Exxon Research and Engineering Company

Tanaka Kikinzoku Kogyo K.k.

Catalytica, Inc.

Ashland Oil, Inc.

Robert L Garten

M Albert Vannice

Gary Brice McVicker

Kazunori Tsurumi

Toru Shoji

Ralph Albert Dalla Betta

Edwin L Kugler

Philippe M Bruylants

Ralph A Della Betta

This invention is a catalyst comprising palladium on a support containing zirconium and a partial combustion process in which the fuel is partially combusted using that catalyst. The choice of catalysts and supports solves a problem dealing with the long term stability of palladium as a partial combustion catalyst. The catalyst structure is stable in operation, has a comparatively low operating temperature, has a low temperature a which oxidation begins, and yet is not susceptible to temperature 'runaway'. The combustion gas produced by the catalytic process typically is at a temperature below the autocombustive temperature and may be used at that temperature or it may be fed to other combustion stages for further use in a gas turbine, furnace, boiler, or the like.

Partial combustion catalyst of palladium on a zirconia support and a

This invention is a catalyst comprising palladium on a support containing zirconium and a partial combustion process in which the fuel is partially combusted using that catalyst. The choice of catalysts and supports solves a problem dealing with the long term stability of palladium as a partial combustion catalyst. The catalyst structure is stable in operation, has a comparatively low operating temperature, has a low temperature at which oxidation begins, and yet is not susceptible to temperature 'runaway'. The combustion gas produced by the catalytic process typically is at a temperature below the autocombustive temperature and may be used at that temperature or it may be fed to other combustion stages for further use in a gas turbine, furnace, boiler, or the like.

Toluene and formaldehyde produce styrene in a gas phase catalytic process using a basic hydroxide of Group I or II, at formaldehyde to toluene mole ratios of from 0.001 to 0.10.

Styrene from toluene and formaldehyde

Higher molecular weight hydrocarbons of from C.sub.2 to C.sub.7 carbon number are prepared from CO and H.sub.2 by the method of passing the CO and H.sub.2 at a ratio of from 10-0.1, a space velocity of from 100 hr.sup.-1 to 50,000 hr.sup.-1 over a bulk nickel catalyst promoted with from 0.001 to 25 wt. % titanium containing oxide (calculated as TiO.sub.2), for a time sufficient to effect the generation of the desired hydrocarbon products, at a temperature of from 100.degree. to 500.degree. C. and a pressure of from 103 to 1.03.times.10.sup.5 kPa. The hydrocarbon products obtained are clean, stable paraffin liquids. The activity of the instant process employing titanium promoted bulk nickel is from 3 to 5 times that of the process employing bulk nickel.

Hydrocarbon synthesis from CO and H.sub.2 using titanium promoted bulk

The instant invention relates to a novel catalyst which comprises a physical mixture of (1) at least one catalytically active transition metal selected from Group VIII of the Periodic Table of the Elements in combination with at least one alkaline earth metal oxide, and (2) an acidic refractory oxide. The combination of one or more of said Group VIII metals and one or more alkaline earth metal oxides may be provided by supporting said metals and said oxides on a nonacidic refractory oxide support. These catalysts are useful in hydrocarbon conversion processes and are characterized as having improved stability under oxidizing conditions, for example, the high temperature oxidation treatments encountered in regenerating deactivated reforming catalysts.

Hydrocarbon conversion processes utilizing a catalyst comprising a Group

A new method for the selective synthesis of olefinic hydrocarbons of from C.sub.2 -C.sub.5 from CO and H.sub.2 which method comprises the steps of passing a synthesis gas stream of CO and H.sub.2 at a H.sub.2 /CO ratio of from 0.1-10 at a space velocity of from 100 hr..sup.-1 to 50,000 hr..sup.-1 over a catalyst system comprising from 0.01 to 10 wt. % rhodium deposited on TiO.sub.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.degree.-500.degree. C. and a pressure of from 100 to 10.sup.5 kPa. The supported rhodium catalyst has a surface area of from 10 to 60 m.sup.2 g.sup.-1 of total catalyst with a preferred rhodium crystallite size .ltoreq. 5 nm. Rhodium supported on TiO.sub.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.

