Catalyst for the conversion of natural or associated gas into synthesis gas in an autothermal reforming process and method for preparing the same

Abstract

A catalyst in a calcined state has a specific surface area of 20-50 m.sup.2/g of catalyst, and a specific surface area of nickel metal after reduction of the catalyst of 8 to 11 m.sup.2/g, wherein the average particle size of nickel metal is 3-8 nm, the dispersion of the particles is 10-16%, and the content of nickel is 5-15 wt. % based on the weight of calcined catalyst. A support has a specific surface area of 40-120 m.sup.2/g with a pore volume of the support of 0.2-0.4 cm.sup.3/g, wherein the support is selected from a mixture of zirconium oxide and cerium oxide or magnesium oxide, cerium oxide and the ballast being zirconium oxide. The catalyst further contains a promoter selected from the group consisting of palladium and ruthenium, in an amount of from 0.01 to 0.5 wt. %. The catalyst is prepared by co-precipitation with ammonium hydroxide from a solution containing nickel, cerium and zirconium precursors and distilled water or from a solution containing nickel, cerium, zirconium, and magnesium precursors and distilled water, and having a pH of 8.0-9.0. The process is carried out under agitation at a temperature of 40-45° C. for 1-2 hours, followed by filtration, drying at a temperature of 100-110° C. for 6-8 hours, and calcining at a temperature of 400-650° C. for 4-6 hours. The invention provides a high average conversion of natural/associated gas of at least 90% in an autothermal reforming reaction of natural or associated gas, and a high synthesis gas output of at least 7000 m.sup.3/m.sup.3.sub.cat.Math.h.

Claims

1. A catalyst prepared by co-precipitation for the conversion of natural/associated gas to synthesis-gas in an autothermal reforming process, having a specific surface area in a calcined state of 20 to 50 m.sup.2/g of catalyst and a specific surface area of nickel metal after reduction of the catalyst of 8 to 11 m.sup.2/g, an average nickel metal particles of 3 to 8 nm, and a dispersion of nickel metal particles within the catalyst of 10 to 16%, the catalyst comprising from 5 to 15 wt. % of nickel based on the weight of the calcined catalyst, and a support having a specific surface area of 40 to 120 m.sup.2/g and a support pore volume of 0.2 to 0.4 cm.sup.3/g, wherein the support is selected from a mixture of zirconia and ceria; or magnesium oxide, ceria, and zirconia.

2. The catalyst of claim 1, further comprising a promoter selected from the group of palladium and ruthenium, in an amount of 0.01 to 0.5 wt. %.

3. A method for preparing a catalyst for the conversion of natural/associated gas to synthesis gas in an autothermal reforming process according to claim 1 by co-precipitating with ammonium hydroxide from a solution comprising nickel, cerium, and zirconium precursors and distilled water or from a solution comprising nickel, cerium, zirconium, magnesium precursors and distilled water and having a pH of 8.0-9.0, under agitation at a temperature of 40-45° C. for 1-2 hours, followed by filtration, drying at a temperature of 100-110° C. for 6-8 hours, and calcining at a temperature of 400-650° C. for 4-6 hours.

4. A catalyst prepared by co-precipitation for the conversion of natural/associated gas to synthesis-gas in an autothermal reforming process, having a specific surface area in a calcined state of 20 to 50 m.sup.2/g of catalyst and a specific surface area of nickel metal after reduction of the catalyst of 8 to 11 m.sup.2/g, an average nickel metal particles of 3 to 8 nm, and a dispersion of nickel metal particles within the catalyst of 10 to 16%, the catalyst comprising from 5 to 15 wt. % of nickel based on the weight of the calcined catalyst, and a support having a specific surface area of 40 to 120 m.sup.2/g and a support pore volume of 0.2 to 0.4 cm.sup.3/g, wherein the support is selected from a mixture of zirconia and ceria; or magnesium oxide, ceria, and the balance being zirconia, and wherein the catalyst further comprises a promoter selected from the group of palladium and ruthenium, in an amount of 0.01 to 0.5 wt. %, and wherein the conversion is at least 90% with a synthesis gas output of at least 7,000 m.sup.3/m.sup.3.sub.cat.Math.h.

