CN111111778B - Preparation method and application of functional material of biomass-based macroporous in-growth carbon nanotube - Google Patents
Preparation method and application of functional material of biomass-based macroporous in-growth carbon nanotube Download PDFInfo
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- CN111111778B CN111111778B CN201911322314.2A CN201911322314A CN111111778B CN 111111778 B CN111111778 B CN 111111778B CN 201911322314 A CN201911322314 A CN 201911322314A CN 111111778 B CN111111778 B CN 111111778B
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- 239000000463 material Substances 0.000 title claims abstract description 56
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 title claims abstract description 50
- 239000002041 carbon nanotube Substances 0.000 title claims abstract description 38
- 229910021393 carbon nanotube Inorganic materials 0.000 title claims abstract description 38
- 239000002028 Biomass Substances 0.000 title claims abstract description 32
- 238000002360 preparation method Methods 0.000 title claims abstract description 8
- 238000006243 chemical reaction Methods 0.000 claims abstract description 50
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 claims abstract description 36
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 claims abstract description 21
- 229910052799 carbon Inorganic materials 0.000 claims abstract description 11
- 150000002815 nickel Chemical class 0.000 claims abstract description 11
- 238000011065 in-situ storage Methods 0.000 claims abstract description 10
- 238000003756 stirring Methods 0.000 claims abstract description 7
- 238000009210 therapy by ultrasound Methods 0.000 claims abstract description 7
- 238000001291 vacuum drying Methods 0.000 claims abstract description 7
- 238000011049 filling Methods 0.000 claims abstract description 6
- 229910052759 nickel Inorganic materials 0.000 claims abstract description 6
- 229910052751 metal Inorganic materials 0.000 claims abstract description 5
- 239000002184 metal Substances 0.000 claims abstract description 5
- 230000001276 controlling effect Effects 0.000 claims abstract description 3
- 230000009467 reduction Effects 0.000 claims abstract description 3
- 230000001105 regulatory effect Effects 0.000 claims abstract description 3
- 239000013590 bulk material Substances 0.000 claims abstract 3
- 235000018185 Betula X alpestris Nutrition 0.000 claims description 15
- 235000018212 Betula X uliginosa Nutrition 0.000 claims description 15
- 238000005984 hydrogenation reaction Methods 0.000 claims description 13
- 241000425037 Toona sinensis Species 0.000 claims description 11
- UGFAIRIUMAVXCW-UHFFFAOYSA-N Carbon monoxide Chemical compound [O+]#[C-] UGFAIRIUMAVXCW-UHFFFAOYSA-N 0.000 claims description 10
- 229910002091 carbon monoxide Inorganic materials 0.000 claims description 10
- 238000000034 method Methods 0.000 claims description 10
- VNWKTOKETHGBQD-UHFFFAOYSA-N methane Chemical compound C VNWKTOKETHGBQD-UHFFFAOYSA-N 0.000 claims description 8
- 238000006722 reduction reaction Methods 0.000 claims description 8
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 8
- 239000002023 wood Substances 0.000 claims description 8
- UHOVQNZJYSORNB-UHFFFAOYSA-N Benzene Chemical compound C1=CC=CC=C1 UHOVQNZJYSORNB-UHFFFAOYSA-N 0.000 claims description 6
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 6
- GRYLNZFGIOXLOG-UHFFFAOYSA-N Nitric acid Chemical compound O[N+]([O-])=O GRYLNZFGIOXLOG-UHFFFAOYSA-N 0.000 claims description 6
- 239000008367 deionised water Substances 0.000 claims description 6
- 229910021641 deionized water Inorganic materials 0.000 claims description 6
- 238000001035 drying Methods 0.000 claims description 6
- 229910017604 nitric acid Inorganic materials 0.000 claims description 6
- 238000010992 reflux Methods 0.000 claims description 6
- 238000007789 sealing Methods 0.000 claims description 6
- 238000005406 washing Methods 0.000 claims description 6
- JUJWROOIHBZHMG-UHFFFAOYSA-N Pyridine Chemical compound C1=CC=NC=C1 JUJWROOIHBZHMG-UHFFFAOYSA-N 0.000 claims description 4
- 238000009903 catalytic hydrogenation reaction Methods 0.000 claims description 4
- 238000006555 catalytic reaction Methods 0.000 claims description 4
- 238000005520 cutting process Methods 0.000 claims description 4
- BDAGIHXWWSANSR-UHFFFAOYSA-N methanoic acid Natural products OC=O BDAGIHXWWSANSR-UHFFFAOYSA-N 0.000 claims description 4
