CN110743555B - Preparation method of nano porous metal nickel catalyst - Google Patents

Preparation method of nano porous metal nickel catalyst Download PDF

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CN110743555B
CN110743555B CN201910951628.2A CN201910951628A CN110743555B CN 110743555 B CN110743555 B CN 110743555B CN 201910951628 A CN201910951628 A CN 201910951628A CN 110743555 B CN110743555 B CN 110743555B
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nickel
zinc
concentration
porous metallic
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CN110743555A (en
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胡勋
亓敬波
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Lanzhou Institute of Chemical Physics LICP of CAS
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    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • 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
    • B01J23/755—Nickel
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J35/00—Catalysts, in general, characterised by their form or physical properties
    • B01J35/40—Catalysts, in general, characterised by their form or physical properties characterised by dimensions, e.g. grain size
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J35/00—Catalysts, in general, characterised by their form or physical properties
    • B01J35/60—Catalysts, in general, characterised by their form or physical properties characterised by their surface properties or porosity
    • B01J35/61—Surface area
    • B01J35/613—10-100 m2/g
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J35/00—Catalysts, in general, characterised by their form or physical properties
    • B01J35/60—Catalysts, in general, characterised by their form or physical properties characterised by their surface properties or porosity
    • B01J35/61—Surface area
    • B01J35/615—100-500 m2/g
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J35/00—Catalysts, in general, characterised by their form or physical properties
    • B01J35/60—Catalysts, in general, characterised by their form or physical properties characterised by their surface properties or porosity
    • B01J35/63—Pore volume
    • B01J35/633—Pore volume less than 0.5 ml/g
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J35/00—Catalysts, in general, characterised by their form or physical properties
    • B01J35/60—Catalysts, in general, characterised by their form or physical properties characterised by their surface properties or porosity
    • B01J35/64—Pore diameter
    • B01J35/647—2-50 nm
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J37/00—Processes, in general, for preparing catalysts; Processes, in general, for activation of catalysts
    • B01J37/0009—Use of binding agents; Moulding; Pressing; Powdering; Granulating; Addition of materials ameliorating the mechanical properties of the product catalyst
    • B01J37/0018—Addition of a binding agent or of material, later completely removed among others as result of heat treatment, leaching or washing,(e.g. forming of pores; protective layer, desintegrating by heat)

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  • Chemical & Material Sciences (AREA)
  • Engineering & Computer Science (AREA)
  • Materials Engineering (AREA)
  • Organic Chemistry (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Catalysts (AREA)

Abstract

The invention provides a preparation method of a nano porous metallic nickel catalyst, which is a method for preparing nano porous metallic nickel by reducing and deoxidizing a zinc template through high-temperature hydrogen. The NiO/ZnO composite metal oxide is prepared by a hydrothermal synthesis method, the obtained composite metal oxide is filtered, washed and dried to obtain a sample, and the sample is subjected to hydrogen reduction under a high-temperature condition to remove zinc oxide and synchronously reduce nickel oxide to obtain the nano porous metallic nickel catalyst. The nickel metal catalyst prepared by the method has smaller size, rich mesopores and larger specific surface area, does not need strong acid or strong alkali to remove the template, can realize the complete removal of the template, and avoids the corrosion to equipment and the pollution to the environment. In addition, the method can recover pure elemental zinc at the tail end of the reduction device, and the overall cost is reduced. The method provided by the invention has the advantages of abundant and cheap raw materials, simple and feasible preparation process, short production period, high yield, good repeatability and good application prospect.

