DE3231469A1 - Titanium-containing zeolites, process for their preparation, and their use - Google Patents
Titanium-containing zeolites, process for their preparation, and their useInfo
- Publication number
- DE3231469A1 DE3231469A1 DE19823231469 DE3231469A DE3231469A1 DE 3231469 A1 DE3231469 A1 DE 3231469A1 DE 19823231469 DE19823231469 DE 19823231469 DE 3231469 A DE3231469 A DE 3231469A DE 3231469 A1 DE3231469 A1 DE 3231469A1
- Authority
- DE
- Germany
- Prior art keywords
- compounds
- titanium
- mixture
- titanoaluminosilicates
- aluminum
- 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.)
- Withdrawn
Links
- 238000002360 preparation method Methods 0.000 title claims abstract description 5
- 229910052719 titanium Inorganic materials 0.000 title claims description 15
- 239000010936 titanium Substances 0.000 title claims description 15
- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical compound [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 title claims description 14
- 238000000034 method Methods 0.000 title claims description 13
- 239000010457 zeolite Substances 0.000 title abstract description 20
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 claims abstract description 21
- 239000000203 mixture Substances 0.000 claims abstract description 15
- 229910001868 water Inorganic materials 0.000 claims abstract description 12
- 239000003054 catalyst Substances 0.000 claims abstract description 8
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 8
- 150000001875 compounds Chemical class 0.000 claims abstract description 6
- OSBSFAARYOCBHB-UHFFFAOYSA-N tetrapropylammonium Chemical class CCC[N+](CCC)(CCC)CCC OSBSFAARYOCBHB-UHFFFAOYSA-N 0.000 claims abstract description 6
- 238000010438 heat treatment Methods 0.000 claims abstract description 4
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 claims description 18
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N Titan oxide Chemical compound O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 claims description 8
- 229910052681 coesite Inorganic materials 0.000 claims description 8
- 229910052906 cristobalite Inorganic materials 0.000 claims description 8
- 229910052682 stishovite Inorganic materials 0.000 claims description 8
- 229910052905 tridymite Inorganic materials 0.000 claims description 8
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 claims description 7
- -1 alkyldiamines Chemical class 0.000 claims description 7
- 229910052782 aluminium Inorganic materials 0.000 claims description 7
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 claims description 7
- 229910000323 aluminium silicate Inorganic materials 0.000 claims description 7
- 229910052593 corundum Inorganic materials 0.000 claims description 7
- 229910052710 silicon Inorganic materials 0.000 claims description 7
- 239000010703 silicon Substances 0.000 claims description 7
- 239000000377 silicon dioxide Substances 0.000 claims description 7
- 229910001845 yogo sapphire Inorganic materials 0.000 claims description 7
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 claims description 6
- 235000012239 silicon dioxide Nutrition 0.000 claims description 6
- KKCBUQHMOMHUOY-UHFFFAOYSA-N Na2O Inorganic materials [O-2].[Na+].[Na+] KKCBUQHMOMHUOY-UHFFFAOYSA-N 0.000 claims description 5
- 150000001336 alkenes Chemical class 0.000 claims description 4
- 150000003973 alkyl amines Chemical class 0.000 claims description 4
- 239000011734 sodium Substances 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
- 229910000272 alkali metal oxide Inorganic materials 0.000 claims description 3
- 125000005210 alkyl ammonium group Chemical group 0.000 claims description 3
- 239000002168 alkylating agent Substances 0.000 claims description 3
- 229940100198 alkylating agent Drugs 0.000 claims description 3
- AZDRQVAHHNSJOQ-UHFFFAOYSA-N alumane Chemical class [AlH3] AZDRQVAHHNSJOQ-UHFFFAOYSA-N 0.000 claims description 3
- 239000013078 crystal Substances 0.000 claims description 3
- 229910052708 sodium Inorganic materials 0.000 claims description 3
