CN114904528B - Ordered mesoporous nickel-based magnesium gallium spinel methanation catalyst and preparation method and application thereof - Google Patents

Ordered mesoporous nickel-based magnesium gallium spinel methanation catalyst and preparation method and application thereof Download PDF

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CN114904528B
CN114904528B CN202210308431.9A CN202210308431A CN114904528B CN 114904528 B CN114904528 B CN 114904528B CN 202210308431 A CN202210308431 A CN 202210308431A CN 114904528 B CN114904528 B CN 114904528B
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韩亚红
裴玉娇
袁铂江
刘建路
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Shandong Haihua Group Co Ltd
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Abstract

The invention discloses an ordered mesoporous nickel-based magnesium gallium spinel methanation catalyst, a preparation method and application thereof, wherein metal Ni is used as an active component, and ordered mesoporous MgGa is used as an active component 2 O 4 The metal Ni is used as a carrier, and the loading of the metal Ni is 10-30 wt%. First MgGa 2 O 4 The catalyst has the characteristics of high temperature resistance and small thermal expansion coefficient, and has strong binding force with metal, and the catalyst can be used as a carrier to exert excellent thermal stability in a high-temperature catalyst bed, so that sintering of the catalyst is effectively avoided, and good catalytic performance is maintained. Next, mgGa in the present invention 2 O 4 The catalyst has the characteristics of ordered mesoporous structure and large specific surface area, and not only can the ordered mesoporous structure protect active species, but also plays a role in limiting the domain, inhibit the agglomeration of nickel particles and the growth of carbon species and avoid the inactivation of the catalyst; and MgGa 2 O 4 The larger specific surface area is beneficial to dispersing active metals, reducing the size of nickel particles, improving the dispersity of nickel and further improving the catalytic activity.

Description

Ordered mesoporous nickel-based magnesium gallium spinel methanation catalyst and preparation method and application thereof
Technical Field
The invention relates to an ordered mesoporous nickel-based magnesium gallium spinel methanation catalyst and a preparation method and application thereof, and belongs to the technical field of preparation and application of catalysts for preparing synthetic natural gas from coal.
Background
The technology of preparing natural gas from coal is not only an effective way for improving clean utilization of coal, but also can meet the rapidly-increasing demand of natural gas. Methanation is a core process of coal-to-natural gas technology, and design and synthesis of methanation catalysts are paid attention as key points of methanation. It is well known that the CO methanation reaction is a strongly exothermic reaction, and that higher catalyst bed temperatures tend to cause sintering and carbon deposition of the catalyst, leading to deactivation of the catalyst. Therefore, the development of the catalyst with excellent low-temperature activity and high-temperature stability has important significance and broad prospect.
Methanation processes in industry are generally carried out under loadThe metal type catalyst is mainly, the Ni-based catalyst has low price and excellent activity, and can be widely applied, and meanwhile, the selection of the carrier plays a vital role in the reaction. Previous studies have shown that the dispersity of the active metal is an important factor affecting the activity of the catalyst, and the high dispersity can increase the area of the active metal, thereby being beneficial to improving the catalytic activity. The ordered mesoporous structure carrier is an effective means for realizing high dispersity of active components, and meanwhile, the limiting domain can effectively inhibit agglomeration of metals and prevent the metals from being stripped by carbon deposition, so that sintering and carbon deposition of the catalyst are avoided, and the stability of the catalyst is improved. Therefore, ordered mesoporous materials are attracting attention in the field of catalysis due to their large specific surface area and regular pore structure. Chinese patent No. CN110339856A discloses mesoporous SiO 2 Molecular sieve KIT-6 as carrier and metal Ni as active component to prepare catalyst for CO methanation reaction and SiO 2 The mesoporous structure of the molecular sieve plays a role in limiting the domain and provides a larger specific surface area, which is helpful for improving the dispersity of nickel particles and further improving the catalytic activity, but SiO 2 The surface is inert, the chemical property is inactive, the anchoring of metal particles is not facilitated, and therefore, the nickel-based SiO 2 The catalyst has certain limitations.
