A scheelite type nickel-based catalyst for hydrogen production by autothermal reforming of acetic acid

Abstract

The present application relates to a kind of scheelite type nickel-based catalyst for hydrogen production by self-thermal reforming of acetic acid.The present application is directed to the problem of oxidation, sintering, carbon deposition of existing catalysts in the process of self-thermal reforming of acetic acid, and a scheelite type Ni-based catalyst with BaWO4 as the main body and containing NiWO4 component is prepared by coprecipitation method, which limits the aggregation of active components and the growth of crystal grains, significantly improves the sintering resistance, carbon deposition resistance and hydrogen production rate of the catalyst. The catalyst of the present application has the following composition by weight percentage of oxides: 12.5%-18.3% nickel oxide, 69.0%-83.5% barium oxide, and 2.1%-15.3% tungsten trioxide, and the sum of the weight percentages of each component is 100%.

Description

TECHNICAL FIELD

[0001] The present application relates to a scheelite type nickel-based catalyst for hydrogen production by self-thermal reforming of acetic acid and a preparation method thereof, and belongs to the technical field of hydrogen production by self-thermal reforming of acetic acid. BACKGROUND

[0002] Hydrogen is a clean energy carrier, and is currently mainly derived from the conversion of fossil fuels such as natural gas and coal. In order to reduce the consumption of fossil fuels, biomass hydrogen production is one of the alternative hydrogen production methods. Biomass is pyrolyzed at high temperature to form liquid bio-oil, and bio-oil is a complex mixture. In the aqueous component of bio-oil, the content of acetic acid accounts for one-third. Therefore, biomass-derived acetic acid can be used as a cheap raw material for large-scale hydrogen production, and is a feasible way for biomass indirect conversion to hydrogen.

[0003] Acetic acid is usually used to produce hydrogen through a reforming process, which mainly includes three ways: steam reforming, partial oxidation reforming, and self-thermal reforming. Steam reforming needs to absorb heat from the outside during the reaction process; partial oxidation reforming is an exothermic process, but the hydrogen yield is relatively low. Self-thermal reforming combines the advantages of steam reforming and partial oxidation reforming, and adjusts the ratio of oxygen and steam in the feed to achieve heat balance during the reaction process, and the hydrogen yield is relatively high.

[0004] In the process of hydrogen production by self-thermal reforming of acetic acid, the selection of catalyst is particularly important. At present, the catalysts for self-thermal reforming mainly include noble metal catalysts and non-metal catalysts. Among them, nickel catalyst, as a non-noble metal, has high ability to activate carbon-carbon bonds and carbon-hydrogen bonds in acetic acid molecules; therefore, nickel is often used as an active component supported on a carrier for self-thermal reforming of acetic acid.

[0005] In the hydrogen production reaction by self-thermal reforming of acetic acid, the Ni-based catalyst promotes the conversion of acetic acid molecules, and the acetic acid is converted into intermediates such as CH3COO*, CH3CO*, CH3* and CO* after conversion, and further dehydrogenation reaction produces H2, CO, CO2, C2H4, CH2CO and other products; among them, CO and CO2 further undergo methanation reaction, and C2H4 and CH2CO undergo polycondensation reaction to form coke, and CH* continuously dehydrogenates at high temperature to generate more C*, which is easy to form coke and cover the active sites of the nickel-based catalyst, reducing the reaction activity. In addition, oxygen is introduced in the self-thermal reforming reaction, and oxidation reaction occurs at the front end of the catalyst bed, so that the active component at the front end is oxidized; at the same time, due to the local temperature of the bed being as high as 1000℃ or more, the nickel-based catalyst is easy to sinter and deactivate.

[0006] The present application is directed to the problems of oxidation, sintering and carbon deposition in the process of hydrogen production by autothermal reforming of acetic acid, and a scheelite type Ni-based catalyst with BaWO4 as the main component and containing NiWO4 component is constructed by co-precipitation method. In the catalyst, the combination of active component Ni and BaWO4 crystal exposes more active sites on the surface, promotes the deep breaking of C-C bond, C-H bond and C-O bond of CH3CO* to form CHx*(x=0-3), and the catalyst takes BaWO4 as the carrier, due to the difference of O-W-O bond angle, the [WO4] tetrahedral structure is distorted and deformed, so that oxygen vacancy appears in the BaWO4 crystal; the existence of oxygen vacancy is beneficial to the adsorption and dissociation of active reactants H2O and O2 to form OH* and O* free radicals, promotes the dehydrogenation reaction of CH x *(x=0-3) species to form C* species, and the combination of C* and O* forms CO and CO2, thereby inhibiting the accumulation of C* species on the catalyst surface to form carbon deposition, and improving the carbon deposition resistance of the nickel-based catalyst. In addition, the formed NiWO4 species contains Ni 2+ and W 6+ species under high temperature reaction, the W 6+ species combines with free Ba 2+ ions to form BaWO4, and Ni 2+ further reacts in the hydrogen atmosphere to form Ni 0 element, and the obtained nickel element is uniformly distributed in the BaWO4 carrier to form Ni-Ba-W-O active center, avoiding the aggregation of active components and improving the sintering resistance of the catalyst.

