CN117380183B - Preparation method and application of supported palladium nanoparticle catalyst - Google Patents

Preparation method and application of supported palladium nanoparticle catalyst Download PDF

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CN117380183B
CN117380183B CN202311638399.1A CN202311638399A CN117380183B CN 117380183 B CN117380183 B CN 117380183B CN 202311638399 A CN202311638399 A CN 202311638399A CN 117380183 B CN117380183 B CN 117380183B
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nanoparticle catalyst
oxide
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冯吉
柴春玲
白立光
赵晓东
李晶
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Liming Research Institute of Chemical Industry Co Ltd
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Abstract

The invention discloses a preparation method and application of a supported palladium nanoparticle catalyst, wherein the method comprises the following steps: (1) Adding a pH regulator into a solution containing a carrier and a palladium precursor, dipping, filtering, washing, drying and reducing to obtain a catalyst precursor; (2) Performing activation pretreatment on a catalyst precursor in a reaction atmosphere to obtain a supported palladium nanoparticle catalyst; the reaction atmosphere comprises: a) Water vapor; b) Optionally other gases selected from one or more of hydrogen, carbon monoxide, ammonia, halogenated hydrocarbons, HCl and air. The supported palladium nanoparticle catalyst prepared by combining the impregnation method and the atmosphere induction dispersion method containing water vapor has higher catalytic activity and stability compared with the traditional palladium nanoparticle catalyst, and has the advantages of simple and safe preparation process, low-cost and easily-obtained raw materials, low preparation cost and easy realization of scale-up.

Description

Preparation method and application of supported palladium nanoparticle catalyst
Technical Field
The invention belongs to the field of catalyst preparation, and particularly relates to a preparation method and application of a supported palladium nanoparticle catalyst.
Background
Hydrogen peroxide is an important inorganic chemical raw material and has wide application in the fields of chemical synthesis, textile, medicine, electronics, food, metallurgy and the like. In recent years, with the rapid development of green production processes of domestic caprolactam, propylene oxide, epichlorohydrin and the like, the hydrogen peroxide industry shows a wider development space. The hydrogen peroxide is produced through electrolysis, anthraquinone process, isopropanol oxidation, direct oxyhydrogen synthesis, oxygen cathode reduction, etc. The anthraquinone process has the advantages of large scale, low energy consumption, low cost, easy operation and the like, and is therefore the mainstream process for producing hydrogen peroxide. The anthraquinone method for producing hydrogen peroxide mainly comprises four steps of hydrogenation, oxidation, extraction and post-treatment, wherein the hydrogenation process is one of the core steps of the whole process, and the selection of a proper anthraquinone hydrogenation catalyst is important for improving the hydrogen peroxide yield.
Pd catalyst is used as one of the alkyl anthraquinone hydrogenation catalyst systems, has the characteristics of high activity, operation resistance, long service life and easy recovery, and is widely focused on, thus becoming the mainstream alkyl anthraquinone hydrogenation catalyst in the current market. The research finds that: the preparation method of the catalyst seriously affects the action mode between the supported metal and the carrier, thereby affecting the dispersity of the active metal, changing the crystalline state, or preparing the catalyst with specific exposed crystal face metal, and finally affecting the catalytic performance of the catalyst. As in CN104549246B, the composite oxide is used as carrier, and the Pd catalyst is pretreated with hydrogen or CO to obtain high-dispersion Pd nano-particle catalystA large amount of auxiliary agents are introduced in the preparation process of the catalyst, the process is complex, the activity is low, and certain limitation is imposed. Patent CN110639512a also reports a Pd catalyst, which is obtained by reducing a catalyst obtained by an impregnation method with a liquid phase reducing agent such as formaldehyde or hydrazine hydrate, and then performing a calcination reduction treatment. Li et Al in the literature [ Li X, su H, ren G, et Al Journal of the Brazilian Chemical Society, 2016, 27 (6): 1060 ] using the ethylene glycol reduction method to prepare Pd/Al 2 O 3 When the catalyst is used for anthraquinone hydrogenation, authors prepare a series of Pd catalysts with different particle sizes by controlling different reflux time and calcination temperature, and find that the catalyst performance is optimal when the Pd particle size is 4 nm, and the space-time yield of hydrogen peroxide can reach 58 g H2O2 ·g Pd -1 About, however, the reduction conditions and the reflux temperature of the method are difficult to control accurately, so that the method is difficult to realize mass production. Patent CN105268433A also adopts an alcohol reducer and a macromolecule protecting agent, and adopts microwave heating to successfully prepare a series of highly dispersed platinum group catalysts, but the catalyst H prepared by the method 2 O 2 The productivity is lower, the complex process also increases the investment of production cost, and the method is also greatly limited.
Disclosure of Invention
In order to solve the problems of complex preparation process, large amount of use of toxic and harmful solvents, difficult precise regulation and control of preparation conditions and poor activity in the existing catalyst system, the invention provides a preparation method and application of a supported palladium nanoparticle catalyst, and the supported palladium nanoparticle catalyst prepared by the method can be used for hydrogenation reaction of alkylanthraquinone and has obviously higher Pd/Al than that prepared by the traditional impregnation method 2 O 3 The catalyst has relatively high activity and stability.
The first aspect of the invention provides a method for preparing a supported palladium nanoparticle catalyst, comprising the following steps:
(1) Adding a pH regulator into a solution containing a carrier and a palladium precursor, dipping, filtering, washing, drying and reducing to obtain a catalyst precursor;
(2) Performing activation pretreatment on a catalyst precursor in a reaction atmosphere to obtain a supported palladium nanoparticle catalyst;
the reaction atmosphere comprises:
a) Water vapor;
b) Optionally other gases selected from one or more of hydrogen, carbon monoxide, ammonia, halogenated hydrocarbons, HCl and air.
