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US4482774A
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Hydrocarbon conversion process with a composite zeolite
Assignee: ExxonMobil Technology and Engineering Co
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Filing: 1983-11-21
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Granted: 1984-11-13
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Expires: 2003-11-21
Abstract
Abstract Hydrocarbon conversion processes which use catalyst compositions comprising a core of silica with an overlying modified-silica zeolite, preferably containing aluminium, gallium or boron, show improved catalytic activity. The composites are prepared by introducing preformed silica particles, preferably with a crystallite size greater than 0.1μ, into a reaction mixture comprising a silicon source, a source of the modifying element, and preferably an organic template such as a tetraalkylammonium compound to form the modified-silica zeolite with a constraint index of from 1 to 12. The weight ratio of the silica core to SiO 2 in the reaction mixture is preferably 1:1 to 10:1.
Inventors
- 👤 Wicher T. Koetsier
Bibliographic Details
Application Number
—
Jurisdiction
US
Data Source
google_patents
Last Synchronized
2026-10-28 19:31
CPC Classifications
B; B01; B01J; B01J29/00; B01J29/87; B01J29/005; B01J2229/00; B01J2229/60; B01J2229/62; B01J2229/64; B01J29/03; B01J29/035
Claims Analysis
Total Claims: 19
Claim 1
Independent Claim
44 words
A hydrocarbon conversion process comprising contacting, under hydrocarbon conversion conditions, a hydrocarbon feed with a catalyst comprising a crystalline modified-silica zeolite having a constraint index of from 1 to 12 overlying a silica core having substantially the same crystalline structure as the modified-silica zeolite.
Claim 2
Dependent Claim
44 words
A hydrocarbon conversion process comprising contacting, under hydrocarbon conversion conditions, a hydrocarbon feed with a catalyst comprising a crystalline modified-silica zeolite having a constraint index of from 1 to 12 overlying a silica core having substantially the same crystalline structure as the modified-silica zeolite.
Claim 3
Dependent Claim
36 words
Process of claim 1 wherein the silica core is a silica polymorph of analogous structure to the modified-silica zeolite, so that the silica core alone and the complete catalyst display substantially the same x-ray diffraction patterns.
Claim 4
Dependent Claim
40 words
Process of claim 1 wherein the silica core is a silica polymorph having, after calcination in air for at least one hour at 600° C., a mean refractive index of 1.39±0.01 and a specific gravity at 25° C. of 1.70±0.05.
Claim 5
Dependent Claim
37 words
Process of claim 3 wherein the silica core is a silica polymorph having an x-ray powder diffraction pattern in which the six strongest d-values are: 11.1±0.2 Å 10.0±0.2 Å 3.85±0.07 Å 3.82±0.07 Å 3.76±0.05 Å 3.72±0.05 Å
Claim 6
Dependent Claim
32 words
Process of claim 3 wherein the silica polymorph has a pore diameter in the range of from 5 to 6 Angstrom units and a pore volume of 0.18 ml/g, determined by adsorption.
Claim 7
Dependent Claim
99 words
Process of claim 3 wherein the silica polymorph has, following calcination in air for at least an hour at 600° C., an adsorptive capacity for water vapour at 23° C. and a water vapour pressure of 4.6 mm Hg of less than 1 wt.%, an infra-red spectrum which exhibits a substantial absence of absorption in the region of 3700-3100 cm -1 , and an x-ray powder diffraction pattern containing at least the following d-values: 11.1±0.2 10.0±0.2 9.75±0.1 3.85±0.04 3.82±0.04 3.71±0.02 3.62±0.02 and showing an absence of reflections intermediate the reflections corresponding to d-spacings of 3.82±0.04 Å and 3.71±0.02 Å.
