CN113215818A - Metal interstitial compound/activated carbon fiber composite material and preparation method and application thereof - Google Patents

Metal interstitial compound/activated carbon fiber composite material and preparation method and application thereof Download PDF

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CN113215818A
CN113215818A CN202110352859.9A CN202110352859A CN113215818A CN 113215818 A CN113215818 A CN 113215818A CN 202110352859 A CN202110352859 A CN 202110352859A CN 113215818 A CN113215818 A CN 113215818A
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activated carbon
carbon fiber
metal
composite material
fiber composite
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CN113215818B (en
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赵佳
李飞彪
岳玉学
冯涛
江曌
于明德
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Zhejiang University of Technology ZJUT
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Zhejiang University of Technology ZJUT
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    • D06M11/80—Treating fibres, threads, yarns, fabrics or fibrous goods made from such materials, with inorganic substances or complexes thereof; Such treatment combined with mechanical treatment, e.g. mercerising with boron or compounds thereof, e.g. borides
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    • B01J21/00—Catalysts comprising the elements, oxides, or hydroxides of magnesium, boron, aluminium, carbon, silicon, titanium, zirconium, or hafnium
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    • 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
    • B01J37/343—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 ultrasonic wave energy
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    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C5/00—Preparation of hydrocarbons from hydrocarbons containing the same number of carbon atoms
    • C07C5/02—Preparation of hydrocarbons from hydrocarbons containing the same number of carbon atoms by hydrogenation
    • C07C5/08—Preparation of hydrocarbons from hydrocarbons containing the same number of carbon atoms by hydrogenation of carbon-to-carbon triple bonds
    • C07C5/09—Preparation of hydrocarbons from hydrocarbons containing the same number of carbon atoms by hydrogenation of carbon-to-carbon triple bonds to carbon-to-carbon double bonds
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    • D06M2101/40—Fibres of carbon
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Abstract

The invention discloses a metal interstitial compound/activated carbon fiber composite material and a preparation method and application thereof. The preparation method of the metal interstitial compound/activated carbon fiber composite material comprises the following steps: dispersing the metal interstitial compound onto the activated carbon fiber by using an impregnation method, and performing ultrasonic treatment on a mixture of the metal interstitial compound, a solvent and the activated carbon fiber before impregnation; then roasting at the high temperature of 300-800 ℃ in an inert atmosphere to obtain a metal interstitial compound/activated carbon fiber composite material; the metal gap-filling compound is one or more of magnesium boride, molybdenum nitride, zirconium carbide, palladium phosphide, ferrotitanium carbide and sodium hexafluoroantimonate, and the mass ratio of the metal gap-filling compound to the activated carbon fiber is 5-10%. The invention provides application of the metal interstitial compound/activated carbon fiber composite material as an adsorbing material in removing VOCs (volatile organic compounds), as a catalyst in synthesizing ethylene by acetylene hydrogenation or in a formaldehyde oxidation reaction at room temperature.

Description

Metal interstitial compound/activated carbon fiber composite material and preparation method and application thereof
(I) technical field
The invention relates to a metal interstitial compound/activated carbon fiber composite material and a preparation method and application thereof.
(II) background of the invention
Transition metal nitrides, carbides, and phosphides are a class of compounds in which non-metallic elements (N, C or P) are interstitially formed in a lattice of metal atoms, and belong to the class of metal interstitial compounds. The properties of metal interstitial compounds are very different from those of pure metals. When the non-metal element is filled in the metal crystal, the structure of the metal and the electronic structure of the outer layer can be changed microscopically, and further the physical and chemical properties of the metal can be changed. The catalyst is particularly characterized by the adsorption and activation of reactants. Transition metal nitrides, carbides, and phosphides are three types of metal interstitial compounds that have attracted much attention in the field of catalysis, and they exhibit excellent catalytic performance in many reactions. Transition metal nitrides and carbides are a class of compounds having metallic properties formed by the incorporation of nitrogen and carbon atoms into the crystal lattice of the transition metal, and their physicochemical properties are also very similar because of the proximity of the non-metallic elements nitrogen and carbon that make up the nitrides and carbides in the periodic table of the elements. They combine the properties of covalent compounds, ionic crystals and transition metals, and thus exhibit particular physical and chemical properties.
Activated Carbon Fiber (ACF), also known as fibrous activated carbon, is a highly efficient activated adsorbent material and an environmentally friendly engineering material with superior performance to activated carbon. More than 50% of carbon atoms are positioned on the inner surface and the outer surface, and a unique adsorption structure is constructed, so that the surface solid is called. It is made up by using fibrous precursor body and making it undergo the processes of carbonization and activation. The developed specific surface area and the narrow pore size distribution enable the adsorbent to have high adsorption and desorption speed and high adsorption capacity, and the adsorbent can be conveniently processed into different shapes such as felt, cloth, paper and the like and has the characteristics of acid resistance, alkali resistance and corrosion resistance, so that people have attracted extensive attention and intensive research. The catalyst is widely applied to the fields of environmental protection, catalysis, medicine, military industry and the like.