Hydrocarbon synthesis from CO and H.sub.2 using Rh supported on titanium

Catalysts and method of their preparation

A method for producing low molecular weight organic compounds, said method comprising the step of passing a mixture of CO and H.sub.2 over palladium supported on a suitable acidic metal oxide at a temperature and pressure sufficient to form said organic compounds. The palladium is highly dispersed on the chosen support and has a crystallite size of less than 100 A, preferably less than 70 A, most preferably, less than 40 A. In this state, the surface Pd atoms have a much higher activity than surface Pd atoms of very large Pd crystallites. To insure maintenance of such high activity and small crystallite size for a substantial period during the course of the reaction, the synthesis reactions are run at reactor bed temperatures below which agglomeration of crystallites is avoided, i.e., at temperatures below 350.degree. C., preferably about 325.degree. C., most preferably 300.degree. C.

Catalytic formation of hydrocarbons from CO, H.sub.2 mixtures and

Nickel supported on TiO.sub.2, other titanium-containing oxides or mixtures of various titanium oxides results in a catalyst system which exhibits superior hydrocarbon synthesis characteristics. Such supported nickel catalysts exhibit selectivity to paraffinic hydrocarbon products of from C.sub.2 to C.sub.7 which are free of olefins and oxygenated products. They generate CO conversions of up to 60% at pressures of 3090 kPa without significant change in product distribution. A large fraction of the product obtained contains 2 or more carbon atoms in the chain up to conversions of 60%. The supported nickel catalysts exhibit enhanced activity, improved selectivity to higher molecular weight normal paraffins, improved longevity and tolerance to sulfur and resistance to nickel carbonyl formation as compared to nickel catalysts on other supports such as Al.sub.2 O.sub.3, silica or carbon. A new method for the selective synthesis of higher molecular weight normal paraffins from CO and H.sub.2 over a wide range of CO conversions at pressures of from 103 to 3090 kPa (1 atm=103 kPa) which method comprises the steps of passing a synthesis gas stream of CO and H.sub.2 at a ratio of from 2 moles CO per .2 to 20 moles H.sub.2 at a space velocity of from 100 hr..sup.-.sup.1 to 30,000 hr..sup.-.sup.1 over a catalyst comprising from 0.01 to 75 wt. % nickel on TiO.sub.2, other titanium-containing oxides or mixtures of said titanium-containing oxides for a time sufficient to effect the generation of desired paraffinic products, at a temperature of from 100 to 500.degree. C. and a pressure of from 103 to 1.03 .times. 10.sup.5 kPa. The supported nickel catalyst has a BET surface area of from 10 to 60 m.sup.2 g.sup..sup.-1 of total catalyst with a nickel crystallite size of &lt; 10 nm (100 A).

Hydrocarbon synthesis from CO and H.sub.2 using Ni supported on a

A new method for the synthesis of hydrocarbons with chain lengths of from 2 to 10 carbon atoms inclusive and for selective generation of olefinic hydrocarbons in this carbon number range with reduced wax formation, said products being synthesized from CO and H.sub.2 at pressures of from 100 to 3100 kPa which method comprises the steps of passing a synthesis gas stream of CO and H.sub.2 at a H.sub.2 /CO ratio of from 0.1-10 at a space velocity of from 100 hr.sup.-.sup.1 to 50,000 hr.sup.-.sup.1 over a catalyst comprising from 0.01 to 15 wt. % ruthenium on TiO.sub.2, other titanium-containing oxides or mixtures of said titanium-containing oxides for a time sufficient to effect the generation of desired olefinic hydrocarbon products, at a temperature of from 100.degree. to 500.degree. C and a pressure of from 100 to 10.sup.5 kPa (1-1000 atm). The supported ruthenium catalyst has a BET surface area of from 10 to 60 m.sup.2 g.sup.-1 of total catalyst with a ruthenium crystallite size of preferably less than 5 nm (50 A).

Hydrocarbon synthesis from CO and H.sub.2 using Ru supported on a

A method for producing ethane, ethylene and dimethyl ether compounds, said method comprising the step of passing a mixture of CO and hydrogen over platinum supported on alumina at a temperature ranging from 100.degree.C. to 400.degree.C. and a pressure ranging from 1 to 100 atmospheres.

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Summit, NJ, United States of America

Robert L Garten