NZ202184A - Titanium-containing zeolites and use as olefin producing catalysts - Google Patents
Titanium-containing zeolites and use as olefin producing catalystsInfo
- Publication number
- NZ202184A NZ202184A NZ202184A NZ20218482A NZ202184A NZ 202184 A NZ202184 A NZ 202184A NZ 202184 A NZ202184 A NZ 202184A NZ 20218482 A NZ20218482 A NZ 20218482A NZ 202184 A NZ202184 A NZ 202184A
- Authority
- NZ
- New Zealand
- Prior art keywords
- titano
- aluminosilicates
- compounds
- titanium
- mixture
- Prior art date
Links
- 239000010936 titanium Substances 0.000 title claims description 11
- 229910052719 titanium Inorganic materials 0.000 title claims description 10
- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical compound [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 title claims description 9
- 239000003054 catalyst Substances 0.000 title claims description 8
- 150000001336 alkenes Chemical class 0.000 title claims description 5
- 239000010457 zeolite Substances 0.000 title description 18
- JRZJOMJEPLMPRA-UHFFFAOYSA-N olefin Natural products CCCCCCCC=C JRZJOMJEPLMPRA-UHFFFAOYSA-N 0.000 title description 3
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 claims description 18
- 229910000323 aluminium silicate Inorganic materials 0.000 claims description 14
- 239000000203 mixture Substances 0.000 claims description 13
- 238000000034 method Methods 0.000 claims description 12
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N silicon dioxide Inorganic materials O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 claims description 11
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 claims description 7
- 229910052782 aluminium Inorganic materials 0.000 claims description 7
- 229910052710 silicon Inorganic materials 0.000 claims description 7
- 239000010703 silicon Substances 0.000 claims description 7
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 claims description 6
- 150000002894 organic compounds Chemical class 0.000 claims description 6
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 6
- 150000003973 alkyl amines Chemical class 0.000 claims description 5
- 125000005210 alkyl ammonium group Chemical group 0.000 claims description 5
- 238000004519 manufacturing process Methods 0.000 claims description 5
- 238000010438 heat treatment Methods 0.000 claims description 4
- 229910052708 sodium Inorganic materials 0.000 claims description 4
- 239000011734 sodium Substances 0.000 claims description 4
- OSBSFAARYOCBHB-UHFFFAOYSA-N tetrapropylammonium Chemical class CCC[N+](CCC)(CCC)CCC OSBSFAARYOCBHB-UHFFFAOYSA-N 0.000 claims description 4
- DGAQECJNVWCQMB-PUAWFVPOSA-M Ilexoside XXIX Chemical compound C[C@@H]1CC[C@@]2(CC[C@@]3(C(=CC[C@H]4[C@]3(CC[C@@H]5[C@@]4(CC[C@@H](C5(C)C)OS(=O)(=O)[O-])C)C)[C@@H]2[C@]1(C)O)C)C(=O)O[C@H]6[C@@H]([C@H]([C@@H]([C@H](O6)CO)O)O)O.[Na+] DGAQECJNVWCQMB-PUAWFVPOSA-M 0.000 claims description 3
- AZDRQVAHHNSJOQ-UHFFFAOYSA-N alumane Chemical class [AlH3] AZDRQVAHHNSJOQ-UHFFFAOYSA-N 0.000 claims description 3
- 150000001298 alcohols Chemical class 0.000 claims description 2
- 239000013078 crystal Substances 0.000 claims description 2
- 150000002170 ethers Chemical class 0.000 claims description 2
- 229940100198 alkylating agent Drugs 0.000 claims 1
- 239000002168 alkylating agent Substances 0.000 claims 1
- 150000001414 amino alcohols Chemical class 0.000 claims 1
- HNPSIPDUKPIQMN-UHFFFAOYSA-N dioxosilane;oxo(oxoalumanyloxy)alumane Chemical compound O=[Si]=O.O=[Al]O[Al]=O HNPSIPDUKPIQMN-UHFFFAOYSA-N 0.000 description 7
- 229910021536 Zeolite Inorganic materials 0.000 description 6
- 238000006243 chemical reaction Methods 0.000 description 6
