CN107159219B

CN107159219B - Cobalt-based catalyst for preparing hydrogen by autothermal reforming of acetic acid and preparation method thereof

Info

Publication number: CN107159219B
Application number: CN201710355478.XA
Authority: CN
Inventors: 黄利宏; 周庆; 王巧; 李辉谷; 杨季龙
Original assignee: Chengdu Univeristy of Technology
Current assignee: Chengdu Univeristy of Technology
Priority date: 2017-05-19
Filing date: 2017-05-19
Publication date: 2020-02-04
Anticipated expiration: 2037-05-19
Also published as: CN107159219A

Abstract

The invention relates to a cobalt-based catalyst for autothermal reforming of acetic acid to produce hydrogen and a preparation method thereof. The invention provides a novel catalyst with sintering resistance, carbon deposit resistance, oxidation resistance and high activity, aiming at the problems of catalyst structure change, active component oxidation and sintering and catalyst deactivation of the existing catalyst in the process of autothermal reforming of acetic acid. The chemical composition of the catalyst of the invention is Co_aZn_bAlO_7.5 ₊ _δWherein a is 0.25-1.00 and b is 0.75-5.00. The invention adopts a coprecipitation method to prepare a Zn-Al type layered hydrotalcite-like structure as a precursor, introduces an active component cobalt, and enters a laminate structure of the hydrotalcite-like structure through isomorphous substitution of the cobalt on the zinc; the composite oxide obtained by roasting effectively inhibits the possible migration, aggregation and sintering of the active component cobalt under the high-temperature reaction condition, and improves the thermal stability of the catalyst; meanwhile, the zinc oxide carrier improves the reducibility, stability and oxidation resistance of the active component cobalt, thereby improving the activity and stability of the catalyst.

Description

Cobalt-based catalyst for preparing hydrogen by autothermal reforming of acetic acid and preparation method thereof

Technical Field

The invention relates to a cobalt-based catalyst for preparing hydrogen by autothermal reforming of acetic acid and a preparation method thereof, in particular to a cobalt-based catalyst which has a hydrotalcite-like structure and is used for preparing hydrogen by autothermal reforming of acetic acid and a preparation method thereof, belonging to the technical field of hydrogen preparation by autothermal reforming of acetic acid.

Background

Hydrogen is a clean energy carrier, particularly for fuel cells, and is considered as an ideal clean energy carrier in the future. At present, hydrogen is mainly prepared by converting primary energy sources such as natural gas, coal and the like, which results in CO in the atmosphere₂The content is increased. Biomass, obtained from plant photosynthesis, is an important renewable energy source. However, it is not without failThe material has low energy density, and can be converted into the material with energy density up to 20 MJ/m by rapid thermal cracking³The biomass oil is converted in a large scale to prepare hydrogen at low cost. In the biomass oil, acetic acid is used as a main liquid-phase component, the mass fraction of the acetic acid can reach 30%, and hydrogen can be obtained through a catalytic reforming process.

The main routes for producing hydrogen from acetic acid are steam reforming, partial oxidation and autothermal reforming. The hydrogen production by steam reforming is a strong endothermic reaction, and needs external continuous heat supply to maintain the reaction; in addition, after the acetic acid molecules are activated on the surface of the catalyst, intermediate products such as ketene and the like are easily generated through decarboxylation and dehydration reactions, and the intermediate products are subjected to polycondensation reaction to form carbon deposit so as to inactivate the catalyst; the partial oxidation hydrogen production reaction does not need external continuous heat supply, but reduces the hydrogen yield. Aiming at the problems, the autothermal reforming hydrogen production can be adopted, namely, a small amount of oxygen or air is introduced into the acetic acid steam reforming reaction, the endothermic steam reforming process and the exothermic partial oxidation process are combined, and the oxygen content in the raw material gas is adjusted to adjust the total reaction to reach the heat balance or moderate heat release; meanwhile, the introduction of oxygen influences the adsorption and activation processes of reactant molecules on the surface of the catalyst, induces the generation and conversion of transition products, and can inhibit the generation of carbon deposit precursors. On the other hand, however, the introduction of oxygen forms an oxidizing atmosphere at the front end of the catalyst bed, and the local temperature can reach over 1000 ℃, which easily causes sintering of the catalyst carrier, clogging of the pore channels, and aggregation and oxidation of active components, and finally leads to catalyst deactivation. Therefore, the development of catalysts with stable structure, oxidation resistance, sintering resistance and carbon deposit resistance is the first problem to be solved in the process of preparing hydrogen by the autothermal reforming reaction of acetic acid.