Disclosure of the invention
It is a first object of the present invention to provide a metal interstitial compound/activated carbon fiber composite.
The second purpose of the invention is to provide a preparation method of the metal interstitial compound/activated carbon fiber composite material.
The third purpose of the invention is to provide the application of the metal interstitial compound/activated carbon fiber composite material as an adsorbing material in removing Volatile Organic Compounds (VOCs).
The fourth purpose of the invention is to provide the application of the metal interstitial compound/activated carbon fiber composite material as a catalyst in the synthesis of ethylene by acetylene hydrogenation.
The fifth purpose of the invention is to provide the application of the metal interstitial compound/activated carbon fiber composite material as a catalyst in the room-temperature formaldehyde oxidation reaction.
In order to achieve the purpose, the invention adopts the following technical scheme:
in a first aspect, the present invention provides a metal interstitial compound/activated carbon fiber composite material prepared by a method comprising the steps of: dispersing the metal gap-filling compound on the activated carbon fiber by using an impregnation method, and performing ultrasonic treatment on a mixture of the metal gap-filling compound, a solvent and the activated carbon fiber before impregnation, wherein the ultrasonic treatment frequency is 20-80 kHz, and the ultrasonic treatment time is 0.5-1 h, so that the metal gap-filling compound is uniformly dispersed on the surface of the activated carbon fiber; then roasting at the high temperature of 300-800 ℃ in an inert atmosphere to obtain a metal interstitial compound/activated carbon fiber composite material; the metal gap-filling compound is one or more of magnesium boride, molybdenum nitride, zirconium carbide, palladium phosphide, ferrotitanium carbide and sodium hexafluoroantimonate, and the mass ratio of the metal gap-filling compound to the activated carbon fiber is 5-10%.
Furthermore, the specific surface area of the activated carbon fiber is 800-1600 m2(ii) in terms of/g. The activated carbon fiber is preferably a viscose-based activated carbon fiber, and commercially available products can be used.
In a second aspect, the present invention provides a method for preparing a metal interstitial compound/activated carbon fiber composite material, comprising the following steps:
1) adding a certain amount of metal interstitial compound into the solvent to obtain a uniformly dispersed mixture;
2) adding activated carbon fibers into the mixture obtained in the step 1), carrying out ultrasonic treatment for 0.5-1 h at the ultrasonic treatment frequency of 20-100 kHz, uniformly dispersing the metal interstitial compound on the surfaces of the activated carbon fibers, and then soaking for 6-12 h;
3) drying the mixture obtained in the step 2) to volatilize the solvent;
4) and (3) roasting the sample obtained in the step 3) at a high temperature of 300-800 ℃ in an inert atmosphere to obtain the metal interstitial compound/activated carbon fiber composite material.
Further, the solvent in the step 1) is one or more of deionized water, absolute ethyl alcohol, methanol and acetone.
Further, the drying temperature in the step 3) is 80-120 ℃, and the drying time is 12-24 hours.
Further, the inert atmosphere in the step 4) is nitrogen.
Further, the roasting temperature in the step 4) is 300-800 ℃, the heating rate is 5-10 ℃/min, and the roasting time is 2-6 h.
In a third aspect, the invention provides the application of the metal interstitial compound/activated carbon fiber composite material as an adsorbing material in removing VOCs (volatile organic compounds).
Further, the application specifically comprises: and (2) filling the metal interstitial compound/activated carbon fiber composite material into a fixed bed reactor, introducing gas containing VOCs, and removing the VOCs under the conditions of the temperature of 25-30 ℃ and the pressure of 0.1-0.2 MPa.
Furthermore, the flow rate of the gas containing VOCs is 50-120 mL x min-1。
In a fourth aspect, the invention provides an application of the metal interstitial compound/activated carbon fiber composite material as a catalyst in the synthesis of ethylene by acetylene hydrogenation.
Further, the application specifically comprises: and (2) filling the metal interstitial compound/activated carbon fiber composite material into a fixed bed reactor, introducing raw material gas acetylene and hydrogen, and reacting at the reaction temperature of 100-300 ℃ and the reaction pressure of 0.1-0.5 MPa to generate ethylene.
Further onThe ratio n (H) of the amount of the substance in the raw material gas2)/n(C2H2) 1.5-2/1, and the space velocity of the acetylene gas is 30-5000 h-1。
In a fifth aspect, the invention provides an application of the metal interstitial compound/activated carbon fiber composite material as a catalyst in a formaldehyde oxidation reaction at room temperature.
Further, the application specifically comprises: and (3) filling the metal interstitial compound/activated carbon fiber composite material into a fixed bed reactor, introducing mixed gas of nitrogen, oxygen and formaldehyde, and reacting at room temperature to generate water and carbon dioxide.
Further, the room temperature is preferably 20 to 30 ℃.
Furthermore, the volume ratio of N in the mixed gas is N2/O2(iii) 3 to 4/1, formaldehyde concentration of 5X 10-4～1×10-3(volume fraction phi, 500-1000 ppm).
