CN106669680B - Rod-shaped nano nickel-containing metal solid solution catalyst and preparation method thereof - Google Patents

Rod-shaped nano nickel-containing metal solid solution catalyst and preparation method thereof Download PDF

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CN106669680B
CN106669680B CN201611055398.4A CN201611055398A CN106669680B CN 106669680 B CN106669680 B CN 106669680B CN 201611055398 A CN201611055398 A CN 201611055398A CN 106669680 B CN106669680 B CN 106669680B
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nickel
solid solution
containing metal
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CN106669680A (en
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祝艳
肖青林
孙予罕
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Shanghai Advanced Research Institute of CAS
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    • B01J23/00—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00
    • B01J23/70—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper
    • B01J23/74—Iron group metals
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    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
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Abstract

The invention provides a rodlike nano nickel-containing metal solid solution catalyst and a preparation method thereof, wherein the rodlike nano nickel-containing metal solid solution catalyst is a nickel-magnesium solid solution formed by mutually doping nickel and magnesium, the size of the rodlike nano nickel-containing metal solid solution catalyst is 200-600 nm, and the section width of the rodlike nano nickel-containing metal solid solution catalyst is 40-70 nm. The preparation method of the rodlike nano nickel-containing metal solid solution catalyst comprises the following steps: uniformly mixing nickel-magnesium metal salt and deionized water at room temperature to 70 ℃, keeping the temperature constant for 5-10 min, stabilizing for a period of time, adding a surfactant, reacting for 20-30 min, adding an organic solvent, drying, cleaning with the organic solvent, and drying in vacuum to obtain the precursor of the rodlike nano nickel-magnesium solid solution catalyst. And roasting the obtained precursor at 550-750 ℃ for 2-8 h to obtain the rodlike nano nickel-magnesium solid solution catalyst with uniform and stable appearance and good dispersibility. The invention has good dispersibility and controllable components; the method is simple and easy to operate, the catalyst is uniform in appearance and good in stability, and has good catalytic activity on the reforming reaction of methane and carbon dioxide.

Description

Rod-shaped nano nickel-containing metal solid solution catalyst and preparation method thereof
Technical Field
The invention relates to the technical field of preparation of nano materials, in particular to a rod-shaped nano nickel-containing metal solid solution catalyst and a preparation method thereof.
Background
With the continuous decline of world oil reserves, mankind has to consider developing alternative new energy sources, and the earth crust, the abundant natural gas in the ocean and the shale gas become the most competitive new energy sources in the 21 st century. The main component of natural gas is methane, and the greenhouse effect of the natural gas is 20 times that of carbon dioxide, thus seriously causing the global greenhouse effect. Methane and carbon dioxide reforming utilizes the greenhouse effectThe carbon dioxide and the methane have great significance for relieving global warming and realizing low-carbon life. Theoretical H produced during the preparation of synthesis gas by this reaction2The ratio of/CO is about 1, and is an ideal raw material for F-T synthesis and oxo synthesis. The methane carbon dioxide reforming process can be used as a medium for energy storage because it is a reversible reaction with a large heat of reaction. The energy required for the positive reaction of the methane carbon dioxide reforming process can be obtained from solar energy, nuclear energy or mineral combustion. This energy will be stored in the product in the form of chemical energy (CO/H)2The mixed gas) is conveyed to a required place through a pipeline, and then the reversible reaction is carried out under the action of a heterogeneous catalyst to release the stored energy, so that the reaction is a good way for developing and utilizing solar energy and nuclear energy.
At present, a great deal of research shows that the noble metals (Pt, Ru, Pb, Ir, Rh and the like) have good catalytic activity and carbon deposit resistance in the reaction of methane and carbon dioxide. However, precious metals are scarce and expensive, so more researchers have focused on non-precious metals, Ni. The Ni-based catalyst under the same conditions is inferior to Pt and Ir only in terms of catalytic activity, and thus becomes the methane carbon dioxide reforming catalyst having the most possible substitution for noble metals.
However, Ni-based catalysts are prone to sintering and carbon deposition. By introducing the carrier magnesium, the carrier magnesium and nickel form a solid solution, so that the nickel is effectively dispersed, and the activity and the carbon deposition resistance of the catalyst can be greatly improved. Therefore, the invention provides an effective preparation method of the nickel-magnesium nanorod catalyst, which can effectively and constantly deposit carbon on the catalyst at low temperature, so that the catalyst has high-efficiency activity.