- FVSKHRXBFJPNKK-UHFFFAOYSA-N propionitrile Chemical compound CCC#N FVSKHRXBFJPNKK-UHFFFAOYSA-N 0.000 claims description 3
- DSSYKIVIOFKYAU-XCBNKYQSSA-N (R)-camphor Chemical compound C1C[C@@]2(C)C(=O)C[C@@H]1C2(C)C DSSYKIVIOFKYAU-XCBNKYQSSA-N 0.000 claims description 2
- OSWFIVFLDKOXQC-UHFFFAOYSA-N 4-(3-methoxyphenyl)aniline Chemical compound COC1=CC=CC(C=2C=CC(N)=CC=2)=C1 OSWFIVFLDKOXQC-UHFFFAOYSA-N 0.000 claims description 2
- 241000218652 Larix Species 0.000 claims description 2
- 235000005590 Larix decidua Nutrition 0.000 claims description 2
- 244000082946 Tarchonanthus camphoratus Species 0.000 claims description 2
- 235000005701 Tarchonanthus camphoratus Nutrition 0.000 claims description 2
- -1 cyclic small molecule Chemical class 0.000 claims description 2
- 235000019253 formic acid Nutrition 0.000 claims description 2
- UMJSCPRVCHMLSP-UHFFFAOYSA-N pyridine Natural products COC1=CC=CN=C1 UMJSCPRVCHMLSP-UHFFFAOYSA-N 0.000 claims description 2
- 239000000126 substance Substances 0.000 claims description 2
- 244000166124 Eucalyptus globulus Species 0.000 claims 1
- 230000000694 effects Effects 0.000 abstract description 9
- 238000005087 graphitization Methods 0.000 abstract description 5
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- CURLTUGMZLYLDI-UHFFFAOYSA-N Carbon dioxide Chemical compound O=C=O CURLTUGMZLYLDI-UHFFFAOYSA-N 0.000 description 10
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- 229910021586 Nickel(II) chloride Inorganic materials 0.000 description 4
- 239000003610 charcoal Substances 0.000 description 4
- 238000010438 heat treatment Methods 0.000 description 4
- QMMRZOWCJAIUJA-UHFFFAOYSA-L nickel dichloride Chemical compound Cl[Ni]Cl QMMRZOWCJAIUJA-UHFFFAOYSA-L 0.000 description 4
- 238000005303 weighing Methods 0.000 description 4
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 3
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- 239000001257 hydrogen Substances 0.000 description 3
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- 238000012546 transfer Methods 0.000 description 3
- KDLHZDBZIXYQEI-UHFFFAOYSA-N Palladium Chemical compound [Pd] KDLHZDBZIXYQEI-UHFFFAOYSA-N 0.000 description 2
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- AOPCKOPZYFFEDA-UHFFFAOYSA-N nickel(2+);dinitrate;hexahydrate Chemical compound O.O.O.O.O.O.[Ni+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O AOPCKOPZYFFEDA-UHFFFAOYSA-N 0.000 description 2
- KBJMLQFLOWQJNF-UHFFFAOYSA-N nickel(ii) nitrate Chemical compound [Ni+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O KBJMLQFLOWQJNF-UHFFFAOYSA-N 0.000 description 2
- 230000003647 oxidation Effects 0.000 description 2
- 238000007254 oxidation reaction Methods 0.000 description 2
- BASFCYQUMIYNBI-UHFFFAOYSA-N platinum Chemical compound [Pt] BASFCYQUMIYNBI-UHFFFAOYSA-N 0.000 description 2
- 238000001878 scanning electron micrograph Methods 0.000 description 2
- KJTLSVCANCCWHF-UHFFFAOYSA-N Ruthenium Chemical compound [Ru] KJTLSVCANCCWHF-UHFFFAOYSA-N 0.000 description 1
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- 238000005516 engineering process Methods 0.000 description 1
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- 150000002739 metals Chemical class 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
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- 229910000510 noble metal Inorganic materials 0.000 description 1
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- MHOVAHRLVXNVSD-UHFFFAOYSA-N rhodium atom Chemical compound [Rh] MHOVAHRLVXNVSD-UHFFFAOYSA-N 0.000 description 1
- 229910052707 ruthenium Inorganic materials 0.000 description 1
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- B01J31/00—Catalysts comprising hydrides, coordination complexes or organic compounds
- B01J31/02—Catalysts comprising hydrides, coordination complexes or organic compounds containing organic compounds or metal hydrides
- B01J31/06—Catalysts comprising hydrides, coordination complexes or organic compounds containing organic compounds or metal hydrides containing polymers
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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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- B01J35/396—Distribution of the active metal ingredient
- B01J35/398—Egg yolk like
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Abstract
