CN112844397A

CN112844397A - Cerium-samarium solid solution nickel-based catalyst for autothermal reforming of acetic acid to produce hydrogen

Info

Publication number: CN112844397A
Application number: CN202110085626.7A
Authority: CN
Inventors: 黄利宏; 丁晨宇; 胡晓敏; 陈慧
Original assignee: Chengdu Univeristy of Technology
Current assignee: Chengdu Univeristy of Technology
Priority date: 2021-01-22
Filing date: 2021-01-22
Publication date: 2021-05-28
Anticipated expiration: 2041-01-22
Also published as: CN112844397B

Abstract

The invention relates to a nickel-based mesoporous composite oxide solid solution catalyst for autothermal reforming of acetic acid to produce hydrogen. Aiming at the problems of carbon deposition, sintering and the like of the existing catalyst, the invention adopts a sol-gel method to prepare the mesoporous composite oxide solid solution Ni/Sm-Ce-O_xCatalyst, molar composition is (NiO)_a(SmO_1.5)_b(CeO₂)_cWherein a is 0.13-0.17, b is 0.38-0.50, and c is 0.01-0.12; Sm-Ce-O formation in catalysts_xThe composite oxide solid solution utilizes the synergistic effect of Ce-Sm, induces the absorption and conversion of acetic acid through the interaction of an active component Ni and a solid solution carrier, strengthens the activation effect on the acetic acid and water, and has the characteristics of carbon deposition resistance, sintering resistance, stable structure and the like in the autothermal reforming process of the acetic acid.

Description

Cerium-samarium solid solution nickel-based catalyst for autothermal reforming of acetic acid to produce hydrogen

Technical Field

The invention relates to a cerium-samarium solid solution nickel-based catalyst for preparing hydrogen by autothermal reforming of acetic acid, belonging to the field of hydrogen preparation by autothermal reforming of acetic acid.

Background

The hydrogen is used as an environment-friendly clean energy source, and has good application prospect in the fields of traffic, power generation, aerospace and the like. In the current hydrogen production process route, about 80% to 85% of hydrogen is produced from fossil fuels such as natural gas through a reforming process. In order to achieve the purposes of energy conservation and emission reduction, renewable biomass resources are used to obtain biomass oil through a fast pyrolysis process, and acetic acid with the water phase component accounting for 30 percent is used as a raw material to prepare hydrogen, so that the method is an attractive hydrogen preparation process with a renewable approach.

The acetic acid steam reforming is a common hydrogen production mode, and high hydrogen yield can be obtained because the reactant steam can participate in the reaction; however, the process is endothermic and requires constant supply of heat from the outside to maintain the reaction. Partial oxidation reforming is another way, oxygen or air is introduced into raw materials, and reactant acetic acid and the oxygen or the air generate partial oxidation reaction to release heat to maintain the reaction; in this process, acetic acid tends to be deeply oxidized into carbon dioxide and water, resulting in a decrease in hydrogen yield.

Compared with the two reforming hydrogen production modes, the autothermal reforming combines the endothermic steam reforming process and the exothermic partial oxidation reaction process, and the heat balance of the whole reaction, namely CH, can be realized by adjusting the oxygen-carbon ratio to change the reaction degree of the partial oxidation reforming₃COOH+xO₂+yH₂O→aCO+bCO₂+cH₂(Δ H ═ 0kJ/mol), while maintaining a high hydrogen yield, the dependence on external heat sources is significantly reduced, and there is a significant advantage in terms of hydrogen production processes.

