CN112337465A - Carbon fiber core-shell catalyst and preparation method and application thereof - Google Patents

Carbon fiber core-shell catalyst and preparation method and application thereof Download PDF

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CN112337465A
CN112337465A CN202011250382.5A CN202011250382A CN112337465A CN 112337465 A CN112337465 A CN 112337465A CN 202011250382 A CN202011250382 A CN 202011250382A CN 112337465 A CN112337465 A CN 112337465A
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carbon fiber
shell
nitrate
solution
core
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CN112337465B (en
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李凯
张伊珊
王飞
宋辛
宁平
王驰
孙鑫
谢雨轩
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Kunming University of Science and Technology
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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
    • B01J23/72—Copper
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    • B01D—SEPARATION
    • B01D53/00—Separation of gases or vapours; Recovering vapours of volatile solvents from gases; Chemical or biological purification of waste gases, e.g. engine exhaust gases, smoke, fumes, flue gases, aerosols
    • B01D53/34—Chemical or biological purification of waste gases
    • B01D53/74—General processes for purification of waste gases; Apparatus or devices specially adapted therefor
    • B01D53/86—Catalytic processes
    • B01D53/8603—Removing sulfur compounds
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    • B01J23/70—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper
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    • B01J23/70—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper
    • B01J23/74—Iron group metals
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    • B01J37/00—Processes, in general, for preparing catalysts; Processes, in general, for activation of catalysts
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    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J37/00—Processes, in general, for preparing catalysts; Processes, in general, for activation of catalysts
    • B01J37/34—Irradiation by, or application of, electric, magnetic or wave energy, e.g. ultrasonic waves ; Ionic sputtering; Flame or plasma spraying; Particle radiation
    • B01J37/341—Irradiation by, or application of, electric, magnetic or wave energy, e.g. ultrasonic waves ; Ionic sputtering; Flame or plasma spraying; Particle radiation making use of electric or magnetic fields, wave energy or particle radiation
    • B01J37/342—Irradiation by, or application of, electric, magnetic or wave energy, e.g. ultrasonic waves ; Ionic sputtering; Flame or plasma spraying; Particle radiation making use of electric or magnetic fields, wave energy or particle radiation of electric, magnetic or electromagnetic fields, e.g. for magnetic separation
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    • B01D2258/025—Other waste gases from metallurgy plants

Abstract

The invention relates to the technical field of catalysts, in particular to a carbon fiber core-shell catalyst and a preparation method and application thereof. The carbon fiber core-shell catalyst provided by the invention takes carbon fibers as a core and metal oxides as a shell; the metal oxide is uniformly distributed on the surface of the carbon fiber; the metal in the metal oxide is one or more of iron, copper, aluminum, zinc, nickel, cobalt, manganese, lanthanum, cerium, praseodymium and neodymium. The carbon fiber is taken as a core, has larger specific surface area and good adsorption performance, and is beneficial to the adsorption of gas on a catalyst and the dispersion of metal oxide; the metal oxide serving as an active component is uniformly dispersed on the surface of the carbon fiber, so that the dispersion degree and the utilization rate of the active component are improved, and the activity of the catalyst is further improved. The results of the examples show that when the carbon fiber core-shell catalyst is used for catalyzing and hydrolyzing carbonyl sulfide and methyl mercaptan in CO-rich tail gas, the removal rate of the carbonyl sulfide and the methyl mercaptan can reach 100%.

Description

Carbon fiber core-shell catalyst and preparation method and application thereof
Technical Field
The invention relates to the technical field of catalysts, in particular to a carbon fiber core-shell catalyst and a preparation method and application thereof.
Background
The tail gas rich in CO is generated in the reduction smelting process of metal and nonmetal ores. These CO-rich tail gases can be used for the preparation of a carbonized chemical feed gas. However, the CO-rich tail gas contains trace organic sulfur impurities, mainly comprising carbonyl sulfide (COS) and methyl mercaptan (CH)3SH), and the like. In one aspect, COS and CH3The existence of SH can influence the utilization of CO in industrial tail gas, not only can cause catalyst poisoning, but also can corrode a pipeline and damage equipment; COS and CH, on the other hand3The discharge of SH into the atmosphere produces serious malodor, and is not easily decomposed, which may have serious influence on the atmospheric environment. Thus, COS and CH3The simultaneous removal of SH has become a problem that must be solved for the preparation of a carbon chemical feed gas.