Description

Preparation method of nano porous metal nickel catalyst
Technical Field
The invention relates to the technical field of preparation of nano catalysts, in particular to a preparation method of a nano porous metal nickel catalyst.
Background
Along with the continuous development and consumption of petrochemical resources, the utilization of heavy and inferior crude oil and the development of low-sulfur and low-nitrogen clean energy are more and more emphasized, and the key is to research an efficient hydrogenation catalytic system to refine and upgrade corresponding oil products. In addition, as a hot spot of current research, biomass resources have complex decomposition products, and further hydrofining is needed for both liquid fuels and platform compounds, so that the corresponding hydrocatalytic technology is urgently needed.
The most commonly used hydrogenation catalysts are metal catalysts, including supported metal catalysts and unsupported metal catalysts. The supported metal catalyst can disperse active components and improve the utilization rate of metal active centers. However, the upper limit of the activity is limited by the loading amount, and the problem that the active component is easy to fall off from the carrier and run off exists. Therefore, the unsupported metal catalyst still has a large proportion in the current industrial hydrogenation production. In order to improve the utilization rate and catalytic activity of metals, unsupported metal catalysts are generally prepared into nanoporous structures, among which skeletal metal catalysts are representative. The earliest skeletal metal catalyst was the skeletal nickel catalyst discovered by m.raney in 1925 and was therefore also named Raney nickel (Raney-Ni). Then, catalysts such as framework copper, framework cobalt and framework iron have been developed in succession and widely used in industrial production such as petrochemical industry and fine chemical industry. The skeletal metal catalyst is prepared by selecting corresponding metal aluminum alloy and removing part of aluminum by using a strong alkaline solution. The skeleton metal catalyst has rich pore structure and high hydrogenation activity. However, the porous metal material prepared by the alkali liquor etching dealloying method is difficult to regulate and control the particle size and the pore channel structure of metal, and has the problem that the active center is covered by residual metallic aluminum. In addition, the use of strong alkaline solutions also tends to cause corrosion of equipment and environmental pollution. In recent years, in order to obtain a metal catalyst having a smaller size and a higher specific surface area, many new synthesis processes have been developed in which a surfactant is added under a liquid phase condition, polymer micelles are utilized, and electrochemistry is performed. However, these synthetic methods are relatively complex and costly, and no industrial application is available at present.
Disclosure of Invention
The invention provides a preparation method of a nano porous metallic nickel catalyst, which is characterized in that metallic zinc oxide is used as a template agent, the template is removed by high-temperature hydrogen reduction, and nickel oxide is synchronously reduced to prepare the nano porous metallic nickel catalyst, so that the technical problems of complex synthesis method and high cost of the metallic catalyst in the prior art are solved.
The invention is realized by the following steps: the method comprises the following steps:
(1) sequentially adding a precursor of metal zinc, a precursor of metal nickel and alkali into deionized water to prepare a solution with a certain concentration, and magnetically stirring until the solution is fully dissolved to obtain a clear solution;
(2) transferring the solution obtained in the step (1) into a hydrothermal kettle for hydrothermal reaction, and filtering, washing and drying the product after the reaction is finished;
(3) and (3) putting the dried sample in the step (2) into a tubular furnace, introducing hydrogen, and reducing at high temperature.
As a preferred embodiment, in the step (1), the precursor of the metallic zinc is one of zinc nitrate hexahydrate, zinc acetate dihydrate, zinc sulfate heptahydrate and anhydrous zinc chloride.
As a preferred embodiment, the precursor of metallic zinc is zinc nitrate hexahydrate.
As a preferred embodiment, in the step (1), the precursor of the metallic nickel is one of nickel nitrate hexahydrate, nickel acetate tetrahydrate, nickel sulfate hexahydrate and nickel dichloride hexahydrate.
As a preferred embodiment, the precursor of the metallic nickel is nickel nitrate hexahydrate.
As a preferred embodiment, in the step (1), the base is one of urea, ammonia water, sodium carbonate, sodium bicarbonate, sodium hydroxide, potassium carbonate and potassium hydroxide.
As a preferred embodiment, in step (1), the base is urea.
As a preferred embodiment, Zn is contained in the solution obtained in the step (1)2+Has a concentration of 0.1 to 0.5mol/L, Ni2+The concentration of the alkali is 0.1-0.5 mol/L, the concentration of the alkali is 0.1-1 mol/L, and the addition amount of the deionized water is 50 mL.
As a preferred embodiment, Zn is contained in the solution obtained in the step (1)2+Concentration of (2) 0.2mol/L, Ni2+The concentration of (B) was 0.2mol/L and the concentration of the alkali was 0.8 mol/L.
As a preferred embodiment, the hydrothermal reaction in the step (2) is carried out at the temperature of 100-180 ℃ for 2-24 h, the hydrogen purity in the step (3) is 99.999%, the flow rate is 100mL/min, and the reduction is carried out at the temperature of 400-800 ℃ for 1-6 h, preferably 2 h.
The invention has the beneficial effects that: the invention has simple process, low cost, short production period, high yield and good repeatability. Compared with the prior art, the method can realize the complete removal of the template and avoid the corrosion and pollution of strong alkali. The obtained nano porous metallic nickel catalyst has small size of 18-106 nm, high specific surface area40～320m2The pore diameter is distributed uniformly, most of the pores are 12-38 nm mesopores, and the pore volume is larger and is 0.1-0.38 cm3The method is suitable for large-scale production, and has high economic value and market application value.