Disclosure of Invention
The invention aims to solve the technical problem of providing an ordered mesoporous nickel-based magnesium gallium spinel methanation catalyst with strong metal-carrier interaction force, high dispersity and excellent methanation high-temperature stability, and a preparation method and application thereof.
In order to solve the technical problems, the catalyst of the invention comprises: ordered mesoporous MgGa with metal Ni as active component 2 O 4 The metal Ni is used as a carrier, and the loading of the metal Ni is 10-30 wt%.
The ordered mesoporous MgGa 2 O 4 Is 200 to 500 and 500 m 2 And/g, the pore diameter is 4-10 nm.
The Ni/MgGa 2 O 4 The specific surface area of the catalyst is 260-450 m 2 And/g, the pore diameter is 3.5-8 nm.
The preparation method of the invention comprises the following steps:
(1) Preparation of ordered mesoporous MgGa 2 O 4
Dissolving nonionic surfactant in solvent to obtain solution, and adding Ga (NO) 3 ) 3 •9H 2 O and magnesium salt react to obtain transparent viscous liquid, and then the transparent viscous liquid is aged, dried and roasted in inert gas atmosphere to obtain ordered mesoporous MgGa 2 O 4 ；
(2) Preparation of Ni/MgGa 2 O 4 Catalyst
Ni (NO) 3 ) 2 •6H 2 O is dissolved in deionized water, mgGa obtained in the step (1) is added 2 O 4 Stirring, ultrasonic drying, evaporating in water bath, and adding N 2 Roasting in atmosphere to obtain Ni/MgGa 2 O 4 A catalyst.
The nonionic surfactant is at least one of P123 and F127, and can be removed in the roasting process of the carrier. In the preparation process of the carrier, a surfactant is added, and an ordered mesoporous structure is formed by a self-assembly mode induced by evaporation.
The solvent in the step (1) is at least one of deionized water, methanol, ethanol and acetone.
The inert gas in the step (1) comprises at least one of argon and helium.
In the step (1) described above, the step of (c) is performed,
the aging temperature is 30-50 ℃, and the aging time is 100-140 h;
the drying temperature is 60-100 ℃ and the drying time is 8-12 h;
the flow rate of inert gas in the roasting atmosphere is 60-100 mL/min, the roasting temperature is 500-800 ℃, and the roasting time is 4-6 h;
in the step (2), the step of (c),
the water bath evaporation temperature is 60-90 ℃;
roasting atmosphere N 2 The flow rate of the water is 60-100 mL/min; the roasting temperature is 400-600 ℃, and the roasting time is 1.5-3 h.
The magnesium salt in the step (1) is magnesium chloride or magnesium nitrate.
The molar ratio of the elemental gallium to the elemental magnesium in the step (1) is 1:2.
The ordered mesoporous MgGa obtained in the step (1) 2 O 4 I.e. ordered mesoporous Kong Meijia spinel.
The Ni/MgGa obtained in the step (2) 2 O 4 The catalyst is an ordered mesoporous nickel-based magnesium gallium spinel catalyst.
The catalyst obtained in the step (2) has different metal Ni loading amounts according to the surfactant, magnesium salt type and final product adopted in the preparation process, and comprises the following structural forms: 10Ni/MgGa 2 O 4 -P-Cl，10Ni/MgGa 2 O 4 -F-Cl，10Ni/MgGa 2 O 4 -P-N，30Ni/MgGa 2 O 4 P-Cl, wherein the number indicates the metal loading, F, P indicates the surfactant employed, and Cl, N indicates the magnesium salt species employed.
The invention also provides an application of the ordered mesoporous nickel-based magnesium gallium spinel methanation catalyst in CO methanation reaction.
The application of the ordered mesoporous nickel-based magnesium gallium spinel methanation catalyst in the CO methanation reaction comprises the following reaction conditions: the temperature is 200-600 ℃, the pressure is 0.1-3.0 MPa, the mass airspeed is 10000-60000 mL h −1 g −1 。
Compared with the prior art, the invention has obvious advancement, and the invention uses MgGa with high temperature resistance and small thermal expansion coefficient 2 O 4 The catalyst is synthesized by loading metal Ni on a carrier, the synthesized catalyst has the characteristic of strong metal-carrier interaction force, excellent thermal stability is exerted in a high-temperature catalyst bed, sintering of the catalyst is effectively avoided, and good catalytic performance is maintained.