The production of hydrogen from an autothermal catalytic reforming process is particularly important to the choice of catalyst. Traditional noble metal catalysts such as platinum, palladium, rhodium, ruthenium, etc. have high catalytic activity, but their wide application is limited by high price. Among non-noble metal catalysts, the nickel-based catalyst has stronger capability of activating C-C bonds and C-H bonds, and has better application prospect. However, in the autothermal reforming of acetic acid, the acetic acid may be subjected to dehydrogenation, dehydroxylation, etc. (CH)₃COOH→CH₃COO*→CH₃CO*/CH₃COOH→CH₃CO) and ketonization (CH)₃CO*+CH₃*→CH₃COCH₃) This generates a large amount of CH₃CO*、CH_xAnd C, and the like, and the intermediate species are subjected to condensation polymerization to form carbon deposit, and the carbon deposit is accumulated on the surface of the active metal nickel crystal to cause the deactivation of the nickel-based catalyst. At the same time, in the autothermal reforming process, fromWhen oxygen is mainly consumed at the front end of the fixed bed reactor, local high temperature of the front end can be generated and can reach 1000 ℃, so that the nickel-based catalyst is subjected to aggregation sintering deactivation; the oxidative atmosphere of the autothermal reforming process also initiates oxidative deactivation of the active component nickel.

In order to solve the problems in the autothermal reforming process of acetic acid, the invention introduces Sm-Ce-O into the nickel-based catalyst_xA solid solution composite oxide. In the composite oxide, oxide CeO₂Has typical fluorite structure, good thermal stability and Ce³⁺And Ce⁴⁺Has excellent oxygen storage and oxygen migration capacity, forms oxygen vacancy through oxygen species migration in crystal lattices, and is beneficial to the transfer and transfer of active O. By this route, the catalyst can promote carbon oxidation (CH) by oxygen migration from the crystal lattice for acetic acid derived carbon-containing species₃*→C*+O*→CO*+O*→CO/CO₂) The carbon deposit is gasified, so that the carbon deposit on the surface of the catalyst is inhibited, and the carbon deposit resistance of the catalyst in the self-heating reforming process of acetic acid is improved. At the same time, CeO₂The Ce-Ni composite material has a discrete molecular orbit, can generate a coupling effect with an electronic state on the surface of a loaded active metal to generate a charge transfer or polarization effect, shows an electron donating effect of low-electronegativity Ce on high-electronegativity Ni to form a strong interaction between Ce and Ni, and can improve the oxidation resistance and stability of active component nickel particles and inhibit oxidation and sintering.

However, the oxygen storage and oxygen transfer characteristics of ceria are not satisfactory for use in autothermal reforming of acetic acid. Because ceria consists of eight oxy cations coordinated at the cube corners, each anion is tetrahedrally coordinated by four cations, which makes the structure of ceria more stable and to some extent suppresses Ce⁴⁺To Ce³⁺Thereby inhibiting the oxygen transport capacity, resulting in inefficient transfer of the actual O species and reduced capacity to mitigate carbon deposition by carbon oxidation reactions.

Thus, the characteristics and CeO for autothermal reforming of acetic acid₂The invention creatively introduces Sm₂O₃And construct Sm-Ce-O_xA solid solution composite oxide. The solid solution has good thermal stability, and more importantly, Sm-Ce-O in the structure of the solid solution_xThe crystal lattice distortion of the composite oxide forms a large number of crystal plane defects, and more oxygen vacancies (Ce) are formed on the surface of the composite oxide carrier⁴⁺-Ov-Sm³⁺) Thereby effectively promoting the conversion of acetic acid molecules into CH in the process of autothermal reforming of acetic acid_3-xBy oxidative gasification of intermediate species such as CO, etc., to form CO/CO₂And the like. Meanwhile, Sm is added to form Sm₂O₃-Sm₂O₃CO₃Catalytic cycle (Sm)₂O₃+CO₂→Sm₂O₃CO₃，Sm₂O₃CO₃+C*→Sm₂O₃+2 CO), while being able to convert C species more efficiently, CO₂The adsorption activation also promotes gasification of the carbonaceous material during autothermal reforming of acetic acid, thereby inhibiting the formation of carbon. In addition, Sm-Ce-O is used in autothermal acetic acid reforming_xSm in solid solution₂O₃The species efficiently activates water molecules in the feed, facilitating the Water Gas Shift Reaction (WGSR) to proceed in the forward direction (H)₂O+CO→H₂+CO₂) The yield of the hydrogen is effectively improved. In addition, CO and CO are generated in the process of autothermal reforming of acetic acid₂Methanation, and the preceding small molecule CH₃The intermediate product combines with H generated by dehydrogenation of macromolecule to generate by-product CH₄In the presence of Sm-Ce-O_xBasic Sm in solid solution₂O₃Species activate methane by adsorption to form ═ CH_xMethyl free radical of (A), effectively increasing CH_xActivity of cracking and conversion to CO/CO promoted by the active metal Ni₂Thereby promoting the methane reforming reaction (CH)₄+H₂O→3H₂+ CO) is carried out in the forward direction, increasing the yield of hydrogen.