The metal cobalt has higher capacity of breaking C-C bonds and C-H bonds, can be applied to the reaction of hydrogen production catalyzed by acetic acid, and also faces the problems of sintering, carbon deposition and the like. In addition, for the catalyst carrier, the optimization of the acidity and alkalinity or the structure of the catalyst carrier is beneficial to improving the activity, the carbon deposition resistance and other performances of the cobalt-based catalyst. Al as carrier₂O₃ZnO, etc. have high thermal stability, among them Al₂O₃The catalyst can be enlargedThe specific surface area is large, but the specific surface area is strong in acidity and easy to deposit a large amount of carbon deposit. ZnO has alkalinity, has inhibiting effect on the generation of carbon deposit, and can promote hydrogenation and dehydrogenation reaction in steam reforming; in addition, the Co-based Zn-Al composite oxide may form a spinel structure (AB)₂O₄) The catalyst has strong interaction, and is beneficial to improving the thermal stability, sintering resistance and carbon deposition resistance of the reforming catalyst. Therefore, ZnO-Al is selected₂O₃The composite oxide is a carrier, and the catalytic performance of the catalyst can be effectively improved.

For the preparation of the zinc-aluminum composite oxide, a Zn-Al hydrotalcite-like structure precursor can be adopted. The hydrotalcite is also called layered double-hydroxide composite oxide, has the characteristics of large specific surface area, interchangeability of interlayer anions, controllability of composition and structure and the like, can inhibit acidity by modulating components, and can inhibit Zn in the hydrotalcite²⁺The catalyst has higher specific surface area, good thermal stability, richer pore structure and stronger alkalinity, thereby effectively inhibiting the migration, sintering and oxidation of the active component cobalt and being beneficial to the reaction of preparing hydrogen by the autothermal reforming of acetic acid.

The hydrotalcite prepared by the coprecipitation method has complete structure, high crystallinity and good layered structure, and is beneficial to the formation of zinc-aluminum composite oxide. The invention adopts a coprecipitation method to prepare Zn-Al hydrotalcite (Zn)₆Al₂(OH)₁₆CO₃·H₂O) structural precursor, and active component cobalt is introduced, so that the composite oxide catalyst with uniformly distributed components is obtained and is applied to the reaction of preparing hydrogen by the autothermal reforming of acetic acid.

Disclosure of Invention

The invention aims to solve the technical problems that the structure of the existing cobalt-based catalyst is easy to change and the active component cobalt is easy to oxidize and sinter in the process of preparing hydrogen by autothermal reforming so as to cause the inactivation of the catalyst, and provides a novel cobalt-based catalyst which is stable in structure, sintering-resistant, oxidation-resistant and stable in activity.

The technical scheme of the invention is as follows:

using Zn-Al hydrotalcite-like structure as precursor of catalyst, introducing cobalt as active component, roasting to obtain the catalyst containing CoAl₂O₄、ZnAl₂O₄、Co₃O₄And ZnO and other composite oxide catalysts, and the active component Co is highly dispersed in the composite oxide, so that the activity and stability of the reaction for preparing hydrogen by autothermal reforming of acetic acid are improved. The chemical composition of the catalyst of the invention is Co_aZn_bAlO_7.5 ₊ _δWherein a is 0.25-1.00 and b is 0.75-5.00. The catalyst oxide comprises the following components in percentage by weight: 14.0 to 14.4 percent of cobalt oxide, 46.6 to 76.4 percent of zinc oxide and 9.5 to 39.0 percent of aluminum oxide.

The preparation method comprises the following steps:

1) co according to catalyst chemistry_aZn_bAlO_7.5 ₊ _δWherein a is 0.25-1.00, b is 0.75-5.00, and nitrate mixed solution #1 of cobalt, zinc and aluminum is prepared;

2) preparing a mixed solution #2 of sodium carbonate and sodium hydroxide according to a molar ratio of carbonate to hydroxyl of 1:16 and a molar ratio of total charges of metal cations Co, Zn and Al to hydroxyl of 1: 8;