The preparation method of the invention, mgGa 2 O 4 The catalyst has the characteristics of ordered mesoporous structure and large specific surface area, and not only can the ordered mesoporous structure protect active species, but also plays a role in limiting the domain, inhibit the agglomeration of nickel particles and the growth of carbon species and avoid the inactivation of the catalyst; and MgGa 2 O 4 The larger specific surface area is beneficial to dispersing active metals, reducing the size of nickel particles, improving the dispersity of nickel and further improving the catalytic activity.
The preparation method adopts a soft template method to prepare ordered mesoporous MgGa 2 O 4 Simple process, and the obtained MgGa 2 O 4 The electron microscope image (figure 1) shows that the electron microscope image is a white solid and has a regularly arranged pore canal structure; and the product purity is high, the XRD result (figure 2) shows that the product purity is high at 2 theta=18.5 o ，30.5 o ，35.9 o ，37.6 o ，43.7 o ，54.2 o ，57.8 o ，63.5 o ，72.1 o ，75.2 o ，76.2 o ，80.2 o Diffraction peaks at the positions are ordered mesoporous MgGa 2 O 4 The characteristic peak of the (C) is not provided with other diffraction peaks, and the structure is stable; in addition, at t=600 ℃, p=1 mpa, whsv=15000 mL h −1 g −1 For 10Ni/MgGa 2 O 4 The life test of 100 h was carried out on the P-Cl catalyst, and the reaction results are shown in Table 1, and the results show that the catalyst is hardly deactivated, thus indicating that the catalyst has excellent performance and is a very ideal method for rapidly preparing the high-stability methanation catalyst.
Figure SMS_1
Drawings
The invention is further illustrated by the following examples in conjunction with the accompanying drawings:
FIG. 1 shows the synthesis of ordered mesoporous MgGa 2 O 4 Is a transmission electron microscope image;
FIG. 2 shows the synthesis of ordered mesoporous MgGa 2 O 4 Is a XRD pattern of (C).
Detailed Description
In order to make the objects, technical solutions and the effects of the present invention clearer, the technical solutions of the present invention will be described in detail below. It will be apparent that the described embodiments are only some, but not all, embodiments of the invention. All other embodiments, based on the examples herein, which are within the scope of the invention as defined by the claims, will be within the scope of the invention as defined by the claims.
The chemical materials used in the invention are as follows: gallium nitrate, magnesium chloride, magnesium nitrate, nickel nitrate, P123, F127, methanol, ethanol, acetone, deionized water, nitrogen, argon, carbon monoxide, and hydrogen.
Gallium nitrate: ga (NO) 3 ) 3 ·9H 2 O 100.00 g±0.01 g
Magnesium chloride: mgCl 6 ·6H 2 O 100.00 g ±0.01 g
Magnesium nitrate: mg (NO) 3 ) 2 •6H 2 O 100.00 g ±0.01 g
Nickel nitrate: ni (NO) 3 ) 2 ·6H 2 O 100.00g±0.01 g
P123： 100.00g±0.01 g
F127： 100.00g±0.01 g
Methanol: CH (CH) 3 OH 1000.00 ml±0.01 ml
Ethanol: c (C) 2 H 5 OH 1000.00 ml±0.01 ml
Acetone: CH (CH) 3 COCH 3 1000.00 ml±0.01 ml
Deionized water: h 2 O 1000.00 ml±0.01 ml
Nitrogen gas: n (N) 2 10000cm 3 ±100 cm 3
Argon: ar 10000cm 3 ±100 cm 3
Carbon monoxide: CO10000cm 3 ±100 cm 3
Hydrogen gas: h 2 10000cm 3 ±100 cm 3
And (3) refining the chemical materials: the chemical materials needed by the preparation are carefully selected, and the quality and purity are controlled:
gallium nitrate: solid solids 98.5%
Magnesium chloride: solid solids 98.5%
Magnesium nitrate: solid solids 98.5%
Nickel nitrate: solid solids 98.5%
P123: solid solids 98.5%
F127: solid solids 98.5%
Methanol: 99.5% of liquid
Ethanol: 99.5% of liquid
Acetone: 99.5% of liquid
Deionized water: 99.5% of liquid
Nitrogen gas: gaseous gas 99.9%
Argon: gaseous gas 99.9%
Carbon monoxide: gaseous gas 99.9%
Hydrogen gas: 99.9% of gaseous gas.