Furthermore, the gas space velocity (GHSV) is 50000-200000 mL (g.h)-1。
Compared with the prior art, the invention has the beneficial effects that:
(1) the metal interstitial compound/activated carbon fiber composite material has a high specific surface area and rich pore channel structures.
(2) The invention adopts the ultrasonic dipping method to prepare the catalyst, and the ultrasonic treatment can lead the metal gap-filling compound to be better dispersed on the surface of the activated carbon fiber and lead the metal gap-filling compound to be anchored on the surface of the activated carbon fiber, thus leading the activated carbon fiber to show higher activity.
(3) The metal interstitial compound/activated carbon fiber composite material is simple to manufacture and has good adsorption selectivity on Volatile Organic Compounds (VOCs).
(4) The metal interstitial compound/activated carbon fiber composite material can be used as a catalyst for synthesizing ethylene by acetylene hydrogenation, and shows high acetylene conversion rate and high ethylene selectivity.
(5) The metal interstitial compound/activated carbon fiber composite material can be used as a catalyst to be applied to room-temperature formaldehyde oxidation reaction, and shows high formaldehyde catalytic oxidation activity.
(IV) detailed description of the preferred embodiments
The invention is illustrated by the following specific examples. It is to be noted that the examples are only intended to illustrate the invention further, but are not to be construed as limiting the scope of the invention, which is not to be limited thereto in any way. Those skilled in the art may make numerous insubstantial modifications and adaptations to the teachings of the invention described above.
The activated carbon fiber used in the embodiment of the present invention is a commercially available viscose-based activated carbon fiber.
Example 1
1) Weighing 1g of magnesium boride, adding into 100ml of deionized water, and carrying out ultrasonic treatment for 0.5h at the ultrasonic frequency of 20 kHz;
2) weighing 20g of the mixture with the specific surface area of 800m2Adding/g of activated carbon fiber into the mixture, then carrying out ultrasonic treatment for 0.5h at the ultrasonic frequency of 20kHz, and soaking for 6h after the ultrasonic treatment is finished;
3) drying the mixture impregnated in the step 2) in an oven at 120 ℃ for 12 hours;
4) and roasting the dried material in a tubular furnace at 300 ℃, wherein the inert atmosphere is nitrogen, the heating rate is 5 ℃/min, and the roasting time is 2 hours, so that the metal interstitial compound/activated carbon fiber composite material is obtained.
5) The obtained metal interstitial compound/activated carbon fiber composite material is used for removing VOCs: the metal gap filling compound/activated carbon fiber composite material is filled in a fixed bed reactor, and the air flow is 120mL multiplied by min-1The concentration of toluene is 0.1%, the temperature is 25 ℃, the pressure is 0.1MPa, and the removal rate of VOCs can reach 98%.
Example 2
1) Weighing 1.2g of magnesium boride, adding into 80ml of deionized water, and carrying out ultrasonic treatment for 0.5h at the ultrasonic frequency of 50 kHz;
2) weighing 20g of the mixture with the specific surface area of 800m2Adding/g of activated carbon fiber into the mixture, then carrying out ultrasonic treatment for 0.5h, wherein the ultrasonic frequency is 50kHz, and soaking for 6h after ultrasonic treatment is finished;
3) drying the mixture impregnated in the step 2) in an oven at 120 ℃ for 12 hours;
4) and roasting the dried material in a tubular furnace at 300 ℃, wherein the inert atmosphere is nitrogen, the heating rate is 5 ℃/min, and the roasting time is 2 hours, so that the metal interstitial compound/activated carbon fiber composite material is obtained.
5) The obtained metal interstitial compound/activated carbon fiber composite material is used for removing VOCs: the metal gap filling compound/activated carbon fiber composite material is filled in a fixed bed reactor, and the air flow is 120mL multiplied by min-1The concentration of toluene is 0.1%, the temperature is 25 ℃, the pressure is 0.1MPa, and the removal rate of VOCs can reach 99%.
Example 3
1) Weighing 1g of molybdenum nitride, adding the molybdenum nitride into 100ml of deionized water, and carrying out ultrasonic treatment for 0.5h at the ultrasonic frequency of 30 kHz;
2) weighing 20g of the mixture with a specific surface area of 1000m2Adding/g of activated carbon fiber into the mixture, then carrying out ultrasonic treatment for 0.5h at the ultrasonic frequency of 50kHz, and soaking for 6h after the ultrasonic treatment is finished;
3) drying the mixture impregnated in the step 2) in an oven at 120 ℃ for 12 hours;
4) and (3) roasting the dried material in a tubular furnace at 500 ℃, wherein the inert atmosphere is nitrogen, the heating rate is 10 ℃/min, and the roasting is carried out for 2h, so as to obtain the metal interstitial compound/activated carbon fiber composite material.
5) The evaluation of the reaction for synthesizing ethylene by acetylene hydrogenation on a fixed bed reactor device: the acetylene hydrogenation reaction temperature is 200 ℃, the reaction pressure is 0.1MPa, and the acetylene airspeed is 30h-1，n(H2)/n(C2H2) 1.5: 1. The reaction conversion was 92% and the ethylene selectivity was 98%.
