NZ201754A - Zeolitic boro-aluminosilicates and use as olefin producing catalysts - Google Patents
Zeolitic boro-aluminosilicates and use as olefin producing catalystsInfo
- Publication number
- NZ201754A NZ201754A NZ201754A NZ20175482A NZ201754A NZ 201754 A NZ201754 A NZ 201754A NZ 201754 A NZ201754 A NZ 201754A NZ 20175482 A NZ20175482 A NZ 20175482A NZ 201754 A NZ201754 A NZ 201754A
- Authority
- NZ
- New Zealand
- Prior art keywords
- boro
- aluminosilicates
- strong
- oxides
- weak
- Prior art date
Links
Classifications
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
- C01B35/00—Boron; Compounds thereof
- C01B35/08—Compounds containing boron and nitrogen, phosphorus, oxygen, sulfur, selenium or tellurium
- C01B35/10—Compounds containing boron and oxygen
- C01B35/1009—Compounds containing boron and oxygen having molecular-sieve properties
-
- 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
- B01J29/86—Borosilicates; Aluminoborosilicates
-
- 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
- C07C2529/86—Borosilicates; Aluminoborosilicates
-
- 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)
- Inorganic Chemistry (AREA)
- Engineering & Computer Science (AREA)
- Materials Engineering (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Silicates, Zeolites, And Molecular Sieves (AREA)
- Catalysts (AREA)
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
Description
New Zealand Paient Spedficaiion for Paient Number £01 754
201754
(.g'-g'i
. 1.&
■ s>"S>2.
• t • • »
Priority
* *• % « ■" ■ | I
Complete Spoc-ir.cslton rusa: .~
Class* . £&•' ^ ■'
. >nU 112 JUL 1985J
Pubhoatjori Data. .. .*
P.O. Journal No:
A 2-1)
fe'l li
MI EM
JGS
NEW ZEALAND Patents Act 1953
COMPLETE SPECIFICATION
N.Z. No.
,/V
- AUG 1982
"BORO-ALUMINOSILICATES HAVING ZEOLITE STRUCTURE, PROCESS FOR THEIR MANUFACTURE , AND THEIR USE"
We, HOECHST AKTIENGESELLSCHAFT, a corporation organized under the laws of the Federal Republic of Germany, of D-62 30 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
201754
Zeolites are crystalline aluminosilicates, in which due to a three-dimensional linkage of SiO^ and AlO^ tetrarhedra regular structures with cavities and pores are formed. In hydrated state, these pores and cavities are filled with 5 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 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, Y, 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.
Because of the numerous application possibilities as 20 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, vadium, or chromium in tetrahedral position.
Subject of the present invention are boro-aluminosili-cates having a zeolite structure which
2017 5 4
- 3 - iioh amm am a) have the following composition:
Si02 : (0.08 ± 0.05) fAl2C>3 + B20^7 :
(0.12 ± 0.10) /Na20 + K2Q7 : (0.10 ± 0.09) R20
expressed as molar ratio of oxides; R being choline 5 /f(CH3)3NCH2CH20H7 +
b) have the characteristic X-ray diffraction pattern set forth below in Table 1:
Table 1
1 u
Interplanar Spacing d Cl J
Relative Intensity
X/Io
11.5 - 0.2
very strong
9.2 ± 0.2
weak
7.6 ±0.2
medium
6.6 ±0.1
strong
.7 ± 0.1
medium
.35 ± 0.1
weak
4.98 ± 0.1
11
4.56 ± 0.1
strong
3.32 ± 0.1
11
4.16 ± 0.1
weak
3.81 ± 0.1
strong
3-75 ± 0.1
very strong
3.59 ± 0.1
medium
3.30 ± 0.1
it
3.15 ± 0.1
weak
2.86 ± 0.1
strong
2.67 ±0.1
weak
I = intensity of the strongest line or peak.
The intensities of Table 1 are defined as follows:
relative intensity
100
I/;Co very strong
80
- 100
strong
50
- 80
medium
- 50
weak
0
- 20
The aluminum/boron ratio of the zeolites of the invention is generally
A12°3
= 0.40 - 0.99
A1203 B2°3
preferably
A12°3
ai2o3 + b2o3
— 0.75 - 0.99
expressed as molar ratio of the oxides.
The novel zeolites of the invention have a structure similar to zeolite T (U.S. Patent No. 2,950,952);
- - • • — however, they have a different composition, especially with respect to 25 the boron content.
The zeolites of the invention 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 following ratio, expressed as molar ratio of the oxides:
Si02 : (0.06 * 0.05) A1203 : (0.06 ± 0.05) B203 (0.2 - 0.15) Na20 : (0.12 ± 0.10) K20 : (0.22 ± 0.2) R20 : (50 ~ 40) H20
preferably in a ratio of
2 017 5 4
- 5 - IIOD OUT QQQ
Si02 : (0.05 - 0.03) A12C>3 : (0.05 - 0.03) BgOji (0.2 i 0.1) Na20 : (0.09 - 0.05) K20 :
(0.22 - 0.2) R20 : (50 ± 40) H20;
R being choline.