COS and CH3Methods for removing SH gas are mainly classified into dry methods and wet methods. Compared with wet methodThe sulfur technology, dry method, has higher anti-poisoning performance, higher selectivity, lower operation cost and less secondary pollution. The catalytic hydrolysis method in the dry method has the advantages of higher catalytic selectivity, lower operation temperature and the like, and the tail gas of the reducing industrial furnace contains a small amount of water vapor which can directly participate in the hydrolysis reaction, and the reaction product is H2S、CO2And CH3OH, wherein H2S can be used for preparing sulfur, CH3OH can be used for the synthesis of formaldehyde and formic acid, etc.
Removing COS and CH at the same time3In the study of SH, the selection of the catalyst is of great importance. Removal of COS and CH commonly used at present3Catalysts for SH include carbon-based, metal oxides, aluminum-based materials, and the like, which react with COS and CH3The SH-removing effect is still to be further improved.
Disclosure of Invention
The invention aims to provide a carbon fiber core-shell catalyst, and a preparation method and application thereof3SH。
In order to achieve the above object, the present invention provides the following technical solutions:
the invention provides a carbon fiber core-shell catalyst, which takes carbon fiber as a core and metal oxide as a shell; the metal in the metal oxide is one or more of iron, copper, aluminum, zinc, nickel, cobalt, manganese, lanthanum, cerium, praseodymium and neodymium.
Preferably, the diameter of the carbon fiber core-shell catalyst is 300-500 nm.
The invention provides a preparation method of the carbon fiber core-shell catalyst, which comprises the following steps: dissolving a high molecular polymer in a dimethylformamide solution to obtain a nuclear solution; the high molecular polymer is polyacrylonitrile or polyvinyl alcohol; the molecular weight of the high molecular polymer is 8-25 ten thousand;
dissolving a metal salt in water to obtain a shell solution; the metal salt is one or more of ferric nitrate, ferric sulfate, copper nitrate, copper sulfate, aluminum nitrate, aluminum sulfate, zinc nitrate, zinc sulfate, nickel nitrate, cobalt nitrate, manganese nitrate, lanthanum nitrate, cerium nitrate, praseodymium nitrate and neodymium nitrate;
injecting the core solution into the inner layer of the coaxial needle, injecting the shell solution into the outer layer of the coaxial needle, and performing coaxial electrostatic spinning to obtain a catalyst precursor with a core-shell structure;
and sintering the catalyst precursor in a protective atmosphere to obtain the carbon fiber core-shell catalyst.
Preferably, the mass content of the high molecular polymer in the nuclear solution is 8-15%.
Preferably, the mass content of the metal salt in the shell solution is 1-20%.
Preferably, the electrospinning conditions include: the voltage is 12-25 kV, the advancing speed of the nuclear solution is 0.5-1.5 mL/h, the advancing speed of the shell solution is 1.0-2.5 mL/h, and the receiving distance is 15-20 cm.
Preferably, the sintering comprises two stages, wherein in the first stage, the temperature is increased to 200-300 ℃ from room temperature, the heat is preserved for 0.5-2 hours, and in the second stage, the temperature is increased to 600-1000 ℃ from the end temperature of the first stage, and the heat is preserved for 1-3 hours.
Preferably, the gas providing the protective atmosphere is nitrogen, argon or helium.
The invention provides an application of the carbon fiber core-shell catalyst or the carbon fiber core-shell catalyst prepared by the preparation method in the scheme in catalytic hydrolysis of carbonyl sulfide and methyl mercaptan in CO-rich tail gas.
Preferably, the reaction temperature of the catalytic hydrolysis is 40-120 ℃.