Example 4
1) Weighing 1.5g of zirconium carbide, adding the zirconium carbide into 200ml of deionized water, and carrying out ultrasonic treatment for 1h at the ultrasonic frequency of 60 kHz;
2) 30g of the powder with the specific surface area of 1000m is weighed2Adding/g of activated carbon fiber into the mixture, then carrying out ultrasonic treatment for 0.5h, wherein the ultrasonic frequency is 80kHz, and soaking for 8h after ultrasonic treatment is finished;
3) drying the mixture impregnated in the step 2) in an oven at 120 ℃ for 12 hours;
4) and roasting the dried material in a tubular furnace at 500 ℃, wherein the inert atmosphere is nitrogen, the heating rate is 10 ℃/min, and the roasting is carried out for 3 hours, so as to obtain the metal interstitial compound/activated carbon fiber composite material.
5) The evaluation of the reaction for synthesizing ethylene by acetylene hydrogenation on a fixed bed reactor device: the acetylene hydrogenation reaction temperature is 200 ℃, the reaction pressure is 0.1MPa, and the acetylene airspeed is 180h-1，n(H2)/n(C2H2) 1.5: 1. The reaction conversion was 90% and the ethylene selectivity was 96%.
Example 5
1) Weighing 1g of zirconium carbide and 0.5g of palladium phosphide, adding the zirconium carbide and the palladium phosphide into 200ml of absolute ethyl alcohol, and carrying out ultrasonic treatment for 1 hour at the ultrasonic frequency of 50 kHz;
2) weighing 30g of the powder with the specific surface area of 1200m2Adding/g of activated carbon fiber into the mixture, then carrying out ultrasonic treatment for 1h, wherein the ultrasonic frequency is 80kHz, and soaking for 6h after ultrasonic treatment is finished;
3) drying the mixture impregnated in the step 2) in an oven at 100 ℃ for 12 hours;
4) and (3) roasting the dried material in a tubular furnace at 500 ℃, wherein the inert atmosphere is nitrogen, the heating rate is 10 ℃/min, and the roasting time is 5 hours, so that the metal interstitial compound/activated carbon fiber composite material is obtained.
5) The evaluation of the reaction for synthesizing ethylene by acetylene hydrogenation on a fixed bed reactor device: the acetylene hydrogenation reaction temperature is 200 ℃, the reaction pressure is 0.2MPa, and the acetylene airspeed is 2000h-1，n(H2)/n(C2H2) Under 2:1 conditions. The reaction conversion was 88% and the ethylene selectivity was 92%.
Example 6
1) Weighing 1g of zirconium carbide and 0.5g of ferrotitanium carbide, adding into 100ml of deionized water and 100ml of absolute ethyl alcohol, and carrying out ultrasonic treatment for 1h at the ultrasonic frequency of 50 kHz;
2) weighing 20g of the mixture with the specific surface area of 1500m2Adding/g of activated carbon fiber into the mixture, and then carrying out ultrasonic treatment for 1h at ultrasonic frequencyThe rate is 100kHz, and the dipping is carried out for 8 hours after the ultrasonic treatment is finished;
3) drying the mixture impregnated in the step 2) in an oven at 120 ℃ for 12 hours;
4) and (3) roasting the dried material in a tubular furnace at 400 ℃, wherein the inert atmosphere is nitrogen, the heating rate is 10 ℃/min, and the roasting is carried out for 3h, so as to obtain the metal interstitial compound/activated carbon fiber composite material.
5) Loading the obtained metal gap filling compound/activated carbon fiber composite material into a fixed bed reactor, introducing mixed gas of nitrogen, oxygen and formaldehyde, and introducing N2/O23/1, formaldehyde concentration 5 × 10-4(500ppm), at 25 ℃ and a gaseous space velocity of 50000mL (g. h)-1The conversion rate of formaldehyde can reach 99 percent by reaction under the condition.
Example 7
1) Weighing 1g of sodium hexafluorophosphate, adding into 200ml of deionized water, and carrying out ultrasonic treatment for 1h at the ultrasonic frequency of 50 kHz;
2) weighing 20g of the mixture with a specific surface area of 1600m2Adding/g of activated carbon fiber into the mixture, then carrying out ultrasonic treatment for 1h at the ultrasonic frequency of 100kHz, and soaking for 8h after the ultrasonic treatment is finished;
3) drying the mixture impregnated in the step 2) in an oven at 120 ℃ for 12 hours;
4) and (3) roasting the dried material in a tubular furnace at 500 ℃, wherein the inert atmosphere is nitrogen, the heating rate is 10 ℃/min, and the roasting is carried out for 2h, so as to obtain the metal interstitial compound/activated carbon fiber composite material.
