CA1195675A - Titanium-containing zeolites, a process for their preparation and their use - Google Patents
Titanium-containing zeolites, a process for their preparation and their useInfo
- Publication number
- CA1195675A CA1195675A CA000427626A CA427626A CA1195675A CA 1195675 A CA1195675 A CA 1195675A CA 000427626 A CA000427626 A CA 000427626A CA 427626 A CA427626 A CA 427626A CA 1195675 A CA1195675 A CA 1195675A
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- titanium
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- molar ratios
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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
-
- 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
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- Chemical & Material Sciences (AREA)
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- Life Sciences & Earth Sciences (AREA)
- General Life Sciences & Earth Sciences (AREA)
- Geology (AREA)
- Engineering & Computer Science (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Materials Engineering (AREA)
- Inorganic Chemistry (AREA)
- Silicates, Zeolites, And Molecular Sieves (AREA)
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
- Catalysts (AREA)
Abstract
Abstract of the disclosure:
The invention relates to titanium-containing zeo-lites, a process for their preparation and their use.
To prepare these compounds, a mixture of silicon compounds, aluminum compounds, sodium compounds, potassium compounds, choline compounds, water and titanium compounds in speci-fied proportions is prepared, and this mixture is heated in a closed vessel. The zeolites are used as catalysts in the preparation of C2-C4-olefines from methanol.
The invention relates to titanium-containing zeo-lites, a process for their preparation and their use.
To prepare these compounds, a mixture of silicon compounds, aluminum compounds, sodium compounds, potassium compounds, choline compounds, water and titanium compounds in speci-fied proportions is prepared, and this mixture is heated in a closed vessel. The zeolites are used as catalysts in the preparation of C2-C4-olefines from methanol.
Description
Zeolites are, in part;cular~ crys~alline alum;no-sil;cates in wh;ch ordered structures conta;ning cavities and pores are formed as a result of three-d;mens;onal l;nk;ng of SiO4 and AlO4 te~rahedra~ In the hydrated sta~e, these pores and cavi~ies are filled with wa~er.
This can be removed or replaced by other molecules~ with ou~ ~he crys~al structure be;ng affected~ The negat;ve charges on the AlO~ tetrahedra are compensated by cat~
ions~ These can, if desired, be exchanged for other ca~-ions~ The properties described make it possible to usethe zeolites as ion exchangers, adsorbents and catalysts tDDW. Breck: Zeolite Molecular Sieves, 197~).
Zeolites of the X, Y, mordeni~e, erionite and offreti~e types, for example~ are of considerable indus-trial interest as catalysts for transformation reactions of hydrocarbons, such as crackingO hydrocracking or ;so-merization. ~eolites of the pentasil type (e.g~ zeolite ZSM-5) are becomir,g increas;ngly ;mpor~ant as catalysts for converting methanol to hydrocarbons.
Because of the very large number of possible uses as catalysts, there is considerable interest in novel zeo~
lites having specific catalytic properties.
For example, very interes~in~ zeol;tes are obta;ned if, instead of alum;num and/or silicon, other elements are incorpora~ed in~o the zeolite frameworks.
Thus, other ~eolites of the pentasil series which contain boron t~erman Offenlegungsschrift 2~830~787), iron (~errnan Offenle~ungsschri~t 2,8319611), arsenic ~German Auslegeschr;~ 2,83~,?830),~ ~n~imony (German Offenle~lJn~s-schr;ft 2~39,787), vanad;um (German Offenlegungsschrift
This can be removed or replaced by other molecules~ with ou~ ~he crys~al structure be;ng affected~ The negat;ve charges on the AlO~ tetrahedra are compensated by cat~
ions~ These can, if desired, be exchanged for other ca~-ions~ The properties described make it possible to usethe zeolites as ion exchangers, adsorbents and catalysts tDDW. Breck: Zeolite Molecular Sieves, 197~).
Zeolites of the X, Y, mordeni~e, erionite and offreti~e types, for example~ are of considerable indus-trial interest as catalysts for transformation reactions of hydrocarbons, such as crackingO hydrocracking or ;so-merization. ~eolites of the pentasil type (e.g~ zeolite ZSM-5) are becomir,g increas;ngly ;mpor~ant as catalysts for converting methanol to hydrocarbons.