5. The catalyst of claim 1, wherein the conversion is at least 90%.

6. The catalyst of claim 1, wherein a synthesis gas output of at least 7,000 m.sup.3/m.sup.3.sub.cat.Math.h.

7. The catalyst of claim 1, wherein the support is the mixture of zirconia and ceria.

8. The catalyst of claim 1, wherein the support is the mixture of magnesium oxide, ceria, and zirconia.

Description

EMBODIMENTS OF THE INVENTION

(1) The method can be implemented according to the following examples.

(2) Example A is a comparative example and illustrates the embodiment of the method in accordance with the prototype.

(3) Examples 1-16 show embodiments of the method according to the present invention.

Example A

(4) A Ni/Ce-Zr/MgAlO.sub.x catalyst is prepared by co-impregnation of MgAlO.sub.x (30) (Pural MG30) with aqueous solutions of cerium acetate, zirconium oxonitrate, and nickel nitrate. The resulting composition of the oxide catalyst is dried for 12 hours at a temperature of 70° C. and at a temperature of 100° C. for 24 hours, after which the catalyst is calcined at a temperature of 850° C. for 6 hours. The resulting catalyst is pressed in a special mold and ground to obtain a catalyst fraction of 0.5-1.0 mm. The catalyst is activated at a temperature of 750° C. in a hydrogen stream with a space velocity of 3000 h.sup.−1 for one hour under a pressure of 0.1 MPa.

Example 1

(5) A 10% Ni/(25% CeO.sub.2+75% ZrO.sub.2) catalyst is prepared by co-precipitation of a solution comprising cerium, zirconium, and nickel precursors with ammonium hydroxide to form the corresponding hydroxides, followed by filtration, drying, and calcining. First, a sample of zirconium oxonitrate and cerium nitrate in CeO.sub.2/ZrO.sub.2 weight ratio of 1:4 and a sample of nickel nitrate in a nickel mass fraction of 10 wt. % are dissolved in distilled water at 40° C. for 1 hour. Then, a 25 wt. % solution of ammonium hydroxide is added by drops to the resulting solution under constant thorough agitation until reaching a pH of the solution of 8.0. The resulting mixture is filtered through a Buchner funnel, dried at a temperature of 110° C. for 6 hours and then calcined at a temperature of 400° C. for 6 hours to obtain solid solutions of cerium, zirconium, and nickel oxides uniformly distributed throughout the volume of the catalyst grains. The resulting catalyst is pressed in a special mold and then ground to obtain a catalyst fraction of 0.5-1.0 mm. The process of the catalyst activation is conducted at 750° C. in a hydrogen stream with a space velocity of 3000 h.sup.−1 for one hour under a pressure of 0.1 MPa. Gas containing 100% CH.sub.4 is used as a feedstock.

Example 2

(6) A 15% Ni/(25% CeO.sub.2+75% ZrO.sub.2) catalyst is prepared by co-precipitation of a solution comprising cerium, zirconium, and nickel precursors with ammonium hydroxide to form the corresponding hydroxides, followed by filtration with washing with distilled water, drying, and calcining. First, a sample of zirconium oxonitrate and cerium nitrate in a CeO.sub.2/ZrO.sub.2 weight ratio of 1:4 and a sample of nickel nitrate in a nickel mass fraction of 10 wt. % are dissolved in distilled water at 45° C. for 2 hours. Then, a 25 wt. % solution of ammonium hydroxide is added by drops to the resulting solution under constant thorough agitation until reaching a pH of the solution of 9.0. The resulting mixture is filtered through a Buchner funnel, dried at a temperature of 100° C. for 8 hours and then calcined at a temperature of 650° C. for 4 hours to obtain solid solutions of cerium, zirconium, and nickel oxides uniformly distributed throughout the volume of the catalyst grains. The resulting catalyst is pressed in a special mold and then ground to obtain a catalyst fraction of 0.5-1.0 mm. The process of the catalyst activation is conducted at a temperature of 750° C. in a hydrogen stream with a space velocity of 3000 h.sup.−1 for one hour under a pressure of 0.1 MPa. Gas containing 100% CH.sub.4 is used as a feedstock.

