CN116786136A - Highly ordered Cu 3 Preparation and application of Pd intermetallic compound nano-catalyst - Google Patents

Highly ordered Cu 3 Preparation and application of Pd intermetallic compound nano-catalyst Download PDF

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CN116786136A
CN116786136A CN202310708581.3A CN202310708581A CN116786136A CN 116786136 A CN116786136 A CN 116786136A CN 202310708581 A CN202310708581 A CN 202310708581A CN 116786136 A CN116786136 A CN 116786136A
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周军
秦高梧
李松
杨鑫雨
王紫璇
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东北大学
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    • 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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Abstract

The invention discloses preparation and application of a highly ordered Cu3Pd intermetallic compound nano catalyst, which mainly comprises the following preparation methods: pretreating metal matrix Mg wires; mixing alloy catalyst precursor salt mixed solution with electrolyte and carrying out microplasma electrolytic oxidation treatment; carrying out heating reduction treatment on the prepared catalyst to finally obtain the intermetallic compound nano catalyst with high order; the preparation process is simple, two metal elements can be uniformly mixed and loaded on the surface of the metal oxide carrier by a one-step method, and the in-situ preparation of the highly ordered intermetallic alloy nano-catalyst is realized; the catalyst is applied to acetylene hydrogenation reaction, is used for eliminating acetylene impurities in ethylene gas, and shows excellent catalytic selectivity; the development of the technology is beneficial to the development of the preparation of a trace noble metal alloy nano catalyst, greatly reduces the noble metal content required by acetylene hydrogenation, and is beneficial to the sustainable utilization and development of resources.

Description

Highly ordered Cu 3 Preparation and application of Pd intermetallic compound nano-catalyst
Technical Field
The invention belongs to the field of catalyst preparation and hydrogenation application, and mainly relates to Cu 3 A preparation method and application of Pd/MgO catalyst.
Background
The catalyst is used as an important composition distribution for social and economic development, and has been widely applied to various fields of society, including agriculture, industry, aerospace and the like. At present, for a common catalyst, noble metals are mainly selected as main raw materials to construct a catalytic material; noble metals such as Pd, pt, etc., exhibit excellent catalytic activity in various catalytic reactions due to their unique electronic structures. However, the use of such metals in the catalytic field is severely inhibited by their relatively low content in the earth, which is relatively expensive. The non-noble metal is doped into the noble metal to form the alloy nano catalyst (comprising intermetallic compound), and the electronic structure of the alloy particles is regulated and controlled, so that the reduction of the consumption of the noble metal is realized while the catalytic performance is maintained or improved, and the method is a feasible and potential development mode. At present, the preparation of the alloy nano-catalyst is mainly carried out by a wet chemical method, the method needs more steps, and the selection of alloy elements has certain limitation; on the other hand, the alloy particles prepared by the methods generally have no strict ordering among alloy elements, and in the catalytic reaction, the selectivity of the catalytic reaction, such as hydrogenation of acetylene, for preparing ethylene, is adversely affected. Therefore, developing a new preparation method of the ordered alloy nano catalyst simplifies the preparation steps, reduces the consumption of noble metals, improves the catalytic reaction performance and is a problem which needs to be solved urgently at present.
Disclosure of Invention
In view of the above problems, the present invention employs a micro-scalePreparation of highly ordered Cu by plasma electrolytic oxidation technology 3 Pd/MgO intermetallic compound nano catalyst; microplasma electrolytic oxidation is a high-temperature high-pressure plasma effect technology which occurs at a metal interface, and a metal matrix can be oxidized in situ on the metal surface to generate a metal oxide to form a catalyst carrier; meanwhile, the plasma effect can decompose catalyst precursor salt, such as chelated Cu salt and chelated Pd salt, near the metal matrix Mg wire to form Cu and Pd alloy nano particles; because the precursor salt is uniformly mixed in the solution near the Mg wire, cu and Pd in the prepared alloy particles are also uniformly distributed; the prepared CuPd alloy nano particles are heated and reduced for 2 hours in a hydrogen atmosphere, cu atoms and Pd atoms are rearranged under the thermal effect, and finally the highly ordered Cu is prepared 3 Pd intermetallic compound nano-catalyst.
