CN114308057B - Manganese-tungsten ore type oxide-supported cobalt-based catalyst for autothermal reforming of acetic acid to produce hydrogen - Google Patents
Manganese-tungsten ore type oxide-supported cobalt-based catalyst for autothermal reforming of acetic acid to produce hydrogen Download PDFInfo
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Abstract
The invention relates to a cobalt-manganese mixed spinel structure-loaded cobalt-manganese cobalt-based catalyst for autothermal reforming of acetic acid to produce hydrogen. Aiming at the problem of deactivation of the existing catalyst, the invention provides a novel catalyst which has stable structure, sintering resistance, carbon deposit resistance, oxidation resistance and high activity. The molar composition of the catalyst of the invention is as follows: (WO) 3 ) a (MnO) b (CoO) c Wherein a is 0-0.07 and not 0,b is 0.68-0.75 and c is 0.24-0.26. The invention adopts a coprecipitation method to prepare a catalyst precursor, and MnWO is obtained by roasting 4 As a carrier, contains (Co, mn) 2 O 4 The cobalt-based catalyst mixed with spinel improves the yield of hydrogen and the stability of active components, and effectively inhibits the generation of byproducts such as methane, acetone and the like.
Description
Technical Field
The invention relates to a wolframite-manganese ore type composite oxide loaded cobalt-manganese mixed spinel structure cobalt-based catalyst for hydrogen production by autothermal reforming of acetic acid and a preparation method thereof, belonging to the field of hydrogen production by autothermal reforming of acetic acid.
Background
With the continuous consumption of traditional fossil fuels, hydrogen energy has the characteristics of cleanness and high efficiency, and thus has attracted the attention of students. In recent years, biomass oil can be obtained by pyrolyzing renewable biomass, has the characteristics of higher energy density, convenience in transportation and storage and the like, and is considered as an ideal hydrogen production raw material. The biomass oil has complex composition, and the content of acetic acid (HAc) which is the main component of a water phase is up to 33 percent, so that the acetic acid can be used as a raw material to prepare hydrogen through a catalytic reforming process.
The hydrogen yield of the hydrogen production by catalytic reforming of acetic acid is not only related to the raw material source and the process conditions, but also closely related to the action of the catalyst. Noble metal catalysts such as platinum, rhodium, ruthenium, etc. have limited their industrial large-scale use due to their expensive price. The cobalt-based catalyst, one of the transition metals, has high activity and selectivity to hydrogen, and becomes an important research object for hydrogen production by reforming acetic acid.
The hydrogen production by reforming acetic acid generally includes a steam reforming reaction (SR), a partial oxidation reaction (POX), and an autothermal reforming reaction (ATR), in which the steam reforming reaction is an endothermic reaction (CH) 3 COOH+2H 2 O→2CO 2 +4H 2 Δ H = +131.4 kJ/mol), heat is continuously provided from the outside, and the reaction can be continuously carried out; partial oxidation does not need an external heat source, but under the strong oxygen atmosphere, active components are easy to oxidize and sinter, and the hydrogen yield is low. While autothermal reforming produces hydrogen (CH) 3 COOH+0.28O 2 +1.44H 2 O→2CO 2 +3.44H 2 Δ H = 0), combining steam reforming and partial oxidation processes, introducing a proportion of O in the feedstock 2 Or air, and the ratio of oxygen to acetic acid is controlled to realize self-heating and balance the heat supply of the reaction system, and the method has the characteristics of quick start, less process investment and the like.