Example 3

(7) A 5% Ni/(17% CeO.sub.2+83% ZrO.sub.2) catalyst is prepared by co-precipitation of a solution comprising cerium, zirconium, and nickel precursors with ammonium hydroxide to form the corresponding hydroxides, followed by filtration, drying, and calcining. First, a sample of zirconium oxonitrate and cerium nitrate in a CeO.sub.2/ZrO.sub.2 weight ratio of 1:6, and a sample of nickel nitrate in a nickel mass fraction of 5 wt. % are dissolved in distilled water at 40° C. for 1 hour. Then, a 25 wt. % solution of ammonium hydroxide is added by drops to the resulting solution under constant thorough agitation until reaching a pH of the solution of 8.0. The resulting mixture is filtered through a Buchner funnel, dried at a temperature of 110° C. for 6 hours and then calcined at a temperature of 400° C. for 6 hours to obtain solid solutions of cerium, zirconium, and nickel oxides uniformly distributed throughout the volume of the catalyst grains. The resulting catalyst is pressed in a special mold and then ground to obtain a catalyst fraction of 0.5-1.0 mm. The process of the catalyst activation is conducted at a temperature of 50° C. in a hydrogen stream with a space velocity of 3000 h.sup.−1 for one hour under a pressure of 0.1 MPa. Gas containing 100% CH.sub.4 is used as a feedstock.

Example 4

(8) A 15% Ni/(34% CeO.sub.2+66% ZrO.sub.2) catalyst is prepared by co-precipitation of a solution comprising cerium, zirconium, and nickel precursors with ammonium hydroxide to form the corresponding hydroxides, followed by filtration, drying, and calcining. First, a sample of zirconium oxonitrate and cerium nitrate in a CeO.sub.2/ZrO.sub.2 weight ratio of 1:2, and a sample of nickel nitrate in a nickel mass fraction of 15 wt. % are dissolved in distilled water at 45° C. for 2 hours. Then, a 25 wt. % solution of ammonium hydroxide is added by drops to the resulting solution under constant thorough agitation until reaching a pH of the solution of 9.0. The resulting mixture is filtered through a Buchner funnel, dried at a temperature of 110° C. for 8 hours and then calcined at a temperature of 650° C. for 4 hours to obtain solid solutions of cerium, zirconium, and nickel oxides uniformly distributed throughout the volume of the catalyst grains. The resulting catalyst is pressed in a special mold and then ground to obtain a catalyst fraction of 0.5-1.0 mm. The process of the catalyst activation is conducted at a temperature of 750° C. in a hydrogen stream with a space velocity of 3000 h.sup.−1 for one hour under a pressure of 0.1 MPa. Gas containing 100% CH.sub.4 is used as a feedstock.

Example 5

(9) A 10% Ni/(23% CeO.sub.2+70% ZrO.sub.2+7% MgO) catalyst is prepared by co-precipitation of a solution comprising cerium, zirconium, magnesium, and nickel precursors with ammonium hydroxide to form the corresponding hydroxides, followed by filtration, drying, and calcining. First, a sample of zirconium oxonitrate and cerium nitrate in a CeO.sub.2/ZrO.sub.2 weight ratio of 1:4 and a sample of magnesium nitrate in a MgO/ZrO.sub.2 weight ratio of 1:10, as well as a sample of nickel nitrate in a nickel mass fraction of 10 wt. %, are dissolved in distilled water at 40° C. for 1 hour. Then, a 25 wt. % solution of ammonium hydroxide is added by drops to the resulting solution under constant thorough agitation until reaching a pH of the solution of 8.0. The resulting mixture is filtered through a Buchner funnel, dried at a temperature of 110° C. for 6 hours and then calcined at a temperature of 400° C. for 6 hours to obtain solid solutions of cerium, zirconium, magnesium, and nickel oxides uniformly distributed throughout the volume of the catalyst grains. The resulting catalyst is pressed in a special mold and then ground to obtain a catalyst fraction of 0.5-1.0 mm. The process of the catalyst activation is conducted at a temperature of 750° C. in a hydrogen stream with a space velocity of 3000 h.sup.−1 for one hour under a pressure of 0.1 MPa. Gas containing 100% CH.sub.4 is used as a feedstock.

