CN109718776B - Hydrogenation catalyst Co @ C/biomass and preparation method and application thereof - Google Patents
Hydrogenation catalyst Co @ C/biomass and preparation method and application thereof Download PDFInfo
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Abstract
The invention relates to the technical field of catalyst preparation, in particular to a hydrogenation catalyst Co @ C/biomass and a preparation method and application thereof, wherein the preparation method comprises the following steps: 1) taking biomass and recycling with acid solutionPerforming flow reaction, washing the biomass by using deionized water, drying at normal temperature, and sealing and storing; 2) respectively weighing cobalt salt and 2-methylimidazole, dissolving in methanol, and uniformly stirring to obtain a ZIF-67 precursor solution; 3) soaking the pretreated biomass in a ZIF-67 precursor solution for aging, or putting the pretreated biomass and the ZIF-67 precursor solution into a hydrothermal reaction kettle for constant-temperature hydrothermal reaction; taking out the massive biomass, and drying at normal temperature; 4) centrifuging and collecting precipitates in the hydrothermal reaction kettle, washing the precipitates with methanol for multiple times, and drying the precipitates to obtain a catalyst precursor ZIF-67; 5) putting the biomass obtained in the step (3) into a porcelain boat, and introducing N2Calcining to prepare a hydrogenation catalyst Co @ C/biomass; the prepared catalyst Co @ C/biomass is used for hydrogenation catalytic synthesis reaction.
Description
Technical Field
The invention relates to the technical field of catalyst preparation, in particular to a hydrogenation catalyst Co @ C/biomass and a preparation method thereof.
Background
The energy is an important material support for national development, and relates to various aspects such as politics, economy, society and military affairs. As is well known, the amount of world energy resources is limited, however, with the continuous development of the world economy, the amount of energy consumption is increasing day by day, and the energy crisis is becoming more and more prominent in various parts of the world due to the dispute caused by energy problems, and the corresponding environmental pollution is one of the current important problems, and the countries in the world are actively taking measures to cope with the situation. Therefore, the reasonable, clean and efficient utilization of the current energy sources has important significance for the health, stability and sustainable development of the global economy and society.
Metal-Organic Frameworks (MOFs) are a new porous network structure material formed by coordination and connection of Metal ions and Organic ligands. The crystal material is a crystal material which is self-assembled by utilizing organic ligands and metal ions or metal clusters through coordination bonds or intermolecular interaction force and has a one-dimensional, two-dimensional or three-dimensional infinite network structure. The metal ions in the MOFs structure are linked by organic ligands and are highly dispersed and isolated, and the high carbonization of the organic ligands in the thermal decomposition process can block the agglomeration of metals, so that highly dispersed metal or metal oxide nanoparticles with small and uniform particle size can be hopefully prepared, and the nanoparticles can be used as active catalytic centers. In addition, the preparation of metals or metal oxides by the thermal decomposition of MOFs has an advantage that the ligands or the porous carbon generated by the pyrolysis of the filled organic matter partially wrap the metal particles, thereby improving the stability of the catalyst.
The hydrogenation synthesis catalyst mainly takes oxides as carriers, and the carriers and metal particles can form stronger interaction to generate cobalt species which are difficult to reduce, thereby reducing the utilization rate of cobalt. Generally speaking, the catalytic performance of a Fischer-Tropsch synthesis reactant is highly correlated with the type of its support. The most commonly used supports for cobalt catalysts are various oxide and molecular sieve supports, e.g. Al2O3、SiO2、TiO2And silica-alumina molecular sieves, etc. for these conventional oxide carriers, the strong acting force between the carrier and the metal, the disordered pore structure of the carrier, the difficult-to-examine position of cobalt on the surface of the carrier, etc. cause the researchers to hardly obtain the mechanism of the influence of the carrier species on the catalyst performance. The force between the carbon carrier and the metal is weak, especially the graphitized carbon material.
Disclosure of Invention
The invention aims to provide a hydrogenation catalyst Co @ C/biomass and a preparation method and application thereof, wherein honeycomb type biomass is used as a carrier of a hydrogenation synthesis reactant to form a honeycomb type hydrogenation catalyst, namely a biomass-based macroporous ingrowth ZIF-67 derivative catalyst.