In the reaction of autothermal reforming of acetic acid to produce hydrogen, the reactant acetic acid CH 3 COOH is adsorbed and activated on a cobalt-based catalyst, dehydroxylated and dehydrogenated to generate CH 3 COO*、CH 3 CO*、CH 3 * And C-containing free radicals such as CO, and further dehydrogenating and deoxidizing the intermediates to form C species, wherein the C species are accumulated on the catalyst in a large quantity to form carbon deposit to cover the active center of the cobalt-based catalyst, so that the activity of the catalyst is gradually reduced; in addition, the oxidation reaction at the front end of the catalyst bed layer enables the local temperature to reach more than 1000 ℃, so that the problems of aggregation, sintering and the like of the catalyst are easy to occur; meanwhile, active metal in the oxidizing atmosphere in the autothermal reforming process is easily oxidized, so that the activity of the catalyst at the front end of the bed is reduced, and the catalyst gradually moves backwards along with the front end of the reaction, and finally the whole catalytic bed is oxidized, sintered and even inactivated. Therefore, aiming at the problems that the cobalt-based catalyst is easy to oxidize, sinter and deposit carbon in the hydrogen production by reforming acetic acid, the key point for improving the reaction activity and selectivity of the hydrogen production by autothermal reforming of acetic acid is to improve the oxidation resistance, sintering resistance and carbon deposit resistance of the cobalt-based catalyst.
Aiming at the characteristics of active metal Co in the process of autothermal reforming conversion of acetic acid, W and Mn are creatively introduced, and a wolframite MnWO is prepared by a coprecipitation method 4 The composite oxide is a carrier and has (Co, mn) 2 O 4 Mixed spinel junctionThe cobalt-based catalyst takes Co-W-Mn-O as an active center. In (Co, mn) 2 O 4 In the mixed spinel structure, mn is used as an electron donor, the electron density on the surface of Co species is improved, and the oxidation resistance of the catalyst is improved. During the reduction process, co is added to (Co, mn) 2 O 4 Reduced in spinel structure, highly dispersed on MnO matrix surface, and loaded on MnWO 4 On the carrier, the dispersion degree of the reduced active metal Co is improved, more active sites are exposed, a Co-W-Mn-O active center is formed, and CH is promoted 3 Conversion of CO intermediates to CH x * (x = 0-3), CO, C, and the like, and inhibits CH 3 CO is accumulated to form acetone as a by-product, and H is increased 2 Of the cell.
Meanwhile, on the Co-W-Mn-O active center, the charge transfer capability of W and Mn species due to the multi-valence state of the W and Mn species enables MnWO 4 The carrier has a large number of oxygen vacancies and can adsorb and activate H 2 O and O 2 Generating a large number of OH and O radicals, CH x * Dehydrogenating under the action of OH to generate C species; on the other hand, mn has redox properties, and Mn of Mn species is present during the reforming reaction 2+ /Mn 3+ The redox cycle helps to improve the oxygen storage capacity and oxygen conversion capacity of the catalyst, and promotes the oxidation reaction in MnWO 4 O generated on the carrier migrates to the surface of the catalyst, and C species and CO combine with O radicals to form CO and CO 2 Improve CH x * And C, thereby effectively inhibiting the accumulation of carbon precursors on the surface of the catalyst to form carbon deposits.
In addition, the mesoporous structure characteristic constructed in the catalyst is beneficial to not only the diffusion of reactant and product molecules in the autothermal reforming process of acetic acid, but also the dispersion of active metal Co, and the activity of the catalyst is effectively improved. Meanwhile, the confinement effect of the pore structure and MnWO 4 The carrier has good thermal stability and mechanical strength, effectively prevents the migration and sintering of metal Co particles at high temperature, and improves the sintering resistance of the catalyst.
Therefore, the catalyst has innovation in catalyst components and structure, so that the catalyst has good activity, stability, sintering resistance and carbon deposit resistance in the autothermal reforming reaction of acetic acid, the selectivity of the conversion rate of acetic acid and hydrogen is improved, and the characteristic of the catalyst is excellent.
Disclosure of Invention
The invention aims to solve the technical problems that the catalyst in the existing acetic acid autothermal reforming reaction has poor selectivity, active components are easy to oxidize, and the activity of the catalyst is reduced or even inactivated due to sintering and carbon deposition, and provides a novel catalyst which has the advantages of stable structure, high conversion rate, good selectivity, sintering resistance and oxidation resistance.