Example 6

(10) A 5% Ni/(22% CeO.sub.2+65% ZrO.sub.2+13% MgO) catalyst is prepared by co-precipitation of a solution comprising cerium, zirconium, magnesium, and nickel precursors with ammonium hydroxide to form the corresponding hydroxides, followed by filtration, drying, and calcining. First, a sample of zirconium oxonitrate and cerium nitrate in a CeO.sub.2/ZrO.sub.2 weight ratio of 1:4 and a sample of magnesium nitrate in a MgO/ZrO.sub.2 weight ratio of 1:5, as well as a sample of nickel nitrate in a nickel mass fraction of 5 wt. %, are dissolved in distilled water at 45° C. for 2 hours. Then, a 25 wt. % solution of ammonium hydroxide is added by drops to the resulting solution under constant thorough agitation until reaching a pH of the solution of 8.5. The resulting mixture is filtered through a Buchner funnel, dried at a temperature of 110° C. for 7 hours and then calcined at a temperature of 550° C. for 5 hours to obtain solid solutions of cerium, zirconium, magnesium, and nickel oxides uniformly distributed throughout the volume of the catalyst grains. The resulting catalyst is pressed in a special mold and then ground to obtain a catalyst fraction of 0.5-1.0 mm. The process of the catalyst activation is conducted at a temperature of 750° C. in a hydrogen stream with a space velocity of 3000 h.sup.−1 for one hour under a pressure of 0.1 MPa. Gas containing 100% CH.sub.4 is used as a feedstock.

Example 7

(11) A 15% Ni/(24% CeO.sub.2+71% ZrO.sub.2+5% MgO) catalyst is prepared by co-precipitation of a solution comprising cerium, zirconium, magnesium, and nickel precursors with ammonium hydroxide to form the corresponding hydroxides, followed by filtration without washing with distilled water, drying, and calcining. First, a sample of zirconium oxonitrate and cerium nitrate in a CeO.sub.2/ZrO.sub.2 weight ratio of 1:4 and a sample of magnesium nitrate in a MgO/ZrO.sub.2 weight ratio of 1:15, as well as a sample of nickel nitrate in a nickel mass fraction of 15 wt. % are dissolved in distilled water at 45° C. for 2 hours. Then, a 25 wt. % solution of ammonium hydroxide is added by drops to the resulting solution under constant thorough agitation until reaching a pH of the solution of 9.0. The resulting mixture is filtered through a Buchner funnel, dried at a temperature of 110° C. for 8 hours and then calcined at a temperature of 650° C. for 4 hours to obtain solid solutions of cerium, zirconium, magnesium, and nickel oxides uniformly distributed throughout the volume of the catalyst grains. The resulting catalyst is pressed in a special mold and then ground to obtain a catalyst fraction of 0.5-1.0 mm. The process of the catalyst activation is conducted at a temperature of 750° C. in a hydrogen stream with a space velocity of 3000 h.sup.−1 for one hour under a pressure of 0.1 MPa. Gas containing 100% CH.sub.4 is used as a feedstock.

Example 8

(12) A (5% Ni+0.01% Pd)/(25% CeO.sub.2+75% ZrO.sub.2) catalyst is prepared by co-precipitation of a solution comprising cerium, zirconium, and nickel precursors with ammonium hydroxide to form the corresponding hydroxides, followed by filtration without washing with distilled water, drying, and calcining, and further introducing palladium by impregnation. First, a sample of zirconium oxonitrate and cerium nitrate in a CeO.sub.2/ZrO.sub.2 weight ratio of 1:4 and a sample of nickel nitrate in a nickel mass fraction of 5 wt. % are dissolved in distilled water at 40° C. for 1 hour. Then, a 25 wt. % solution of ammonium hydroxide is added by drops to the resulting solution under constant thorough agitation until reaching a pH of the solution of 8.0. The resulting mixture is filtered through a Buchner funnel, dried at a temperature of 110° C. for 6 hours and then calcined at a temperature of 400° C. for 6 hours to obtain solid solutions of cerium, zirconium, and nickel oxides uniformly distributed throughout the volume of the catalyst grains. At the second step of the catalyst preparation, a nickel, cerium-zirconium powder composition is impregnated with a solution of tetraaminepalladium chloride based on 0.01 wt. % Pd at room temperature for 1 hour. After the termination of the impregnation process, the catalyst is dried for 6 hours at a temperature of 110° C. and then calcined in air at a temperature of 550° C. for 4 hours. The resulting catalyst is pressed in a special mold and then ground to obtain a catalyst fraction of 0.5-1.0 mm. The process of the catalyst activation is conducted at a temperature of 750° C. in a hydrogen stream with a space velocity of 3000 h.sup.−1 for one hour under a pressure of 0.1 MPa. Gas containing 100% CH.sub.4 is used as a feedstock.