Claim 8
Dependent Claim
137 words
Process of claim 1 wherein the silica core is a silicate resulting from thermal treatment at a temperature of from 200° C. to 600° C. for from 1 to 48 hours of a crystal metal organosilicate having a composition, in its anhydrous state, in terms of mole ratios of oxides as follows: 0.9±0.2(xR.sub.2 O+(1-x)M.sub.2/n O):<0.005Al.sub.2 O.sub.3 :>1 where M is sodium or sodium in combination with tin, calcium, nickel or zinc, R is a tetraalkylammonium and x is a number greater than 0 but not exceeding 1, the organosilicate having the following characteristic x-ray diffraction lines: ______________________________________
Interplanar spacing d (Å)
Relative Intensity
______________________________________
11.1±0.2 s
10.0±0.2 s
7.4±0.15 w
7.1±0.15 w
6.3±0.1 w
6.04
±0.1 w
5.97
5.56±0.1 w
5.01±0.1 w
4.60±0.08 w
4.25±0.08 w
3.85±0.07 vs
3.71±0.05 s
3.04±0.03 w
2.99±0.02 w
2.94±0.02 w
______________________________________
Claim 9
Dependent Claim
53 words
Process of claim 1 wherein the silica core has the following characteristic x-ray diffraction pattern: ______________________________________
Interplanar spacing d (Å)
Relative Intensity
______________________________________
11.2 ±0.2 m
10.1±0.2 m
6.73±0.2 w
5.75±0.1 w
5.61±0.1 w
5.03±0.1 w
4.62±0.1 w
4.39±0.08 w
3.86±0.07 vs
3.73±0.07 m
3.49±0.07 w
3.07
±0.05 w
3.00
2.01±0.02 w
______________________________________
Claim 10
Dependent Claim
73 words
Process of claim 1 wherein the silica core is a silica having the following significant lines in its x-ray pattern: ______________________________________
Interplanar spacing d (Å)
Relative Intensity
______________________________________
11.9 ± 0.2 s
10.2 ± 0.2 m
4.76 ± 0.1 w
4.29 ± 0.08 vs
3.87 ± 0.07 vs
3.66 ± 0.07 w
3.49 ± 0.07 w
3.38 ± 0.07 m
3.20 ± 0.06 w
3.05 ± 0.05 w
2.64 ± 0.03 w
______________________________________
Claim 11
Dependent Claim
23 words
Process of claim 1 wherein the silica core alone and the catalyst composition display the significant x-ray diffraction lines of a ZSM-5 zeolite.
Claim 12
Dependent Claim
57 words
Process of claim 1 wherein the modified-silica zeolite has a formula (expressed in terms of the mole ratios of oxides) as follows: M.sub.2/n O:W.sub.2/x O:YSiO.sub.2 :zH.sub.2 O wherein M is at least one cation of valence n, W is the modifying element of valence x, Y is at least 5 and z is from 0 to 40.
Claim 13
Dependent Claim
28 words
Process of claim 11 wherein modifying element W is Al, B, Ga, Cr, Fe, V, Ti, Be, AS or a combination of two or more of those elements.
Claim 14
Dependent Claim
40 words
Process of claim 11 wherein the modified-silica zeolite is of the formula (expressed in terms of mole ratios of oxides): M.sub.2/n O:W'.sub.2 O.sub.3 :Y'SiO.sub.2 :zH.sub.2 O wherein W' is one or more of Al, Ga and B, Y' is 20-5000.
Claim 15
Dependent Claim
34 words
Process of claim 11 wherein the mean ratio of silicon to modifying element W or W' in the complete catalyst (expressed in terms of mole ratios of their oxides) is from 20 to 500.
Claim 16
Dependent Claim
18 words
Process of claim 1 wherein the silica core has a crystalline size of greater than 0.1μ mean diameter.
Claim 17
Dependent Claim
19 words
Process of claim 15 wherein the silica core has a crystallite size of from 0.5μ to 20μ mean diameter.
Claim 18
Dependent Claim
46 words
Process of claim 1 wherein the weight ratio of the silica core to the overlying modified-silica zeolite (expressed in terms of the weight ratio of the SiO 2 core to the SiO 2 in the reaction mixture for the modified-silica zeolite) is from 1:1 to 10:1.
Claim 19
Dependent Claim
21 words
Process of claim 17 wherein the weight ratio of the silica core to the overlying modified-silica is from 1:1 to 4:1.
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USPTO Annuity & Maintenance Windows
| Annuity Stage | Window Opens | Payment Deadline | Surcharge Period Until | Estimated Fee | Status |
|---|---|---|---|---|---|
| 3.5 Years (Year 4) | 1987-11-13 | 1988-05-14 | 1988-11-13 | $2000.00 | Window Closed / Lapsed |
| 7.5 Years (Year 8) | 1991-11-13 | 1992-05-14 | 1992-11-13 | $3760.00 | Window Closed / Lapsed |
| 11.5 Years (Year 12) | 1995-11-13 | 1996-05-14 | 1996-11-13 | $7700.00 | Window Closed / Lapsed |