- 150000001298 alcohols Chemical class 0.000 claims description 2
- 150000001414 amino alcohols Chemical class 0.000 claims description 2
- 150000002170 ethers Chemical class 0.000 claims description 2
- 150000002894 organic compounds Chemical class 0.000 claims 3
- 238000004519 manufacturing process Methods 0.000 claims 1
- OGIDPMRJRNCKJF-UHFFFAOYSA-N titanium oxide Inorganic materials [Ti]=O OGIDPMRJRNCKJF-UHFFFAOYSA-N 0.000 claims 1
- 238000002156 mixing Methods 0.000 abstract description 2
- 150000003388 sodium compounds Chemical class 0.000 abstract description 2
- 150000001399 aluminium compounds Chemical class 0.000 abstract 1
- 229940077746 antacid containing aluminium compound Drugs 0.000 abstract 1
- 229920001296 polysiloxane Chemical class 0.000 abstract 1
- 150000003609 titanium compounds Chemical class 0.000 abstract 1
- HNPSIPDUKPIQMN-UHFFFAOYSA-N dioxosilane;oxo(oxoalumanyloxy)alumane Chemical compound O=[Si]=O.O=[Al]O[Al]=O HNPSIPDUKPIQMN-UHFFFAOYSA-N 0.000 description 10
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 6
- 229910021536 Zeolite Inorganic materials 0.000 description 6
- 238000006243 chemical reaction Methods 0.000 description 4
- 229930195733 hydrocarbon Natural products 0.000 description 4
- 150000002430 hydrocarbons Chemical class 0.000 description 4
- 238000002441 X-ray diffraction Methods 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
- 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
- JRZJOMJEPLMPRA-UHFFFAOYSA-N olefin Natural products CCCCCCCC=C JRZJOMJEPLMPRA-UHFFFAOYSA-N 0.000 description 2
- 239000011148 porous material 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
- 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
- 229910018072 Al 2 O 3 Inorganic materials 0.000 description 1
- ZOXJGFHDIHLPTG-UHFFFAOYSA-N Boron Chemical compound [B] ZOXJGFHDIHLPTG-UHFFFAOYSA-N 0.000 description 1
- VYZAMTAEIAYCRO-UHFFFAOYSA-N Chromium Chemical compound [Cr] VYZAMTAEIAYCRO-UHFFFAOYSA-N 0.000 description 1
- GYHNNYVSQQEPJS-UHFFFAOYSA-N Gallium Chemical compound [Ga] GYHNNYVSQQEPJS-UHFFFAOYSA-N 0.000 description 1
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 description 1
- 239000004115 Sodium Silicate Substances 0.000 description 1
- 239000003463 adsorbent Substances 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
- 238000004458 analytical method Methods 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
- 230000015572 biosynthetic process Effects 0.000 description 1
- 229910001593 boehmite Inorganic materials 0.000 description 1
- 229910052796 boron Inorganic materials 0.000 description 1
- 238000001354 calcination Methods 0.000 description 1
- 125000004432 carbon atom Chemical group C* 0.000 description 1
- 230000003197 catalytic effect Effects 0.000 description 1
- 238000004517 catalytic hydrocracking Methods 0.000 description 1
- 150000001768 cations Chemical class 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
- 239000008119 colloidal silica Substances 0.000 description 1
- 230000000052 comparative effect Effects 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
- 150000004820 halides Chemical class 0.000 description 1
- XLYOFNOQVPJJNP-UHFFFAOYSA-M hydroxide Chemical compound [OH-] XLYOFNOQVPJJNP-UHFFFAOYSA-M 0.000 description 1
- FAHBNUUHRFUEAI-UHFFFAOYSA-M hydroxidooxidoaluminium Chemical compound O[Al]=O FAHBNUUHRFUEAI-UHFFFAOYSA-M 0.000 description 1
- 229910001387 inorganic aluminate Inorganic materials 0.000 description 1
- 229910052909 inorganic silicate Inorganic materials 0.000 description 1
- 238000005342 ion exchange Methods 0.000 description 1
- 238000006317 isomerization reaction Methods 0.000 description 1
- 229910052680 mordenite Inorganic materials 0.000 description 1
- 235000013348 organic food Nutrition 0.000 description 1
- DCKVFVYPWDKYDN-UHFFFAOYSA-L oxygen(2-);titanium(4+);sulfate Chemical compound [O-2].[Ti+4].[O-]S([O-])(=O)=O DCKVFVYPWDKYDN-UHFFFAOYSA-L 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
- 239000000741 silica gel Substances 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