As for the nickel-magnesium catalyst, the previously reported morphology structure is very rare, and no report is made at home and abroad about the rod-shaped structure.
Disclosure of Invention
In view of the above-mentioned disadvantages of the prior art, the present invention aims to provide a rod-shaped nano nickel-containing metal solid solution catalyst and a preparation method thereof, wherein the catalyst is synthesized from nickel nitrate and magnesium nitrate, has good dispersibility and controllable components; the preparation method adopts a hydrothermal synthesis method, and obtains the nickel-magnesium nanorod-shaped catalyst with different components by regulating and controlling the proportion, the reaction time and the temperature of the metal precursor, the method is simple, the operation is easy, the shape of the catalyst is uniform, the stability is good, the catalyst shows good catalytic activity when being applied to the reforming reaction of methane and carbon dioxide, and the preparation method has certain industrial application prospect.
In order to achieve the above objects and other related objects, the present invention provides a method for preparing a rod-shaped nano nickel-containing metal solid solution catalyst, comprising the steps of: step 1), adding nickel salt, first metal salt and deionized water into a reaction vessel simultaneously, and uniformly mixing to obtain a first solution, wherein the first metal salt comprises one of magnesium salt, copper salt and iron salt; step 2), stirring the first solution, adding a surfactant after the temperature is stabilized for a period of time, and reacting to obtain a second solution; step 3), adding an organic solution into the second solution, and stirring to obtain a third solution; step 4), transferring the third solution into a hydrothermal kettle for reaction, washing the solution obtained by the reaction with an organic solvent and deionized water, and drying to obtain a precursor of the rodlike nano nickel-containing metal catalyst; and 5) roasting the precursor of the rodlike nano nickel-containing metal catalyst to obtain the rodlike nano nickel-containing metal catalyst.
As a preferable scheme of the preparation method of the rodlike nano nickel-containing metal solid solution catalyst, in the step 1), the molar ratio of the nickel salt to the first metal salt is 0.2-0.6: 1, the nickel salt and the first metal salt are nitrates or acetates, the temperature for uniformly mixing is room temperature-70 ℃, and the heat preservation time is 5-20 min.
As a preferable scheme of the preparation method of the rodlike nano nickel-containing metal solid solution catalyst, in the step 2), a magnetic stirrer is adopted to stir the first solution, the rotating speed of the magnetic stirrer is 400-600 r/min, the temperature stabilizing time is 5-10 min, the surfactant is selected from one of polyethylene glycol and PVP, and the reaction time is 20-30 min.
As a preferable embodiment of the preparation method of the rodlike nano nickel-containing metal solid solution catalyst according to the present invention, in step 3), the organic solution includes one of ethylene glycol and PVP.
As a preferable scheme of the preparation method of the rodlike nano nickel-containing metal solid solution catalyst, in the step 4), the reaction temperature is 150-200 ℃, and the reaction time is 12-18 h.
As a preferable embodiment of the preparation method of the rod-shaped nano nickel-containing metal solid solution catalyst of the present invention, in the step 4), the organic solvent used for washing is one or a mixture of two or more selected from ethanol, chloroform and isopropanol.
As a preferable scheme of the preparation method of the rodlike nano nickel-containing metal solid solution catalyst, in the step 5), the roasting temperature is 550-750 ℃, and the roasting time is 2-8 h.
The invention also provides a rodlike nano nickel-containing metal solid solution catalyst which is a nano rodlike structure formed by nickel and a first metal solid solution, wherein the first metal comprises one of magnesium, copper and iron.
As a preferable scheme of the rodlike nano nickel-containing metal solid solution catalyst, the length of the nano rodlike structure is 200-600 nm, and the cross section width is 30-70 nm.
The invention also provides an application method of the rodlike nano nickel-containing metal solid solution catalyst, and the rodlike nano nickel-containing metal solid solution catalyst is applied to a methane carbon dioxide reforming reaction.