Because of the very large number of possible uses as catalysts, there is considerable interest in novel zeo~
lites having specific catalytic properties.
For example, very interes~in~ zeol;tes are obta;ned if, instead of alum;num and/or silicon, other elements are incorpora~ed in~o the zeolite frameworks.
Thus, other ~eolites of the pentasil series which contain boron t~erman Offenlegungsschrift 2~830~787), iron (~errnan Offenle~ungsschri~t 2,8319611), arsenic ~German Auslegeschr;~ 2,83~,?830),~ ~n~imony (German Offenle~lJn~s-schr;ft 2~39,787), vanad;um (German Offenlegungsschrift
2,831,631), çhromium (Gernan Offen(egungsschr;ft ~,B31,S30) S or ~alli~m (Bel~ian Paten~ 882,~84) in te~rahedral sites have been d7sclosed. Titanosi l;cates (U.Su Paterlt
3,32~,481 and ~erman Offenlegungsschrift 3~047,79B~ and zirconosilicates ~U.5. Patent 3~329,~80) having a zeolite structure have also been d;sclosed.
~0 Fur~hermore, boron-containing zeoli~es~ ~allium-containing and~or indiur-containing zeolites, ~;tanium-conta;n;ng 2eol;tes and z;rcon;um=contain;ng and/or haf~
nium-cont~in;ng zeol;tes have already been described (German Offenlegungsschri~ten ~os. 31 34 316,31-34 317 3l 36 ~86 ~ 31 36 68l. ~ 31 41 2B3 and 31 b1 285 ~.
The ;nvention rela~es to titanium-çon~ainin~ zeo-li~es wh~ch ~ ;n ~dd;tion ~o sodium~ po~ass;u~ and chol7ne, r,ontain the elelnents sil;con, alum;num and ~itanium ;n the ~ol-low;ng ratio, expressed as molar ra~ios of ox;des:
(SiO2 ~ T;O~) o ~ooO2 ~ ~30) Al203 nnd b) exh;bit the character;s~ic si~nals l;sted ;n Table 1 .
in ~he X~ray diffraction diagram - ~.
Table 1 Interplanar spac;ngs Re~ative intensity d~A] ~/Io .. . .
11.4 ~ 0.3 strong to very strong 9.2 + 0.2 weak 706 ~ 0.2 weak to mediu~
6.~ ~ 0.1 ` medium to strong 5.7 + 0~1 weak to medium 5.35 ~ 0.1 weak _
~0 Fur~hermore, boron-containing zeoli~es~ ~allium-containing and~or indiur-containing zeolites, ~;tanium-conta;n;ng 2eol;tes and z;rcon;um=contain;ng and/or haf~
nium-cont~in;ng zeol;tes have already been described (German Offenlegungsschri~ten ~os. 31 34 316,31-34 317 3l 36 ~86 ~ 31 36 68l. ~ 31 41 2B3 and 31 b1 285 ~.
The ;nvention rela~es to titanium-çon~ainin~ zeo-li~es wh~ch ~ ;n ~dd;tion ~o sodium~ po~ass;u~ and chol7ne, r,ontain the elelnents sil;con, alum;num and ~itanium ;n the ~ol-low;ng ratio, expressed as molar ra~ios of ox;des:
(SiO2 ~ T;O~) o ~ooO2 ~ ~30) Al203 nnd b) exh;bit the character;s~ic si~nals l;sted ;n Table 1 .
in ~he X~ray diffraction diagram - ~.
Table 1 Interplanar spac;ngs Re~ative intensity d~A] ~/Io .. . .
11.4 ~ 0.3 strong to very strong 9.2 + 0.2 weak 706 ~ 0.2 weak to mediu~
6.~ ~ 0.1 ` medium to strong 5.7 + 0~1 weak to medium 5.35 ~ 0.1 weak _
4.56 ~ 0.1 rnedium to strong 4.32 ~ 0~1 strong 4.16 ~ 001 weak 3.~1 + 0~1 med1um to strong 3.75 ~ 0.1 s~rong to very strong 3.59 ~ 0.1 strong to very strong 3.30 ~ 0.1 medium -3.15 ~ 0~1 medium 2.8~ ~ 0.1 stron~ to very stron0 2.80 ~ 0.1 weak to med1um _.
