STEAM REFORMING PROCESS AND CATALYST

Abstract: Hydrocarbon feedstocks including those containing sul­ fur are steam-reformed in the presence of a catalyst which in the unreduced condition contains nickel oxide, rare earth metal oxide, and zirconium oxide. The catalyst consists of 20-50% of nickel oxide, 10-25% of rare earth metal oxide and 25-70% of zirconium oxide. Preparation by treating an aqueous solution of nitrates or acetates of the metals with hydroxides or carbonates of ammonia or sodium to form precipitates, then drying, shap­ ing and calcining.

Description: STEAM REFORMING PROCESS AND CATALYST This invention relates to catalytic steam reforming of hydrocarbons. Commercial steam reforming is typically carried out in fired tubular reactors by passing hydrocarbon feed with steam and, optionally, recycle gas over nickel catalyst supported on a refractory oxide. The catalyst compositions often contain small amounts of other constituents such as other metals, rare earth metal oxides, alkali and alkali earth metal compounds and cements which, variously, enhance the catalytic effect of nickel, inhibit carbon formation on the catalyst or impart some physical property to the catalyst composition. The product gas from steam reforming typically contains hydrogen, carbon monoxide, carbon dioxide, and methane. The presence of these components and composition of product gas is to large extent a function of particular reforming conditions as well as choice of feedstock. Depending upon the extent and type of processing following reforming, typical product gas compositions are known as hydrogen-rich gas, synthesis gas, reducing gas, and town gas which are useful for, variously, hydrode sulfurization, hydrogenation, Fischer-Tropsch synthesis, synthesis of ammonia and methanol, ore reduction, heating and power fuel, power generation from fuel cells, and other applications. In the past, steam reforming feedstocks have been limited to sulfur-free gas containing predominantly methane and desulfurized naphthas boiling up to about 200 C. Where available, methane has been the feed of choice owing to its low steam to carbon requirement, low carbon fouling tendency, and, until recent years, low cost. Quite naturally, where methane was not readily available, the feasibility of steam reforming desulfurized liquid hydrocarbons was explored and improved catalysts were developed which, to varying degrees, could inhibit the well known tendency of liquid feeds to lay down carbon on the catalyst More often than not, available liquids contain sulfur (as do some gas feeds) which poisons nickel in the reforming catalyst. It is generally accepted, therefore, that feedstocks must be desulfurized to less than about one part per million sulfur. Despite use of improved catalysts, it is still necessary to use higher steam to C1 ratios for liquid feed than is the case for gas feed. In general, the steam to C1 ratio increases with increasing average boiling point of the feed as well as with increasing proportions of the nonparaffinic constituents. While steam reforming of desulfurized naphthas is well established commercially, the restraints of high molecular weight, often decreased paraffinic hydrocarbon content, and generally high desulfurization burden have effectively precluded use of gas oils, fuel oils, and heavier materials as reformer feedstock despite their general availability and somewhat lower cost than naph tha. While the desirability of reforming sulfur-containing feeds and/or heavy feeds has existed for many years, decreasing availability of methane and naphtha in recent years has made use of these feeds very important in most industrial countries. It is an object of this invention to provide a hydrocarbon steam reforming catalyst and process that is useful in converting sulfur containing and/or heavy liquid feedstocks, as well as conventional feedstocks, to product gas containing hydrogen and carbon oxides. According to the invention a catalyst composition and process for steam reforming hydrocarbons are provided wherein hydrocarbon feed with steam is passed over a catalyst of mixed oxides which, in the unreduced condition, consists essentially of a) from about lo to about 60 weight percent nickel oxide in optional admixture with a minor portion of another Group VIII, fourth period metal oxide (i. e. oxides of iron and cobalt); b) from about 4 to about 30 weight percent of at least one oxide of the group consisting of the lanthanons and yttrium; and c) from about lo to about 80 weight percent zirconium dioxide optionally mixed with less than about 75 weight percent of component c) of one or more inert oxides of the group consisting of hafnium oxide, titanium oxide, magnesium oxide, calcium oxide, and alpha-aluminum oxide. The catalyst composition is composed of a plurality of oxides and does not have the unitary oxide crystal structure characteristic of perovskite and materials such as lanthanum cobaltate, LaCoO3, and zirconium/ra re earth metal nickelate, Zr (YLaCeNdSm)NiO . That is x y to say, apart from any crystallinity in a given con stituent, the catalyst composition as a whole is substantially amorphous. In a preferred embodiment of the invention, the catalyst components are a) from about 20 to about 50 weight percent nickel oxide; b) from about 10 to about 25 weight percent of one or more oxides of the lanthanons; and c) from about 25 to about 75 weight percent zirconium dioxide. As stated, component a) is nickel oxide in optional admixture with cobalt or iron oxide