The invention provides a carbon fiber core-shell catalyst, which takes carbon fiber as a core and metal oxide as a shell; the metal in the metal oxide is one or more of iron, copper, aluminum, zinc, nickel, cobalt, manganese, lanthanum, cerium, praseodymium and neodymium. The carbon fiber is taken as a core, has larger specific surface area and good adsorption performance, and is beneficial to the adsorption of gas on a catalyst and the dispersion of metal oxide; the metal oxide is used as an active component, and the metal oxide is used as a shell and uniformly dispersed on the surface of the carbon fiber, so that the dispersion degree and the utilization rate of the active component are improved, and the activity of the catalyst is further improved.
The results of the examples show that when the carbon fiber core-shell catalyst is used for catalyzing and hydrolyzing carbonyl sulfide and methyl mercaptan in CO-rich tail gas, the removal rate of the carbonyl sulfide and the methyl mercaptan can reach 100%.
The invention provides a preparation method of the carbon fiber core-shell catalyst, which comprises the following steps: dissolving a high molecular polymer in a dimethylformamide solution to obtain a nuclear solution; the high molecular polymer is polyacrylonitrile or polyvinyl alcohol; the molecular weight of the high molecular polymer is 8-25 ten thousand;
dissolving a metal salt in water to obtain a shell solution; the metal salt is one or more of ferric nitrate, ferric sulfate, copper nitrate, copper sulfate, aluminum nitrate, aluminum sulfate, zinc nitrate, zinc sulfate, nickel nitrate, cobalt nitrate, manganese nitrate, lanthanum nitrate, cerium nitrate, praseodymium nitrate and neodymium nitrate;
injecting the core solution into the inner layer of the coaxial needle, injecting the shell solution into the outer layer of the coaxial needle, and performing coaxial electrostatic spinning to obtain a catalyst precursor with a core-shell structure;
and sintering the catalyst precursor in a protective atmosphere to obtain the carbon fiber core-shell catalyst.
The carbon fiber core-shell catalyst prepared by the coaxial electrospinning method can be stably prepared into the core-shell carbon fiber catalyst with uniform specification. Compared with the traditional loading method, such as a sol-gel method, a coprecipitation method, an ultrasonic impregnation method and the like, the method can form a stable core-shell structure and save the preparation time.
The invention uses the coaxial electrospinning method, so that the metal oxide as an active component is uniformly covered, and the diameter structure of the inner carbon fiber is uniform, thereby being beneficial to improving the catalytic performance of the catalyst.
In addition, the preparation method provided by the invention is simple to operate, has fewer steps and is easy to control, the preparation time of the catalyst is relatively short, the yield is relatively high, the raw materials and the metal salt are cheap and easy to obtain, the raw materials are not limited by time and regions, and the obtained catalyst is high in catalytic activity, regular in form, good in controllability and easy to realize industrial application.
Drawings
FIG. 1 shows COS and CH of the carbon fiber core-shell catalyst of example 13SH catalytic conversion plot;
FIG. 2 depicts COS and CH of the carbon fiber core-shell catalyst of example 23SH catalytic conversion plot;
FIG. 3 depicts COS and CH of the carbon fiber core-shell catalyst of example 33SH catalytic conversion plot;
FIG. 4 depicts COS and CH for the carbon fiber core-shell catalyst of example 43Graph of SH catalytic conversion.
Detailed Description
The invention provides a carbon fiber core-shell catalyst, which takes carbon fiber as a core and metal oxide as a shell; the metal in the metal oxide is one or more of iron, copper, aluminum, zinc, nickel, cobalt, manganese, lanthanum, cerium, praseodymium and neodymium.
In the present invention, the metal in the metal oxide is preferably one or more of copper, iron, cobalt and nickel. When the metal in the metal oxide is various, the proportion of each metal oxide is not specially required, and any proportion can be adopted.
The carbon fiber core-shell catalyst is fibrous as a whole; the diameter of the carbon fiber core-shell catalyst is preferably 500-600 nm, more preferably 520-580 nm, and most preferably 540-560 nm.
In the present invention, the diameter of the carbon fiber is preferably 300 to 400nm, and more preferably 320 to 380 nm.
The carbon fiber is taken as a core, has larger specific surface area and good adsorption performance, and is beneficial to the adsorption of gas on a catalyst and the dispersion of oxides; the metal oxide is used as an active component, and the metal oxide is used as a shell and uniformly dispersed on the surface of the carbon fiber, so that the dispersion degree and the utilization rate of the active component are improved, and the activity of the catalyst is further improved.
