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
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B63—SHIPS OR OTHER WATERBORNE VESSELS; RELATED EQUIPMENT
- B63B—SHIPS OR OTHER WATERBORNE VESSELS; EQUIPMENT FOR SHIPPING
- B63B35/00—Vessels or similar floating structures specially adapted for specific purposes and not otherwise provided for
- B63B35/28—Barges or lighters
- B63B35/30—Barges or lighters self-discharging
-
- 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
-
- E—FIXED CONSTRUCTIONS
- E02—HYDRAULIC ENGINEERING; FOUNDATIONS; SOIL SHIFTING
- E02D—FOUNDATIONS; EXCAVATIONS; EMBANKMENTS; UNDERGROUND OR UNDERWATER STRUCTURES
- E02D15/00—Handling building or like materials for hydraulic engineering or foundations
- E02D15/10—Placing gravel or light material under water inasmuch as not provided for elsewhere
-
- F—MECHANICAL ENGINEERING; LIGHTING; HEATING; WEAPONS; BLASTING
- F16—ENGINEERING ELEMENTS AND UNITS; GENERAL MEASURES FOR PRODUCING AND MAINTAINING EFFECTIVE FUNCTIONING OF MACHINES OR INSTALLATIONS; THERMAL INSULATION IN GENERAL
- F16L—PIPES; JOINTS OR FITTINGS FOR PIPES; SUPPORTS FOR PIPES, CABLES OR PROTECTIVE TUBING; MEANS FOR THERMAL INSULATION IN GENERAL
- F16L11/00—Hoses, i.e. flexible pipes
- F16L11/04—Hoses, i.e. flexible pipes made of rubber or flexible plastics
- F16L11/10—Hoses, i.e. flexible pipes made of rubber or flexible plastics with reinforcements not embedded in the wall
-
- 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
-
- 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
-
- 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
Abstract
Abstract of the disclosure:
The invention provides titanium-containing zeolites, a pro-cess for their manufacture, and their use. For their manu-facture, a mixture of titanium, silicon, aluminum, sodium, tetrapropylammonium compounds and water in specific quanti-tative amounts is for example prepared and heated in a closed vessel. The zeolites are used as catalysts for the manufacture of C2-C4 olefins from methanol.
The invention provides titanium-containing zeolites, a pro-cess for their manufacture, and their use. For their manu-facture, a mixture of titanium, silicon, aluminum, sodium, tetrapropylammonium compounds and water in specific quanti-tative amounts is for example prepared and heated in a closed vessel. The zeolites are used as catalysts for the manufacture of C2-C4 olefins from methanol.
Description
35~
- 2 - HOE 81~F 273 K
Zeolites are crystalline al~minosilicates, in which due to a three-dimensional linkage of SiOI~ and Al04 tetrahedra regular structures with cavities and pores are formed. In hydrated state, these pores and cavities are filled with water, which, on the other hand, can be easily removed without influencing the crystalline structure, or replaced by other molecules. The negative charges of the AlOL~
tetrahedra are balanced by cations, which can be replaced by other ions of positive charge. These properties allow the use of the zeolites as ion exchangers, adsorbents and catalysts (D.W. Breck: Zeolite Molecular Sieves, 1974).
Zeolites of the X, Y, mordenite, erionite or of~re-tite type, ~or example, are o~ considerable interest in the industrial practice as catalysts for hydrocarbon conversion reactions such as cracking, hydrocracking or lsomerization.
Zeolites of the pentasil type (for example Zeolite ~SM-5) become increasingly important as catalysts ~or the conver-sion of methanol to hydrocarbons.
Because of the numerous application possibilities as 20 catalysts, there is great interest in novel zeolites having specific catalytical properties.
Very interesting zeolites are for example obtained by incorporating other elements in~tead of aluminum and/or silicon into the zeolite frame. Thus, zeolites of the 25 pentasil series are known which contain boron (German Offenlegungsschrift No. 2,746,790), iron (German Offenle- j gungsschriPt No. 2,831,611), arsenic (German Auslegeschrift No. 2,830,830), antimony (German Offenle~ungsschrift No.