[0007] The construction of BaWO4 / NiWO4 composite oxides in the present application provides a highly stable structure, not only enhances the stability of the catalyst, but also maintains high activity of the catalyst and improves the hydrogen production rate; at the same time, it provides a stable reaction interface for the autothermal reforming of acetic acid, thereby promoting the adsorption of reactant molecules on the catalyst surface and accelerating the reaction.

[0008] The precursor is obtained by co-precipitation method in the present application, and after high temperature calcination, the composite oxide with Ni element highly dispersed on the BaWO4 carrier is obtained, forming a mesoporous structure, which avoids the aggregation of active components through the confinement effect of the mesoporous structure, improves the thermal stability of Ni nanoparticles, and inhibits the condensation of intermediate species such as CH2CO and C2H4 to form carbon deposition.

[0009] It can be seen that the innovation of the catalyst composition and structure in the present application makes the catalyst exhibit good activity, stability, sintering resistance and carbon deposition resistance in the autothermal reforming reaction of acetic acid, and improves the selectivity of acetic acid conversion to hydrogen, showing excellent catalytic properties. SUMMARY

[0010] The technical problem to be solved by the present application is to provide a novel catalyst with stable structure, high conversion rate, good selectivity, sintering resistance and oxidation resistance, aiming at the problems of poor selectivity, instability, easy oxidation of active components, sintering and carbon deposition leading to reduction of catalyst activity and even deactivation of the catalyst in the existing acetic acid autothermal reforming reaction.

[0011] The present application uses Ni as the active component, introduces Ba and W components, and obtains a scheelite type Ni-based catalyst with BaWO4 as the main body and containing NiWO4 component by using the coprecipitation method. The active component nickel is uniformly dispersed in the BaWO4 carrier, thereby improving the dispersion degree of nickel. The catalyst of the present application is used in the hydrogen production reaction of acetic acid autothermal reforming, and in the case that the reaction temperature is 700 DEG C, the conversion rate of acetic acid is close to 100%, and the hydrogen production rate is about 2.5 mol-H2 / mol-HAc.

[0012] The technical scheme of the present application is as follows:

[0013] The present application is prepared according to the characteristics of acetic acid autothermal reforming, and the scheelite type nickel-based catalyst is prepared by using the coprecipitation method. Ni is used as the active component, the carrier takes BaWO4 as the main body, contains NiWO4 component, forms Ni-Ba-W-O active center, has the characteristics of high catalytic activity and good stability, and improves the hydrogen production rate. The molar composition of the catalyst of the present application is (NiO) a (BaO) b (WO3) c , wherein a is 0.75-0.86, b is 1.81-2.16, and c is 0.04-0.26; the weight percentage composition calculated as an oxide is: 12.5%-18.3% of nickel oxide, 69.0%-83.5% of barium oxide, and 2.1%-15.3% of tungsten trioxide, and the sum of the weight percentages of the components is 100%.

[0014] The specific preparation method is as follows:

[0015] 1) according to the molar composition of the components in the catalyst (NiO) a (BaO) b (WO3) c , wherein a is 0.75-0.86, b is 1.81-2.16, and c is 0.04-0.26, a certain amount of nickel nitrate, barium nitrate and ammonium metatungstate is weighed in a beaker, 50 mL of deionized water is added, and the solution is dissolved by stirring in a 65 DEG C water bath to obtain 1# solution;

[0016] 2) according to the molar ratio of [Ni 2+ +W 6+ +Ba 2+ ]:[OH - ]:[CO3 2-] = 1:8:16, a certain amount of sodium hydroxide and anhydrous sodium carbonate are weighed to prepare precipitant 2#;

[0017] 3) Under the condition of 65 DEG C and pH = 10.0 + 0.5, solution 1# and solution 2# are slowly added and mixed to carry out coprecipitation reaction, and the temperature is kept stirring for 24 hours;