The invention uses Co as an active component, introduces Mn and W, and adopts a coprecipitation method to prepare the supported MnWO 4 Containing (Co, mn) 2 O 4 Mixing spinel structure, reducing spinel structure to obtain Co simple substance, uniformly dispersing Co simple substance on MnO base body surface, and loading it on tungsten manganese ore MnWO 4 The mesoporous cobalt-based catalyst with the Co-W-Mn-O active center is formed on the carrier. When the catalyst is used in the reaction of autothermal reforming of acetic acid to produce hydrogen, the conversion rate of the catalyst to the acetic acid is preferably close to 100 percent and the hydrogen yield is stabilized at 2.65mol-H under the condition that the reaction temperature is 700 DEG C 2 about/mol-HAc.
The technical scheme of the invention is as follows:
the method aims at the characteristic of autothermal reforming of acetic acid and prepares MnWO by a coprecipitation method 4 The supported Co-Mn mixed spinel catalyst uses Co as active component and MnO as matrix and is supported on MnWO 4 Co-W-Mn-O active centers are formed on the carrier, so that the catalyst has excellent catalytic activity and stability, and the hydrogen yield of the autothermal reforming reaction of acetic acid is improved. The molar composition of the catalyst related to the invention is (WO) 3 ) a (MnO) b (CoO) c Wherein a is 0-0.07 and not 0,b is 0.68-0.75 and c is 0.24-0.26; the weight percentage composition calculated by oxide is as follows: cobalt oxide 9.0-11.0%, tungsten oxide 0-8.0% but not 0%, manganese oxide 82.0-90.0%. A preferred catalyst of the present invention is (WO) 3 ) 0.02 (MnO) 0.73 (CoO) 0.25 The weight percentage composition is as follows: 10.0 percent of cobalt oxide, 2.0 percent of tungsten oxide,the manganese oxide content was 88.0%.
The specific preparation method comprises the following steps:
1) Preparing a metal nitrate solution: according to the molar composition of the catalyst (WO) 3 ) a (MnO) b (CoO) c Wherein a is 0-0.07 and is not 0,b is 0.68-0.75, c is 0.24-0.26, respectively weighing a certain amount of cobalt nitrate, manganese nitrate and ammonium tungstate, adding deionized water, and uniformly stirring to prepare a nitrate mixed solution;
2) Preparing a precipitator: according to [ Co ] 2+ +Mn 2+ +W 6+ ]:[CO 3 2- ]:[OH - ]1, weighing a certain amount of sodium hydroxide and sodium carbonate, and dissolving the sodium hydroxide and the sodium carbonate in deionized water to form a mixed solution;
3) Simultaneously dropwise adding the solutions prepared in the steps 1) and 2) into a beaker, keeping the temperature at about 65 ℃, controlling the pH value of the solution at 11 +/-0.5, continuously stirring for coprecipitation reaction, and keeping the temperature for aging for 24 hours; after the aging is finished, carrying out suction filtration and washing on the mixture for 3 times, and drying the obtained precipitate in a vacuum drying oven at 60 ℃ for 12h to obtain a catalyst precursor;
4) Heating the precursor to 750 ℃ at the heating rate of 10 ℃/min, and roasting at the temperature for 5h to obtain MnWO 4 Supported cobalt manganese mixed spinel structure catalyst having a main component of (Co, mn) 2 O 4 Mixed spinel and MnWO 4 As shown in the XRD pattern of fig. 1, it shows that the active metal Co combines with the Mn species to form a mixed spinel structure; simultaneously has a mesoporous structure as shown in figure 2; in the reduction process of the catalyst, co species are reduced into simple substances in a spinel structure and uniformly dispersed on a MnO matrix to form a catalyst supported on MnWO 4 Co-W-Mn-O active centers with mesoporous structures are formed on the carrier, as shown in an XRD (X-ray diffraction) pattern of an attached figure 3.