2,830,787), vanadium (German Offenlegungsschrift No.
30 2,831,631) chromium (German Offenlegungsschrift No. 2,831,630) or gallium ~Belgian Patent No. 842,484) in tetrahedral posi~ion.
Furthermore, titanosilicates (U.S. Patent No. 3,329,481 and zirconosilicates (U.S. Patent No. 3,329,480) have been 35 described.
Sub~ect of the invention are titano-aluminosilicates having a pentasil structure.
5~
Zeolites are crystalline al~minosilicates, in which due to a three-dimensional linkage of SiOI~ and Al04 tetrahedra regular structures with cavities and pores are formed. In hydrated state, these pores and cavities are filled with water, which, on the other hand, can be easily removed without influencing the crystalline structure, or replaced by other molecules. The negative charges of the AlOL~
tetrahedra are balanced by cations, which can be replaced by other ions of positive charge. These properties allow the use of the zeolites as ion exchangers, adsorbents and catalysts (D.W. Breck: Zeolite Molecular Sieves, 1974).
Zeolites of the X, Y, mordenite, erionite or of~re-tite type, ~or example, are o~ considerable interest in the industrial practice as catalysts for hydrocarbon conversion reactions such as cracking, hydrocracking or lsomerization.
Zeolites of the pentasil type (for example Zeolite ~SM-5) become increasingly important as catalysts ~or the conver-sion of methanol to hydrocarbons.
Because of the numerous application possibilities as 20 catalysts, there is great interest in novel zeolites having specific catalytical properties.
Very interesting zeolites are for example obtained by incorporating other elements in~tead of aluminum and/or silicon into the zeolite frame. Thus, zeolites of the 25 pentasil series are known which contain boron (German Offenlegungsschrift No. 2,746,790), iron (German Offenle- j gungsschriPt No. 2,831,611), arsenic (German Auslegeschrift No. 2,830,830), antimony (German Offenle~ungsschrift No.
2,830,787), vanadium (German Offenlegungsschrift No.
30 2,831,631) chromium (German Offenlegungsschrift No. 2,831,630) or gallium ~Belgian Patent No. 842,484) in tetrahedral posi~ion.
Furthermore, titanosilicates (U.S. Patent No. 3,329,481 and zirconosilicates (U.S. Patent No. 3,329,480) have been 35 described.
Sub~ect of the invention are titano-aluminosilicates having a pentasil structure.
5~
- 3 - HOE 81/F 273 K
By pentasils, there are to be understood those defined by Ko-kotailo and Meier t~'Pentasil family of high silica crystal~
line materials" in: Special Publication No. 33 of the Chemi-cal Society, London 1980). The pentasil family comprises for example the synthetic zeolites ZSM-5 (US Patent No. 3,702,886), 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).
The titano-aluminosilicate of the invention differs from the titanosilicate according to U.S. PLatent No. 3,329,481 with respect to the structure and the aluminum content.
Subject of the invention are especially titano-alu-minosilicates having a ZSM-5 structure, preferably those having the following composition, expressed as molar ratio of oxides:
SiO2 : (0.001 - 0.15) Al2O3 : (0.002 - 1.0) TiO2 especially SiO2 : (0.005 - 0.1) Al2O3 : (0.01 - 0.4) TiO2.
The titano~aluminosilicates can be prepared according to the same methods and with the use o~ the same organic compounds as described for the synthesis of the titanium-~ree zeolite ~SM-5, for example with the use o~
alkylammonium compounds (U.S. Patent No. 3,702,886) alkylamines (U.g. Patent No. 4,151,189) alkyldiamines (German Offenlegungsschriften Nos. 2,817,576 and 2,831,334) alkylamines in the presence of alkylation agents (Published European Patent Application No. 11362, German Auslegeschrift No. 2,212,810) aminoalcohols (British Patent No. 2,023,562) alcohols (German Offenlegungsschri~ten Nos. 2,935,123, 2,643,929, U.S. Patents No3. 4,199,556, 4,175,114, Pub-lished European Patent Application No. 42225) ethers (European Patent Application No. 51741).
