Note: Descriptions are shown in the official language in which they were submitted.
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Zeolites are crystalline aluminosilicates 9 in which due to
a three-dimensional linkage of SiO4 and AlOI~ tetrahedra
regular structures with cavities and pores are formed. In
hydrated state, these pores and cavities are filled with
water, which, on the other hand, can be easily removed
without influencing the crystalline structure, or replaced
by other molecules. The negative charges of the Al04
tetrahedra are balanced by cations, which can be replaced by
other ions of positive charge. These properties allow the
use of the zeolites as ion exchan~ers, adsorbents and
c~talysts (D.W. Breck: Zeolite Molecular Sieves, 1974).
Zeolites of the X, Y, mordenite, erionite or offre-
tite type, for example, are of considerable interest in the
industrial practice as catalysts for hydrocarbon conversion
reactions such as cracking, hydrocracking or isomerization.
Zeolites of the pentasil type (for example Zeolite ZSM-5)
become increasingly important as catalysts for the conver-
slon of methanol to hy~rocarbons.
Because of the numerous application possibilities as
catalysts, there is great interest in novel zeolites having
~p~cific catalytical properties.
Very interesting zeolites are for example obtained by
incorporating other elements instead of aluminum and/or
~ilicon into the zeolite frame. Thus, zeolites of the
pentasil series are known which contain boron (German
Offenlegungsschrift No. 2,830,787), iron (German Offenle-
gungsschrift No. 2,831,611), arsenic (German Auslegeschrift
No. 2,830,830), antimony (German Offenlegungsschrift No.
2,830,787), vanadium (German Offenlegungsschrift No.
2,831,631), chromium (German Offenlegungsschrift No.
2,831,630), or gallium (Belgian Patent No. 882,484) in
tetrahedral position.
Subject of the present invention are gallium- and/or
indium containing zeolites which
..;~
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a~ have the foilowing composition:
SiO2 : (0020 ~ 0.10) ~Al203 t M20~7
(0.15 - 0.1) ~Na20 + K2Q7 : (0.15 - 0~4) R20
expressed as molar ratio of oxides; M being gallium
and/or indium and R being tetramethylammonium, and
b) have the characteristic X-ray diffraction pattern set
forth below in Table l:
Table 1
1 0 . _ _ _
Interplanar Spacing Relative Intensity
d ~ R 7 I/Io
_
11.50 + 0.2 very strong
7.56 + 0.1 weak to medium
6.62 + 0.1 medium to strong
6.32 + 0.1 weak
5.74 + 0.1 ,.
4.56 ~ 0.1 medium
4.33 ~ 0.1 medium to strong
3.76 + 0.1 very strong
3.58 - 0.1 medium to strong
3.31 ~ 0.1 weak
3.15 + 0.1 weak to medium
2.84 + 0.1 strong to very strong
2.68 + 0.1 weak to medium
2.48 + 0.1 I weak I
Io = intensity of the strongest line or peak.
3o
The inten~ities of Table 1 are defined as follows:
relative intensity 100 I/Io
.
very strong 80 - 100
strong 50 80
medium 20 - 50
weak O - 20
1 ~ 8 ~
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The novel zeolites of the invention have a structure similar
to offretite (German Offenlegungsschrift No. 1,806,154);
however, they have a different composition.
The follo-~ing is valid for tne zeolite of the inYention:
generally
A1203 _ = 0.01 ~ 0.99
2 3 2 3
preferably
Al23 = 0.40 - 0.99
A1203 + M203
especially
_ A123 _ _ - 0.60 - 0.99
A1203 ~ M203
expressed as molar ratio of the oxides; M being ~allium
and/or indium.
The zeolites of the invention are prepared by mixing
gallium and/or indium compounds with aluminum, silicon,
~5 ~odlum, pota~sium, tetramethylammonium compounds and water,
and heating the mixture in a closed vessel.
The starting compounds are generally used in the
following ratio, expres~ed as molar ratio of the oxides:
SiO2 : (0.03 ~ 0.028) Al203 : (0.03 - 0.028) M203 :
(0.2 + o.o8) Na20 : (0.2 ~ 0.15) K20 : (0.1 + 0.08) R20:
(20 ~ 10) H~O
preferably in a ratio of
SiO2 : (O.G3 - 0.01) Al203 : (0.03 ~ 0.028) M203:
(0.2 - 0.08) Na20 : (0.2 - 0.10) K20 : (0.035 + 0.015) R20:
(20 ~ 10) H20
5 ~
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M being ~allium and/or indium and R being tetramethylam-
moniurn.
As compounds, there are used for example silicic acid,
potassium silicate, sodium silicate, aluminum hydroxide,
aluminum sulfate, sodium aluminate, potassium aluminate,
aluminum halides, aluminum methahydroxyide, gallium(III)
oxide, gallium(III) nitrate, gallium(III~ sulfate,
gallium(III) halides, gallium(III) hydroxide, indium(III)
oxide, indium(III) nitrate, indium(III) ulfate, indium(III)
halides, indium(III) hydroxide, sodium hydroxide, sodium
sulfate, sodium halides, potassium hydroxide, potassium
~ulfate, potassium halides, tetramethylammonium hydroxide,
tetramethylam~onium chloride. Other silicon, aluminum,
gallium, indium, potassium, sodium and tetramethylammonium
compound~ are also suitable for the manufacture of the
~eolites according to the invention.