[0018] 5) After 3 times of suction filtration and washing, the obtained precipitate is transferred into an 80 DEG C oven for drying for 24 hours to obtain a catalyst precursor;

[0019] 6) The dried sample is placed in a tube furnace, and the temperature is increased from room temperature to 700 DEG C at a rate of 10 DEG C / min and kept at this temperature for 4 hours to obtain the white tungsten ore type nickel-based catalyst of the application, which is mainly composed of BaWO4 and contains NiWO4 component, Ni is the active component, and the structure of Ni / BaWO4-NiWO4 is formed;

[0020] 7) After the catalyst is crushed, tabletized, broken and sieved, 20-40 mesh particles are obtained, and 50-300 mg is weighed and loaded into a quartz reaction tube, and the catalyst is reduced in H2 atmosphere at 600-800 DEG C for 1 hour, and after activation treatment, the acetic acid self-thermal reforming reaction is carried out, and nitrogen is used as the internal standard gas, and the mixed gas with a molar ratio of CH3COOH / H2O / O2 / N2 = 1.0 / (1.3-5.0) / (0.21-0.35) / (2.5-4.5) is introduced, and the reaction is carried out through the catalyst bed, and the reaction temperature is 600 DEG C-800 DEG C.

[0021] The beneficial effects of the application are as follows:

[0022] 1) The catalyst of the application adopts Ni as the active component, and a white tungsten ore type Ni-based catalyst mainly composed of BaWO4 and containing NiWO4 component is constructed by coprecipitation method; the addition of the active component Ni constructs the surface defects of BaWO4 crystal, exposes more active sites, promotes the deep rupture of C-C bond, C-H bond and C-O bond of CH3CO* to form CH x *(x = 0-3); the catalyst takes the white tungsten ore BaWO4 with tetragonal bipyramidal structure as the carrier, due to the difference of O-W-O bond angle, the [WO4] tetrahedral structure is twisted and distorted, so that oxygen defect vacancies appear in the BaWO4 crystal; the existence of oxygen defect vacancies is beneficial to the adsorption and dissociation of active reactants H2O and O2 to form OH* and O* free radicals, which promotes the dehydrogenation reaction of CH x *(x = 0-3) species to generate C* species, and the combination of C* and O* generates CO and CO2, thereby inhibiting the accumulation of C* species on the catalyst surface to form coke, and improving the anti-coking property of the nickel-based catalyst.

[0023] 2) The Ni2+ and W 6+ species, under the high-temperature reaction condition of acetic acid autothermal reforming, W 6+ species and free Ba 2+ ions combine to form BaWO4, while Ni 2+ further reacts in a hydrogen atmosphere to form Ni 0 element, the obtained nickel element is uniformly distributed in the BaWO4 carrier, forming a Ni-Ba-W-O active center, avoiding the aggregation of active components, and improving the sintering resistance of the catalyst.

[0024] 3) The construction of BaWO4 / NiWO4 composite oxides provides a highly stable structure, not only enhances the stability of the catalyst, makes the catalyst maintain high activity, and improves the hydrogen production rate; at the same time, provides a stable reaction interface for acetic acid autothermal reforming, promotes the adsorption of reactant molecules on the catalyst surface, and speeds up the reaction.

[0025] 4) In the present application, the coprecipitation method is used to control the pH at 10.0±0.5, to obtain a composite oxide with Ni element highly dispersed on the BaWO4 carrier, forming a mesoporous structure, avoiding the aggregation of active components through the confinement effect of the mesoporous structure, improving the thermal stability of Ni nanoparticles, and inhibiting the condensation of CH2CO, C2H4 and other intermediate species to form carbon.

[0026] 5) The results of acetic acid autothermal reforming reaction show that the catalyst of the present application has high efficiency in the conversion of acetic acid, high hydrogen production rate, and excellent properties such as stability, oxidation resistance, sintering resistance, and carbon deposition resistance. BRIEF DESCRIPTION OF DRAWINGS

[0027] Figure 1 : X-ray diffraction spectrum of the composite oxide of the catalyst of the present application Figure 1

[0028] Figure 2 : BJH pore size distribution graph of the catalyst of the present application

[0029] Figure 3 : X-ray diffraction spectrum of the post-reaction sample of the catalyst of the present application Figure 2

[0030] Figure 4 : X-ray diffraction spectrum of the composite oxide of the catalyst of the present application Figure 3