5) The catalyst is prepared at 600-800 deg.c in H before autothermal reforming reaction of acetic acid 2 Reducing for 1h, activating, introducing nitrogen as internal standard gas, and introducing acetic acid/water/oxygen = CH 3 COOH/H 2 O/O 2 The mixed gas of = 1/(1.3-5.0)/(0.21-0.35) passes through the catalyst bed layerThe reaction is carried out at the temperature of 600-800 ℃.
The invention has the beneficial effects that:
1) The invention adopts Co as an active component, introduces W and Mn, and prepares MnWO by a coprecipitation method 4 As a carrier, co-W-Mn-O as an active center and having (Co, mn) 2 O 4 A cobalt-based catalyst of mixed spinel structure is shown in FIG. 1. The catalyst has a mixed spinel structure, so that the dispersity of an active component Co after reduction is effectively improved, and the catalytic activity is improved; meanwhile, the catalyst forms a mesoporous structure, and the sintering resistance of the catalyst is improved through the confinement effect of the pore channel.
2) The manganese tungsten ore MnWO introduced into the catalyst of the invention 4 The carrier is a material with good thermal stability and mechanical stability, promotes the uniform dispersion of the active component, can effectively inhibit the sintering of the active component Co at high temperature, and improves the high-temperature activity and stability of the catalyst; the manganese tungsten ore MnWO is caused by the strong charge transfer capability of W and Mn species 4 The carrier generates a large number of oxygen vacancies which are beneficial to adsorbing and dissociating activated H 2 O and O 2 Form OH and O radicals, promoting CH x * (x = 0-3) dehydrogenation of the species to C species, promoting the combination of O and C to CO and CO 2 And C species are inhibited from being accumulated on the surface of the catalyst to form carbon deposit, so that the carbon deposit resistance of the cobalt-based catalyst is improved.
3) Mn and Co introduced by the invention are combined to form a cobalt-manganese mixed spinel structure, wherein the electron donating effect of Mn modulates the electron cloud density on the surface of the catalyst, so that the spinel Dan Gengyi is reduced into a metal Co simple substance in a hydrogen atmosphere; therefore, co is highly dispersed on the surface of the MnO matrix after the cobalt-manganese mixed spinel is reduced, the aggregation of an active component Co is prevented, co particles are prevented from being sintered at high temperature, and the sintering resistance of the catalyst is improved.
4) On a Co-W-Mn-O active center formed by the catalyst, mnO matrix is used for modifying Co particles, so that the aggregation and growth of the Co particles are inhibited, and the activity and stability of the acetic acid conversion process are improved; meanwhile, the high-efficiency oxygen transfer capacity of the Co-W-Mn-O active center effectively inhibits the generation of carbon deposit; in addition, in Co-W-Mn-Presence of Mn on O active centers 2+ /Mn 3+ The oxidation-reduction cycle of the catalyst effectively promotes the migration of O on the active center of Co-W-Mn-O and accelerates CH 3 The CO intermediate is converted into CH on the active center through dehydrogenation and decarbonylation x * C, and the like, inhibit ketonization reaction, reduce the formation of byproduct acetone, and ensure that the acetic acid conversion process has good carbon deposition resistance and higher H 2 And (4) selectivity.
5) The results of the autothermal reforming reaction of acetic acid show that the catalyst of the invention has high efficiency conversion of acetic acid, high hydrogen yield, effectively inhibits the generation of byproducts, and has the excellent characteristics of oxidation resistance, sintering resistance, carbon deposit resistance and the like in the process of converting acetic acid.