3) the solution #1 and the solution #2 are subjected to coprecipitation reaction at 65-80 ℃, and the pH value is controlled at 10.5 at the rate of dropwise adding the solution+0.5, and keeping constant temperature, stirring and aging for 15-24 hours; after three times of suction filtration and washing, placing the catalyst in a drying oven at 105 ℃, and drying for 12 hours to obtain a catalyst with a hydrotalcite-like structure as a main body, wherein the typical hydrotalcite-like structure is shown as an X-ray diffraction diagram (attached figure 1);

4) heating the precursor obtained in the step 3) to 500-800 ℃ at the speed of 10 ℃ per minute and roasting for 4 hours to obtain the catalyst, wherein the structure of the catalyst is shown as an X-ray diffraction diagram (figure 2);

5) loading the catalyst (50-200 mg) prepared in the step 4) into a fixed bed reactor, and firstly introducing H with the flow rate of 20mL/min₂Reducing for 1 hour at 600-800 ℃ in the atmosphere, and performing activation treatmentThen purging with nitrogen at a flow rate of 30mL/min, and finally introducing vaporized AC/H₂O/O₂/N₂The mixed gas (wherein AC is acetic acid) with the molar ratio of 1.0/(2.5-5.0)/(0.2-0.5)/(2.5-4.5) is reacted through a catalyst bed layer at the reaction temperature of 600 ℃ and 800 ℃.

The invention has the beneficial effects that:

(1) according to the Zn-Co-Al-O catalyst prepared by adopting a coprecipitation method, a Zn-Al hydrotalcite-like structure is taken as a precursor, an active component cobalt is introduced, partial substitution of cobalt for zinc is carried out, and the active component cobalt enters a layered plate structure of the hydrotalcite-like structure, so that the dispersity of the active component of the catalyst is improved, the number of catalytic activity centers on the surface of the catalyst is increased, and the activity of the catalyst is improved; the composite oxide obtained by roasting effectively inhibits the possible migration, aggregation and sintering of the active component cobalt under the high-temperature reaction condition, thereby improving the thermal stability of the catalyst in the autothermal reforming process.

(2) The invention introduces zinc oxide as an alkaline carrier, reduces the acidity of aluminum oxide, effectively inhibits carbon deposition, and increases the reducibility of cobalt due to the existence of zinc, thereby effectively improving the activity and stability of the catalyst.

(3) The results of the autothermal reforming reaction of acetic acid show that the catalyst has the characteristics of stable structure, sintering resistance, carbon deposition resistance, oxidation resistance, stable activity, high hydrogen yield and the like.

Drawings

FIG. 1 is an X-ray diffraction pattern of a precursor of the catalyst of the present invention.

FIG. 2 is an X-ray diffraction pattern of the catalyst of the present invention.

Reference example 1

5.5651 g Co (NO) were weighed out₃)₃.6H₂O, 17.0648 g Zn (NO)₃)₃.6H₂O and 28.6913 g Al (NO)₃)₃.9H₂O, 153 ml of deionized water was added and mixed to form solution # 1. 30.5943 g of sodium hydroxide and 5.06656 g of sodium carbonate were weighed and 813 ml of deionized water was added to form solution # 2. The solutions #1 and #2 were mixed at pH 10.5+0.And (3) carrying out coprecipitation operation in a water bath at 78 ℃ within the range of 5, maintaining the temperature, stirring and aging for 24 hours, filtering and washing the obtained precipitate with deionized water for three times, and drying in an oven at 105 ℃ for 12 hours to obtain the hydrotalcite-like precursor, wherein the typical structure of the hydrotalcite-like precursor is shown in the attached figure 1. The precursor is roasted for 4 hours at 700 ℃ to obtain the catalyst CDUT-ZC1A, and the typical structure of the catalyst is shown in FIG. 2. The result of nitrogen adsorption/desorption experiments shows that the specific surface area of the material is 16.28 m²(ii) in terms of/g. The catalyst comprises the following components in percentage by weight: 14.3 percent of cobalt oxide, 46.7 percent of zinc oxide and 39.0 percent of aluminum oxide.