The invention discloses a preparation method and application of a functional material of a biomass-based macroporous in-growth carbon nanotube, wherein the preparation method comprises the following steps: (1) pretreating the massive biomass to obtain a material A; (2) dissolving nickel salt in methanol, uniformly stirring to obtain a solution B, putting A into B, performing ultrasonic treatment, and putting into a vacuum drying oven for reaction to obtain a bulk material C; (3) filling the blocky material C into a fixed bed microreactor for in-situ reduction to obtain a material D loading metallic nickel in a biomass macropore; (4) and introducing a carbon source, and regulating and controlling the parameters of the micro-reactor to obtain the functional material E. The functional material has the characteristics of regular macroporous channels, larger specific surface area, high graphitization degree and the like, increases the contact surface with active substances, and improves the reaction airspeed and catalytic activity; the carbon nano tube wraps the nickel metal core-shell structure, so that electron transfer between core shells is promoted, the surface electron cloud density is increased, and the domain-limiting effect is favorable for improving the selectivity of products.
Description
Technical Field
The invention relates to the field of comprehensive utilization research of biomass wastes, in particular to a preparation method and application of a functional material of a biomass-based macroporous in-growth carbon nanotube.
Background
The carbon-based catalyst has higher reaction activity and product selectivity, and is better utilized in the fields of catalyst hydrogenation and water electrolysis hydrogen production. The traditional precursor for preparing the carbon-based catalyst is mainly a petroleum-based product which is generally non-renewable, has limited reserves and high price, and causes great burden to the environment due to transitional development and utilization.
In recent years, biomass carbon-based catalysts have attracted wide attention in the aspects of catalytic hydrogenation and hydrogen production by water electrolysis, and have the advantages of richness, ecological friendliness, renewability, diversity in raw material selection, cost effectiveness and the like. Compared with carbon powder, the raw wood charcoal certainly has a more regular pore structure and a mass transfer effect, but the raw wood charcoal has a lower specific surface area and poor electrical conductivity, so that the reaction activity is lower.
Therefore, the development of a carbon-based catalyst with high specific surface area and regular pore channels has important significance for improving the hydrogenation activity and reaction space velocity of carbon monoxide or carbon dioxide.
Disclosure of Invention
Aiming at the problems in the prior art, the invention adopts the in-situ growth technology to grow the carbon nano tube in the raw wood charcoal pore canal, thereby not only increasing the specific surface area of the raw wood charcoal, but also improving the graphitization degree, further improving the reaction activity and the selectivity of the product, and being hopeful to be applied to the fields of the existing carbon monoxide low-temperature oxidation, air purification and the like.
The technical scheme of the invention is as follows: a preparation method of a functional material of a biomass-based macroporous in-growth carbon nanotube comprises the following steps:
(1) pretreatment: taking 1-5 g of blocky biomass and 30-150 mL of nitric acid solution to perform reflux reaction at the temperature of 50-110 ℃ for 5-36 h, washing with deionized water for 3-6 times, drying at normal temperature to obtain a pretreatment material A, and sealing and storing for later use;
(2) dissolving a certain mass of nickel salt in methanol, uniformly stirring to obtain a solution B, putting A into B, carrying out ultrasonic treatment for 1-5 h, and then putting the solution A into a vacuum drying oven to react for 12-36 h to obtain a block material C;
(3) filling the blocky material C into a micro reactor for in-situ reduction to obtain a material D loading metallic nickel in a biomass macropore;
(4) and introducing a carbon source, and regulating and controlling the parameters of the microreactor to obtain the functional material E of the biomass-based macroporous grown carbon nanotube.
In the step 1, the massive biomass is branch materials of fir, birch, camphor wood, Chinese toon, larch, eucalyptus and the like, and the branch materials can be obtained from leftovers of furniture factories.
