BORO-ALUMINOSILICATES A STRUCTURE ZEOLITIQUE, LEUR PRODUCTION ET LEUR EMPLOI

BORO-ALUMINOSILICATES HAVING ZEOLITE STRUCTURE, PROCESS FOR THEIR MANUFACTURE, AND THEIR USE

Abrégé anglais

Abstract of the disclosure:
The invention provides boro-aluminosilicates having a zeo-
lite structure, a process for their manufacture, and their
use. For their manufacture, a mixture of silicon, aluminum,
boron, sodium, potassium and choline compounds and water
is prepared in a specific quantitative ratio, and heated
in a closed vessel. The boro-aluminosilicates are used as
catalysts in the manufacture of hydrocarbons, especially
C2-C4-olefins, from methanol.

Revendications

THE EMBODIMENTS OF THE INVENTION IN WHICH AN EXCLUSIVE PROPERTY
OR PRIVILEGE IS CLAIMED ARE DEFINED AS FOLLOWS:
1. A boro-aluminosilicate having a zeolite structure which
(a) has the following composition:
SiO2 : (0.08 ? 0.05) [Al2O3 + B2O3] :
(0.12 ? 0.10) [Na2O = K2O] : (0.10 ? 0.09) R2O
expressed as molar ratio of oxides; R being
choline [(CH3)3NCH2CH2OH] +
(b) have the characteristic X-ray diffraction pattern
set forth below
<IMG>

2. A boro-aluminosilicate as claimed in claim 1 in which
the aluminum/boron ratio is
<IMG> = 0.40 - 0.99,
expressed as molar ratio of oxides.
3. A boro-aluminosilicate as claimed in claim 1 in which
the aluminum/boron ratio is
<IMG> = 0.75 - 0.99,
expressed as molar ratio of the oxides.
4. A process for the prepration of a boro-aluminosilicate
as claimed in claim 1 in which a mixture of silicon, aluminum,
boron, sodium, potassium and choline compound and water is
prepared, which is composed as follows, expressed as a molar
ratio of oxides:
SiO2 : (0.06 ? 0.05) Al2O3 : (0.06 ? 0.05) B2O3 :
(0.2 ? 0.15) Na2O : (0.12 ? 0.10) K2O :
(0.22 ? 0.2) R2O : (50 ? 40) H2O
R being choline, and the mixture is heated in a closed vessel.
5. A process as claimed in claim 4 in which the mixture
to be heated is composed as follows, expressed as molar ratio
of oxides:
SiO2 : (0.0f ? 0.03) Al2O3 : (0.05 ? 0.03) B2O3 :
(0.2 + 0.1) Na2O : (0.09 ? 0.05) K2O :
(0.22 ? 0.2) R2O : (50 + 40) H2O
R being choline.
6. A process for the preparation of a C2-C4-olefin in
which methanol is reacted in the presence of a catalyst as
claimed in claim 1, claim 2 or claim 3.

Description

0 9 9
~ 2 - HOE 81/F 222
Zeolites are crystalline aluminosilicates, in which due to
a three-dimensional linkage of SiO4 and Al04 tetrahedra
regular structures with cavit es and pores are formed~ In
hydrated state, these pores and cavities are filled with
~ater, ~rhich, 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 exchangers, adsorbents and
catalysts (D.W. Breck: Zeolite Molecular Sieves, 1974).
~ eolites of the X, Y, mordenite, erionite or offre-
tite type, for example, are of considerable interest in the
industrial practice as catalysts for h~drocarbon conversion
reactions such as cracking, hydrocracl~ing or isomeri~ation.
Zeolites of the pentasil type (for example Zeolite ZSM-5)
become increasingly important as catalysts for the conver-
sion of' methanol to hydrocarbons.
Because of' the numerous app].ication possibilities as
catalysts, there is great interest in novel zeolites having
speclfic catalytical properties.
Very interesting zeolites are for example obtained by
inoorporatine other elemen's instead of aluminum and/or
~licon 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) or chromium (German Offenlegungsschrift No.
2,831,630) in tetrahedr~al position.
Subject of the present invention are boro-aluminosili-
cates having a zeolite structure which

~ ~20~9
3 HOE 81 /F 222
a~ have the following composition:
SiO2 : (0.08 - 0.05) ~Al203 + B~O ~ :
(0.12 0.10) rNa20 + K20~ : (0.10 + 0.09) R20
expressed 2s molar ratio of oxides; R being choline
5C(CH3)3NCH2CH20H7 ~
b) have the characteristic X~ray diffraction pattern set
forth below in Table 1
Tabl _
10Interplanar Spacing Relative Intensity
d ~ ~ 7 I/Io
_ __
11.5 ~ 0.2 very strong
159.2 + 0.2 ~eak
7.6 ~ 0.2 medium
6.6 ~ 0.1 skrong
5.7 - 0.1 medium
~.35 - 0.1 weak
;~01~,9~0.1 "
1J.56 - 0.1 strong
3.32 ~ 0.1 1~
4.16 + 0.1 weak
3.81 + 0.1 strong
253.75 + 0.1 very strong
3.59 + 0.1 medium
3.30 ~ 0.1 ll
3.15 + 0.1 weak
. 2.86 ~ 0.1 strong
302.67 ~ 0.1 weak
____ _
Io - intensity of the strongest line or peak.
The intensities of Table 1 are defined as follows:

