CN113559879A - Low-temperature synthesis method and application of corrosion-resistant high-entropy alloy nano-catalyst - Google Patents
Low-temperature synthesis method and application of corrosion-resistant high-entropy alloy nano-catalyst Download PDFInfo
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- CN113559879A CN113559879A CN202110849102.0A CN202110849102A CN113559879A CN 113559879 A CN113559879 A CN 113559879A CN 202110849102 A CN202110849102 A CN 202110849102A CN 113559879 A CN113559879 A CN 113559879A
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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
- B01J23/89—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper combined with noble metals
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- C07C51/00—Preparation of carboxylic acids or their salts, halides or anhydrides
- C07C51/347—Preparation of carboxylic acids or their salts, halides or anhydrides by reactions not involving formation of carboxyl groups
- C07C51/36—Preparation of carboxylic acids or their salts, halides or anhydrides by reactions not involving formation of carboxyl groups by hydrogenation of carbon-to-carbon unsaturated bonds
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- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07D—HETEROCYCLIC COMPOUNDS
- C07D307/00—Heterocyclic compounds containing five-membered rings having one oxygen atom as the only ring hetero atom
- C07D307/02—Heterocyclic compounds containing five-membered rings having one oxygen atom as the only ring hetero atom not condensed with other rings
- C07D307/34—Heterocyclic compounds containing five-membered rings having one oxygen atom as the only ring hetero atom not condensed with other rings having two or three double bonds between ring members or between ring members and non-ring members
- C07D307/56—Heterocyclic compounds containing five-membered rings having one oxygen atom as the only ring hetero atom not condensed with other rings having two or three double bonds between ring members or between ring members and non-ring members with hetero atoms or with carbon atoms having three bonds to hetero atoms with at the most one bond to halogen, e.g. ester or nitrile radicals, directly attached to ring carbon atoms
- C07D307/60—Two oxygen atoms, e.g. succinic anhydride
Abstract
The invention discloses a low-temperature synthesis method and application of a corrosion-resistant high-entropy alloy nano catalyst, belonging to the technology in the fields of catalyst engineering and fine chemical engineering. The invention creatively applies the high-entropy alloy nano-catalyst which can still keep relatively stable in a severe service environment to the reaction. Synthesizing the corrosion-resistant high-entropy alloy nano-catalyst by adopting a liquid phase reduction method under mild conditions, wherein the reaction temperature is 60-140 ℃, the pressure is 0.5-1.0MPa, and the mass airspeed is 0.5-3h in a fixed bed reactor‑1The maleic anhydride is selectively hydrogenated to generate the succinic acid, the conversion rate can reach more than 95 percent, the selectivity can reach more than 98 percent, and the succinic acid has good stability. The catalystThe catalyst has the advantages of simple preparation process, small particle size, more exposed active sites, strong corrosion resistance, good catalytic property in a harsh reaction environment and wide application prospect.
Description
Technical Field
The invention belongs to the field of catalyst engineering, and relates to a low-temperature synthesis method and application of a corrosion-resistant high-entropy alloy nano catalyst.
Background
With the progress of science and technology and the great improvement of the living standard of human, the substances basically meet the requirements of human beings, and people want to seek a beautiful environment and touch green water and green mountains better at present, so that the environmental protection is pursued by all human beings. The succinic acid as the main raw material of the current biodegradable plastic poly (butylene succinate) is more and more concerned by researchers, and the search for synthesizing the succinic acid by adopting an environment-friendly production method with high yield and low cost has become a hotspot of the current research. In addition, succinic acid is widely used in surfactants, food additives, and the like. The method for selectively hydrogenating the maleic anhydride to generate the succinic acid by using the water as the solvent effectively avoids the use of an organic solvent, so that the process route is more in line with the standard of green chemical industry, and the production cost can be reduced. On the aspect of product separation, on one hand, the aqueous phase hydrogenation by-product of maleic anhydride is less, and on the other hand, the solubility difference between succinic acid and reactant maleic anhydride in water is larger, so that relatively pure succinic acid can be obtained by a temperature-reducing crystallization method in the later period. Because the reaction system has strong acidity, although the catalyst applied to the reaction can achieve high conversion rate and selectivity at present, the problems of short service life and poor stability of the catalyst generally exist, so that the method is particularly important for searching the catalyst applied to the reaction system with strong acidity.
