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US4116994A
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Hydrocarbon synthesis from CO and H2 using Rh supported on titanium oxides
Assignee: ExxonMobil Technology and Engineering Co
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Filing: 1977-07-28
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Granted: 1978-09-26
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Expires: 1997-07-28
Abstract
Abstract A new method for the selective synthesis of olefinic hydrocarbons of from C 2 -C 5 from CO and H 2 which method comprises the steps of passing a synthesis gas stream of CO and H 2 at a H 2 /CO ratio of from 0.1-10 at a space velocity of from 100 hr. -1 to 50,000 hr. -1 over a catalyst system comprising from 0.01 to 10 wt. % rhodium deposited on TiO 2 , other titanium-containing oxides or mixtures of said titanium-containing oxides for a time sufficient to effect the generation of desired olefinic products, at a temperature of from 100°-500° C. and a pressure of from 100 to 10 5 kPa. The supported rhodium catalyst has a surface area of from 10 to 60 m 2 g -1 of total catalyst with a preferred rhodium crystallite size ≦ 5 nm. Rhodium supported on TiO 2 , other titanium-containing oxides, or mixtures of titanium oxides results in a catalyst system which exhibits superior hydrocarbon synthesis characteristics. Such supported rhodium catalysts exhibit selectivity to olefinic products of from 2 to 5 carbons inclusive in processes for olefin generation accompanied by greater product yields and exhibit improved longevity, tolerance to sulfur and activity maintenance.
Inventors
- 👤 M. Albert Vannice
- 👤 Robert L. Garten
Bibliographic Details
Application Number
—
Jurisdiction
US
Data Source
google_patents
Last Synchronized
2026-10-29 06:19
CPC Classifications
B; B01; B01J; B01J23/00; B01J23/38; B01J23/40; B01J23/46; B01J23/70; B01J23/74; B01J23/755; C; C07; C07C; C07C1/00; C07C1/02; C07C1/04; C07C2521/00; C07C2521/02; C07C2521/04; C07C2521/18; C07C2523/00; C07C2523/02; C07C2523/04; C07C2523/10; C07C2523/38; C07C2523/40; C07C2523/46; C07C2523/70; C07C2523/89
Claims Analysis
Total Claims: 22
Claim 1
Independent Claim
156 words
A process for the enhanced synthesis of olefins and paraffins, wherein said paraffins are other than methane, comprising the steps of passing H 2 and CO in a H 2 /CO ratio of 0.1 to 10 over a catalyst comprising rhodium on a titanium-containing oxide support, wherein said titanium-containing oxide support is selected from the group consisting of TiO 2 , ZrTiO 4 , TiO 2 -carbon, TiO 2 - Al 2 O 3 , TiO 2 -SiO 2 , alkaline earth titanates, alkali titanates, rare earth titanates and mixtures thereof, at a space velocity of from 100 to 50,000 V/V/Hr and at a temperature of from 100° to 500° C., at a pressure of from 100 to 10 5 kPa for a time sufficient to effect the generation of the desired olefinic and paraffinic products in the desired ratio, wherein the concentration of said rhodium in said catalyst is from 0.01 to 10% by weight.
Claim 2
Dependent Claim
156 words
A process for the enhanced synthesis of olefins and paraffins, wherein said paraffins are other than methane, comprising the steps of passing H 2 and CO in a H 2 /CO ratio of 0.1 to 10 over a catalyst comprising rhodium on a titanium-containing oxide support, wherein said titanium-containing oxide support is selected from the group consisting of TiO 2 , ZrTiO 4 , TiO 2 -carbon, TiO 2 - Al 2 O 3 , TiO 2 -SiO 2 , alkaline earth titanates, alkali titanates, rare earth titanates and mixtures thereof, at a space velocity of from 100 to 50,000 V/V/Hr and at a temperature of from 100° to 500° C., at a pressure of from 100 to 10 5 kPa for a time sufficient to effect the generation of the desired olefinic and paraffinic products in the desired ratio, wherein the concentration of said rhodium in said catalyst is from 0.01 to 10% by weight.
Claim 3
Dependent Claim
13 words
The process of claim 1 wherein the titanium-containing oxide is TiO 2 .