- HEMHJVSKTPXQMS-UHFFFAOYSA-M sodium hydroxide Inorganic materials [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 5
- 150000001875 compounds Chemical class 0.000 description 4
- 229930195733 hydrocarbon Natural products 0.000 description 4
- 150000002430 hydrocarbons Chemical class 0.000 description 4
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 description 2
- PMZURENOXWZQFD-UHFFFAOYSA-L Sodium Sulfate Chemical compound [Na+].[Na+].[O-]S([O-])(=O)=O PMZURENOXWZQFD-UHFFFAOYSA-L 0.000 description 2
- 238000002441 X-ray diffraction Methods 0.000 description 2
- -1 aluminum halides Chemical class 0.000 description 2
- ANBBXQWFNXMHLD-UHFFFAOYSA-N aluminum;sodium;oxygen(2-) Chemical compound [O-2].[O-2].[Na+].[Al+3] ANBBXQWFNXMHLD-UHFFFAOYSA-N 0.000 description 2
- 230000015572 biosynthetic process Effects 0.000 description 2
- 125000004432 carbon atom Chemical group C* 0.000 description 2
- 150000004820 halides Chemical class 0.000 description 2
- NAQMVNRVTILPCV-UHFFFAOYSA-N hexane-1,6-diamine Chemical group NCCCCCCN NAQMVNRVTILPCV-UHFFFAOYSA-N 0.000 description 2
- 150000002500 ions Chemical class 0.000 description 2
- 239000002808 molecular sieve Substances 0.000 description 2
- 239000011148 porous material Substances 0.000 description 2
- 239000000741 silica gel Substances 0.000 description 2
- 229910002027 silica gel Inorganic materials 0.000 description 2
- 229910001388 sodium aluminate Inorganic materials 0.000 description 2
- URGAHOPLAPQHLN-UHFFFAOYSA-N sodium aluminosilicate Chemical compound [Na+].[Al+3].[O-][Si]([O-])=O.[O-][Si]([O-])=O URGAHOPLAPQHLN-UHFFFAOYSA-N 0.000 description 2
- 239000000126 substance Substances 0.000 description 2
- 238000003786 synthesis reaction Methods 0.000 description 2
- LPSKDVINWQNWFE-UHFFFAOYSA-M tetrapropylazanium;hydroxide Chemical compound [OH-].CCC[N+](CCC)(CCC)CCC LPSKDVINWQNWFE-UHFFFAOYSA-M 0.000 description 2
- PAWQVTBBRAZDMG-UHFFFAOYSA-N 2-(3-bromo-2-fluorophenyl)acetic acid Chemical compound OC(=O)CC1=CC=CC(Br)=C1F PAWQVTBBRAZDMG-UHFFFAOYSA-N 0.000 description 1
- ZOXJGFHDIHLPTG-UHFFFAOYSA-N Boron Chemical compound [B] ZOXJGFHDIHLPTG-UHFFFAOYSA-N 0.000 description 1
- 239000004215 Carbon black (E152) Substances 0.000 description 1
- VYZAMTAEIAYCRO-UHFFFAOYSA-N Chromium Chemical compound [Cr] VYZAMTAEIAYCRO-UHFFFAOYSA-N 0.000 description 1
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 description 1
- GYHNNYVSQQEPJS-UHFFFAOYSA-N Gallium Chemical compound [Ga] GYHNNYVSQQEPJS-UHFFFAOYSA-N 0.000 description 1
- 239000004115 Sodium Silicate Substances 0.000 description 1
- 239000003463 adsorbent Substances 0.000 description 1
- 230000029936 alkylation Effects 0.000 description 1
- 238000005804 alkylation reaction Methods 0.000 description 1
- WNROFYMDJYEPJX-UHFFFAOYSA-K aluminium hydroxide Chemical compound [OH-].[OH-].[OH-].[Al+3] WNROFYMDJYEPJX-UHFFFAOYSA-K 0.000 description 1
- DIZPMCHEQGEION-UHFFFAOYSA-H aluminium sulfate (anhydrous) Chemical compound [Al+3].[Al+3].[O-]S([O-])(=O)=O.[O-]S([O-])(=O)=O.[O-]S([O-])(=O)=O DIZPMCHEQGEION-UHFFFAOYSA-H 0.000 description 1
- 208000028462 aluminosis Diseases 0.000 description 1
- 238000004458 analytical method Methods 0.000 description 1
- 229910052787 antimony Inorganic materials 0.000 description 1
- WATWJIUSRGPENY-UHFFFAOYSA-N antimony atom Chemical compound [Sb] WATWJIUSRGPENY-UHFFFAOYSA-N 0.000 description 1
- 229910052785 arsenic Inorganic materials 0.000 description 1
- RQNWIZPPADIBDY-UHFFFAOYSA-N arsenic atom Chemical compound [As] RQNWIZPPADIBDY-UHFFFAOYSA-N 0.000 description 1
- 239000011230 binding agent Substances 0.000 description 1