in an amount less than about 50 weight percent of component a). Depending upon the particular stage of manufacture or use, component a) or part thereof may be present in equivalent elemental or sulfide conditions. The elemental condition is necessary for steam reforming activity of the catalyst and is typically brought about by treatment of oxidic or sulfided catalyst with reducing gas, a mixture of hydrogen and carbon monoxide, or preferably, a hydrogenrich gas subsequent to charging the reforming reactor tubes with catalyst. The sulfided condition may result from a particular method of catalyst manufacture or from use of the catalyst with sulfur containing feeds. In the latter instance, an equilibrium appears to exist between sulfide and elemental conditions. Component b), as stated, is one or more oxides of yttrium, the rare earth metals, or mixtures thereof. The rare earth metals referred to herein are metallic elements of the lanthanide series having atomic numbers 57 through 71 commonly known as lanthanons. Of these, the oxides of lanthanum, mischmetal, didymium, or mixtures thereof are convenient and suitable constituents of component b). The ratio of component a) to component b) may be from about o.8 to about 15 and is preferably from about 1.5 to about 5. Component c) is preferably zirconium dioxide which has catalytic effect in combination with components a) and b) and, additionally functions as catalyst support. Other refractory oxides such as hafnium oxide, titanium oxide, magnesium oxide, calcium oxide, aluminum oxide, and mixtures thereof may be incorporated in the catalyst composition up to about 75 weight percent of component c) provided that they are inert with respect to the active catalyst and are not reactive during catalyst preparation. Alpha-alumina is particularly useful as an inert diluent for component c). Care should be exercised in preparation to avoid spinel-type structures such as nickel aluminate since these formations reduce the effective nickel content. Additionally, the catalyst composition may contain a binding cement that is substantially inert. This may be, for example, Portland cement or low-silica aluminous cement. In general, employment of customary sintering techniques used in preparation of nickel reforming catalyst is preferred to the use of binding cement. The catalyst may be prepared by mixing a water solution of the nitrates, acetates, sulfates, or halides of components a), b) and c) in concentrations calculated to yield the specific desired catalyst within the stated ranges. These ranges for the preferred catalyst composition are a) from about 20 to about 50 weight percent of a Group VIII, fourth period metal oxide; b) from about 1o to 25 weight percent of one or more oxides of the lanthanons having atomic numbers 57 through 71; and c) from about 25 to about 70 weight percent zirconium dioxide. Metallic compounds are then precipitated by treating the combined solution with sodium or ammonium hydroxide, sulfide, or carbonate. Preferably, the catalyst is prepared from water solutions of nitrates or acetates followed by precipitation with the hydroxides or carbonates of ammonia or sodium. The precipitates are repeatedly washed and filtered until no precipitating agent remains and are then dried at low temperature, for example, from about 80 to 200C to a moisture content dependent upon method of forming catalyst shapes. For extruded catalyst shapes, final moisture content may be from about 15 to about 60 weight percent water. For pelletized catalyst, the moisture content may be from o to about 25 weight percent water and the dried cake crushed to a particle size suitable for the pelletizing equipment utilized. The dried or partially dried catalyst is then pelletized or extruded as the case may be into shapes resulting, preferably, in large surface to weight ratio at a size resulting in low pressure drop of the reaction mixture through the reformer tubes. A typical catalyst shape is an annular cylinder approximately 1.5 cm in diameter and 1.6 cm in length. The catalyst shapes are then calcined in the presence of oxygen at a temperature of from about 370 C to about 760 C to convert the metalic carbonates, sulfides, or hydroxides to plural oxides of the catalyst composition. The catalyst may then be treated with reducing gas such as hydrogen to reduce the Group VIII, fourth period metal component to elemental condition but, as previously noted, this step is preferably deferred subsequent to placement of catalyst in production equipment. The catalyst composition of the present invention is useful in steam reforming customary feeds such as methane and naphtha to product gases previously described but is particularly useful in reforming feedstocks containing from a trace, i.e. - about 1 part per million, to about 5 weight percent sulfur which may be present in combined or uncombined form. Under steam reforming conditions, sulfur in the feedstock is converted to hydrogen sulfide which is then contained in the product gas stream. It is evident that, in the presence of hydrogen, the catalyst composition also functions as a hydrodesulfurization catalyst. Most particularly, the process and catalyst composition of the invention is useful in steam reforming normally liquid hydrocarbon feeds which may contain sulfur in the above-mentioned amount and boiling between from about C5 to about 55o0C such as fuel oil and light through heavy gas oils. Other hydrocarbon feedstocks include coal liquefaction products and shale oil fractions as