Therefore, the cerium-samarium solid solution nickel-based catalyst provided by the invention utilizes the synergistic effect of Ce-Sm, effectively improves the oxygen storage and oxygen transfer performance and the electron transfer capacity, and has a large amount of forms in the catalystThe oxygen vacancy is capable of effectively inducing H in the reactant of the autothermal reforming of acetic acid₂O and O₂The adsorption activation of (3); simultaneously Sm in the catalyst³⁺And Ce⁴⁺The reaction forms Lewis alkali site, further increases the integral alkalinity of the catalyst, inhibits the ketonization of acetic acid and enhances the reaction of CO₂The adsorption and activation function of the catalyst can promote the gasification of carbon-containing products so as to reduce carbon deposition; the cerium-samarium solid solution nickel-based catalyst has the advantages of high catalytic activity on H₂Activation of O can also promote the water gas reaction to increase hydrogen yield. These physicochemical properties effectively improve the autothermal reforming reaction of acetic acid on H₂Has good thermal stability and is excellent in the autothermal reforming reaction of acetic acid.

Therefore, the catalyst of the invention is innovative in components and structure, and the carbon deposit resistance, sintering resistance and thermal stability of the catalyst in the autothermal reforming reaction of acetic acid are improved. The activity test result of the catalyst applied to the autothermal reforming reaction of acetic acid also shows that the catalyst has excellent activity, selectivity and stability.

Disclosure of Invention

The invention aims to solve the technical problems of low activity, poor stability, serious carbon deposition and sintering intolerance of the existing catalyst in the autothermal reforming reaction of acetic acid, so as to cause the inactivation of the catalyst, and provides a novel catalyst which has stable activity, carbon deposition resistance, sintering resistance and stable structure. The invention takes nickel as an active component, introduces Ce and Sm components, and adopts a sol-gel method to create the nickel-based mesoporous composite oxide solid solution Ni/Sm-Ce-O_xA catalyst; the catalyst is used in the reaction of autothermal reforming of acetic acid to prepare hydrogen, the conversion rate of acetic acid is close to 100 percent under the condition that the reaction temperature is 650 ℃, and the hydrogen yield can be stabilized at 2.61mol-H₂mol-HAc. The results of activity test and phase analysis and the like carried out on the catalyst prove that the catalyst has the advantages of carbon deposition resistance, sintering resistance, stable structure and activity.

The technical scheme of the invention is as follows:

the invention aims at the characteristic of autothermal reforming of acetic acid and prepares Ni/Sm-Ce-O by a sol-gel method_xSolid solution of mesoporous composite oxideA bulk catalyst. The chemical composition of the catalyst of the invention is (NiO)_a(SmO_1.5)_b(CeO₂)_cWherein a is 0.13-0.17, b is 0.38-0.50, and c is 0.01-0.12; comprises the following components in percentage by weight: 10.0 to 13.0 percent of nickel oxide, 66.8 to 87.8 percent of samarium oxide and 1.9 to 20.9 percent of cerium oxide; wherein the preferred weight percentages of the typical catalyst CDUT-NSC10 are: 12.1 percent of nickel oxide, 77.5 percent of samarium oxide and 10.4 percent of cerium oxide.

