CN108554416B - Modified cobalt-based catalyst and preparation method and application thereof - Google Patents

Modified cobalt-based catalyst and preparation method and application thereof Download PDF

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CN108554416B
CN108554416B CN201810274407.1A CN201810274407A CN108554416B CN 108554416 B CN108554416 B CN 108554416B CN 201810274407 A CN201810274407 A CN 201810274407A CN 108554416 B CN108554416 B CN 108554416B
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based catalyst
carbon sphere
water
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cobalt
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CN108554416A (en
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李森
徐思遥
彭东辉
张雪洪
张杨
张宏玲
许明言
宋一帆
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Shanghai Research Institute of Chemical Industry SRICI
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    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
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    • B01J23/00—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00
    • B01J23/70—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper
    • B01J23/76—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper combined with metals, oxides or hydroxides provided for in groups B01J23/02 - B01J23/36
    • B01J23/83—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper combined with metals, oxides or hydroxides provided for in groups B01J23/02 - B01J23/36 with rare earths or actinides
    • F—MECHANICAL ENGINEERING; LIGHTING; HEATING; WEAPONS; BLASTING
    • F23—COMBUSTION APPARATUS; COMBUSTION PROCESSES
    • F23G—CREMATION FURNACES; CONSUMING WASTE PRODUCTS BY COMBUSTION
    • F23G7/00—Incinerators or other apparatus for consuming industrial waste, e.g. chemicals
    • F23G7/06—Incinerators or other apparatus for consuming industrial waste, e.g. chemicals of waste gases or noxious gases, e.g. exhaust gases
    • F23G7/07—Incinerators or other apparatus for consuming industrial waste, e.g. chemicals of waste gases or noxious gases, e.g. exhaust gases in which combustion takes place in the presence of catalytic material
    • F—MECHANICAL ENGINEERING; LIGHTING; HEATING; WEAPONS; BLASTING
    • F23—COMBUSTION APPARATUS; COMBUSTION PROCESSES
    • F23G—CREMATION FURNACES; CONSUMING WASTE PRODUCTS BY COMBUSTION
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Abstract

The invention relates to a modified cobalt-based catalyst and preparation and application thereof, and the modified cobalt-based catalyst comprises the following steps: (1) dissolving glucose in an ethanol/water solution, reacting in a reaction kettle after ultrasonic oscillation, performing suction filtration after the reaction is finished, alternately washing with water and absolute ethyl alcohol, and drying to obtain a carbon sphere carrier; (2) dissolving soluble Co salt and soluble transition metal salt in water to obtain a mixed solution; (3) adding a carbon sphere carrier into the mixed solution, performing ultrasonic oscillation, then dropwise adding ammonia water, adjusting the pH, aging, filtering, washing and drying to obtain metal hydroxide loaded carbon sphere powder; (4) and roasting the metal hydroxide loaded carbon sphere powder to obtain the modified cobalt-based catalyst. Compared with the prior art, the raw materials used in the invention have low price and environmental protection, the preparation conditions are mild, and the obtained catalyst has high catalytic activity and strong stability in the catalytic reaction process, and can be used in various environmental catalytic processes such as catalytic combustion and degradation of volatile organic compounds.

Description

Modified cobalt-based catalyst and preparation method and application thereof
Technical Field
The invention relates to the technical field of environmental protection, in particular to a modified cobalt-based catalyst and a preparation method and application thereof.
Background
Volatile Organic Compounds (VOCs) are the major pollutants in the atmosphere and they react with atmospheric nitrogen oxides to produce photochemical smog, thereby compromising urban air quality and human health. In recent years, with the development of chemical industry in China and the increase of the number of motor vehicles, the problem of VOCs pollution is increasingly serious. The catalytic oxidation process can efficiently and completely degrade the VOCs into carbon dioxide and water at a relatively low temperature, and is one of the most promising VOCs treatment methods.
Noble metal catalysts are commonly used in the catalytic oxidation of VOCs, which have excellent low temperature catalytic activity. However, they are expensive and susceptible to poisoning deactivation. The transition metal oxide has the advantages of low cost, high catalytic activity, high toxicity resistance and the like, and is considered to be one of substitutes of noble metal catalysts.
Among the existing non-noble metal catalysts, cobalt (Co) oxide has excellent catalytic activity at a low temperature stage, has been widely used in various catalytic reactions, and is considered to be one of the most effective catalysts for completely oxidizing VOCs such as toluene and propane.