The invention can be realized by the following technical scheme:
highly ordered Cu 3 The preparation method of the Pd intermetallic compound nano catalyst comprises the following steps: mixing copper sulfate and sodium chloropalladate with EDTA chelating agent, respectively, and mixing the two mixtures with electrolyte to obtain copper element and palladium element with concentration of 2×10 respectively -3 -5×10 -3 mol/L，3×10 -4 -8×10 -4 The mol/L and the temperature of electrolyte are kept between 5 ℃ and 25 ℃, metal magnesium wires are used as anodes, microplasma electrolytic oxidation is carried out, the CuPd alloy nano-catalyst is prepared, and the Cu is finally prepared by carrying out thermal reduction treatment in hydrogen atmosphere 3 Pd intermetallic compound nano-catalyst.
Further improvement and optimization of the technical proposal, the electrolyte main salt is sodium silicate Na 2 SjO 3 ·9H 2 O, the concentration is 4g/L-9g/L; other components comprise KF and KOH, the concentrations of which are 5-9g/L and 5-8g/L respectively, and the total volume of the electrolyte is 500mL.
Further improvement and optimization of the technical scheme, and parameters of the microplasma electrolytic oxidation process: pulse number 250-400Hz, pulse width 50-80 μs, constant current mode, current setting 0.5-2A/cm 2 The action time is 1-2min.
According to the technical scheme, the catalyst precursor salt is prepared by respectively coordinating 0.1mol/L of copper sulfate solution and 0.01mol/L of sodium chloropalladate solution with EDTA chelating agent, then respectively taking a certain amount of chelated solution, adding the chelated solution into electrolyte, and uniformly stirring for 5 minutes to complete the mixing of the precursor salt in the electrolyte.
Further improvement and optimization of the technical proposal, the concentrations of the copper element and the palladium element of the catalyst precursor in the mixed solution are respectively 2 multiplied by 10 -3 ，3×10 -4 。
Further improvement and optimization of the technical scheme are that the temperature of the mixed solution is kept at 10-25 ℃, and liquid nitrogen is used for cooling.
Further improvement and optimization of the technical scheme are that the metal magnesium wire is sanded for 3 times, braided into a spiral shape, ultrasonically cleaned in ethanol for 15min, dried and stored.
Further improvement and optimization of the technical scheme, wherein the chelating agent EDTA concentration is 4 multiplied by 10 -3 -9×10 -3 mol/L。
Further improvement and optimization of the technical scheme, wherein the catalyst is heated (350-420 ℃) in a hydrogen atmosphere for reduction for 2 hours, and is stored in a sealing bag after completion;
the catalyst takes metal magnesium wires as a matrix, and a layer of three-dimensional porous MgO and Cu are attached to the surfaces of the wires 3 Pd nano particles are uniformly loaded on the MgO surface and in the pore canal, and the loading amount of noble metal Pd is 100mg/kg.
Another object of the present invention is to provide a Cu 3 The use of a Pd/MgO intermetallic catalyst in the hydrogenation of acetylene, said catalyst being used to convert acetylene impurities in ethylene to ethylene.
Further, the conversion rate of the catalyst in the acetylene hydrogenation reaction is 70-80%, the selectivity of the catalyst is 95% -96%, and the whole service life can reach 125 hours.
The invention utilizes microplasma electrolytic oxidation technology and combines the thermal reduction process to prepare MgO-loaded Cu on the metal magnesium wire substrate in situ 3 Pd intermetallic compound nanoparticles; compared with other methodsThe technical process is simple, and the designed technology is simpler and more convenient; prepared Cu 3 Pd intermetallic compound, cu atoms and Pd atoms of which are arranged in a highly ordered manner in nano particles, provide a uniform catalytic environment, show excellent catalytic performance in acetylene hydrogenation reaction, and have selectivity to ethylene up to 95% at 80% conversion; importantly, the intermetallic compound nano catalyst greatly reduces the dosage of noble metal Pd, the load of the noble metal Pd is only 100-360mg/kg, and the equivalent or synergistic decrement of the noble metal catalyst is realized. In addition, the catalyst also has excellent catalytic stability, and can keep stable aging for 125 hours under the condition of 95% selectivity. The catalyst preparation technology disclosed by the invention can be used for conveniently and efficiently preparing the acetylene hydrogenation catalyst, and greatly promotes the development and application of the metal catalyst.
Drawings
FIG. 1 shows Cu in example 1 of the present invention 3 Physical diagram of Pd/MgO catalyst.
FIG. 2 is a diagram showing Cu in example 1 of the present invention 3 Spherical aberration electron microscope (HAADF-STEM) diagram of Pd/MgO catalyst.
FIG. 3 is a diagram showing Cu in example 1 of the present invention 3 Pd/MgO catalyst catalytic conversion acetylene hydrogenation conversion rate diagram.