- 239000007858 starting material Substances 0.000 description 1
- 238000003756 stirring Methods 0.000 description 1
- 239000000725 suspension Substances 0.000 description 1
- 238000003786 synthesis reaction Methods 0.000 description 1
- 229910000348 titanium sulfate Inorganic materials 0.000 description 1
- XJDNKRIXUMDJCW-UHFFFAOYSA-J titanium tetrachloride Chemical compound Cl[Ti](Cl)(Cl)Cl XJDNKRIXUMDJCW-UHFFFAOYSA-J 0.000 description 1
Classifications
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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
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J29/00—Catalysts comprising molecular sieves
- B01J29/89—Silicates, aluminosilicates or borosilicates of titanium, zirconium or hafnium
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C1/00—Preparation of hydrocarbons from one or more compounds, none of them being a hydrocarbon
- C07C1/20—Preparation of hydrocarbons from one or more compounds, none of them being a hydrocarbon starting from organic compounds containing only oxygen atoms as heteroatoms
-
- 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)
- Organic Chemistry (AREA)
- Life Sciences & Earth Sciences (AREA)
- General Life Sciences & Earth Sciences (AREA)
- Geology (AREA)
- Engineering & Computer Science (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Materials Engineering (AREA)
- Inorganic Chemistry (AREA)
- Silicates, Zeolites, And Molecular Sieves (AREA)
- Catalysts (AREA)
Abstract
Description
Titanhaltige Zeolithe und Verfahren zu ihrer HerstellungTitanium-containing zeolites and processes for their preparation
sowie ihre Verwendung ~~~~~~~~~~~~~~~~~~~~--~~~~~~~ Zeolithe sind kristalline Aluminosilicate, bei denen durch eine dreidimensionale Verknüpfung von SiO4- und AlO14-Tetraedern regelmäßige Strukturen mit Hohlräumen und Poren entstehen. Im hydratisierten Zustand sind diese Poren und Hohlräume mit Wasser gefüllt. Dieses läßt sich ohne Beeinflussung der Kristallstruktur entfernten oder durch andere Moleküle ersetzen. Die negativen Ladungen-der Al04-Tetraeder werden durch Kationen kompensiert. Diese können gegen andere positiv geladene Ionen ausgetauscht werden. Die geschilderten Eigenschaften ermöglichen die Verwendung der Zeolithe als Ionenaustauscher, Adsorbentien und Katalysatoren (D.W. Breck: Zeolite Molecular Sieves, 1974).as well as their use ~~~~~~~~~~~~~~~~~~~~ - ~~~~~~~ zeolites crystalline aluminosilicates, in which a three-dimensional linkage of SiO4 and AlO14 tetrahedra result in regular structures with cavities and pores. When hydrated, these pores and cavities are filled with water. This can be removed without affecting the crystal structure or by other molecules substitute. The negative charges of the AlO4 tetrahedra are compensated for by cations. These can be exchanged for other positively charged ions. The described Properties enable the use of zeolites as ion exchangers, adsorbents and catalysts (D.W. Breck: Zeolite Molecular Sieves, 1974).
Zeolithe des X-, Y-, Mordenit-, Erionit- und Offretit-Typs beispielsweise besitzen als Katalysatoren für Umwandlungsreaktionen von Kohlenwasserstoffen wie Cracken, Hydrocracken oder Isomerisierungen beträchtliches technisches Interesse.Zeolites of the X, Y, mordenite, erionite and offretite types, for example have as catalysts for conversion reactions of hydrocarbons such as Cracking, hydrocracking or isomerizations of considerable technical interest.
Zeolithe vom Pentasil-Typ (z.B. Zeolith ZSM-5) gewinnen als Katalysatoren für die Umwandlung von Methanol zu Kohlenwasserstoffen steigende Bedeutung.Zeolites of the pentasil type (e.g. zeolite ZSM-5) are used as catalysts increasing importance for the conversion of methanol to hydrocarbons.
Aufgrund der zahlreichen Einsatzmöglichkeiten als Katalysatoren besteht großes Interesse an neuen Zeolithen mit spezifischen katalytischen Eigenschaften.Because of the numerous possible uses as catalysts great interest in new zeolites with specific catalytic properties.