5) Loading the obtained metal gap filling compound/activated carbon fiber composite material into a fixed bed reactor, introducing mixed gas of nitrogen, oxygen and formaldehyde, and introducing N2/O24/1, formaldehyde concentration 5 × 10-4(500ppm), a gas space velocity of 100000mL (g.h) at 20 ℃-1The conversion rate of formaldehyde can reach 97 percent by reaction under the condition.
Example 8
1) Weighing 1g of sodium hexafluorophosphate and 1g of ferrotitanium carbide, adding into 200ml of deionized water, and carrying out ultrasonic treatment for 0.5h at the ultrasonic frequency of 80 kHz;
2) weighing 20g of the mixture with a specific surface area of 1600m2Adding/g of activated carbon fiber into the mixture, then carrying out ultrasonic treatment for 1h at the ultrasonic frequency of 100kHz, and soaking for 8h after the ultrasonic treatment is finished;
3) drying the mixture impregnated in the step 2) in an oven at 120 ℃ for 12 hours;
4) and (3) roasting the dried material in a tubular furnace at 400 ℃, wherein the inert atmosphere is nitrogen, the heating rate is 10 ℃/min, and the roasting is carried out for 4 hours, so as to obtain the metal interstitial compound/activated carbon fiber composite material.
5) Loading the obtained metal gap filling compound/activated carbon fiber composite material into a fixed bed reactor, introducing mixed gas of nitrogen, oxygen and formaldehyde, and introducing N2/O24/1, formaldehyde concentration 1 × 10-3(1000ppm) at 30 ℃ and a gas space velocity of 100000mL (g.h)-1The conversion rate of formaldehyde can reach 100 percent by reaction under the condition.
Comparative example 1
Comparative example 1 is a comparison with example 3, which shows that the ultrasonic treatment greatly increases the dispersibility of the metal interstitial compound on the surface of the activated carbon fiber, and anchors the metal interstitial compound on the activated carbon fiber, so that the metal interstitial compound/activated carbon fiber composite material shows higher acetylene hydrogenation catalytic activity.
1) Weighing 1g of molybdenum nitride, adding the molybdenum nitride into 100ml of deionized water, and carrying out ultrasonic treatment for 0.5h at the ultrasonic frequency of 30 kHz;
2) weighing 20g of the mixture with a specific surface area of 1000m2Adding activated carbon fiber per gram into the mixture, and soaking for 6 hours;
3) drying the mixture impregnated in the step 2) in an oven at 120 ℃ for 12 hours;
4) and (3) roasting the dried material in a tubular furnace at 500 ℃, wherein the inert atmosphere is nitrogen, the heating rate is 10 ℃/min, and the roasting is carried out for 2h, so as to obtain the metal interstitial compound/activated carbon fiber composite material.
5) The evaluation of the reaction for synthesizing ethylene by acetylene hydrogenation on a fixed bed reactor device: the acetylene hydrogenation reaction temperature is 200 ℃, the reaction pressure is 0.1MPa, and the acetylene airspeed is 30h-1Hydrogen gas: acetylene 1.5: 1. Reaction conversion of 50%, ethyleneThe selectivity was 61%.
Comparative example 2
Comparative example 2 is a comparison with example 2, showing that the ultrasonic treatment greatly increases the dispersibility of the metal interstitial compound on the surface of the activated carbon fiber and anchors the metal interstitial compound on the activated carbon fiber, so that the metal interstitial compound/activated carbon fiber composite material exhibits a higher removal rate of VOCs.
1) Weighing 1.2g of magnesium boride, adding into 80ml of deionized water, and carrying out ultrasonic treatment for 0.5h at the ultrasonic frequency of 50 kHz;
2) weighing 20g of the mixture with the specific surface area of 800m2Adding activated carbon fiber per gram into the mixture, and soaking for 6 hours;
3) drying the mixture impregnated in the step 2) in an oven at 120 ℃ for 12 hours;
4) and roasting the dried material in a tubular furnace at 300 ℃, wherein the inert atmosphere is nitrogen, the heating rate is 5 ℃/min, and the roasting time is 2 hours, so that the metal interstitial compound/activated carbon fiber composite material is obtained.
5) The obtained metal interstitial compound/activated carbon fiber composite material is used for removing VOCs: the metal gap filling compound/activated carbon fiber composite material is filled in a fixed bed reactor, and the air flow is 120mL multiplied by min-1The concentration of toluene is 0.1%, the temperature is 25 ℃, the pressure is 0.1MPa, and the removal rate of VOCs is only 53%.
Comparative example 3
Comparative example 3 is a comparison with example 6, which shows that the ultrasonic treatment greatly increases the dispersibility of the metal interstitial compound on the surface of the activated carbon fiber, and anchors the metal interstitial compound on the activated carbon fiber, so that the metal interstitial compound/activated carbon fiber composite material shows better formaldehyde oxidation catalytic activity.