such or as may be contained in shale oil. Since heavy sulfur loading decreases the level of sustained catalyst activity, process economics may indicate the desirability of desulfurizing fuel and gas oil feeds, i. e. - feeds boiling from about 175 C to about 480 C to a sulfur level of from about 0.01 to about o.5 weight percent which may be economically attained in commercial hydrodesulfurization units. An unreduced catalyst composition suitable for these sulfur-containing liquid feeds contains from about 20 to about 50 weight percent nickel oxide, from about lo to about 25 weight percent rare earth metal oxide preferably lanthanum oxide, and from about 25 to about 70 percent zirconium dioxide. A particularly effective catalyst for this service will contain from about 30 to about 40 weight percent nickel oxide, from about 1o to about 20 weight percent lanthanum oxide, and the balance zirconium dioxide. In general, customary steam reforming conditions and apparatus are used in carrying out the process of the invention. The process may be carried out at reforming pressures of from about 1 to about 50 kg/cm2 absolute with reformer outlet temperatures in the range from about 500C to loooOC. Suitable steam to C1 ratios vary according to molecular weight of the feedstock and PONA analysis and can be as low as about o.75 to 1 for methane and as high as about 7 to 1 for shale oil. Space velocities of the steam and hydrocarbon mixture over the catalyst composition may vary from about looo to about 20,ooo volumes per hour per volume. Conventional steam reforming furnaces such as described in U.S. Patent No. 3,257,172 may be used in carrying out the process with appropriate regard to design for high boiling range feedstocks when these are used. In Table 1 we have listed an array of catalyst compositions, including those of the present invention, intended for use in steam reforming. Catalysts are listed generally in the order of increasing nickel (or other Group VIII, 4th period metal) content. TABLE 1 EMI9.1 <tb> Cat. <SEP> . <SEP> Prep. <SEP> (l) <SEP> Catalyst,Composition(Wt.Xoxide) <SEP> <tb> No. <SEP> Group <SEP> VIII, <tb> <SEP> (2) <SEP> (6) <SEP> 4th <SEP> per, <SEP> # <SEP> Lanth. <SEP> . <SEP> Zr. <SEP> Other <tb> <SEP> 1 <SEP> (d) <SEP> 8 <SEP> 488- <SEP> <tb> <SEP> 2 <SEP> (a) <SEP> 19 <SEP> - <SEP> 81 <SEP> <tb> <SEP> 3* <SEP> (a) <SEP> 14 <SEP> 15 <SEP> 71 <SEP> <tb> <SEP> 4 <SEP> (a) <SEP> 14 <SEP> 41 <SEP> 41 <SEP> - <SEP> <tb> <SEP> 5* <SEP> (a) <SEP> 22 <SEP> 11 <SEP> 67 <SEP> <tb> <SEP> 6(3) <SEP> (b) <SEP> 24 <SEP> 10 <SEP> 33 <SEP> 33 <SEP> Mg(3) <tb> <SEP> 7(5) <SEP> (e) <SEP> 26 <SEP> - <SEP> - <SEP> (5) <tb> <SEP> 8(5) <SEP> (f) <SEP> 23 <SEP> 10 <SEP> - <SEP> (5) <tb> <SEP> 9 <SEP> (b) <SEP> 24 <SEP> 18 <SEP> 53 <SEP> - <SEP> <tb> <SEP> 10 <SEP> (d) <SEP> 29 <SEP> 10 <SEP> 53 <SEP> <tb> <SEP> 11 <SEP> (a) <SEP> 36 <SEP> 15 <SEP> - <SEP> 49 <SEP> Al <tb> <SEP> 12 <SEP> (a) <SEP> 36 <SEP> 15 <SEP> - <SEP> 49 <SEP> Ca <tb> <SEP> * <tb> <SEP> 13 <SEP> (a) <SEP> 36 <SEP> 15 <SEP> 49 <tb> <SEP> 13A <SEP> (b) <SEP> 36 <SEP> 15 <SEP> 49 <SEP> <tb> <SEP> 14 <SEP> (a) <SEP> 36 <SEP> 15 <SEP> Misch <SEP> 49 <SEP> <tb> <SEP> 15 <SEP> (a) <SEP> 36 <SEP> 15 <SEP> Nd <SEP> 49 <SEP> <tb> <SEP> * <SEP> (a) <SEP> 36 <SEP> 15 <SEP> Di <SEP> 49 <SEP> - <SEP> <tb> <SEP> 16 <tb> TABLE 1 (contZd) EMI10.1 <tb> Cat. <SEP> Prep. <SEP> (1) <SEP> Catalyst <SEP> (Wt, <SEP> %oxide) <tb> No. <SEP> Group <SEP> VIII, <tb> <SEP> (2) <SEP> (6) <SEP> 4th <SEP> per. <SEP> Lanth. <SEP> Zr <SEP> Other <tb> <SEP> 17 <SEP> (a) <SEP> 36 <SEP> 15 <SEP> Ce <SEP> 49 <SEP> <tb> <SEP> 18 <SEP> (a) <SEP> 36 <SEP> 15 <SEP> 39 <SEP> 10 <SEP> Mg <tb> <SEP> 19 <SEP> (a) <SEP> 36 <SEP> 15 <SEP> 39 <SEP> 10 <SEP> Hf <tb> <SEP> (a) <SEP> 36 <SEP> 15 <SEP> 39 <SEP> 10Al(3) <tb> <SEP> 21 <SEP> (i) <SEP> 36 <SEP> 15 <SEP> 24 <SEP> 25 <SEP> &alpha; ;Al <SEP> <tb> <SEP> 22 <SEP> (a) <SEP> 36 <SEP> Co <SEP> 15 <SEP> 49 <SEP> - <SEP> <tb> <SEP> 23 <SEP> (a) <SEP> 36 <SEP> Fe <SEP> 15 <SEP> 49 <SEP> - <SEP> <tb> <SEP> 24 <SEP> (c) <SEP> 37 <SEP> 17 <SEP> 47 <SEP> - <SEP> <tb> <SEP> 25 <SEP> (c) <SEP> 38 <SEP> 17 <SEP> 42 <SEP> - <SEP> <tb> <SEP> 26* <SEP> (a) <SEP> 40 <SEP> 18 <SEP> 37 <SEP> <tb> <SEP> 27 <SEP> (a) <SEP> 46 <SEP> 4 <SEP> 50 <SEP> - <SEP> <tb> <SEP> 28 <SEP> (a) <SEP> 47 <SEP> 20 <SEP> - <SEP> 33 <SEP> Al <tb> <SEP> 29 <SEP> (a) <SEP> 50 <SEP> 15 <SEP> 35 <SEP> - <SEP> <tb> <SEP> (4) <SEP> (g) <SEP> 68 <SEP> as <SEP> Ni <SEP> 32as <SEP> La <SEP> - <SEP> <tb> <SEP> 31 <SEP> (a) <SEP> 70 <SEP> 30 <SEP> - <SEP> Explanatory notes to Table 1 follow: : (1) The catalyst compositions are described by the nomi nal weight percent oxide of the metals indicated ba sed on the total weight of the catalyst composition. Where components do not total loo %, analysis weight percents are given. In the column headed "Group VIII, 4th period", the component is nickel oxide except as otherwise indicated. In the column headed "Lanth.", the lanthanon component is lanthanum oxide except as otherwise indicated. (2) An asterisk following the catalyst number in the first column indicates a catalyst of the present invention. (3) Catalyst numbers 6 and 20 were prepared respectively with reactive magnesium and aluminum components. Since the resulting magnesium and aluminum oxides were not inert, these catalysts are not, therefore, considered as catalyst compositions of the inven tion. (4) Catalyst number 30 is an alloy of nickel and lan thanum. (5) Catalyst number 7 is a commercial steam reforming catalyst designated as