Preferably, in the step (1), the reducing agent used for reduction is hydrazine hydrate; the reduction temperature was room temperature. The traditional high-temperature reduction of the reducing gas can lead the metal Pd to be quickly agglomerated, and the invention adopts the hydrazine hydrate at room temperature for reduction to improve the dispersivity of Pd.
Preferably, in the step (1), the pH adjuster is at least one selected from the group consisting of hydrochloric acid, sulfuric acid, nitric acid, acetic acid, oxalic acid, sodium bicarbonate, potassium bicarbonate, ammonia water, urea, potassium hydroxide, sodium hydroxide, potassium carbonate and sodium carbonate. Preferably, a pH regulator is added in the step (1) to regulate the pH value to 2-7. The invention greatly improves the interaction between the carrier and Pd by adding the pH regulator, and remarkably reduces the difficult problem of serious Pd loss in the reaction process.
Preferably, in the step (1), the carrier is an oxide, preferably at least one of silicon oxide, magnesium oxide, aluminum oxide, titanium oxide, lanthanum oxide, cerium oxide, calcium oxide, and the like, and more preferably aluminum oxide.
Preferably, in step (1), the palladium precursor is a palladium salt. The palladium salt is at least one selected from palladium chloride, palladium acetate, palladium nitrate and sodium chloropalladate.
Preferably, in the step (1), the soaking temperature is 25-30 ℃ and the soaking time is 0.5-2.5 h; the drying temperature is 80-120 ℃, and the drying time is 1-4 hours.
Preferably, in step (2), the activating pretreatment operation includes: the catalyst precursor is placed in a tube furnace, activated gas is introduced before the reaction, and the temperature is raised to a certain temperature raising rateAnd reacting for a certain time at a certain temperature to obtain the supported palladium nanoparticle catalyst. Preferably, the pretreatment reaction temperature is 200-500 ℃; the reaction time is 1-48 h; the temperature rising rate is 1-10 ℃ min -1 . The volume content of the water vapor in the reaction atmosphere is 5-100%, and further, the volume content of the water vapor can be 15-90% and 20-50%. The halogenated hydrocarbon is selected from one or more of methyl iodide, ethyl chloride, methyl bromide, ethyl iodide, methyl chloride, ethyl bromide and the like. According to the invention, the catalyst precursor is treated by adopting the reaction atmosphere containing water vapor, metal Pd in the catalyst precursor reacts with weak oxidant water to generate palladium oxide and hydrogen, and in addition, the carrier oxide is subjected to hydroxylation modification by the water vapor atmosphere, so that the dispersion of palladium on the carrier can be promoted, and the dispersibility of palladium nano particles on the carrier can be improved. Carrying out high-temperature induction reconstruction on the surface of the carrier on the other gas side in the reaction atmosphere to cause more defects on the surface, thereby providing more muelled sites for Pd dispersion; another aspect is to promote the adequate reaction of metallic palladium with water vapor while reducing H 2 The partial pressure of O promotes the dispersion of palladium, while pure water vapor is good, too high a concentration of water vapor can destroy the strength of the support, causing the catalyst to powder.
Preferably, in the supported palladium nanoparticle catalyst, the load of the palladium nanoparticle is 0.01-2% of the mass of the carrier, preferably 0.05-2%, and more preferably 0.2-2%; the mass of the palladium nanoparticle is calculated as the mass of active metallic palladium. The size of the palladium nano particles is 0.01-7.0 nm.
The second aspect of the invention provides an application of the supported palladium nanoparticle catalyst prepared by the method, wherein the supported palladium nanoparticle catalyst is used for hydrogenation catalytic reaction of alkylanthraquinone. Preferably, the conditions of the hydrogenation catalytic reaction of the alkylanthraquinone are as follows: the flow rate of hydrogen is 10-5000 mL/min -1 The method comprises the steps of carrying out a first treatment on the surface of the The reaction temperature is 25-80 ℃; the reaction pressure is 0.1-2.0 MPa.
The supported palladium nanoparticle catalyst prepared by the method has the advantages of high activity, good stability and low cost, and compared with the prior art, the supported palladium nanoparticle catalyst provided by the invention has the beneficial effects that:
1. the invention combines the impregnation method and the atmosphere induction dispersion method to prepare a series of oxide supported palladium nanoparticle catalysts, and the catalysts show higher catalytic activity and stability under the hydrogenation reaction condition of alkylanthraquinone, and the dispersibility and the electronic property of Pd are greatly improved by adjusting the type and the concentration of the pH regulator, the pretreatment time and the atmosphere. Compared with the Pd-based catalyst prepared by the traditional impregnation method, the catalyst has the characteristics of higher activity, higher Pd metal utilization rate, simple and green preparation process and low cost, and provides a new idea for developing a high-efficiency palladium-based alkylanthraquinone hydrogenation catalyst system;
2. the preparation method of the supported palladium-based catalyst provided by the invention has the advantages that the required raw materials such as oxides, palladium salts, pH regulators and the like are bulk chemicals, and the cost is low;
3. the preparation method of the supported palladium-based catalyst provided by the invention has the advantages of simple and green preparation process and the like, and is easy to realize large-scale preparation.