The invention provides a preparation method of the carbon fiber core-shell catalyst, which comprises the following steps: dissolving a high molecular polymer in a dimethylformamide solution to obtain a nuclear solution; the high molecular polymer is polyacrylonitrile or polyvinyl alcohol; the molecular weight of the high molecular polymer is 8-25 ten thousand;
dissolving a metal salt in water to obtain a shell solution; the metal salt is one or more of ferric nitrate, ferric sulfate, copper nitrate, copper sulfate, aluminum nitrate, aluminum sulfate, zinc nitrate, zinc sulfate, nickel nitrate, cobalt nitrate, manganese nitrate, lanthanum nitrate, cerium nitrate, praseodymium nitrate and neodymium nitrate;
injecting the core solution into the inner layer of the coaxial needle, injecting the shell solution into the outer layer of the coaxial needle, and performing coaxial electrostatic spinning to obtain a catalyst precursor with a core-shell structure;
and sintering the catalyst precursor in a protective atmosphere to obtain the carbon fiber core-shell catalyst.
In the present invention, the starting materials used are all commercially available products well known in the art, unless otherwise specified.
The invention dissolves high molecular polymer in dimethyl formamide solution to obtain nuclear solution.
In the invention, the high molecular polymer is polyacrylonitrile or polyvinyl alcohol, and is preferably polyacrylonitrile. In the present invention, the molecular weight of the high molecular weight polymer is 8 to 25 ten thousand, preferably 10 to 22 ten thousand, and more preferably 13 to 20 ten thousand. The invention controls the molecular weight of the high molecular weight polymer within the range, on one hand, the spun fiber filaments can be prevented from being adhered, and simultaneously, the filament interruption in the spinning process can be avoided, the filament is discontinuous after roasting, and the fiber is not easy to form.
The invention adopts the dimethyl formamide to dissolve the high molecular polymer, and can ensure that the high molecular polymer has higher dispersibility.
In the present invention, the process of dissolving the high molecular weight polymer in the dimethylformamide solution is preferably: and mixing the high molecular polymer and dimethylformamide, and stirring at 50-70 ℃ for 12-18 h to obtain a nuclear solution. The invention controls the dissolving temperature to be 50-70 ℃, on one hand, the dimethyl formamide volatilization caused by overhigh temperature can be prevented, and on the other hand, the nuclear solution solidification caused by overlow temperature can be prevented.
In the invention, the mass content of the polymer in the nuclear solution is preferably 8-15%, more preferably 9-14%, and even more preferably 10-13%.
The invention dissolves metal salt in water to obtain shell solution.
In the present invention, the metal salt is one or more of iron nitrate, iron sulfate, copper nitrate, copper sulfate, aluminum nitrate, aluminum sulfate, zinc nitrate, zinc sulfate, nickel nitrate, cobalt nitrate, manganese nitrate, lanthanum nitrate, cerium nitrate, praseodymium nitrate and neodymium nitrate, and preferably one or more of iron nitrate, iron sulfate, copper nitrate, copper sulfate, nickel nitrate and cobalt nitrate. When the metal salt is a plurality of the above substances, the proportion of each metal salt is not particularly required and can be any. In the embodiment of the present invention, when the metal salt is iron nitrate and nickel nitrate, the mass ratio of the iron nitrate to the nickel nitrate is 3: 1; when the metal salt is copper nitrate and ferric nitrate, the mass ratio of the copper nitrate to the ferric nitrate is 5: 1.
In the present invention, the mass content of the metal salt in the shell solution is preferably 1 to 20%, more preferably 5 to 16%, even more preferably 7 to 14%, and most preferably 9 to 13%.
After obtaining a core solution and a shell solution, injecting the core solution into the inner layer of the coaxial needle, injecting the shell solution into the outer layer of the coaxial needle, and performing coaxial electrostatic spinning to obtain a catalyst precursor with a core-shell structure.
The invention has no special requirements on the equipment adopted by the coaxial electrostatic spinning, and the coaxial electrostatic spinning equipment well known in the field can be adopted.