In step 3, the step of performing the in situ reduction reaction is:
firstly, 10% of H2introducing/Ar into the micro-reactor at the flow rate of 30-100 mL/min; then the temperature of the micro-reactor is raised to 1 ℃/min400-550 ℃; reacting for 12-36 h at the temperature to obtain a material D.
In step 4, the carbon source is a linear chain small molecule or a cyclic small molecule substance such as ethanol, methanol, propionitrile, carbon monoxide, benzene, pyridine and the like.
In step 4, the parameters of the microreactor are: the reaction temperature is 700 ℃ and 900 ℃, the time is 0.5-3 h, and the carbon source adding speed is 20-50 mL/h.
The functional material of the biomass-based macroporous in-growth carbon nano tube prepared by the method can be applied to catalytic hydrogenation reaction, and is particularly mainly used for preparing methane or CO through CO hydrogenation catalysis2Hydrogenation catalysis to produce methane, methanol or formic acid.
In addition, in the actual preparation process, not only can transition metals such as nickel salt be loaded into the biomass pore channel, but also noble metals or rare metals such as platinum, palladium, rhodium, ruthenium and the like can be loaded into the biomass pore channel to form the honeycomb-like catalyst with the 3D pore channel structure, and the honeycomb-like catalyst has good effects when being applied to the fields of carbon monoxide low-temperature oxidation, air purification, energy storage and the like.
The invention has the beneficial effects that:
1. the functional material of the biomass-based macroporous internally-grown carbon nanotube has the characteristics of regular macroporous channels, larger specific surface area, high graphitization degree and the like, is used in the field of gas-phase catalysis, is beneficial to strengthening gas-phase mass transfer, increasing the contact surface with active substances, and improving the reaction space velocity and catalytic activity.
2. The carbon nano tube wraps the nickel metal core-shell structure, so that electron transfer between core shells is promoted, the surface electron cloud density is increased, and the domain-limiting effect is favorable for improving the selectivity of products.
Drawings
FIG. 1 is an XRD pattern of a material of a biomass-based macroporous nickel-loaded and growing carbon nanotube prepared in accordance with the first example;
fig. 2 is an SEM image of a biomass-based macroporous grown-in carbon nanotube material prepared in example one, wherein a and b are SEM images of a cross section and a longitudinal section of a functional material of a biomass pore grown-in carbon nanotube, respectively, c is an enlarged view of a square portion in a, and d is an enlarged view of a square portion in b;
FIG. 3 shows N of the biomass-based macroporous Ni-loaded and growing carbon nanotube material prepared in example one2Adsorption and desorption curves.
Detailed Description
The following examples further illustrate the present invention but are not to be construed as limiting the invention. Modifications and substitutions to methods, procedures, or conditions of the invention may be made without departing from the spirit of the invention.
Example 1
(1) Taking 1 g of blocky fir, carrying out reflux reaction on the blocky fir with 50 mL of nitric acid at the temperature of 80 ℃ for 12 hours, washing the blocky fir with deionized water for 3-6 times, drying the blocky fir at normal temperature, and sealing and storing the blocky fir for later use;
(2) weighing 0.58 g of nickel nitrate hexahydrate, dissolving in 50 mL of methanol, stirring until the nickel nitrate is dissolved, then putting the fir pretreated in the step 1 into the solution, carrying out ultrasonic treatment for 4 hours, and putting the fir into a vacuum drying oven for reaction for 12 hours to obtain a composite material of the fir and nickel salt;
(3) cutting the composite material of the fir and the nickel salt to a proper size by using a tool, and then filling the composite material into a microreactor to perform an in-situ reduction reaction, wherein the method comprises the following specific steps: firstly, 10% of H2introducing/Ar into the micro-reactor at the flow rate of 40 mL/min, raising the temperature of the micro-reactor to 500 ℃ at the speed of 1 ℃/min, and reacting for 16 hours at the temperature to obtain a material loaded with metallic nickel in the fir pore channel;
(4) heating the temperature of the micro-reactor to 800 ℃, injecting ethanol into the micro-reactor at the speed of 30 mL/h, and reacting for 0.5 h to obtain a functional material of the carbon nano tube growing in the fir pore channel;
(5) the prepared functional material of the carbon nano tube growing in the fir pore canal is used for the carbon monoxide hydrogenation catalytic synthesis reaction, and the airspeed reaches 50 L.h-1·g-1The CO conversion rate can reach 82.38 percent under the conditions that the reaction temperature is 350 ℃ and the reaction pressure is 0.1 MPa, and the CH4The selectivity of the catalyst can reach 97.81 percent.