Drawings
FIG. 1 is 0.2. 0.2 wt.% Pd/Al in example 1 2 O 3 A high-resolution transmission electron microscope image (a) and a particle size distribution statistical result (b) of the catalyst after the reaction;
FIG. 2 is a graph of 0.2. 0.2 wt% Pd/Al in comparative example 1 2 O 3 A high-resolution transmission electron microscope image (a) and a particle size distribution statistical result (b) of the catalyst after the reaction;
FIG. 3 is 0.2. 0.2 wt.% Pd/Al in comparative example 8 2 O 3 High-resolution transmission electron microscope pictures of the catalyst after the reaction;
FIG. 4 is the results of the catalyst anthraquinone hydrogenation cycle performance test in example 1 and comparative example 1;
fig. 5 is a nitrogen adsorption/desorption isothermal curve of example 1, comparative example 1, and comparative example 8.
Detailed Description
The present invention is described in detail below with reference to examples, but is not limited to the examples. Unless otherwise indicated, all numbers expressing quantities of values such as loading, temperature, time, conversion, and the like used in the specification and claims are to be understood as being absolute precise values, and the measured values are inevitably subject to some experimental error due to standard deviations of the measurement techniques.
The presence form and the size of palladium in the catalyst sample were observed by a transmission electron microscope (model: JEOL 2100X, available from JEOL, japan).
The palladium loading is tested by adopting an inductively coupled plasma atomic emission spectrometry technology, and the actual loading of the catalyst after reaction is obtained.
The prepared catalyst is subjected to reaction performance evaluation by utilizing an alkylanthraquinone hydrogenation device, wherein the device is a 1000 mL glass fiber reinforced plastic reaction tube, and N is introduced before the reaction 2 Performing multiple replacement, and introducing H after the replacement is clean 2 . The working solution consists of heavy aromatic hydrocarbon, tetrabutyl urea and 2-ethyl anthraquinone, wherein the volume ratio of Ar to TBU is 3:1, and the dissolution amount of alkyl anthraquinone is 120 g.L -1 The method comprises the steps of carrying out a first treatment on the surface of the Adding a 5 g catalyst into a reaction kettle, reacting for 30 min, stopping ventilation, extracting the obtained hydrogen peroxide, and titrating with a standard potassium permanganate solution to calculate the hydrogenation efficiency.
Here, the dispersity of Pd is tested by adopting a CO chemical adsorption mode, pre-reduction is carried out before the test, and the final dispersity of Pd is obtained according to the number ratio of Pd atoms to CO molecules being 1:1 (namely, one Pd atom adsorbs one CO molecule).
Example 1
Dissolving 0.1 g palladium chloride in 40 mL water, adding 20 g aluminum oxide into a solution containing palladium under stirring, adding 0.02 g potassium carbonate into the suspension after stirring uniformly, adding partial hydrochloric acid to adjust pH to 4-5, immersing and adsorbing for 1h, filtering, washing the product with deionized water until the solution is neutral, drying in a 50 ℃ oven for 2h, adding 0.1 mL hydrazine hydrate to reduce to 1h at room temperature, and then pretreating 2h in an air and steam atmosphere (volume ratio of 1:1) at 350 ℃ to obtain the aluminum oxide supported palladium nanoparticle catalyst (0.2 wt Pd/Al) with palladium loading of 0.2 wt% 2 O 3 ）。
The reaction performance of the catalyst obtained was evaluated in an alkylanthraquinone hydrogenation apparatus, and the catalyst was obtained byThe hydrogenation efficiency was 13. g.L as measured under the reaction condition that the reaction pressure of hydrogen is 0.1 MPa and the temperature is 50 DEG C -1 。
The high resolution transmission electron microscope characterization result of FIG. 1 shows that the Pd/Al content is 0.2 wt% 2 O 3 Pd in the catalyst showed a highly dispersed state with an average size of 3.3. 3.3 nm.
Example 2
Dissolving 0.1 g palladium chloride in 40 mL water, adding 20 g aluminum oxide into a solution containing palladium under stirring, adding 1.0 g potassium hydroxide into the suspension after stirring uniformly, adding part of nitric acid to adjust pH to 5-6, immersing and adsorbing for 1h, filtering after the reaction is finished, washing the product with deionized water until the solution is neutral, and drying in a 50 ℃ oven for 2h. Adding 0.1 mL hydrazine hydrate, reducing at room temperature to 1h, and pretreating at 350deg.C in water vapor atmosphere for 2h to obtain alumina-supported palladium nanoparticle catalyst (0.2 wt Pd/Al) with palladium load of 0.2 wt% 2 O 3 ）。
The catalyst obtained was evaluated for reactivity in an alkylanthraquinone hydrogenation apparatus, and the hydrogenation efficiency was 13.51 g.L under the reaction conditions of a hydrogen reaction pressure of 0.1 MPa and a temperature of 50 ℃ -1 。