Detailed Description
For further disclosure, but not limitation, the present invention is described in further detail below with reference to examples.
Example 1
A preparation method of a nano-porous metallic nickel catalyst comprises the following steps:
(1) adding 10mmol of Zn (NO)3)2·6H2O、10mmol Ni(NO3)2·6H2O and 40mmol CO (NH)2)2Sequentially adding into a beaker filled with 50mL of deionized water, magnetically stirring for 30min to fully dissolve the deionized water to obtain a clear solution, and adding Zn into the clear solution2+Has a concentration of 0.2mol/L, Ni2+The concentration of (B) was 0.2mol/L and the concentration of the alkali was 0.8 mol/L.
(2) Transferring the solution to a hydrothermal reaction kettle with the capacity of 100mL, putting the reaction kettle into a constant-temperature drying oven, heating to 100 ℃, keeping for 18 hours, naturally cooling to room temperature, carrying out vacuum filtration on a sample, repeatedly washing the sample to be neutral by deionized water, and finally drying in the constant-temperature drying oven at 60 ℃.
(3) And (3) placing the dried sample in a tubular furnace, introducing flowing hydrogen at the flow rate of 100mL/min, heating to 700 ℃ at the speed of 5 ℃/min, preserving the temperature for 2h, cooling, collecting the sample, and sealing and storing.
The sample was observed by SEM and the particle size was counted, and the specific surface area and the pore size distribution of the sample were measured by BET specific surface area analyzer, and the average particle size, the total pore volume, the specific surface area, and the average pore size of the nanoporous nickel prepared in this example are shown in table 1.
Example 2
A preparation method of a nano-porous metallic nickel catalyst comprises the following steps:
(1) adding 6mmol of Zn (NO)3)2·6H2O、14mmol Ni(NO3)2·6H2O and 20mmol NaHCO3Sequentially adding into a beaker filled with 50mL of deionized water, magnetically stirring for 30min to fully dissolve the deionized water to obtain a clear solution, and adding Zn into the clear solution2+Has a concentration of 0.12mol/L, Ni2+The concentration of (3) was 0.28mol/L and the concentration of the base was 0.4 mol/L.
(2) Transferring the solution to a hydrothermal reaction kettle with the capacity of 100mL, putting the reaction kettle into a constant-temperature drying oven, heating to 140 ℃, keeping for 18h, naturally cooling to room temperature, carrying out vacuum filtration on a sample, repeatedly washing the sample with deionized water to be neutral, and finally drying in the constant-temperature drying oven at 60 ℃.
(3) And (3) placing the dried sample in a tubular furnace, introducing flowing hydrogen at the flow rate of 100mL/min, heating to 700 ℃ at the speed of 5 ℃/min, preserving heat for 1h, cooling, collecting the sample, and sealing and storing.
The sample was observed by SEM and the particle size was counted, and the specific surface area and the pore size distribution of the sample were measured by BET specific surface area analyzer, and the average particle size, the total pore volume, the specific surface area, and the average pore size of the nanoporous nickel prepared in this example are shown in table 1.
Example 3
A preparation method of a nano-porous metallic nickel catalyst comprises the following steps:
(1) 12mmol of Zn (CH)3COO)2·2H2O、8mmol Ni(NO3)2·6H2O and 50mmol Na2CO3Sequentially adding into a beaker filled with 50mL of deionized water, magnetically stirring for 30min to fully dissolve the deionized water to obtain a clear solution, and adding Zn into the clear solution2+Has a concentration of 0.24mol/L, Ni2+The concentration of (2) is 0.16mol/L and the concentration of the base is 1 mol/L.
(2) Transferring the solution to a hydrothermal reaction kettle with the capacity of 100mL, putting the reaction kettle into a constant-temperature drying oven, heating to 180 ℃ and keeping for 18 hours, then naturally cooling to room temperature, carrying out vacuum filtration on a sample, repeatedly washing the sample with deionized water to be neutral, and finally drying in the constant-temperature drying oven at 60 ℃.
(3) And (3) placing the dried sample in a tubular furnace, introducing flowing hydrogen at the flow rate of 100mL/min, heating to 600 ℃ at the speed of 5 ℃/min, preserving the temperature for 2h, cooling, collecting the sample, and sealing and storing.
The sample was observed by SEM and the particle size was counted, and the specific surface area and the pore size distribution of the sample were measured by BET specific surface area analyzer, and the average particle size, the total pore volume, the specific surface area, and the average pore size of the nanoporous nickel prepared in this example are shown in table 1.
Example 4
A preparation method of a nano-porous metallic nickel catalyst comprises the following steps:
(1) 15mmol of Zn (NO)3)2·6H2O、25mmol Ni(NO3)2·6H2Sequentially adding O and 5mmol NaOH into a beaker filled with 50mL of deionized water, magnetically stirring for 30min to fully dissolve the O and the 5mmol NaOH to obtain a clear solution, wherein Zn is contained in the clear solution2+Has a concentration of 0.3mol/L, Ni2+The concentration of (2) is 0.5mol/L and the concentration of the base is 0.1 mol/L.
(2) Transferring the solution to a hydrothermal reaction kettle with the capacity of 100mL, putting the reaction kettle into a constant-temperature drying oven, heating to 120 ℃, keeping the temperature for 18 hours, naturally cooling to room temperature, carrying out vacuum filtration on a sample, repeatedly washing the sample with deionized water to be neutral, and finally drying in the constant-temperature drying oven at 60 ℃.
(3) And (3) placing the dried sample in a tubular furnace, introducing flowing hydrogen at the flow rate of 100mL/min, heating to 800 ℃ at the speed of 5 ℃/min, preserving heat for 1h, cooling, collecting the sample, and sealing for storage.