Preferably, alkylammonium compounds, alkyl diamines or alkylamines are used in the presence of alkylation agentq.
Especially preferred alkylammonium compounds are tetrapro-
By pentasils, there are to be understood those defined by Ko-kotailo and Meier t~'Pentasil family of high silica crystal~
line materials" in: Special Publication No. 33 of the Chemi-cal Society, London 1980). The pentasil family comprises for example the synthetic zeolites ZSM-5 (US Patent No. 3,702,886), 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).
The titano-aluminosilicate of the invention differs from the titanosilicate according to U.S. PLatent No. 3,329,481 with respect to the structure and the aluminum content.
Subject of the invention are especially titano-alu-minosilicates having a ZSM-5 structure, preferably those having the following composition, expressed as molar ratio of oxides:
SiO2 : (0.001 - 0.15) Al2O3 : (0.002 - 1.0) TiO2 especially SiO2 : (0.005 - 0.1) Al2O3 : (0.01 - 0.4) TiO2.
The titano~aluminosilicates can be prepared according to the same methods and with the use o~ the same organic compounds as described for the synthesis of the titanium-~ree zeolite ~SM-5, for example with the use o~
alkylammonium compounds (U.S. Patent No. 3,702,886) alkylamines (U.g. Patent No. 4,151,189) alkyldiamines (German Offenlegungsschriften Nos. 2,817,576 and 2,831,334) alkylamines in the presence of alkylation agents (Published European Patent Application No. 11362, German Auslegeschrift No. 2,212,810) aminoalcohols (British Patent No. 2,023,562) alcohols (German Offenlegungsschri~ten Nos. 2,935,123, 2,643,929, U.S. Patents No3. 4,199,556, 4,175,114, Pub-lished European Patent Application No. 42225) ethers (European Patent Application No. 51741).
Preferably, alkylammonium compounds, alkyl diamines or alkylamines are used in the presence of alkylation agentq.
Especially preferred alkylammonium compounds are tetrapro-
- 4 - HOE 81/F 273 K
pylammonium compounds, for example the hydroxide or one of the halides. A particularly suitable alkyldiarnine is hexa-methylene diamine.
For the synthe3is of the titano-aluminosilicates of the invention, one or more compounds from the cited classes are mixed with titanium, silicon, ~odium and aluminum com-pounds and water, and the mixture is heated in a closed ves-sel. 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, ex~
pressed as molar ratio of oxides:
SiO2 : (0.01 - 0.2) Al203 : (0.01 - 1.0) TiO2 :
(0.01 - 0.5) Na20 : (0~02 ~ 1~0) R20 : (5 ~ 100) H2O, preferably in a ratio of:
SiO2 : (0.01 - 0.1) Al203 : (0.01 - 0.4) TiO2 :
(0~02 ~ 0~3) Na2O : (0~03 ~ 0~6) R20 (10 ~ 40) H2O, R being tetrapropylammonium.
A~s silicon, aluminum, titanium and sodium compounds, there are used for example silica gel, sodium silicate, aluminum hydroxide, aluminum sulfate, sodium aluminate, aluminum ha~
lides, aluminum metahydroxide, titanium halides, titanium sulfate, sodium hydroxide, sodium sulfate, sodium halides.
Other compounds of the four cited elements are also suit-able for the manufacture of the zeolites according to the invention.
The mixture of the compounds chosen and water is ge-nerally heated for 18 to 360, preferably 24 to 240~ hoursat a temperature of from 100 to 200 C~ peferably 130 to 170 C, in a closed vessel.
The crystalline zeolites which are formed are isola-ted :in usual manner, for example by filtration, washed and dried. They can be converted according to known methods to catalytically active forms, for example by calcination and/or ion exchange (D.W. Breck, ~eolite Molecular Sieves, 1974)o ~5~
pylammonium compounds, for example the hydroxide or one of the halides. A particularly suitable alkyldiarnine is hexa-methylene diamine.