Example 3
Dissolving 0.1 g palladium chloride in 40 mL water, adding 20 g aluminum oxide into a solution containing palladium under stirring, adding 0.02 g ammonia water into the suspension after stirring uniformly, adding part of sulfuric acid to adjust pH to 6-7, immersing and adsorbing for 1h, filtering after the reaction is finished, washing the product with deionized water until the solution is neutral, and drying in a 50 ℃ oven for 2h. Adding 0.1 mL hydrazine hydrate, reducing at room temperature for 1h, and then pretreating 1h in a mixed gas of air, water vapor and methyl iodide (volume ratio is 10:1:1) at 200 ℃ to obtain the alumina-supported palladium nanoparticle catalyst (0.2 wt Pd/Al) with palladium loading of 0.2 wt percent 2 O 3 ）。
The catalyst obtained was evaluated for reactivity in an alkylanthraquinone hydrogenation apparatus, and the hydrogenation efficiency was 13.4 g.L under the reaction conditions of a hydrogen reaction pressure of 0.1 MPa and a temperature of 50 ℃ -1 。
Example 4
Dissolving 0.15 g sodium chloropalladate in 40 mL water, adding 20 g aluminum oxide into a solution containing palladium under stirring, adding 0.02 g sodium carbonate into the suspension after stirring uniformly, adding part of acetic acid to adjust the pH to 3-4, immersing and adsorbing for 1h, filtering after the reaction is finished, washing the product with deionized water until the solution is neutral, and drying in a 50 ℃ oven for 2h. Adding 0.1 mL hydrazine hydrate, reducing at room temperature for 1h, and then treating 0.5 h in an atmosphere of air, water vapor, HCl and methyl iodide (volume ratio of 10:1:1:1) at 400 ℃ to obtain the alumina-supported palladium nanoparticle catalyst (0.2 wt) with palladium loading of 0.2 wt percent 2 O 3 ）。
The catalyst obtained was evaluated for reactivity in an alkylanthraquinone hydrogenation apparatus, and the hydrogenation efficiency was 13.61 g.L under the reaction conditions of a hydrogen reaction pressure of 0.1 MPa and a temperature of 50 ℃ -1 。
Example 5
Dissolving 0.16 g palladium acetate in 40 mL water, adding 20 g aluminum oxide into a solution containing palladium under stirring, adding 0.1 g potassium hydroxide into the suspension after stirring uniformly, adding part of oxalic acid to adjust pH to 2-3, soaking and adsorbing for 1h, filtering after the reaction is finished, washing the product with deionized water until the solution is neutral, and drying in a 50 ℃ oven for 2h. Adding 0.1 mL hydrazine hydrate, reducing at room temperature for 1h, and then treating 2h under the condition of 300 ℃ in an atmosphere of ammonia gas, water vapor and carbon monoxide (volume ratio is 5:1:1) to obtain the alumina-supported palladium nanoparticle catalyst with palladium loading of 0.2 wt percent (0.2 wt percent Pd/Al) 2 O 3 ）。
The catalyst obtained was evaluated for reactivity in an alkylanthraquinone hydrogenation apparatus, and the hydrogenation efficiency was 13.67 g.L under the reaction conditions of a hydrogen reaction pressure of 0.1 MPa and a temperature of 50 ℃ -1 。
Example 6
Dissolving 0.15. 0.15 g sodium chloropalladate in 40. 40 mL water, adding 20. 20 g silicon oxide into palladium-containing solution under stirring, adding 0.02. 0.02 g into the above suspensionAnd adding part of acetic acid to regulate the pH to 3-4, immersing and adsorbing for 1h, filtering after the reaction is finished, washing the product with deionized water until the solution is neutral, and drying in a 50 ℃ oven for 2h. Adding 0.1 mL hydrazine hydrate, reducing at room temperature for 1h, and then treating 1.5 h in the atmosphere of water vapor and carbon monoxide (volume ratio of 1:4) at 250 ℃ to obtain the silica-supported palladium nanoparticle catalyst with palladium loading of 0.2 wt percent (0.2 wt percent Pd/SiO) 2 ）。
The catalyst obtained was evaluated for reactivity in an alkylanthraquinone hydrogenation apparatus, and the hydrogenation efficiency was 7.68 g.L under the reaction conditions of a hydrogen reaction pressure of 0.1 MPa and a temperature of 50 ℃ -1 。
Example 7
Dissolving 0.15 g sodium chloropalladate in 40 mL water, adding 20 g magnesium oxide into a solution containing palladium under stirring, adding 0.02 g sodium bicarbonate into the suspension after stirring uniformly, adding part of acetic acid to adjust the pH to 3-4, immersing and adsorbing for 1h, filtering after the reaction is finished, washing the product with deionized water until the solution is neutral, and drying in a 50 ℃ oven for 2h. Adding 0.1 mL hydrazine hydrate, reducing at room temperature for 1h, and then pretreating for 2h under the condition of 500 ℃ in the atmosphere of water vapor, air and HCl (volume ratio of 1:6:1) to obtain the magnesium oxide supported palladium nanoparticle catalyst (0.2 wt) with palladium loading of 0.2 wt percent.