1) Weighing 1g of zirconium carbide and 0.5g of ferrotitanium carbide, adding into 100ml of deionized water and 100ml of absolute ethyl alcohol, and carrying out ultrasonic treatment for 1h at the ultrasonic frequency of 50 kHz;
2) weighing 20g of the mixture with the specific surface area of 1500m2Adding activated carbon fiber per gram into the mixture, and soaking for 8 hours;
3) drying the mixture impregnated in the step 2) in an oven at 120 ℃ for 12 hours;
4) and (3) roasting the dried material in a tubular furnace at 400 ℃, wherein the inert atmosphere is nitrogen, the heating rate is 10 ℃/min, and the roasting is carried out for 3h, so as to obtain the metal interstitial compound/activated carbon fiber composite material.
5) Loading the obtained metal gap filling compound/activated carbon fiber composite material into a fixed bed reactor, introducing mixed gas of nitrogen, oxygen and formaldehyde, and introducing N2/O23/1, formaldehyde concentration 5 × 10-4(500ppm), at 25 ℃ and a gaseous space velocity of 50000mL (g. h)-1The conversion rate of formaldehyde is only 56 percent.
Comparative example 4
Comparative example 4 is a comparison with example 3, showing that a composite catalyst formed by combining a metal interstitial compound with activated carbon fibers by calcination exhibits higher catalytic activity for acetylene hydrogenation.
1) Weighing 1g of molybdenum nitride, adding the molybdenum nitride into 100ml of deionized water, and carrying out ultrasonic treatment for 0.5h at the ultrasonic frequency of 30 kHz;
2) weighing 20g of the mixture with a specific surface area of 1000m2Adding/g of activated carbon fiber into the mixture, then carrying out ultrasonic treatment for 0.5h at the ultrasonic frequency of 50kHz, and soaking for 6h after the ultrasonic treatment is finished;
3) drying the mixture impregnated in the step 2) in an oven at 120 ℃ for 12 hours;
4) and cooling and standing the dried material to obtain the metal interstitial compound/activated carbon fiber composite material.
5) The evaluation of the reaction for synthesizing ethylene by acetylene hydrogenation on a fixed bed reactor device: the acetylene hydrogenation reaction temperature is 200 ℃, the reaction pressure is 0.1MPa, and the acetylene airspeed is 30h-1Hydrogen gas: acetylene 1.5: 1. The reaction conversion was 79% and the ethylene selectivity was 80%.
Comparative example 5
Comparative example 5, by comparison with example 2, shows that a composite catalyst formed by combining a metal interstitial compound with activated carbon fibers by calcination exhibits better removal of VOCs.
1) Weighing 1.2g of magnesium boride, adding into 80ml of deionized water, and carrying out ultrasonic treatment for 0.5h at the ultrasonic frequency of 50 kHz;
2) weighing 20g of the mixture with the specific surface area of 800m2Adding/g of activated carbon fiber into the mixture, then carrying out ultrasonic treatment for 0.5h, wherein the ultrasonic frequency is 50kHz, and soaking for 6h after ultrasonic treatment is finished;
3) drying the mixture impregnated in the step 2) in an oven at 120 ℃ for 12 hours;
4) and cooling and standing the dried material to obtain the metal interstitial compound/activated carbon fiber composite material.
5) The obtained metal interstitial compound/activated carbon fiber composite material is used for removing VOCs: the metal gap filling compound/activated carbon fiber composite material is filled in a fixed bed reactor, and the air flow is 120mL multiplied by min-1The concentration of toluene is 0.1%, the temperature is 25 ℃, the pressure is 0.1MPa, and the removal rate of VOCs is only 53%.
Comparative example 6
Comparative example 6 is a comparison with example 7, and shows that a composite catalyst is formed by combining a metal interstitial compound with activated carbon fibers by calcination, thereby showing better catalytic activity for formaldehyde oxidation.
1) Weighing 1g of sodium hexafluorophosphate, adding into 200ml of deionized water, and carrying out ultrasonic treatment for 1h at the ultrasonic frequency of 50 kHz;
2) weighing 20g of the mixture with a specific surface area of 1600m2Adding/g of activated carbon fiber into the mixture, then carrying out ultrasonic treatment for 1h at the ultrasonic frequency of 100kHz, and soaking for 8h after the ultrasonic treatment is finished;
3) drying the mixture impregnated in the step 2) in an oven at 120 ℃ for 12 hours;
4) and cooling and standing the dried material to obtain the metal interstitial compound/activated carbon fiber composite material.
5) Loading the obtained metal gap filling compound/activated carbon fiber composite material into a fixed bed reactor, introducing mixed gas of nitrogen, oxygen and formaldehyde, and introducing N2/O24/1, formaldehyde concentration 5 × 10-4(500ppm), at 20 ℃ in the airSpeed is 100000mL (g. h)-1The conversion rate of formaldehyde is only 60 percent.
Comparative example 7
Comparative example 7 is a comparison with example 2 showing that the metal interstitial compound/activated carbon fiber composite exhibits higher removal efficiency of VOCs than the single activated carbon fiber material.