Claim 4
Dependent Claim
29 words
The process of claim 2 wherein the rhodium on titanium oxide catalyst has a weight loading of rhodium of from 0.1 to 2 wt. % based on total catalyst.
Claim 5
Dependent Claim
23 words
The process of claim 2 wherein the rhodium on titanium oxide catalyst has a rhodium crystallite size of from 1 to 5 nm.
Claim 6
Dependent Claim
33 words
The process of claim 2 wherein the H 2 /CO ratio is from 4.0 to 0.5, the temperature is from 150° to 400° C. and the pressure is from 100 to 3000 kPa.
Claim 7
Dependent Claim
33 words
The process of claim 2 wherein the H 2 /CO ratio is from 3 to 1, the temperature is from 150° to 300° C and the pressure is from 100 to 2000 kPa.
Claim 8
Dependent Claim
16 words
The process of claim 2 wherein the rhodium concentration is from 0.05 to 5 wt. %.
Claim 9
Dependent Claim
26 words
The process of claim 2 wherein the catalyst comprising rhodium supported on TiO 2 has a rhodium particle crystallite size of from 1 to 20 nm.
Claim 10
Dependent Claim
26 words
The process of claim 2 wherein the catalyst comprising rhodium supported on TiO 2 has a rhodium particle crystallite size of from 1 to 10 nm.
Claim 11
Dependent Claim
21 words
The process of claim 2 wherein the TiO 2 has a surface area of from 1-200 m 2 g -1 .
Claim 12
Dependent Claim
21 words
The process of claim 2 wherein the TiO 2 has a surface area of from 25-100 m 2 g -1 .
Claim 13
Dependent Claim
23 words
The process of claim 1 wherein the titanium-containing oxide has a surface area of from 1 to 200 m 2 g -1 .
Claim 14
Dependent Claim
16 words
The process of claim 1 wherein the rhodium concentration is from 0.1 to 2 wt. %.
Claim 15
Dependent Claim
27 words
The process of claim 1 wherein the catalyst comprising rhodium supported on a titanium-containing oxide has a rhodium particle crystallite size of from 1 to 20 nm.
Claim 16
Dependent Claim
27 words
The process of claim 13 wherein the catalyst comprising rhodium supported on a titanium-containing oxide has a rhodium particle crystallite size of from 1 to 5 nm.
Claim 17
Dependent Claim
16 words
The process of claim 1 wherein the rhodium concentration is from 0.05 to 5 wt. %.
Claim 18
Dependent Claim
27 words
The process of claim 1 wherein the catalyst comprising rhodium supported on a titanium-containing oxide has a rhodium particle crystallite size of from 1 to 10 nm.
Claim 19
Dependent Claim
33 words
The process of claim 1 wherein the H 2 /CO ratio is from 4.0 to 0.5, the temperature is from 150° to 400° C. and the pressure is from 100 to 3000 kPa.
Claim 20
Dependent Claim
33 words
The process of claim 1 wherein the H 2 /CO ratio is from 3 to 1, the temperature is from 150° to 300° C. and the pressure is from 100 to 2000 kPa.
Claim 21
Dependent Claim
21 words
The process of claim 1 wherein the titanium-containing oxide has a surface area of from 10-100 m 2 g -1 .
Claim 22
Dependent Claim
21 words
The process of claim 1 wherein the titanium-containing oxide has a surface area of from 25-100 m 2 g -1 .
References Cited (Backward Citations)
USPTO Annuity & Maintenance Windows
| Annuity Stage | Window Opens | Payment Deadline | Surcharge Period Until | Estimated Fee | Status |
|---|---|---|---|---|---|
| 3.5 Years (Year 4) | 1981-09-25 | 1982-03-27 | 1982-09-26 | $2000.00 | Window Closed / Lapsed |
| 7.5 Years (Year 8) | 1985-09-25 | 1986-03-27 | 1986-09-26 | $3760.00 | Window Closed / Lapsed |
| 11.5 Years (Year 12) | 1989-09-25 | 1990-03-27 | 1990-09-26 | $7700.00 | Window Closed / Lapsed |