As a preferable scheme of the application method of the rodlike nano nickel-containing metal solid solution catalyst, the temperature of catalytic reaction is 550-750 ℃, the pressure is normal pressure, and the flow rate ratio of methane to carbon dioxide is CH4: CO 2: 1-2.
As described above, the rod-shaped nano nickel-containing metal solid solution catalyst and the preparation method thereof of the present invention have the following beneficial effects:
according to the rod-shaped nickel-magnesium solid solution nano catalyst provided by the invention, in an ethylene glycol system, a nickel salt and a magnesium salt are subjected to mutual doping reaction, and a high-dispersion noble nickel-magnesium solid solution nanorod is obtained through hydrothermal and roasting. Moreover, the catalyst has the advantages of good stability, long service life, high activity and the like, has no obvious inactivation phenomenon after continuous operation for 300 hours, and has good industrial application prospect.
Drawings
FIG. 1 is a flow chart showing the steps of the preparation method of the rodlike nano nickel-containing metal solid solution catalyst.
FIG. 2 is an SEM photograph of a rod-shaped nickel-magnesium solid solution catalyst prepared in example 1.
FIG. 3 is an SEM photograph of a rod-shaped nickel-magnesium solid solution catalyst prepared in example 3.
Fig. 4 is an XRD pattern of the rod-shaped nickel-magnesium solid solution catalyst prepared in example 4.
FIG. 5 is a graph showing the reaction effect of the rod-shaped nickel-magnesium solid solution catalyst prepared in example 2.
Description of the element reference numerals
S11-S15 steps 1) -5)
Detailed Description
The embodiments of the present invention are described below with reference to specific embodiments, and other advantages and effects of the present invention will be easily understood by those skilled in the art from the disclosure of the present specification. The invention is capable of other and different embodiments and of being practiced or of being carried out in various ways, and its several details are capable of modification in various respects, all without departing from the spirit and scope of the present invention.
Please refer to fig. 1 to 5. It should be noted that the drawings provided in the present embodiment are only for illustrating the basic idea of the present invention, and the drawings only show the components related to the present invention rather than being drawn according to the number, shape and size of the components in actual implementation, and the type, quantity and proportion of each component in actual implementation may be changed arbitrarily, and the layout of the components may be more complicated.
Example 1
As shown in fig. 1 and fig. 2, this embodiment provides a preparation method of a rod-shaped nano nickel-containing metal solid solution catalyst, which includes the following steps:
as shown in fig. 1, step 1) S11 is first performed, nickel salt, a first metal salt and deionized water are simultaneously added into a reaction vessel, and uniformly mixed to obtain a first solution, where the first metal salt includes one of magnesium salt, copper salt and iron salt.
For example, in the step 1), the molar ratio of the nickel salt to the first metal salt is 0.2-0.6: 1, the nickel salt and the first metal salt are nitrates or acetates, the mixture is uniformly mixed at the temperature of room temperature-70 ℃, and the holding time is 5-20 min.
As shown in fig. 1, step 2) S12 is then performed, the first solution is stirred, after a period of temperature stabilization, a surfactant is added, and a second solution is obtained after reaction.
In the step 2), a magnetic stirrer is used for stirring the first solution, the rotation speed of the magnetic stirrer is 400-600 r/min, the temperature stabilization time is 5-10 min, the surfactant is selected from one of polyethylene glycol and PVP, and the reaction time is 20-30 min.
As shown in fig. 1, step 3) S13 is then performed, and the organic solution is added to the second solution and stirred to obtain a third solution.
As an example, in step 3), the organic solution includes one of ethylene glycol and PVP.
As shown in fig. 1, then, step 4) S14 is performed, the third solution is moved into a hydrothermal kettle for reaction, the solution obtained by the reaction is washed with an organic solvent and deionized water, and a precursor of the rod-shaped nano nickel-containing metal catalyst is obtained after drying;
as an example, in the step 4), the reaction temperature is 150 ℃ to 200 ℃, and the reaction time is 12h to 18 h.
For example, in step 4), the organic solvent used for washing is one or a mixture of two or more selected from ethanol, chloroform and isopropanol.
As shown in fig. 1, step 5) S15 is finally performed, and the precursor of the rod-shaped nano nickel-containing metal catalyst is calcined to obtain the rod-shaped nano nickel-containing metal catalyst.