1 ~20g~
- 4 ~ ~OE 81/F 222
relative intensity 100 I/Io
very strong 80 - 100
strong 50 - 8Q
5 medium 20 ~ 50
weak O - 20
The aluminum/boron ratio of the zeolites of the invention is
generally
1 0
Al23 = o.40 o.99
A1203 ~ B203
preferably
Al203 _ 0.75 _ 0.99
A1203 ~ B203
expressed as molar ratio of the oxides.
The novel æeolites of the invention have a structure
~lmllar to ~eolite T (U.S. Patent No. 2,950,952) or ZSM-34
(Ccrman Offenlegungsschrift No. 2,749,024); however, they
have a di~fererlt composition, especially with respect to
the boron content.
~ he zeolites of the i.nvention are prepared by mixing
water with silicon, aluminum, boron, sodium, potassium and
choline compounds, and heating the mixture in a closed vessel.
The starting compounds are generally used in the
followi.ng ratio, expressed as molar ratio of the oxides:
3o
SiO2 : (0.06 - 0.05) Al203 : (0.06 0.05) B203 :
(0.2 ~ 0.15) Na20 : (0.12 ~ 0.10) K20 :
(0.22 ~ 0.2) R20 : (50 ~ 40) H20
3~ preferably in a ratio of

20~9
- 5 ~ HOE 81/F 222
SiO2 : (0.05 - 0.03) Al203 : (0.05 + 0.03) B203:
(0.2 ~ 0.1) Na20 : ~0009 ~ 0.05) K20 :
(0.22 ~ 0.2) X20 : (50 ~ 40) H20;
R being choline.
As compounds, there are used for example silica gel, potas-
sium silicate, sodium silicate, aluminum hydroxide, aluminum
sulfate, boron trioxide, boric acid, borax, sodium hydroxide,
sodium sulfate, potassium hydroxide, potassium sulfate,
choline hydroxide, choline chloride. Other silicon, aluminum,
boron, potassium, sodium and choline compounds are also
suitable for the manufacture of the zeolites according to
the invention.
The mixture of the compounds chosen and water is ge-
nerally heated for 48 to 2,000, preferably 48 to 1,000, hours
at a temperature of from 80 to 160C, peferably 90 to 150C,
in a c10sed vesse1.
The crystalline zeolites which are formed are isola-
t~d in usual manner, for example by filtration, washed and
drJ.od. 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 ~orm,
the zeolites of the invention are distinguished by a high
selectlvity and reduced deposition of coke in the conversion
of methanol to lower olefins. It is surprising that zeolites
having the characteristics according to the invention can
be obtained by means of the indicated method.
The following Examples illustrate the invention with-
out limiting it in its scope. All X-ray diffraction data as
indicated were obtained by means of a computer-controlled
powder diffractometer D-500 of the Siemens company. The
radiation was the K-~ doublet of copper.

- 6 - HOE 81/F 222
Example 1
9.0 g of sodium aluminate (54 weight % of Al203,
41 weight % of Na20), 0083 g of boron trioxidej 5.9 g of
sodium hydroxide, 5.3 g of potassium hydroxidej and ll5.6 g
of chollne chloride are dissolved in 150 g of water. 117 g
of 40 weight % colloidal silica gel are added to this
solution, and the suspension SG formed is homogenized
and heated for 8 days at 150C. The product obtained
is filtered off, washed with water and dried at 120C.
Chemical analysis yields the following composition,
expressed as molar ratio of oxides:
SiO2 : 0.075 A1203 : 0.003 B203 : o~o48 Na20 : 0.023 K20 : 0-060 R20,
R - choline.
The result Or X-ray diffraction is listed in Table 2.

~ ~2~9
- 7 -HOE 81/F 222
Table 2
Interplanar Spacing Relative Intensity
d C ~ ~ I/Io
11.51 100
9.14 4
7.54 2~
6.60 43
6.37
5.73 22
5~35 3
4.98 6
l~.56 58
4.32 60
4.16 9
3.81 60
3-75 93
3.59 81
3.30 31
3.15 33
2.92 6
2.86 89
2.67 6
2.119 9
~5 2.29 3
2.21 ~
2.11 5
1.89 17
.
Example 2
2.27 g of borax, 1.43 g of aluminum hydroxide (75
weight ~ of Al2O3), 1.18 g of sodium hydroxide, 1.o6 g
of potassium hydroxide, and 9.12 g of choline chloride are
dissolved in 30 g water. 23.ll g of 40 welght % colloidal
silica gel are introduced into this solution, the suspension
so formed is homogenized and heated for 1,200 hours at

9 ~
~ 8 - ~IOE 81/F 222
105C under its own vapor pressure. After the usual
work-up, a crystalline product having the following com-
position, expressed as molar ratio of oxides, is obtained:
5 SiO2 . 0.073 Al203 : 0.010 B203 : 0.043 Na20 : 0.029 K20 : 0.055 R20,
R = choline.
The X-ray diffraction pattern correspcnds to that of Table 1.
Example 3
As in Example 2, a suspension is prepared from 5.6 g
of sodium aluminate, 4.1 g of boron trioxide, 7.2 g of sodium
hydroxide, 5.3 g of potassium hydroxide, 45.6 g of choline
chloride, 117 g of 40 weight ~ colloidal silica gel and
150 g of water. This suspension is heated for 1,200 hours at
100C. After usual work-up, a crystalline product having
the following composition, expressed as molar ratio of
oxides, is obtained:
SiO2 : 0.050 Al203 : 0.038 B203 : 0.034 Na20 : 0.027 K20 : 0.058 R20,
R - choline.
The product has the X-ray diffraction pattern of Table 1.