Example 1
The preparation method of the ordered mesoporous nickel-based magnesium gallium spinel methanation catalyst comprises the following steps of:
(1) Preparation of ordered mesoporous Kong Meijia spinel
Weighing 3.0000 g +/-0.0001 g surfactant P123, dissolving in 30 g ethanol, and stirring in a water bath kettle at 35 ℃ until dissolving;
5.1148 g + -0.0001 g Ga (NO) 3 ) 3 ·9H 2 O and MgCl in corresponding molar quantity 6 ·6H 2 Adding O into the solution, and continuously stirring to obtain transparent viscous liquid;
the resulting viscous liquid was poured into a glass dish and placed in an oven at 40 ℃ for aging 120 h. Transferring the glass dish to an 80 ℃ oven for drying 10 h to obtain a honeycomb precursor;
taking out the sample by using a medicine spoon, grinding, placing the sample into a quartz boat, placing under a furnace chamber thermocouple of a tube furnace, introducing Ar at a flow rate of 60 mL/min, heating the set temperature to 700 ℃ from room temperature at a rate of 2 ℃/min, keeping the temperature at a constant temperature of 5 h, cooling, taking out after the temperature is cooled to the room temperature, and obtaining the white ordered medium Kong Meijia spinel, collecting the white ordered medium Kong Meijia spinel by using a sample bag, and placing the white ordered medium Kong Meijia spinel in a dryer for storage.
The obtained ordered mesoporous MgGa 2 O 4 Is 500 m in specific surface area 2 /g, pore size 10 nm.
(2) Preparation of nickel-based magnesium gallium spinel catalyst
1.096+ -0.001. 0.001 g Ni (NO) 3 ) 2 ·6H 2 Placing the O solid in a beaker of 100 mL, adding 50 mL deionized water, and stirring until the O solid is completely dissolved into nickel nitrate water solution;
weighing 2. g + -0.0001 g MgGa 2 O 4 Adding into the solution, stirring for 30 min, transferring into an ultrasonic cleaner, performing ultrasonic treatment for 30 min, transferring the beaker into a water bath, heating the water bath to 80 ℃, and continuously stirring until all the liquid is completely evaporated to obtain light blue solid;
grinding the obtained sample, transferring to a quartz boat, placing the quartz boat in the central position of a hearth of a tube furnace, and introducing N at a flow rate of 80 mL/min 2 Raising the temperature from room temperature to 550 ℃ at the speed of 2 ℃/min, keeping the temperature at 2 h, reducing the temperature, closing the gas after the temperature is reduced to the room temperature, taking out the sample, and obtaining the gray solid catalyst 10Ni/MgGa 2 O 4 P-Cl (10 means metal Ni loading of 10 wt%, P means surfactant P123, cl means magnesium salt MgCl) 6 ·6H 2 O）。
The obtained ordered mesoporous nickel-based magnesium gallium spinel methanation catalyst has the metal Ni loading of 10 wt percent and the specific surface area of 450 m 2 /g, pore size 8 nm.