（6）The prepared functional material of the carbon nano tube growing in the fir pore channel is used for the carbon dioxide hydrogenation catalytic synthesis reaction at the airspeed of 16 L.h-1·g-1Under the conditions that the reaction temperature is 380 ℃ and the reaction pressure is 2 MPa, the CO is2The conversion rate of the catalyst can reach 62.31 percent, and CH4The selectivity can reach 85.81%.
Fig. 1 is an XRD spectrum of the material D loaded with metallic nickel in the prepared fir pore channel, from which it can be seen that three characteristic peaks appear at 2 θ angles of 44.5 °, 51.8 °, and 76.4 °, and these characteristic peaks are attributed to the (111), (200), and (220) crystal planes of metallic nickel. Compared with the material D, the long carbon nanotube material E in the biomass pore channel has an additional sharp characteristic front at the 2 theta angle of 26.1 degrees, which is the characteristic front of graphitized carbon, and shows that the material with a certain graphitization degree is grown in the biomass pore channel.
FIG. 2 is an SEM photograph of the prepared material of carbon nanotubes grown in the channels of the fir, wherein the cross-sectional view shows that the size of the channels of the fir is 10-20 μm, and the inner walls of the channels are full of carbon nanotubes, and the longitudinal section and the enlarged view show that the channels of the fir are through, so that the mass transfer effect of the through channels can be improved, and the reaction space velocity and the catalytic activity can be improved. The existence of the carbon nano tube not only improves the specific surface area of the fir, but also increases the graphitization degree of the fir, and simultaneously, the carbon nano tube wraps the metal structure, thereby promoting the electron transfer between the core shell, increasing the surface electron cloud density and being beneficial to improving the selectivity of the product.
From N of FIG. 32The adsorption and desorption isotherm shows that the surface area of the material loaded with nickel in the fir pore channel is 196.6 m/g, while the specific area of the carbon nanotube material growing in the fir pore channel is as high as 396.9 m/g, and the larger specific area is favorable for the adsorption, reaction and product dissociation of hydrogen on the surface of the catalyst.
Example 2
(1) Taking 1 g of blocky toona sinensis, carrying out reflux reaction on the blocky toona sinensis and 50 mL of nitric acid at 90 ℃ for 18 h, washing the reaction product for 3-6 times by using deionized water, drying the reaction product at normal temperature, and sealing and storing the reaction product for later use;
(2) weighing 0.358 g of nickel chloride, dissolving in 50 mL of methanol, stirring until the nickel chloride is dissolved, then putting the pretreated toona sinensis into the solution, carrying out ultrasonic treatment for 3 hours, and putting the toona sinensis into a vacuum drying oven for reaction for 24 hours to obtain a composite material of the toona sinensis and nickel salt;
(3) cutting the composite material of the toona sinensis and the nickel salt to a proper size by using a tool, and then filling the composite material into a micro reactor for in-situ reduction reaction, wherein the method comprises the following specific steps: firstly, 10% of H2introducing/Ar into the micro-reactor at the flow rate of 50 mL/min, raising the temperature of the micro-reactor to 450 ℃ at the speed of 1 ℃/min, and reacting for 12 hours at the temperature to obtain a material loaded with metallic nickel in the pores of the Chinese toon;
(4) heating the temperature of the micro-reactor to 750 ℃, then injecting methanol into the micro-reactor at the speed of 20 mL/min, and reacting for 1 h to obtain a functional material of the carbon nano tube growing in the pores of the toona sinensis;
(5) the prepared functional material of the carbon nano tube growing in the biomass-based pore channel is used for the catalytic synthesis reaction of carbon monoxide hydrogenation, and the airspeed reaches 38 L.h-1·g-1The CO conversion rate can reach 87.96 percent under the conditions that the reaction temperature is 350 ℃ and the reaction pressure is 0.1 MPa, and the CH4The selectivity of the catalyst can reach 96.71 percent.
(6) The prepared functional material of the carbon nano tube growing in the Chinese toon pore canal is used for the carbon dioxide hydrogenation catalytic synthesis reaction, and the space velocity is 12 L.h-1·g-1At a reaction temperature of 390 ℃ and a reaction pressure of 2 MPa, the reaction pressure is CO2The conversion rate of the catalyst can reach 78.56 percent, and CH4The selectivity can reach 89.31%.