As an example, in the step 5), the roasting temperature is 550 to 750 ℃, and the roasting time is 2 to 8 hours.
The embodiment also provides a rodlike nano nickel-containing metal solid solution catalyst, which is a nano rodlike structure formed by nickel and a first metal solid solution, wherein the first metal comprises one of magnesium, copper and iron.
As an example, the length of the nanorod structures is 200-600 nm, and the cross-sectional width is 30-70 nm.
The embodiment also provides an application method of the rod-shaped nano nickel-containing metal solid solution catalyst, and the rod-shaped nano nickel-containing metal solid solution catalyst is applied to methane carbon dioxide reforming reaction.
For example, the temperature of the catalytic reaction is 550 to 750 ℃, the pressure is normal pressure, and the flow rate ratio of methane to carbon dioxide is CH4: CO2 is 1:1 to 2.
In a specific implementation process, the preparation method of the rodlike nano nickel-containing metal solid solution catalyst comprises the following steps:
weighing 4mmol of nickel nitrate and 12mmol of magnesium nitrate, putting the nickel nitrate and the magnesium nitrate into a beaker, adding 18ml of deionized water, and dissolving the mixture for 15 minutes at the temperature of 50 ℃ to obtain a first solution. And quickly transferring the first solution to a magnetic stirrer, stabilizing the temperature for 5min, and adding 0.9g of polyethylene glycol to react for 30min to obtain a second solution. 30ml of ethylene glycol was added to the second solution, and after reacting for 2 hours, a third solution was obtained. And transferring the third solution into a hydrothermal kettle, reacting for 18h at 170 ℃, cooling to room temperature, centrifuging the obtained solution, washing for 4 times by using ethanol and deionized water to obtain a light green precursor, grinding the precursor uniformly, and roasting for 3h at 650 ℃. And finally grinding the roasted body into fine powder, performing extrusion forming in a die under the pressure of 40kN, and crushing and screening to obtain catalyst particles with the particle size of 40-60 meshes. The catalytic reaction conditions are as follows: the temperature of the catalytic reaction is 650 ℃, and the pressure is normal pressure; the total flow rate of the reaction was 66mL/min, where the flow rate ratio of the two gases CH4:CO21: 1.2; the space velocity is 70000 mL/(g.h). The SEM image of the rod-shaped nickel-magnesium solid solution catalyst prepared in this example is shown in FIG. 2.
Example 2
The embodiment provides a preparation method of a rod-shaped nano nickel-containing metal solid solution catalyst, which comprises the following steps:
weighing 4mmol of nickel nitrate and 12mmol of magnesium nitrate, putting the nickel nitrate and the magnesium nitrate into a beaker, adding 18ml of deionized water, and dissolving the mixture for 15 minutes at the temperature of 50 ℃ to obtain a first solution. And quickly transferring the first solution to a magnetic stirrer, stabilizing the temperature for 5min, and adding 1.1g of polyethylene glycol to react for 30min to obtain a second solution. 30ml of ethylene glycol was added to the second solution, and after reacting for 2 hours, a third solution was obtained. And transferring the third solution into a hydrothermal kettle, reacting for 18h at 170 ℃, cooling to room temperature, centrifuging the obtained solution, washing for 4 times by using ethanol and deionized water to obtain a light green precursor, grinding the precursor uniformly, and roasting for 2h at 650 ℃. And finally grinding the roasted body into fine powder, performing extrusion forming in a die under the pressure of 40kN, and crushing and screening to obtain catalyst particles with the particle size of 40-60 meshes. The catalytic reaction conditions are as follows: the temperature of the catalytic reaction is 650 ℃, and the pressure is normal pressure; the total flow rate of the reaction was 66mL/min, where the flow rate ratio of the two gases CH4:CO21: 1.2; the space velocity is 70000 mL/(g.h). The catalytic reaction effect of the rod-shaped nickel-magnesium solid solution catalyst prepared in this example is shown in fig. 5. Of course, the magnesium nitrate may be replaced with copper nitrate or iron nitrate to prepare a rod-shaped nickel-copper solid solution catalyst or a rod-shaped nickel-iron solid solution catalyst.
