CN117753199A - Application of spherical mesoporous Kong Gaoshang metal catalyst in carbon dioxide hydrogenation catalysis - Google Patents

Application of spherical mesoporous Kong Gaoshang metal catalyst in carbon dioxide hydrogenation catalysis Download PDF

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CN117753199A
CN117753199A CN202311634237.0A CN202311634237A CN117753199A CN 117753199 A CN117753199 A CN 117753199A CN 202311634237 A CN202311634237 A CN 202311634237A CN 117753199 A CN117753199 A CN 117753199A
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catalyst
metal
gaoshang
solution
spherical mesoporous
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倪志江
陈晓宇
苏林
沈含虞
钟石宇
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Changzhou University
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Changzhou University
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Abstract

The invention belongs to the technical field of carbon dioxide hydrogenation, and provides application of a spherical mesoporous Kong Gaoshang metal catalyst in carbon dioxide hydrogenation catalysis. The metal salt can be uniformly distributed in the polyphenol-formaldehyde polymer network, and then is calcined and decomposed at high temperature, so that the spherical mesoporous Kong Gaoshang oxide can be prepared. The catalyst not only has excellent stability of high-entropy materials, but also has larger specific surface area for enhancing catalytic activity due to the unique spherical mesoporous structure, and the narrow pore canal in the structure can effectively help to prepare olefin. The catalyst has the advantages of simple preparation method, low cost and wide application, and the final purpose is to efficiently and stably prepare high-value chemicals such as olefin and the like.

Description

Application of spherical mesoporous Kong Gaoshang metal catalyst in carbon dioxide hydrogenation catalysis
Technical field:
the invention belongs to the field of new material preparation technology and application, and particularly relates to a preparation method and application of a high-entropy metal oxide catalyst material.
The background technology is as follows:
catalytic conversion of carbon dioxide is a promising approach to solve the problem of excessive carbon dioxide emissions by the principle of excess CO in the atmosphere by fischer-tropsch synthesis (FTS) 2 And H 2 To liquid oils and other high value chemicals such as olefins and diesel, etc. However, effective achievement of this objective requires the catalyst to be catalyzed and regulated during its reaction. Therefore, a large number of iron-based catalysts have been studied for efficient olefin production, and sodium and zinc have been studied for the production of olefins by iron carbide catalysts, such as Zhang Zhijiang et al, which show that Na in the catalyst is expressed according to their respective characterizations + By adjusting the hydrogenation capacity of the olefin and promoting the desorption of the olefin, the selectivity of the C2-C12 olefin is enhanced, while the presence of ZnO can effectively catalyze RWGS reaction, change the size of the active phase and improve the catalytic activity and performance. Nonetheless, changes in the surface and interface structure of iron-based catalysts are relative to CO 2 The catalytic effect of the hydrogenation activation rate is also controversial, with CO on iron-based catalysts 2 The reaction pathways and kinetics of the hydrogenation to olefins are not well defined, which limits the precise control of the active sites of the catalyst and the design of industrial catalytic reactors. All catalysts which tend to have high catalytic performance require the addition of noble metals, which in turn greatly limit CO 2 And (3) large-scale production of olefins by hydrogenation.
The high-entropy catalyst material has higher structural stability and unique physicochemical properties such as element adjustability compared with the traditional catalyst. The precise catalysis mediation of the active phase can be realized by reasonably adjusting the constituent elements of the high-entropy catalyst material, and the catalyst can be applied to various catalysis aspects. However, no research on the use of high entropy materials for Fischer-Tropsch olefin production is currently performed.
Disclosure of Invention
In order to solve the problems in the background technology, the high-entropy spherical mesoporous metal oxide catalyst prepared by the sol-gel method can achieve good effect in the field of preparing low-carbon olefin by hydrogenation of carbon dioxide. The reaction process is simple and feasible, the requirement on reaction equipment is low, the prepared catalyst has excellent catalytic performance and consistently excellent thermal stability of high-entropy materials, and therefore the large-scale industrial production and use of the catalyst are expected to be realized through the amplification experiment.