Example 9

(13) A (10% Ni+0.1% Pd)/(25% CeO.sub.2+75% ZrO.sub.2) catalyst is prepared by co-precipitation of a solution comprising cerium, zirconium, and nickel precoursors with ammonium hydroxide to form the corresponding hydroxides, followed by filtration without washing with distilled water, drying, and calcining and further introducing palladium by impregnation. First, a sample of zirconium oxonitrate and cerium nitrate in a CeO.sub.2/ZrO.sub.2 weight ratio of 1:4, and a sample of nickel nitrate in a nickel mass fraction of 10 wt. % are dissolved in distilled water at 45° C. for 2 hours. Then, a 25 wt. % solution of ammonium hydroxide is added by drops to the resulting solution under constant thorough agitation until reaching a pH of the solution of 8.5. The resulting mixture is filtered through a Buchner funnel, dried at a temperature of 110° C. for 7 hours and then calcined at a temperature of 550° C. for 5 hours to obtain solid solutions of cerium, zirconium, and nickel oxides uniformly distributed throughout the volume of the catalyst grains. At the second step of the catalyst preparation, a nickel, cerium-zirconium powder composition is impregnated with a solution of tetraaminepalladium chloride based on 0.1 wt. % Pd at room temperature for 1 hour. After the termination of the impregnation process, the catalyst is dried at a temperature of 110° C. for 6 hours and then calcined in air at a temperature of 550° C. for 4 hours. The resulting catalyst is pressed in a special mold and then ground to obtain a catalyst fraction of 0.5-1 mm. The process of the catalyst activation is conducted at a temperature of 750° C. in a hydrogen stream with a space velocity of 3000 h.sup.−1 for one hour under a pressure of 0.1 MPa. Gas containing 100% CH.sub.4 is used as a feedstock.

Example 10

(14) A (15% Ni+0.5% Pd)/(25% CeO.sub.2+75% ZrO.sub.2) catalyst is prepared by co-precipitation of a solution comprising cerium, zirconium, and nickel precoursors with ammonium hydroxide to form the corresponding hydroxides, followed by filtration without washing with distilled water, drying, and calcining and further introducing palladium by impregnation. First, a sample of zirconium oxonitrate and cerium nitrate in a CeO.sub.2/ZrO.sub.2 weight ratio of 1:4, and a sample of nickel nitrate in a nickel mass fraction of 15 wt. % are dissolved in distilled water at 45° C. for 2 hours. Then, a 25 wt. % solution of ammonium hydroxide is added by drops to the resulting solution under constant thorough agitation until reaching a pH of the solution of 9.0. The resulting mixture is filtered through a Buchner funnel, dried at a temperature of 110° C. for 8 hours and then calcined at a temperature of 650° C. for 4 hours to obtain solid solutions of cerium, zirconium, and nickel oxides uniformly distributed throughout the volume of the catalyst grains. At the second step of the catalyst preparation, a nickel, cerium-zirconium powder composition is impregnated with a solution of tetraaminepalladium chloride based on 0.5 wt. % Pd at room temperature for 1 hour. After the termination of the impregnation process, the catalyst is dried at a temperature of 110° C. for 6 hours and then calcined in air at a temperature of 550° C. for 4 hours. The resulting catalyst is pressed in a special mold and then ground to obtain a catalyst fraction of 0.5-1.0 mm. The process of the catalyst activation is conducted at a temperature of 750° C. in a hydrogen stream with a space velocity of 3000 h.sup.−1 for one hour under a pressure of 0.1 MPa. Gas containing 100% CH.sub.4 is used as a feedstock.