In order to achieve the purpose, the invention provides the following technical scheme:
a preparation method of a hydrogenation catalyst Co @ C/biomass comprises the following steps:
(1) pretreatment of a catalyst carrier: taking 1-5 g of blocky biomass and 30-150 mL of acid solution to perform reflux reaction at 50-120 ℃ for 1-36 hours, washing the biomass with deionized water, drying at normal temperature, and storing in a sealed manner for later use;
(2) weighing a mixture with a molar ratio of 1: dissolving 1-25 parts of cobalt salt and 2-methylimidazole in a methanol solution, and uniformly stirring to obtain a ZIF-67 precursor solution;
(3) dipping the pretreated biomass in a ZIF-67 precursor solution and aging for 3-48 hours, or putting the pretreated biomass and the ZIF-67 precursor solution into a polytetrafluoroethylene hydrothermal reaction kettle together for hydrothermal reaction at a constant temperature of 60-150 ℃ for 3-48 hours; taking out the massive biomass, and drying at normal temperature;
(4) centrifuging and collecting the precipitate in the reaction kettle, washing the precipitate with methanol for multiple times, and drying to obtain a catalyst precursor ZIF-67;
(5) putting the biomass obtained in the step (3) into a porcelain boat, and introducing N2Calcining under the condition of (1) to prepare the hydrogenation catalyst Co @ C/biomass.
The preparation method of the hydrogenation catalyst Co @ C/biomass comprises the step (1) of preparing an acid solution from nitric acid, hydrogen peroxide or potassium permanganate.
The preparation method of the hydrogenation catalyst Co @ C/biomass comprises the step (1), wherein the biomass in the step (1) is a biomass material with natural macropores, preferably wood blocks, bamboo or flax stems.
The preparation method of the hydrogenation catalyst Co @ C/biomass comprises the step (1) of washing for 3-6 times.
The preparation method of the hydrogenation catalyst Co @ C/biomass comprises the step (2), wherein the cobalt salt is cobalt nitrate hexahydrate, cobalt acetate tetrahydrate or cobalt chloride.
The preparation method of the hydrogenation catalyst Co @ C/biomass comprises the step (5) of calcining at the temperature of 300-900 ℃.
The preparation method of the hydrogenation catalyst Co @ C/biomass comprises the step (5) of calcining for 0.5-6 hours.
The hydrogenation catalyst Co @ C/biomass prepared by any one of the preparation methods is provided.
The hydrogenation catalyst Co @ C/biomass is used for carrying out hydrogenation catalytic synthesis reaction on CO and carrying out hydrogenation catalytic synthesis reaction on CO2Carrying out hydrogenation catalytic synthesis reaction.
The combination of metal catalyst derived from MOFs material and massive biomass catalyst carrier, wherein the massive biomass has a pore canal without bending, H2And CO is limited to pass through the pore canal, and is more favorable for H2And CO, so that the CO is forced to be fully contacted with the MOFs-derived metal catalyst and react. Therefore, the hydrogenation catalyst Co @ C/biomass synthesized by the method can become a novel catalyst with excellent performance.
Compared with the prior art, the invention has the beneficial effects that:
according to the preparation method, the impregnation and hydrothermal methods are used as assistance, and carbonization is carried out, so that the ZIF-67 derived metal catalyst is generated in a pore channel by taking a carbon pore channel as a reaction container through reaction, and the hydrogenation catalyst Co @ C/biomass with good activity and high thermal stability is effectively generated. The preparation method optimizes the process reaction conditions, greatly simplifies the synthesis process and reduces the experiment cost.
Drawings
FIG. 1 is an XRD pattern of ZIF-67 crystals obtained in example 1;
FIG. 2 is an SEM topography of ZIF-67 crystals prepared in example 1;
FIG. 3 is an XRD pattern of Co @ C/biomass of the hydrogenation catalyst prepared in example 1;
FIG. 4 is an SEM topography of the hydrogenation catalyst Co @ C/biomass prepared in example 1.
Detailed Description
The technical solutions in the embodiments of the present invention will be clearly and completely described below with reference to the drawings in the embodiments of the present invention, and it is obvious that the described embodiments are only a part of the embodiments of the present invention, and not all of the embodiments. All other embodiments, which can be derived by a person skilled in the art from the embodiments given herein without making any creative effort, shall fall within the protection scope of the present invention.