As compounds, there are used for example silica gel, potassium silicate, sodium silicate, aluminum hydroxide, aluminum sulfate, boron trioxide, boric acid, borax, sodium hydroxide, 10 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 160°C, peferably 90 to 150°C, in a closed vessel.
The crystalline zeolites which are formed are isola-20 ted in usual manner, for example by filtration, 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 are distinguished by a high selectivity 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 30 be obtained by means of the indicated method.
The following Examples illustrate the invention without 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 35 radiation was the K-<^ doublet of copper.
201754
Example 1
9.0 g of sodium aluminate (54 weight % of Al^O^, 41 weight % of Na20) , 0.83 8 of boron trioxide, 5.9 g of sodium hydroxide, 5.3 g of potassium hydroxide, and 45.6 g 5 of choline chloride are dissolved in 150 g of water. 117 g of 40 weight % colloidal silica gel are added to this solution, and the suspension so formed is homogenized and heated for 8 days at 150°C. The product obtained is filtered off, washed with water and dried at 120°C. 10 Chemical analysis yields the following composition,
expressed as molar ratio of oxides:
Si02 : 0.075 Al^ : 0.003 : 0.048 Na20 : 0.023 K20 : 0.060 R20, 15 R = choline.
The result of X-ray diffraction is listed in Table 2.
2 01 7
- 7 - rnir m/r< "7
Table 2
Interplanar Spacing
Relative Intensity d Clj
I7Io
11.51
100
9.14
4
7.54
24
6.60
43
6.37
8
.73
22
.35
3
4.98
6
4.56
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
2.49
9
2.29
3
2.21
4
2.11
1.89
17
Example 2
2.27 g of borax, 1.43 g of aluminum hydroxide (75 weight % of Al^O^), 1.18 g of sodium hydroxide, 1.06 g of potassium hydroxide, and 9-12 g of choline chloride are 35 dissolved in 30 g water. 23-4 g of 40 weight % colloidal silica gel are introduced into this solution, the suspension so formed is homogenized and heated for 1,200 hours at
2 017 5 4
105°C under its own vapor pressure. After the usual work-up, a crystalline product having the following composition, expressed as molar ratio of oxides, is obtained:
Si02 : 0.073 A1203 : 0.010 B203 : 0.043 Na20 : 0.029 K20 : 0.055 R20,
R = choline.
The X-ray diffraction pattern corresponds 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 15 chloride, 117 g of 40 weight % colloidal silica gel and
150 g of water. This suspension is heated for 1,200 hours at 100°C. After usual work-up, a crystalline product having the following composition, expressed as molar ratio of oxides, is obtained:
Si02 : 0.050 A1203 : 0.038 B2C>3 : 0.034 Na20 : 0.027 K20 : 0.058 R20, R = choline.
The product has the X-ray diffraction pattern of Table 1.
201754
Claims (7)
- WHAT WE CLAIM IS: Boro-aluminosilicates having a zeolite structure which a) have the following composition: SiO 2 : (0.08 t 0.05) /A1203 + B^^ (0.12 ± 0.10) /Na20 + K2Q7 : (0.10 ± 0.09) R20 expressed as a molar ratio of the oxides; R being choline Z"(CH3)3nch2CH2OH7 + b) have the characteristic X-ray diffraction pattern set forth below in Table 1: 10 Table 1 15 20 30 Interplanar Spacing d C%J Relative Intensity I/]to 11.5 - 0.2 very strong 9.2 - 0.2 weak 7.6 - 0.2 medium 6.6 i 0.1 strong 5.7 i 0.1 medium 5.35 - 0.1 weak 4.98 - 0.1 it 4.56 - 0.1 strong 3.32 t o.1 m 4.16 - 0.1 weak 3.81 t o.1 strong 3-75 ± 0.1 very strong 3.59 ± 0.1 medium 3-30 - 0.1 n 3.15 - 0.1 weak 2.86 - 0.1 strong 2.67 - 0.1 weak = intensity of the strongest line or peak. 201754 - 10 -
- 2. Boro-aluminosilicates as claimed in Claim 1, wherein the aluminum/boron ratio is ai2O3 = 0.40 - 0.99 Al^O^ + B203 expressed as a molar ratio of the oxides.