The existing preparation methods of Co catalysts comprise a coprecipitation method, a sol-gel method or a solvothermal method, for example, the preparation methods disclosed in patents CN103894200A, CN101791559A and CN105983408A, but the catalysts prepared by the methods often have an agglomeration phenomenon, a low specific surface area and poor activity and stability. This is caused by improper doping of the metal ions and morphology of the material. Therefore, it is important to find a catalyst with simple synthesis and strong stability to realize the catalytic oxidation of VOCs.
Disclosure of Invention
The invention aims to overcome the defects of the prior art and provide a modified cobalt-based catalyst with simple synthesis and strong stability, and a preparation method and application thereof.
The purpose of the invention can be realized by the following technical scheme: a modified cobalt-based catalyst comprising a carbon sphere support and, supported on the carbon sphere support, cobalt oxide and a transition metal oxide, said transition metal oxide comprising an oxide of Cu, Ce or La and Co-existing with the transition elements, said cobalt oxide and transition metal oxide being present in a molar ratio of 4: (0 to 1). The presence of the transition element in the invention has a promoting effect on the catalytic activity of the Co element.
A method for preparing a modified cobalt-based catalyst as described above, comprising the steps of:
(1) dissolving glucose in an ethanol/water solution, reacting in a reaction kettle after ultrasonic oscillation, performing suction filtration after the reaction is finished, alternately washing with water and absolute ethyl alcohol, and drying to obtain a carbon sphere carrier;
(2) dissolving soluble Co salt and soluble transition metal salt in water to obtain a mixed solution, wherein the molar ratio of Co element and transition metal element in the soluble Co salt to the soluble transition metal salt is 4: (0-1), wherein the total molar concentration of the Co element and the transition metal element in the mixed solution is (0.1-0.15) mol/L;
(3) adding the carbon sphere carrier obtained in the step (1) into the mixed solution obtained in the step (2), performing ultrasonic oscillation, then dropwise adding ammonia water, adjusting the pH value to 7-10, aging, then filtering, washing and drying to obtain metal hydroxide loaded carbon sphere powder;
(4) and (4) roasting the metal hydroxide loaded carbon sphere powder obtained in the step (3) in an inert atmosphere to obtain the modified cobalt-based catalyst.
The ethanol/water solution in the step (1) has a volume ratio of ethanol to water of 1: (1-89), wherein the ratio of the mass of the added glucose to the volume of the ethanol/water solution is (5-15) g: (70-90) mL, wherein the ultrasonic oscillation time in the step (1) is 30-90 min.
The reaction in the step (1) is carried out in a reaction kettle with a polytetrafluoroethylene inner container, the reaction temperature is 120-180 ℃, and the reaction time is 5-12 hours. The invention adopts glucose as the source of the carbon sphere carrier, because the glucose is firstly polymerized into long-chain linear or dendritic oligosaccharide molecules, when the solution reaches a supersaturated state, the molecules are subjected to a cross-linking reaction, and finally the carbon spheres with a large number of hydroxyl groups and carbonyl groups distributed on the surface are formed, cobalt ions are more easily adsorbed on the surfaces of the carbon spheres in the subsequent preparation steps, and the unit content of active components is further improved.
And (2) after the reaction in the step (1) is finished, performing suction filtration, alternately washing for 3-5 times by using water and absolute ethyl alcohol, and performing vacuum drying for 6-10 hours at the temperature of 60-120 ℃.
And (3) the volume ratio of the added mass of the carbon sphere carrier to the mixed solution is (45-55): 1, and the time of ultrasonic oscillation in the step (3) is 1-2 h.
The aging temperature is 15-25 ℃, the aging time is 12-15 h, the water is used for washing 3-5 times after aging, and then the vacuum drying is carried out for 12-24 h at the temperature of 60-120 ℃. The invention takes ammonia water solution as a precipitator, and the prepared material has relatively optimal catalytic degradation activity.
The roasting temperature is 400-500 ℃, preferably 440-460 ℃, and the roasting time is 2-4 hours, preferably 2-2.5 hours. The crystal form in the catalyst has no obvious change after being roasted under the condition.