Example 1
A preparation method of a hydrogenation catalyst Co @ C/biomass comprises the following steps:
(1) taking 1.5g of cubic wood block, carrying out reflux reaction on the cubic wood block and 50mL of nitric acid solution at the temperature of 60 ℃ for 24 hours, repeatedly washing the wood block for 5 times under the boiling condition by using deionized water, drying at normal temperature, and sealing for later use;
(2) weighing 0.359g of cobalt nitrate hexahydrate, dissolving the cobalt nitrate hexahydrate in 25ml of methanol, uniformly stirring to obtain a solution A, weighing 0.811g of 2-methylimidazole, dissolving the 2-methylimidazole in 25ml of methanol, uniformly stirring to obtain a solution B, pouring the solution A into the solution B, and stirring at room temperature for 1 hour to obtain a mixed solution C;
(3) soaking the cubic wood block pretreated in the step (1) in the solution C at normal temperature for 24 hours, taking out the cubic wood block, drying at normal temperature, centrifuging the rest solution, collecting a sample, washing with methanol for 3 times, and drying to obtain a catalyst precursor ZIF-67;
(4) putting the wood blocks obtained in the step (3) into a porcelain boat, and introducing N2Calcining for 3 hours at 600 ℃ under the condition of (1) to prepare a sample hydrogenation catalyst Co @ C/biomass;
FIG. 1 is an XRD pattern of the ZIF-67 crystal material obtained in step (3), and as can be seen from FIG. 1, the positions of diffraction peaks of the phase pattern of the crystal structure of ZIF-67 obtained in this example coincide, thus confirming that the obtained sample is a pure-phase ZIF-67 crystal.
The SEM image of the ZIF-67 material obtained in this example is shown in FIG. 2, from which it can be seen that the ZIF-67 material prepared according to this example was dodecahedral in shape.
Fig. 3 is an XRD pattern of the hydrogenation catalyst Co @ C/biomass obtained in this example, and it is obvious from fig. 3 that after wood block is carbonized, metal cobalt is prominent, which is more beneficial to improving catalytic activity.
The SEM appearance picture of the hydrogenation catalyst Co @ C/biomass obtained in the example is shown in FIG. 4, and it can be seen from the SEM appearance picture that ZIF-67 derived porous materials are obviously grown in the carbon pore channels prepared according to the test method.
The hydrogenation catalyst Co @ C/biomass prepared by the method is used for hydrogenation catalytic synthesis reaction.
Example 2
A preparation method of a hydrogenation catalyst Co @ C/biomass comprises the following steps:
(1) taking 2g of blocky bamboo chips, carrying out reflux reaction on the blocky bamboo chips and 100mL of hydrogen peroxide at the temperature of 80 ℃ for 36 hours, repeatedly washing the blocky bamboo chips for 5 times under the boiling condition by using deionized water, drying at normal temperature, and sealing for later use;
(2) weighing 0.83g of cobalt acetate tetrahydrate, dissolving the cobalt acetate tetrahydrate in 25ml of methanol, uniformly stirring to obtain a solution A, weighing 0.821g of 2-methylimidazole, dissolving the 2-methylimidazole in 25ml of methanol, uniformly stirring to obtain a solution B, pouring the solution A into the solution B, and stirring at room temperature for 1 hour to obtain a mixed solution C;
(3) putting the pretreated massive bamboo chips in the step (1) and the mixed solution C into a hydrothermal reaction kettle with polytetrafluoroethylene as an inner lining, carrying out hydrothermal reaction at 80 ℃ for 36h, cooling to room temperature, taking out the bamboo chips, drying at normal temperature, centrifuging the rest solution, collecting a sample, washing with methanol for 3 times, and drying to obtain a catalyst precursor ZIF-67;
(4) putting the bamboo chips obtained in the step (3) into a porcelain boat, and introducing N2Calcining for 3 hours at 800 ℃ under the condition of (1) to prepare a sample hydrogenation catalyst Co @ C/biomass;
the hydrogenation catalyst Co @ C/biomass prepared by the method is used for hydrogenation catalytic synthesis reaction.
Example 3
A preparation method of a hydrogenation catalyst Co @ C/biomass comprises the following steps:
(1) taking 1g of blocky flax stems, carrying out reflux reaction on the blocky flax stems with 80mL of potassium permanganate solution at the temperature of 100 ℃ for 12 hours, repeatedly washing the blocky flax stems for 5 times under the boiling condition by using deionized water, drying at normal temperature, and sealing for later use;
(2) weighing 0.2425g of cobalt chloride, dissolving the cobalt chloride in 30ml of methanol, uniformly stirring to obtain a solution A, weighing 0.821g of 2-methylimidazole, dissolving the 2-methylimidazole in 30ml of methanol, uniformly stirring to obtain a solution B, pouring the solution A into the solution B, and stirring at room temperature for 0.5h to obtain a mixed solution C;
(3) putting the blocky flax stems pretreated in the step (1) and the mixed solution C into a hydrothermal reaction kettle with polytetrafluoroethylene as an inner liner, carrying out hydrothermal reaction for 18h at 100 ℃, cooling to room temperature, taking out the flax stems, drying at normal temperature, centrifuging the rest solution, collecting a sample, washing with methanol for 3 times, and drying to obtain a catalyst precursor ZIF-67;
(4) putting the flax stems obtained in the step (3) in a porcelain boat, and introducing N2Calcining for 4 hours at 700 ℃ under the condition of (1) to prepare a sample hydrogenation catalyst Co @ C/biomass;
(5) the prepared hydrogenation catalyst Co @ C/biomass is used for hydrogenation catalytic synthesis reaction.