The high-entropy alloy has proved to be excellent in electrocatalytic reaction process, not only can reduce the use amount of noble metal, but also has high stability and high activity. Therefore, research into the application of high-entropy alloys to catalytic reactions is increasing. In terms of the characteristics of the high-entropy alloy, the high-temperature stability of the high-entropy alloy cannot be fully utilized only by applying the high-entropy alloy to a corrosive environment and an electro-catalysis field with a low temperature, so that the high-temperature stability and the corrosion resistance of the material are fully utilized, and the application of the high-entropy alloy to the thermo-catalysis field is extremely important for the development of the thermo-catalysis and the development of the material. The current common preparation methods of the high-entropy alloy comprise vacuum arc melting, a carbon thermal impact method, a polyol method, a dealloying method, a nano-droplet mediated electrodeposition method and other preparation methods. In the existing methods for synthesizing the high-entropy alloy, the synthesis is carried out at a high temperature of more than 200 ℃ or can be carried out only by a special reaction device, and the synthesis of the high-entropy alloy nano catalyst at a low temperature is still challenging.
Chinese patent CN106861702A discloses a Cu-Ni/Al of carbon-coated nickel-copper for aqueous phase hydrogenation of maleic anhydride2O3The catalyst has better conversion rate and selectivity in maleic anhydride hydrogenation, but the description of the catalytic process shows that the carbon deposition problem of the catalyst is serious, and the problem of short service life of the catalyst in the existing maleic anhydride aqueous phase hydrogenation is not solved.
Chinese patent CN110339850A discloses a preparation method of Fe-Co-Ni-P-C high-entropy alloy electrocatalyst for hydrogen evolution reaction, which comprises the steps of mixing Fe, Co and Ni metal simple substances, C powder and P powder, smelting by using a vacuum arc smelting furnace, spraying molten alloy onto a copper roller rotating at high speed under high vacuum condition, and rapidly cooling the molten alloy through the heat conduction of the copper roller to obtain the electrocatalyst for catalytic hydrogen evolution. The synthesis method has high requirements on synthesis devices and synthesis technologies, and the process consumes more energy and has more complicated steps.
Chinese patent CN112475315A discloses a universal method for preparing high-entropy alloy nanoparticles, which comprises the steps of respectively dissolving or dispersing more than two metal organic precursors with equal atomic ratio or near equal atomic ratio, a carrier with a certain mass or a carrier and an organic ligand in solvents such as chloroform, acetone, water, ethanol and the like with a certain volume, then carrying out ultrasonic treatment on the two dispersed liquids, volatilizing the liquid for dispersion to obtain a precursor, then placing the precursor in a tubular furnace in vacuum or reducing atmosphere, heating to a required reduction temperature, keeping for a certain time, and carrying out pyrolysis reduction on the metal organic precursors to obtain the load-type high-entropy alloy nanoparticles. The method still needs high-temperature treatment and has harsh preparation conditions.
Disclosure of Invention
The invention provides a low-temperature synthesis method of an anti-corrosion high-entropy alloy nano catalyst and an application of maleic anhydride in water-phase hydrogenation. Aiming at the problem of poor stability of the existing maleic anhydride aqueous phase hydrogenation catalyst, the invention creatively applies the high-entropy alloy material which can still keep relatively stable in severe service environment (high temperature, corrosion and high electrochemical potential) to the reaction, and provides a simple solution at low temperature aiming at the defect that the existing high-entropy alloy needs to be synthesized at high temperature or under a special device. Compared with other preparation methods, the method has the advantages that no special device is needed; secondly, the synthesis temperature is lower, and is 30-75 ℃, so that the problems of agglomeration, growth and the like of catalyst particles in the synthesis process are avoided; thirdly, the synthesized high-entropy alloy nano-catalyst shows high catalytic activity, high selectivity to succinic acid and lasting stability in the aqueous-phase hydrogenation reaction of maleic anhydride.