- 229910052796 boron Inorganic materials 0.000 description 1
- 238000001354 calcination Methods 0.000 description 1
- 229910052799 carbon Inorganic materials 0.000 description 1
- 238000004517 catalytic hydrocracking Methods 0.000 description 1
- 150000001768 cations Chemical class 0.000 description 1
- 239000003795 chemical substances by application Substances 0.000 description 1
- 229910052804 chromium Inorganic materials 0.000 description 1
- 239000011651 chromium Substances 0.000 description 1
- 239000000571 coke Substances 0.000 description 1
- 230000000052 comparative effect Effects 0.000 description 1
- 229910052802 copper Inorganic materials 0.000 description 1
- 239000010949 copper Substances 0.000 description 1
- 238000005336 cracking Methods 0.000 description 1
- 239000002178 crystalline material Substances 0.000 description 1
- 230000008021 deposition Effects 0.000 description 1
- 229910052675 erionite Inorganic materials 0.000 description 1
- 238000001914 filtration Methods 0.000 description 1
- 229910052733 gallium Inorganic materials 0.000 description 1
- 239000007792 gaseous phase Substances 0.000 description 1
- XLYOFNOQVPJJNP-UHFFFAOYSA-M hydroxide Chemical compound [OH-] XLYOFNOQVPJJNP-UHFFFAOYSA-M 0.000 description 1
- 238000005342 ion exchange Methods 0.000 description 1
- 229910052742 iron Inorganic materials 0.000 description 1
- 238000006317 isomerization reaction Methods 0.000 description 1
- 229910052680 mordenite Inorganic materials 0.000 description 1
- 239000000843 powder Substances 0.000 description 1
- 230000005855 radiation Effects 0.000 description 1
- 239000011541 reaction mixture Substances 0.000 description 1
- 238000000926 separation method Methods 0.000 description 1
- 239000000377 silicon dioxide Substances 0.000 description 1
- 150000003388 sodium compounds Chemical class 0.000 description 1
- NTHWMYGWWRZVTN-UHFFFAOYSA-N sodium silicate Chemical compound [Na+].[Na+].[O-][Si]([O-])=O NTHWMYGWWRZVTN-UHFFFAOYSA-N 0.000 description 1
- 229910052911 sodium silicate Inorganic materials 0.000 description 1
- 229910052938 sodium sulfate Inorganic materials 0.000 description 1
- 235000011152 sodium sulphate Nutrition 0.000 description 1
- 239000007858 starting material Substances 0.000 description 1
- 238000003756 stirring Methods 0.000 description 1
- XJDNKRIXUMDJCW-UHFFFAOYSA-J titanium tetrachloride Chemical compound Cl[Ti](Cl)(Cl)Cl XJDNKRIXUMDJCW-UHFFFAOYSA-J 0.000 description 1
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
Landscapes
- Chemical & Material Sciences (AREA)
- Engineering & Computer Science (AREA)
- Organic Chemistry (AREA)
- General Engineering & Computer Science (AREA)
- Life Sciences & Earth Sciences (AREA)
- General Life Sciences & Earth Sciences (AREA)
- Geology (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Materials Engineering (AREA)
- Structural Engineering (AREA)
- Mechanical Engineering (AREA)
- Paleontology (AREA)
- Ocean & Marine Engineering (AREA)
- Combustion & Propulsion (AREA)
- Civil Engineering (AREA)
- Mining & Mineral Resources (AREA)
- Transportation (AREA)
- Inorganic Chemistry (AREA)
- Catalysts (AREA)
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
- Silicates, Zeolites, And Molecular Sieves (AREA)
Description
New Zealand Paient Spedficaiion for Paient Number £02184
i
Pr»o»^- • • •
Complete Specification Filed: •*??•
mi r t>\S>2zf2&- &c{^3.£l lc£*. .
Class »••••• •"/• • ■1 ■'1 •J ' *
co-id 10-3- R 2 JUL 1985
PubHoation Date: ... •.
H 0. Me: ...•••• t • • •»
202184
I
NO
N.Z. No.
NEW ZEALAND
Patents Act 1953
COMPLETE SPECIFICATION
^T%>
[* iS°cT I9&2
&
"Titanium-containing zeolites, process for their manufacture, and their use."