- 3. Boro-aluminosilicates as claimed in Claim 1, wherein the 10 aluminum/boron ratio is 15 ai2O3 0.75 - 0.99 Al2°3 + B203 expressed as a molar ratio of the oxides. 20
- 4. A process for the manufacture of boro-aluminosilicates as claimed in one of Claims 1 to 3, which comprises preparing a mixture of silicon, aluminum, boron, sodium, potassium and choline compounds and water which is composed as follows, expressed as a molar ratio of the oxides 25 Si02 : (0.06 i 0.05) A1203 : (0.06 - 0.05) B203 : (0.2 - 0.15) Na20 : (0.12 ± 0.10) KgO : (0.22 - 0.2) R20 : (50 - 40) H20 R being choline, and heating this mixture in a closed vessel
- 5. The process as claimed in Claim 4, wherein the mixture 30 to be heated is composed as follows, expressed as a molar ratio of the oxides. 35 Si02 : (0.05 i 0.03) Al^ : (0.05 - 0.03) B2°3: (0.2 - 0.1) Na20 : (0.09-0.05) K20 : (0.22 - 0.2) R50 : (50 - 40) H50; :\c to g \»N OQ 40 R being choline.
- 6. Use of boro-aluminosilicates as claimed in one of Claims 1 to 3 as catalysts in the manufacture of C2-C^-olefins from methanol. - 11 - 201754
- 7. A boro-aluminosilicate according to claim 1 substantially as herein described. HOECHST AKTIENGESELLSCHAFT By Their Attorneys HENRY HUGHES LIMITED By: $fc>
Applications Claiming Priority (1)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
DE19813134317 DE3134317A1 (en) | 1981-08-31 | 1981-08-31 | BORO ALUMOSILICATES WITH ZEOLITE STRUCTURE AND METHOD FOR THE PRODUCTION THEREOF |
Publications (1)
Publication Number | Publication Date |
---|---|
NZ201754A true NZ201754A (en) | 1985-07-12 |
Family
ID=6140481
Family Applications (1)
Application Number | Title | Priority Date | Filing Date |
---|---|---|---|
NZ201754A NZ201754A (en) | 1981-08-31 | 1982-08-30 | Zeolitic boro-aluminosilicates and use as olefin producing catalysts |
Country Status (7)
Country | Link |
---|---|
EP (1) | EP0073482A3 (en) |
JP (1) | JPS5841715A (en) |
AU (1) | AU8782082A (en) |
CA (1) | CA1182099A (en) |
DE (1) | DE3134317A1 (en) |
NZ (1) | NZ201754A (en) |
ZA (1) | ZA826311B (en) |
Families Citing this family (4)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
DE3323022A1 (en) * | 1983-06-25 | 1985-01-03 | Basf Ag, 6700 Ludwigshafen | METHOD FOR VALUE ISOMERIZATION OF OLEFINS |
FI76005C (en) * | 1983-10-17 | 1988-09-09 | Neste Oy | ALUMINUM-BOR-SILICATE CATALYST, FREQUENCY FOR FRAMSTAELLNING AV DENNA OCH ALKYLERINGSPROCESS. |
US4952383A (en) * | 1984-04-13 | 1990-08-28 | Uop | Boron-aluminum-phosphorus-oxide molecular sieve compositions |
AU584127B2 (en) * | 1984-10-25 | 1989-05-18 | Mobil Oil Corporation | Hydrocracking catalyst composition and hydrocracking process using same |
Family Cites Families (4)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
NL238953A (en) * | 1958-05-08 | |||
NZ185397A (en) * | 1976-11-04 | 1979-12-11 | Mobil Oil Corp | Crystalline aluminosilicate zeolites and use as catalysts |
DE2830787B2 (en) * | 1978-07-13 | 1981-02-19 | Basf Ag, 6700 Ludwigshafen | Process for the production of nitrogen-containing crystalline metal silicates with a zeolite structure |
DE2909929A1 (en) * | 1979-03-14 | 1980-09-25 | Basf Ag | METHOD FOR PRODUCING A ZSM-5 STRUCTURAL TYPE |
-
1981
- 1981-08-31 DE DE19813134317 patent/DE3134317A1/en not_active Withdrawn
-
1982
- 1982-08-26 EP EP82107847A patent/EP0073482A3/en not_active Withdrawn
- 1982-08-30 CA CA000410415A patent/CA1182099A/en not_active Expired
- 1982-08-30 ZA ZA826311A patent/ZA826311B/en unknown
- 1982-08-30 NZ NZ201754A patent/NZ201754A/en unknown
- 1982-08-30 AU AU87820/82A patent/AU8782082A/en not_active Abandoned
- 1982-08-30 JP JP57149373A patent/JPS5841715A/en active Pending
Also Published As
Publication number | Publication date |
---|---|
EP0073482A2 (en) | 1983-03-09 |
JPS5841715A (en) | 1983-03-11 |
EP0073482A3 (en) | 1983-10-26 |
AU8782082A (en) | 1983-03-10 |
ZA826311B (en) | 1983-07-27 |
DE3134317A1 (en) | 1983-03-10 |
CA1182099A (en) | 1985-02-05 |
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