For the synthe3is of the titano-aluminosilicates of the invention, one or more compounds from the cited classes are mixed with titanium, silicon, ~odium and aluminum com-pounds and water, and the mixture is heated in a closed ves-sel. 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, ex~
pressed as molar ratio of oxides:
SiO2 : (0.01 - 0.2) Al203 : (0.01 - 1.0) TiO2 :
(0.01 - 0.5) Na20 : (0~02 ~ 1~0) R20 : (5 ~ 100) H2O, preferably in a ratio of:
SiO2 : (0.01 - 0.1) Al203 : (0.01 - 0.4) TiO2 :
(0~02 ~ 0~3) Na2O : (0~03 ~ 0~6) R20 (10 ~ 40) H2O, R being tetrapropylammonium.
A~s silicon, aluminum, titanium and sodium compounds, there are used for example silica gel, sodium silicate, aluminum hydroxide, aluminum sulfate, sodium aluminate, aluminum ha~
lides, aluminum metahydroxide, titanium halides, titanium sulfate, sodium hydroxide, sodium sulfate, sodium halides.
Other compounds of the four cited elements are also suit-able for the manufacture of the zeolites according to the invention.
The mixture of the compounds chosen and water is ge-nerally heated for 18 to 360, preferably 24 to 240~ hoursat a temperature of from 100 to 200 C~ peferably 130 to 170 C, in a closed vessel.
The crystalline zeolites which are formed are isola-ted :in usual manner, for example by filtration, washed and dried. They can be converted according to known methods to catalytically active forms, for example by calcination and/or ion exchange (D.W. Breck, ~eolite Molecular Sieves, 1974)o ~5~
- 5 ~ HOE ~l/F 273 K
After conversion to the catalytically active ~orm, the zeolites of the invention display high selectivity and a considerably reduced deposition of coke in the con~ersion of methanol to lower olefins. This reaction is carried out, for example, at temperatures between 350 and 430C using methanol with a water contant of O to 80 ~7 by weight or raw methanol.
The following Examples illustrate the invention with-out limiting it in its scope. All X-ray dif~raction data as indicated were obtained by means of a computer oontrolled powder diffractometer D-500 of the Siemens company. The radiation was the K- ~ doublet of copper.
Example 1 1.66 g of sodium aluminate (54 weight ~7 Al203, 41 weight % Na20) and 2.74 g o~ sodium hydroxide are dis-solved in 20 g oP 20 weight % aqueous tetrapropylammonium hydroxide solution (solution A). A further solution (solu-tion B) is obtained by dissolving 62 g of 40 weight % col-loidal silica gel in 230 g of 20 weight % aqueous tetrapro-pylammonium hydroxide solution and concentrating this solu-tion to a total 230 g in a rotation evaporator. The solu-tions A and B are mixed, and 2.2 g of titanium tetrachloride are added to this mixture with thorough stirring. The sus pension obtaiend is homogenized and heated for 120 hours at 160C in a closed vessel. The product formed is filtered oPf7 washed with water and dried at 120C. 29.7 g o~ ti-tano-aluminosilicate according to the invention is obtained.
An X-ray diffraction analysis shows a well crystal-li~ed product having a ZSM-5 structure. According to a chemical analysis of the product calcined for 16 hours at 540C, it has the following composition, expressed as molar ratio of oxides:
SiO2 : 0.047 TiO2 : 0.023 Al203 : 0.051 Na20.
~1 ~ ~ . . . _ s~
After conversion to the catalytically active ~orm, the zeolites of the invention display high selectivity and a considerably reduced deposition of coke in the con~ersion of methanol to lower olefins. This reaction is carried out, for example, at temperatures between 350 and 430C using methanol with a water contant of O to 80 ~7 by weight or raw methanol.
The following Examples illustrate the invention with-out limiting it in its scope. All X-ray dif~raction data as indicated were obtained by means of a computer oontrolled powder diffractometer D-500 of the Siemens company. The radiation was the K- ~ doublet of copper.