The modified cobalt-based catalyst is used for a catalyst for catalytic combustion degradation of volatile organic compounds, wherein the volatile organic compounds comprise one or a mixture of more of butane, 2-methylbutane, pentane, 2-toluene, 1, 3-butadiene, methylpentane, 3-methylhexane, methylheptane, isopropylbenzene, propylbenzene, m-ethyltoluene, o-ethyltoluene, mesitylene, m-diethylbenzene, dodecane, methyl sulfide, limonene, propylene, acetone and n-hexane. The modified cobalt-based catalyst prepared by the method has a multi-stage structure, and the metal oxide on the catalyst has high dispersity, so that the catalyst is more suitable for degrading the volatile organic compounds.
The combustion degradation adopts air as an oxidant, the reaction temperature is 100-400 ℃, and the preferable reaction temperature is 150-225 ℃.
The amount of the catalyst is that each gram of the catalyst treats waste gas containing 600-18000 ppm of volatile organic compounds, and the flow rate of the waste gas is 10-30L/h.
Compared with the prior art, the beneficial effects of the invention are embodied in the following aspects:
(1) the activity is high, the stability is good, and the complete combustion of low-concentration volatile organic compounds can be realized at relatively low temperature;
(2) the preparation process is simple, the raw materials are low in price and environment-friendly, and industrial amplification can be further realized;
(3) has potential application prospect in the aspects of environment protection such as degradation of volatile organic compounds and the like.
Drawings
FIGS. 1a, 1b, and 1c are Scanning Electron Microscope (SEM) images of catalysts prepared in examples 1, 2, and 3, respectively;
FIG. 2 is a graph of toluene combustion performance for experiments conducted on catalysts prepared in examples 1, 2, and 3;
FIG. 3 is a toluene combustion stability curve of the catalyst of example 3 tested at 200 ℃.
Detailed Description
The following examples are given for the detailed implementation and specific operation of the present invention, but the scope of the present invention is not limited to the following examples.
Example 1
6g of glucose is dissolved in 90mL of deionized water, and the obtained solution is ultrasonically vibrated for 30min until the glucose is uniformly dispersed in the solution. Pouring the glucose solution into a 100m L polytetrafluoroethylene liner, and placing the liner in a reaction kettle for reaction at 170 ℃ for 10 hours. Cooling to room temperature, filtering, washing with deionized water and anhydrous ethanol for 3 times alternately, and vacuum drying at 80 deg.C for 6 hr to obtain carbon sphere powder.
Taking soluble cobalt salt and lanthanum salt as precursors, wherein the molar ratio of La to Co is 0:1, adding a proper amount of deionized water to enable the concentration of metal ions in the solution to be equal to 0.12mol/L, and stirring to obtain a transparent mixed solution.
To the resulting solution, 0.05g of carbon spheres was added, and after ultrasonic oscillation for 1 hour, the carbon sphere powder was uniformly dispersed in the solution, and then an aqueous ammonia solution was slowly added dropwise with stirring to adjust the pH to 8.5. Aging for 12h, filtering, washing with deionized water for several times, and vacuum drying at 80 ℃ for 12h to obtain the metal hydroxide loaded carbon sphere powder. And then placing the cobalt-based catalyst in a muffle furnace for roasting at 400 ℃ for 2h to obtain a modified cobalt-based catalyst, scanning the modified cobalt-based catalyst by an electron microscope to obtain an SEM image as shown in figure 1a, wherein the obtained SEM image shows that the La-free Co-based catalyst material is mainly formed by stacking sheet structures with certain thicknesses, and has few gaps and poor dispersibility.
0.15g of the catalyst powder was weighed, mixed uniformly with 0.75g of quartz sand, and charged into a quartz microreactor (. phi. sup.4 mm). The reaction gas is ABenzene/air/nitrogen mixed gas with space velocity of 15000h-1，O2The volume fraction was 10%, and the volume fraction of toluene was 0.06%. The catalytic activity is measured within the range of 150-225 ℃, and the conversion rate of toluene is used as an index. The catalyst stability test temperature is 200 ℃, and the reaction time is more than 10 hours.
The catalyst prepared in example 1 was tested for its toluene light-off temperature (temperature corresponding to 10% toluene conversion) T by the above experiment10T of toluene at 186 ℃90At 210 ℃ complete conversion of toluene at 225 ℃ is achieved, as shown in FIG. 2.
Example 2:
this example is an example of a process for the preparation of a modified cobalt-based catalyst according to the invention.