1) Measuring 80ml of deionized water, and carrying out ultrasonic treatment for 0.5h at an ultrasonic frequency of 50 kHz;
2) weighing 20g of the mixture with the specific surface area of 800m2Adding/g of activated carbon fiber into the deionized water, then carrying out ultrasonic treatment for 0.5h, wherein the ultrasonic frequency is 50kHz, and standing for 6h after the ultrasonic treatment is finished;
3) drying the mixture obtained in the step 2) in an oven at 120 ℃ for 12 hours;
4) and roasting the dried material in a tubular furnace at 300 ℃, wherein the inert atmosphere is nitrogen, the heating rate is 5 ℃/min, and the roasting time is 2 hours, so that the single activated carbon fiber material is obtained.
5) The obtained activated carbon fiber material is used for removing VOCs: the active carbon fiber material is filled in the fixed bed reactor, and the air flow is 120mL multiplied by min-1The concentration of toluene is 0.1%, the temperature is 25 ℃, the pressure is 0.1MPa, and the removal rate of VOCs is only 50%.
Comparative example 8
Comparative example 8 is a comparison with example 2 showing that the metal interstitial compound/activated carbon fiber composite exhibits higher removal efficiency of VOCs than the single metal interstitial compound material.
1) Weighing 1.2g of magnesium boride, adding into 80ml of deionized water, and carrying out ultrasonic treatment for 0.5h at the ultrasonic frequency of 50 kHz;
2) continuously carrying out ultrasonic treatment on the mixture for 0.5h, wherein the ultrasonic frequency is 50kHz, and standing for 6h after the ultrasonic treatment is finished;
3) drying the mixture obtained in the step 2) in an oven at 120 ℃ for 12 hours;
4) and roasting the dried material in a tubular furnace at 300 ℃, wherein the inert atmosphere is nitrogen, the heating rate is 5 ℃/min, and the roasting time is 2h, so that the single-metal gap-filling compound material is obtained.
5) The obtained single-metal interstitial compound material is used for removing VOCs: charging metal gap filling compound material into a fixed bed reactor, wherein the air flow is 120mL multiplied by min-1The concentration of toluene is 0.1%, the temperature is 25 ℃, the pressure is 0.1MPa, and the removal rate of VOCs is only 38%.
Comparative example 9
Comparative example 9 is a comparison with example 3, which shows that the metal interstitial compound/activated carbon fiber composite material shows higher catalytic activity of acetylene hydrogenation to synthesize ethylene than the single activated carbon fiber material as a catalyst.
1) Measuring 100ml of deionized water, and carrying out ultrasonic treatment for 0.5h at an ultrasonic frequency of 30 kHz;
2) weighing 20g of the mixture with a specific surface area of 1000m2Adding activated carbon fiber per gram into the deionized water, carrying out ultrasonic treatment for 0.5h at the ultrasonic frequency of 50kHz, and standing for 6h after finishing ultrasonic treatment;
3) drying the mixture obtained in the step 2) in an oven at 120 ℃ for 12 hours;
4) and (3) roasting the dried material in a tubular furnace at 500 ℃, wherein the inert atmosphere is nitrogen, the heating rate is 10 ℃/min, and the roasting time is 2 hours, so that the single activated carbon fiber material is obtained.
5) The evaluation of the reaction for synthesizing ethylene by acetylene hydrogenation on a fixed bed reactor device: the acetylene hydrogenation reaction temperature is 200 ℃, the reaction pressure is 0.1MPa, and the acetylene airspeed is 30h-1，n(H2)/n(C2H2) 1.5: 1. The reaction conversion was 30% and the ethylene selectivity was 43%.
Comparative example 10
Comparative example 10 is a comparison with example 3, which shows that the metal interstitial compound/activated carbon fiber composite material shows higher catalytic activity of acetylene hydrogenation to ethylene than the single metal interstitial compound material as a catalyst.
1) Weighing 1g of molybdenum nitride, adding the molybdenum nitride into 100ml of deionized water, and carrying out ultrasonic treatment for 0.5h at the ultrasonic frequency of 30 kHz;
2) continuously carrying out ultrasonic treatment on the mixture for 0.5h, wherein the ultrasonic frequency is 50kHz, and standing for 6h after the ultrasonic treatment is finished;
3) drying the mixture obtained in the step 2) in an oven at 120 ℃ for 12 hours;
4) and roasting the dried material in a tubular furnace at 500 ℃, wherein the inert atmosphere is nitrogen, the heating rate is 10 ℃/min, and the roasting time is 2h, so that the single-metal gap-filling compound material is obtained.
5) The evaluation of the reaction for synthesizing ethylene by acetylene hydrogenation on a fixed bed reactor device: the acetylene hydrogenation reaction temperature is 200 ℃, the reaction pressure is 0.1MPa, and the acetylene airspeed is 30h-1，n(H2)/n(C2H2) 1.5: 1. The reaction conversion was 48% and the ethylene selectivity was 52%.
Comparative example 11
Comparative example 11 is a comparison with example 8, showing that the metal interstitial compound/activated carbon fiber composite exhibits higher catalytic oxidation conversion of formaldehyde than a single activated carbon fiber material as a catalyst.