Xn th;s ~able~ Io denotes the intensity of che stron~est s;gnal.
The followin~ values apply to ~he intensity data ;n Table 1:
Relative ;ntensity 10C I/Io _ very strong 80 ~ 100 strong S0 ~ 80 medium 20 - 50 weak 0 ~ 20 The rat;o of silicon to t;tanium, expressed as 7~i s molar rat;os o~ the oxidesr is ;n g~neral as ~ollows:
S i~2 __ - = O~D 4 ~ ~ 99 J
SiO2 ~ TiO2 preferably ~i2 --- - = 0~7 - 0~99, SiO2 + TiO2 The novel zeol;~es a~cordiny ~o the ;nven~;on possess a struc~ure s;milar to tha~ of the T ~U.SO Patent 2,~50,952) or ZSM~34 (German Offenle~ungsschr;f~
2,74~,024) zeol;tes, but differ from these ;n composit;on in particular as a result of the titan;um con~ent.
The t;tanium-contain;ng zeoli~es according to ~he invention d;ffer in structure from ~he titanosilicates accord;ng to U.S. Patent 3,329,481 and German Offenle-gungsschrift 3,047,7~87 The æeolites according to the invent;on can be prepàred by mix;ng tit~nium cornpounds ~lith aluminum com-pounds, silicon compounds, sodium compounds, potass;~lm compounds, choline compounds and water, and h~at;ng the m;xture ;n a closed vessel. I~ is also possible to add seed crystals to th;s m;xture before it is heated~
The starting compounds are employed in ~eneral in the follol~;ny rat;o, expressed as molar rat;os of the ox~des:
(S;2 ~ T;02) : (0.02 - o~3a)Al2o3: (o~os - 3.70)Na20 : (O.Q2 - Q~30~K20 : ~0.02 - 0.5)R20 = S10 - 90)H20 pr`eferably in ~he ratio (SiO2 ~ TiO~) tO.02 ~ 0018)Al203 : ~0~10 ~ 0060)i~a20 : ( 0 . 0 4 - 0 ~ 2 0 ) K 2 : ( 0 . 1 0 - 0 a 40)R20 . (10 - 40)H2~o ~5~
~ 6 --wherein R is cholineO
The rat;o of s; l;con ~o t;tanium ;n the mixture of ~he st~rting compounds, expressed as molar ratios of che oxides, ;s ;n general as follows:
~;i2 -- = 64 -- 0~99 s io 2 ~ Tio~
preferably S i2 Oq ~ ~ O~99t SiO2 ~ TiO2 Examples of compounds which can be employed arP:
silica ~el, potassium silicate, sodium silicate, aluminum hydroxide, aluminum sulfate, sodium aluminate, potassium aluminate, aluminum halides, aluminum metahydroxide, tit--anium hal;des, t;tan;um sulfate, t;tanium ox;de sulfate, sod;um titanate, potassium ~;tanate, titan;um diox;de, sod;um hydrox;de, sodium sulfate, sodium halides, poras~
s;um hydroxide, potassium sulfate, potassium halides, choline hydroxide and chol;ne chloride~ However, other sil;con, aluminumO ~;tan;um, potass;um, sod;urn and chol;ne compounds are also suitable for the preparat;on of the ~eol;tes accord;ng to the ;nvent;onO
A m;xture of the parc;cular selected compounds ~;th water ;s heated in general for 48 to 2,000 hours, preferably ~8 to 1,000 hours, at a tempera~ure between 80 and 160C~ preferably between ~0 and 150~C~ in a closed ~essel.
The zeol;tes formed are isolated in a customary manner~ for example by filtration~ and are washed and dr;ed. They can be converted ~o the cataLytically ac~;ve forms by known methods, e.g. by calc;nation and/or ;on exrhange (D.W. Ereck, Zeoli~e Mo(ecular Sieves~ 1974~.
