US4478950A
Expired / Lapsed
US
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Activity enhancement of high silica zeolites by thermal treatment with alkaline aluminate
Assignee: Mobil Oil AS
•
Filing: 1983-04-25
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Granted: 1984-10-23
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Expires: 2003-04-25
Abstract
Abstract A crystalline high silica-containing zeolite, such as ZSM-5, is hydrothermally treated with aluminate ion to enhance the catalytic activity.
Inventors
- 👤 Pochen Chu
Bibliographic Details
Application Number
—
Jurisdiction
US
Data Source
google_patents
Last Synchronized
2026-11-03 10:08
CPC Classifications
B; B01; B01J; B01J29/00; B01J29/04; B01J29/06; B01J29/40; B01J29/70; Y; Y10; Y10S; Y10S423/00; Y10S423/22; Y10S423/29; Y10S423/33
Claims Analysis
Total Claims: 33
Claim 1
Independent Claim
115 words
A method for enhancing the activity of a high silica-containing crystalline zeolite material having a silica-to-alumina ratio greater than 20 which comprises contacting said material with a solution containing organic cations selected from the group consisting of tetraalkylammonium, cations of alkylamines and mixtures thereof and aluminum ions for a period of time of from 1 hour to 30 days at a temperature of from 50° C. to 300° C. at autogenous pressures and at a pH of at least 7, calcining said solution contacted material at a tempeature of from 200° C. to 600° C., ion exchanging said calcined material, and calcining said ion-exchanged material at a temperature of from 200° C. to 600° C.
Claim 2
Independent Claim
115 words
A method for enhancing the activity of a high silica-containing crystalline zeolite material having a silica-to-alumina ratio greater than 20 which comprises contacting said material with a solution containing organic cations selected from the group consisting of tetraalkylammonium, cations of alkylamines and mixtures thereof and aluminum ions for a period of time of from 1 hour to 30 days at a temperature of from 50° C. to 300° C. at autogenous pressures and at a pH of at least 7, calcining said solution contacted material at a tempeature of from 200° C. to 600° C., ion exchanging said calcined material, and calcining said ion-exchanged material at a temperature of from 200° C. to 600° C.
Claim 3
Dependent Claim
18 words
The method of claim 1 wherein the aluminum ions are supplied by an organic or inorganic aluminum salt.
Claim 4
Dependent Claim
12 words
The method of claim 1 wherein the organic cations comprise tetraalkylammonium cations.
Claim 5
Dependent Claim
13 words
The method of claim 2 wherein the aluminum salt comprises alkali metal aluminate.
Claim 6
Dependent Claim
18 words
The method of claim 4 wherein the zeolite material has a silica-to-alumina mole ratio in excess of 500:1.
Claim 7
Dependent Claim
18 words
The method of claim 5 wherein the zeolite material has a silica-to-alumina mole ratio in excess of 1600:1.
Claim 8
Dependent Claim
17 words
The method of claim 6 wherein the zeolite material has a silica-to-alumina mole ratio greater than 30,000:1.
Claim 9
Dependent Claim
13 words
The method of claim 5 wherein the alkali metal aluminate is sodium aluminate.
Claim 10
Dependent Claim
24 words
The method of claim 3 wherein the tetraalkylammonium cations are selected from the group consisting of tetraethylammonium, tetrapropylammonium, tetrabutylammonium, methyltriethylammonium, methyltripropylammonium and mixtures thereof.
Claim 11
Dependent Claim
12 words
The method of claim 1 wherein the organic cations are of alkylamine.
Claim 12
Dependent Claim
20 words
The method of claim 10 wherein the alkylamine is selected from the group consisting of propylamine, butylamine and mixtures thereof.
Claim 13
Dependent Claim
23 words
The method of claim 1 wherein the zeolite material comprises an acid zeolite selected from the group consisting of ZSM-5, ZSM-11 and ZSM-12.
Claim 14
Dependent Claim
43 words
The method of claim 1 wherein the solution contacting step is conducted for a period of time of from 1 day to 5 days, at a temperature of from 80° C. to 160° C. and at a pH of from 7 to 13.
Claim 15
Dependent Claim
34 words
The method of claim 1 wherein the ion exchanging step comprises exchanging originally present cations of the zeolite material with cations selected from the group consisting of hydrogen, ammonium, rare earth and mixtures thereof.
Claim 16
Independent Claim
123 words
A method for enhancing the activity of a high silica-containing crystalline zeolite material having the crystal structure of zeolite ZSM-5 and a silica-to-alumina mole ratio greater than 20 which comprises contacting said material with a solution containing organic cations selected from the group consisting of tetraalkylammonium, cations of alkylamine and mixtures thereof and aluminum ions for a period of time of from 1 hour to 30 days at a temperature of from 50° C. to 300° C. at autogenous pressures and at a pH of at least 7, calcining said solution contacted material at a temperature of from 200° C. to 600° C., ion exchanging said calcined material, and calcining said ion-exchanged material at a temperature of from 200° C. to 600° C.
Claim 17
Independent Claim
123 words
A method for enhancing the activity of a high silica-containing crystalline zeolite material having the crystal structure of zeolite ZSM-5 and a silica-to-alumina mole ratio greater than 20 which comprises contacting said material with a solution containing organic cations selected from the group consisting of tetraalkylammonium, cations of alkylamine and mixtures thereof and aluminum ions for a period of time of from 1 hour to 30 days at a temperature of from 50° C. to 300° C. at autogenous pressures and at a pH of at least 7, calcining said solution contacted material at a temperature of from 200° C. to 600° C., ion exchanging said calcined material, and calcining said ion-exchanged material at a temperature of from 200° C. to 600° C.