The specific preparation method comprises the following steps:

1) according to the proportion of each component (NiO) in the catalyst_a(SmO_1.5)_b(CeO₂)_cWherein a is 0.13-0.17, b is 0.38-0.50, c is 0.01-0.12, nickel nitrate, samarium nitrate and cerous nitrate are dissolved in deionized water to prepare a mixed solution # 1;

2) preparing a mixed solution #2 of citric acid and ethylene glycol according to the total molar ratio of the citric acid to the ethylene glycol to the metal nitrate of 1:1: 1; mixing the solution #1 and the solution #2, keeping the water bath heating at 60 ℃, continuing stirring until gel appears, moving the gel into an oven, and foaming and expanding the sample at the temperature of 105 ℃ for 12 hours;

3) crushing the sample obtained in the step 2), putting the crushed sample into a tubular furnace for roasting, raising the temperature from room temperature to 600-800 ℃ at the heating rate of 10 ℃/min, and keeping the roasting for 4 hours to obtain the Ni/Sm-Ce-O-based catalyst of the invention_xThe typical crystal structure of the composite oxide solid solution catalyst is shown as an XRD (X-ray diffraction) pattern of figure 1 and is represented as a main component Sm₂O₃Doped CeO₂Phase, formation of Ce species intercalated Sm₂O₃Composite oxide solid solution Sm-Ce-O with structure_xAnd the NiO phase is weak, which indicates that Ni is highly dispersed and embedded into a solid solution Sm-Ce-O_xThe crystal structure of (a); the typical BJH pore size distribution is shown in figure 2, and Sm-Ce-O with a mesoporous structure is formed_xA solid solution;

4) the catalyst is used at the temperature of 600-800 ℃ and the flow rate of H of 30mL/min₂Reducing the mixture for 1h, then blowing the mixture with nitrogen, passing the mixture gas with the molar ratio of acetic acid/water/oxygen being 1/(1.3-5.0)/(0.21-0.35) through a catalyst bed layerThe autothermal reforming reaction is carried out at the reaction temperature of 500-800 ℃, the normal pressure and the space velocity of 20000-60000mL/(g-catalyst h).

The invention has the beneficial effects that:

1) the invention prepares Sm-Ce-O by taking Ni as an active component and introducing Sm and Ce components through a sol-gel method_xThe composite oxide solid solution nickel-based catalyst has the advantages that in the solid solution, the Ce-Sm doping causes lattice defects to form more oxygen vacancies on the surface of a carrier, and the oxygen vacancies are generated to H₂O、O₂The oxygen-containing species have excellent adsorption and activation capabilities, and can be converted into O species, and the O species promote the gasification of intermediate products such as carbon deposition precursors C and CO, so that carbon deposition is reduced.

2) Sm-Ce-O constructed by the catalyst of the invention_xIn the solid solution, Ce has an electron-donating effect on Ni with high electronegativity, so that the Ni and the loaded metal Ni have strong interaction, the stability of the nano nickel particles is improved, and the sintering of the nano nickel particles due to agglomeration is prevented.

3) Sm-Ce-O constructed by the catalyst of the invention_xSolid solution, existing stable Sm³⁺Cation, obviously improves the alkalinity of the whole catalyst, and can effectively inhibit CH_xAnd CH₃Acetone (CH) formed by CO bonding₃CO*+CH₃*→CH₃COCH₃) Promoting the reaction pathway to CH₃CO*→CH₃Transfer of + CO, promoting subsequent gasification to CO/CO₂The reduction of the reactivity caused by carbon deposition is reduced; at the same time, Sm-Ce-O_xThe solid solution effectively activates acetyl and methyl free radicals generated after acetic acid dehydrogenation and O, inhibits acetone generation and promotes CH_xConverting with small molecules such as CO;

4) Sm-Ce-O constructed by the catalyst of the invention_xSolid solution of Sm having high dispersibility and good stability³⁺Species, capable of efficiently passing Sm₂O₃Adsorption of CO₂Form Sm₂O₃CO₃And combining the C species to generate CO to form a catalytic cycle, effectively converting the C species serving as the carbon deposition precursor, and reacting the CO₂The adsorption activation also promotes the carbon-containing substance in the autothermal reforming process of acetic acidGasifying; at the same time Sm³⁺The species effectively promote and activate water molecules, further promote the water-gas shift reaction activity and improve the hydrogen yield.

