US4299808A
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Crystalline chromosilicates and process of preparation
Assignee: BP Corp North America Inc
•
Filing: 1979-08-23
•
Granted: 1981-11-10
•
Expires: 1999-08-23
Abstract
Abstract There are provided crystalline chromosilicates, their methods of preparation, and process uses. A first crystalline chromosilicate comprises a molecular sieve material providing a specific X-ray diffraction pattern and having the following composition in terms of mole ratios of oxides: 0.9±0.2 [WR.sub.2 O+(1-W)M.sub.2/n O]: Cr.sub.2 O.sub.3 : YSiO.sub.2 : ZH 2 O, wherein R is an alkylammonium cation, M is at least one cation having a valence of n, Y is a value within the range of about 4 to about 500, Z is a value within the range of about 0 to about 160, and W is a value that is greater than or equal to 0 and less than or equal to 1. A second crystalline chromosilicate comprises a molecular sieve material providing a specific X-ray diffraction pattern and having the following composition in terms of mole ratios of oxides: 0.9±0.2 M.sub.2/n O: Cr.sub.2 O.sub.3 : YSiO.sub.2 : ZH.sub.2 O, wherein M is at least one cation having a valence of n, Y is within the range of about 4 to about 500, and Z is within the range of about 0 to about 160. The first crystalline chromosilicate is a precursor of the second. There is provided also a process for the conversion of a hydrocarbon stream, which process comprises contacting said stream under hydrocarbon conversion conditions with a catalyst comprising the second crystalline chromosilicate. In addition, there is provided a process for the isomerization of a xylene feed, which process comprises contacting said feed under isomerization conditions with a catalyst comprising the second crystalline chromosilicate.
Inventors
- 👤 Marvin R. Klotz
Bibliographic Details
Application Number
—
Jurisdiction
US
Data Source
google_patents
Last Synchronized
2026-10-29 07:29
CPC Classifications
B; B01; B01J; B01J29/00; B01J29/04; B01J29/046; C; C07; C07C; C07C5/00; C07C5/22; C07C5/27; C07C5/2702; C07C5/2705; B01J2229/00; B01J2229/30; B01J2229/40; Y; Y02; Y02P; Y02P20/00; Y02P20/50; Y02P20/52
Claims Analysis
Total Claims: 56
Claim 1
Independent Claim
139 words
A crystalline chromosilicate, which chromosilicate comprises a molecular sieve material providing an X-ray diffraction pattern comprising the following X-ray diffraction lines and assigned strengths: ______________________________________
Interplanar Spacing Assigned
d, A Strength
______________________________________
11.04 ± 0.2 S
10.04 ± 0.2 S
3.80 ± 0.07 VS
3.74 ± 0.05 M
3.70 ± 0.05 S
3.64 ± 0.05 MS
______________________________________ and having the following composition in terms of mole ratios of oxides: 0.9±0.2[WR.sub.2 O+(1-W)M.sub.2/n O]:Cr.sub.2 O.sub.3 :YSiO.sub.2 :ZH.sub.2 O, wherein R is an alkylammonium cation, M is at least one cation having a valence of n, Y is a value within the range of about 4 to about 500, Z is a value within the range of about 0 to about 160, and W is a value that is greater than or equal to 0 and less than or equal to 1.
Claim 2
Dependent Claim
139 words
A crystalline chromosilicate, which chromosilicate comprises a molecular sieve material providing an X-ray diffraction pattern comprising the following X-ray diffraction lines and assigned strengths: ______________________________________
Interplanar Spacing Assigned
d, A Strength
______________________________________
11.04 ± 0.2 S
10.04 ± 0.2 S
3.80 ± 0.07 VS
3.74 ± 0.05 M
3.70 ± 0.05 S
3.64 ± 0.05 MS
______________________________________ and having the following composition in terms of mole ratios of oxides: 0.9±0.2[WR.sub.2 O+(1-W)M.sub.2/n O]:Cr.sub.2 O.sub.3 :YSiO.sub.2 :ZH.sub.2 O, wherein R is an alkylammonium cation, M is at least one cation having a valence of n, Y is a value within the range of about 4 to about 500, Z is a value within the range of about 0 to about 160, and W is a value that is greater than or equal to 0 and less than or equal to 1.