The technical scheme of the invention is as follows:
a low-temperature synthesis method of a corrosion-resistant high-entropy alloy nano catalyst comprises the following steps:
by utilizing a liquid phase co-reduction method, taking lithium naphthalene as a reducing agent, taking an acetylacetone complex of metal with equal molar weight as a precursor, and taking a metal oxide or a carbon material as a carrier, and controlling the molar ratio of the reducing agent to the precursor to be 1.3-2.0 in a tetrahydrofuran solution: 1, reducing for 3-7h at the temperature of 30-75 ℃, and washing, centrifuging and drying to obtain the corrosion-resistant high-entropy alloy nano catalyst with the load of 0.5-5 wt.%.
The corrosion-resistant high-entropy alloy nano catalyst comprises the following components in parts by weight: PtFeCoNiCu/CNTs, PdFeCoNiCu/CNTs, RuFeCoNiCu/C, PtFeCoNiCu/ZrO2、PdFeCoNiCu/ZrO2、RuFeCoNiCu/ZrO2、PtFeCoNiCu/CeO2、PdFeCoNiCu/CeO2、RuFeCoNiCu/CeO2Wherein the proportion of each atom of the high-entropy alloy is 1:1:1:1: 1.
Aiming at maleic anhydride aqueous solution with the substrate concentration of 5-20 wt.%, the reaction temperature in a fixed bed reactor is 60-140 ℃, the reaction pressure is 0.5-1.0MPa, and the mass space velocity is 0.5-3h-1The molar ratio of hydrogen to maleic anhydride was 200: 1, selectively catalyzing maleic anhydride aqueous phase hydrogenation to prepare succinic acid by using the prepared high-entropy alloy nano catalyst.
The corrosion-resistant high-entropy alloy nano catalyst is also suitable for selective hydrogenation of unsaturated organic acid, such as selective hydrogenation of acrylic acid to generate propionic acid.
The invention has the beneficial effects that: the preparation process is simple, the obtained particle size is small, active sites are exposed much, and the high conversion rate and selectivity can be ensured and the stability can be good when the catalyst is used for aqueous phase hydrogenation of maleic anhydride.
Drawings
FIG. 1 is an XRD pattern of a PtFeCoNiCu/CNTs supported catalyst prepared by a low-temperature reduction method.
FIG. 2 shows the stability test data of PtFeCoNiCu/CNTs catalyst for aqueous hydrogenation of maleic anhydride.
Detailed Description
The present invention will be described in detail below by way of embodiments, which are illustrative and are only for the purpose of explaining the present invention, but the present invention is not limited to these embodiments.
Example 1 preparation of PtFeCoNiCu/CNTs catalyst
0.7434g of naphthalene, 0.0352g of Li and 0.8642g of carbon nanotubes are sequentially added into 60mL of tetrahydrofuran and stirred overnight to obtain uniformly dispersed reduction sites on the carbon nanotubes, 0.0811g (0.2mmol) of platinum acetylacetonate, 0.0721g of iron acetylacetonate, 0.0530g of cobalt acetylacetonate, 0.0541g of nickel acetylacetonate and 0.0540g of copper acetylacetonate are added into 20mL of tetrahydrofuran and stirred to be dissolved to obtain a metal salt solution, the carbon nanotubes stirred overnight are heated to 30 ℃, rapidly added into the metal salt precursor solution under vigorous stirring to react for 7 hours, and then washed, centrifuged and dried to obtain PtNiCu/CNTs black solid powder, namely the PtoNiCu/CNTs catalyst with the load of 5 wt.%.