Drawings
FIG. 1: x-ray diffraction spectrum of the catalyst oxide of the present invention
FIG. 2: BJH pore size distribution diagram of catalyst of the invention
FIG. 3: x-ray diffraction spectrum of catalyst reduction product of the invention
Detailed Description
Reference example 1
1.555g of Co (NO) is weighed out 3 ) 2 ·6H 2 O and 5.640g Mn (NO) 3 ) 2 (50% solution), adding 50mL of deionized water to prepare solution #1; in molar ratio of (Co) 2+ +Mn 2+ ]:[CO 3 2- ]:[OH - ]1, =2 2 CO 3 Preparing a precipitator # 2 with NaOH; dropwise adding the solution #1 and the solution # 2 into a beaker under the conditions that the temperature is 65 ℃ and the pH value of the solution is 11 +/-0.5, continuously stirring for carrying out coprecipitation reaction, and continuously stirring and aging for 24 hours; after the aging is finished, carrying out suction filtration and washing on the mixture for 3 times, and drying the obtained precipitate in a vacuum drying oven at 60 ℃ for 12h to obtain a catalyst precursor; the precipitate was calcined at 750 ℃ for 5 hours to obtain a CM catalyst. The molar composition of the catalyst calculated by oxide is (MnO) 0.75 (CoO) 0.25 The weight percentage composition is as follows: 10.0 percent of cobalt oxide and 90.0 percent of manganese oxide;
the activity evaluation of the reaction for autothermal reforming of acetic acid to produce hydrogen is carried out in a miniature fixed bed reactor. The catalyst is preparedTabletting, pulverizing, tabletting, crushing, sieving to obtain 20-40 mesh granules, weighing 0.2g, placing into quartz reaction tube, and feeding at 700 deg.C and 30mL/min flow rate of H 2 Reducing in the flow for 1h. Pumping the mixed solution of acetic acid and water with the molar ratio of 1:4 into a gasification chamber by a high-pressure constant flow pump for gasification, mixing with oxygen, taking nitrogen as internal standard gas, and fully mixing to form a molar composition of CH 3 COOH/H 2 O/O 2 Reaction raw material gas of = 1/(1.3-5.0)/(0.21-0.35), and the raw material gas is introduced into a reaction bed layer under the conditions of normal pressure, space velocity of 10000-35000 mL/(g-catalyst.h), and reaction temperature of 600-800 ℃, and the reaction tail gas is analyzed on line by adopting a gas chromatograph.
The activity of the CM catalyst is inspected by the autothermal reforming reaction of acetic acid, and the reaction condition is normal pressure, space velocity 30000 mL/(g-catalyst h), reaction temperature is 700 ℃, and raw material gas CH 3 COOH/H 2 O/O 2 With =1/4.0/0.28, the CM catalyst has good catalytic activity in the initial stage of the reforming reaction, but as the reaction time increases, the hydrogen yield is from the initial 2.12mol-H 2 the/mol-HAc is reduced to 1.73mol-H 2 mol-HAc. The CM catalyst is characterized by low-temperature nitrogen physical adsorption, and the result is as follows: the specific surface area is 5.3m 2 Per g, pore volume 0.016cm 3 In terms of/g, the mean pore diameter is 12.2nm. The particle size of the active component Co in the catalyst is calculated by a Scherrer formula, the particle size is 28.8nm before reaction, and the particle size is increased to 32.9nm after 10h of autothermal reforming reaction, which shows that the catalyst has sintering or agglomeration phenomenon in the reaction process, and the activity of the catalyst is reduced.