We, HOECHST AKTIENGESELLSCHAFT, a corporation organized under the laws of the Federal Republic of Germany,of D-6230 Frankfurt/Main 80, 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
2 -
ttqq^ ..•'Pitriii
Zeolites are crystalline aluminosi.licates, in which due to a three-dimensional linkage of SiO^ and AlO^ tetrahedra regular structures with cavities and pores are formed. In hydrated state, these pores and cavities are filled v/itb 5 »ater, which, on the other hand, can be easily removed without influencing the crystalline structure, or replaced by other molecules. The negative charges of the AlO^ tetrahedra are balanced by cations, which can be replaced by other ions of positive charge. These properties allow the 10 use of the zeolites as ion exchangers, adsorbents and catalysts (D.W. Breck: Zeolite Molecular Sieves, 1974).
Zeolites of the X, If, mordenite, erionite or offre-tite type, for example, are of considerable interest in the industrial practice as catalysts for hydrocarbon conversion 15 reactions such as cracking, hydrocracking or isomerization. Zeolites of the pentasil type (for example Zeolite ZSM-5) become increasingly important as catalysts for the conversion of methanol to hydrocarbons.
catalysts, there is great interest in novel zeolites having specific catalytical properties.
Very interesting zeolites are for example obtained by incorporating other elements instead of aluminum and/or silicon into the zeolite frame. Thus, zeolites of the 25 pentasil series are known which contain boron,
iron, arsenic, antimony, vanadium^ chromium or gallium in tatrahedral position.
Furthermore, titanosilicates (U.S. Patent No.3,329,481) and zirconosilicates (U.S. Patent No.3,329,480) have been described.
Subject of the invention are titano—aluminosilicates having a pentasil structure.
Because of the numerous application possibilities as
&Q2184
O*1 ' T? O: T **"
By pentasils, there are to be understood those defined by Kc»-kotailo and Meier ("Pentasil family of high silica crystalline materials" in: Special Publication No. 33 of the Chemical Society, London 1980). The pentasil family comprises for 5 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. 3,709,579) 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 10 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:
Si02 : (0.001 - 0.15) Al^ : (0.002 - 1.0) Ti02 especially
Si02 : (0.005 - 0.1) ^2°3 : (0-01 " Ti02.
The titano-aluminosilicates can be prepared according to the same methods and with the use of the same organic compounds as described for the synthesis of the titanium-free zeolite ZSM-5, for example with the use of alkylammonium compounds (U.S. Patent No. 3,702,886) 25 alkylamines (U.S. Patent No. 4,151,189)
alkyldiamines alkylamines in the presence of alkylation agents (Published European Patent Application No. 1 1362 )
aiuinoalcohols (British Patent No. 2,023,562)
alcohols
(U.S. Patents Nos. 4,199,556, 4,175,114, Published European Patent Application No. 42225)
ethers (European Patent Application No. 51741).
Preferably, alkylammonium compounds, alkyl^.-diaK.ines or
;■ ^ l'y ^ ^ ^
alkylamines are used in the presence of alkylaxion agfen-ts.
/ >V o
Especially preferred alkylammonium compounds^j©re tetrap'tj.iD-
202184
pylammonium compounds, for example the hydroxide or one of the halides. A particularly suitable allcyldiamine is hexa-methylene diamine. ■
For the synthesis of the titano-aluminosilicates of 5 the invention, one or more compounds from the cited classes are mixed with titanium, silicon, sodium and aluminum compounds and water, 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 10 tetrapropylammonium compounds are used, the starting compounds are generally used in the following ratio, 3x~ pressed as molar ratio of oxides: . ,
Si02 : (0.01 - 0.2) AlgO : (0.01 - 1.0) Ti.02 :
(0.01 - 0.5) Na20 : (0.02 - 1.0) R20 : (5 - 100) H20, preferably in a ratio of:
Si02 : (0.01 - 0.1) A12C>3 : (0.01 - 0.4) Ti02 :
(0.02 - 0.3) Na20 : (0.03 - 0.6) 3^0 : (10 - 40) Ho0>
R being tetrapropylamnioniurfi.
As silicon, aluminum, titanium and sodium compounds, there are used for example silica gel, sodium silicate, aluminum hydroxide, aluminum sulfate, sodium aluminate, aluminum halides, aluminum metahydroxide, titanium halides, titanium 25 sulfate, sodium hydroxide, sodium sulfate, sodium halides. Other compounds of the four cited elements are also suitable for the manufacture of the zeolites according to the invention.