1) Measuring 200ml of deionized water, and carrying out ultrasonic treatment for 0.5h at an ultrasonic frequency of 80 kHz;
2) weighing 20g of the mixture with a specific surface area of 1600m2Adding/g of activated carbon fiber into the deionized water, then carrying out ultrasonic treatment for 1h, wherein the ultrasonic frequency is 100kHz, and standing for 8h after finishing ultrasonic treatment;
3) drying the mixture obtained in the step 2) in an oven at 120 ℃ for 12 hours;
4) and (3) roasting the dried material in a tubular furnace at 400 ℃, wherein the inert atmosphere is nitrogen, the heating rate is 10 ℃/min, and the roasting time is 4 hours, so that the single activated carbon fiber material is obtained.
5) The obtained activated carbon fiber material is filled into a fixed bed reactor, mixed gas of nitrogen, oxygen and formaldehyde is introduced,
N2/O24/1, formaldehyde concentration 1 × 10-3(1000ppm) at 30 ℃ and a gas space velocity of 100000mL (g.h)-1The formaldehyde conversion rate is only 39 percent.
Comparative example 12
Comparative example 12 is a comparison with example 8 and shows that the metal interstitial compound/activated carbon fiber composite exhibits higher catalytic oxidation conversion of formaldehyde than a single metal interstitial compound material as a catalyst.
1) Weighing 1g of sodium hexafluorophosphate and 1g of ferrotitanium carbide, adding into 200ml of deionized water, and carrying out ultrasonic treatment for 0.5h at the ultrasonic frequency of 80 kHz;
2) carrying out ultrasonic treatment on the mixture for 1h, wherein the ultrasonic frequency is 100kHz, and standing for 8h after the ultrasonic treatment is finished;
3) drying the mixture obtained in the step 2) in an oven at 120 ℃ for 12 hours;
4) and (3) roasting the dried material in a tubular furnace at 400 ℃, wherein the inert atmosphere is nitrogen, the heating rate is 10 ℃/min, and the roasting is carried out for 4h, so as to obtain the single-metal gap-filling compound material.
5) Loading the obtained single metal gap-filling compound material into a fixed bed reactor, introducing a mixed gas of nitrogen, oxygen and formaldehyde, and introducing N2/O24/1, formaldehyde concentration 1 × 10-3(1000ppm) at 30 ℃ and a gas space velocity of 100000mL (g.h)-1The conversion rate of formaldehyde is only 30 percent.

Claims (9)

1. A metal interstitial compound/activated carbon fiber composite material is characterized in that: the metal interstitial compound/activated carbon fiber composite material is prepared by a method comprising the following steps: dispersing the metal gap-filling compound onto the activated carbon fiber by using an impregnation method, and performing ultrasonic treatment on a mixture of the metal gap-filling compound, a solvent and the activated carbon fiber before impregnation, wherein the ultrasonic treatment frequency is 20-80 kHz, and the ultrasonic treatment time is 0.5-1 h; then roasting at the high temperature of 300-800 ℃ in an inert atmosphere to obtain a metal interstitial compound/activated carbon fiber composite material; the metal gap-filling compound is one or more of magnesium boride, molybdenum nitride, zirconium carbide, palladium phosphide, ferrotitanium carbide and sodium hexafluoroantimonate, and the mass ratio of the metal gap-filling compound to the activated carbon fiber is 5-10%.
2. The metal interstitial compound/activated carbon fiber composite material of claim 1, wherein: the specific surface area of the activated carbon fiber is 800-1600 m2/g。
3. A method for preparing the metal interstitial compound/activated carbon fiber composite material of claim 1 or 2, comprising the steps of:
1) adding a certain amount of metal interstitial compound into the solvent to obtain a uniformly dispersed mixture;
2) adding activated carbon fibers into the mixture obtained in the step 1), carrying out ultrasonic treatment for 0.5-1 h at the ultrasonic treatment frequency of 20-100 kHz, uniformly dispersing the metal interstitial compound on the surfaces of the activated carbon fibers, and then soaking for 6-12 h;
3) drying the mixture obtained in the step 2) to volatilize the solvent;
4) and (3) roasting the sample obtained in the step 3) at a high temperature of 300-800 ℃ in an inert atmosphere to obtain the metal interstitial compound/activated carbon fiber composite material.
4. The method of claim 3, wherein: the solvent in the step 1) is one or more of deionized water, absolute ethyl alcohol, methanol and acetone.
5. The method of claim 3, wherein: and 3) drying at the temperature of 80-120 ℃ for 12-24 h.
6. The method of claim 3, wherein: the roasting temperature in the step 4) is 300-800 ℃, the heating rate is 5-10 ℃/min, and the roasting time is 2-6 h.
7. The metal interstitial compound/activated carbon fiber composite material according to claim 1 for use as an adsorbent material for the removal of VOCs.
8. The use of the metal interstitial compound/activated carbon fiber composite material of claim 1 as a catalyst in the synthesis of ethylene by hydrogenation of acetylene.
9. The use of the metal interstitial compound/activated carbon fiber composite of claim 1 as a catalyst in formaldehyde oxidation reactions at room temperature.
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