Preparing the high-entropy metal catalyst of the high-value chemical. The high-entropy metal catalyst is prepared by adopting a sol-gel method, and has simple operation process and low cost. The finally prepared spherical mesoporous Kong Gaoshang metal oxide catalyst can be used in a thermal catalytic system for preparing low-carbon olefin by carbon dioxide hydrogenation.
The invention provides a preparation method of a high-entropy oxide catalyst, which comprises the following specific preparation steps:
A. preparing F127 solution: the powdery F127 is dissolved in a mixed solution of water and ethanol, and then ammonia solution is added for standing, so that F127 solution is obtained.
B. Adding 0.025g/ml tannic acid solution and 37-40wt% formaldehyde solution during the stirring process of F127 solution, and mixing and stirring to obtain polyphenol resin solution; f127, tannic acid and formaldehyde solution with the mass ratio of 1:1:3.8.
C. adding a plurality of soluble metal salt solutions into the polyphenol resin solution, and further mixing and stirring uniformly to obtain a mixed solution. The mass ratio of the soluble metal salt to F127 is 1-1.5:1, wherein the mass ratio of various metal atoms in the catalyst in the total catalyst is 5-35%;
D. carrying out hydrothermal reaction on the obtained mixed solution; the hydrothermal reaction conditions are as follows: the reaction temperature is 80-200 ℃ and the reaction time is 2-48 h.
E. After the hydrothermal reaction is finished and cooled to room temperature, collecting the reacted solution, and performing centrifugal washing operation on the solution under the centrifugal conditions: the rotating speed is 7000r/min-12000r/min, and the rotating speed is kept for 3-5 minutes. Washing conditions: the water and absolute ethanol are alternately washed for 3-5 times. And removing excessive aqueous solution, and putting the centrifugally washed product into an oven for drying to obtain the metal/polymer composite material. Drying conditions: the temperature is 80-200 ℃ and the holding time is 2-24 h.
F. And (3) placing the dried product into a tubular furnace for air calcination, maintaining the temperature at 200-900 ℃ for 4-8 hours at a speed of 1-20 ℃/min, and finally preparing the spherical mesoporous Kong Gaoshang oxide catalyst after calcination.
Further, the soluble metal salt in the step C is five or more of cobalt nitrate hexahydrate, copper nitrate hexahydrate, zinc nitrate hexahydrate, ferric nitrate nonahydrate, sodium nitrate, manganese nitrate tetrahydrate and nickel nitrate hexahydrate.
Further, the preferred calcination temperature in step F is 800 ℃, and too high a temperature higher than 800 ℃ can cause collapse of the spherical mesoporous structure to reduce the specific surface area, thereby reducing CO 2 Conversion and catalytic performance.
The high-entropy catalyst material provided by the invention is prepared by adopting the method.
The invention provides an application of a high-entropy catalyst material in chemical catalysis, in particular to an application of the high-entropy catalyst material in catalyzing carbon dioxide and hydrogen to prepare high-value chemicals such as olefin under high temperature and high pressure. The specific application is as follows: the catalyst is used in hydrogenation reaction of carbon dioxide, and is subjected to reduction treatment, namely high-purity hydrogen is introduced, and the catalyst is reduced for 18 hours under the conditions of the temperature of 400 ℃, the pressure of 0.4MPa and the airspeed of 2000 ml/(g.times.h). After the reduction is finished, the catalyst is filled into a reactor, and the molar ratio of the catalyst to the catalyst is 1: CO of 3 2 /H 2 The mixed gas is hydrogenated to prepare olefin under the conditions of temperature 340 ℃, pressure 2.5MPa, airspeed 2500 ml/(g.h), reaction time is 100h,
the spherical mesoporous structure of the prepared catalyst has the following characteristics:
the invention adopts a sol-gel method and F127 is used asAs a template, polyphenols as polymerizable ligands polymerize with formaldehyde to form colloidal spheres. The catechol groups rich in the polyphenol tightly chelate 5 metal ions with the colloid balls, after high-temperature calcination, the metal substances are gathered together to form high-entropy oxide, and the organic resin is fully decomposed to generate mesopores; 1. the F127 organic template molecule is used for regulating the porosity of the metal oxide, which means that the formation of long-chain hydrocarbon is directionally inhibited and C is promoted 2 -C 4 Is synthesized by (1); 2. compared with the high-entropy oxide structure synthesized by solid phase reaction, the high-entropy oxide prepared by the wet chemical method has more specific surface area and excellent nano-pores. 3. With the increase of the calcination temperature, the metal oxide nanocrystalline can grow continuously, migrate from the inside of the sphere to the surface of the sphere, and prevent the catalytic performance from being greatly reduced after the mesoporous structure collapses.