After they have been converted to the catalyt;c-ally act;ve -forms, ~he zeol;tes accord;ng to the in~ention are d;stincuished ;n part;cular by h;gh selec~ivity and by a low le~el of coking in the conversion of me~hanol to lower olefines. It is surpr;sing that it is at all possible to obta;n zeolites hav;ng the character;stics according to the ;nvention w;th the aid of the stated method~
The examples wh;ch follow are in~ended to illus-trate the invention, but are not intended to restrict it in any way. All X-ray diffraction data given have been recorded using a computer-controlled D 500 powder dif-fractometer from Siemens. Copper K~ radîation was used._a~ple 1 1.5 ~ of sodium alum;nate (54% by weight of Al~03 and 41% by weight of Na~0), 7~7 9 of sodium hydroxide~
~ of potass;um hydroxide and 12.7 g of choline chloride are dissolved in l~3 g of water. F;rst 401 ~ of t;tan;um tetrachloride and then 29~4 y of 40% stren~th by ~e;ght collo;dal s;lica ~el are introduced ;nto this solution, wh;le st;rr;n~ thoroughly~ The resulting rnixture is homo-~en;zed, and heated for 8 days at 150C in a closed ves~
2S sel. The product formed is f;ltered off, washed with water and dr;ed at 120C.
The product contains silicon, aluminum and tit-anium in the following amoun~s, expressed as molar ratios of oxides:
Xn th;s ~able~ Io denotes the intensity of che stron~est s;gnal.
The followin~ values apply to ~he intensity data ;n Table 1:
Relative ;ntensity 10C I/Io _ very strong 80 ~ 100 strong S0 ~ 80 medium 20 - 50 weak 0 ~ 20 The rat;o of silicon to t;tanium, expressed as 7~i s molar rat;os o~ the oxidesr is ;n g~neral as ~ollows:
S i~2 __ - = O~D 4 ~ ~ 99 J
SiO2 ~ TiO2 preferably ~i2 --- - = 0~7 - 0~99, SiO2 + TiO2 The novel zeol;~es a~cordiny ~o the ;nven~;on possess a struc~ure s;milar to tha~ of the T ~U.SO Patent 2,~50,952) or ZSM~34 (German Offenle~ungsschr;f~
2,74~,024) zeol;tes, but differ from these ;n composit;on in particular as a result of the titan;um con~ent.
The t;tanium-contain;ng zeoli~es according to ~he invention d;ffer in structure from ~he titanosilicates accord;ng to U.S. Patent 3,329,481 and German Offenle-gungsschrift 3,047,7~87 The æeolites according to the invent;on can be prepàred by mix;ng tit~nium cornpounds ~lith aluminum com-pounds, silicon compounds, sodium compounds, potass;~lm compounds, choline compounds and water, and h~at;ng the m;xture ;n a closed vessel. I~ is also possible to add seed crystals to th;s m;xture before it is heated~
The starting compounds are employed in ~eneral in the follol~;ny rat;o, expressed as molar rat;os of the ox~des:
(S;2 ~ T;02) : (0.02 - o~3a)Al2o3: (o~os - 3.70)Na20 : (O.Q2 - Q~30~K20 : ~0.02 - 0.5)R20 = S10 - 90)H20 pr`eferably in ~he ratio (SiO2 ~ TiO~) tO.02 ~ 0018)Al203 : ~0~10 ~ 0060)i~a20 : ( 0 . 0 4 - 0 ~ 2 0 ) K 2 : ( 0 . 1 0 - 0 a 40)R20 . (10 - 40)H2~o ~5~
~ 6 --wherein R is cholineO
The rat;o of s; l;con ~o t;tanium ;n the mixture of ~he st~rting compounds, expressed as molar ratios of che oxides, ;s ;n general as follows:
~;i2 -- = 64 -- 0~99 s io 2 ~ Tio~
preferably S i2 Oq ~ ~ O~99t SiO2 ~ TiO2 Examples of compounds which can be employed arP:
silica ~el, potassium silicate, sodium silicate, aluminum hydroxide, aluminum sulfate, sodium aluminate, potassium aluminate, aluminum halides, aluminum metahydroxide, tit--anium hal;des, t;tan;um sulfate, t;tanium ox;de sulfate, sod;um titanate, potassium ~;tanate, titan;um diox;de, sod;um hydrox;de, sodium sulfate, sodium halides, poras~
s;um hydroxide, potassium sulfate, potassium halides, choline hydroxide and chol;ne chloride~ However, other sil;con, aluminumO ~;tan;um, potass;um, sod;urn and chol;ne compounds are also suitable for the preparat;on of the ~eol;tes accord;ng to the ;nvent;onO
A m;xture of the parc;cular selected compounds ~;th water ;s heated in general for 48 to 2,000 hours, preferably ~8 to 1,000 hours, at a tempera~ure between 80 and 160C~ preferably between ~0 and 150~C~ in a closed ~essel.