The catalyst obtained was evaluated for reactivity in an alkylanthraquinone hydrogenation apparatus, and the hydrogenation efficiency was 9.32 g.L under the reaction conditions of a hydrogen reaction pressure of 0.1 MPa and a temperature of 80 ℃ -1 。
Example 8
Dissolving 0.15 g sodium chloropalladate in 40 mL water, adding 20 g titanium oxide into a solution containing palladium under stirring, adding 0.02 g oxalic acid into the suspension after stirring uniformly, adjusting the pH to 3-4, immersing and adsorbing for 1h, filtering after the reaction is finished, washing the product with deionized water until the solution is neutral, and drying in a 50 ℃ oven for 2h. Adding 0.1 mL hydrazine hydrate, reducing at room temperature for 1h, and treating at 450deg.C in the atmosphere of water vapor, ammonia gas and methyl iodide (volume ratio of 10:1:1) for 2h to obtain the final productTitanium oxide supported palladium nanoparticle catalyst to palladium loading of 0.2. 0.2 wt% (0.2 wt% Pd/TiO) 2 ）。
The catalyst obtained was evaluated for reactivity in an alkylanthraquinone hydrogenation apparatus, and hydrogenation efficiency was 10.01 g.L under a reaction condition of a hydrogen reaction pressure of 0.1 MPa and a temperature of 50 ℃ -1 。
Example 9
Dissolving 0.15 g sodium chloropalladate in 40 mL water, adding 20 g lanthanum oxide into a solution containing palladium under stirring, adding 0.02 g potassium carbonate into the suspension after stirring uniformly, adding part of acetic acid to adjust the pH to 3-4, immersing and adsorbing for 1h, filtering after the reaction is finished, washing the product with deionized water until the solution is neutral, and drying in a 50 ℃ oven for 2h. Adding 0.1 mL hydrazine hydrate, reducing at room temperature for 1h, and then treating 2h in an atmosphere of ammonia gas, carbon monoxide and water vapor (volume ratio is 6:1:1) at 500 ℃ to obtain the lanthanum oxide supported palladium nanoparticle catalyst with palladium loading of 0.2 wt percent (0.2 wt percent Pd/La) 2 O 3 ）。
The catalyst obtained was evaluated for reactivity in an alkylanthraquinone hydrogenation apparatus, and the hydrogenation efficiency was 7.09 g.L under the reaction conditions of a hydrogen reaction pressure of 0.1 MPa and a temperature of 50 ℃ -1 。
Example 10
Dissolving 0.15 g sodium chloropalladate in 40 mL water, adding 20 g cerium oxide into a solution containing palladium under stirring, adding 0.02 g potassium carbonate into the suspension after stirring uniformly, adding part of acetic acid to adjust the pH to 3-4, immersing and adsorbing for 1h, filtering after the reaction is finished, washing the product with deionized water until the solution is neutral, and drying in a 120 ℃ oven for 2h. Adding 0.1 mL hydrazine hydrate, reducing at room temperature for 1h, and then treating 2h in hydrogen and water vapor (volume ratio is 1:1) at 300 ℃ to obtain the cerium oxide-supported palladium nanoparticle catalyst (0. 0.2 wt) with palladium loading of 0.2 wt percent and Pd/CeO 2 ）。
The prepared catalyst was evaluated for reactivity in an alkylanthraquinone hydrogenation apparatus, and reacted at a hydrogen reaction pressure of 0.1 MPa and a temperature of 50 ℃The hydrogenation efficiency was found to be 7.23 g.L -1 。
Example 11
Dissolving 0.003. 0.003 g palladium chloride in 40 mL water, adding 20. 20 g aluminum oxide into a solution containing palladium under stirring, adding 0.02. 0.02 g potassium carbonate into the suspension after stirring uniformly, adding part of acetic acid to adjust the pH to 3-4, immersing and adsorbing for 1h, filtering after the reaction is finished, washing the product with deionized water until the solution is neutral, and drying in a 50 ℃ oven for 2h. Adding 0.1 mL hydrazine hydrate, reducing at room temperature for 1h, and then treating 2h in an atmosphere of hydrogen, HCl and water vapor (volume ratio is 1:3:1) at 450 ℃ to obtain the alumina-supported palladium nanoparticle catalyst with palladium loading of 0.01 wt percent (0.01 wt percent Pd/Al) 2 O 3 ）。
The catalyst obtained was evaluated for reactivity in an alkylanthraquinone hydrogenation apparatus, and hydrogenation efficiency was 1.24 g.L under a reaction condition of a hydrogen reaction pressure of 2.0 MPa and a temperature of 25 ℃ -1 。
Example 12
Dissolving 0.015 and g palladium chloride in 40 and mL water, adding 20 and g aluminum oxide into a solution containing palladium under stirring, adding 0.02 and g potassium carbonate into the suspension after stirring uniformly, adding part of acetic acid to adjust the pH to 3-4, immersing and adsorbing for 1h, filtering after the reaction is finished, washing the product with deionized water until the solution is neutral, and drying in a 50 ℃ oven for 2h. Adding 0.1 mL hydrazine hydrate, reducing at room temperature for 1h, and then treating 2h in ammonia gas and water vapor (volume ratio of 1:1) at 200 ℃ to obtain the alumina-supported palladium nanoparticle catalyst with palladium loading of 0.05 wt percent (0.05 wt percent Pd/Al) 2 O 3 ）。
The catalyst obtained was evaluated for reactivity in an alkylanthraquinone hydrogenation apparatus, and hydrogenation efficiency was 10.56 g.L under the reaction conditions of a hydrogen reaction pressure of 1.0 MPa and a temperature of 50 ℃ -1 。