The activity evaluation of the catalyst for the autothermal reforming reaction of acetic acid was carried out in a continuous flow fixed bed reactor. Grinding and tabletting the catalyst, sieving to 20-40 mesh, loading into a reactor, and feeding at 700 deg.C with 20.0mL/min of H₂And reducing for 1 hour. Injecting the mixed solution of acetic acid and water into a vaporizer by an injection pump, vaporizing, mixing oxygen, and adding nitrogen as an internal standard gas to form AC/H₂O/O₂/N₂The molar ratio of 1.0/(2.5-5.0)/(0.2-0.5)/(2.5-4.5), and introducing the raw material gas into the reaction bed layer under the reaction conditions of normal pressure and space velocity of 11000-^-1h^-1The reaction tail gas was analyzed by gas chromatography equipped with a thermal conductivity detector and a hydrogen flame ionization detector, as well as packed columns (Porapaq-QS and 5A) and capillary columns (Q-Plot).

The catalyst CDUT-ZC1A is examined by the activity of the autothermal reforming reaction of acetic acid, and the reaction temperature is 650 ℃ and AC/H₂O/O₂/N₂The molar ratio of (1.0/4.0/0.28/3.9) and the space velocity of 15000h^-1When the initial acetic acid conversion was about 96.18%, the hydrogen yield was about 2.85 mol-H₂mol-AC, hydrogen yield of about 2.51 mol-H after a 15 hour investigation period₂Permol-AC, the selectivity to by-product methane was 2.39% and the selectivity to acetone was 2.49%. The characterization of XRD, XPS, SEM, TG and the like is carried out on the catalyst after the reaction, and the result shows that the activity of the CDUT-ZC1A catalyst is reduced in the autothermal reforming reaction of acetic acid due to obvious carbon deposit generation and active component cobalt burning in the reaction processAnd (6) knotting.

Reference example 2

5.4622 g Co (NO) were weighed out₃)₃.6H₂O, 27.9172 g Zn (NO)₃)₃.6H₂O and 7.0406 g Al (NO)₃)₃.9H₂O, adding 131 ml of deionized water and mixing to form solution # 1. Solution #2 was formed by weighing 12.012 grams of sodium hydroxide and 1.9893 grams of sodium carbonate, and adding 319 milliliters of deionized water. The solutions #1 and #2 were mixed at pH 10.5+The coprecipitation operation was carried out in a water bath at 78 degrees celsius in the range of 0.5 and was aged for 24 hours with stirring while maintaining this temperature. And filtering and washing the precipitate with deionized water for three times, and drying in an oven at 105 ℃ for 12 hours to obtain the hydrotalcite-like precursor, wherein the typical structure of the hydrotalcite-like precursor is shown in the attached figure 1. The precursor is roasted for 4 hours at 700 ℃ to obtain the catalyst CDUT-ZC6A, and the typical structure of the catalyst is shown in FIG. 2. The result of the nitrogen adsorption/desorption experiment shows that the specific surface area is 11.73 m²(ii) in terms of/g. The catalyst comprises the following components in percentage by weight: 14.0 percent of cobalt oxide, 76.4 percent of zinc oxide and 9.6 percent of aluminum oxide.

The catalyst CDUT-ZC6A is examined by the activity of the autothermal reforming reaction of acetic acid, and the reaction temperature is 650 ℃ and AC/H₂O/O₂/N₂The molar ratio of (1.0/4.0/0.28/3.9) and the space velocity of 15000h^-1At this time, the conversion of acetic acid was initially 99.13% and the hydrogen yield was initially 2.95 mol-H over a 15 hour investigation period₂The mol-AC, due to the sintering of the catalyst, the generation of carbon deposit and the increase of the aggregation of the active components, resulted in a final acetic acid conversion of 94.60% and a hydrogen yield of 2.18 mol-H₂mol-AC; the selectivity of the byproduct methane is increased from 1.03% to 3.29%, the selectivity of acetone is increased from 1.12% to 7.31%, the selectivity of carbon monoxide is reduced from 23.09% to 12.67%, and the selectivity of carbon dioxide is reduced from 70.25% to 39.83%. The characterization of XRD, XPS, SEM, TG and the like is carried out on the catalyst after the reaction, and the result shows that the surface of the CDUT-ZC6A catalyst has obvious carbon deposit generation, and the activity of the catalyst is reduced due to the sintering of an active component cobalt.