FIG. 4 shows Cu in example 1 of the present invention 3 Pd/MgO catalyst for catalyzing hydrogenation stabilization of acetylene.
Detailed Description
The following non-limiting examples will enable those of ordinary skill in the art to more fully understand the invention and are not intended to limit the invention in any way.
The test methods described in the following examples, unless otherwise specified, are all conventional; the reagents and materials, unless otherwise specified, are commercially available.
Example 1
Highly ordered Cu 3 The preparation method of the Pd intermetallic compound nano catalyst mainly comprises the following steps:
(1) braiding 1m long metal magnesium wires into a spiral shape, sequentially polishing with 1000# and 3000#, ultrasonically cleaning in ethanol for 15min, and drying and preserving;
(2) preparing electrolyte, namely adding sodium silicate, potassium fluoride and potassium hydroxide into 500ml of water respectively, and dissolving; the concentration of the potassium fluoride is 4g/L of sodium silicate, 5g/L of potassium fluoride and 6g/L of potassium hydroxide respectively;
(3) dissolving copper sulfate in water to prepare a copper sulfate solution with the concentration of 0.1 mol/L; dissolving sodium chloropalladate in water to prepare 0.01mol/L sodium chloropalladate solution; EDTA is dissolved in water to prepare 0.5mol/L EDTA solution; respectively adding a proper amount of EDTA into the catalyst precursor salt to form chelate salts of Cu and Pd;
(4) adding a proper amount of the chelate solution prepared in the step (3) into an electrolyte, and uniformly mixing, wherein the final concentrations of Cu salt and Pd salt in the electrolyte are respectively 2 multiplied by 10 -3 mol/L，3×10 -4 mol/L；
(5) Performing liquid nitrogen cooling treatment on the solution obtained in the step (4) to keep the temperature between 5 and 10 ℃;
(6) the spiral metal magnesium wire is used as anode to carry out microplasma electrolytic oxidation treatment, the pulse width is 80 mu s, the pulse number is 250Hz, and the pulse current density is 0.5A/cm 2 The action time is 2min;
(7) and (3) carrying out thermal reduction treatment on the prepared CuPd/MgO catalyst under the hydrogen atmosphere, wherein the heating temperature is 350 ℃, the time is 2 hours, and then sealing the bag for preservation after the completion.
For the spiral magnesium wire prepared in the example as a matrix, mgO is loaded with Cu 3 Pd intermetallic compound nano-catalyst, the entity of which is shown in figure 1: cu with gray color uniformly distributed on magnesium wire surface 3 Pd nanoparticle catalyst.
For the Cu prepared in this example and using spiral magnesium wire as matrix, mgO is loaded 3 The Pd intermetallic compound nano-catalyst and the ICP result show that the Pd content of the prepared catalyst is 100mg/kg.
For the Cu prepared in this example and using spiral magnesium wire as matrix, mgO is loaded 3 Pd intermetallic compound nano-catalyst, HAADF-STEM electron microscope thereof is shown in figure 2: cu (Cu) 3 Pd nano particles are uniformly distributed on the surface of the carrier and in the pore canal, and Cu atoms and Pd atoms are in a highly ordered arrangement state in the nano particles, so that the nano particles have a tetragonal structure.
For the Cu prepared in this example and using spiral magnesium wire as matrix, mgO is loaded 3 Pd intermetallic compound nano-catalyst, the acetylene hydrogenation conversion rate of which is shown in figure 3; with the increase of the catalytic reaction temperature, the conversion rate of acetylene gradually increases and finally reaches 100%.
For the Cu prepared in this example and using spiral magnesium wire as matrix, mgO is loaded 3 Pd intermetallic compound nano catalyst, is used for detecting the catalytic stability of acetylene hydrogenation reaction; placing the catalyst in a glass tube reactor for catalytic reaction, and monitoring in real time by using gas chromatography; the reaction process is detected every 25 hours, the stability of the catalytic reaction is detected, and the experimental result is shown in fig. 4: after 125h reaction, the catalyst has no obvious change in catalytic reaction selectivity and conversion rate, and has excellent catalytic stability.