The zeol;tes formed are isolated in a customary manner~ for example by filtration~ and are washed and dr;ed. They can be converted ~o the cataLytically ac~;ve forms by known methods, e.g. by calc;nation and/or ;on exrhange (D.W. Ereck, Zeoli~e Mo(ecular Sieves~ 1974~.
After they have been converted to the catalyt;c-ally act;ve -forms, ~he zeol;tes accord;ng to the in~ention are d;stincuished ;n part;cular by h;gh selec~ivity and by a low le~el of coking in the conversion of me~hanol to lower olefines. It is surpr;sing that it is at all possible to obta;n zeolites hav;ng the character;stics according to the ;nvention w;th the aid of the stated method~
The examples wh;ch follow are in~ended to illus-trate the invention, but are not intended to restrict it in any way. All X-ray diffraction data given have been recorded using a computer-controlled D 500 powder dif-fractometer from Siemens. Copper K~ radîation was used._a~ple 1 1.5 ~ of sodium alum;nate (54% by weight of Al~03 and 41% by weight of Na~0), 7~7 9 of sodium hydroxide~
~ of potass;um hydroxide and 12.7 g of choline chloride are dissolved in l~3 g of water. F;rst 401 ~ of t;tan;um tetrachloride and then 29~4 y of 40% stren~th by ~e;ght collo;dal s;lica ~el are introduced ;nto this solution, wh;le st;rr;n~ thoroughly~ The resulting rnixture is homo-~en;zed, and heated for 8 days at 150C in a closed ves~
2S sel. The product formed is f;ltered off, washed with water and dr;ed at 120C.
The product contains silicon, aluminum and tit-anium in the following amoun~s, expressed as molar ratios of oxides:
5~
SiO2 : 0.064 Al203 : 00175 TiO2 The result of the X-ray diffraction analysis is reproduced in Table 2 Table 2 5 In~e rp lanar spacings Relative in~ensity d[A] 100 I/Io 11 .45 'IOD
~.16 3 7.S6 14 106 . 62 41
SiO2 : 0.064 Al203 : 00175 TiO2 The result of the X-ray diffraction analysis is reproduced in Table 2 Table 2 5 In~e rp lanar spacings Relative in~ensity d[A] 100 I/Io 11 .45 'IOD
~.16 3 7.S6 14 106 . 62 41
6.. 33 15 5.34 3 4 ~ 56 42 `i 154.33 51 4.14 3.~0 ~4 3 ~ 76 ~9 3 . 58 74 20 3.3~ 3S
3.16 32 2.92 8 2 . 86 ~3 2.~0 5 25 2.67 2.48 . 7 ~ .
5.0 g of sodium alulninate, 19.5 g of sodium hydrox-ide, 4.4 g of po~assium hydrox;de and 42 g of choline ~ 9 _ chloride are d;ssolved in 135 g of water~ F;rst 102 g of ~0~ strength by ~/e;ght collcl;dal s;lica sel and then 6.8 9 of t;tan;um tetrachloride are introduced into th;s solu-t;on, wh; le stirring ~horoughly. The resulting mixture is heated for 30 days at 105C in a closed vessel~ The product formed is filtered off, washed with water and dried a~ 120C.
The product conta;ns s;l;con~ alum;num and t;t-an;um ;n the following amounts~ expressed as molar ratios of oxides:
SiO2 ~ 0.072 Al203 : 0.103 T;02.