Claim 3
Dependent Claim
115 words
The chromosilicate of claim 1, said chromosilicate having been prepared by the method which comprises: (1) preparing a mixture containing an oxide of silicon, a compound of chromium, a hydroxide of an alkali metal or an alkaline earth metal, an alkylammonium cation or a precursor of an alkylammonium cation, and water; (2) maintaining said mixture at suitable reaction conditions to effect formation of said chromosilicate, said reaction conditions comprising a temperature within the range of about 25° C. to about 300° C., a pressure of at least the vapor pressure of water at said temperature, and a reaction time that is sufficient to effect crystallization to crystals of said chromosilicate; and (3) drying said crystals.
Claim 4
Dependent Claim
32 words
The chromosilicate of claim 1, wherein said compound of chromium is Cr 2 (SO 4 ) 3 .xH 2 O or Cr(C 2 H 3 O 2 ) 3 .H 2 O.
Claim 5
Dependent Claim
32 words
The chromosilicate of claim 2, wherein said compound of chromium is Cr 2 (SO 4 ) 3 .xH 2 O or Cr(C 2 H 3 O 2 ) 3 .H 2 O.
Claim 6
Dependent Claim
69 words
The chromosilicate of claim 2, wherein said mixture that is prepared in step (1) of said method of preparation has ratios of the initial reactant concentrations in the following ranges: ______________________________________
SiO.sub.2 /Cr.sub.2 O.sub.3
1-500
R.sub. N.sup.+ /(R.sub.4 'N.sup.+ + Na.sup.+)
0.1-1
OH.sup.- /SiO.sub.2
0.1-10
H.sub.2 O/OH.sup.- 10-500
______________________________________ wherein R' is an alkyl group and Na + represents sodium, any other alkali metal, or an alkaline earth metal.
Claim 7
Dependent Claim
32 words
The chromosilicate of claim 5, wherein said compound of chromium is Cr 2 (SO 4 ) 3 .xH 2 O or Cr(C 2 H 3 O 2 ) 3 .H 2 O.
Claim 8
Dependent Claim
125 words
A crystalline chromosilicate, which chromosilicate comprises a molecular sieve material providing an X-ray diffraction pattern comprising the following X-ray diffraction lines and assigned strengths: ______________________________________
Interplanar Spacing
Assigned
d, A Strength
______________________________________
11.15 ± 0.2 W
9.96 ± 0.2 VS
5.99 ± 0.1 VW
5.71 ± 0.1 VW
4.97 ± 0.1 W
3.85 ± 0.07 M
3.82 ± 0.07 MS
3.75 ± 0.05 M
3.32 ± 0.05 VW
1.99 ± 0.02 W
______________________________________ and having the following composition in terms of mole ratios of oxides: 0.9±0.2M.sub.2/n O:Cr.sub.2 O.sub.3 :YSiO.sub.2 :ZH.sub.2 O, wherein M is an least one cation having a valence of n, Y is within the range of about 4 to about 5000, and Z is within the range of 0 to about 160.
Claim 9
Dependent Claim
125 words
A crystalline chromosilicate, which chromosilicate comprises a molecular sieve material providing an X-ray diffraction pattern comprising the following X-ray diffraction lines and assigned strengths: ______________________________________
Interplanar Spacing
Assigned
d, A Strength
______________________________________
11.15 ± 0.2 W
9.96 ± 0.2 VS
5.99 ± 0.1 VW
5.71 ± 0.1 VW
4.97 ± 0.1 W
3.85 ± 0.07 M
3.82 ± 0.07 MS
3.75 ± 0.05 M
3.32 ± 0.05 VW
1.99 ± 0.02 W
______________________________________ and having the following composition in terms of mole ratios of oxides: 0.9±0.2M.sub.2/n O:Cr.sub.2 O.sub.3 :YSiO.sub.2 :ZH.sub.2 O, wherein M is an least one cation having a valence of n, Y is within the range of about 4 to about 5000, and Z is within the range of 0 to about 160.
Claim 10
Dependent Claim
19 words
The chromosilicate of claim 7, wherein Y is a value within the range of about 4 to about 80.
Claim 11
Dependent Claim
18 words
The chromosilicate of claim 7, wherein Z is a value within the range of 0 to about 40.
Claim 12
Dependent Claim
25 words
The chromosilicate of claim 7, wherein M is selected from the group consisting of alkylammonium cations, ammonium cation, hydrogen cation, metal cations, and mixtures thereof.