Beispielsweise erhält man sehr interessante Zeolithe, wenn man anstelle von Aluminium und/oder Silizium andere Elemente in das Zeolith-Gerüst einbaut. So wurden unter anderem Zeolithe der Pentasil-Re,hc bekannt, die Bor (DE-OS 2 746 790), Eisen (DE-OS 2 831 611), Arsen (D-AS 2 830 830), I\ntjmon (DE-OS 2 830 787 Vnnadtn (DF.-O,'; 2 ;d-i t 1) Chrom CDE-OS 2 83. 630) (ial Gallium (BE-PS 882 484) auf Tetraderplätzen v.'n enthalten Auch wurden Titanosilicate ( US-PS 3 329 481) und Zirkonosiiicate (US-PS 3 329 480) mit Zeolithstruktur bekannt.For example, you get very interesting zeolites if you instead of of aluminum and / or silicon incorporates other elements into the zeolite framework. So were among other things zeolites of Pentasil-Re, hc known, the boron (DE-OS 2 746 790), Eisen (DE-OS 2 831 611), arsenic (D-AS 2 830 830), I \ ntjmon (DE-OS 2 830 787 Vnnadtn (DF.-O, '; 2; d-i t 1) Chromium CDE-OS 2 83. 630) (ial Gallium (BE-PS 882 484) on tetrader sites v.'n included Titanosilicates (US Pat. No. 3,329,481) and Zirkonosiiicate (US-PS 3,329,480) known with zeolite structure.
Gegenstand der Erfindung sind Titanoaluminosilicate mit Pentasil-Struktur.The invention relates to titanium aluminosilicates with a pentasil structure.
Für den Begriff Pentasile gilt dabei die Definition von Kokotailo und Meier ("Pentasil family of high silica crystalline materials in Special Publication No. 33 of the Chemical Society, London 1980). Die Pentasil-Familie umfaßt beispielsweise die synthetischen Zeolithe ZSM-5 (US-PS 3 702 886), ZSM-8 (GB-PS 1 334 243), ZSM-11 (US-PS 3 709 979) und ZSM-23 (US-PS 4 076 8142).The definition of Kokotailo applies to the term pentasile and Meier ("Pentasil family of high silica crystalline materials in Special Publication No. 33 of the Chemical Society, London 1980). For example, the Pentasil family includes the synthetic zeolites ZSM-5 (U.S. Patent 3,702,886), ZSM-8 (British Patent 1,334,243), ZSM-11 (U.S. Patent 3,709,979) and ZSM-23 (U.S. Patent 4,076,8142).
Von dem Titanosilicat gemäß US-PS 3 329 480 unterscheidet sich das erfindungsgemäße Titanoaluminosilicat sowohl durch die Struktur wie auch durch den Aluminiumgehalt.This differs from the titanosilicate according to US Pat. No. 3,329,480 inventive titanoaluminosilicate both by the structure and by the Aluminum content.
Gegenstand der Erfindung sind vor allem Titanoaluminosilicate mit ZSM-5-Struktur, vorzugsweise solche mit folgender Zusammensetzung, ausgedrückt in Molverhältnissen der Oxide: SiO2 : (0,001 - 0,15) Al203 : (0,002 - 1,0) Ti02 insbesondere SiO2 : (0,005 - 0,1) Al20 : (0,01 - 0,4) Ti02, 23 Die erfindungsgemäßen Titanoaluminosilicate lassen sich nach den gleichen Methoden und unter Einsatz der gleichen organischen Verbindungen herstellen, wie sie auch für die Synthese des titanfreien Zeolithen ZSM-5 beschrieben wurden, beispielsweise unter Verwendung von Alkylammorliumverbindullgen (US-PS 3 702 886) Alkylaminen (US-PS 4 151 189) Alkyldiaminen (DE-OS 2 817 576> DE-OS 2 831 334) Alkylaminen in Gegenwart von Alkylierungsmitteln (EP-OS 11362, DE-AS 2 212 810) Aminoalkoholen (GB-PS 2 023 562) Alkoholen (DE-OS 2 935 123, US-PS 4 199 556, US-PS 4 175 1114, EP-OS 142 225, DE-OS 2 643 929) Ethern (EP-OS 51 741) Vorzugsweise verwendet man Alkylammoniumverbindungen, Alkyldiamine, oder Alkylamine in Gegenwart von Alkylierungsmitteln. Unter den Alkylammoniumverbindungen sind besonders bevorzugt die Tetrapropylammoniumverbindungen, beispielsweise das Hydroxid oder eines der Halogenide. Ein besonders geeignetes Alkyldiamin ist Hexamethylendiamin.The invention primarily relates to titanium aluminosilicates ZSM-5 structure, preferably those with the following composition, expressed in Molar ratios of the oxides: SiO2: (0.001-0.15) Al203: (0.002-1.0) Ti02 in particular SiO2: (0.005-0.1) Al20: (0.01-0.4) Ti02.23 The titanoaluminosilicates according to the invention can be prepared using the same methods and using the same organic Produce compounds as they are for the synthesis of the titanium-free zeolite ZSM-5, for example using alkylammorlium compounds (US-PS 3,702,886) alkylamines (US-PS 4,151,189) alkyldiamines (DE-OS 2,817,576> DE-OS 2 831 334) alkylamines in the presence of alkylating agents (EP-OS 11362, DE-AS 2 212 810) Amino alcohols (GB-PS 2 023 562) alcohols (DE-OS 2,935,123, US-PS 4,199,556, US-PS 4,175,114, EP-OS 142,225, DE-OS 2,643,929) ethers (EP-OS 51 741) It is preferred to use alkylammonium compounds, alkyldiamines, or alkylamines in the presence of alkylating agents. Among the alkylammonium compounds the tetrapropylammonium compounds are particularly preferred, for example that Hydroxide or one of the halides. A particularly suitable alkyl diamine is hexamethylene diamine.