Girdler G 56 B nominally con taining 25 weight percent nickel. Catalyst number 8 is the same catalyst impregnated with lanthanum ni trate to yield 1o weight percent lanthanum oxide in the final catalyst. (6) The second column headed "Prep." indicates prepara tion method of the catalyst according to the per tinent technique following: (a) Water solution of nitrates treated with ammonium hydroxide to coprecipitate metal hydroxides. The reaction mass was agitated during precipitation and pH maintained below about 12. Upon substantial completion of reactions, water was evaporated from the mixed precipitate and the precipitate dried at too-105 C. The dried precipitate was heated for two hours up to 540 C, crushed to pass a 30 mesh U.S. standard sieve, and then formed into pellets about 3 mm in length and diameter. The catalyst pellets were then calcined in the temperature range of 54o0C to 76o0C. (b) Same as (a) except that the nitrate solution was precipitated with sodium hydroxide following initial treatment with ammonium hydroxide and the mass was filtermed, washed, and refiltered until no sodium was detected by platinum hot wire test. (c) Water solution of nitrates was added to a water solution of sodium carbonate to coprecipitate metal carbonates. After filtering and washing as in (b), the remainder of technique was essentially the same as (a). (d) Zirconium dioxide pellets were placed under vacuum and evacuated. The vacuum was released and a water solution of nickel and lanthanum nitrates added in sufficient amount to completely wet the zirconia. Excess liquid was decanted, the pellets dried at too-105 C and calcined about 54o0C. The impregnation was repeated sufficient number of times to achieve the final composition and the catalyst was finally calcined at about 76o0C. (e) Commercial catalyst sample. (f) Commercial catalyst sample impregnated with lanthanum nitrate by technique (d). (g) Nickel - lanthanum alloy in granular form of 10 to 40 mesh. (h) Magnesium oxide powder was added to the solution of the nitrates of nickel, lanthanum, and zirconium. Some precipitation of hydroxides of the catalyst components occurred upon initial mixing due to the alkalinity of the magnesium oxide. The remainder of the procedure was as in (a). (i) Fused alpha aluminum oxide powder was added to the solution of the nitrates of nickel, lanthanum, and zirconium. Precipitation of the hydroxides was carried out in the presence of the suspended solid material by treatment with NH4OH. The remainder of the method is according to (a) above. In Tables 2 through 9 we have listed steam reforming runs using the catalysts listed in Table 1. Feedstocks, reforming conditions, and results are indicated in the tables. Normally liquid feedstocks inspections are: EMI14.1 <tb> Feedstock <SEP> No. <SEP> F <SEP> 7128 <SEP> F <SEP> 7139 <SEP> F <SEP> 7669 <tb> <SEP> Desulf. <SEP> No.2 <tb> Type <SEP> Gas <SEP> Oil <SEP> Gas <SEP> Oil <SEP> Fuel <SEP> Oil <tb> <SEP> OKAPI <SEP> 34.1 <SEP> 35.6 <SEP> 34 <tb> <SEP> Distilation: <SEP> ( C) <tb> <SEP> IBP <SEP> 191 <SEP> 176 <SEP> 177 <tb> <SEP> 20 <SEP> Vol. <SEP> % <SEP> 313 <SEP> 308 <SEP> -236 <tb> <SEP> 40 <SEP> " <SEP> 333 <SEP> 330 <SEP> 256 <tb> <SEP> 60 <SEP> " <SEP> <SEP> 348 <SEP> 344 <SEP> 276 <tb> <SEP> 80 <SEP> " <SEP> 364 <SEP> 359 <SEP> 300 <tb> <SEP> 95 <SEP> " <SEP> 396 <SEP> 379 <SEP> 334 <tb> <SEP> % <SEP> S <SEP> 0.41 <SEP> 0.022 <SEP> 0.27 <tb> H <SEP> H <SEP> 13.41 <SEP> 12.42 <SEP> 13.03 <tb> <SEP> % <SEP> C <SEP> 86.14 <SEP> 87.55 <SEP> 86.70 <tb> The enumerated reforming conditions are: reformer outlet temperature in 0C, reformer outlet pressure in kilograms per square centimeter, steam to C1 ratio which is the mole feed rate of steam divided by the mole feed rate of carbon in the hydrocarbon feedstock, and C1 space velocity which is the volumes per hour of the hydrocarbon expressed as its molar equivalent on a carbon basis divided by the volume of catalyst. Catalyst activity is indicated firstly by mole % conversion of fresh feed to (CO + C02) in the reformer product gas and secondly by mole % conversion to (CO + CO2 + CH4). The first indication is a direct measure of the activity of the catalyst for conversion of the feed hydrocarbon to hydrogen and carbon oxides by reaction with steam according to the well known steam reforming reactions: EMI15.1 The second indication is a measure of the activity of the catalyst for the conversion of the feed hydrocarbon to single carbon atom gaseous products which, in addition to the carbon oxides formed in reactions 1) and 2), includes methane produced either by destructive hydrogenolysis: EMI15.2 or by methanation: : EMI15.3 Net hydrogen gas production by direct conversion of the hydrocarbon feedstock with steam under the action of the catalyst of this invention is equal to that resulting from the summation of the effects of reactions 1), 2), 3) and 4). Using the above described indications of catalyst activity, the ability of catalysts to produce hydrogen at a steady rate in the presence of sulfur compounds are measured and compared. The higher the sustained rate of conversion as described above, the better the catalyst performance. Except for run number 804 in Table 8, all runs were carried out in a vertical reactor made of type 316 stainless steel tubing (2.54 cm diameter x 91 cm length). The reactor was heated by a Lindberg Three Zone Tubular Furnace Model 54357 at a reactor outlet temperature range of 55o0C to 9oo0C. Beckman pumps were used to pump feedstock and distilled water which