Example 2
(1) Preparation of ordered mesoporous Kong Meijia spinel
Weighing 3.0000 g +/-0.0001 g surfactant F127, dissolving in 30 g methanol, and stirring in a water bath kettle at 35 ℃ until the surfactant F127 is dissolved;
5.1148 g + -0.0001 g Ga (NO) 3 ) 3 ·9H 2 O and MgCl in corresponding molar quantity 6 ·6H 2 Adding O into the solution, and continuously stirring to obtain transparent viscous liquid;
the resulting viscous liquid was poured into a glass dish and placed in a 30 ℃ oven for aging 140, h. Transferring the glass dish to a 60 ℃ oven for drying 12 h to obtain a honeycomb precursor;
taking out the sample by using a medicine spoon, grinding, placing the sample into a quartz boat, placing under a thermocouple of a furnace chamber of a tube furnace, introducing Ar at a flow rate of 80 mL/min, heating the set temperature to 500 ℃ from room temperature at a rate of 2 ℃/min, keeping the temperature at a constant temperature of 6 h, cooling, taking out after the temperature is cooled to the room temperature, and obtaining the white ordered medium Kong Meijia spinel, collecting the white ordered medium Kong Meijia spinel by using a sample bag, and placing the white ordered medium Kong Meijia spinel in a dryer for storage.
The obtained ordered mesoporous MgGa 2 O 4 Is 325 m 2 /g, pore size 5.3. 5.3 nm.
(2) Preparation of nickel-based magnesium gallium spinel catalyst
1.096+ -0.001. 0.001 g Ni (NO) 3 ) 2 ·6H 2 Placing the O solid in a beaker of 100 mL, adding 50 mL deionized water, and stirring until the O solid is completely dissolved into nickel nitrate water solution;
weighing 2. g + -0.0001 g MgGa 2 O 4 Adding into the solution, stirring for 30 min, transferring into an ultrasonic cleaner, performing ultrasonic treatment for 30 min, transferring the beaker into a water bath, heating the water bath to 60 ℃, and continuously stirring until all the liquid is completely evaporated to obtain light blue solid;
grinding the obtained sample, transferring to a quartz boat, placing the quartz boat in the central position of a hearth of a tube furnace, and introducing N at a flow rate of 80 mL/min 2 Raising the temperature from room temperature to 600 ℃ at the speed of 2 ℃/min, keeping the temperature at 1.5 and h, reducing the temperature, closing the gas after the temperature is reduced to the room temperature, taking out the sample, and obtaining the gray solid catalyst 10Ni/MgGa 2 O 4 F-Cl (10 means a metal Ni loading of 10 wt%, F means a surface)The active agent F127, cl represents magnesium salt MgCl 6 ·6H 2 O）。
The obtained ordered mesoporous nickel-based magnesium gallium spinel methanation catalyst has the metal Ni loading of 10 wt percent and the specific surface area of 300 m 2 /g, pore size 4.5. 4.5 nm.
Example 3
(1) Preparation of ordered mesoporous Kong Meijia spinel
Weighing 3.0000 g +/-0.0001 g surfactant P123, dissolving in 30 g ethanol, and stirring in a water bath kettle at 35 ℃ until dissolving;
5.1148 g + -0.0001 g Ga (NO) 3 ) 3 ·9H 2 O and corresponding molar amount of Mg (NO 3 ) 2 •6H 2 Adding O into the solution, and continuously stirring to obtain transparent viscous liquid;
the resulting viscous liquid was poured into a glass dish and placed in a 50 ℃ oven for aging 100 h. Transferring the glass dish to an 80 ℃ oven for drying 10 h to obtain a honeycomb precursor;
taking out the sample by using a medicine spoon, grinding, placing the sample into a quartz boat, placing under a furnace chamber thermocouple of a tube furnace, introducing He at a flow rate of 60 mL/min, heating the set temperature to 800 ℃ from room temperature at a rate of 2 ℃/min, keeping the temperature at a constant temperature of 4 h, cooling, taking out after the temperature is cooled to the room temperature, and obtaining the white ordered medium Kong Meijia spinel, collecting the white ordered medium Kong Meijia spinel by using a sample bag, and placing the white ordered medium Kong Meijia spinel in a dryer for storage.
The obtained ordered mesoporous MgGa 2 O 4 Is 356 m in specific surface area 2 /g, pore size 5.9. 5.9 nm.