Example one
1.555g of Co (NO) is weighed out 3 ) 2 ·6H 2 O, (NH) 1.050g 4 ) 10 H 2 (W 2 O 7 ) 6 And 5.517g of Mn (NO) 3 ) 2 (50% solution), adding 50mL of deionized water to prepare solution #1; by molar ratio [ Co ] 2+ +Mn 2+ +W 6+ ]:[CO 3 2- ]:[OH - ]1 =2, with Na 2 CO 3 Preparing a precipitator # 2 with NaOH; adding solution #1 and solution # 2 dropwise to the flask at 65 deg.C under conditions of solution pH =11Continuously stirring in the cup to perform coprecipitation reaction, and continuously stirring and aging for 24h; after the aging is finished, carrying out suction filtration and washing on the mixture for 3 times, and drying the obtained precipitate in a vacuum drying oven at 60 ℃ for 12 hours to obtain a catalyst precursor; the precipitate was calcined at 750 ℃ for 5 hours to give a CM2W catalyst. The molar composition of the catalyst is (WO) 3 ) 0.02 (MnO) 0.73 (CoO) 0.25 The weight percentage composition is as follows: 10.0 percent of cobalt oxide, 2.0 percent of tungsten oxide and 88.0 percent of manganese oxide. The CM2W catalyst oxide forms (Co, mn) 2 O 4 The cobalt-manganese mixed spinel structure forms stable manganese tungsten ore MnWO 4 The carrier has a typical structure shown in figure 1, and the catalyst has a mesoporous structure, and has a typical structure shown in figure 2.
The activity of the CM2W catalyst is examined by the autothermal reforming reaction of acetic acid, and the reaction conditions are normal pressure, space velocity 30000 mL/(g-catalyst.h), reaction temperature of 700 ℃ and feeding ratio of CH 3 COOH/H 2 O/O 2 =1/4.0/0.28. The acetic acid conversion rate of the catalyst is stabilized at about 99.0 percent, and the hydrogen yield is stabilized at 2.65mol-H 2 about/mol-HAc, CO 2 The selectivity is stabilized at about 57.5 percent, the CO selectivity is maintained at about 41.6 percent, and a byproduct CH 4 The selectivity of (A) is about 1.6%, and almost no acetone is produced as a by-product. The CM2W catalyst is characterized by low-temperature nitrogen physical adsorption, and the result is as follows: the specific surface area is 2.8m 2 Per g, pore volume 0.012cm 3 In terms of/g, the mean pore diameter is 14.6nm. Characterization of the reduced CM2W catalyst, whose typical structure is shown in FIG. 3, shows that the Co species are selected from (Co, mn) 2 O 4 Reducing in a mixed spinel structure, converting into Co simple substance, uniformly dispersing on the surface of MnO matrix, and loading on the MnWO 4 Forming a mesoporous cobalt-based catalyst with a Co-W-Mn-O active center on a carrier; the active component of the catalyst keeps stable in the reaction process, no obvious sintering phenomenon exists, and no obvious carbon deposit exists on the surface of the catalyst.
Example two
Weigh 1.554g of Co (NO) 3 ) 2 ·6H 2 O, 4.199g of (NH) 4 ) 10 H 2 (W 2 O 7 ) 6 And 5.140g of Mn (NO) 3 ) 2 (50% solution), adding 50mL of deionized water to prepare solution #1; by molar ratio [ Co ] 2+ +Mn 2+ +W 6+ ]:[CO 3 2- ]:[OH - ]1 =2, with Na 2 CO 3 Preparing a precipitator # 2 with NaOH; dropwise adding the solution #1 and the solution # 2 into a beaker under the conditions that the temperature is 65 ℃ and the pH value of the solution is 11 +/-0.5, continuously stirring for carrying out coprecipitation reaction, and continuously stirring and aging for 24 hours; after the aging is finished, carrying out suction filtration and washing on the mixture for 3 times, and drying the obtained precipitate in a vacuum drying oven at 60 ℃ for 12h to obtain a catalyst precursor; the precipitate was calcined at 750 ℃ for 5 hours to give a CM8W catalyst. The molar composition of the catalyst is (WO) 3 ) 0.07 (MnO) 0.68 (CoO) 0.25 The weight percentage composition is as follows: 10.0 percent of cobalt oxide, 8.0 percent of tungsten oxide and 82.0 percent of manganese oxide.