[0031] Figure 5 : X-ray diffraction spectrum of the composite oxide of the catalyst of the present application Figure 4 DETAILED DESCRIPTION

[0032] Reference Example 1

[0033] Take 2.344 g of nickel nitrate and 5.793 g of barium nitrate in a beaker, add 50 mL of deionized water, and dissolve thoroughly under stirring in a 65°C water bath to obtain solution 1#; then according to [Ni 2+ +W 6+ +Ba 2+ ]:[OH - ]:[CO3 2- ]=1:8:16, take 5.803 g of sodium hydroxide and 0.961 g of anhydrous sodium carbonate to prepare precipitant 2#; then under the conditions of 65°C and pH=10.0±0.5, slowly drop mix solution 1# and solution 2#, carry out coprecipitation reaction, and keep the temperature and stir for 24 h; then after 3 times of suction filtration and washing, the obtained precipitate is transferred into an 80°C oven for drying for 24 h to obtain catalyst precursor; after drying, the sample is placed in a tube furnace, heated to 700°C at a heating rate of 10°C / min, and kept for 4 h to obtain CDUT-NB catalyst, forming NiO and BaO phases. The molar composition of the catalyst is (NiO) 0.81 (BaO) 2.22 The weight percentage composition of oxides is: nickel oxide 15.1%, barium oxide 84.9%.

[0034] The hydrogen production reaction activity evaluation of acetic acid autothermal reforming was carried out in a micro fixed bed reactor. After crushing, tabletting, crushing and sieving, 20-40 mesh particles were obtained, and 200 mg was loaded into a quartz reaction tube and reduced at 700°C for 1 h under a flow of H2 of 30 mL / min; the mixed solution of acetic acid and water was pumped into a vaporizer by a high-pressure constant-flow pump, mixed with oxygen, and nitrogen was used as internal standard gas to form a reaction raw gas with a molar composition of CH3COOH / H2O / O2 / N2=1.0 / (1.3-5.0) / (0.21-0.35) / (2.5-4.5); the raw gas was passed into the reaction bed for acetic acid autothermal reforming reaction, and the reaction conditions were atmospheric pressure, space velocity 10000-40000 mL / (g-catalyst·h), reaction temperature 600-800°C, and the reaction tail gas was analyzed online by gas chromatograph.

[0035] The CDUT-NB catalyst was subjected to activity investigation by acetic acid autothermal reforming reaction, with space velocity of 11000 mL / (g-catalyst·h), reaction temperature of 700℃, feed ratio of CH3COOH / H2O / O2 / N2=1.0 / 4.0 / 0.28 / 3.9, and reaction time of 10 h. With the reaction proceeding, the acetic acid conversion rate of the catalyst decreased from 97.0% to about 79.0%, the hydrogen production rate decreased from 1.4 mol-H2 / mol-HAc to 1.0 mol-H2 / mol-HAc, and the methane selectivity increased from 5.4% to 15.6%; the results show that the catalyst has poor stability in the acetic acid autothermal reforming process, sintering, carbon deposition and partial oxidation occur, the activity is low, and the hydrogen production rate is low.

[0036] Example One

[0037] 2.344 g of nickel nitrate, 5.647 g of barium nitrate and 0.090 g of ammonium metatungstate were weighed into a beaker, 50 mL of deionized water was added, and the mixture was fully stirred and dissolved in a 65℃ water bath to obtain solution 1#; then, according to the molar ratio of [Ni 2+ +W 6+ +Ba 2+ ]:[OH - ]:[CO3 2- ]=1:8:16, 5.703 g of sodium hydroxide and 0.944 g of anhydrous sodium carbonate were weighed to prepare precipitant 2#; then, under the conditions of 65℃ and pH=10.0±0.5, solution 1# and solution 2# were slowly added and mixed, a co-precipitation reaction was carried out, and the temperature was kept for aging for 24 h while stirring; then, the obtained precipitate was washed by suction filtration for 3 times, and then was transferred into a 80℃ oven for drying for 24 h to obtain a catalyst precursor; the dried sample was placed in a tube furnace, heated to 700℃ at a heating rate of 10℃ / min, and kept for 4 h to obtain CDUT-NB W-2 catalyst, which has a scheelite-type BaWO4 phase and contains NiWO4 component and NiO component, and the structure is shown in the X-ray diffraction pattern (attached Figure 1 ), forms Ni-Ba-W-O active center, and has mesoporous structure, and the typical structure is shown in the attached Figure 2 . The molar composition of the catalyst is (NiO) 0.81 (BaO) 2.16 (WO3) 0.04 , and the weight percentage composition of oxides is: nickel oxide 15.1%, barium oxide 82.8%, and tungsten trioxide 2.1%.