Example 1 1.66 g of sodium aluminate (54 weight ~7 Al203, 41 weight % Na20) and 2.74 g o~ sodium hydroxide are dis-solved in 20 g oP 20 weight % aqueous tetrapropylammonium hydroxide solution (solution A). A further solution (solu-tion B) is obtained by dissolving 62 g of 40 weight % col-loidal silica gel in 230 g of 20 weight % aqueous tetrapro-pylammonium hydroxide solution and concentrating this solu-tion to a total 230 g in a rotation evaporator. The solu-tions A and B are mixed, and 2.2 g of titanium tetrachloride are added to this mixture with thorough stirring. The sus pension obtaiend is homogenized and heated for 120 hours at 160C in a closed vessel. The product formed is filtered oPf7 washed with water and dried at 120C. 29.7 g o~ ti-tano-aluminosilicate according to the invention is obtained.
An X-ray diffraction analysis shows a well crystal-li~ed product having a ZSM-5 structure. According to a chemical analysis of the product calcined for 16 hours at 540C, it has the following composition, expressed as molar ratio of oxides:
SiO2 : 0.047 TiO2 : 0.023 Al203 : 0.051 Na20.
~1 ~ ~ . . . _ s~
- 6 - HOE 81/F 273 K
Example 2 The titano-aluminosilicate having a ZSM-5 structura prepared according to Example 1 (calcined form) is exchan-ged with ammonium nitrate solution, and to~ether with a binder (Boehmit) extruded (zeolite content 65 weight %), and calcined again as indicated in Example 1.
520 ml/h of 33 weight % aqueous methanol are dosed at a temperature of 350C under normal pressure to a verti-cally positioned, electrically heated tube reactor having a length of l m and packed with 250 ml of this catalyst. The reaction mixture which forms is cooled, and after separa-tion of the condensable portions the gaseous phase is ana-ly~ed. The C2-C4 olefin selectivity is 64 %, and the se-lectivlty to hydrocarbons having more than 4 carbon atoms is 13 %.
Comparative Example Operations are as in Example 2; however, instead of the titano-aluminosilicate a commercial aluminosilicate catalyst having a ZSM-5 structure is used.
The C2-C4 olefin selectivit~ is 56 %, and the se-lectivity to hydrocarbons having more than 4 carbon atoms is 23 %.
Example 2 The titano-aluminosilicate having a ZSM-5 structura prepared according to Example 1 (calcined form) is exchan-ged with ammonium nitrate solution, and to~ether with a binder (Boehmit) extruded (zeolite content 65 weight %), and calcined again as indicated in Example 1.
520 ml/h of 33 weight % aqueous methanol are dosed at a temperature of 350C under normal pressure to a verti-cally positioned, electrically heated tube reactor having a length of l m and packed with 250 ml of this catalyst. The reaction mixture which forms is cooled, and after separa-tion of the condensable portions the gaseous phase is ana-ly~ed. The C2-C4 olefin selectivity is 64 %, and the se-lectivlty to hydrocarbons having more than 4 carbon atoms is 13 %.
Comparative Example Operations are as in Example 2; however, instead of the titano-aluminosilicate a commercial aluminosilicate catalyst having a ZSM-5 structure is used.
The C2-C4 olefin selectivit~ is 56 %, and the se-lectivity to hydrocarbons having more than 4 carbon atoms is 23 %.
Claims (13)
PROPERTY OR PRIVILEGE IS CLAIMED ARE DEFINED AS FOLLOWS:
1. A titano-aluminosilicate having a pentasil structure.
2. A titano-aluminosilicate as claimed in claim 1 having a ZSM-5 structure.
3. A titano-aluminosilicate as claimed in claim 1 which contains silicon, aluminum and titanium in the following ratio:
SiO2 : (0.001 - 0.15) Al2O3 : (0.002 - 1.0) TiO2, expressed as molar ratio of oxides.
SiO2 : (0.001 - 0.15) Al2O3 : (0.002 - 1.0) TiO2, expressed as molar ratio of oxides.
4. A titano-aluminosilicate as claimed in claim 1 or claim 2 which contains silicon, aluminum and titanium in the following ratio:
SiO2 : (0.005 - 0.1) Al2O3 : (0.01 - 0.4) TiO2, expressed as molar ratio of oxides.