5) The catalyst of the invention synthesizes Ni/Sm-Ce-O by a sol-gel method_xThe XRD patterns of the composite oxide solid solution catalyst are shown as figures 1, 3 and 4, and Sm is shown after roasting, reduction and reaction₂O₃Ce is embedded into Sm as main phase₂O₃A stable solid solution structure is formed in the structure, and Ni enters Sm-Ce-O_xThe stability of the crystal lattice of the solid solution is improved; as shown in the attached figure 2, the BJH pore size distribution diagram forms a mesoporous structure, the overall specific surface area of the catalyst is increased, and the porous structure and the pore passages with developed internal openings are suitable for the transmission and diffusion of reactant and product molecules, so that the thermal stability of the catalyst is improved.

6) The Ni/Sm-Ce-O formed after the roasting of the invention_xThe composite oxide solid solution catalyst utilizes the synergistic effect of Ce-Sm to promote the active component nickel, can induce acetic acid to carry out efficient adsorption conversion in the acetic acid conversion process, and effectively inhibits ketonization reaction, thereby inhibiting the generation of byproducts such as acetone, ketene and methane, and the like, and has the characteristics of carbon deposition resistance, sintering resistance, stable activity, high hydrogen yield and the like.

Drawings

FIG. 1: x-ray diffraction spectrum of calcined catalyst

FIG. 2: BJH pore size distribution diagram of catalyst of the invention

FIG. 3: x-ray diffraction spectrum of reduced catalyst

FIG. 4: x-ray diffraction spectrum of catalyst after reaction

Detailed Description

Reference example 1

Weighing 1.889gNi (NO)₃)₂·6H₂O、0.195gCe(NO₃)₂·6H₂O and 8.763gSm (NO)₃)₃·9H₂O, adding 27mL of deionized water to prepare a solution # 1; weighing 5.602gC₆H₈O₇·H₂O and 1.655g (CH)₂OH)₂Adding 113ml of deionized water to prepare a solution # 2; mixing the solutions #1 and #2, and continuously stirring the mixture at the constant-temperature water bath of 60 ℃ until green gel is formed; then drying the gel in a drying oven at 105 ℃ for 12 hours; after crushing the dried and foamed sample, raising the temperature from room temperature to 650 ℃ at the heating rate of 10 ℃/min, and roasting for 4h to obtain the CDUT-NSC2 catalyst. The molar composition of the catalyst is (NiO)_0.16(SmO_1.5)_0.49(CeO₂)_0.01The composite material comprises the following components in percentage by weight calculated on oxides: 12.1 percent of nickel oxide, 85.9 percent of samarium oxide and 2.0 percent of cerium oxide.

The activity evaluation of the autothermal reforming reaction of acetic acid was carried out in a continuous flow fixed bed reactor. Grinding and tabletting the catalyst, sieving into 20-40 mesh granules, placing into a reaction tube, and feeding into a reaction tube at 600-800 deg.C and with a flow rate of 30mL/min H₂Reducing for 1h in the flow, injecting the mixed solution of acetic acid and water into a vaporizer by a constant flow pump for vaporization, mixing oxygen, and taking nitrogen as internal standard gas to form a molar composition of CH₃COOH/H₂O/O₂The reaction raw material gas is 1/(1.3-5.0)/(0.21-0.35), the raw material gas is introduced into a reaction bed layer to carry out the autothermal reforming reaction of acetic acid, the reaction conditions are 500-.

The CDUT-NSC2 catalyst is subjected to activity investigation through an autothermal reforming reaction of acetic acid, and has the reaction conditions of normal pressure, space velocity of 50000 mL/(g-catalyst.h), reaction temperature of 650 ℃ and feeding ratio of CH₃COOH/H₂O/O₂When the reaction time is 10H and is 1/4.0/0.28, the acetic acid conversion rate of the catalyst is about 96.2 percent, and the hydrogen yield reaches 2mol-H₂/mol-HAc，CO₂The selectivity is about 59.5 percent, the CO selectivity is about 38.5 percent, and CH₄The selectivity is between 0.5% and 1.5%, and the selectivity of the byproduct acetone is about 0.2%.