Zur Synthese der erfindungsgemäßen Titanoaluminosilicate mischt man eine oder mehrere Verbindungen aus den genannten Klassen mit Titan-, Silizium-, Natrium- und Aluminiumverbindungen sowie Wasser und erhitzt dieses Gemisch in einem geschlossenen Gefäß. Dem Gemisch werden vorzugsweise darüberhinaus vor dem Erhitzen Impfkristalle eines Pentasils zugesetzt. Falls man Tetrapropylammoniumverbindungen verwendet, werden die Ausgangsverbindungen im allgemeinen in folgendem Verhältnis eingesetzt, ausgedrückt in Molverhältnissen der Oxide: Si02 : (0,01 - 0,2) Al203 : (0,01 - 1,0) TiO2 (0,01 - 0,5) Na20 : (0,02 - 1,0) R20 : (5 - 100) H20, vorzugsweise im Verhältnis: Ski02 (0,01 - 0,1) Al203: (0,01 - Q,4) Ei02: (0,02 - 0,3) Na20 : (0,03 - 0,6) R20 : (10 - 140) H20, wobei R gleich Tetrapropylammonium ist.To synthesize the titanoaluminosilicates according to the invention, mixing is carried out one or more compounds from the classes mentioned with titanium, silicon, Sodium and aluminum compounds as well as water and heats this mixture in one closed vessel. The mixture is preferably further added prior to heating Seed crystals of a pentasil added. If you have tetrapropylammonium compounds are used, the starting compounds are generally in the following ratio used, expressed in molar ratios of the oxides: Si02: (0.01-0.2) Al203 : (0.01-1.0) TiO2 (0.01-0.5) Na20: (0.02-1.0) R20: (5-100) H20, preferably in the ratio: Ski02 (0.01 - 0.1) Al203: (0.01 - Q.4) Ei02: (0.02 - 0.3) Na20: (0.03-0.6) R20: (10-140) H20, where R is tetrapropylammonium.
Als Silizium-, Aluminium-, Titan- bzw. Natrium-Verbindungen können beispielsweise eingesetzt werden: Kieselsäuregel, Natriumsilicat, Aluminiumhydroxid, Alurniniumsulfat, Natriumaluminat, Aluminiumhalogenide, Aluminiurnmethahydroxid, Titanhalogenide, Titansul fat, Natriumhydroxid Ntriunsul fat, Ntriumhalogenidc. Aber auch andere Verbindungen der vier genanntcti Elemente eignen sich für die t1er stellung der erfindungsgernäßen Zeolithe.As silicon, aluminum, titanium or sodium compounds can for example: silica gel, sodium silicate, aluminum hydroxide, Aluminum sulfate, sodium aluminate, aluminum halides, aluminum methahydroxide, Titanium halides, titanium sulfate, sodium hydroxide Ntriunsul fat, Ntriumhalogenidc. But other combinations of the four elements mentioned are also suitable for the t1er position of the zeolites according to the invention.
Das Gemisch der jeweils gewählten Verbindungen mit Wasser wird im allgemeinen 18 bis 360 Stunden, vorzugsweise 214 bis 2140 Stunden lang, auf eine Temperatur zwischen 100 und 2000C vorzugsweise zwischen 130 und 1700C, in einem geschlossenen Gefäß erhitzt.The mixture of the compounds selected in each case with water is im generally 18 to 360 hours, preferably 214 to 2140 hours, to one Temperature between 100 and 2000C, preferably between 130 and 1700C, all in one closed vessel heated.