Example 11

(15) A (5% Ni+0.01% Ru)/(25% CeO.sub.2+75% ZrO.sub.2) catalyst is prepared by co-precipitation of a solution comprising cerium, zirconium, and nickel precoursors with ammonium hydroxide to form the corresponding hydroxides, followed by filtration, drying, and calcining and further introducing ruthenium by impregnation. First, a sample of zirconium oxonitrate and cerium nitrate in a CeO.sub.2/ZrO.sub.2 weight ratio of 1:4, and a sample of nickel nitrate in a nickel mass fraction of 5 wt. % are dissolved in distilled water at 40° C. for 1 hours. Then, a 25 wt. % solution of ammonium hydroxide is added by drops to the resulting solution under constant thorough agitation until reaching a pH of the solution of 8.0. The resulting mixture is filtered through a Buchner funnel, dried at a temperature of 110° C. for 6 hours and then calcined at a temperature of 400° C. for 6 hours to obtain solid solutions of cerium, zirconium, and nickel oxides uniformly distributed throughout the volume of the catalyst grains. At the second step of the catalyst preparation, a nickel, cerium-zirconium powder composition is impregnated with a solution of ruthenium chloride based on 0.01 wt. % Ru at room temperature for 1.5 hour. After the termination of the impregnation process, the catalyst is dried at a temperature of 110° C. for 7 hours and then calcined in air at a temperature of 400° C. for 5 hours. The resulting catalyst is pressed in a special mold and then ground to obtain a catalyst fraction of 0.5-1.0 mm. The process of the catalyst activation is conducted at a temperature of 750° C. in a hydrogen stream with a space velocity of 3000 h.sup.−1 for one hour under a pressure of 0.1 MPa. Gas containing 100% CH.sub.4 is used as a feedstock.

Example 12

(16) A (10% Ni+0.1% Ru)/(25% CeO.sub.2+75% ZrO.sub.2) catalyst is prepared by co-precipitation of a solution comprising cerium, zirconium, and nickel precoursors with ammonium hydroxide to form the corresponding hydroxides, followed by filtration without washing with distilled water, drying, and calcining and further introducing ruthenium by impregnation. First, a sample of zirconium oxonitrate and cerium nitrate in a CeO.sub.2/ZrO.sub.2 weight ratio of 1:4, and a sample of nickel nitrate in a nickel mass fraction of 10 wt. % are dissolved in distilled water at 45° C. for 2 hours. Then, a 25 wt. % solution of ammonium hydroxide is added by drops to the resulting solution under constant thorough agitation until reaching a pH of the solution of 8.5. The resulting mixture is filtered through a Buchner funnel without washing with distilled water, dried at a temperature of 110° C. for 7 hours and then calcined at a temperature of 550° C. for 5 hours to obtain solid solutions of cerium, zirconium, and nickel oxides uniformly distributed throughout the volume of the catalyst grains. At the second step of the catalyst preparation, a nickel, cerium-zirconium powder composition is impregnated with a solution of ruthenium chloride based on 0.1 wt. % Ru at room temperature for 1.5 hour. After the termination of the impregnation process, the catalyst is dried at a temperature of 110° C. for 7 hours and then calcined in air at a temperature of 400° C. for 5 hours. The resulting catalyst is pressed in a special mold and then ground to obtain a catalyst fraction of 0.5-1.0 mm. The process of the catalyst activation is conducted at a temperature of 750° C. in a hydrogen stream with a space velocity of 3000 h.sup.−1 for one hour under a pressure of 0.1 MPa. Gas containing 100% CH.sub.4 is used as a feedstock.

Example 13

(17) A (15% Ni+0.5% Ru)/(25% CeO.sub.2+75% ZrO.sub.2) catalyst is prepared by co-precipitation of a solution comprising cerium, zirconium, and nickel precoursors with ammonium hydroxide to form the corresponding hydroxides, followed by filtration without washing with distilled water, drying, and calcining and further introducing ruthenium by impregnation. First, a sample of zirconium oxonitrate and cerium nitrate in a CeO.sub.2/ZrO.sub.2 weight ratio of 1:4, and a sample of nickel nitrate in a nickel mass fraction of 15 wt. % are dissolved in distilled water at 45° C. for 2 hours. Then, a 25 wt. % solution of ammonium hydroxide is added by drops to the resulting solution under constant thorough agitation until reaching a pH of the solution of 9.0. The resulting mixture is filtered through a Buchner funnel, dried at a temperature of 110° C. for 8 hours and then calcined at a temperature of 650° C. for 4 hours to obtain solid solutions of cerium, zirconium, and nickel oxides uniformly distributed throughout the volume of the catalyst grains. At the second step of the catalyst preparation, a nickel, cerium-zirconium powder composition is impregnated with a solution of ruthenium chloride based on 0.5 wt. % Ru at room temperature for 1.5 hour. After the termination of the impregnation process, the catalyst is dried at a temperature of 110° C. for 7 hours and then calcined in air at a temperature of 400° C. for 5 hours. The resulting catalyst is pressed in a special mold and then ground to obtain a catalyst fraction of 0.5-1.0 mm. The process of the catalyst activation is conducted at a temperature of 750° C. in a hydrogen stream with a space velocity of 3000 h.sup.−1 for one hour under a pressure of 0.1 MPa. Gas containing 100% CH.sub.4 is used as a feedstock.