6g of glucose is dissolved in 90mL of deionized water, and the obtained solution is ultrasonically vibrated for 30min until the glucose is uniformly dispersed in the solution. Pouring the glucose solution into a 100m L polytetrafluoroethylene liner, and placing the liner in a reaction kettle for reaction at 170 ℃ for 10 hours. Cooling to room temperature, filtering, washing with deionized water and anhydrous ethanol for 3 times alternately, and vacuum drying at 80 deg.C for 6 hr to obtain carbon sphere powder.
Taking soluble cobalt salt and lanthanum salt as precursors, wherein the molar ratio of La to Co is 1:10, adding a proper amount of deionized water to enable the concentration of metal ions in the solution to be equal to 0.12mol/L, and stirring to obtain a transparent mixed solution.
To the resulting solution, 0.05g of carbon spheres was added, and after ultrasonic oscillation for 1 hour, the carbon sphere powder was uniformly dispersed in the solution, and then an aqueous ammonia solution was slowly added dropwise with stirring to adjust the pH to 8.5. Aging for 12h, filtering, washing with deionized water for several times, and vacuum drying at 80 ℃ for 12h to obtain the metal hydroxide loaded carbon sphere powder. And then placing the cobalt-based catalyst in a muffle furnace to roast for 2 hours at the temperature of 400 ℃ to obtain the modified cobalt-based catalyst. The scanning electron microscope is used for scanning, an obtained SEM image is shown in figure 1b, and it can be seen from the SEM image that when a small amount of La is contained in the material, the number of material holes is increased, and the structure is changed to a petal shape on the whole.
0.15g of the catalyst powder was weighed, mixed uniformly with 0.75g of quartz sand, and charged into a quartz microreactor (. phi. sup.4 mm). Reaction ofThe gas is toluene/air/nitrogen mixed gas, wherein the space velocity is 15000h-1，O2The volume fraction was 10%, and the volume fraction of toluene was 0.06%. The catalytic activity is measured within the range of 150-225 ℃, and the conversion rate of toluene is used as an index. The catalyst stability test temperature is 200 ℃, and the reaction time is more than 10 hours.
The catalyst prepared in example 2 was tested for its toluene light-off temperature (temperature corresponding to 10% toluene conversion) T by the above experiment10T of toluene at 169 ℃90At 205 deg.C, complete conversion of toluene at 210 deg.C was achieved, as shown in FIG. 2.
Example 3:
this example is an example of a process for the preparation of a modified cobalt-based catalyst according to the invention.
6g of glucose is dissolved in 90mL of deionized water, and the obtained solution is ultrasonically vibrated for 30min until the glucose is uniformly dispersed in the solution. Pouring the glucose solution into a 100m L polytetrafluoroethylene liner, and placing the liner in a reaction kettle for reaction at 170 ℃ for 10 hours. Cooling to room temperature, filtering, washing with deionized water and anhydrous ethanol for 3 times alternately, and vacuum drying at 80 deg.C for 6 hr to obtain carbon sphere powder.
Taking soluble cobalt salt and lanthanum salt as precursors, wherein the molar ratio of La to Co is 1:4, adding a proper amount of deionized water to enable the concentration of metal ions in the solution to be equal to 0.12mol/L, and stirring to obtain a transparent mixed solution.
To the resulting solution, 0.05g of carbon spheres was added, and after ultrasonic oscillation for 1 hour, the carbon sphere powder was uniformly dispersed in the solution, and then an aqueous ammonia solution was slowly added dropwise with stirring to adjust the pH to 8.5. Aging for 12h, filtering, washing with deionized water for several times, and vacuum drying at 80 ℃ for 12h to obtain the metal hydroxide loaded carbon sphere powder. And then placing the cobalt-based catalyst in a muffle furnace to roast for 2 hours at the temperature of 400 ℃ to obtain the modified cobalt-based catalyst. Scanning the catalyst by an electron microscope to obtain an SEM image as shown in figure 1c, wherein the SEM image shows that the La content is continuously increased, the flaky structure of the material is obviously thinned, the flaky structure is overlapped and stacked to form a petal shape, the sheets are uniformly distributed, rich inter-granular pores are formed between the flaky structure and the petal-shaped flaky structure, and the contact area between the catalyst and a reactant is increased.
