US4658081A
Expired / Lapsed
US
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Propylene and ethylene selectivity with H2 S
Assignee: Phillips Petroleum Co
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Filing: 1985-07-25
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Granted: 1987-04-14
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Expires: 2005-07-25
Abstract
Abstract Feed hydrocarbons comprising propane and butanes are cracked to selectively maximize the production of ethylene or propylene by contacting the feed hydrocarbons with a cracking catalyst, adapted to convert the feed hydrocarbons to less saturated hydrocarbons, under conditions sufficient to thus crack the feed hydrocarbons, to thereby selectively maximize the production of ethylene, and, at least intervally, hydrogen sulfide or a hydrogen sulfide precursor is added to the feed hydrocarbons to thereby maximize the production of propylene. Preferred catalysts which may be utilized in the process and which are highly selective to the production of ethylene, as opposed to propylene, (in the absence of hydrogen sulfide or hydrogen sulfide precursor) include mixed oxides of manganese and magnesium, mixed oxides of manganese and Lanthanum Series metal and/or niobium, mixed oxides of iron and magnesium and mixed oxides of iron and Lanthanum Series metal and/or niobium. The effective life of the catalyst, particularly for the selective production of ethylene, is increased by carrying out the process in the presence of steam. When the catalyst contains manganese, the steam is optional whereas, when the catalyst contains iron, the steam is essential. The life of the magnesium based catalysts as well as their selectivity, particularly to ethylene, can also be extended by adding small promoting amounts of oxides of calcium, strontium, barium, tin, antimony, silicone, aluminum, titanium and/or chromium. All of the above promoters are useful in the iron/magnesium catalysts except the calcium, strontium, barium, tin and antimony. Only chromium is useful as a promoter for the Lanthanum Series and niobium based catalysts.
Inventors
- 👤 John H. Kolts
Bibliographic Details
Application Number
—
Jurisdiction
US
Data Source
google_patents
Last Synchronized
2026-11-08 06:40
CPC Classifications
C; C07; C07C; C07C4/00; C07C4/02; C07C4/06; C07C2521/00; C07C2521/02; C07C2521/04; C07C2521/06; C07C2521/08; C07C2521/10; C07C2523/00; C07C2523/10; C07C2523/14; C07C2523/16; C07C2523/18; C07C2523/20; C07C2523/24; C07C2523/26; C07C2523/32; C07C2523/34; C07C2523/70; C07C2523/74; C07C2523/745; C07C2523/76; C07C2523/83; C07C2523/84; C07C2523/847; Y; Y02; Y02P; Y02P20/00; Y02P20/50; Y02P20/52
Claims Analysis
Total Claims: 17
Claim 1
Independent Claim
484 words
A method for cracking feed hydrocarbons comprising at least one of propane and butanes to produce less saturated hydrocarbon products and selectively maximize the content of one of ethylene and propylene in said less saturated hydrocarbon products, comprising: (a) contacting said feed hydrocarbons with a cracking catalyst selected from the group consisting of: (1) a catalyst composition, consisting essentially of: 0.1 to 30 wt. % of (A) at least one oxide of manganese and the balance of (B) at least one oxide of magnesium; (2) a catalyst composition, consisting essentially of: 1 to 15 wt.% of (A) at least one oxide of one metal selected from the group consisting of calcium, strontium, barium, tin and antimony, 0.1 to 30 wt.% of (B) at least one oxide of manganese and the balance of (C) at least one oxide of magnesium; (3) a catalyst composition, consisting essentially of: 1 to 15 wt.% of (A) at least one oxide of a metal selected from the group consisting of silicon, aluminum and titanium, 0.1 to 30 wt.% of (B) at least one oxide of manganese and the balance of (C) at least one oxide of magnesium; (4) a catalyst composition, consisting essentially of: 1 to 15 wt.% of (A) at least one oxide of a metal selected from the group consisting of calcium, strontium, barium, tin and antimony, 1 to 15 wt.% of (B) at least one oxide of a metal selected from the group consisting of silicon, aluminum and titanium, 0.1 to 30 wt.% of (C) at least one oxide of manganese and the balance of (D) at least one oxide of magnesium; (5) a catalyst composition, consisting essentially of: 1 to 15 wt.% of (A) at least one oxide of chromium, 0.1 to 30 wt.% of (B) at least one oxide of manganese and the balance of (C) at least one oxide of magnesium; and (6) a catalyst composition, consisting essentially of: 1 to 15 wt.% of (A) at least one oxide of chromium, 1 to 15 wt.% of (B) at least one oxide of a metal selected from the group consisting of calcium, strontium, barium, tin and antimony, 0.1 to 30 wt.% of (C) at least one oxide of manganese and the balance of (D) at least one oxide of magnesium, said amounts being expressed in terms of wt.% of the elemental metal based on the total weight of the catalyst; in the absence of significant amounts of hydrogen sulfide and hydrogen sulfide precursors and under predetermined conditions to produce said less saturated hydrocarbon products containing substantially greater quantities of ethylene than propylene; and (b) at least intervally, adding a material selected from the group consisting of hydrogen sulfide and hydrogen sulfide precursors to said feed hydrocarbons, in the presence of said cracking catalyst, under said predetermined conditions to produce said less saturated hydrocarbons containing substantially increased quantities of propylene and decreased quantities of ethylene.