In the present invention, the conditions of the coaxial electrospinning preferably include: the voltage is 12-25 kV, the advancing speed of the nuclear solution is 0.5-1.5 mL/h, the advancing speed of the shell solution is 1.0-2.5 mL/h, and the receiving distance is 15-20 cm. Further preferably, the voltage is 15-22 kV, the advancing speed of the core solution is 0.7-1.2 mL/h, the advancing speed of the shell solution is 1.5-2.0 mL/h, and the receiving distance is 16-18 cm.
The invention can stably prepare the catalyst precursor with uniform specification and a core-shell fiber structure by controlling the conditions of coaxial electrostatic spinning.
In the present invention, the ambient temperature of the coaxial electrospinning is preferably room temperature.
In the present invention, the receiver used for the electrospinning is preferably a flat plate receiver, a rotating drum receiver, or a roll shaft receiver. When a rotary drum receiver or a roll shaft receiver is used, the roller rotation speed is preferably 500 to 1500rmp, more preferably 700 to 1200 rmp. In the present invention, when a flat plate receiver or a roll receiver is employed, the present invention preferably covers a copper foil on the receiver for receiving the catalyst precursor. In the present invention, when the receiver is a rotating drum receiver, the present invention does not require the attachment of copper foil paper.
The catalyst precursor with the core-shell structure is obtained by coaxial electrostatic spinning, the inner layer is organic high-molecular polymer fiber, the outer layer is a film formed by metal salt solution, and the whole body is fibrous.
After the catalyst precursor with the core-shell structure is obtained, the catalyst precursor is sintered under a protective atmosphere to obtain the carbon fiber core-shell catalyst.
In the present invention, the gas for providing the protective atmosphere is preferably nitrogen, argon or helium.
In the invention, the sintering preferably comprises two stages, wherein the first stage preferably comprises heating from room temperature to 200-300 ℃ and keeping the temperature for 0.5-2 h; preferably, the temperature of the second stage is raised to 600-1000 ℃ from the end temperature of the first stage, and the temperature is kept for 1-3 h. Further preferably, the temperature rise in the first stage is 220-280 ℃, and the heat preservation time is 1.0-1.5 h; the temperature rise temperature of the second stage is 700-900 ℃, and the heat preservation time is 1.5-2.5 h. In the present invention, the temperature increase rate in the first and second stages is preferably 5 ℃/min.
The first stage sintering of the invention aims to volatilize the dimethylformamide in the inner layer and the solvent in the solution in the outer layer, and fix the fiber shape of the inner layer; the purpose of the second stage sintering is to carbonize the inner high molecular polymer into carbon fibers and oxidize the outer metal salt into metal oxide at high temperature.
The invention provides an application of the carbon fiber core-shell catalyst or the carbon fiber core-shell catalyst prepared by the preparation method in the scheme in catalytic hydrolysis of carbonyl sulfide and methyl mercaptan in CO-rich tail gas.
In the invention, the concentration of carbonyl sulfide in the CO-rich tail gas is preferably 100-400 ppm, and the concentration of methyl mercaptan is preferably 100-200 ppm; the water content of the CO-rich tail gas is preferably 1-5%, and more preferably 2-4%.
In the present invention, the process of the catalytic hydrolysis reaction is preferably: and placing the carbon fiber core-shell catalyst in a fixed quartz reactor, and then continuously introducing CO-rich tail gas containing carbonyl sulfide and methyl mercaptan to perform catalytic hydrolysis reaction.
In the invention, the temperature of the catalytic hydrolysis reaction is preferably 40-120 ℃, preferably 50-100 ℃, and more preferably 60-80 ℃; the space velocity of the reaction is preferably 10000h-1。
In the invention, carbonyl sulfide (COS) and methyl mercaptan (CH) are removed by using a carbon fiber core-shell catalyst3SH) are as follows:
Figure BDA0002771392690000071
Figure BDA0002771392690000072
the carbon fiber core-shell catalyst provided by the present invention, the preparation method and the application thereof are described in detail with reference to the following examples, but they should not be construed as limiting the scope of the present invention.