Weighing catalysis0.15g of the powder was mixed with 0.75g of quartz sand and the mixture was packed in a quartz microreactor (. phi. ═ 4 mm). The reaction gas is toluene/air/nitrogen mixed gas, wherein the space velocity is 15000h-1，O2The volume fraction was 10%, and the volume fraction of toluene was 0.06%. The catalytic activity is measured within the range of 150-225 ℃, and the conversion rate of toluene is used as an index. The catalyst stability test temperature is 200 ℃, and the reaction time is more than 10 hours.
The catalyst prepared in example 3 was tested for its toluene light-off temperature (temperature corresponding to 10% toluene conversion) T by the above experiment10T of toluene at less than 150 DEG C90At 178 ℃ toluene achieved complete conversion at 195 ℃. As shown in fig. 2.
The toluene combustion stability curve during combustion is shown in FIG. 3, from which we can see that the catalyst stability is high throughout the combustion process.
Example 4
This example is an example of a process for the preparation of a modified cobalt-based catalyst according to the invention.
6g of glucose is dissolved in 90mL of deionized water, and the obtained solution is ultrasonically vibrated for 30min until the glucose is uniformly dispersed in the solution. Pouring the glucose solution into a 100m L polytetrafluoroethylene liner, and placing the liner in a reaction kettle for reaction at 170 ℃ for 10 hours. Cooling to room temperature, filtering, washing with deionized water and anhydrous ethanol for 3 times alternately, and vacuum drying at 80 deg.C for 6 hr to obtain carbon sphere powder.
Taking soluble cobalt salt and lanthanum salt as precursors, wherein the molar ratio of La to Co is 1:4, adding a proper amount of deionized water to enable the concentration of metal ions in the solution to be equal to 0.12mol/L, and stirring to obtain a transparent mixed solution.
To the resulting solution, 0.05g of carbon spheres was added, and after ultrasonic oscillation for 1 hour, the carbon sphere powder was uniformly dispersed in the solution, and then an aqueous ammonia solution was slowly added dropwise with stirring to adjust the pH to 8.5. Aging for 12h, filtering, washing with deionized water for several times, and vacuum drying at 80 ℃ for 12h to obtain the metal hydroxide loaded carbon sphere powder. And then placing the cobalt-based catalyst in a muffle furnace to roast for 3 hours at the temperature of 400 ℃ to obtain the modified cobalt-based catalyst.
Weighing catalyst powder0.15g of silica sand was mixed homogeneously with 0.75g of silica sand and the mixture was charged into a silica microreactor (. phi. sup.4 mm). The reaction gas is toluene/air/nitrogen mixed gas, wherein the space velocity is 15000h-1，O2The volume fraction was 10%, and the volume fraction of toluene was 0.06%. The catalytic activity is measured within the range of 150-225 ℃, and the conversion rate of toluene is used as an index. The catalyst stability test temperature is 200 ℃, and the reaction time is more than 10 hours.
The catalyst prepared in example 4 was tested for its toluene light-off temperature (temperature corresponding to 10% toluene conversion) T by the above experiment10T of toluene at 168 ℃90At 195 deg.C, toluene achieved complete conversion at 255 deg.C.
Example 5:
this example is an example of a process for the preparation of a modified cobalt-based catalyst according to the invention.
6g of glucose is dissolved in 90mL of deionized water, and the obtained solution is ultrasonically vibrated for 30min until the glucose is uniformly dispersed in the solution. Pouring the glucose solution into a 100m L polytetrafluoroethylene liner, and placing the liner in a reaction kettle for reaction at 170 ℃ for 10 hours. Cooling to room temperature, filtering, washing with deionized water and anhydrous ethanol for 3 times alternately, and vacuum drying at 80 deg.C for 6 hr to obtain carbon sphere powder.
Taking soluble cobalt salt and lanthanum salt as precursors, wherein the molar ratio of La to Co is 1:4, adding a proper amount of deionized water to enable the concentration of metal ions in the solution to be equal to 0.12mol/L, and stirring to obtain a transparent mixed solution.
To the resulting solution, 0.05g of carbon spheres was added, and after ultrasonic oscillation for 1 hour, the carbon sphere powder was uniformly dispersed in the solution, and then an aqueous ammonia solution was slowly added dropwise with stirring to adjust the pH to 8.5. Aging for 12h, filtering, washing with deionized water for several times, and vacuum drying at 80 ℃ for 12h to obtain the metal hydroxide loaded carbon sphere powder. And then placing the cobalt-based catalyst in a muffle furnace to roast for 4 hours at the temperature of 400 ℃ to obtain the modified cobalt-based catalyst.