Example one

Weighing 1.880gNi (NO)₃)₂·6H₂O、1.053gCe(NO₃)₂·6H₂O and 7.902gSm (NO)₃)₃·9H₂O, adding 27mL of deionized water to prepare a solution # 1; weighing 5.604gC₆H₈O₇·H₂O and 1.655g (CH)₂OH)₂Adding 113ml of deionized water to prepare a solution # 2; the subsequent steps are the same as the reference example 1, and the Ce species embedded main body Sm is obtained after roasting for 4 hours at 650 DEG C₂O₃Mesoporous composite oxide solid solution Ni/Sm-Ce-O with structure_xThe catalyst, namely CDUT-NSC10 catalyst, has a typical structure as shown in figure 1, and has a typical pore size distribution of a mesoporous structure as shown in figure 2; the molar composition of the catalyst is (NiO)_0.16(SmO_1.5)_0.44(CeO₂)_0.06The composite material comprises the following components in percentage by weight calculated on oxides: 12.1 percent of nickel oxide, 77.5 percent of samarium oxide and 10.4 percent of cerium oxide.

The CDUT-NSC10 catalyst is subjected to activity investigation through an autothermal reforming reaction of acetic acid, and has the reaction conditions of normal pressure, space velocity of 50000 mL/(g-catalyst.h), reaction temperature of 650 ℃ and feeding ratio of CH₃COOH/H₂O/O₂When the reaction time is 10H and is 1/4.0/0.28, the acetic acid conversion rate of the catalyst is stabilized to be about 99.4 percent, and the hydrogen yield is 2.61mol-H₂/mol-HAc，CO₂The selectivity is about 60 percent, the CO selectivity is about 39.5 percent, and CH₄The selectivity approaches to 0, and the selectivity of the byproduct acetone is only about 0.02%. The catalyst activity remained stable as the reaction proceeded. The NSC10 catalyst was characterized by low temperature nitrogen adsorption as shown in FIG. 2, with the results: the specific surface area is 7.83m²Pore volume of 0.044 cm/g³(ii)/g, average pore diameter 9.3 nm. The catalyst after reaction is characterized, as shown in XRD spectrogram of the catalyst after reduction in figure 3 and reaction in figure 4, the catalyst also keeps stable formation of Ce species embedded in Sm after reduction₂O₃Composite oxide Sm-Ce-O formed by structure_xThe existence of solid solution structure, weak phase Ni also indicates the high dispersion of the active component nickel and enters Sm-Ce-O_xSolid solution structure, no coalescence, no carbon deposition species found; the reacted catalyst also shows stable Ni/Sm-Ce-O_xComposite oxidationSolid solution structure. The results show that the catalyst of the invention has the advantages of carbon deposition resistance, sintering resistance, high hydrogen yield, stable structure and the like in the autothermal reforming reaction of acetic acid.

Example two

Weighing 1.891gNi (NO)₃)₂·6H₂O、2.061gCe(NO₃)₂·6H₂O and 6.876gSm (NO)₃)₃·9H₂O, adding 27ml of deionized water to prepare a solution # 1; weighing 5.615gC₆H₈O₇·H₂O and 1.659g (CH)₂OH)₂Adding 114ml of deionized water to prepare a solution # 2; the subsequent steps are the same as the reference example 1, and the Ni/Sm-Ce-O is obtained after roasting for 4 hours at the temperature of 650 DEG C_xA composite oxide solid solution catalyst, namely CDUT-NSC20 catalyst, the typical structure of which is shown in figure 1; the catalyst is a mesoporous material, and the typical pore size distribution of the catalyst is shown in figure 2; the molar composition of the catalyst is (NiO)_0.16(SmO_1.5)_0.38(CeO₂)_0.12The composite material comprises the following components in percentage by weight calculated on oxides: 12.1 percent of nickel oxide, 67.5 percent of samarium oxide and 20.4 percent of cerium oxide.