Example 14

(18) A (10% Ni+0.1% Pd)/(25% CeO.sub.2+75% ZrO.sub.2) catalyst is prepared by co-precipitation of a solution comprising cerium, zirconium, and nickel precoursors with ammonium hydroxide to form the corresponding hydroxides, followed by filtration without washing with distilled water, drying, and calcining and further introducing palladium by impregnation. First, a sample of zirconium oxonitrate and cerium nitrate in a CeO.sub.2/ZrO.sub.2 weight ratio of 1:4, and a sample of nickel nitrate in a nickel mass fraction of 10 wt. % are dissolved in distilled water at 45° C. for 2 hours. Then, a 25 wt. % solution of ammonium hydroxide is added by drops to the resulting solution under constant thorough agitation until reaching a pH of the solution of 8.5. The resulting mixture is filtered through a Buchner funnel, dried at a temperature of 110° C. for 7 hours and then calcined at a temperature of 550° C. for 5 hours to obtain solid solutions of cerium, zirconium, and nickel oxides uniformly distributed throughout the volume of the catalyst grains. At the second step of the catalyst preparation, a nickel, cerium-zirconium powder composition is impregnated with a solution of tetraaminepalladium chloride based on 0.1 wt. % Pd at room temperature for 1 hour. After the termination of the impregnation process, the catalyst is dried at a temperature of 110° C. for 6 hours and then calcined in air at a temperature of 550° C. for 4 hours. The resulting catalyst is pressed in a special mold and then ground to obtain a catalyst fraction of 0.5-1.0 mm. The process of the catalyst activation is conducted at a temperature of 750° C. in a hydrogen stream with a space velocity of 3000 h.sup.−1 for one hour under a pressure of 0.1 MPa. Gas simulating the composition of associated petroleum gas, comprising 10% C.sub.2H.sub.6 and 90% CH.sub.4 is used as a feed methane-containing mixture.

Example 15

(19) A (10% Ni+0.1% Pd)/(25% CeO.sub.2+75% ZrO.sub.2) catalyst is prepared by co-precipitation a solution comprising cerium, zirconium, and nickel precoursors with ammonium hydroxide to form the corresponding hydroxides, followed by filtration without washing with distilled water, drying, and calcining, and further introducing palladium by impregnation. First, a sample of zirconium oxonitrate and cerium nitrate in a CeO.sub.2/ZrO.sub.2 weight ratio of 1:4 and a sample of nickel nitrate in a nickel mass fraction of 10 wt. % are dissolved in distilled water at 45° C. for 2 hours. Then, a 25 wt. % solution of ammonium hydroxide is added by drops to the resulting solution under constant thorough agitation until reaching a pH of the solution of 8.5. The resulting mixture is filtered through a Buchner funnel, dried at a temperature of 110° C. for 7 hours and then calcined at a temperature of 550° C. for 5 hours to obtain solid solutions of cerium, zirconium, and nickel oxides uniformly distributed throughout the volume of the catalyst grains. At the second step of the catalyst preparation, a nickel, cerium-zirconium powder composition is impregnated with a solution of tetraaminepalladium chloride based on 0.1 wt. % Pd at room temperature for 1 hour. After the termination of the impregnation process, the catalyst is dried at a temperature of 110° C. for 6 hours and then calcined in air at a temperature of 550° C. for 4 hours. The resulting catalyst is pressed in a special mold and then ground to obtain a catalyst fraction of 0.5-1.0 mm. The process of the catalyst activation is conducted at a temperature of 750° C. in a hydrogen stream with a space velocity of 3000 h.sup.−1 for one hour under a pressure of 0.1 MPa. Gas simulating the composition of associated petroleum gas, comprising 25% C.sub.2H.sub.6, 5% C.sub.3H.sub.8 and 70% CH.sub.4 is used as a feed methane-containing mixture.