The high entropy catalyst contains Fe and Co atoms which play the role of an active phase in catalysis, zn and Na are used as dispersing agents, the strong interaction among metal ions is reduced, cu has high activity in WGS and RWGS, and the most important function is that the Cu can inhibit CH 4 Promotes olefin selectivity. The preparation of metal in the catalyst is simple and easy to obtain, and the unique design and preparation concept of the spherical mesoporous Kong Gaoshang metal oxide catalyst are beneficial to breaking through the bottleneck that the high-entropy oxide catalyst has a low specific surface area and the organic-inorganic composite material structure is difficult to coexist, so that the resource conversion with higher efficiency is realized.
Drawings
FIG. 1 is a schematic diagram of the catalytic conversion of a spherical mesoporous Kong Gaoshang oxide to a lower olefin product.
FIG. 2 is an X-ray powder diffraction (XRD) pattern of samples of the high entropy metal oxides obtained for each example.
Fig. 3 is a graph of isothermal adsorption/desorption profiles of example 1, example 2, and example 3.
Fig. 4 is a TEM image of example 1.
Fig. 5 is a TEM image of example 2.
Fig. 6 is a TEM image of example 3.
FIG. 7 is a graph of CO in the catalytic reactions of examples 1-4 2 Conversion is plotted against time.
Detailed Description
Example 1
A. 2.0g of F127 was dissolved in a mixture of water (184 mL) and ethanol (32 mL), then 2mL of ammonia solution was added and stirred for 0.5 h.
B. To the above solution was added tannic acid solution (80 mL,0.025 g/mL). After the tannic acid solution is completely dissolved, formaldehyde solution (3.8 mL, 37-40 wt%) is added and stirred for 24h.
C. To the solution obtained in step B, 10mL of a solution containing Co (NO) 3 ) 2 ·6H 2 O(0.6g)、Cu(NO 3 ) 2 ·6H 2 O(0.6g)、Zn(NO 3 ) 2 ·6H 2 O(0.6g)、Fe(NO 4 ) 3 ·9H 2 O(0.6g)、NaNO 3 (0.6 g) of a metal precursor solution, and stirring for a further 12 hours.
D. And (3) placing the metal precursor solution into a reaction kettle, and keeping the temperature at 100 ℃ for 12 hours.
E. After the reaction is finished, cooling the reaction kettle completely, centrifugally washing the solution with deionized water and absolute ethyl alcohol, collecting a sample with the surface solvent removed, and placing the sample in a culture dish.
F. The samples in the petri dishes were dried in an oven at 80℃for 12h.
G. The sample was taken out of the reaction vessel and calcined in a tube furnace at 600 c for 4h at a rate of 5 c/min. The catalyst material FCCZN-600 is finally obtained.