The X~ray data correspond to those shown in Table 1.
3.16 32 2.92 8 2 . 86 ~3 2.~0 5 25 2.67 2.48 . 7 ~ .
5.0 g of sodium alulninate, 19.5 g of sodium hydrox-ide, 4.4 g of po~assium hydrox;de and 42 g of choline ~ 9 _ chloride are d;ssolved in 135 g of water~ F;rst 102 g of ~0~ strength by ~/e;ght collcl;dal s;lica sel and then 6.8 9 of t;tan;um tetrachloride are introduced into th;s solu-t;on, wh; le stirring ~horoughly. The resulting mixture is heated for 30 days at 105C in a closed vessel~ The product formed is filtered off, washed with water and dried a~ 120C.
The product conta;ns s;l;con~ alum;num and t;t-an;um ;n the following amounts~ expressed as molar ratios of oxides:
SiO2 ~ 0.072 Al203 : 0.103 T;02.
The X~ray data correspond to those shown in Table 1.
Claims (8)
PROPERTY OR PRIVILEGE IS CLAIMED ARE DEFINED AS FOLLOWS:
1. A titanium-containing zeolite which a) contains sodium, potassium and choline, and also contains the elements silicon, aluminum and titanium in the following ratio, expressed as molar ratios of oxides:
(SiO2 + TiO2) : (0.02 - 0.30)Al2O3 and b) exhibits the following characteristic signals in the X-ray diffraction diagram:
where I0 denotes the intensity of the strongest signal.
(SiO2 + TiO2) : (0.02 - 0.30)Al2O3 and b) exhibits the following characteristic signals in the X-ray diffraction diagram:
where I0 denotes the intensity of the strongest signal.
2. A titanium-containing zeolite as claimed in claim 1, wherein the ratio of silicon to titanium, expressed as molar ratios of the oxides, is as follows:
3. A titanium-containing zeolite as claimed in claim 1, wherein the ratio of silicon to titanium, expressed as molar ratios of the oxides, is as follows:
4. A process for the preparation of a titanium-containing zeolite as claimed in claim 1, wherein a mixture of a silicon compound, a titanium compound, an aluminum compound, a sodium compound, a potassium compound, a choline compound and water is prepared, which has the following composition, expressed as molar ratios of the oxides:
(SiO2 + TiO2) : (0.02 - 0.30)Al2O3 : (0.05 - 0.70)Na2O :
(0.02 - 0.30)K2O : (0.02 - 0.5)R2O : (10-90)H2O, where R is choline, and this mixture is heated in a closed vessel.
(SiO2 + TiO2) : (0.02 - 0.30)Al2O3 : (0.05 - 0.70)Na2O :
(0.02 - 0.30)K2O : (0.02 - 0.5)R2O : (10-90)H2O, where R is choline, and this mixture is heated in a closed vessel.
5. A process as claimed in claim 4, in which the mixture to be heated has the following composition, expressed as molar ratios of the oxides:
(SiO2 + TiO2) : (0.02 - 0.18)Al2O3 : (0.10 - 0.60)Na2O :
(0.04 - 0.20)K2O : (0.10 - 0.40)R2O : (10 - 40)H2O, where R is choline.
(SiO2 + TiO2) : (0.02 - 0.18)Al2O3 : (0.10 - 0.60)Na2O :
(0.04 - 0.20)K2O : (0.10 - 0.40)R2O : (10 - 40)H2O, where R is choline.
6. A process as claimed in claim 4 or claim 5 in which the ratio of silicon to titanium in the mixture of the starting compounds, expressed as molar ratios of the oxides, is as follows:
7. A process as claimed in claim 4 or claim 5, in which the ratio of silicon to titanium in the mixture of the starting compounds, expressed as molar ratios of the oxides, is as follows:
8. A process for the preparation of a C2- to C4-olefin in which methanol is reacted in the presence of a titanium-containing zeolite as claimed in claim 1, claim 2 or claim 3.