Example 1

5.5134 g Co (NO) were weighed out₃)₃.6H₂O, 22.5415 g Zn (NO)₃)₃.6H₂O and 17.7653 g Al (NO)₃)₃.9H₂O, add 142 ml of deionized water and mix to form solution # 1. 21.2162 g of sodium hydroxide and 3.5136 g of sodium carbonate were weighed and 564 ml of deionized water was added to form solution # 2. The solutions #1 and #2 were mixed at pH 10.5+The coprecipitation operation was carried out in a water bath at 78 degrees celsius in the range of 0.5 and was aged for 24 hours with stirring while maintaining this temperature. And filtering and washing the precipitate with deionized water for three times, and drying in an oven at 105 ℃ for 12 hours to obtain the hydrotalcite-like precursor, wherein the typical structure of the hydrotalcite-like precursor is shown in the attached figure 1. The precursor is roasted for 4 hours at 700 ℃ to obtain the catalyst CDUT-ZC2A, and the typical structure of the catalyst is shown in FIG. 2. The result of nitrogen adsorption/desorption experiments shows that the specific surface area of the material is 14.89 m²(ii) in terms of/g. The catalyst comprises the following components in percentage by weight: the cobalt oxide content is 14.2%, the zinc oxide content is 61.7% and the alumina content is 24.1%.

The catalyst CDUT-ZC2A is examined by the activity of the autothermal reforming reaction of acetic acid, and the reaction temperature is 650 ℃ and AC/H₂O/O₂/N₂The molar ratio of (1.0/4.0/0.28/3.9) and the space velocity of 15000h^-1At 15 hours, the acetic acid conversion was 92.56%, and the hydrogen yield was approximately 2.88 mol-H₂Permol-AC, the selectivity to by-product methane was 0.92% and the selectivity to acetone was 1.29%. The selectivity of carbon monoxide is 19.76-20.40%, and the selectivity of carbon dioxide is 55.79-58.19%. The characterization of XRD, XPS, SEM, TG, etc. is carried out to the catalyst after the reaction, and the result shows that: the CDUT-ZC2A catalyst has a relatively stable structure and has no obvious change after reaction.

Example 2

5.4898 g Co (NO) were weighed out₃)₃.6H₂O, 24.9974 g Zn (NO)₃)₃.6H₂O and 12.8658 g Al (NO)₃)₃.9H₂O, add 137 ml of deionized water and mix to form solution # 1. 17.0113 g of sodium hydroxide and 2.8172 g of sodium carbonate were weighed and 452 ml of deionized water was added to form solution # 2. The solutions #1 and #2 were mixed at pH 10.5+In the water bath at 78 deg.C in the range of 0.5The precipitation operation was carried out and the temperature was maintained and aged with stirring for 24 hours. And filtering and washing the precipitate with deionized water for three times, and drying in an oven at 105 ℃ for 12 hours to obtain the hydrotalcite-like precursor, wherein the typical structure of the hydrotalcite-like precursor is shown in the attached figure 1. The precursor is roasted for 4 hours at 700 ℃ to obtain the catalyst CDUT-ZC3A, and the typical structure of the catalyst is shown in FIG. 2. The result of nitrogen adsorption/desorption experiments shows that the specific surface area of the material is 16.35m²(ii) in terms of/g. The catalyst comprises the following components in percentage by weight: the cobalt oxide content is 14.1%, the zinc oxide content is 68.4%, and the aluminum oxide content is 17.5%.

The catalyst CDUT-ZC3A is examined by the activity of the autothermal reforming reaction of acetic acid, and the reaction temperature is 650 ℃ and AC/H₂O/O₂/N₂The molar ratio of (1.0/4.0/0.28/3.9) and the space velocity of 15000h^-1In a 15 hour investigation period, the acetic acid conversion was 98.88% and the hydrogen yield was 2.85 mol-H₂The by-products methane and acetone are effectively inhibited. The characterization of XRD, XPS, SEM, TG, etc. is carried out to the catalyst after the reaction, and the result shows that: the CDUT-ZC3A catalyst has stable structure, stable cobalt valence state as the active component and no obvious carbon deposit.

Example 3

5.4770 g Co (NO) were weighed out₃)₃.6H₂O, 26.3915 g Zn (NO)₃)₃.6H₂O and 10.0846 g Al (NO)₃)₃.9H₂O, 134 ml of deionized water was added and mixed to form solution # 1. 14.6243 g of sodium hydroxide and 2.4219 g of sodium carbonate were weighed and 388 ml of deionized water was added to form solution # 2. The solutions #1 and #2 were mixed at pH 10.5+The coprecipitation operation was carried out in a water bath at 78 degrees celsius in the range of 0.5 and was aged for 24 hours with stirring while maintaining this temperature. And filtering and washing the precipitate with deionized water for three times, and drying in an oven at 105 ℃ for 12 hours to obtain the hydrotalcite-like precursor, wherein the typical structure of the hydrotalcite-like precursor is shown in the attached figure 1. The precursor is roasted for 4 hours at 700 ℃ to obtain the catalyst CDUT-ZC4A, and the typical structure of the catalyst is shown in FIG. 2. The result of nitrogen adsorption/desorption experiments shows that the specific surface area of the material is 11.24m²(ii) in terms of/g. The catalyst comprises the following components in percentage by weight: the cobalt oxide content is 14.1%, and the oxidation is carried outThe zinc content was 72.2% and the alumina content was 13.7%.