Example 3
The embodiment provides a preparation method of a rod-shaped nano nickel-containing metal solid solution catalyst, which comprises the following steps:
weighing 4mmol of nickel acetate and 12mmol of magnesium acetate, placing the nickel acetate and the magnesium acetate into a beaker, adding 18ml of deionized water, and dissolving the mixture at the temperature of 50 ℃ for 15 minutes to obtain a first solution. And quickly transferring the first solution to a magnetic stirrer, stabilizing the temperature for 5min, and adding 0.9g of polyethylene glycol to react for 30min to obtain a second solution. To the second solution was added 30ml of ethylene glycolAnd reacting for 2 hours to obtain a third solution. And transferring the third solution into a hydrothermal kettle, reacting for 18h at 170 ℃, cooling to room temperature, centrifuging the obtained solution, washing for 4 times by using ethanol and deionized water to obtain a light green precursor, grinding the precursor uniformly, and roasting for 3h at 650 ℃. And finally grinding the roasted body into fine powder, performing extrusion forming in a die under the pressure of 40kN, and crushing and screening to obtain catalyst particles with the particle size of 40-60 meshes. The catalytic reaction conditions are as follows: the temperature of the catalytic reaction is 650 ℃, and the pressure is normal pressure; the total flow rate of the reaction was 66mL/min, where the flow rate ratio of the two gases CH4:CO21: 1.2; the space velocity is 60000 mL/(g.h). The SEM image of the rod-shaped nickel-magnesium solid solution catalyst prepared in this example is shown in FIG. 3. Of course, the magnesium nitrate may be replaced with copper acetate or iron acetate to prepare a rod-shaped nickel-copper solid solution catalyst or a rod-shaped nickel-iron solid solution catalyst.
Example 4
The embodiment provides a preparation method of a rod-shaped nano nickel-containing metal solid solution catalyst, which comprises the following steps:
weighing 4mmol of nickel nitrate and 12mmol of magnesium nitrate, putting the nickel nitrate and the magnesium nitrate into a beaker, adding 18ml of deionized water, and dissolving the mixture for 15 minutes at the temperature of 50 ℃ to obtain a first solution. And quickly transferring the first solution to a magnetic stirrer, stabilizing the temperature for 5min, and adding 0.9g of polyethylene glycol to react for 30min to obtain a second solution. 30ml of ethylene glycol was added to the second solution, and after reacting for 2 hours, a third solution was obtained. And transferring the third solution into a hydrothermal kettle, reacting for 15h at 180 ℃, cooling to room temperature, centrifuging the obtained solution, washing for 4 times by using ethanol and deionized water to obtain a light green precursor, uniformly grinding the precursor, and roasting for 3h at 650 ℃. And finally grinding the roasted body into fine powder, performing extrusion forming in a die under the pressure of 40kN, and crushing and screening to obtain catalyst particles with the particle size of 40-60 meshes. The catalytic reaction conditions are as follows: the temperature of the catalytic reaction is 650 ℃, and the pressure is normal pressure; the total flow rate of the reaction was 66mL/min, where the flow rate ratio of the two gases CH4:CO21: 1.2; the space velocity is 70000 mL/(g.h). XRD pattern of rod-like nickel-magnesium solid solution catalyst prepared in this exampleAs shown in fig. 3.
Example 5
The embodiment provides a preparation method of a rod-shaped nano nickel-containing metal solid solution catalyst, which comprises the following steps:
weighing 4mmol of nickel nitrate and 12mmol of magnesium nitrate, putting the nickel nitrate and the magnesium nitrate into a beaker, adding 18ml of deionized water, and dissolving the mixture for 15 minutes at the temperature of 50 ℃ to obtain a first solution. And quickly transferring the first solution to a magnetic stirrer, stabilizing the temperature for 5min, and adding 0.9g of polyethylene glycol to react for 30min to obtain a second solution. 30ml of ethylene glycol was added to the second solution, and after reacting for 2 hours, a third solution was obtained. And transferring the third solution into a hydrothermal kettle, reacting for 18h at 170 ℃, cooling to room temperature, centrifuging the obtained solution, washing for 4 times by using ethanol and deionized water to obtain a light green precursor, grinding the precursor uniformly, and roasting for 5h at 650 ℃. And finally grinding the roasted body into fine powder, performing extrusion forming in a die under the pressure of 40kN, and crushing and screening to obtain catalyst particles with the particle size of 40-60 meshes. The catalytic reaction conditions are as follows: the temperature of the catalytic reaction is 650 ℃, and the pressure is normal pressure; the total flow rate of the reaction was 66mL/min, where the flow rate ratio of the two gases CH4:CO21: 1.2; the space velocity is 80000 mL/(g.h).