[0038] The CDUT-NBW-2 catalyst was subjected to activity investigation by acetic acid autothermal reforming reaction, with a space velocity of 11000 mL / (g-catalyst.h), a reaction temperature of 700 DEG C, a feed ratio of CH3COOH / H2O / O2 / N2 = 1.0 / 4.0 / 0.28 / 3.9, and a reaction time of 10 h. The acetic acid conversion rate of the catalyst was about 100%, the hydrogen production rate was 2.5 mol-H2 / mol-HAc, the CO2 selectivity was about 59.4%, the CO selectivity was about 38.3%, and no by-products of acetone and methane were detected. Nitrogen low-temperature physical adsorption characterization was performed on the CDUT-NBW-2 catalyst, and the results, as shown in the accompanying Figure 2 X-ray diffraction pattern, showed that the specific surface area was 13.3 m 2 / g, the pore volume was 0.15 cm 3 / g, and the average pore size was 44.6 nm. H2-TPR characterization showed that the BaWO4 carrier could be stabilized and provided a stable interface for the reaction. XRD characterization of the catalyst after the reaction showed that, after the reduction reaction, the catalyst formed a mesoporous composite oxide Ni / BaWO4-NiWO4 mainly in the form of scheelite BaWO4, containing Ni element and NiWO4 components, and formed a Ni-Ba-W-O active center, providing a composite interface for the acetic acid autothermal reforming reaction. The reaction results showed that the catalyst had no carbon deposition and no sintering phenomenon, indicating that the catalyst had good thermal stability, carbon deposition resistance, activity stability, high hydrogen production rate and other characteristics. Figure 3

[0039] Example Two

[0040] 2.348 g of nickel nitrate, 5.445 g of barium nitrate and 0.216 g of ammonium metatungstate were weighed into a beaker, 50 mL of deionized water was added, and the mixture was fully stirred and dissolved in a 65 DEG C water bath to obtain solution 1#. According to the formula [Ni 2+ +W 6+ +Ba 2+ ]:[OH - ]:[CO3 2- ] = 1:8:16, 5.565 g of sodium hydroxide and 0.922 g of anhydrous sodium carbonate were weighed to prepare precipitant 2#. Then, under the conditions of 65 DEG C and pH = 10.0 ± 0.5, solution 1# and solution 2# were slowly added and mixed, a coprecipitation reaction was performed, and the temperature was kept for 24 h of aging while stirring. After being washed by filtration for 3 times, the obtained precipitate was transferred into a 80 DEG C oven for drying for 24 h to obtain a catalyst precursor. The dried sample was placed in a tube furnace, heated to 700 DEG C at a heating rate of 10 DEG C / min, and kept for 4 h to obtain the CDUT-NBW-5 catalyst, which had a structure of scheelite BaWO4 phase and contained NiWO4 components and NiO components, as shown in the X-ray diffraction pattern (the accompanying​Figure 4 ) as shown. The molar composition of the catalyst is (NiO) 0.81 (BaO) 2.08 (WO3) 0.09 The weight percentage composition in terms of oxides is: nickel oxide 15.1%, barium oxide 79.8%, tungsten trioxide 5.1%.

[0041] The CDUT-NBW-5 catalyst was subjected to activity test by acetic acid autothermal reforming reaction, the space velocity was 11000 mL / (g-catalyst·h), the reaction temperature was 700℃, the feed ratio was CH3COOH / H2O / O2 / N2=1.0 / 4.0 / 0.28 / 3.9, and the reaction time was 10h. The acetic acid conversion rate of the catalyst was about 100%, the hydrogen production rate was 2.3mol-H2 / mol-HAc, the CO2 selectivity was about 58.0%, the CO selectivity was about 37.4%, the CH4 selectivity was 4.6%, and there was no by-product acetone. It showed that the catalyst effectively inhibited the generation of by-product acetone, and had high catalytic activity.