0.15g of the catalyst powder was weighed, mixed uniformly with 0.75g of quartz sand, and charged into a quartz microreactor (. phi. sup.4 mm). The reaction gas is toluene/air/nitrogen mixed gas, wherein the space velocity is 15000h-1，O2The volume fraction is 10%The volume fraction of toluene was 0.06%. The catalytic activity is measured within the range of 150-225 ℃, and the conversion rate of toluene is used as an index. The catalyst stability test temperature is 200 ℃, and the reaction time is more than 10 hours.
The catalyst prepared in example 5 was tested for its toluene light-off temperature (temperature corresponding to 10% toluene conversion) T by the above experiment10T of toluene at 180 DEG C90At 209 ℃ toluene achieved complete conversion at 270 ℃.
Example 6
Dissolving 5g of glucose in a mixed solution of 89mL of deionized water and 1mL of absolute ethyl alcohol, and ultrasonically oscillating the obtained solution for 30min until the glucose is uniformly dispersed in the solution. Pouring the glucose solution into a 100m L polytetrafluoroethylene liner, and placing the liner in a reaction kettle to react for 20 hours at 120 ℃. Cooling to room temperature, filtering, washing with deionized water and anhydrous ethanol for 3 times alternately, and vacuum drying at 60 deg.C for 10 hr to obtain carbon sphere powder.
Taking soluble cobalt salt and lanthanum salt as precursors, wherein the molar ratio of La to Co is 1:4, adding a proper amount of deionized water to enable the concentration of metal ions in the solution to be equal to 0.1mol/L, and stirring to obtain a transparent mixed solution.
Weighing 2.75g of the solution, adding 0.05g of carbon spheres into the solution, carrying out ultrasonic oscillation for 1h, uniformly dispersing carbon sphere powder into the solution, slowly dropwise adding an ammonia water solution while stirring, and adjusting the pH value to 7. Aging at room temperature for 12h, filtering, washing with deionized water for 3 times, vacuum drying at 60 ℃ for 24h to obtain metal hydroxide loaded carbon sphere powder, and roasting at 400 ℃ for 4h to obtain the modified cobalt-based catalyst.
Through detection, the modified cobalt-based catalyst obtained by the embodiment has strong stability and high catalytic activity.
Example 7
Dissolving 15g of glucose in a mixed solution of 35mL of deionized water and 35mL of absolute ethyl alcohol, and ultrasonically oscillating the obtained solution for 90min until the glucose is uniformly dispersed in the solution. Pouring the glucose solution into a 100m L polytetrafluoroethylene liner, and placing the liner in a reaction kettle for reaction at 180 ℃ for 5 hours. Cooling to room temperature, filtering, washing with deionized water and anhydrous ethanol for 5 times alternately, and vacuum drying at 120 deg.C for 6 hr to obtain carbon sphere powder.
Taking soluble cobalt salt and lanthanum salt as precursors, wherein the molar ratio of La to Co is 1:3, adding a proper amount of deionized water to enable the concentration of metal ions in the solution to be equal to 0.15mol/L, and stirring to obtain a transparent mixed solution.
Weighing 2.25g of the solution, adding 0.05g of carbon spheres, ultrasonically shaking for 1h, uniformly dispersing carbon sphere powder in the solution, slowly dropwise adding an ammonia water solution while stirring, and adjusting the pH value to 10. Aging at room temperature for 15h, filtering, washing with deionized water for 5 times, and vacuum drying at 1200 ℃ for 12h to obtain metal hydroxide loaded carbon sphere powder. Roasting for 2 hours at 500 ℃ to obtain the modified cobalt-based catalyst.
Through detection, the modified cobalt-based catalyst obtained by the embodiment has strong stability and high catalytic activity.