Claim 13
Dependent Claim
151 words
The chromosilicate of claim 7, said chromosilicate having been prepared by the method which comprises: (1) preparing a mixture containing an oxide of silicon, a compound of chromium, a hydroxide of an alkali metal or an alkaline earth metal, an alkylammonium cation or a precursor of an alkylammonium cation, and water; (2) maintaining said mixture at suitable reaction conditions to effect formation of said chromosilicate, said reaction conditions comprising a temperature within the range of about 25° C. to about 300° C., a pressure of at least the vapor pressure of water at said temperature, and a reaction time that is sufficient to effect crystallization to crystals of said chromosilicate; (3) drying said crystals; and (4) activating said crystals of chromosilicate by heat treating said crystals at a temperature within the range of about 800° F. (427° C.) to about 1,700° F. (927° C.) in the presence of a hydrogen-containing atmosphere.
Claim 14
Dependent Claim
18 words
The chromosilicate of claim 8, wherein Z is a value within the range of 0 to about 40.
Claim 15
Dependent Claim
9 words
The chromosilicate of claim 10, wherein M comprises nickel.
Claim 16
Dependent Claim
69 words
The chromosilicate of claim 11, wherein said mixture that is prepared in step (1) of said method of preparation has ratios of the initial reactant concentrations in the following ranges: ______________________________________
SiO.sub.2 /Cr.sub.2 O.sub.3
1-500
R.sub. N.sup.+ /(R.sub.4 'N.sup.+ + Na.sup.+)
0.1-1
OH.sup.- /SiO.sub.2
0.1-10
H.sub.2 O/OH.sup.- 10-500
______________________________________ wherein R' is an alkyl group and Na + represents sodium, any other alkali metal, or an alkaline earth metal.
Claim 17
Dependent Claim
25 words
The chromosilicate of claim 12, wherein M is selected from the group consisting of alkylammonium cations, ammonium cation, hydrogen cation, metal cations, and mixtures thereof.
Claim 18
Dependent Claim
151 words
The chromosilicate of claim 12, said chromosilicate having been prepared by the method which comprises: (1) preparing a mixture containing an oxide of silicon, a compound of chromium, a hydroxide of an alkali metal or an alkaline earth metal, an alkylammonium cation or a precursor of an alkylammonium cation, and water; (2) maintaining said mixture at suitable reaction conditions to effect formation of said chromosilicate, said reaction conditions comprising a temperature within the range of about 25° C. to about 300° C., a pressure of at least the vapor pressure of water of said temperature, and a reaction time that is sufficient to effect crystallization to crystals of said chromosilicate; (3) drying said crystals; and (4) activating said crystals of chromosilicate by heat treating said crystals at a temperature within the range of about 800° F. (427° C.) to about 1,700° F. (927° C.) in the presence of a hydrogen-containing atmosphere.
Claim 19
Dependent Claim
32 words
The chromosilicate of claim 14, wherein said compound of chromium is Cr 2 (SO 4 ) 3 .xH 2 O or Cr(C 2 H 3 O 2 ) 3 .H 2 O.
Claim 20
Dependent Claim
9 words
The chromosilicate of claim 15, wherein M comprises nickel.
Claim 21
Dependent Claim
69 words
The chromosilicate of claim 16, wherein said mixture that is prepared in step (1) of said method of preparation has ratios of the initial reactant concentration in the following ranges: ______________________________________
SiO.sub.2 /Cr.sub.2 O.sub.3
1-500
R.sub. N.sup.+ /(R.sub.4 'N.sup.+ + Na.sup.+)
0.1-1
OH.sup.- /SiO.sub.2
0.1-10
H.sub.2 O/OH.sup.- 10-500
______________________________________ wherein R' is an alkyl group and Na + represents sodium, any other alkali metal, or an alkaline earth metal.
Claim 22
Dependent Claim
32 words
The chromosilicate of claim 19, wherein said compound of chromium is Cr 2 (SO 4 ) 3 .xH 2 O or Cr(C 2 H 3 O 2 ) 3 .H 2 O.
Claim 23
Independent Claim
112 words
A method for preparing a crystalline chromosilicate, which method comprises: (1) preparing a mixture containing an oxide of silicon, a compound of chromium, a hydroxide of an alkali metal or an alkaline earth metal, an alkylammonium cation or a precursor of an alkylammonium cation, and water; (2) maintaining said mixture at suitable reaction conditions to effect formation of the chromosilicate, said reaction conditions comprising a reaction temperature within the range of about 25° C. to about 300° C., a pressure of at least the vapor pressure of water at the reaction temperature, and a reaction time that is sufficient to effect crystallization to crystals of said chromosilicate; and (3) drying said crystals.