The catalyst CDUT-ZC4A is examined by the activity of the autothermal reforming reaction of acetic acid, and the reaction temperature is 650 ℃ and AC/H₂O/O₂/N₂The molar ratio of (1.0/4.0/0.28/3.9) and the space velocity of 15000h^-1At 15 hours, the acetic acid conversion was 100% and the hydrogen yield was about 3.01 mol-H₂The selectivity of the byproduct methane is close to 0%, the acetone is lower than the detection limit, the selectivity of the carbon monoxide is stabilized at 26.19%, and the selectivity of the carbon dioxide is stabilized at 69.67%; the characterization of XRD, XPS, SEM, TG and the like is carried out on the catalyst after the reaction, and the result shows that the CDUT-ZC4A catalyst has high stability and activity, and has stronger oxidation resistance and carbon deposition resistance in the process of preparing hydrogen by heating and reforming acetic acid due to the stable crystal structure and electronic performance of the catalyst.

The test result shows that the catalyst has the characteristics of sintering resistance, carbon deposition resistance, oxidation resistance, high acetic acid conversion rate, stable activity, high hydrogen yield and the like.

Claims

The application of the cobalt-based catalyst derived from Zn-Al hydrotalcite in the autothermal reforming of acetic acid to prepare hydrogen is characterized in that: taking 50-200mg of catalyst, and introducing H with the flow rate of 20mL/min₂Reducing at the temperature of 600-; the catalyst is prepared by the following method: preparing a mixed solution #1 of cobalt nitrate, zinc nitrate and aluminum nitrate; preparing a mixed solution #2 of sodium carbonate and sodium hydroxide according to the molar ratio of the total charge of metal cations cobalt, zinc and aluminum to hydroxyl being 1:8 and the molar ratio of carbonate to hydroxyl being 1:16, carrying out coprecipitation reaction on the solution #1 and the solution #2 at 65-80 ℃, controlling the pH value of the reaction solution within the range of 10.5 +/-0.5, and maintaining water bath, stirring and aging for 15-24 hours; carrying out suction filtration and washing for three times, placing the mixture in a drying oven at 105 ℃, and drying for 12 hours to obtain a Zn-Al hydrotalcite precursor sample; baking at 800 ℃ under 500-Firing for 4 hours to obtain the product containing CoAl₂O₄、ZnAl₂O₄、Co₃O₄And ZnO, the active component Co is highly dispersed in the composite oxide, and the chemical component is Co_aZn_bAlO_7.5±δWherein a is 0.25-1.00 and b is 0.75-5.00; the composite material comprises the following oxides in percentage by weight: 14.0 to 14.3 percent of cobalt oxide, 46.6 to 76.4 percent of zinc oxide and 9.5 to 39.0 percent of aluminum oxide, wherein the sum of the weight percentages of the components is 100 percent.
2. The use of a Zn-Al hydrotalcite-derived cobalt-based catalyst according to claim 1 in autothermal reforming of acetic acid to produce hydrogen, characterized in that: the catalyst comprises the following components in percentage by weight: 14.2% of cobalt oxide, 61.7% of zinc oxide and 24.1% of aluminum oxide.
3. The use of a Zn-Al hydrotalcite-derived cobalt-based catalyst according to claim 1 in autothermal reforming of acetic acid to produce hydrogen, characterized in that: the catalyst comprises the following components in percentage by weight: 14.1% of cobalt oxide, 68.4% of zinc oxide and 17.5% of aluminum oxide.
4. The use of a Zn-Al hydrotalcite-derived cobalt-based catalyst according to claim 1 in autothermal reforming of acetic acid to produce hydrogen, characterized in that: the catalyst comprises the following components in percentage by weight: 14.1% of cobalt oxide, 72.2% of zinc oxide and 13.7% of aluminum oxide.