The hydrogenation catalyst Co @ C/biomass was obtained as in example 1 and tested for Fischer-Tropsch synthesis reaction activity at various temperatures, from which the results are shown in Table 1. It can be seen that the hydrogenation catalyst Co @ C/biomass prepared according to the above-described embodiment has a higher catalytic activity. The preparation success of the biomass-based macroporous ingrowth ZIF-67 derived catalyst, namely the hydrogenation catalyst Co @ C/biomass is shown, and the effect is obvious.
TABLE 1
Although embodiments of the present invention have been shown and described, it will be appreciated by those skilled in the art that changes, modifications, substitutions and alterations can be made in these embodiments without departing from the principles and spirit of the invention, the scope of which is defined in the appended claims and their equivalents.
Claims (5)
1. A preparation method of a hydrogenation catalyst Co @ C/biomass is characterized by comprising the following steps:
(1) pretreatment of a catalyst carrier: taking 1-5 g of blocky biomass and 30-150 mL of acid solution to perform reflux reaction at 50-120 ℃ for 1-36 hours, washing the biomass with deionized water, drying at normal temperature, and storing in a sealed manner for later use; the biomass is a biomass material with natural macropores and comprises wood blocks, bamboos and flax stems; the acid solution is nitric acid, hydrogen peroxide or potassium permanganate solution;
(2) weighing a mixture with a molar ratio of 1: dissolving 1-25 parts of cobalt salt and 2-methylimidazole in a methanol solution, and uniformly stirring to obtain a ZIF-67 precursor solution;
(3) dipping the pretreated biomass in a ZIF-67 precursor solution and aging for 3-48 hours, or putting the pretreated biomass and the ZIF-67 precursor solution into a polytetrafluoroethylene hydrothermal reaction kettle together for hydrothermal reaction at a constant temperature of 60-150 ℃ for 3-48 hours; taking out the massive biomass, and drying at normal temperature;
(4) centrifuging and collecting the precipitate in the reaction kettle, washing the precipitate with methanol for multiple times, and drying to obtain a catalyst precursor ZIF-67;
(5) putting the biomass obtained in the step (3) into a porcelain boat, and introducing N2Calcining at the temperature of 600-800 ℃ for 3-4 hours to obtain the hydrogenation catalyst Co @ C/biomass.
2. The method for preparing the hydrogenation catalyst Co @ C/biomass as claimed in claim 1, wherein: and (2) washing in the step (1) for 3-6 times.
3. The method for preparing the hydrogenation catalyst Co @ C/biomass as claimed in claim 1, wherein: and (3) in the step (2), the cobalt salt is cobalt nitrate hexahydrate, cobalt acetate tetrahydrate or cobalt chloride.
4. A hydrogenation catalyst Co @ C/biomass prepared by the preparation method as described in any one of claims 1 to 3.
5. Use of the hydrogenation catalyst Co @ C/biomass as claimed in claim 4, wherein: used for carrying out hydrogenation catalytic synthesis reaction on CO and carrying out hydrogenation catalytic synthesis reaction on CO2Carrying out hydrogenation catalytic synthesis reaction.
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| CN112774682B (en) * | 2019-11-11 | 2023-04-07 | 中国科学院城市环境研究所 | Aluminum-cobalt composite catalyst and preparation method and application thereof |
| CN112892593B (en) * | 2021-01-18 | 2022-11-08 | 广东工业大学 | MOFs/water hyacinth derived material, preparation method thereof and degradation method of organic pollutants |
| CN114797927A (en) * | 2021-01-27 | 2022-07-29 | 中国科学院大连化学物理研究所 | Composite carrier material loaded cobalt-based catalyst, preparation and application thereof |
| CN113351207B (en) * | 2021-04-09 | 2023-02-28 | 临涣焦化股份有限公司 | Multi-wall catalyst for preparing liquid fuel by carbon dioxide hydrogenation and preparation method and application thereof |
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