The mixture of the compounds chosen and water is ge-30 nerally heated for 18 to 360, preferably 24 to 240, hours at a temperature of from 100 to 200°C, peferably 130 to 170°C, in a closed vessel.
The crystalline zeolites which are formed are isolated in usual manner, for example by filtration, washed and 35 dried. They can be converted according to known methods to catalytically active forms, for example by calcination and/or ion exchange (D.W. Breck, Zeolite Molecular Sieves, 1974).
20218 A
- 5 -•
Aftav conversion to the catalytically active form, the zeolites of the invention display high selectivity and a considerably reduced deposition of coke in the conversion of methanol to lower olefins. This reaction is carried out, for 5 example, at temperatures between 350 and 430°C using methanol with a water content of 0 to 80 % by weight or raw methanol.
The following Examples illustrate the invention without limiting it in its scope. All X-ray diffraction data as 10 indicated were obtained by means of a computer-controlled powder diffractometer D-500 of the Siemens company. The radiation was the K-c^doublet of copper.
Example 1
1.66 g of sodium aluminate (54 weight % Al^O^,
41 weight % Na^O) and 2.74 g of sodium hydroxide are dissolved in 20 g of 20 weight % aqueous tetrapropylammonium hydroxide, solution (solution A).-A further solution (solution B) is obtained by.dissolving 62 g of 40 weight % col-20 loidal silica gel in 230 g of 20 weight % aqueous tetrapropylammonium hydroxide solution and concentrating this solution to a total 230 g in a rotation evaporator. The solutions A and B are mixed, and 2.2 g of titanium tetrachloride are added to this mixture'with thorough stirring. The sus-25 pension obtaiend is homogenized and heated for 120 hours at 160°C in a closed vessel. The product formed is filtered off, washed with water and dried at 120°C. 29*7 g of ti-tano-aluminosilieate according to the invention is obtained.
An X-ray diffraction analysis shows a well crystal-30 lised product having a ZSM-5 structure. According to a chemical analysis of the product calcined for 16 hours at 540°C, it has the following composition, expressed as molar ratio of oxides:
SiO^ : 0.047 Ti02 : 0.023 Al^ : 0.051 Na20.
S;: amp la 2
The titano-aluminosilicate having a ZSM-5 structure prepared according to Example 1 (calcined form) is exchanged with ammonium nitrate solution,, and together with a 5 binder (Boehmit) extruded (zeolite content 65 weight %), and calcined again as indicated in Example 1.
520 ral/h of 33 weight % aqueous methanol, are dosed at a temperature of 350°C under normal pressure to a vertically positioned, electrically heated tube reactor having a 10 length of 1 ra and packed with 250 ml of this catalyst. The reaction mixture which forms is cooled, and after separation of the condensable portions the gaseous phase is analyzed. The olefin selectivity is 64 %, and the selectivity to hydrocarbons having more than 4 carbon atoms 15 is 13 %.
■ Comparative Example
Operations are as in Example 2; however, instead of the t^tano—alumi nosilic-^ate a connnercj-al aluriiinosxlicate 20 catalyst having a ZSM-5 structure is used.
The olefin selectivity is 56 and the se lectivity to hydrocarbons having more than 4 carbon atoms is 23 %.
* *uzl84
Claims (14)
1. Titano-aluminosilicates having a pentsil structure.
2. Titano-aluminosilicates having a ZSM-5 structure. 5 3. Titano-aluminosilicates as claimed in Claim 1 or 2, which contain silicon, aluminum and titanium in the following ratio: 10
Si02 : (0.001 - 0.15) AlgO : (0.002 - 1.0) Ti02, expressed as molar ratio of oxides.
4. Titano-aluminosilicates as claimed in Claims 1 to 3, which contain silicon, aluminum and titanium in the 15 following ratio: Si02 : (0.005 - 0. 1) Al^ : (0.01 - C.'i) Ti02> expressed as molar ratio of oxides. 20
5. A process for the manufacture of titano-aluminosilicates as claimed in one of Claims 1 to 4, which comprises mixing titanium, silicon, sodium, aluminum compounds and water with one or more organic compounds from the group 25 consisting of alkylammonium compounds, alkylamines, alkyldiamines, aminoalcohols, alcohols and ethers, and heating this mixture in a closed vessel.