[0042] Example Three

[0043] 2.344g of nickel nitrate, 5.099g of barium nitrate and 0.434g of ammonium metatungstate were weighed in a beaker, 50mL of deionized water was added, and the solution was dissolved by stirring in a 65℃ water bath to obtain solution 1#; then, according to the molar ratio of [Ni 2+ +W 6+ +Ba 2+ ]:[OH - ]:[CO3 2- ]=1:8:16, 5.322g of sodium hydroxide and 0.881g of anhydrous sodium carbonate were weighed to prepare precipitant 2#; then, under the conditions of 65℃ and pH=10.0±0.5, solution 1# and solution 2# were slowly added and mixed, a co-precipitation reaction was carried out, and the temperature was kept for aging for 24h by stirring; then, the obtained precipitate was washed by suction filtration for 3 times, and then was transferred into a 80℃ oven for drying for 24h to obtain a catalyst precursor; the dried sample was placed in a tube furnace, heated to 700℃ at a heating rate of 10℃ / min, and kept for 4h to obtain the CDUT-NBW-10 catalyst, and the crystal phase structure was scheelite type BaWO4, NiWO4 and NiO, and the structure was shown in the X-ray diffraction pattern (attached Figure 5 ) as shown. The molar composition of the catalyst is (NiO) 0.81 (BaO) 1.95 (WO3) 0.18 The weight percentage composition in terms of oxides is: nickel oxide 15.1%, barium oxide 74.7%, tungsten trioxide 10.2%.

[0044] The CDUT-NB catalyst was subjected to activity investigation by acetic acid autothermal reforming reaction, with space velocity of 11000 mL / (g-catalyst·h), reaction temperature of 700℃, feed ratio of CH3COOH / H2O / O2 / N2=1.0 / 4.0 / 0.28 / 3.9, and reaction time of 10 h. The acetic acid conversion rate of the catalyst was about 100%, the hydrogen production rate was 2.1 mol-H2 / mol-HAc, the CO2 selectivity was about 54.9%, the CO selectivity was about 37.6%, the CH4 selectivity was 7.5%, and there was no by-product acetone.

Claims

1. The application of scheelite-type nickel-based catalysts in the autothermal reforming of acetic acid to produce hydrogen, characterized in that: Weigh 50-300 mg of catalyst and reduce it in an H2 atmosphere at 600-800°C for 1 h. Use nitrogen as an internal standard and pass a mixed gas with a molar ratio of CH3COOH / H2O / O2 / N2 = 1.0 / (1.3-5.0) / (0.21-0.35) / (2.5-4.5) through the catalyst bed for reaction at a temperature of 600°C-800°C. The catalyst is prepared by the following method: Weigh a certain amount of nickel nitrate, barium nitrate, and ammonium metatungstate into a beaker, add 50 mL of deionized water, and stir thoroughly in a 65°C water bath to dissolve and obtain solution #1; then, according to [Ni 2+ +W 6+ +Ba 2+ ]:[OH - ]:[CO3 2- The ratio of sodium hydroxide to anhydrous sodium carbonate was 1:8:

16. A certain amount of sodium hydroxide and anhydrous sodium carbonate were weighed to prepare precipitant 2#. Under the conditions of 65℃ and pH=10.0±0.5, solution 1# and precipitant 2# were slowly added dropwise and mixed to carry out a co-precipitation reaction. The mixture was then stirred and aged at this temperature for 24 hours. After three filtration and washing cycles, the precipitate was transferred to an 80℃ oven and dried for 24 hours to obtain the catalyst precursor. The dried sample was placed in a tube furnace and heated from room temperature to 700℃ at a heating rate of 10℃ / min and held at this temperature for 4 hours. The weight percentage composition based on oxides was as follows: nickel oxide 12.5%-18.3%, barium oxide 69.0%-83.5%, and tungsten trioxide 2.1%-15.3%, with the sum of the weight percentages of each component being 100%. Its main component was BaWO4, containing NiWO4 component, with Ni as the active component, forming Ni-Ba-WO active centers.

2. The application of the scheelite-type nickel-based catalyst according to claim 1 in the autothermal reforming of acetic acid to produce hydrogen, characterized in that: The catalyst is composed of the following oxides by weight percentage: nickel oxide 15.1%, barium oxide 82.8%, and tungsten trioxide 2.1%.

3. The application of the scheelite-type nickel-based catalyst according to claim 1 in the autothermal reforming of acetic acid to produce hydrogen, characterized in that: The catalyst is composed of the following oxides by weight percentage: nickel oxide 15.1%, barium oxide 79.8%, and tungsten trioxide 5.1%.

4. The application of the scheelite-type nickel-based catalyst according to claim 1 in the autothermal reforming of acetic acid to produce hydrogen, characterized in that: The catalyst is composed of the following oxides by weight percentage: nickel oxide 15.1%, barium oxide 74.7%, and tungsten trioxide 10.2%.

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