Claim 18
Dependent Claim
18 words
The method of claim 15 wherein the zeolite material has a silica-to-alumina mole ratio in excess of 500.
Claim 19
Dependent Claim
18 words
The method of claim 16 wherein the zeolite material has a silica-to-alumina mole ratio in excess of 1600.
Claim 20
Dependent Claim
117 words
A crystalline zeolite material having enhanced activity prepared by the method of contacting a high silica-containing crystalline zeolite material having a silica-to-alumina mole ratio greater than 20 with a solution containing organic cations selected from the group consisting of tetraalkylammonium, cations of alkylamine and mixtures thereof and aluminum ions for a period of time of from 1 hour to 30 days at a temperature of from 50° C. to 300° C. at autogenous pressures and at a pH of at least 7, calcining said solution contacted material at a temperature of from 200° C. to 600° C., ion exchanging said calcined material, and calcining said ion-exchanged material at a temperature of from 200° C. to 600° C.
Claim 21
Dependent Claim
117 words
A crystalline zeolite material having enhanced activity prepared by the method of contacting a high silica-containing crystalline zeolite material having a silica-to-alumina mole ratio greater than 20 with a solution containing organic cations selected from the group consisting of tetraalkylammonium, cations of alkylamine and mixtures thereof and aluminum ions for a period of time of from 1 hour to 30 days at a temperature of from 50° C. to 300° C. at autogenous pressures and at a pH of at least 7, calcining said solution contacted material at a temperature of from 200° C. to 600° C., ion exchanging said calcined material, and calcining said ion-exchanged material at a temperature of from 200° C. to 600° C.
Claim 22
Dependent Claim
16 words
The zeolite material of claim 18 which has the crystal structure of ZSM-5, ZSM-11 or ZSM-12.
Claim 23
Dependent Claim
13 words
The zeolite material of claim 19 which has the crystal structure of ZSM-5.
Claim 24
Independent Claim
80 words
A method for increasing acid cracking activity of a high silica-containing zeolite having crystalline acid structure and having a silica-to-alumina mole ratio greater than 20, which comprises contacting said zeolite with an aqueous alkaline solution containing aluminate ion for a period of time ranging from 1 hour to 30 days at a temperature of from 80° C. to 160° C. at autogenous pressures at a pH of at least 9, thereby introducing tetrahedrally coordinated aluminum into the crystalline zeolite sructure.
Claim 25
Independent Claim
80 words
A method for increasing acid cracking activity of a high silica-containing zeolite having crystalline acid structure and having a silica-to-alumina mole ratio greater than 20, which comprises contacting said zeolite with an aqueous alkaline solution containing aluminate ion for a period of time ranging from 1 hour to 30 days at a temperature of from 80° C. to 160° C. at autogenous pressures at a pH of at least 9, thereby introducing tetrahedrally coordinated aluminum into the crystalline zeolite sructure.
Claim 26
Dependent Claim
14 words
The method of claim 21 wherein the aluminate ion is supplied by sodium aluminate.
Claim 27
Dependent Claim
15 words
The method of claim 21 wherein the solution contains quaternary ammonium cation or amine cation.
Claim 28
Independent Claim
39 words
A method for treating high silica crystalline zeolite to increase cracking activity which comprises contacting the zeolite with an aqueous alkaline aluminate solution at elevated temperature under conditions effective to introduce tetrahedrally coordinated aluminum in the zeolite crystalline structure.
Claim 29
Independent Claim
39 words
A method for treating high silica crystalline zeolite to increase cracking activity which comprises contacting the zeolite with an aqueous alkaline aluminate solution at elevated temperature under conditions effective to introduce tetrahedrally coordinated aluminum in the zeolite crystalline structure.
Claim 30
Dependent Claim
75 words
A process for enhancing cracking activity of an acid ZSM-5 type crystalline zeolite catalyst having a silica:alumina mole ratio greater than 50:1 which comprises contacting the zeolite under hydrothermal conditions with an alkaline metallate solution comprising at least one tetrahedrally bound hydroxylated metallate at a pH of about 9 to 12, and maintaining the zeolite in contact with the solution at elevated temperature under conditions effective to introduce tetrahedrally coordinated metallate into the crystalline zeolite.
Claim 31
Dependent Claim
75 words
A process for enhancing cracking activity of an acid ZSM-5 type crystalline zeolite catalyst having a silica:alumina mole ratio greater than 50:1 which comprises contacting the zeolite under hydrothermal conditions with an alkaline metallate solution comprising at least one tetrahedrally bound hydroxylated metallate at a pH of about 9 to 12, and maintaining the zeolite in contact with the solution at elevated temperature under conditions effective to introduce tetrahedrally coordinated metallate into the crystalline zeolite.
Claim 32
Dependent Claim
23 words
The process of claim 25 wherein the solution contains an activating amount of aluminate ion together with nitrogenous base cation and alkali-metal ion.
Claim 33
Dependent Claim
31 words
The process of claim 26 wherein the solution contains an activating amount of aluminate ion together with nitrogenous base cation and alkali metal ion at a pH of at least 9.
References Cited (Backward Citations)
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| 3.5 Years (Year 4) | 1987-10-23 | 1988-04-23 | 1988-10-23 | $2000.00 | Window Closed / Lapsed |
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