The sample was observed by SEM and the particle size was counted, and the specific surface area and the pore size distribution of the sample were measured by BET specific surface area analyzer, and the average particle size, the total pore volume, the specific surface area, and the average pore size of the nanoporous nickel prepared in this example are shown in table 1.
Example 5
A preparation method of a nano-porous metallic nickel catalyst comprises the following steps:
(1) adding 25mmol of Zn (NO)3)2·6H2O、5mmol Ni(CH3COO)2·4H2O and 30mmol K2CO3Sequentially adding into a beaker filled with 50mL of deionized water, magnetically stirring for 30min to fully dissolve the deionized water to obtain a clear solution, and adding Zn into the clear solution2+The concentration of (b) is 0.5mol/L, Ni2+The concentration of (B) was 0.1mol/L and the concentration of the alkali was 0.6 mol/L.
(2) Transferring the solution to a hydrothermal reaction kettle with the capacity of 100mL, putting the reaction kettle into a constant-temperature drying oven, heating to 120 ℃, keeping the temperature for 18 hours, naturally cooling to room temperature, carrying out vacuum filtration on a sample, repeatedly washing the sample with deionized water to be neutral, and finally drying in the constant-temperature drying oven at 60 ℃.
(3) And (3) placing the dried sample in a tubular furnace, introducing flowing hydrogen at the flow rate of 100mL/min, heating to 500 ℃ at the speed of 5 ℃/min, preserving the temperature for 4h, cooling, collecting the sample, and sealing and storing.
The sample was observed by SEM and the particle size was counted, and the specific surface area and the pore size distribution of the sample were measured by BET specific surface area analyzer, and the average particle size, the total pore volume, the specific surface area, and the average pore size of the nanoporous nickel prepared in this example are shown in table 1.
Example 6
A preparation method of a nano-porous metallic nickel catalyst comprises the following steps:
(1) 20mmol of ZnCl2、18mmol NiCl2·6H2Sequentially adding O and 20mmol KOH into a beaker filled with 50mL deionized water, and magnetically stirring for 30min to fully dissolve the O and the KOH to obtain a clear solution, wherein Zn is contained in the clear solution2+Has a concentration of 0.4mol/L, Ni2+The concentration of (2) was 0.36mol/L and the concentration of the base was 0.4 mol/L.
(2) Transferring the solution to a hydrothermal reaction kettle with the capacity of 100mL, putting the reaction kettle into a constant-temperature drying oven, heating to 160 ℃, keeping the temperature for 18 hours, naturally cooling to room temperature, carrying out vacuum filtration on a sample, repeatedly washing the sample with deionized water to be neutral, and finally drying in the constant-temperature drying oven at 60 ℃.
(3) And (3) placing the dried sample in a tubular furnace, introducing flowing hydrogen at the flow rate of 100mL/min, heating to 700 ℃ at the speed of 5 ℃/min, preserving the temperature for 4h, cooling, collecting the sample, and sealing and storing.
Example 7
A preparation method of a nano-porous metallic nickel catalyst comprises the following steps:
(4) adding 10mmol of ZnSO4·7H2O、15mmol NiSO4·6H2O and 45mmol NH3·H2Sequentially adding O into a beaker filled with 50mL of deionized water, and magnetically stirring for 30min to fully dissolve O to obtain a clear solution, wherein Zn is contained in the clear solution2+Has a concentration of 0.2mol/L, Ni2+The concentration of (B) was 0.3mol/L and the concentration of the alkali was 0.9 mol/L.
(5) Transferring the solution to a hydrothermal reaction kettle with the capacity of 100mL, putting the reaction kettle into a constant-temperature drying oven, heating to 160 ℃, keeping the temperature for 18 hours, naturally cooling to room temperature, carrying out vacuum filtration on a sample, repeatedly washing the sample with deionized water to be neutral, and finally drying in the constant-temperature drying oven at 60 ℃.
(6) And (3) placing the dried sample in a tubular furnace, introducing flowing hydrogen at the flow rate of 100mL/min, heating to 700 ℃ at the speed of 5 ℃/min, preserving heat for 6h, cooling, collecting the sample, and sealing and storing.
The sample was observed by SEM and the particle size was counted, and the specific surface area and the pore size distribution of the sample were measured by BET specific surface area analyzer, and the average particle size, the total pore volume, the specific surface area, and the average pore size of the nanoporous nickel prepared in this example are shown in table 1.
TABLE 1 average particle diameter, total pore volume, specific surface area and average pore diameter of catalysts of examples 1-7
Figure BDA0002224874020000061
The particle size, pore volume, specific surface area and average pore size of the nanoporous nickel catalysts obtained in the examples listed in the present invention are shown in table 1. As can be seen from table 1, nanoporous nickel metals can be obtained in all of examples 1 to 7 of the present invention. By comparison, the nanoporous nickel prepared under the conditions of example 1 has the smallest size, the largest specific surface area, and the optimal pore structure.
The invention has the beneficial effects that: the invention has simple process, low cost, short production period, high yield and good repeatability. Compared with the prior art, the method can realize the complete removal of the template and avoid the corrosion and pollution of strong alkali. The obtained nano porous metallic nickel catalyst rulerSmall size of 18-106 nm, high specific surface area of 40-320 m2The pore diameter is distributed uniformly, most of the pores are 12-38 nm mesopores, and the pore volume is larger and is 0.1-0.38 cm3The method is suitable for large-scale production, and has high economic value and market application value.
The above description is only for the purpose of illustrating the preferred embodiments of the present invention and is not to be construed as limiting the invention, and any modifications, equivalents, improvements and the like that fall within the spirit and principle of the present invention are intended to be included therein.