Die gebildeten Zeolithe werden in üblicher Weise, z.B. durch Filtration, isoliert, gewaschen und getrocknet. Sie können nach bekannten Methoden in die katalytisch aktiven Formen überführt werden, z.B. durch Kalzinierung und/oder lonenaustausch (D.W. Breck, Zeolite Molecular Sieves, 1974).The zeolites formed are in the usual way, e.g. by filtration, isolated, washed and dried. You can use known methods in the catalytically active forms are transferred, e.g. by calcination and / or ion exchange (D.W. Breck, Zeolite Molecular Sieves, 1974).
Die erfindungsgemäßen Zeolithe zeichnen sich nach ihrer Uberführung in die katalytisch aktive Form insbesondere aus durch eine hohe Selektivität und durch eine geringe Koksabscheidung bei der Umwandlung von Methanol in niedere Olefine. Diese Reaktion führt man beispielsweise bei Temperaturen von 350 bis 4300C und einem Wasseranteil im Methanol von 0 bis 80 Gew.-% oder mit Rohmethanol durch.The zeolites according to the invention are notable for their conversion in the catalytically active form in particular due to a high selectivity and due to a low coke deposition in the conversion of methanol to lower olefins. This reaction is carried out, for example, at temperatures from 350 to 4300C and a Water content in methanol from 0 to 80% by weight or with raw methanol.
Die Erfindung soll durch die folgenden Beispiele erläutert werden, wobei die Beispiele aber in keiner Weise einschränkend sein sollen. Alle angegebenen Röntgenbeugungsdaten wurden mit einem computergesteuerten Pulverdiffraktometer D-500 der Firma Siemens aufgenonimen. Es wurde Kupfer-K-t-Strahlung verwandt.The invention is to be illustrated by the following examples, however, the examples are not intended to be limiting in any way. All specified X-ray diffraction data were obtained using a computer-controlled powder diffractometer D-500 from Siemens. Copper-K-t radiation was used.
Beispiel 1 1,66 g Natriumaluminat (54 Gew.-% Al203, 41 Gew.-% Na20) und 2,74 g Natriwnhydroxid werden in 20 g 20 Gew.-%iger wäßriger Tetrapropylammoniumhydroxid-Lösung gelöst (Lösung A).Example 1 1.66 g sodium aluminate (54% by weight Al203, 41% by weight Na20) and 2.74 g of sodium hydroxide are dissolved in 20 g of 20% strength by weight aqueous tetrapropylammonium hydroxide solution dissolved (solution A).
Eine weitere Lösung (Lösung B) wird hergestellt, indem man 62 g 140 Gew-%iges kolloidales Kieselgel in 230 g 20 Gew.-%iger wäßriger Tetrapropylammoniumhydroxid-Lösung löst und diese Lösung am Rotationsverdampfer auf insgesamt 230 g einengt. Lösung A und B werden miteinander vermischt.Another solution (solution B) is prepared by adding 62 g of 140 % By weight colloidal silica gel in 230 g of 20% by weight aqueous tetrapropylammonium hydroxide solution dissolves and this solution is concentrated on a rotary evaporator to a total of 230 g. solution A and B are mixed together.
Zu dieser Mischung werden unter intensivem Rühren 2,2 g Titantetrachlorid gegeben. Die entstandene Suspension wird homogenisiert und in einem geschlossenen Gefäß 12Q h auf 1600C erhitzt. Das entstandene Produkt wird abfiltriert, mit Wasser gewaschen und bei 1200C getrocknet. Man erhält 29,7 g erfindungsgemäßes Titanoaluminosilicat.2.2 g of titanium tetrachloride are added to this mixture with vigorous stirring given. The resulting suspension is homogenized and in a closed Vessel heated to 1600C for 12Q h. The resulting product is filtered off with water washed and dried at 1200C. 29.7 g of titanium aluminosilicate according to the invention are obtained.