Example 13
Dissolving 0.67. 0.67 g palladium chloride in 40. 40 mL water, adding 20. 20 g aluminum oxide into palladium-containing solution under stirring, stirring uniformly, and adding into the above suspensionAdding 0.01-g potassium carbonate, adding partial acetic acid to adjust the pH to 3-4, soaking and adsorbing for 1h, filtering after the reaction is finished, washing the product with deionized water until the solution is neutral, and then drying in a 50 ℃ oven for 2h. Adding 0.1 mL hydrazine hydrate, reducing at room temperature for 1h, and then treating 2h in air and steam (volume ratio of 1:6) at 350 ℃ to obtain the alumina-supported palladium nanoparticle catalyst (2 wt) with palladium loading of 2 wt percent 2 O 3 ）。
The catalyst obtained was evaluated for reactivity in an alkylanthraquinone hydrogenation apparatus, and hydrogenation efficiency was 15.25 g.L under a reaction condition of a hydrogen reaction pressure of 0.1 MPa and a temperature of 50 ℃ -1 。
Example 14
Dissolving 0.1. 0.1 g palladium chloride in 40 mL water, adding 20 g calcium oxide, aluminum oxide and lanthanum oxide (the mass ratio of substances is 1:1:1) into a solution containing palladium under stirring, adding 0.01 g potassium carbonate into the suspension after stirring uniformly, adding part of acetic acid to adjust the pH to 3-4, immersing and adsorbing for 1h, filtering after the reaction is finished, washing the product with deionized water until the solution is neutral, and drying in a 50 ℃ oven for 2h. Adding 0.1 mL hydrazine hydrate, reducing at room temperature for 1h, and then treating 2h in air and steam (volume ratio of 1:10) at 350 ℃ to obtain the composite carrier supported palladium nanoparticle catalyst (0. 0.2 wt Pd/CaO-Al) with palladium loading of 0.2 wt percent 2 O 3 -La 2 O 3 ）。
The catalyst obtained was evaluated for reactivity in an alkylanthraquinone hydrogenation apparatus, and the hydrogenation efficiency was 4.76 g.L under the reaction conditions of a hydrogen reaction pressure of 0.1 MPa and a temperature of 50 ℃ -1 。
Example 15
Dissolving 0.1. 0.1 g palladium chloride in 40 mL water, adding a mixed carrier of 20 g aluminum oxide and calcium oxide (the mass ratio of the aluminum oxide to the calcium oxide is 1:1) into a solution containing palladium under stirring, adding 0.02 g potassium carbonate into the suspension after stirring uniformly, adding part of acetic acid to adjust the pH to 3-4, immersing and adsorbing for 1h, filtering after the reaction is finished, and washing the product with deionized water until the solution is neutralSex, then dried in an oven at 50 ℃ for 2h. Adding 0.1 mL hydrazine hydrate, reducing at room temperature for 1h, and then treating 2h in the atmosphere of air and water vapor (volume ratio of 1:10) at 250 ℃ to obtain the alumina-calcium oxide supported palladium nanoparticle catalyst (0.2 wt% Pd/Al) with palladium loading of 0.2 wt% 2 O 3 -CaO）。
The catalyst obtained was evaluated for reactivity in an alkylanthraquinone hydrogenation apparatus, and hydrogenation efficiency was 10.1 g.L under a reaction condition of a hydrogen reaction pressure of 0.1 MPa and a temperature of 50 ℃ -1 。
Comparative example 1
Dissolving 0.1 g palladium chloride in 40 mL water, adding 20 g aluminum oxide into a solution containing palladium under stirring, adding 0.02 g potassium carbonate into the suspension after stirring uniformly, adding part of hydrochloric acid to adjust pH to 4-5, immersing and adsorbing for 1h, filtering after the reaction is finished, washing the product with deionized water until the solution is neutral, and drying in a 50 ℃ oven for 2h. Adding 0.1 mL hydrazine hydrate, reducing at room temperature to 1h, and pretreating at 350deg.C in air atmosphere for 2h to obtain aluminum oxide supported palladium nanoparticle catalyst (0.2 wt Pd/Al) with palladium load of 0.2 wt% 2 O 3 ）。
The catalyst obtained was evaluated for reactivity in an alkylanthraquinone hydrogenation apparatus, and hydrogenation efficiency was 5.67 g.L under the reaction conditions of a hydrogen reaction pressure of 0.1 MPa and a temperature of 50 ℃ -1 。
The high resolution transmission electron microscope characterization result of FIG. 2 shows that the Pd/Al content is 0.2 wt% 2 O 3 Pd in the catalyst was poorly dispersed and had an average size of 4.7. 4.7 nm.
Comparative example 2
Dissolving 0.15 g sodium chloropalladate in 40 mL water, adding 20 g magnesium oxide into a solution containing palladium under stirring, adding 0.02 g sodium bicarbonate into the suspension after stirring uniformly, adding part of acetic acid to adjust the pH to 3-4, immersing and adsorbing for 1h, filtering after the reaction is finished, washing the product with deionized water until the solution is neutral, and drying in a 50 ℃ oven for 2h. Adding 0.1 mL hydrazine hydrate, reducing at room temperature for 1h, and then pretreating at 500 ℃ in an atmosphere of air and HCl (volume ratio of 6:1) for 2h to obtain the magnesium oxide supported palladium nanoparticle catalyst (0.2 wt Pd/MgO) with palladium loading of 0.2 wt percent.