Example 2
Highly ordered Cu 3 The preparation method of the Pd intermetallic compound nano catalyst mainly comprises the following steps:
(1) weaving magnesium wires with the diameter of 500 mu m and the length of 1m into a spiral shape, polishing the magnesium wires by using sand paper, ultrasonically cleaning the magnesium wires in ethanol for 20min, and drying and preserving the magnesium wires in an oven;
(2) preparing electrolyte, namely adding sodium silicate, potassium fluoride and potassium hydroxide into 500ml of water respectively, and dissolving; the concentration of the potassium fluoride is 6g/L of sodium silicate, 7g/L of potassium fluoride and 8g/L of potassium hydroxide respectively;
(3) dissolving copper sulfate in water to prepare a copper sulfate solution with the concentration of 0.1 mol/L; dissolving sodium chloropalladate in water to obtain
Forming 0.01mol/L sodium chloropalladate solution; EDTA is dissolved in water to prepare 0.5mol/L EDTA solution; respectively adding a proper amount of EDTA into the catalyst precursor salt to form chelate salts of Cu and Pd;
(4) adding a proper amount of the chelate solution prepared in the step (3) into an electrolyte, and uniformly mixing, wherein the final concentrations of Cu salt and Pd salt in the electrolyte are respectively 4 multiplied by 10 -3 mol/L，6×10 -4 mol/L；
(5) Performing liquid nitrogen cooling treatment on the solution obtained in the step (4) to keep the temperature between 10 and 15 ℃;
(6) the spiral metal magnesium wire is used as anode to carry out microplasma electrolytic oxidation treatment, the pulse width is 50 mu s, the pulse number is 400Hz, and the pulse current density is 1A/cm 2 The action time is 1min;
(7) and (3) carrying out thermal reduction treatment on the prepared CuPd/MgO alloy nano catalyst under the hydrogen atmosphere, wherein the heating temperature is 380 ℃, the time is 2 hours, and then sealing the bag for preservation after the completion.
Example 3
The preparation method of the highly ordered Cu3Pd intermetallic compound nano-catalyst mainly comprises the following steps:
(1) weaving magnesium wires with the diameter of 500 mu m and the length of 1.5m into a spiral shape, polishing the magnesium wires by using sand paper, ultrasonically cleaning the magnesium wires in ethanol for 25min, and drying and preserving the magnesium wires in an oven;
(2) preparing electrolyte, namely adding sodium silicate, potassium fluoride and potassium hydroxide into 500ml of water respectively, and dissolving; the concentration of the potassium fluoride is 8g/L of sodium silicate, 8g/L of potassium fluoride and 5g/L of potassium hydroxide respectively;
(3) dissolving copper sulfate in water to prepare a copper sulfate solution with the concentration of 0.1 mol/L; dissolving sodium chloropalladate in water to prepare 0.01mol/L sodium chloropalladate solution; EDTA is dissolved in water to prepare 0.5mol/L EDTA solution; respectively adding a proper amount of EDTA into the catalyst precursor salt to form chelate salts of Cu and Pd;
(4) adding a proper amount of the chelate solution prepared in the step (3) into an electrolyte, and uniformly mixing, wherein the final concentrations of Cu salt and Pd salt in the electrolyte are 5 multiplied by 10 respectively -3 mol/L，8×10 -4 mol/L；
(5) Performing liquid nitrogen cooling treatment on the solution obtained in the step (4) to keep the temperature of the electrolyte between 15 and 25 ℃;
(6) the spiral magnesium wire is used as an anode to carry out microplasma electrolytic oxidation treatment, the pulse width is 60 mu s, the pulse number is 335Hz, the pulse current density is 2A/cm < 2 >, and the action time is 1.5min;
(7) and (3) carrying out thermal reduction treatment on the prepared CuPd/MgO alloy nano catalyst under the hydrogen atmosphere, wherein the heating temperature is 400 ℃, the time is 2 hours, and then sealing the bag for preservation after the completion.