6. The process as claimed in Claim 5, which comprises using 30 alkylammonium compounds as organic compounds.
7. The process as claimed in Claim 5, which comprises using tetrapropylammonium compounds as organic compounds. 1 •sa — IJ ~ 202184
8. The process as claimed in Claim 5, which comprises using alkylamines in the presence of alkylating agents as organic compounds. 5
9. The process as claimed in Claim 5, which comprises using alkyldiamines as organic compounds.
10. The process as claimed in one of Claims 5 to 9, which comprises adding seed crystals of a pentasil to the mixture 10 before heating.
11. A process for the manufacture of titano-aluminosilicates as claimed in one of Claims 1 to 4, which comprises preparing a mixture of titanium, silicon, sodium, tetrapro-15 pylammonium, aluminum compounds and water having the following composition, expressed as molar ratio of oxides: p n .rnp-tI=0'^ • Vrir>i^in,jT-;r> . \ w • v i ij « l. / n a ^ v • \ u ♦ v i i • v / j. j. V/n • C. d. j 20 (0.01 - 0.5) Na20 : (0.02 - 1.0) R20 : (5 - 100) H20, R being tetrapropylammonium, and heating this mixture in a closed vessel. 25
12. The process as claimed in Claim 11, wherein the mixture to be heated has the following composition, expressed as molar ratio of oxides: Si02 : (0.01 - 0.1) A1203 : (0.01 - 0.4) TiC>2 : 30 (0.02 - 0.3) Na20 : (0.03 - 0.6) R20 : (10 - 40) H20, R being tetrapropylammonium. 35
13. Use of titano-aluminosilicates as claimed in one of Claims 1 to 4 as catalysts for the manufacture of Cp-C^ olefins from methanol. - 9 - 202184
14. Titano-aluminosilicates according to claim 1 or claim 2 substantially as hereinbefore described. HOECHST AKTIENGESELLSCHAFT By Their Attorneys
Applications Claiming Priority (3)
| 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 |
| DE19823219495 DE3219495A1 (en) | 1982-05-25 | 1982-05-25 | Titanium-containing zeolites, process for their preparation and their use |
| DE19823231469 DE3231469A1 (en) | 1982-08-25 | 1982-08-25 | Titanium-containing zeolites, process for their preparation, and their use |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| NZ202184A true NZ202184A (en) | 1985-07-12 |
Family
ID=27189626
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| NZ202184A NZ202184A (en) | 1981-10-17 | 1982-10-15 | Titanium-containing zeolites and use as olefin producing catalysts |
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) |
Families Citing this family (20)
| 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 |
| 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 |
| US5160717A (en) * | 1984-04-26 | 1992-11-03 | Uop | Titanium-aluminum-silicon-oxide molecular sieve compositions |
| US5271761A (en) * | 1984-04-26 | 1993-12-21 | Uop | Substituted aluminosilicate compositions and process for preparing |
| US5098687A (en) * | 1984-04-26 | 1992-03-24 | Uop | Substituted aluminosilicate compositions and process for preparing same |
| AU580781B2 (en) * | 1984-04-26 | 1989-02-02 | Union Carbide Corporation | Titanium-aluminum-silicon-oxide molecular sieve compositions |
| 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. |
| US5453511A (en) * | 1993-12-23 | 1995-09-26 | Arco Chemical Technology, L.P. | Bis-piperidinium compounds |
| US5374747A (en) * | 1993-12-23 | 1994-12-20 | Arco Chemical Technology, L.P. | Epoxidation process and catalyst therefore |
| FR2715647B1 (en) * | 1994-01-28 | 1996-04-05 | Elf Aquitaine | Process for obtaining zeolites containing titanium. |
| 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 |
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 DE DE8282109451T patent/DE3266412D1/en not_active Expired
- 1982-10-13 EP EP82109451A patent/EP0077522B1/en not_active Expired
- 1982-10-15 CA CA000413523A patent/CA1185224A/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
Also Published As
| Publication number | Publication date |
|---|---|
| AU544046B2 (en) | 1985-05-16 |
| DE3266412D1 (en) | 1985-10-24 |
| CA1185224A (en) | 1985-04-09 |
| AU8340182A (en) | 1982-11-11 |
| EP0077522B1 (en) | 1985-09-18 |
| EP0077522A3 (en) | 1984-03-07 |
| EP0077522A2 (en) | 1983-04-27 |
| AU8940182A (en) | 1983-04-28 |
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