Example 16

(20) A (10% Ni+0.1% Pd)/(25% CeO.sub.2+75% ZrO.sub.2) catalyst is prepared by co-precipitation of a solution comprising cerium, zirconium, and nickel precoursors with ammonium hydroxide to form the corresponding hydroxides, followed by filtration without washing with distilled water, drying, and calcining, and further introducing palladium by impregnation. First, a sample of zirconium oxonitrate and cerium nitrate in a CeO.sub.2/ZrO.sub.2 weight ratio of 1:4 and a sample of nickel nitrate in a nickel mass fraction of 10 wt. % are dissolved in distilled water at 45° C. for 2 hours. Then, a 25 wt. % solution of ammonium hydroxide is added by drops to the resulting solution under constant thorough agitation until reaching a pH of the solution of 8.5. The resulting mixture is filtered through a Buchner funnel, dried at a temperature of 110° C. for 7 hours and then calcined at a temperature of 550° C. for 5 hours to obtain solid solutions of cerium, zirconium, and nickel oxides uniformly distributed throughout the volume of the catalyst grains. At the second step of the catalyst preparation, a nickel, cerium-zirconium powder composition is impregnated with a solution of tetraaminepalladium chloride based on 0.1 wt. % Pd at room temperature for 1 hour. After the termination of the impregnation process, the catalyst is dried at a temperature of 110° C. for 6 hours and then calcined in air at a temperature of 550° C. for 4 hours. The resulting catalyst is pressed in a special mold and then ground to obtain a catalyst fraction of 0.5-1.0 mm. The process of the catalyst activation is conducted at a temperature of 750° C. in a hydrogen stream with a space velocity of 3000 h.sup.−1 for one hour under a pressure of 0.1 MPa. Gas simulating the composition of associated petroleum gas, comprising 15% C.sub.2H.sub.6, 10% C.sub.3H.sub.8, 5% C.sub.4H.sub.10, and 70% CH.sub.4 is used as a feed methane-containing mixture.

(21) The table shows the average conversion of a mixture that simulates the composition of natural or associated gas, in the presence of the catalysts prepared in accordance with the prototype (example A) and examples 1-16 of the present invention, and their average productivity in producing synthesis gas. The distribution of nickel, cerium, zirconium, and, in some examples, magnesium in the volume of particles of the catalysts synthesized by the co-precipitation according to examples 1-16 is uniform throughout the volume of the catalyst.

(22) The table also shows the surface area of the supports and catalysts, as well as the values of the specific area of nickel, its dispersion, and average particle size.

(23) TABLE-US-00001 Support Catalyst Synthesis physicochemical physicochemical NG/APG gas properties properties conversion, output, S.sub.area, V.sub.pore, S.sub.area, S.sub.Ni, D.sub.Ni, d.sub.Ni, Examp. % m.sup.3/m.sup.3.sub.cat .Math. h m.sup.2/ml cm.sup.3/g m.sup.2/ml m.sup.2/ml % nm A 81 5610 40 0.2 20 5.8 7 14 1 93 7030 90 0.3 44 9.4 11 7 2 90 7000 40 0.2 20 10.8 10 8 3 91 7025 78 0.3 38 8.0 14 6 4 93 7100 71 0.2 33 10.4 12 7 5 93 7280 115 0.3 56 10.6 16 3 6 91 7060 94 0.3 50 8.4 11 8 7 93 7110 86 0.2 42 10.9 14 6 8 92 7050 92 0.3 46 8.2 16 4 9 94 7320 120 0.4 60 11.0 16 3 10 94 7120 84 0.2 40 10.7 13 6 11 92 7040 88 0.3 42 8.3 16 4 12 94 7180 102 0.4 54 10.5 16 4 13 93 7115 74 0.2 32 10.9 12 7 14 94 7345 120 0.4 60 11.0 16 3 15 95 7386 120 0.4 60 11.0 16 3 16 96 7495 120 0.4 60 11.0 16 3

(24) The catalyst prepared in accordance with the comparative example has a low efficiency in autothermal reforming of natural/associated gas, which is characterized by a low hydrocarbon conversion and a low productivity of the catalyst. In addition, this catalyst has the smallest active surface area of nickel, a lower dispersion, and the largest average nickel particle size in reduced state at minimum values of the surface area of the support and catalyst. This is the reason of a low methane conversion and a low synthesis gas output. The catalysts synthesized according to the examples described in this invention are free from these drawbacks and demonstrate stable operation during the experiment, have a high average methane conversion of at least 90% in an autothermal reforming reaction of natural/associated gas and a high synthesis gas output of at least 7000 m.sup.3/m.sup.3 cat.Math.h.