The catalyst obtained was evaluated for reactivity in an alkylanthraquinone hydrogenation apparatus, and hydrogenation efficiency was 3. g.L under a reaction condition of a hydrogen reaction pressure of 0.1 MPa and a temperature of 50 ℃ -1 。
Comparative example 3
Dissolving 0.15 g sodium chloropalladate in 40 mL water, adding 20 g silicon oxide into a solution containing palladium under stirring, adding 0.02 g potassium bicarbonate into the suspension after stirring uniformly, adding part of acetic acid to adjust the pH to 3-4, immersing and adsorbing for 1h, filtering after the reaction is finished, washing the product with deionized water until the solution is neutral, and drying in a 50 ℃ oven for 2h. Adding 0.1 mL hydrazine hydrate, reducing at room temperature to 1h, and treating at 250deg.C in carbon monoxide atmosphere to 1.5 h to obtain silica-supported palladium nanoparticle catalyst (0.2 wt Pd/SiO) with palladium loading of 0.2 wt% 2 ）。
The catalyst obtained was evaluated for reactivity in an alkylanthraquinone hydrogenation apparatus, and hydrogenation efficiency was measured at a reaction condition of a hydrogen reaction pressure of 0.1 MPa and a temperature of 50℃and was 6.1 g.L -1 。
Comparative example 4
Dissolving 0.15 g sodium chloropalladate in 40 mL water, adding 20 g lanthanum oxide into a solution containing palladium under stirring, adding 0.02 g potassium carbonate into the suspension after stirring uniformly, adding part of acetic acid to adjust the pH to 3-4, immersing and adsorbing for 1h, filtering after the reaction is finished, washing the product with deionized water until the solution is neutral, and drying in a 50 ℃ oven for 2h. Adding 0.1 mL hydrazine hydrate, reducing at room temperature for 1h, and then treating 2h in ammonia gas and carbon monoxide (volume ratio of 6:1) at 500 ℃ to obtain the lanthanum oxide supported palladium nanoparticle catalyst (0.2 wt Pd/La) with palladium loading of 0.2 wt percent 2 O 3 ）。
The prepared catalyst was evaluated for reactivity in an alkylanthraquinone hydrogenation apparatus under a reaction condition of a hydrogen reaction pressure of 0.1 MPa and a temperature of 50 ℃The hydrogenation efficiency was found to be 4.34 g.L -1 。
Comparative example 5
Dissolving 0.15 g sodium chloropalladate in 40 mL water, adding 20 g titanium oxide into a solution containing palladium under stirring, adding 0.02 g oxalic acid into the suspension after stirring uniformly, adjusting the pH to 3-4, immersing and adsorbing for 1h, filtering after the reaction is finished, washing the product with deionized water until the solution is neutral, and drying in a 50 ℃ oven for 2h. Adding 0.1 mL hydrazine hydrate, reducing at room temperature for 1h, and then treating 2h in ammonia gas and methyl iodide (volume ratio of 1:1) at 450 ℃ to obtain the titanium oxide supported palladium nanoparticle catalyst (0.2 wt Pd/TiO) with palladium loading of 0.2 wt percent 2 ）。
The catalyst obtained was evaluated for reactivity in an alkylanthraquinone hydrogenation apparatus, and hydrogenation efficiency was 3.21 g.L under a reaction condition of a hydrogen reaction pressure of 0.1 MPa and a temperature of 50 ℃ -1 。
Comparative example 6
Dissolving 0.1. 0.1 g palladium chloride in 40 mL water, adding 20 g calcium oxide, aluminum oxide and lanthanum oxide (the mass ratio of substances is 1:1:1) into a solution containing palladium under stirring, adding 0.01 g potassium carbonate into the suspension after stirring uniformly, adding part of acetic acid to adjust the pH to 3-4, immersing and adsorbing for 1h, filtering after the reaction is finished, washing the product with deionized water until the solution is neutral, and drying in a 50 ℃ oven for 2h. Adding 0.1 mL hydrazine hydrate, reducing at room temperature to 1h, and then treating at 350deg.C in air atmosphere for 2h to obtain composite carrier supported palladium nanoparticle catalyst (0.2 wt Pd/CaO-Al) with palladium load of 0.2 wt% 2 O 3 -La 2 O 3 ）。
The catalyst obtained was evaluated for reactivity in an alkylanthraquinone hydrogenation apparatus, and hydrogenation efficiency was 1.2 g.L under a reaction condition of a hydrogen reaction pressure of 0.1 MPa and a temperature of 50 ℃ -1 。
Comparative example 7
Dissolving 0.15. 0.15 g sodium chloropalladate in 40. 40 mL water, adding 20. 20 g cerium oxide into palladium-containing solution under stirring, adding into the above suspension0.02 And g, potassium carbonate, adding partial acetic acid to regulate the pH value to 3-4, immersing and adsorbing for 1h, filtering after the reaction is finished, washing the product with deionized water until the solution is neutral, and then drying in a baking oven at 120 ℃ for 2h. Adding 0.1 mL hydrazine hydrate, reducing at room temperature to 1h, and then treating 2h in hydrogen atmosphere at 300 ℃ to obtain the cerium oxide supported palladium nanoparticle catalyst (0.2 wt Pd/CeO) with palladium loading of 0.2 wt% 2 ）。
The catalyst obtained was evaluated for reactivity in an alkylanthraquinone hydrogenation apparatus, and hydrogenation efficiency was 2.12 g.L under a reaction condition of a hydrogen reaction pressure of 0.1 MPa and a temperature of 50 ℃ -1 。
Comparative example 8
Dissolving 0.1 g palladium chloride in 40 mL water, adding 20 g aluminum oxide into a solution containing palladium under stirring, adding 0.02 g potassium carbonate into the suspension after stirring uniformly, adding part of hydrochloric acid to adjust pH to 4-5, soaking and adsorbing for 1h, filtering, washing the product with deionized water until the solution is neutral, drying in a 50 ℃ oven for 2h, adding 0.1 mL hydrazine hydrate, reducing to 1h at room temperature, and then adding CO 2 Pretreatment of 2h at 350deg.C in a steam atmosphere (volume ratio of 3:2) gave an alumina-supported palladium nanoparticle catalyst (0.2. 0.2 wt) with a palladium loading of 0.2 wt%Pd/Al 2 O 3 ）。
The catalyst obtained was evaluated for reactivity in an alkylanthraquinone hydrogenation apparatus, and hydrogenation efficiency was 1.21 g.L under a reaction condition of a hydrogen reaction pressure of 0.1 MPa and a temperature of 50 ℃ -1 。
As shown by the characterization result of the high-resolution transmission electron microscope in FIG. 3, the Pd/Al content of the alloy is 0.2 wt% 2 O 3 Pd in the catalyst is in an agglomerated state, and part of the Pd in the catalyst is already 20 nm in size.