Claim 24
Independent Claim
112 words
A method for preparing a crystalline chromosilicate, which method comprises: (1) preparing a mixture containing an oxide of silicon, a compound of chromium, a hydroxide of an alkali metal or an alkaline earth metal, an alkylammonium cation or a precursor of an alkylammonium cation, and water; (2) maintaining said mixture at suitable reaction conditions to effect formation of the chromosilicate, said reaction conditions comprising a reaction temperature within the range of about 25° C. to about 300° C., a pressure of at least the vapor pressure of water at the reaction temperature, and a reaction time that is sufficient to effect crystallization to crystals of said chromosilicate; and (3) drying said crystals.
Claim 25
Dependent Claim
68 words
The method of claim 21, wherein said mixture that has been prepared in step (1) of said method has ratios of the initial reactant concentrations in the following ranges: ______________________________________
SiO.sub.2 /Cr.sub.2 O.sub.3
1-500
R.sub. N.sup.+ /(R.sub.4 'N.sup.+ + Na.sup.+)
0.1-1
OH.sup.- /SiO.sub.2
0.1-10
H.sub.2 O/OH.sup.- 10-500
______________________________________ wherein R' is an alkyl group and Na + represents sodium, any other alkali metal, or an alkaline earth metal.
Claim 26
Dependent Claim
44 words
The method of claim 21, which method comprises further activating said crystals of chromosilicate by heat treating said crystals at a temperature within the range of about 800° F. (427° C.) to about 1,700° F. (927° C.) in the presence of a hydrogen-containing atmosphere.
Claim 27
Dependent Claim
32 words
The method of claim 21, wherein said compound of chromium is Cr 2 (SO 4 ) 3 .xH 2 O or Cr(C 2 H 3 O 2 ) 3 .H 2 O.
Claim 28
Dependent Claim
44 words
The method of claim 22, which method comprises further activating said crystals of chromosilicate by heat treating said crystals at a temperature within the range of about 800° F. (427° C.) to about 1,700° F. (927° C.) in the presence of a hydrogen-containing atmosphere.
Claim 29
Dependent Claim
32 words
The method of claim 22, wherein said compound of chromium is Cr 2 (SO 4 ) 3 .xH 2 O or Cr(C 2 H 3 O 2 ) 3 .H 2 O.
Claim 30
Dependent Claim
78 words
The method of claim 23, wherein said chromosilicate is cation exchanged with a catalytically active metal to provide a chromosilicate containing cations of said metal; drying said chromosilicate containing cations of said metal; and activating the dried chromosilicate containing cations of said metal by heat treating said chromosilicate containing cations of said metal in the presence of a hydrogen-containing atmosphere at a temperature within the range of about 800° F. (427° C.) to about 1,700° F. (927° C.).
Claim 31
Dependent Claim
44 words
The method of claim 24, which method comprises further activating said crystals of chromosilicate by heat treating said crystals at a temperature within the range of about 800° F. (427° C.) to about 1,700° F. (927° C.) in the presence of a hydrogen-containing atmosphere.
Claim 32
Dependent Claim
78 words
The method of claim 25, wherein said chromosilicate is cation exchanged with a catalytically active metal to provide a chromosilicate containing cations of said metal; drying said chromosilicate containing cations of said metal; and activating the dried chromosilicate containing cations of said metal by heat treating said chromosilicate containing cations of said metal in the presence of a hydrogen-containing atmosphere at a temperature within the range of about 800° F. (427° C.) to about 1,700° F. (927° C.).
Claim 33
Dependent Claim
44 words
The method of claim 26, which method comprises further activating said crystals of chromosilicate by heat treating said crystals at a temperature within the range of about 800° F. (427° C.) to about 1,700° F. (927° C.) in the presence of a hydrogen-containing atmosphere.
Claim 34
Dependent Claim
10 words
The method of claim 27, wherein said metal is nickel.
Claim 35
Dependent Claim
78 words
The method of claim 28, wherein said chromosilicate is cation exchanged with a catalytically active metal to provide a chromosilicate containing cations of said metal; drying said chromosilicate containing cations of said metal; and activating the dried chromosilicate containing cations of said metal by heat treating said chromosilicate containing cations of said metal in the presence of a hydrogen-containing atmosphere at a temperature within the range of about 800° F. (427° C.) to about 1,700° F. (927° C.).
Claim 36
Dependent Claim
10 words
The method of claim 29, wherein said metal is nickel.
Claim 37
Dependent Claim
78 words
The method of claim 30, wherein said chromosilicate is cation exchanged with a catalytically active metal to provide a chromosilicate containing cations of said metal; drying said chromosilicate containing cations of said metal; and activating the dried chromosilicate containing cations of said metal by heat treating said chromosilicate containing cations of said metal in the presence of a hydrogen-containing atmosphere at a temperature within the range of about 800° F. (427° C.) to about 1,700° F. (927° C.).