Example 4
Highly ordered Cu 3 The preparation method of the Pd intermetallic compound nano catalyst mainly comprises the following steps:
(1) weaving 500 μm diameter magnesium wire with length of 2m into spiral shape, polishing with sand paper, ultrasonically cleaning in ethanol for 30min, and drying in oven; the method comprises the steps of carrying out a first treatment on the surface of the
(2) Preparing electrolyte, namely adding sodium silicate, potassium fluoride and potassium hydroxide into 500ml of water respectively, and dissolving; the concentration of the potassium fluoride is 9g/L of sodium silicate, 9g/L of potassium fluoride and 8g/L of potassium hydroxide respectively;
(3) dissolving copper sulfate in water to prepare a copper sulfate solution with the concentration of 0.1 mol/L; dissolving sodium chloropalladate in water to prepare 0.01mol/L sodium chloropalladate solution; EDTA is dissolved in water to prepare 0.5mol/L EDTA solution; respectively adding a proper amount of EDTA into the catalyst precursor salt to form chelate salts of Cu and Pd;
(4) adding a proper amount of the chelate solution prepared in the step (3) into an electrolyte, and uniformly mixing, wherein the final concentrations of Cu salt and Pd salt in the electrolyte are respectively 4 multiplied by 10 -3 mol/L，7×10 -4 mol/L；
(5) Performing liquid nitrogen cooling treatment on the solution obtained in the step (4) to keep the temperature of the electrolyte between 15 and 25 ℃;
(6) the spiral magnesium wire is used as an anode to carry out microplasma electrolytic oxidation treatment, the pulse width is 70 mu s, the pulse number is 285Hz, the pulse current density is 2A/cm < 2 >, and the action time is 1.5min;
(7) and (3) carrying out thermal reduction treatment on the prepared CuPd/MgO alloy nano catalyst under the hydrogen atmosphere, wherein the heating temperature is 420 ℃, the time is 2 hours, and then sealing the bag for preservation after the completion.

Claims (10)

1. Highly ordered Cu 3 The preparation method of the Pd intermetallic compound nano catalyst is characterized by comprising the following steps: mixing copper sulfate and sodium chloropalladate with EDTA chelating agent, respectively, and mixing the two mixtures with electrolyte to obtain copper element and palladium element with concentration of 2×10 respectively -3 -5×10 -3 mol/L，3×10 -4 -8×10 -4 mol/L，The temperature of the electrolyte is kept between 5 ℃ and 25 ℃, metal magnesium wires are used as anodes, microplasma electrolytic oxidation is carried out, the CuPd alloy nano-catalyst is prepared, and the Cu is finally prepared by carrying out thermal reduction treatment in hydrogen atmosphere 3 Pd intermetallic compound nano-catalyst.
2. A highly ordered Cu according to claim 1 3 The preparation process of nanometer Pd intermetallic compound catalyst features that the electrolyte solution is sodium silicate Na as main salt 2 SiO 3 ·9H 2 0, the concentration is 4g/L-9g/L; other components comprise KF and KOH, the concentrations of which are 5-9g/L and 5-8g/L respectively, and the total volume of the electrolyte is 500mL.
3. A highly ordered Cu according to claim 2 3 The preparation method of the Pd intermetallic compound nano catalyst is characterized in that the parameters of the microplasma electrolytic oxidation process are as follows: pulse number 250-400Hz, pulse width 50-80 μs, constant current mode, current setting 0.5-2A/cm 2 The action time is 1-2min.
4. The method according to claim 3, wherein the catalyst precursor salt is prepared by respectively complexing 0.1mol/L of copper sulfate solution and 0.01mol/L of sodium chloropalladate solution with EDTA chelating agent, respectively taking a certain amount of chelated solution, adding the chelated solution into the electrolyte, and uniformly stirring for 5 minutes to complete the mixing of the precursor salt in the electrolyte.
5. The method according to any one of claims 1 to 4, wherein the concentrations of copper element and palladium element in the catalyst precursor in the mixed solution are 2X 10, respectively -3 ，3×10 -4 。
6. The method according to any one of claims 1 to 4, wherein the temperature of the mixed liquor is maintained at 10 to 25 ℃, and the temperature is reduced by using liquid nitrogen.
7. The method according to any one of claims 1 to 4, wherein the metal magnesium wire is sanded 3 times, braided in a spiral shape, and ultrasonically washed in ethanol for 15min, and dried and stored.
8. The method according to any one of claims 1 to 4, wherein the chelating agent EDTA is used at a concentration of 4X 10 -3 -9×10 -3 mol/L。
9. The method according to any one of claims 1 to 4, wherein the catalyst is heated in a hydrogen atmosphere (350 ℃ to 420 ℃) for 2 hours of reduction and is kept in a sealed bag after completion;
the catalyst takes metal magnesium wires as a matrix, and a layer of three-dimensional porous MgO and Cu are attached to the surfaces of the wires 3 Pd nano particles are uniformly loaded on the MgO surface and in the pore canal, and the loading amount of noble metal Pd is 100mg/kg.
10. A Cu as claimed in any one of claims 1 to 4 3 The application of Pd/MgO catalyst in acetylene hydrogenation is characterized in that the catalyst is applied to eliminating acetylene impurity gas in ethylene gas.
CN202310708581.3A 2023-06-15 2023-06-15 Highly ordered Cu 3 Preparation and application of Pd intermetallic compound nano-catalyst Pending CN116786136A (en)

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