Example 1
Polyacrylonitrile (PAN) powder with a polymer molecular weight of 15 ten thousand and dimethylformamide solution (DMF) were mixed and stirred at 60 ℃ for 12h to obtain a core solution (concentration 10 wt.%); preparing a copper nitrate solution with the concentration of 10 wt.% to obtain a shell solution; injecting a core solution into the inner layer of a coaxial needle head, injecting a shell solution into the outer layer of the coaxial needle head, using a roller shaft receiver of an electrostatic spinning device, wherein the rotating speed of the roller shaft is 1000rmp, covering a copper foil on the receiver, the distance between the needle head of the receiver and the receiver is 15cm, the needle head is connected with an anode, the receiver is connected with a cathode, the voltage is 18kV (15 kV of the anode and 3kV of the cathode), the propelling speed of the outer layer solution is 2.0mL/h, the propelling speed of the inner layer solution is 1.0mL/h, and a catalyst precursor with a core-shell structure is obtained under the above; and (2) taking off the catalyst precursor from the copper foil paper, putting the copper foil paper into a tubular furnace, and carrying out stage-type heating roasting in a nitrogen atmosphere, wherein the temperature is increased from room temperature to 200 ℃ in the first stage and is kept for 1h, the temperature is increased from the end temperature of the first stage to 800 ℃ in the second stage and is kept for 1h, the heating rate is 5 ℃/min, and the carbon fiber core-shell catalyst with the inner layer being carbon fiber and the outer layer being copper oxide (including copper oxide and cuprous oxide, mainly copper oxide) is obtained. The diameter of the carbon fiber core-shell catalyst is 500-600 nm, and the diameter of the carbon fiber of the inner layer is 300-400 nm.
The activity test of the catalyst is carried out in a fixed quartz reactor with the diameter of 6mm multiplied by 110mm, and the reaction conditions are as follows: COS concentration 500ppm, CH3SH concentration of 200ppm, water content of 2.42 percent and airspeed of 10000h-1The reaction temperature was 60 ℃ and no H was detected at the reaction outlet2S, and COS, CH3SH hydrolysis catalytic conversion results are shown in FIG. 1, from which it can be concluded that 100% COS removal rate can be maintained for 300min, and 100% CH3The SH removal rate can be maintained for 210min, which shows that the carbon fiber core-shell carbon fiber catalyst can be used for treating COS and CH3The removal of SH has a significant effect.
Example 2
Polyacrylonitrile (PAN) powder with a polymer molecular weight of 15 ten thousand and dimethylformamide solution (DMF) were mixed and stirred at 60 ℃ for 12h to obtain a core solution (concentration 10 wt.%); preparing a metal salt solution with the concentration of 10 wt% (the mass ratio of copper nitrate to ferric nitrate is 5: 1) to obtain a shell solution; injecting the core solution into the inner layer of the coaxial needle, injecting the shell solution into the outer layer of the coaxial needle, using a roller shaft receiver of electrostatic spinning equipment, wherein the rotating speed of the roller shaft is 1000rmp, covering copper foil on the receiver, the distance from the needle of the receiver to the receiver is 15cm, the needle is connected with an anode, the receiver is connected with a cathode, the voltage is 18kV (15 kV of the anode and 3kV of the cathode), the propelling speed of the outer layer solution is 2.0mL/h, and the propelling speed of the inner layer solution is 1.0mL/h, thus obtaining the catalyst precursor with the core-shell structure under the above conditions; and (2) taking off the catalyst precursor from the copper foil paper, putting the copper foil paper into a tubular furnace, and carrying out stage-type heating roasting in a nitrogen atmosphere, wherein in the first stage, the temperature is increased from room temperature to 200 ℃ and is kept for 1h, in the second stage, the temperature is increased from the end temperature of the first stage to 800 ℃ and is kept for 1h, the heating rate is 5 ℃/min, and the carbon fiber core-shell catalyst with the inner layer being carbon fiber and the outer layer being copper oxide and iron oxide attached is obtained. The diameter of the carbon fiber core-shell catalyst is 500-600 nm, and the diameter of the carbon fiber of the inner layer is 300-400 nm.