Example 3
(1) Taking 1 g of blocky eucalyptus, carrying out reflux reaction on the blocky eucalyptus with 50 mL of nitric acid at 100 ℃ for 16 hours, washing the blocky eucalyptus with deionized water for 3-6 times, drying the blocky eucalyptus at normal temperature, and sealing and storing the blocky eucalyptus for later use;
(2) weighing 0.354 g of nickel chloride, dissolving in 50 mL of methanol, stirring until the nickel chloride is dissolved, then putting the pretreated eucalyptus wood into the solution, carrying out ultrasonic treatment for 1 h, and putting the solution into a vacuum drying oven for reaction for 36 h to obtain a composite material of the eucalyptus wood and nickel salt;
(3) compounding eucalyptus with nickel saltThe composite material is cut to a proper size by a tool and then filled into a micro reactor for in-situ reduction reaction, and the method comprises the following specific steps: firstly, 10% of H2Introducing Ar into the micro-reactor at the flow rate of 80 mL/min, raising the temperature of the micro-reactor to 550 ℃ at the speed of 1 ℃/min, and reacting for 16 hours at the temperature to obtain a material loaded with metallic nickel in the eucalyptus pore canal;
(4) heating the temperature of the micro-reactor to 750 ℃, then injecting propionitrile into the micro-reactor at the speed of 30 mL/h, and reacting for 1 h to obtain a functional material of the carbon nano tube growing in the eucalyptus pore channel;
(5) the prepared functional material of the carbon nano tube growing in the eucalyptus pore canal is used for the catalytic synthesis reaction of carbon monoxide hydrogenation, and the space velocity reaches 46 L.h-1·g-1The CO conversion rate can reach 76.52 percent under the conditions that the reaction temperature is 350 ℃ and the reaction pressure is 0.1 MPa, and the CH4The selectivity of the catalyst can reach 93.85 percent;
(6) the prepared functional material of the carbon nano tube growing in the eucalyptus pore canal is used for the carbon dioxide hydrogenation catalytic synthesis reaction, and the space velocity is 30 L.h-1·g-1At a reaction temperature of 390 ℃ and a reaction pressure of 2 MPa, the reaction pressure is CO2The conversion rate of the catalyst can reach 72.39 percent, and CH4The selectivity can reach 91.42 percent.
Example 4
(1) Taking 1 g of blocky birch, carrying out reflux reaction on the blocky birch and 50 mL of nitric acid at the temperature of 80 ℃ for 12 hours, washing the blocky birch with deionized water for 3-6 times, drying the birch at normal temperature, and sealing and storing the birch for later use;
(2) weighing 0.58 g of nickel nitrate hexahydrate, dissolving in 50 mL of methanol, stirring until the nickel nitrate is dissolved, then putting the pretreated birch into the solution, carrying out ultrasonic treatment for 4 hours, and putting the birch into a vacuum drying oven for reaction for 12 hours to obtain a composite material of the birch and nickel salt;
(3) cutting the composite material of birch and nickel salt to a proper size by using a tool, and then filling the composite material into a micro reactor for in-situ reduction reaction, wherein the method comprises the following specific steps: firstly, 10% of H2introducing/Ar into the microreactor at a flow rate of 40 mL/min, and then introducing the microreactor at a speed of 1 ℃/minThe temperature is increased to 500 ℃, and the reaction is carried out for 16 hours at the temperature, and finally the material loaded with the metallic nickel in the birch pore canal is obtained;
(4) heating the temperature of the microreactor to 800 ℃, then injecting carbon monoxide into the microreactor at the speed of 50 mL/h, and reacting for 0.5 h to obtain a functional material of the carbon nano tube growing in the birch pore channel;
(5) the prepared functional material of the carbon nano tube growing in the birch pore canal is used for the catalytic synthesis reaction of carbon monoxide hydrogenation, and the space velocity reaches 61 L.h-1·g-1The CO conversion rate can reach 79.13 percent under the conditions that the reaction temperature is 350 ℃ and the reaction pressure is 0.1 MPa, and the CH4The selectivity of the catalyst can reach 96.01%;
(6) the prepared functional material of the carbon nano tube growing in the birch pore canal is used for the carbon dioxide hydrogenation catalytic synthesis reaction with the airspeed of 16 L.h-1·g-1At a reaction temperature of 390 ℃ and a reaction pressure of 2 MPa, the reaction pressure is CO2The conversion rate of the catalyst can reach 81.16 percent, and CH4The selectivity can reach 90.42%.