Example 2 preparation of PtFeCoNiCu/CNTs catalyst
0.7434g of naphthalene, 0.0352g of Li and 8.642g of carbon nanotubes are sequentially added into 60mL of tetrahydrofuran and stirred overnight to obtain uniformly dispersed reduction sites on the carbon nanotubes, 0.0811g (0.2mmol) of platinum acetylacetonate, 0.0721g of iron acetylacetonate, 0.0530g of cobalt acetylacetonate, 0.0541g of nickel acetylacetonate and 0.0540g of copper acetylacetonate are added into 20mL of tetrahydrofuran and stirred to be dissolved to obtain a metal salt solution, the carbon nanotubes stirred overnight are heated to 30 ℃, rapidly added into the metal salt precursor solution under vigorous stirring to react for 3 hours, and then washed, centrifuged and dried to obtain black solid powder, namely the PtFeCoNiCu/CNTs catalyst with the load of 0.5 wt.%.
Example 3 PdFeCoNiCu/ZrO2Preparation of the catalyst
0.7434g of naphthalene, 0.0352g of Li and 0.8642g of zirconium oxide are sequentially added into 60mL of tetrahydrofuran and stirred overnight to obtain uniformly dispersed reduction sites on the zirconium oxide, 0.0609g (0.2mmol) of palladium acetylacetonate, 0.0721g of iron acetylacetonate, 0.0530g of cobalt acetylacetonate, 0.0541g of nickel acetylacetonate and 0.0540g of copper acetylacetonate are added into 20mL of tetrahydrofuran and stirred to be dissolved to obtain a metal salt solution, the zirconium oxide stirred overnight is heated to 75 ℃, the mixture is rapidly added into the metal salt precursor solution under vigorous stirring to react for 3 hours, and then the mixture is centrifuged and dried to obtain 5 wt.% PdFeCoNiCu/ZrO2A catalyst.
Example 4 RuFeCoNiCu/CeO2Preparation of the catalyst
0.7434g of naphthalene, 0.0352g of Li and 0.8642g of cerium oxide were added to 60mL of tetrahydrofuran in this order, and stirred overnight to obtain uniformly dispersed reduction sites on the cerium oxide, 0.0797g (0.2mmol) of ruthenium acetylacetonate, 0.0721g of iron acetylacetonate, 0.0530g of cobalt acetylacetonate, 0.0 g of cobalt acetylacetonate541g of nickel acetylacetonate and 0.0540g of copper acetylacetonate are added into 20mL of tetrahydrofuran, stirred and dissolved to obtain a metal salt solution, the cerium oxide stirred overnight is heated to 62 ℃, rapidly added into the metal salt precursor solution under vigorous stirring, reacted for 7 hours, washed, centrifuged and dried to obtain solid powder, namely RuFeCoNiCu/CeO with the load of 5 wt%2A catalyst.
Example 5 aqueous maleic anhydride hydrogenation was carried out over a PtFeCoNiCu/CNTs catalyst in a fixed bed.
The selective hydrogenation reaction was carried out with 5 wt.% maleic anhydride, water as solvent, in a fixed bed, first maleic anhydride was hydrolyzed in the aqueous phase to maleic acid. The reaction conditions are as follows: catalyst PtFeCoNiCu/CNTs: 0.2g, the reaction pressure is 1MPa, the reaction temperature is 80 ℃, and the molar ratio of hydrogen to maleic anhydride is 200: 1, mass space velocity of 3h-1And the substrate is analyzed by high performance liquid chromatography, the conversion rate reaches 95%, and the selectivity is over 99%.
Example 6 RuFeCoNiCu/CeO in a fixed bed2The catalyst hydrogenates the aqueous phase of maleic anhydride.