Claim 2
Independent Claim
484 words
A method for cracking feed hydrocarbons comprising at least one of propane and butanes to produce less saturated hydrocarbon products and selectively maximize the content of one of ethylene and propylene in said less saturated hydrocarbon products, comprising: (a) contacting said feed hydrocarbons with a cracking catalyst selected from the group consisting of: (1) a catalyst composition, consisting essentially of: 0.1 to 30 wt. % of (A) at least one oxide of manganese and the balance of (B) at least one oxide of magnesium; (2) a catalyst composition, consisting essentially of: 1 to 15 wt.% of (A) at least one oxide of one metal selected from the group consisting of calcium, strontium, barium, tin and antimony, 0.1 to 30 wt.% of (B) at least one oxide of manganese and the balance of (C) at least one oxide of magnesium; (3) a catalyst composition, consisting essentially of: 1 to 15 wt.% of (A) at least one oxide of a metal selected from the group consisting of silicon, aluminum and titanium, 0.1 to 30 wt.% of (B) at least one oxide of manganese and the balance of (C) at least one oxide of magnesium; (4) a catalyst composition, consisting essentially of: 1 to 15 wt.% of (A) at least one oxide of a metal selected from the group consisting of calcium, strontium, barium, tin and antimony, 1 to 15 wt.% of (B) at least one oxide of a metal selected from the group consisting of silicon, aluminum and titanium, 0.1 to 30 wt.% of (C) at least one oxide of manganese and the balance of (D) at least one oxide of magnesium; (5) a catalyst composition, consisting essentially of: 1 to 15 wt.% of (A) at least one oxide of chromium, 0.1 to 30 wt.% of (B) at least one oxide of manganese and the balance of (C) at least one oxide of magnesium; and (6) a catalyst composition, consisting essentially of: 1 to 15 wt.% of (A) at least one oxide of chromium, 1 to 15 wt.% of (B) at least one oxide of a metal selected from the group consisting of calcium, strontium, barium, tin and antimony, 0.1 to 30 wt.% of (C) at least one oxide of manganese and the balance of (D) at least one oxide of magnesium, said amounts being expressed in terms of wt.% of the elemental metal based on the total weight of the catalyst; in the absence of significant amounts of hydrogen sulfide and hydrogen sulfide precursors and under predetermined conditions to produce said less saturated hydrocarbon products containing substantially greater quantities of ethylene than propylene; and (b) at least intervally, adding a material selected from the group consisting of hydrogen sulfide and hydrogen sulfide precursors to said feed hydrocarbons, in the presence of said cracking catalyst, under said predetermined conditions to produce said less saturated hydrocarbons containing substantially increased quantities of propylene and decreased quantities of ethylene.
Claim 3
Dependent Claim
34 words
A method in accordance with claim 1 wherein addition of a material selected from the group consisting of hydrogen sulfide and hydrogen sulfide precursors is discontinued and step (a) is repeated, at least once.
Claim 4
Dependent Claim
13 words
A method in accordance with claim 1 wherein the feed hydrocarbons comprise propane.
Claim 5
Dependent Claim
13 words
A method in accordance with claim 1 wherein the feed hydrocarbons comprise butanes.
Claim 6
Dependent Claim
18 words
A method in accordance with claim 1 wherein the feed hydrocarbons comprise a mixture of propane and butanes.
Claim 7
Dependent Claim
21 words
A method in accordance with claim 1 wherein the temperature of contacting is between about 550° C. and about 850° C.
Claim 8
Dependent Claim
18 words
A method in accordance with claim 1 wherein the contacting is carried out in the presence of steam.
Claim 9
Dependent Claim
18 words
A method in accordance with claim 7 wherein the steam/feed hydrocarbons mol ratio is less than about 10/1.
Claim 10
Dependent Claim
40 words
A method in accordance with claim 1 wherein the material selected from the group consisting of hydrogen sulfide and hydrogen sulfide precursors is added in the amount of about 0.1 to 30 mol percent, expressed in terms of hydrogen sulfide.
Claim 11
Dependent Claim
26 words
A method in accordance with claim 1 wherein the catalyst consists essentially of at least one oxide of manganese and at least one oxide of magnesium.
Claim 12
Dependent Claim
45 words
A method in accordance with claim 1 wherein the catalyst consists essentially of at least one oxide of a metal selected from the group consisting of calcium, strontium, barium, tin and antimony, at least one oxide of manganese and at least one oxide of magnesium.
Claim 13
Dependent Claim
24 words
A method in accordance with claim 11 wherein the metal selected from the group consisting of calcium, strontium, barium, tin and antimony is calcium.
Claim 14
Dependent Claim
43 words
A method in accordance with claim 1 wherein the catalyst consists essentially of at least one oxide of a metal selected from the group consisting of silicon, aluminum and titanium, at least one oxide of manganese and at least one oxide of magnesium.
Claim 15
Dependent Claim
62 words
A method in accordance with claim 1 wherein the catalyst consists essentially of at least one oxide of a metal selected from the group consisting of calcium, strontium, barium, tin and antimony, at least one oxide of a metal selected from the group consisting of silicon, aluminum and titanium, at least one oxide of manganese and at least one oxide of magnesium.
Claim 16
Dependent Claim
32 words
A method in accordance with claim 1 wherein the catalyst consists essentially of at least one oxide of chromium, at least one oxide of manganese and at least one oxide of magnesium.
Claim 17
Dependent Claim
51 words
A method in accordance with claim 1 wherein the catalyst consists essentially of at least one oxide of chromium, at least one oxide of a metal selected from the group consisting of calcium, strontium, barium, tin and antimony, at least one oxide of manganese and at least one oxide of magnesium.
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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) | 1990-04-13 | 1990-10-13 | 1991-04-14 | $2000.00 | Window Closed / Lapsed |
| 7.5 Years (Year 8) | 1994-04-13 | 1994-10-13 | 1995-04-14 | $3760.00 | Window Closed / Lapsed |
| 11.5 Years (Year 12) | 1998-04-13 | 1998-10-13 | 1999-04-14 | $7700.00 | Window Closed / Lapsed |