were then metered, preheated, vaporized, mixed, and fed to the catalyst bed. Hydrogen or helium served as a carrier gas. The catalyst bed, about 7.6 cm in height and 30 cc in volume, was located at the center of the reactor tube. Prior to introduction of the feed, the catalyst Group VIII, 4th period component was converted to a substantially reduced condition by heating for several hours at 425 0C to 76o0C while maintaining a flow of hydrogen containing gas through the catalyst bed in the reactor. Product gases from the reactor were cooled by a water condenser. At times, the product gases were cooled to oOC to separate solid and liquid products. When feedstocks with a low sulfur level (0.4 wt %) were used, practically no liquid or solid compounds were condensed from product gases, except unreacted water. Product gases were passed through Drierite before sampling for gas chromatograph or mass spectrometric analysis. Concentrations of hydrogen, carbon monoxide, methane, carbon dioxide, ethylene, ethane and benzene in the product gases were determined. Mole percentages of carbon monoxide, carbon dioxide, and methane were then used in calculating steam reforming activity. Run number 804 in Table 8 was carried out in a small pilot plant unit using a catalyst bed of 45 centimeters height and 240 cubic centimeters volume. Except for operating on a large scale and at higher pressures, operating conditions were similar to those described previously. Table 2 is a compilation of reforming runs made with catalysts containing varying proportions of the oxides of nickel, lanthanum, and zirconium. Criticality of nickel content is shown by runs 201 and 207. In these runs, catalyst no. 1 containing only 8 weight percent nickel oxide and 4 weight percent lanthanum oxide performed poorly as compared with catalyst no. 27 containing 46 weight percent nickel oxide and the same amount of lanthanum oxide. Run nos. 202 and 203 illustrate the effect of nickel-lanthanum ratios. In run no. 202, catalyst no. 4 contained 41 weight percent lanthanum oxide and 14 weight percent nickel oxide. This catalyst performed poorly compared with catalyst no. 3 in run no. 203 which contained 15 weight percent lanthanum oxide and 14 weight percent nickel oxide. Table 3 is a compilation of reforming runs carried out with various nickel containing catalysts which are not of the present invention. In each run, a significant decline in catalyst activity within 72 hours of opera tion is indicated. Each of the catalysts tested in these runs does not have either a lanthanon oxide component or a zirconium dioxide component. Table 4 is a compilation of reforming runs carried out with catalysts of the present invention and illustrates good performance with catalysts having different lanthanon constituents in combination with the same levels of nickel oxide and zirconium oxide. Table 5 is a compilation of reforming runs carried out with catalysts containing respectively in runs 205, 501 and 502 the oxides of nickel, cobalt, and iron as the Group VIII, fourth period metal component. These runs illustrate that complete substitution of nickel with cobalt or iron result in lower levels of catalyst activity. Table 6 is a compilation of reforming runs carried out with catalysts containing, in addition to zirconium dioxide, other refractory oxides. Notably, catalyst numbers 6 and 20 in run numbers 603 and 604 contained reactive rather than inert refractory oxides and performed poorly in comparison with the others. Table 7 is a compilation of reforming runs carried out with catalysts of the present invention prepared by four different techniques. With the exception of catalyst no. 1o in run no. 701, these catalysts were prepared by preferred coprecipitation techniques and performed well. Catalyst no. lo was prepared by the particular impregnation technique described in explanatory note (6) (d) to Table 1. Table 8 is a compilation of reforming runs carried out with catalysts of the present invention under different conditions of temperature and pressure. Catalyst activity was good in all instances. Run numbers 801, 802, and 803 illustrate reforming of various feedstocks at temperatures of 7050C, 787 0C, and 9040C respectively. Run number 804 was carried out at higher pressure in the small pilot plant apparatus previously described. In this continuous run, initial operation up to 129 hours was carried out at a pressure of about 5.9 kg/cm2 whereupon the pressure was increased to 11.4 kg/cm2 and then to 25.3 kg/cm2 for the time intervals shown. Table 9 is a compilation of reforming runs carried out with catalysts of the present invention on gaseous and liquid hydrocarbon feedstocks which contain various levels of sulfur. In general, the level of catalyst activity varies inversely with sulfur content of the feedstock, however, these runs illustrate a sustained level of catalyst activity. Table 2 EMI20.1 R <SEP> C <SEP> FEEDSTOCK <SEP> REFORMINC <SEP> CONDITIONS <SEP> Mole <SEP> % <SEP> Conversion <SEP> to <SEP> Mole <SEP> % <SEP> Conversion <SEP> to <tb> <SEP> (CO <SEP> + <SEP> CO2) <SEP> (CO <SEP> + <SEP> CO2 <SEP> + <SEP> CH4) <tb> U <SEP> A <SEP> No. <SEP> Type <SEP> Sulfur <SEP> Temp. <SEP> Abs. <SEP> S/C1 <SEP> Space <SEP> 4 <SEP> hrs <SEP> 24 <SEP> hrs <SEP> 72 <SEP> hrs <SEP> 96 <SEP> hrs <SEP> 4 <SEP> hrs <SEP> 24 <SEP> hrs <SEP> 72 <SEP> hrs <SEP> 96 <SEP> hrs <tb> N <SEP> T <SEP> ppm <SEP> C <SEP> press <SEP> Val. <tb> <SEP> kg/cm2 <tb> 201 <SEP> 1 <SEP> F <SEP> 7128 <SEP> Gas <SEP> Oil <SEP> 4100 <SEP> 843 <SEP> atm <SEP> 5 <SEP> 1000 <SEP> 64 <SEP> 36 <SEP> 79 <SEP> 51 <tb> 202 <SEP> 4 <SEP> F <SEP> 7669 <SEP> Fuel <SEP> Oil <SEP> 2700 <SEP> 843 <SEP> 4.5 <SEP> 5 <SEP> 500 <SEP> 86 <SEP> 72 <SEP> 98 <SEP> 90 <tb> 203 <SEP> 3+ <SEP> F <SEP> 7669 <SEP> Fuel <SEP> Oil <SEP> 2700 <SEP> 843 <SEP> 4.5 <SEP> 5 <SEP> 500 <SEP> 84 <SEP> 80 <SEP> 75 <SEP> 74 <SEP> 97 <SEP> 95 <SEP> 92 <SEP> 91 <tb> 204 <SEP> 5+ <SEP> F <SEP> 7128 <SEP> Gas <SEP> Oil <SEP> & 20000 <SEP> 843 <SEP> atm <SEP> 5 <SEP> 1000 <SEP> 65 <SEP> 65 <SEP> 64 <SEP> 65 <SEP> 80 <SEP> 84 <SEP> 80 <SEP> <SEP> Thiophene <tb> 205 <SEP> 13+ <SEP> F <SEP> 7128 <SEP> Gas <SEP> Oil <SEP> 4100 <SEP> 843 <SEP> atm <SEP> 5 <SEP> 1000 <SEP> 84 <SEP> 82 <SEP> - <SEP> 77 <SEP> 95 <SEP> 95 <SEP> 93 <SEP> 92 <tb> 206 <SEP> 25+ <SEP> F <SEP> 7669 <SEP> Fuel <SEP> Oil <SEP> 2700 <SEP> 843 <SEP> 4.5 <SEP> 5 <SEP> 500 <SEP> 77 <SEP> 76 <SEP> 75 <SEP> 75 <SEP> 93 <SEP> 92 <SEP> 92 <SEP> 92 <tb> 207 <SEP> 27+ <SEP> F <SEP> 7128 <SEP> Gas <SEP> Oil <SEP> 4100 <SEP> 843 <SEP> atm <SEP> 5 <SEP> 1000 <SEP> 85 <SEP> 83 <SEP> 77 <SEP> 98 <SEP> 97 <SEP> 91 <tb> 208 <SEP> 29+ <SEP> F <SEP> 7669 <SEP> Fuel <SEP> OIl <SEP> 2700 <SEP> 843 <SEP> 4.5 <SEP> 5 <SEP> 500 <SEP> 92 <SEP> 90 <SEP> 89 <SEP> 89 <SEP> 99 <SEP> 99 <SEP> 99 <SEP> 99 <tb> Table 3 EMI21.1 R <SEP> C <SEP> FEEDSTOCK <SEP> REFORMINC <SEP> CONDITIONS <SEP> Mole <SEP> % <SEP> Conversion <SEP> to <SEP> Mole <SEP> % <SEP> Conversion <SEP> to <tb> U <SEP> A <SEP> (CO <SEP> + <SEP> CO2) <SEP> (CO <SEP> + <SEP> CO2 <SEP> + <SEP> CH4) <tb> N <SEP> T <SEP> No. <SEP> Type <SEP> Sulfur <SEP> Temp. <SEP> Abs. <SEP> S/C1 <SEP> Space <SEP> 4 <SEP> hrs <SEP> 24 <SEP> hrs <SEP> 48 <SEP> hrs <SEP> 72 <SEP> hrs <SEP> 4 <SEP> hrs <SEP> 24 <SEP> hrs <SEP> 48 <SEP> hrs <SEP> 72 <SEP> hrs <tb> <SEP> ppm <SEP> C <SEP> press <SEP> Val. <tb> <SEP> kg/cm2 <tb> 301 <SEP> 2 <SEP> F <SEP> 7128 <SEP> Gas <SEP> Oil <SEP> + <SEP> 20000 <SEP> 843 <SEP> atm <SEP> 5 <SEP> 1000 <SEP> 64 <SEP> 63 <SEP> 59 <SEP> 54 <SEP> 82 <SEP> 76 <SEP> 78 <SEP> 71 <tb> <SEP> Thiophne <tb> 302 <SEP> 7 <SEP> F <SEP> 7128 <SEP> Gas <SEP> Oil <SEP> 4100 <SEP> 843 <SEP> atm. <SEP> 5 <SEP> 1000 <SEP> 84 <SEP> 78 <SEP> 61 <SEP> 95 <SEP> 90 <SEP> 74 <tb> 303 <SEP> 8 <SEP> F <SEP> 2128 <SEP> Gas <SEP> Oil <SEP> 4100 <SEP> 843 <SEP> atm. <SEP> 5 <SEP> 500 <SEP> 90 <SEP> 81 <SEP> 69 <SEP> 32 <SEP> 100 <SEP> 91 <SEP> 92 <SEP> 42 <tb> 304 <SEP> 12 <SEP> F <SEP> 7669 <SEP> Fuel <SEP> Oil <SEP> 2700 <SEP> 843 <SEP> 4.5 <SEP> 5 <SEP> 500 <SEP> 86 <SEP> 79 <SEP> 64 <SEP> 40 <SEP> 98 <SEP> 97 <SEP> 85 <SEP> 67 <tb> 305 <SEP> 11 <SEP> F <SEP> 7669 <SEP> Fuel <SEP> Oil <SEP> 2700 <SEP> 843 <SEP> 4.5 <SEP> 5 <SEP> 500 <SEP> 94 <SEP> 49 <SEP> 98 <SEP> 78 <tb> 306 <SEP> 28 <SEP> F <SEP> 7669 <SEP> Fuel <SEP> Oil <SEP> 2700 <SEP> 843 <SEP> 4.5 <SEP> 5 <SEP> 500 <SEP> 98 <SEP> 74 <SEP> 53 <SEP> 99 <SEP> 86 <SEP> 73 <tb> <SEP> (31hrs) <SEP> (31hrs) <tb> 307 <SEP> 30 <SEP> F <SEP> 7128 <SEP> Gas <SEP> Oil <SEP> 4100 <SEP> 843 <SEP> atm <SEP> 5 <SEP> 1000 <SEP> 80 <SEP> 34 <SEP> 96 <SEP> 51 <tb> 308 <SEP> 31 <SEP> F <SEP> 7669 <SEP> Fuel <SEP> OIl <SEP> 2700 <SEP> 843 <SEP> 4.5 <SEP> 5 <SEP> 500 <SEP> 87 <SEP> 83 <SEP> 11 <SEP> 96 <SEP> 96 <SEP> 91 <tb> <SEP> (40hrs) <SEP> (40hrs) <tb> Table 4 EMI22.1 R <SEP> C <SEP> FEEDSTOCK <SEP> REFORMINC <SEP> CONDITIONS <SEP> Mole <SEP> % <SEP> Conversion <SEP> to <SEP> Mole <SEP> % <SEP> Conversion <SEP> to <tb> U <SEP> A <SEP> (CO <SEP> + <SEP> CO2) <SEP> (CO <SEP> + <SEP> CO2 <SEP> + <SEP> CH4) <tb> N <SEP> T <SEP> No. <SEP> Type <SEP> Sulfur <SEP> Temp. <SEP> Abs. <SEP> S/C1 <SEP> Space <SEP> 4 <SEP> hrs <SEP> 24 <SEP> hrs <SEP> 72 <SEP> hrs <SEP> 4 <SEP> hrs <SEP> 24 <SEP> hrs <SEP> 72 <SEP> hrs <tb> <SEP> ppm <SEP> C <SEP> press <SEP> val. <tb> <SEP> kg/cm2 <tb> 401 <SEP> 14+ <SEP> F <SEP> 769 <SEP> Fuel <SEP> Oil <SEP> 2700 <SEP> 843 <SEP> 4.5 <SEP> 5 <SEP> 500 <SEP> 92 <SEP> 90 <SEP> 89 <SEP> 99 <SEP> 98 <SEP> 98 <tb> 402 <SEP> 15+ <SEP> F <SEP> 7669 <SEP> Fuel <SEP> Oil <SEP> 2700 <SEP> 843 <SEP> 4.5 <SEP> 5 <SEP> 500 <SEP> 88 <SEP> 87 <SEP> 84 <SEP> 98 <SEP> 97 <SEP> 97 <tb> 403 <SEP> 16+ <SEP> F <SEP> 7669 <SEP> Fuel <SEP> Oil <SEP> 2700 <SEP> 843 <SEP> 4.5 <SEP> 5 <SEP> 500 <SEP> 89 <SEP> 86 <SEP> 86 <SEP> 98 <SEP> 97 <SEP> 97 <tb> 404 <SEP> 17+ <SEP> F <SEP> 7669 <SEP> Fuel <SEP> Oil <SEP> 2700 <SEP> 843 <SEP> 4.5 <SEP> 5 <SEP> 500 <SEP> 84 <SEP> 80 <SEP> 79 <SEP> 96 <SEP> 94 <SEP> 94 <tb> Table 5 EMI23.1 R <SEP> C <SEP> FEEDSTOCK <SEP> REFORMINC <SEP> CONDITIONS <SEP> Mole <SEP> % <SEP> Conversion <SEP> to <SEP> Mole <SEP> % <SEP> Conversion <SEP> to <tb> U <SEP> A <SEP> (CO <SEP> + <SEP> CO2) <SEP> (CO <SEP> + <SEP> CO2 <SEP> + <SEP> CH4) <tb> N <SEP> T <SEP> No. <SEP> Type <SEP> Sulfur <SEP> Temp. <SEP> Abs. <SEP> S/C1 <SEP> Space <SEP> 4 <SEP> hrs <SEP> 24 <SEP> hrs <SEP> 48 <SEP> hrs <SEP> 96 <SEP> hrs <SEP> 4 <SEP> hrs <SEP> 24 <SEP> hrs <SEP> 48 <SEP> hrs <SEP> 96 <SEP> hrs <tb> <SEP> ppm <SEP> C <SEP> press <SEP> Val. <tb> <SEP> kg/cm2 <tb> 205 <SEP> 13+ <SEP> F <SEP> 7128 <SEP> Gas <SEP> Oil <SEP> 4100 <SEP> 843 <SEP> atm <SEP> 5 <SEP> 1000 <SEP> 84 <SEP> 82 <SEP> - <SEP> 77 <SEP> 95 <SEP> 95 <SEP> 93 <SEP> 92 <tb> 501 <SEP> 22 <SEP> F <SEP> 7128 <SEP> Gas <SEP> Oil <SEP> 4100 <SEP> 843 <SEP> atm. <SEP> 5 <SEP> 1000 <SEP> 61 <SEP> 58 <SEP> 55 <SEP> 77 <SEP> 75 <SEP> 71 <tb> 502 <SEP> 23 <SEP> F <SEP> 7128 <SEP> Gas <SEP> Oil <SEP> 4100 <SEP> 843 <SEP> atm. <SEP> 5 <SEP> 1000 <SEP> 58 <SEP> 58 <SEP> 80 <SEP> 84 <SEP> 60 <tb> Table 6 EMI24.1 R <SEP> C <SEP> FEEDSTOCK <SEP> REFORMINC <SEP> CONDITIONS <SEP> Mole <SEP> % <SEP> Conversion <SEP> to <SEP> Mole <SEP> % <SEP> Conversion <SEP> to <tb> U <SEP> A <SEP> (CO <SEP> + <SEP> CO2) <SEP> (CO <SEP> + <SEP> CO2 <SEP> + <SEP> CH4) <tb> N <SEP> T <SEP> No. <SEP> Type <SEP> Sulfur <SEP> Temp. <SEP> Abs. <SEP> S/C1 <SEP> Space <SEP> 4 <SEP> hrs <SEP> 24 <SEP> hrs <SEP> 72 <SEP> hrs <SEP> 4 <SEP> hrs <SEP> 24 <SEP> hrs <SEP> 72 <SEP> hrs <tb> <SEP> ppm <SEP> C <SEP> press <SEP> Val. <tb> <SEP> kg/cm2 <tb> 601 <SEP> 19+ <SEP> F <SEP> 7669 <SEP> Fuel <SEP> Oil <SEP> 2700 <SEP> 843 <SEP> 4.5 <SEP> 5 <SEP> 500 <SEP> 88 <SEP> 88 <SEP> 85 <SEP> 98 <SEP> 97 <SEP> 95 <tb> 602 <SEP> 18+ <SEP> F <SEP> 7669 <SEP> Fuel <SEP> Oil <SEP> 2700 <SEP> 843 <SEP> 4.5 <SEP> 5 <SEP> 500 <SEP> 91 <SEP> 90 <SEP> 84 <SEP> 98 <SEP> 98 <SEP> 97 <tb> 603 <SEP> 6 <SEP> F <SEP> 7669 <SEP> Fuel <SEP> Oil <SEP> 2700 <SEP> 843 <SEP> 4.5 <SEP> 5 <SEP> 500 <SEP> 82 <SEP> 55 <SEP> 95 <SEP> 77 <tb> 604 <SEP> 20 <SEP> F <SEP> 7669 <SEP> Fuel <SEP> Oil <SEP> 2700 <SEP> 843 <SEP> 4.5 <SEP> 5 <SEP> 500 <SEP> 88 <SEP> 50 <SEP> 98 <SEP> 60 <tb> 605 <SEP> 21+ <SEP> F <SEP> 7669 <SEP> Fuel <SEP> Oil <SEP> 2700 <SEP> 843 <SEP> 4.5 <SEP> 5-7 <SEP> 500 <SEP> 92 <SEP> 92 <SEP> 86 <SEP> 99 <SEP> 99 <SEP> 96 <tb> Tabele 7 EMI25.1 R <SEP> C <SEP> FEEDSTOCK <SEP> REFORMINC <SEP> CONDITIONS <SEP> Mole <SEP> % <SEP> Conversion <SEP> to <SEP> Mole <SEP> % <SEP> Conversion <SEP> to <tb> U <SEP> A <SEP> (CO <SEP> + <SEP> CO2) <SEP> (CO <SEP> + <SEP> CO2 <SEP> + <SEP> CH4) <tb> N <SEP> T <SEP> No. <SEP> Type <SEP> Sulfur <SEP> Temp. <SEP> Abs. <SEP> S/C1 <SEP> Space <SEP> 4 <SEP> hrs <SEP> 24 <SEP> hrs <SEP> 72 <SEP> hrss <SEP> 4 <SEP> hrs <SEP> 24 <SEP> hrs <SEP> 72 <SEP> hrs <tb> <SEP> ppm <SEP> C <SEP> press <SEP> Val. <tb> <SEP> kg/cm2 <tb> 204 <SEP> 5+ <SEP> F <SEP> 7128 <SEP> Gas <SEP> Oil & <SEP> 20000 <SEP> 843 <SEP> atm <SEP> 5 <SEP> 1000 <SEP> 65 <SEP> 65 <SEP> 64 <SEP> 80 <SEP> 84 <SEP> 80 <tb> <SEP> Thiophene <tb> 701 <SEP> 10+ <SEP> F <SEP> 7669 <SEP> Fuel <SEP> Oil <SEP> 2700 <SEP> 843 <SEP> 4.5 <SEP> 5 <SEP> 500 <SEP> 80 <SEP> 64 <SEP> 98 <SEP> 86 <tb> 702 <SEP> 24+ <SEP> F <SEP> 7669 <SEP> Fuel <SEP> Oil <SEP> 2700 <SEP> 843 <SEP> 4.5 <SEP> 5 <SEP> 500 <SEP> 85 <SEP> 81 <SEP> 79 <SEP> 97 <SEP> 95 <SEP> 94 <tb> 703 <SEP> 9+ <SEP> F <SEP> 7669 <SEP> Fuel <SEP> Oil <SEP> 2700 <SEP> 843 <SEP> 4.5 <SEP> 5 <SEP> 500 <SEP> 90 <SEP> 86 <SEP> 81 <SEP> 98 <SEP> 97 <SEP> 95 <tb> Table 8 EMI26.1 R <SEP> C <SEP> FEEDSTOCK <SEP> REFORMINC <SEP> CONDITIONS <SEP> Mole <SEP> % <SEP> Conversion <SEP> to <SEP> Mole <SEP> % <SEP> Conversion <SEP> to <tb> U <SEP> A <SEP> (CO <SEP> + <SEP> CO2) <SEP> (CO <SEP> + <SEP> CO2 <SEP> + <SEP> CH4) <tb> N <SEP> T <SEP> No. <SEP> Type <SEP> Sulfur <SEP> Temp. <SEP> Abs. <SEP> S/C1 <SEP> Space <SEP> 4 <SEP> hrs <SEP> 24 <SEP> hrs <SEP> 72 <SEP> hrs <SEP> 96 <SEP> hrs <SEP> 4 <SEP> hrs <SEP> 24 <SEP> hrs <SEP> 72 <SEP> hrs <SEP> 96 <SEP> hrs <tb> <SEP> ppm <SEP> C <SEP> press <SEP> val. <tb> <SEP> kg/cm2 <tb> 801 <SEP> 26+ <SEP> - <SEP> CH4 <SEP> nona <SEP> 705 <SEP> atm <SEP> 3.5 <SEP> 500 <SEP> - <SEP> - <SEP> - <SEP> 98 <SEP> - <SEP> - <SEP> - <SEP> 98 <tb> 802 <SEP> 26+ <SEP> F <SEP> 7139 <SEP> Gas <SEP> Oil <SEP> 220 <SEP> 787 <SEP> 4.5 <SEP> 5 <SEP> 500 <SEP> 89 <SEP> 89 <SEP> 89 <SEP> 99 <SEP> 99 <SEP> 99 <tb> 803 <SEP> 13+ <SEP> F <SEP> 7128 <SEP> Gas <SEP> Oil <SEP> 4100 <SEP> 904 <SEP> atm. <SEP> 5 <SEP> 500 <SEP> - <SEP> - <SEP> 88 <SEP> 88 <SEP> 100 <SEP> 100 <SEP> 100 <tb> <SEP> 190hrs <SEP> 390hrs <SEP> 670hrs <SEP> 730hrs <SEP> 190hrs <SEP> 390 <SEP> hrs <SEP> 670 <SEP> hrs <SEP> 730 <SEP> hrs <tb> 804 <SEP> 13A+ <SEP> F <SEP> 7669 <SEP> Fuel <SEP> Oil <SEP> 2700 <SEP> #890 <SEP> 11.4 <SEP> 5.7 <SEP> #400 <SEP> 92.3 <SEP> 91.1 <SEP> 97.9 <SEP> 98.6 <tb> <SEP> #885 <SEP> 25.3 <SEP> 5.7 <SEP> #435 <SEP> 81.4 <SEP> 76.6 <SEP> 95.2 <SEP> 95.6 <tb> Table 9 EMI27.1 R <SEP> C <SEP> FEEDSTOCK <SEP> REFORMING <SEP> CONDITIONS <SEP> Mole <SEP> % <SEP> Conversion <SEP> to <SEP> Mole <SEP> % <SEP> Conversion <SEP> to <tb> U <SEP> A <SEP> (CO <SEP> + <SEP> CO2) <SEP> (CO <SEP> + <SEP> CO2 <SEP> + <SEP> CH4) <tb> N <SEP> T <tb> <SEP> No. <SEP> Type <SEP> Sulfur <SEP> Temp. <SEP> Abs. <SEP> S/C1 <SEP> Space <SEP> 4 <SEP> hrs <SEP> 24 <SEP> hrs <SEP> 48 <SEP> hrs <SEP> 96 <SEP> hrs <SEP> 4 <SEP> hrs <SEP> 24 <SEP> hrs <SEP> 48 <SEP> hrs <SEP> 96 <SEP> hrs <tb> <SEP> ppm <SEP> C <SEP> Press. <SEP> vel. <tb> <SEP> kg/cm2 <tb> 901 <SEP> 26+ <SEP> - <SEP> CH4 <SEP> none <SEP> 760 <SEP> atm <SEP> 3.5 <SEP> 500 <SEP> - <SEP> - <SEP> 99 <SEP> 99 <SEP> - <SEP> - <SEP> - <SEP> 902 <SEP> 26+ <SEP> - <SEP> CH4 <SEP> + <SEP> H2S <SEP> 310 <SEP> 904 <SEP> atm <SEP> 3.5 <SEP> 500 <SEP> - <SEP> 89 <SEP> 88 <SEP> 86 <SEP> - <SEP> - <SEP> - <SEP> 903 <SEP> 26+ <SEP> - <SEP> CH4 <SEP> + <SEP> H2S <SEP> 1060 <SEP> 904 <SEP> atm <SEP> 3.5 <SEP> 500 <SEP> - <SEP> 64 <SEP> 64 <SEP> 65 <SEP> - <SEP> - <SEP> - <SEP> 904 <SEP> 26+ <SEP> - <SEP> CH4 <SEP> + <SEP> H2S <SEP> 3220 <SEP> 904 <SEP> 4.5 <SEP> 3 <SEP> 500 <SEP> - <SEP> - <SEP> - <SEP> 55 <SEP> - <SEP> - <SEP> - <SEP> 55 <tb> 905 <SEP> 26+ <SEP> F <SEP> 7669 <SEP> Fuel <SEP> Oil <SEP> 2700 <SEP> 904 <SEP> atm <SEP> 5 <SEP> 500 <SEP> 91 <SEP> 91 <SEP> 91 <SEP> 91 <SEP> 97 <SEP> 100 <SEP> 98 <SEP> 97 <tb> 906 <SEP> 26+ <SEP> F <SEP> 7139 <SEP> Gas <SEP> Oil <SEP> 220 <SEP> 904 <SEP> 1.4 <SEP> 5 <SEP> 500 <SEP> 98 <SEP> 97 <SEP> 97 <SEP> 100 <SEP> 100 <SEP> 100 <tb> 907 <SEP> 26+ <SEP> F <SEP> 7128 <SEP> Gas <SEP> Oil <SEP> 4100 <SEP> 904 <SEP> 4.5 <SEP> 5 <SEP> 500 <SEP> 87 <SEP> 87 <SEP> 86 <SEP> 99 <SEP> 99 <SEP> 99 <tb> 803 <SEP> 26+ <SEP> F <SEP> 7128 <SEP> Gas <SEP> Oil <SEP> 4100 <SEP> 904 <SEP> atm <SEP> 5 <SEP> 500 <SEP> - <SEP> 88 <SEP> 89 <SEP> 88 <SEP> 100 <SEP> 100 <SEP> 100 <tb> 204 <SEP> 5+ <SEP> F <SEP> 7128 <SEP> Gas <SEP> Oil <SEP> & <SEP> 20000 <SEP> 843 <SEP> atm <SEP> 5 <SEP> 1000 <SEP> 65 <SEP> 65 <SEP> 65 <SEP> 65 <SEP> 80 <SEP> 84 <SEP> 78 <SEP> 72 <SEP> hrs <tb> <SEP> Triophena <SEP> 80 <tb>