Example 6
The embodiment provides a preparation method of a rod-shaped nano nickel-containing metal solid solution catalyst, which comprises the following steps:
weighing 4mmol of nickel acetate and 12mmol of magnesium acetate, placing the nickel acetate and the magnesium acetate into a beaker, adding 22ml of deionized water, and dissolving the mixture for 15 minutes at the temperature of 40 ℃ to obtain a first solution. And quickly transferring the first solution to a magnetic stirrer, stabilizing the temperature for 5min, and adding 0.9g of polyethylene glycol to react for 30min to obtain a second solution. 30ml of ethylene glycol was added to the second solution, and after reacting for 2 hours, a third solution was obtained. And transferring the third solution into a hydrothermal kettle, reacting for 18h at 170 ℃, cooling to room temperature, centrifuging the obtained solution, washing for 4 times by using ethanol and deionized water to obtain a light green precursor, grinding the precursor uniformly, and roasting for 3h at 650 ℃. Grinding the roasted product into fine powder, extruding and molding in a mold under 40kN pressure, and crushingAnd screening to obtain catalyst particles with the particle size of 40-60 meshes. The catalytic reaction conditions are as follows: the temperature of the catalytic reaction is 650 ℃, and the pressure is normal pressure; the total flow rate of the reaction was 66mL/min, where the flow rate ratio of the two gases CH4:CO21: 1.2; the space velocity is 55000 mL/(g.h).
Example 7
The embodiment provides a preparation method of a rod-shaped nano nickel-containing metal solid solution catalyst, which comprises the following steps:
5mmol of nickel nitrate and 10mmol of magnesium nitrate are weighed into a beaker, 18ml of deionized water is added, and the mixture is dissolved for 15 minutes at the temperature of 50 ℃ to obtain a first solution. And quickly transferring the first solution to a magnetic stirrer, stabilizing the temperature for 5min, and adding 0.9g of polyethylene glycol to react for 30min to obtain a second solution. 36ml of ethylene glycol was added to the second solution, and after 2 hours of reaction, a third solution was obtained. And transferring the third solution into a hydrothermal kettle, reacting for 18h at 165 ℃, cooling to room temperature, centrifuging the obtained solution, washing for 4 times by using ethanol and deionized water to obtain a light green precursor, uniformly grinding the precursor, and roasting for 3h at 650 ℃. And finally grinding the roasted body into fine powder, performing extrusion forming in a die under the pressure of 40kN, and crushing and screening to obtain catalyst particles with the particle size of 40-60 meshes. The catalytic reaction conditions are as follows: the temperature of the catalytic reaction is 650 ℃, and the pressure is normal pressure; the total flow rate of the reaction was 66mL/min, where the flow rate ratio of the two gases CH4:CO21: 1.2; the space velocity is 30000 mL/(g.h).
Example 8
The embodiment provides a preparation method of a rod-shaped nano nickel-containing metal solid solution catalyst, which comprises the following steps:
weighing 4mmol of nickel nitrate and 12mmol of magnesium nitrate, putting the nickel nitrate and the magnesium nitrate into a beaker, adding 25ml of deionized water, and dissolving the mixture for 15 minutes at the temperature of 50 ℃ to obtain a first solution. And quickly transferring the first solution to a magnetic stirrer, stabilizing the temperature for 5min, and adding 0.9g of polyethylene glycol to react for 30min to obtain a second solution. 45ml of ethylene glycol was added to the second solution, and after 1.5 hours of reaction, a third solution was obtained. Transferring the third solution into a hydrothermal kettle to react for 14h at the temperature of 170 ℃, and cooling toAfter room temperature, centrifuging the obtained solution, washing with ethanol and deionized water for 4 times to obtain a light green precursor, grinding the precursor uniformly, and roasting at 650 ℃ for 3 h. And finally grinding the roasted body into fine powder, performing extrusion forming in a die under the pressure of 40kN, and crushing and screening to obtain catalyst particles with the particle size of 40-60 meshes. The catalytic reaction conditions are as follows: the temperature of the catalytic reaction is 650 ℃, and the pressure is normal pressure; the total flow rate of the reaction was 66mL/min, where the flow rate ratio of the two gases CH4:CO21: 1.2; the space velocity was 65000 mL/(g.h).