The experimental operation steps of the catalytic evaluation system are as follows: firstly, weighing a certain amount of catalyst material and quartz sand, uniformly mixing, then, disassembling a reaction tube in a high-pressure catalytic evaluation system, sequentially putting a small amount of quartz cotton and quartz sand from top to bottom, putting the catalyst after the quartz sand reaches half of the height, putting the quartz sand until the top end of the reaction tube, and finally filling Xu Shaoliang quartz sand at the top. The screws at each location were tightened and reconnected to the high pressure catalytic evaluation system. On the premise of determining that the whole system is airtight. Firstly, reducing the catalyst by hydrogen, and specifically: first go through H 2 The reaction is carried out by the reduction,the reducing condition is 0.4MPa pressure, temperature is 400 ℃, space velocity is 2073 ml/(g.h) (the accurate space velocity is obtained by 0.4g of catalyst, 5ml/21.7 s.3600/0.5), and the catalyst is used for subsequent catalytic reaction after 18h of reduction. After the reduction is finished, the catalyst is filled into a reactor, and the molar ratio of the catalyst to the catalyst is 1: CO of 3 2 /H 2 The mixed gas is hydrogenated under the conditions of the temperature of 340 ℃, the pressure of 2.5MPa and the airspeed of 2500 ml/(g.h) to prepare olefin, and the reaction time is 100h.
20 samples are taken within 100 hours, and the CO of the catalyst obtained after the average of 20 groups of data is calculated 2 Conversion was 56.3%, methane selectivity was 35.1%, C 2 ＝ -C 4 ＝ The selectivity of (C) was 38.6% 5+ The selectivity of (2) was 14.6%.
Example 2
Example 2 differs from example 1 in that: the calcination temperature was increased from 600 ℃ to 700 ℃. The A-F steps are the same as in example 1.
G. The sample was taken out of the reaction vessel and calcined in a tube furnace at 700 c for 4 hours at a rate of 5 c/min. The catalyst material FCCZN-700 is finally obtained.
The procedure of the catalytic reaction is the same as in example 1, 20 groups of data are obtained through experiments, and the average value is taken, and the CO of the catalyst is 2 Conversion was 61.9%, methane selectivity was 28%, C 2 ＝ -C 4 ＝ The selectivity of (C) was 40.4%, C 5+ The selectivity of (2) was 16.1%.
Example 3
Example 3 differs from example 2 in that: the calcination temperature was increased from 700 ℃ to 800 ℃. The A-F procedure is as in example 1.
G. The sample was taken out of the reaction vessel and calcined in a tube furnace at 800 c for 4 hours at a rate of 5 c/min. Finally, the catalyst material FCCZN-800 is obtained.
The procedure of the catalytic reaction is the same as in example 1, 20 groups of data are obtained through experiments, and the average value is taken, and the CO of the catalyst is 2 Conversion was 62.3%, methane selectivity was 30.7%, C 2 ＝ -C 4 ＝ The selectivity of (C) was 45.7% 5+ The selectivity of (2) was 7.7%.
Experiments prove that the catalyst has excellent catalytic effect and higher heat stability activity, and still has good catalytic activity after a long time (100 h). The surface areas of the catalysts with the three different calcining temperatures of 600 ℃, 700 ℃ and 800 ℃ are 72.2m respectively after BET test 2 /g、63.6m 2 /g、51.3m 2 The pore diameters are concentrated at 7.8nm, 6.7nm and 5.5nm, respectively. It follows that as the calcination temperature increases, the spherical structure of the catalyst slowly collapses, but may be enhanced due to strong interactions between the metals, resulting in enhanced catalytic activity.
Example 3 compared to examples 1 and 2, CO 2 Has improved conversion rate of C 2 ＝ -C 4 ＝ Has relatively large improvement in selectivity. And at 900 ℃ and above, due to the fact that a large amount of metal elements volatilize, part of particles are sintered, and the catalyst is basically deactivated. Thus, catalysts calcined at 800℃are described as optimal preparation schemes for the present series of catalysts.
Example 4
Example 4 differs from example 3 in that: the preparation method adopts the same element composition and adopts a hand milling method.
A. Will contain Co (NO) 3 ) 2 ·6H 2 O(0.6g)、Cu(NO 3 ) 2 ·6H 2 O(0.6g)、Zn(NO 3 ) 2 ·6H 2 O(0.6g)、Fe(NO 4 ) 3 ·9H 2 O(0.6g)、NaNO 3 (0.6 g) of a metal precursor solution, and stirring for a further 12 hours.
B. After stirring, the solution was washed by centrifugation with deionized water and absolute ethanol, and the samples from which the surface solvents were removed were collected and placed in a petri dish.