The activity test of the catalyst is carried out in a fixed quartz reactor with the diameter of 6mm multiplied by 110mm, and the reaction conditions are as follows: COS concentration 500ppm, CH3SH concentration of 200ppm, water content of 2.42 percent and airspeed of 10000h-1The reaction temperature was 60 ℃ and no H was detected at the reaction outlet2S, and COS, CH3SH hydrolysis catalytic conversion results are shown in FIG. 2, from which it can be seen that 100% COS removal rate can be maintained for 270min, and 100% CH3The SH removal rate can be maintained for 240min, which shows that the carbon fiber core-shell catalyst can be used for treating COS and CH3The removal of SH has a significant effect.
Example 3
Polyacrylonitrile (PAN) powder with a polymer molecular weight of 20 ten thousand and dimethylformamide solution (DMF) were mixed and stirred at 50 ℃ for 18h to obtain a core solution (concentration 10 wt.%); preparing a cobalt nitrate solution with the concentration of 20 wt.% as a shell solution; injecting the core solution into the inner layer of the coaxial needle, injecting the shell solution into the outer layer of the coaxial needle, covering a copper foil on a receiver by using an electrostatic spinning equipment flat receiver, wherein the distance between the receiver needle and the receiver is 20cm, the needle is connected with an anode, the receiver is connected with a cathode, the voltage is 25kV (20 kV of the anode and the cathode-5 kV of the receiver), the propelling speed of the outer layer solution is 2.5mL/h, the propelling speed of the inner layer solution is 1.5mL/h, and the catalyst precursor with the core-shell structure is obtained under the above conditions; and (2) taking off the catalyst precursor from the copper foil paper, putting the copper foil paper into a tubular furnace, and carrying out stage-type heating roasting in a nitrogen atmosphere, wherein the temperature is increased to 250 ℃ from room temperature in the first stage and is kept for 1.5h, the temperature is increased to 900 ℃ from the end temperature in the second stage and is kept for 2h, the heating rate is 5 ℃/min, and the carbon fiber core-shell catalyst with the inner layer being carbon fiber and the outer layer being attached with metal oxide (cobalt oxide) is obtained. The diameter of the carbon fiber core-shell catalyst is 500-600 nm, and the diameter of the carbon fiber of the inner layer is 300-400 nm.
The activity test of the catalyst is carried out in a fixed quartz reactor with the diameter of 6mm multiplied by 110mm, and the reaction conditions are as follows: COS concentration 500ppm, CH3SH concentration of 200ppm, water content of 2.42 percent and airspeed of 10000h-1The reaction temperature was 60 ℃ and no H was detected at the reaction outlet2S, and COS, CH3SH hydrolysis catalytic conversion results are shown in FIG. 3, from which it can be seen that 100% COS removal rate can be maintained for 240min, and 100% CH3The SH removal rate can be maintained for 180min, which shows that the carbon fiber core-shell catalyst can be used for treating COS and CH3The removal of SH has a significant effect.
Example 4
Polyacrylonitrile (PAN) powder with a polymer molecular weight of 25 million and dimethylformamide solution (DMF) were mixed and stirred at 70 ℃ for 18h to obtain a core solution (concentration 15 wt.%); preparing a metal salt solution with the concentration of 20 wt% (the mass ratio of ferric nitrate to nickel nitrate is 3: 1) as a shell solution; injecting the core solution into the inner layer of the coaxial needle, injecting the shell solution into the outer layer of the coaxial needle, rotating a roller receiver by using electrostatic spinning equipment, wherein the distance from the receiver needle to the receiver is 20cm, the needle is connected with a positive electrode, the receiver is connected with a negative electrode, the voltage is 20kV (the positive electrode is 15kV, and the negative electrode is-5 kV), the propelling speed of the outer layer solution is 1.5mL/h, the propelling speed of the inner layer solution is 0.8mL/h, and a catalyst precursor with a core-shell structure is obtained under the conditions; and (2) removing the catalyst precursor, putting the catalyst precursor into a tubular furnace, and carrying out stage-type heating roasting in a nitrogen atmosphere, wherein the temperature is increased to 300 ℃ from room temperature in the first stage and is kept for 2 hours, the temperature is increased to 980 ℃ from the end temperature in the second stage and is kept for 3 hours, the heating rate is 5 ℃/min, and the carbon fiber core-shell catalyst with the inner layer being carbon fiber and the outer layer being iron oxide and nickel oxide attached is obtained. The diameter of the carbon fiber core-shell catalyst is 500-600 nm, and the diameter of the carbon fiber of the inner layer is 300-400 nm.