The mixture of the compounds chosen and water is ge-
nerally heated for 12 to 300, preferably 24 to 200, hours
at a temperatur-e of from 60 to 150C, pe~erably 80 to 140C,
20 in a ¢losed ves3el.
The crystalline zeolites which are formed are isola-
~ed in usual manner, for example by f ltration, washed and
dried. They can be converted according to known methods to
catalytically active forms, for example by calcination and/or
ion exchange (D.W. Breck, Zeolite Molecular Sieves, 1974~.
After conversion to the catalytically active form,
the zeolites of the invention display a considerably re-
duced deposition of coke and a pronouncedly increased
activity especially in the conversion of methanol to hy-
drocarbons, as compared to the gallium- or indium~free
o~fretites according to German Offenlegungsschrift No.
19806,154. This reaction is earried out, for example, at
temperatures between 350 and 430C using methanol with
a water content of O to 80 % by weight or raw methanol,
The following Examples illustrate the invention with-
out limiting it in its scope. All X-ray diffraction data as
~ndicated were obtained by means of a cornputer-controlled
powder diffractometer D-500 of the Siemens company. The
radiation was the K-~ doublet of copper.
1 ~82~6
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Example 1
98 g of 40 weight % colloidal ~ilica gel are introduced
into a solution of 4.3 g OL gallium(III) oxide, 7.2 g of so~
dium hydroxide, 17.8 g of potassium hydroxide, 4.5 g of sodium
aluminate (54 weight ~ of Al203, 41 weight % of Na20)
and 4.2 g of tetramethylam~onium chloride in 125 g of water.
The mixture so obtained i,5 homogenized by thorough
stirring, and heated for 95 hours at 95C in a closed
vessel. The product obtained is filtered off, washed with
water and dried at 120C. According to chemical analysis,
the product is composed as folllows~ expressed as molar
ratio of oxides:
SiO2 : 0.088 Al203 : 0~056 Ga203 : 0.028 Na20 : o.o84 ~2 : 0 034 R20
R = tetrarnethylammonium.
The result o~ X-ray diffraction is listed in Table 2.
~0 Tab
___ . _.
Interplanar Spacing Relative Intensity
d C ~ ~ I/Io
11.48 ~3
7.52 24
6.60 48
6.3l~ 12
5.73 13
4.58 39
4.34 55
3.75 100
3.58 74
3.31 18
3~15 33
2.86 90
2.67 17
2.48 13
_ _
~ ~2~9~
7 - HOE 81/F 252
Example 2
A mixture of 1.7 g of gallium(III) oxide, 21.4 g of
sodium hydroxide, 35.6 g of potassium hydroxide, 7.0 g of
aluminum hydroxide, 8.4 g of tetramethylammonium chlorlde,
250 g of water and 195 g of 40 weight % colloidal silica
gel is manufactured, and heated for 72 hours in a closed
vessel to 110C. After work-up as indicated in Example 1
a crystalline product having the following composition,
expressed as molar ratio of oxides, is obtained:
1 0
SiO2 : 0.101 Al203 : 0.011 Ga2O3 : 0.022 Na2O : o.o66 K20 0.042 R2O
R = tetramethylammonium.
The X-ray diffraction data correspond to those indicated in
Table 1~
Example 3
A mixture of 12.9 g of gallium(III) oxide, 21.4 g of
~odium hydroxide, 35.6 g of potassi.um hydroxide, 0.7 g of alu-
mlnurn hydroxide, 8.4 g of tetramethylammonium chlor-ide, 250 g
o~ water and 195 e Of 40 weight ~ oolloidal silica gel is
prepared, and heated for 120 hours at 95C in a closed
vessel. After work-up as in Example 1, a crystalline product
having the following composition, expressed as molar ratio
of oxides, is obtained:
SiO2 : 0.018 Al203 : 0.102 Ga203 : 0.031 Na2O : 0.076 K20 : 0-043 R2O
R = tetramethylammonium.
The X-ray diffraction data correspond to those indicated in
Ta~le 1.
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Example 4
98 g of 40 weight % colloidal silica gel are intro-
duced into a solution of 10.1 g of indium trichloride, 7.2 g
of sodium hydroxide, 17.8 g of potassium hydroxide, 4.5
of sodium aluminate (54 weight g Al203, 41 weight %
Na20) and 4.2 g of tetramethylammonium chloride in 125 g
of water. The mixture so obtained is homogenized by thorough
stirring and heated for 95 hours at 95C in a closed ~essel.
The product obtained is filtered, washed with water, and
dried at 120C.
A chemical analysis results in the following compo-
~ition, expressed as molar ratio of oxides:
SiO2: 0.099 A1203: 0.038 In203: 0.032 Na20 o.o84 K20 : 0.032 R20
R = tetramethylammonium.
The X-ray diffraction data correspond to those li~ted in
Table 1.