Die Röntgenbeugungsanalyse zeigt ein gut kristallines Produkt mit ZSM-5-Struktur. Die chemische Analyse des 16 Stunden bei 514000 kalzinierten Produktes zeigt folgende Zusammensetzung, ausgedrückt in Molverhältnissen der Oxide: SiO2 : 0,0147 TiQ : 0,023 Al203 : 0.051 Na20.The X-ray diffraction analysis shows a well-crystalline product ZSM-5 structure. The chemical analysis of the product calcined for 16 hours at 514,000 shows the following composition, expressed in molar ratios of the oxides: SiO2 : 0.0147 TiQ: 0.023 Al 2 O 3: 0.051 Na 2 O.
Beispiel 2 Das in Beispiel 1 hergestellte Titanoalyminosilicat mit ZSM-5-Struktur (kalzinierte Form) wird mit Ammoniumnitrat-Lösung ausgetauscht, zusammen mit einem Binder (Boehmit) zu Strängen gepreßt (Zeolith-Anteil 65 Gew.-%) und erneut wie in Beispiel 1 kalziniert.Example 2 The titanium alyminosilicate prepared in Example 1 with ZSM-5 structure (calcined form) is exchanged together with ammonium nitrate solution pressed into strands with a binder (boehmite) (zeolite content 65% by weight) and again Calcined as in Example 1.
In einen senkrecht angeordneten, elektrisch beheizten Rohrreaktor von 1 m Länge, der mit 250 ml dieses Katalysators gefüllt ist, dosiert man stündlich 520 ml 33 Gew.-%iges wasserhaltiges Methanol bei einer Temperatur von 350C und Normaldruck. Das entstehende Reaktionsgemisch wird abgekühlt, und nach Abtrennung der kondensierbaren Anteile wird die gasförmige Phase analysiert.In a vertically arranged, electrically heated tubular reactor 1 m long, which is filled with 250 ml of this catalyst, is metered every hour 520 ml of 33% by weight aqueous methanol at a temperature of 350 ° C. and normal pressure. The resulting reaction mixture is cooled, and after the condensables have been separated off The gaseous phase is analyzed.
Die C2-C4-Olefin-Selektivität ist 64 % und die Selektivität zu Kohlenwasserstoffen mt mehr als 4 C-,Xtomen ist 13 %.The C2-C4 olefin selectivity is 64% and the selectivity to hydrocarbons mt more than 4 C-, Xtomen is 13%.
Vergleichsbeispiel Die Arbeitsweise ist wie in Beispiel 2, nur daß statt des Titanoaluminosilicats ein handelsüblicher Aluminosilicatkatalysator mit ZSM-5-Struktur eingesetzt wird.Comparative Example The procedure is as in Example 2, only that instead of the titanoaluminosilicate a commercially available aluminosilicate catalyst with ZSM-5 structure is used.
Die C2C14 -Olefin-Selektivität ist 56 % und die Selektivität zu Kohlenwasserstoffen mit mehr als 4 C-Atomen ist 23 %.The C2C14 olefin selectivity is 56% and the selectivity to hydrocarbons with more than 4 carbon atoms is 23%.
Claims (13)
Priority Applications (7)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| AU83401/82A AU544046B2 (en) | 1981-10-17 | 1982-05-05 | Unloading chute for vessels |
| DE19823231469 DE3231469A1 (en) | 1982-08-25 | 1982-08-25 | Titanium-containing zeolites, process for their preparation, and their use |
| EP82109451A EP0077522B1 (en) | 1981-10-17 | 1982-10-13 | Titanium-containing zeolites, process for their preparation and their use |
| DE8282109451T DE3266412D1 (en) | 1981-10-17 | 1982-10-13 | Titanium-containing zeolites, process for their preparation and their use |
| AU89401/82A AU8940182A (en) | 1981-10-17 | 1982-10-15 | Titanium-containing zeolites |
| NZ202184A NZ202184A (en) | 1981-10-17 | 1982-10-15 | Titanium-containing zeolites and use as olefin producing catalysts |
| CA000413523A CA1185224A (en) | 1981-10-17 | 1982-10-15 | Titanium-containing zeolites, process for their manufacture, and their use |
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| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| DE19823231469 DE3231469A1 (en) | 1982-08-25 | 1982-08-25 | Titanium-containing zeolites, process for their preparation, and their use |
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| DE3231469A1 true DE3231469A1 (en) | 1984-03-01 |
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| DE19823231469 Withdrawn DE3231469A1 (en) | 1981-10-17 | 1982-08-25 | Titanium-containing zeolites, process for their preparation, and their use |
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