The activity of the CM8W catalyst is examined by the autothermal reforming reaction of acetic acid, and the reaction conditions are normal pressure, space velocity 30000 mL/(g-catalyst.h), reaction temperature of 700 ℃ and feeding ratio of CH 3 COOH/H 2 O/O 2 =1/4.0/0.28. The catalyst has acetic acid conversion rate stabilized at about 99.0%, and H 2 The yield is 2.20mol-H 2 about/mol-HAc; simultaneous CH 4 The selectivity of (A) is about 2.0%, and almost no acetone is produced as a by-product. The CM8W catalyst is characterized by low-temperature nitrogen physical adsorption, and the result is as follows: the specific surface area is 2.6m 2 Per g, pore volume 0.015cm 3 (ii)/g, average pore diameter 23.1nm. According to the characteristics of BET, XRD and the like, the catalyst has good stability and has no obvious phenomena of carbon deposition and sintering.
Claims (3)
1. The application of the cobalt-manganese mixed spinel structure derived cobalt-based catalyst loaded by the tungsten-manganese composite oxide in the process of hydrogen production by autothermal reforming of acetic acid is characterized in that: taking 50-300mg of catalyst at the temperature of 600-800 ℃ under the condition of H 2 Reducing for 1h, purging with nitrogen, introducing mixed gas with the molar ratio of acetic acid/water/oxygen of 1/(1.3-5.0)/(0.21-0.35) with the flow rate of 50-250ml/min, and reacting through a catalyst bed layer at the reaction temperature ofIs 600-800 ℃; the catalyst is prepared by the following method: preparing a mixed solution #1 of cobalt nitrate, manganese nitrate and ammonium tungstate; preparing a precipitator #2 according to the requirement that the molar ratio of the sum of the mole numbers of the metal cations cobalt, manganese and tungsten to the mole numbers of carbonate and hydroxyl is 2; controlling the pH value to be 11 +/-0.5 in a water bath at 65 ℃, carrying out coprecipitation reaction on the solution #1 and the solution #2 under the stirring state, aging for 24 hours, carrying out suction filtration and washing for 3 times, drying the precipitate for 12 hours in a vacuum drying oven at 60 ℃, and then roasting for 5 hours in a tube furnace at 750 ℃ to obtain the load-type wolframite MnWO 4 Above (Co, mn) 2 O 4 Mixing spinel structure, reducing spinel structure to obtain Co simple substance, uniformly dispersing Co simple substance on MnO matrix surface, and loading onto manganese tungsten ore MnWO 4 Forming a mesoporous cobalt-based catalyst with a Co-W-Mn-O active center on a carrier; the chemical components calculated by oxides are as follows: (WO) 3 ) a (MnO) b (CoO) c Wherein a is 0 to 0.07 and not 0,b is 0.68 to 0.75 and c is 0.24 to 0.26; the weight percentage composition calculated by oxide is as follows: 9.0 to 11.0 percent of cobalt oxide, 0 to 8.0 percent but not 0 percent of tungsten oxide and 82.0 to 90.0 percent of manganese oxide, wherein the sum of the weight percentage of the components is 100 percent.
2. The application of the tungsten-manganese composite oxide supported cobalt-manganese mixed spinel structure derived cobalt-based catalyst in the process of autothermal reforming of acetic acid to produce hydrogen according to claim 1 is characterized in that: the catalyst comprises the following oxides in percentage by weight: 10.0% of cobalt oxide, 2.0% of tungsten oxide and 88.0% of manganese oxide.
3. The application of the cobalt-manganese mixed spinel structure derived cobalt-based catalyst loaded by the tungsten-manganese composite oxide in the process of autothermal reforming of acetic acid to produce hydrogen according to the claim 1 is characterized in that: the catalyst comprises the following components in percentage by weight: 10.0% of cobalt oxide, 8.0% of tungsten oxide and 82.0% of manganese oxide.
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