Therefore, the invention effectively overcomes various defects in the prior art and has high industrial utilization value.
The foregoing embodiments are merely illustrative of the principles and utilities of the present invention and are not intended to limit the invention. Any person skilled in the art can modify or change the above-mentioned embodiments without departing from the spirit and scope of the present invention. Accordingly, it is intended that all equivalent modifications or changes which can be made by those skilled in the art without departing from the spirit and technical spirit of the present invention be covered by the claims of the present invention.

Claims (9)

1. A preparation method of a rod-shaped nano nickel-containing metal solid solution catalyst is characterized by comprising the following steps:
step 1), adding nickel salt, first metal salt and deionized water into a reaction vessel simultaneously, and uniformly mixing to obtain a first solution, wherein the first metal salt comprises one of magnesium salt, copper salt and iron salt;
step 2), stirring the first solution, adding one of surfactant polyethylene glycol and PVP after the temperature is stabilized for a period of time, and reacting to obtain a second solution;
step 3), adding organic solution ethylene glycol into the second solution, and stirring to obtain a third solution;
step 4), transferring the third solution into a hydrothermal kettle for reaction, washing the solution obtained by the reaction with an organic solvent and deionized water, and drying to obtain a precursor of the rodlike nano nickel-containing metal catalyst;
and 5) roasting the precursor of the rodlike nano nickel-containing metal catalyst to obtain the rodlike nano nickel-containing metal catalyst, wherein the length of the nano rodlike structure is 200-600 nm, and the width of the cross section is 30-70 nm.
2. The preparation method of the rod-shaped nanometer nickel-containing metal solid solution catalyst according to claim 1, wherein in the step 1), the molar ratio of the nickel salt to the first metal salt is 0.2-0.6: 1, the nickel salt and the first metal salt are nitrates or acetates, the temperature for uniform mixing is room temperature-70 ℃, and the holding time is 5-20 min.
3. The method for preparing a rod-shaped nano nickel-containing metal solid solution catalyst according to claim 1, wherein in the step 2), a magnetic stirrer is used for stirring the first solution, the rotating speed of the magnetic stirrer is 400-600 r/min, the temperature stabilizing time is 5-10 min, and the reaction time is 20-30 min.
4. The method for preparing a rod-shaped nano nickel-containing metal solid solution catalyst according to claim 1, wherein the reaction temperature in the step 4) is 150 ℃ to 200 ℃ and the reaction time is 12h to 18 h.
5. The method for preparing a rod-shaped nano nickel-containing metal solid solution catalyst according to claim 1, wherein in the step 4), the organic solvent used for washing is one or more of ethanol, chloroform and isopropanol.
6. The method for preparing a rod-shaped nano nickel-containing metal solid solution catalyst according to claim 1, wherein in the step 5), the roasting temperature is 550-750 ℃ and the roasting time is 2-8 h.
7. A rod-shaped nanometer nickel-containing metal solid solution catalyst prepared by the method of any one of claims 1 to 6, which is characterized in that: the nano rod-shaped structure is formed by nickel and a first metal solid solution, wherein the first metal comprises one of magnesium, copper and iron, the length of the nano rod-shaped structure is 200-600 nm, and the cross section width of the nano rod-shaped structure is 30-70 nm.
8. An application method of the rod-shaped nano nickel-containing metal solid solution catalyst prepared by the method of any one of claims 1 to 6 is characterized in that the rod-shaped nano nickel-containing metal solid solution catalyst is applied to a methane carbon dioxide reforming reaction, wherein the length of the nano rod-shaped structure is 200 to 600nm, and the cross section width is 30 to 70 nm.
9. The method for applying a rod-shaped nano nickel-containing metal solid solution catalyst according to claim 8, wherein: the temperature of the catalytic reaction is 550-750 ℃, the pressure is normal pressure, and the flow rate ratio CH of methane and carbon dioxide4:CO2＝1:1～2。
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