Claims (10)

1. A modified cobalt-based catalyst, which is characterized by comprising a carbon sphere carrier and cobalt oxide and a transition metal oxide which are loaded in the carbon sphere carrier, wherein the transition metal oxide comprises an oxide of Cu, Ce or La, and the molar ratio of the cobalt oxide to the transition metal oxide is 4: (0-1);
the preparation method of the modified cobalt-based catalyst comprises the following steps:
(1) dissolving glucose in an ethanol/water solution, reacting in a reaction kettle after ultrasonic oscillation, performing suction filtration after the reaction is finished, alternately washing with water and absolute ethyl alcohol, and drying to obtain a carbon sphere carrier;
(2) dissolving soluble Co salt and soluble transition metal salt in water to obtain a mixed solution, wherein the molar ratio of Co element and transition metal element in the soluble Co salt to the soluble transition metal salt is 4: (0-1), wherein the total molar concentration of the Co element and the transition metal element in the mixed solution is (0.1-0.15) mol/L;
(3) adding the carbon sphere carrier obtained in the step (1) into the mixed solution obtained in the step (2), performing ultrasonic oscillation, then dropwise adding ammonia water, adjusting the pH value to 7-10, aging, then filtering, washing and drying to obtain metal hydroxide loaded carbon sphere powder;
(4) and (4) roasting the metal hydroxide loaded carbon sphere powder obtained in the step (3) in an inert atmosphere to obtain the modified cobalt-based catalyst.
2. A process for the preparation of a modified cobalt-based catalyst according to claim 1, comprising the steps of:
(1) dissolving glucose in an ethanol/water solution, reacting in a reaction kettle after ultrasonic oscillation, performing suction filtration after the reaction is finished, alternately washing with water and absolute ethyl alcohol, and drying to obtain a carbon sphere carrier;
(2) dissolving soluble Co salt and soluble transition metal salt in water to obtain a mixed solution, wherein the molar ratio of Co element and transition metal element in the soluble Co salt to the soluble transition metal salt is 4: (0-1), wherein the total molar concentration of the Co element and the transition metal element in the mixed solution is (0.1-0.15) mol/L;
(3) adding the carbon sphere carrier obtained in the step (1) into the mixed solution obtained in the step (2), performing ultrasonic oscillation, then dropwise adding ammonia water, adjusting the pH value to 7-10, aging, then filtering, washing and drying to obtain metal hydroxide loaded carbon sphere powder;
(4) and (4) roasting the metal hydroxide loaded carbon sphere powder obtained in the step (3) in an inert atmosphere to obtain the modified cobalt-based catalyst.
3. The method of claim 2, wherein the ethanol/water solution in step (1) has a volume ratio of ethanol to water of 1: (1-89), wherein the ratio of the mass of the added glucose to the volume of the ethanol/water solution is (5-15) g: (70-90) mL, wherein the ultrasonic oscillation time in the step (1) is 30-90 min.
4. The preparation method of the modified cobalt-based catalyst according to claim 2, wherein the reaction in the step (1) is carried out in a reaction kettle with a polytetrafluoroethylene inner container, the reaction temperature is 120-180 ℃, and the reaction time is 5-12 h.
5. The preparation method of the modified cobalt-based catalyst according to claim 2, wherein after the reaction in the step (1) is finished, the cobalt-based catalyst is subjected to suction filtration, is alternately washed with water and absolute ethyl alcohol for 3-5 times, and is dried in vacuum at the temperature of 60-120 ℃ for 6-10 hours.
6. The preparation method of the modified cobalt-based catalyst according to claim 2, wherein the ratio of the mass of the added carbon sphere carrier to the volume of the mixed solution in the step (3) is (45-55): 1, and the time of ultrasonic oscillation in the step (3) is 1-2 h.
7. The preparation method of the modified cobalt-based catalyst according to claim 2, wherein the aging temperature is 15-25 ℃ and the aging time is 12-15 h, the modified cobalt-based catalyst is washed with water for 3-5 times after aging, and then dried in vacuum at 60-120 ℃ for 12-24 h.
8. The preparation method of the modified cobalt-based catalyst according to claim 2, wherein the roasting temperature is 400-500 ℃ and the roasting time is 2-4 h.
9. The use of a modified cobalt-based catalyst according to claim 1 for the catalytic combustion degradation of volatile organic compounds comprising one or a mixture of butane, 2-methylbutane, pentane, 2-toluene, 1, 3-butadiene, methylpentane, 3-methylhexane, methylheptane, cumene, propylbenzene, m-ethyltoluene, o-ethyltoluene, mesitylene, m-diethylbenzene, dodecane, dimethylsulfide, limonene, propylene, acetone, n-hexane.
10. The application of the modified cobalt-based catalyst according to claim 9, wherein the catalyst is used in an amount of 600-18000 ppm of volatile organic compounds in each gram of catalyst, and the flow rate of the exhaust gas is 10-30L/h.
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