The activity test of the catalyst is carried out in a fixed quartz reactor with the diameter of 6mm multiplied by 110mm, and the reaction conditions are as follows: COS concentration 500ppm, CH3SH concentration of 200ppm, water content of 2.42 percent and airspeed of 10000h-1The reaction temperature was 60 ℃ and no H was detected at the reaction outlet2S, and COS, CH3SH hydrolysis catalytic conversion results are shown in FIG. 4, from which it can be concluded that 100% COS removal rate can be maintained for 210min, and 100% CH3The SH removal rate can be maintained for 240min, which shows that the carbon fiber core-shell catalyst can be used for treating COS and CH3The removal of SH has a significant effect.
The foregoing is only a preferred embodiment of the present invention, and it should be noted that, for those skilled in the art, various modifications and decorations can be made without departing from the principle of the present invention, and these modifications and decorations should also be regarded as the protection scope of the present invention.

Claims (10)

1. A carbon fiber core-shell catalyst takes carbon fiber as a core and metal oxide as a shell; the metal in the metal oxide is one or more of iron, copper, aluminum, zinc, nickel, cobalt, manganese, lanthanum, cerium, praseodymium and neodymium.
2. The carbon fiber core-shell catalyst according to claim 1, wherein the diameter of the carbon fiber core-shell catalyst is 300 to 500 nm.
3. The preparation method of the carbon fiber core-shell catalyst according to claim 1 or 2, comprising the steps of: dissolving a high molecular polymer in a dimethylformamide solution to obtain a nuclear solution; the high molecular polymer is polyacrylonitrile or polyvinyl alcohol; the molecular weight of the high molecular polymer is 8-25 ten thousand;
dissolving a metal salt in water to obtain a shell solution; the metal salt is one or more of ferric nitrate, ferric sulfate, copper nitrate, copper sulfate, aluminum nitrate, aluminum sulfate, zinc nitrate, zinc sulfate, nickel nitrate, cobalt nitrate, manganese nitrate, lanthanum nitrate, cerium nitrate, praseodymium nitrate and neodymium nitrate;
injecting the core solution into the inner layer of the coaxial needle, injecting the shell solution into the outer layer of the coaxial needle, and performing coaxial electrostatic spinning to obtain a catalyst precursor with a core-shell structure;
and sintering the catalyst precursor in a protective atmosphere to obtain the carbon fiber core-shell catalyst.
4. The method according to claim 3, wherein the polymer in the core solution is contained in an amount of 8 to 15% by mass.
5. The method according to claim 3, wherein the metal salt is contained in the shell solution in an amount of 1 to 20% by mass.
6. The production method according to claim 3, wherein the conditions for the electrospinning include: the voltage is 12-25 kV, the advancing speed of the nuclear solution is 0.5-1.5 mL/h, the advancing speed of the shell solution is 1.0-2.5 mL/h, and the receiving distance is 15-20 cm.
7. The preparation method according to claim 3, wherein the sintering comprises two stages, the temperature is raised from room temperature to 200-300 ℃ in the first stage and is kept for 0.5-2 h, and the temperature is raised from the end temperature of the first stage to 600-1000 ℃ in the second stage and is kept for 1-3 h.
8. The method of claim 3, wherein the gas providing the protective atmosphere is nitrogen, argon or helium.
9. The carbon fiber core-shell catalyst of claim 1 or 2 or the carbon fiber core-shell catalyst prepared by the preparation method of any one of claims 3 to 8 is applied to catalytic hydrolysis of carbonyl sulfide and methyl mercaptan in CO-rich tail gas.
10. The use according to claim 9, wherein the reaction temperature of the catalytic hydrolysis is 40 to 120 ℃.
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