Applications Claiming Priority (2)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| DE19823217324 DE3217324A1 (en) | 1982-05-08 | 1982-05-08 | TITANIUM-CONTAINING ZEOLITES AND METHOD FOR THE PRODUCTION THEREOF AND THEIR USE |
| DEP3217324.5 | 1982-05-08 |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| CA1195675A true CA1195675A (en) | 1985-10-22 |
Family
ID=6163074
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CA000427626A Expired CA1195675A (en) | 1982-05-08 | 1983-05-06 | Titanium-containing zeolites, a process for their preparation and their use |
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| Country | Link |
|---|---|
| EP (1) | EP0094024A1 (en) |
| JP (1) | JPS58204818A (en) |
| AU (1) | AU1434483A (en) |
| CA (1) | CA1195675A (en) |
| DE (1) | DE3217324A1 (en) |
| NZ (1) | NZ204154A (en) |
| ZA (1) | ZA833240B (en) |
Families Citing this family (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| EP0132550A1 (en) * | 1983-06-27 | 1985-02-13 | Norton Company | Novel zeolite and process for preparation |
| US4707345A (en) * | 1984-04-26 | 1987-11-17 | Union Carbide Corporation | Titanium-aluminum-silicon-oxide molecular sieve compositions and process for preparing the same |
| AU580781B2 (en) * | 1984-04-26 | 1989-02-02 | Union Carbide Corporation | Titanium-aluminum-silicon-oxide molecular sieve compositions |
| US4892720A (en) * | 1984-04-26 | 1990-01-09 | Uop | Substituted aluminosilicate compositions and process for preparing same |
| JP2573511B2 (en) * | 1988-04-06 | 1997-01-22 | 久俊 浅岡 | Composition by combination of titanium, aluminum, silicon and boron tetrahedral oxides and method for producing the same |
| US5244650A (en) * | 1989-06-29 | 1993-09-14 | Engelhard Corporation | Large-pored molecular sieves with charged octahedral titanium and charged tetrahedral aluminum sites |
| ZA902718B (en) * | 1989-06-29 | 1991-10-30 | Engelhard Corp | Large-pored molecular sieves with charged octahedral titanium and charged tetrahedral aluminum sites |
Family Cites Families (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| NL238953A (en) * | 1958-05-08 | |||
| US3329481A (en) * | 1963-10-18 | 1967-07-04 | Union Oil Co | Crystalline titano-silicate zeolites |
| GB1217861A (en) * | 1967-02-22 | 1970-12-31 | Peter Spence & Sons Ltd | Improvements in or relating to synthetic zeolitic compounds |
| US4022714A (en) * | 1975-07-17 | 1977-05-10 | W. R. Grace & Co. | Silica hydrosol bound cracking catalysts |
| NZ185397A (en) * | 1976-11-04 | 1979-12-11 | Mobil Oil Corp | Crystalline aluminosilicate zeolites and use as catalysts |
| US4329328A (en) * | 1979-10-19 | 1982-05-11 | National Research Development Corporation | Method of synthesizing zincosilicate or stannosilicate or titanosilicate material |
| AU544046B2 (en) * | 1981-10-17 | 1985-05-16 | Aannemers Combinatie Zinkwerken B.V. | Unloading chute for vessels |
-
1982
- 1982-05-08 DE DE19823217324 patent/DE3217324A1/en not_active Withdrawn
-
1983
- 1983-05-04 EP EP83104387A patent/EP0094024A1/en not_active Withdrawn
- 1983-05-06 ZA ZA833240A patent/ZA833240B/en unknown
- 1983-05-06 AU AU14344/83A patent/AU1434483A/en not_active Abandoned
- 1983-05-06 CA CA000427626A patent/CA1195675A/en not_active Expired
- 1983-05-06 NZ NZ204154A patent/NZ204154A/en unknown
- 1983-05-07 JP JP58078930A patent/JPS58204818A/en active Pending
Also Published As
| Publication number | Publication date |
|---|---|
| EP0094024A1 (en) | 1983-11-16 |
| JPS58204818A (en) | 1983-11-29 |
| NZ204154A (en) | 1985-10-11 |
| AU1434483A (en) | 1983-11-10 |
| ZA833240B (en) | 1984-01-25 |
| DE3217324A1 (en) | 1983-11-10 |
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