SiO2 : (0.005 - 0.1) Al2O3 : (0.01 - 0.4) TiO2, expressed as molar ratio of oxides.
5. A process for the preparation of a titano-aluminosilicate as claimed in claim 1 in which titanium, silicon, sodium, aluminum compounds and water are mixed with one or more organic compounds from the group consisting of alkylammonium compounds, alkylamines, alkyldiamines, aminoalcohols, alcohols and ethers, and the 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 or 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 : (0.01 - 0.2) Al2O3 : (0.01 - 1.0) TiO2 : (0.01 - 0.5) Na2O : (0.02 - 1.0) R2O : (5 - 100) H2O, R being tetrapropylammonium.
SiO2 : (0.01 - 0.2) Al2O3 : (0.01 - 1.0) TiO2 : (0.01 - 0.5) Na2O : (0.02 - 1.0) R2O : (5 - 100) H2O, R being tetrapropylammonium.
12. A process as claimed in claim 11 wherein the mixture has the following composition, expressed as molar ratio of oxides:
SiO2 : (0.01 - 0.1) Al2O3 : (0.01 - 0.4) TiO2 : (0.02 - 0.3) Na2O : (0.03 - 0.6) R2O : (10 - 40) H2O, R being tetrapropylammonium.
SiO2 : (0.01 - 0.1) Al2O3 : (0.01 - 0.4) TiO2 : (0.02 - 0.3) Na2O : (0.03 - 0.6) R2O : (10 - 40) H2O, 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 |
|---|---|---|---|
| DE19813141283 DE3141283A1 (en) | 1981-10-17 | 1981-10-17 | Titanium-containing zeolites and a process for their preparation, and their use |
| DEP3141283.1 | 1981-10-17 | ||
| DE19823219495 DE3219495A1 (en) | 1982-05-25 | 1982-05-25 | Titanium-containing zeolites, process for their preparation and their use |
| DEP3219495.1 | 1982-05-25 | ||
| DE19823231469 DE3231469A1 (en) | 1982-08-25 | 1982-08-25 | Titanium-containing zeolites, process for their preparation, and their use |
| DEP3231469.8 | 1982-08-25 |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| CA1185224A true CA1185224A (en) | 1985-04-09 |
Family
ID=27189626
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CA000413523A Expired CA1185224A (en) | 1981-10-17 | 1982-10-15 | Titanium-containing zeolites, process for their manufacture, and their use |
Country Status (5)
| Country | Link |
|---|---|
| EP (1) | EP0077522B1 (en) |
| AU (2) | AU544046B2 (en) |
| CA (1) | CA1185224A (en) |
| DE (1) | DE3266412D1 (en) |
| NZ (1) | NZ202184A (en) |
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US5656252A (en) * | 1994-01-28 | 1997-08-12 | Elf Aquitaine Production | Process for obtaining zeolites containing titanium |
Families Citing this family (19)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| DE3217324A1 (en) * | 1982-05-08 | 1983-11-10 | Hoechst Ag, 6230 Frankfurt | TITANIUM-CONTAINING ZEOLITES AND METHOD FOR THE PRODUCTION THEREOF AND THEIR USE |
| US4623526A (en) * | 1982-08-26 | 1986-11-18 | Centre De Recherche Industrielle Du Quebec | Process for the preparation of a crystalline titanoborosilicate |
| EP0132550A1 (en) * | 1983-06-27 | 1985-02-13 | Norton Company | Novel zeolite and process for preparation |
| US4917876A (en) * | 1984-04-13 | 1990-04-17 | Uop | Iron-titanium-aluminum-phosphorus-oxide molecular sieve compositions |
| US5098687A (en) * | 1984-04-26 | 1992-03-24 | Uop | Substituted aluminosilicate compositions and process for preparing same |