Table 1 shows the hydrogenation reactivity of alkylanthraquinone of the catalysts of examples 1-15 and comparative examples 1-8, and it can be seen that Pd/Al was prepared by the impregnation method and the atmosphere induction method containing water vapor 2 O 3 The catalyst activity and Pd dispersity are greatly improved, and Pd is not lost.
Table 1 comparison of the hydrogenation activities of alkylanthraquinone with different catalysts
Example 16
Anthraquinone hydrogenation reaction cycle test: the palladium nanoparticle catalysts of example 1 and comparative example 1 were tested for stability in an alkylanthraquinone hydrogenation apparatus (reaction conditions: 50 ℃ C., 0.1 MPa,5 g catalyst for reaction temperature), and the catalysts were tested in a working fluid for multiple times, with the working fluid replaced every 30 minutes, and the activity change was tested in cycles. The results are shown in FIG. 4: 0.2. 0.2 wt% Pd/Al in example 1 2 O 3 The catalyst has higher stability than Pd/Al prepared in comparative example 1 2 O 3 The catalyst activity is also greatly improved.
Example 17
Adsorption isothermal curve test: the catalysts prepared in example 1, comparative example 1 and comparative example 8 were dehydrated and degassed at 300℃under vacuum before testing, and then N was added 2 As a result of the adsorption and desorption at room temperature of (a) to obtain an isothermal adsorption-desorption curve (FIG. 5), the specific surface area of the catalyst material was calculated according to the BET theory, and it was found that the adsorption amount was significantly decreased in the curve of comparative example 8 as compared with that of example 1 and comparative example 1, and the specific surface area of the alumina carrier was also from 168 m 2 Reduced/g (example 1) to 57 m 2 Per g (comparative example 8), indicating the presence of a large number of pores blocked by the material, can be presumed to be CO 2 The resulting carbon deposition causes a significant decrease in specific surface area. Meanwhile, in combination with the high-resolution transmission electron microscope characterization of comparative example 8, it can be found that the metal palladium rapidly and greatly aggregates along with the reduction of the specific surface area, and the maximum size of the metal palladium can reach about 50 and nm, so that the performance of the metal palladium in anthraquinone hydrogenation reaction is severely limited.
As previously mentioned, the present invention relates to a process for preparing an alkylanthraquinone hydrogenation catalyst. The catalyst takes oxide as a carrier, and adopts an impregnation method and an atmosphere induction dispersion method containing water vapor to prepare the alkylanthraquinone hydrogenation supported palladium nanoparticle catalyst. Compared with the existing palladium-based catalyst system, the supported palladium-based catalyst prepared by the method has higher catalytic activity and selectivity. Has good application prospect.
While the invention has been described in terms of preferred embodiments, it is to be understood that the invention is not limited to the disclosed embodiments. Any person skilled in the art, using the disclosure of the present invention, may make some variations or modifications equivalent to the equivalent embodiments without departing from the scope of the present invention, and all such variations or modifications are within the scope of the present invention.

Claims (9)

1. The preparation method of the supported palladium nanoparticle catalyst comprises the following steps:
(1) Adding a pH regulator into a solution containing a carrier and a palladium precursor, dipping, filtering, washing, drying and reducing to obtain a catalyst precursor;
(2) Performing activation pretreatment on a catalyst precursor in a reaction atmosphere to obtain a supported palladium nanoparticle catalyst;
the reaction atmosphere comprises:
a) Water vapor;
b) Optionally other gases selected from one or more of hydrogen, carbon monoxide, ammonia, halogenated hydrocarbons, HCl and air;
in the step (1), the carrier is at least one of silicon oxide, magnesium oxide, aluminum oxide, titanium oxide, lanthanum oxide, cerium oxide and calcium oxide;
the pretreatment reaction temperature in the step (2) is 200-500 ℃; the reaction time is 1-48 h; the temperature rising rate is 1-10 ℃ min -1 。
2. The method according to claim 1, wherein in the step (1), the pH adjuster is at least one selected from the group consisting of hydrochloric acid, sulfuric acid, nitric acid, acetic acid, oxalic acid, sodium bicarbonate, potassium bicarbonate, ammonia water, urea, potassium hydroxide, sodium hydroxide, potassium carbonate and sodium carbonate.
3. The method of claim 1, wherein in step (1), the palladium precursor is a palladium salt.
4. The method according to claim 3, wherein in the step (1), the palladium salt is at least one selected from the group consisting of palladium chloride, palladium acetate, palladium nitrate and sodium chloropalladate.
5. The method according to claim 1, wherein in the step (1), the reducing agent used for the reduction is hydrazine hydrate; the reduction temperature was room temperature.
6. The method according to claim 1, wherein in the step (2), the volume content of the water vapor in the reaction atmosphere is 5 to 100%.
7. The preparation method of claim 1, wherein in the supported palladium nanoparticle catalyst, the load of palladium nanoparticles is 0.01-2% of the mass of the carrier, and the mass of the palladium nanoparticles is calculated as the mass of active metal palladium.
8. The application of the supported palladium nanoparticle catalyst prepared by the preparation method of any one of claims 1-7, wherein the supported palladium nanoparticle catalyst is used for hydrogenation catalytic reaction of alkylanthraquinone.
9. The use of the supported palladium nanoparticle catalyst according to claim 8, wherein the conditions of the alkylanthraquinone hydrogenation catalytic reaction are: the flow rate of hydrogen is 10-5000 mL/min -1 The method comprises the steps of carrying out a first treatment on the surface of the The reaction temperature is 25-80 ℃; the reaction pressure is 0.1-2.0 MPa.
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