Claims (8)

1. A preparation method of a nano-porous metallic nickel catalyst is characterized by comprising the following steps:
(1) sequentially adding a precursor of metal zinc, a precursor of metal nickel and alkali into deionized water to prepare a solution with a certain concentration, and magnetically stirring until the solution is fully dissolved to obtain a clear solution;
(2) transferring the solution obtained in the step (1) into a hydrothermal kettle for hydrothermal reaction, and filtering, washing and drying the product after the reaction is finished;
(3) and (3) putting the dried sample in the step (2) into a tubular furnace, introducing hydrogen, and reducing at high temperature.
2. The method for preparing a nano-porous metallic nickel catalyst according to claim 1, wherein in the step (1), the precursor of the metallic zinc is one of zinc nitrate hexahydrate, zinc acetate dihydrate, zinc sulfate heptahydrate and anhydrous zinc chloride.
3. The method of claim 2, wherein the zinc metal precursor is zinc nitrate hexahydrate.
4. The method for preparing a nano-porous metallic nickel catalyst according to claim 1, wherein in the step (1), the precursor of metallic nickel is one of nickel nitrate hexahydrate, nickel acetate tetrahydrate, nickel sulfate hexahydrate and nickel dichloride hexahydrate.
5. The method of claim 4, wherein the precursor of the metal nickel is nickel nitrate hexahydrate.
6. The method for preparing a nano-porous metallic nickel catalyst according to any one of claims 1 to 5, wherein Zn is contained in the solution obtained in the step (1)2+ Has a concentration of 0.1 to 0.5mol/L, Ni2+ The concentration of the alkali is 0.1-0.5 mol/L, the concentration of the alkali is 0.1-1 mol/L, and the addition amount of the deionized water is 50 ml.
7. The method for preparing a nano-porous metallic nickel catalyst according to claim 6, wherein Zn in the solution obtained in the step (1)2+ Has a concentration of 0.2mol/L, Ni2+ The concentration of (B) is 0.2mol/L and the concentration of the alkali is 0.8 mol/L.
8. The preparation method of the nano-porous metallic nickel catalyst according to claim 5, wherein the hydrothermal reaction in the step (2) is performed at a temperature of 100 ℃ to 180 ℃ for 2 to 24 hours, the hydrogen purity in the step (3) is 99.999%, the flow rate is 100mL/min, and the reduction is performed at a temperature of 400 ℃ to 800 ℃ for 1 to 6 hours.
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