Claims: CLAIMS: 1. A process for steam reforming hydrocarbons which comprises passing hydrocarbon feed with steam over a reduced catalyst composition having a plurality of oxides which in the unreduced condition consists essentially of: a) from about lo to about 60 weight percent nickel oxide in optional mixture with a minor portion of another Group VIII, fourth period metal oxide; b) from about 4 to about 30 weight percent of one or more oxides selected from a group consisting of oxides of yttrium and the lanthanons having atomic numbers 57 through 71; and c) from about lo to about 80 weight percent zirconium dioxide in optional admixture with less than about 75 weight percent of component c) of one or more inert oxides selected from the group consisting of hafnium oxide, titanium oxide magnesium oxide, calcium oxide, and alpha-aluminum oxide. 2. A process for steam reforming hydrocarbons which comprises passing hydrocarbon feed with steam over a reduced catalyst composition having a plurality of oxides which in the unreduced condition consists essentially of: a) from about 20 to about 50 weight percent nickel oxide; b) from about 1o to about 25 weight percent of one or more oxides of the lanthanons having atomic numbers 57 through 71; and c) from about 25 to about 70 weight percent zirconium dioxide. 3. The process of claim 2 wherein the lanthanon oxide component is lanthanum oxide. 4. The process of claim 2 wherein the oxides of the lanthanons are oxides of mischmetal. 5. The process of claim 2 wherein the oxides of the lanthanons are didymium oxide. 6. The process of either claim 1 or claim 2 wherein the hydrocarbon feed is predominantly methane containing from a trace to about 5 weight percent sulfur. 7. The process of either claim 1 or claim 2 wherein the hydrocarbon feed is normally liquid hydrocarbon boiling between from C5 about 550 C and containing from a trace to about 5 weight percent sulfur. 8. The process of either claim 1 or claim 2 wherein the hydrocarbon feed contains a shale oil fraction. 9. The process of either claim 1 or claim 2 wherein steam reforming is carried out in a tubular reformer at a pressure of from about 1 to about 50 kg/cm2 absolute and an outlet temperature of from about 500C to about loooOC and the steam to C1 ratio of the feed mixture is from about o.75 to 1 to about 7 to 1. 1o. The process of either claim 1 or claim 2 wherein the Group VIII, fourth period, metal oxides of the catalyst composition are reduced to elemental condition by treatment with reducing gas containing hydrogen. 11. A process for steam reforming normally liquid hydorcarbons boiling between about 1750C to about 48o0C and containing from about .o1 to about o.5 weight per cent sulfur which comprises passing hydrocarbon feed with steam over a reduced, mixed oxides; catalyst composition which in unreduced condition consists essentially of: a) from about 20 to about 50 weight percent nickel oxide; b) from about 1o to about 25 weight percent of one or more oxides of the lanthanons having atomic numbers 57 through 71; and c) from about 25 to about 70 weight percent zirconium dioxide. 12. A catalyst having a plurality of oxides which in the unreduced condition consists essentially of: a) from about 20 to about 50 weight percent nickel oxide; b) from about lo to about 25 weight percent of one or more oxides of the lanthanons having atomic numbers 57 through 71; and c) from about 25 to about 70 weight percent zirconium dioxide. 13. The catalyst of claim 12 wherein the lanthanon oxide component is lanthanum oxide. 14. The catalyst of claim 12 wherein the oxides of the lanthanons are oxides of'mischmetal. 15. The catalyst of claim 12 wherein the oxides of the lanthanons are didymium oxide. 16. A method for manufacture of a catalyst which in unreduced condition consists essentially of from about 20 to about 50 weight percent of a Group VIII, fourth period metal oxide; from about 1o to about 25 weight percent of one or more oxides of the lanthanons having atomic numbers 57 through 71; and from about 25 to about 70 weight percent zirconium dioxide which comprises a) preparing a water solution of salts of a Group VIII, fourth period metal, one or more lanthanons, and zirconium selected from the group consisting of nitrates and acetates, in proportions calculated to yield the catalyst; b) treating the water solution with a reagent selected from the group consisting of the hydroxides and carbonates of ammonia and sodium to form precipitates; c) at least partially drying the precipitates; d) forming the at least partially dried precipitates into catalyst shapes; and e) calcining the catalyst shapes at a temperature of from about 37o0C to about 76o0C to produce mixed oxides catalyst. 17. The method of claim 16 which additionally comprises treating the mixed oxides catalyst with reducing gas containing hydrogen wherein the Group VIII, fourth period metal oxide is reduced to elemental condition.

Inventors: LEFTIN, HARRY PAUL, PATIL, KASHINATH Z.
Applicants: THE M. W. KELLOGG COMPANY
Application year: 1981
Main classification: C01B3
IPC codes: C01B3, B01J23