C. The samples in the petri dishes were dried in an oven at 80℃for 12h.
D. The sample was taken out of the reaction vessel and calcined in a tube furnace at 800 c for 4 hours at a rate of 5 c/min. The catalyst material FCCZN@MG-800 is finally obtained. Catalytic reaction procedure same as in example1, obtaining 20 groups of data through experiments, and taking an average value, wherein the CO of the catalyst 2 The conversion was 63.1%, the methane selectivity was 39.7%, C 2 ＝ -C 4 ＝ The selectivity of (2) was 34.7% and the selectivity of C5+ was 15.5%. Compared with the spherical high-entropy catalyst FCCZN prepared by a wet chemical method, the high-entropy catalyst prepared by the hand milling method has extremely low specific surface area, and has low hydrogenation performance because no carrier structure exists for promoting adsorption of reaction gas
Example 5
Example 5 differs from example 3 in that: an element Al is additionally added.
A. 2.0g of F127 was dissolved in a mixture of water (184 mL) and ethanol (32 mL), then 2mL of ammonia solution was added and stirred for 0.5 h.
B. To the above solution was added tannic acid solution (80 mL,0.025 g/mL). After the tannic acid solution is completely dissolved, formaldehyde solution (3.8 mL, 37-40 wt%) is added and stirred for 24h.
C. To the solution obtained in step B, 10mL of a solution containing Co (NO) 3 ) 2 ·6H 2 O(0.6g)、Cu(NO 3 ) 2 ·6H 2 O(0.6g)、Zn(NO 3 ) 2 ·6H 2 O(0.6g)、Fe(NO 4 ) 3 ·9H 2 O(0.6g)、NaNO 3 (0.6 g) and Al (NO) 3 ) 3 ·9H 2 O (0.6 g) was further stirred for 12h.
D. And (3) placing the metal precursor solution into a reaction kettle, and keeping the temperature at 100 ℃ for 12 hours.
E. After the reaction is finished, cooling the reaction kettle completely, centrifugally washing the solution with deionized water and absolute ethyl alcohol, collecting a sample with the surface solvent removed, and placing the sample in a culture dish.
F. The samples in the petri dishes were dried in an oven at 80℃for 12h.
The sample was taken out of the reaction vessel and calcined in a tube furnace at 800 c for 4 hours at a rate of 5 c/min. The catalyst material FCCZNA-800 is finally obtained.
Catalytic reactionThe procedure is as in example 1, and the average value is taken after 20 groups of data are obtained through experiments, and the CO of the catalyst 2 Conversion was 53.8%, methane selectivity was 45.8%, C 2 ＝ -C 4 ＝ Is 16.19%, C 5+ The selectivity of (2) was 10.45%.
Therefore, in summary, the spherical high-entropy catalyst FCCZN has more excellent catalytic reaction structure and more reasonable element composition, so that FCCZN-800 is the preparation of the optimal catalyst of the patent.
Table 1 shows BET data of examples 1, 2, 3 and 4
The average performance of the catalyst over a period of 100 hours at different calcination temperatures is given in table 1. Notably, the catalysts of examples 1, 2 and 3 exhibited superior catalytic performance during the reaction compared to the catalyst of example 4 prepared by ball milling. This may be due to the unique advantage provided by the inherent macroporous spherical structure of FCCZN catalysts. Furthermore, we compared FCCZN catalysts prepared at different calcination temperatures, and found that calcination temperatures had a significant impact on the performance of the catalyst. As the FCCZN calcination temperature increases from 600 ℃ to 800 ℃, CO 2 The conversion rate is rapidly improved and then becomes stable, and the CO selectivity is reduced from 34.7% to 8.4%. CH with increasing FCCZN calcination temperature 4 Is significantly reduced, C 2 -C 4 The selectivity of the compound is uniformly improved. Thus, FCCZN-700 and FCCZN-800 have a higher CO 2 Conversion and lower CO selectivity.