Claim 38
Dependent Claim
10 words
The method of claim 32, wherein said metal is nickel.
Claim 39
Dependent Claim
10 words
The method of claim 34, wherein said metal is nickel.
Claim 40
Dependent Claim
68 words
A crystalline chromosilicate having a composition in terms of mole ratios of oxides as follows: 0.9±0.2M.sub.2/n O: Cr.sub.2 O.sub.3 :YSiO.sub.2 :ZH.sub.2 O, wherein M is at least one cation having a valence of n, Y is between 4 and about 200 and Z is between 0 and about 160, said chromosilicate having the X-ray diffraction lines and assigned strengths substantially as described in Table II of the specification.
Claim 41
Dependent Claim
68 words
A crystalline chromosilicate having a composition in terms of mole ratios of oxides as follows: 0.9±0.2M.sub.2/n O: Cr.sub.2 O.sub.3 :YSiO.sub.2 :ZH.sub.2 O, wherein M is at least one cation having a valence of n, Y is between 4 and about 200 and Z is between 0 and about 160, said chromosilicate having the X-ray diffraction lines and assigned strengths substantially as described in Table II of the specification.
Claim 42
Dependent Claim
23 words
The composition of claim 37 further characterized in that Y is a value in the range of from about 4 to about 80.
Claim 43
Dependent Claim
25 words
The composition of claim 37 further characterized in that M is selected from the group consisting of alkylammonium, ammonium, hydrogen, metal cations, and mixtures thereof.
Claim 44
Dependent Claim
12 words
The composition of claim 39 further characterized in that M comprises nickel.
Claim 45
Dependent Claim
17 words
The composition of claim 37 further characterized in that M comprises hydrogen, nickel, and an alkali metal.
Claim 46
Dependent Claim
14 words
The composition of claim 37 further characterized in that M comprises hydrogen and nickel.
Claim 47
Dependent Claim
21 words
The composition of claim 37 further characterized in that Y is in the range of from about 4 to about 40.
Claim 48
Dependent Claim
20 words
The composition of claim 43 further characterized in that Z is in the range of from 0 to about 40.
Claim 49
Dependent Claim
20 words
The composition of claim 37 further characterized in that Z is in the range of from 0 to about 40.
Claim 50
Dependent Claim
13 words
The composition of claim 37 further characterized in that Y is about 16.
Claim 51
Dependent Claim
27 words
The composition of claim 37 further characterized in that said chromosilicate has X-ray diffraction lines and assigned strengths substantially as described in Table I of the specification.
Claim 52
Dependent Claim
24 words
The composition of claim 47 further characterized in that Y is between 4 and about 80 and Z is between 0 and about 40.
Claim 53
Dependent Claim
73 words
A crystalline chromosilicate having a composition in terms of oxides as follows: 0.9±0.2 [WR.sub.2 O+(1-W)M.sub.2/n O]:Cr.sub.2 O.sub.3 :YSiO.sub.2 :ZH.sub.2 O, wherein R is tetrapropylammonium, M is an alkali metal cation, W is greater than 0 and less than or equal to 1, Y is between 4 and 200, Z is between 0 and about 160 and having the X-ray diffraction lines and assigned strengths substantially as described in Table III of the specification.
Claim 54
Dependent Claim
73 words
A crystalline chromosilicate having a composition in terms of oxides as follows: 0.9±0.2 [WR.sub.2 O+(1-W)M.sub.2/n O]:Cr.sub.2 O.sub.3 :YSiO.sub.2 :ZH.sub.2 O, wherein R is tetrapropylammonium, M is an alkali metal cation, W is greater than 0 and less than or equal to 1, Y is between 4 and 200, Z is between 0 and about 160 and having the X-ray diffraction lines and assigned strengths substantially as described in Table III of the specification.
Claim 55
Dependent Claim
21 words
The chromosilicate of claim 49 further characterized in that Y is in the range of from about 5 to about 100.
Claim 56
Dependent Claim
25 words
The composition formed by contacting the composition of claim 49 at a temperature in excess of about 500° F. (260° C.) with a hydrogen-containing atmosphere.
References Cited (Backward Citations)
NL6802468A
Cited
GB1264545A
Cited
DE2017807A1
Cited
US3707886A
Cited
US3941871A
Cited
US4061724A
Cited
US4100214A
Cited
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