| US5160717A (en) * | 1984-04-26 | 1992-11-03 | Uop | Titanium-aluminum-silicon-oxide molecular sieve compositions |
| US4892720A (en) * | 1984-04-26 | 1990-01-09 | Uop | Substituted aluminosilicate compositions and process for preparing same |
| US4707345A (en) * | 1984-04-26 | 1987-11-17 | Union Carbide Corporation | Titanium-aluminum-silicon-oxide molecular sieve compositions and process for preparing the same |
| US5271761A (en) * | 1984-04-26 | 1993-12-21 | Uop | Substituted aluminosilicate compositions and process for preparing |
| BR8506691A (en) * | 1984-04-26 | 1986-04-15 | Union Carbide Corp | COMPOSITIONS OF MOLECULAR SIEVE OF TITANIUM ALUMINUM-SILICON OXIDE |
| IT1207519B (en) * | 1985-12-19 | 1989-05-25 | Eniricerche Spa | SYNTHETIC MATERIAL POROUS CRYSTALLINE CONTAINING SILICON OXIDE TITANIUM AND ALUMINUM. |
| AU586321B2 (en) * | 1986-02-24 | 1989-07-06 | General Environmental Technologies Limited | Sewage disposal |
| IT1204005B (en) * | 1987-05-05 | 1989-02-23 | Eniricerche Spa | PROCEDURE FOR OLIGOMIZING LIGHT OLEFINS OR THEIR MIXTURES |
| IT1222022B (en) * | 1987-07-14 | 1990-08-31 | Montedipe Spa | METHOD FOR THE PREPARATION OF A CATALYST FOR THE AMMOSSIMATION OF CARBONYL COMPOUNDS |
| NL9000501A (en) * | 1990-03-05 | 1991-10-01 | Oord Acz B V Van | VESSEL. |
| US5374747A (en) * | 1993-12-23 | 1994-12-20 | Arco Chemical Technology, L.P. | Epoxidation process and catalyst therefore |
| US5453511A (en) * | 1993-12-23 | 1995-09-26 | Arco Chemical Technology, L.P. | Bis-piperidinium compounds |
| US5474754A (en) | 1994-08-15 | 1995-12-12 | Arco Chemical Technology, L.P. | Preparation of an aluminosilicotitanate isomorphous with zeolite beta |
| JP2002239381A (en) * | 2001-02-22 | 2002-08-27 | Sumitomo Chem Co Ltd | Method for producing titanium-containing silicon oxide catalyst and catalyst prepared thereby |
Family Cites Families (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US3329481A (en) * | 1963-10-18 | 1967-07-04 | Union Oil Co | Crystalline titano-silicate zeolites |
| IT1127311B (en) * | 1979-12-21 | 1986-05-21 | Anic Spa | SYNTHETIC, CRYSTALLINE, POROUS MATERIAL CONSTITUTED BY SILICON AND TITANIUM OXIDES, METHOD FOR ITS PREPARATION AND ITS USES |
-
1982
- 1982-05-05 AU AU83401/82A patent/AU544046B2/en not_active Expired
- 1982-10-13 EP EP82109451A patent/EP0077522B1/en not_active Expired
- 1982-10-13 DE DE8282109451T patent/DE3266412D1/en not_active Expired
- 1982-10-15 NZ NZ202184A patent/NZ202184A/en unknown
- 1982-10-15 AU AU89401/82A patent/AU8940182A/en not_active Abandoned
- 1982-10-15 CA CA000413523A patent/CA1185224A/en not_active Expired
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US5656252A (en) * | 1994-01-28 | 1997-08-12 | Elf Aquitaine Production | Process for obtaining zeolites containing titanium |
Also Published As
| Publication number | Publication date |
|---|---|
| AU8340182A (en) | 1982-11-11 |
| AU8940182A (en) | 1983-04-28 |
| DE3266412D1 (en) | 1985-10-24 |
| NZ202184A (en) | 1985-07-12 |
| EP0077522A2 (en) | 1983-04-27 |
| AU544046B2 (en) | 1985-05-16 |
| EP0077522A3 (en) | 1984-03-07 |
| EP0077522B1 (en) | 1985-09-18 |
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| MKEX | Expiry |