The foregoing illustrates and describes the principles, general features, and advantages of the present invention. However, the above description is only an example of the present invention, the technical features of the present invention are not limited thereto, and any other embodiments that can be obtained by those skilled in the art without departing from the technical solution of the present invention should be covered by the claims of the present invention.
Claims (4)
1. A preparation method of a functional material of a biomass-based macroporous in-growth carbon nanotube is characterized by comprising the following steps:
(1) pretreatment: taking 1-5 g of blocky biomass and 30-150 mL of nitric acid solution to perform reflux reaction at the temperature of 50-110 ℃ for 5-36 h, washing with deionized water for 3-6 times, drying at normal temperature to obtain a pretreatment material A, and sealing and storing for later use;
(2) dissolving a certain mass of nickel salt in methanol, uniformly stirring to obtain a solution B, putting A into B, carrying out ultrasonic treatment for 1-5 h, and then putting the solution A into a vacuum drying oven to react for 12-36 h to obtain a block material C;
(3) cutting the bulk material C to a proper size, filling the bulk material C into a micro reactor for in-situ reduction, wherein the step of performing in-situ reduction reaction comprises the following steps: firstly, 10% of H2introducing/Ar into the micro-reactor at the flow rate of 30-100 mL/min; then the temperature of the micro-reactor is raised to 400-550 ℃ at the speed of 1 ℃/min, and the material D of the biomass macroporous load metal nickel is obtained after the reaction is carried out for 12-36 h at the temperature;
(4) introducing a carbon source, regulating and controlling the parameters of the micro-reactor, wherein the reaction temperature is 700-.
2. The method for preparing a functional material of biomass-based macroporous in-growth carbon nanotubes as claimed in claim 1, wherein in step 1, the bulk biomass material comprises bulk fir wood, birch wood, camphor wood, Chinese toon, larch and eucalyptus.
3. The method for preparing a functional material of biomass-based macroporous in-growth carbon nanotubes as claimed in claim 1, wherein in step 4, the carbon source is selected from linear or cyclic small molecule substances including ethanol, methanol, propionitrile, carbon monoxide, benzene and pyridine.
4. Use of the functional material of biomass-based macroporous in-growth carbon nanotubes prepared by the method for preparing the functional material of biomass-based macroporous in-growth carbon nanotubes according to any one of claims 1 to 3 in catalytic hydrogenation reactions, particularly in the catalytic hydrogenation of CO to methane or CO2Hydrogenation catalysis to produce methane, methanol or formic acid.
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| CN103769106A (en) * | 2014-02-20 | 2014-05-07 | 厦门大学 | Nickel-based methanation catalyst promoted by in-situ grew carbon nano tube and preparation method for nickel-based methanation catalyst |
| CN108264034A (en) * | 2018-02-06 | 2018-07-10 | 陕西师范大学 | The method of growth spiral shape carbon nanotube on the porous carbon of timber |
| CN109659161A (en) * | 2018-12-11 | 2019-04-19 | 中南林业科技大学 | Electrode material for super capacitor and preparation method thereof based on aligned carbon nanotube |
| CN109794246A (en) * | 2019-01-11 | 2019-05-24 | 江苏理工学院 | A kind of monolithic devices honeycomb Ni@C/C catalyst and its preparation method and application |
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| CN103769106A (en) * | 2014-02-20 | 2014-05-07 | 厦门大学 | Nickel-based methanation catalyst promoted by in-situ grew carbon nano tube and preparation method for nickel-based methanation catalyst |
| CN108264034A (en) * | 2018-02-06 | 2018-07-10 | 陕西师范大学 | The method of growth spiral shape carbon nanotube on the porous carbon of timber |
| CN109659161A (en) * | 2018-12-11 | 2019-04-19 | 中南林业科技大学 | Electrode material for super capacitor and preparation method thereof based on aligned carbon nanotube |
| CN109794246A (en) * | 2019-01-11 | 2019-05-24 | 江苏理工学院 | A kind of monolithic devices honeycomb Ni@C/C catalyst and its preparation method and application |
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