The selective hydrogenation reaction was carried out with 20 wt.% maleic anhydride and water as solvent in a fixed bed. The reaction conditions are as follows: catalyst PtFeCoNiCu/CNTs: 0.2g, the reaction pressure is 1MPa, and the mass space velocity is 0.5h-1The molar ratio of hydrogen to maleic anhydride is 200: 1, reaction is carried out at the temperature of 140 ℃, and the product is analyzed by high performance liquid chromatography, the conversion rate reaches 99 percent, and the selectivity to succinic acid is 96 percent.
Example 7 aqueous maleic anhydride hydrogenation was carried out over a PtFeCoNiCu/CNTs catalyst in a fixed bed.
The selective hydrogenation reaction was carried out with 5 wt.% maleic anhydride and water as solvent in a fixed bed. The reaction conditions are as follows: catalyst PtFeCoNiCu/CNTs: 0.2g, the reaction pressure is 1MPa, and the mass space velocity is 0.75h-1At 80 ℃, the molar ratio of hydrogen to maleic anhydride is 200: 1, stability test is carried out under these conditions for 100 h. The product was analyzed by high performance liquid chromatographyIt was found that the conversion of maleic anhydride was maintained above 96% and the selectivity to succinic acid was maintained above 98%. The reaction results are shown in FIG. 2.
Example 8 PdFeCoNiCu/ZrO in a fixed bed2The catalyst hydrogenates the acrylic acid aqueous phase.
The selective hydrogenation reaction was carried out with 20 wt.% of acrylic acid, and the reaction was carried out in a fixed bed with water as solvent. The reaction conditions are as follows: catalyst PdFeCoNiCu/ZrO2: 0.2g, the reaction pressure is 1MPa, the reaction temperature is 140 ℃, and the molar ratio of hydrogen to acrylic acid is 200: 1, mass space velocity of 3h-1The substrate is analyzed by high performance liquid chromatography, the conversion rate can reach 98 percent at most, and the selectivity of propionic acid is over 99 percent.
Claims (4)
1. The low-temperature synthesis method of the corrosion-resistant high-entropy alloy nano catalyst is characterized by comprising the following steps of:
by utilizing a liquid phase co-reduction method, taking lithium naphthalene as a reducing agent, taking an acetylacetone complex of metal with equal molar weight as a precursor, and taking a metal oxide or a carbon material as a carrier, and controlling the molar ratio of the reducing agent to the precursor to be 1.3-2.0 in a tetrahydrofuran solution: 1, reducing for 3-7h at the temperature of 30-75 ℃, and washing, centrifuging and drying to obtain the corrosion-resistant high-entropy alloy nano catalyst with the load of 0.5-5 wt.%.
2. The method according to claim 1, wherein the corrosion-resistant high-entropy alloy nano-catalyst is: PtFeCoNiCu/CNTs, PdFeCoNiCu/CNTs, RuFeCoNiCu/C, PtFeCoNiCu/ZrO2、PdFeCoNiCu/ZrO2、RuFeCoNiCu/ZrO2、PtFeCoNiCu/CeO2、PdFeCoNiCu/CeO2、RuFeCoNiCu/CeO2Wherein the proportion of each atom of the high-entropy alloy is 1:1:1:1: 1.
3. Use of the corrosion-resistant high-entropy alloy nanocatalyst synthesized by the synthesis method according to claim 1 or 2, characterized in that cis-anhydride aqueous solution with a substrate concentration of 5-20 wt.% is subjected to reverse reaction in a fixed bed reactorThe reaction temperature is 60-140 ℃, the reaction pressure is 0.5-1.0MPa, and the mass space velocity is 0.5-3h-1The molar ratio of hydrogen to maleic anhydride was 200: 1, selectively catalyzing maleic anhydride aqueous phase hydrogenation to prepare succinic acid by using the prepared high-entropy alloy nano catalyst.
4. The corrosion-resistant high-entropy alloy nano-catalyst synthesized by the synthesis method according to claim 1 or 2 is suitable for selective hydrogenation of unsaturated organic acid.
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