FIG. 2 is an X-ray powder diffraction (XRD) pattern of a sample of the high entropy metal oxide prepared in accordance with the examples. From fig. 2 we can observe that examples 1, 2 and 3 show more pronounced spinel characteristic peaks than examples 4 and 5, indicating that the former structure remains good and the stability is high. In examples 1, 2 and 3, however, it was found that the characteristic peaks became sharper and the degree of crystallization increased with increasing calcination temperature.
Fig. 3 is an isothermal desorption graph of example 1, example 2, and example 3; FIG. 3 we can obtain an isotherm of FCCZN-600 of type iv and hysteresis of type h3, probably because a calcination temperature of 800℃would result in a fraction of medium Kong Tanta. Thus, catalysts calcined at lower temperatures exhibit slightly higher N 2 Adsorption capacity. At the same time we can also obtain the total BET specific surface area of these catalysts is FCCZN-600>FCCZN-700>FCCZN-800. The smaller specific surface area of FCCZN-800 means the disappearance of the carbon skeleton, which greatly increases the surface metal sites and oxygen exposure, thereby accelerating the gas phase catalytic reaction.
By observing the TEM images of the different embodiments of FIGS. 4, 5 and 6, it can be seen that the FCCZN-600 catalyst has more obvious agglomeration phenomenon than the FCCZN-700 and FCCZN-800 catalysts, and a large number of active sites cannot be exposed to react with the reaction gas, which is consistent with the result of FIG. 3.

Claims (5)

1. The application of the spherical mesoporous Kong Gaoshang metal catalyst in the hydrogenation catalysis of carbon dioxide is characterized in that the metal in the high-entropy metal catalyst is composed of five or more of cobalt, copper, zinc, iron, sodium, manganese and nickel;
the preparation method of the spherical mesoporous Kong Gaoshang metal catalyst comprises the following steps:
(1) Preparing F127 solution, adding tannic acid solution and formaldehyde solution in the stirring process of the F127 solution, mixing and stirring for reaction to obtain polyphenol resin solution;
(2) Adding a plurality of soluble metal salt solutions into the polyphenol resin solution, and uniformly mixing and stirring to obtain a mixed solution; carrying out hydrothermal reaction on the mixed solution; the hydrothermal reaction condition is 80-200 ℃;
(3) Cooling to room temperature after the hydrothermal reaction is finished, collecting the reacted solution, centrifuging, washing and drying the solution to obtain a metal/polymer composite material; and (3) placing the dried metal/polymer composite material into a tubular furnace for air calcination, wherein the calcination temperature is 200-800 ℃, and the calcination is kept for 4-8 hours, so as to obtain the spherical mesoporous Kong Gaoshang metal oxide catalyst.
2. The application of the spherical mesoporous Kong Gaoshang metal catalyst in the hydrogenation catalysis of carbon dioxide according to claim 1, wherein the metal in the soluble metal salt is composed of five components of cobalt, copper, zinc, iron and sodium, and the atomic mass ratio of each metal in the catalyst is 5-35%.
3. The use of a spherical mesoporous Kong Gaoshang metal catalyst according to claim 1, characterized in that the mass ratio of soluble metal salt to F127 is 1-1.5:1, a step of; f127, tannic acid and formaldehyde solution with the mass ratio of 1:1:3.8.
4. the use of a spherical metal Kong Gaoshang catalyst according to claim 1 for the hydrogenation of carbon dioxide, wherein the calcination temperature in step (3) is 800 ℃.
5. Use of a spherical mesoporous Kong Gaoshang metal catalyst according to any one of claims 1 to 4 in the hydrogenation catalysis of carbon dioxide, characterized in that: the high-entropy metal catalyst is put into a catalytic reactor after reduction, and CO is introduced 2 /H 2 The mixed gas is subjected to hydrogenation reaction under the conditions of the temperature of 340 ℃ and the pressure of 2.5 MPa.
CN202311634237.0A 2023-12-01 2023-12-01 Application of spherical mesoporous Kong Gaoshang metal catalyst in carbon dioxide hydrogenation catalysis Pending CN117753199A (en)

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