The CDUT-NSC20 catalyst is subjected to activity investigation through an autothermal reforming reaction of acetic acid, and has the reaction conditions of normal pressure, space velocity of 50000 mL/(g-catalyst.h), reaction temperature of 650 ℃ and feeding ratio of CH₃COOH/H₂O/O₂When the reaction time is 10H and is 1/4.0/0.28, the acetic acid conversion rate of the catalyst can reach about 99.7 percent, and the hydrogen yield is 2.59mol-H₂/mol-HAc，CO₂The selectivity is about 59 percent, the CO selectivity is about 40 percent, and CH₄The selectivity to acetone is close to 0. The overall activity of the catalyst is stable during the test. BET characterization of the CDUT-NSC10 catalyst resulted in: the specific surface area is 2.74m²Per g, pore volume of 0.016cm³(ii)/g, average pore diameter is 10.9 nm.

As can be seen from the activity test results, the catalyst of the invention has the acetic acid conversion rate approaching 100% in the autothermal reforming reaction of acetic acid, and the hydrogen yield of the catalyst reaches 2.61mol-H₂mol-HAc and remains stableDetermining; the active component Ni of the catalyst can be effectively dispersed in the samarium cerium solid solution by combining the characteristics of XRD, BET and the like, and the catalyst has the characteristics of stable valence state, carbon deposition resistance, sintering resistance and the like.

Claims

1. The application of the cerium samarium solid solution nickel-based catalyst in the process of autothermal reforming of acetic acid to prepare hydrogen is characterized in that: 0.1-0.2g of catalyst in H₂After reduction for 1h at 600 ℃ and 800 ℃, introducing CH with the molar ratio₃COOH/H₂O/O₂1/(1.3-5.0)/(0.21-0.35) of mixed gas, and carrying out the autothermal reforming reaction of acetic acid through a catalyst bed layer at the reaction temperature of 500-; the catalyst is prepared by the following method: preparing a mixed solution #1 of nickel nitrate, samarium nitrate and cerium nitrate; preparing a mixed solution #2 of citric acid and ethylene glycol according to the total molar ratio of the citric acid to the ethylene glycol to the metal nitrate of 1:1: 1; mixing the solutions #1 and #2, continuously stirring at a constant temperature of 60 ℃ in a water bath to form gel, drying at 105 ℃ for 12 hours, and then roasting at 600-800 ℃ for 4 hours to obtain the main component Sm₂O₃Doped CeO₂Phase of Ni/Sm-Ce-O with mesoporous structure_xThe composite oxide solid solution catalyst comprises the components with the molar ratio of (NiO)_a(SmO_1.5)_b(CeO₂)_cWherein a is 0.13-0.17, b is 0.38-0.50, and c is 0.01-0.12; the weight percentage composition calculated by oxide is as follows: nickel oxide (NiO) 10.0-13.0 wt%, and samarium oxide (Sm)₂O₃) 66.8 to 87.8 percent of cerium oxide (CeO)₂) 1.9 to 20.9 percent.

2. The application of the samarium cerium solid solution nickel-based catalyst in the autothermal reforming of acetic acid to produce hydrogen according to claim 1, wherein the samarium cerium solid solution nickel-based catalyst comprises the following components in percentage by weight: the catalyst comprises the following components in percentage by weight: 12.1 percent of nickel oxide, 85.9 percent of samarium oxide and 2.0 percent of cerium oxide.

3. The application of the samarium cerium solid solution nickel-based catalyst in the autothermal reforming of acetic acid to produce hydrogen according to claim 1, wherein the samarium cerium solid solution nickel-based catalyst comprises the following components in percentage by weight: the catalyst comprises the following components in percentage by weight: 12.1 percent of nickel oxide, 77.5 percent of samarium oxide and 10.4 percent of cerium oxide.

4. The application of the samarium cerium solid solution nickel-based catalyst in the autothermal reforming of acetic acid to produce hydrogen according to claim 1, wherein the samarium cerium solid solution nickel-based catalyst comprises the following components in percentage by weight: the catalyst comprises the following components in percentage by weight: 12.1 percent of nickel oxide, 67.5 percent of samarium oxide and 20.4 percent of cerium oxide.