(2) Preparation of nickel-based magnesium gallium spinel catalyst
1.096+ -0.001. 0.001 g Ni (NO) 3 ) 2 ·6H 2 Placing the O solid in a beaker of 100 mL, adding 50 mL deionized water, and stirring until the O solid is completely dissolved into nickel nitrate water solution;
weighing 2. g + -0.0001 g MgGa 2 O 4 Adding into the above solution, stirring for 30 min, transferring to ultrasonic cleaning machine, ultrasonic treating for 30 min, transferring beaker into water bath, heating water bath to 90deg.C, and stirring to obtain all liquidCompletely evaporating to obtain light blue solid;
grinding the obtained sample, transferring to a quartz boat, placing the quartz boat in the central position of the hearth of the tubular furnace, and introducing N at a flow rate of 100 mL/min 2 Raising the temperature from room temperature to 400 ℃ at the speed of 2 ℃/min, keeping the temperature at 3 h, reducing the temperature, closing the gas after the temperature is reduced to the room temperature, taking out the sample, and obtaining the gray solid catalyst 10Ni/MgGa 2 O 4 P-N (10 means a metal Ni loading of 10 wt%, P means a surfactant P123, N means magnesium salt Mg (NO) 3 ) 2 •6H 2 O）。
The obtained ordered mesoporous nickel-based magnesium gallium spinel methanation catalyst has the metal Ni loading of 10 wt percent and the specific surface area of 325 m 2 /g, pore size 5.1. 5.1 nm.
Example 4
(1) Preparation of ordered mesoporous Kong Meijia spinel
Weighing 3.0000 g +/-0.0001 g surfactant P123, dissolving in 30 g ethanol, and stirring in a water bath kettle at 35 ℃ until dissolving;
5.1148 g + -0.0001 g Ga (NO) 3 ) 3 ·9H 2 O and MgCl in corresponding molar quantity 6 ·6H 2 Adding O into the solution, and continuously stirring to obtain transparent viscous liquid;
the resulting viscous liquid was poured into a glass dish and placed in an oven at 40 ℃ for aging 120 h. Transferring the glass dish to a 100 ℃ oven for drying 8 h to obtain a honeycomb precursor;
taking out the sample by using a medicine spoon, grinding, placing the sample into a quartz boat, placing under a furnace chamber thermocouple of a tube furnace, introducing He at a flow rate of 60 mL/min, heating the set temperature to 600 ℃ from room temperature at a rate of 2 ℃/min, keeping the temperature at a constant temperature of 5 h, cooling, taking out after the temperature is cooled to the room temperature, and obtaining the white ordered medium Kong Meijia spinel, collecting the white ordered medium Kong Meijia spinel by using a sample bag, and placing the white ordered medium Kong Meijia spinel in a dryer for storage.
The obtained ordered mesoporous MgGa 2 O 4 Is 386 m 2 /g, pore size 6.1. 6.1 nm.
(2) Preparation of nickel-based magnesium gallium spinel catalyst
Weighing 3.288 + -0.001 g Ni (NO) 3 ) 2 ·6H 2 Placing the O solid in a beaker of 100 mL, adding 50 mL deionized water, and stirring until the O solid is completely dissolved into nickel nitrate water solution;
weighing 2. g + -0.0001 g MgGa 2 O 4 Adding into the solution, stirring for 30 min, transferring into an ultrasonic cleaner, performing ultrasonic treatment for 30 min, transferring the beaker into a water bath, heating the water bath to 80 ℃, and continuously stirring until all the liquid is completely evaporated to obtain light blue solid;
grinding the obtained sample, transferring to a quartz boat, placing the quartz boat in the central position of a hearth of a tube furnace, and introducing N at a flow rate of 80 mL/min 2 Raising the temperature from room temperature to 550 ℃ at the speed of 2 ℃/min, keeping the temperature at 2 h, reducing the temperature, closing the gas after the temperature is reduced to the room temperature, taking out the sample, and obtaining the gray solid catalyst 30Ni/MgGa 2 O 4 P-Cl (30 means a metal Ni loading of 30 wt%, P means a surfactant P123, cl means magnesium salt MgCl) 6 ·6H 2 O）。
The obtained ordered mesoporous nickel-based magnesium gallium spinel methanation catalyst has the loading of metal Ni of 30-wt percent and MgGa 2 O 4 Is 295 and 295 m 2 /g, pore size 4.5. 4.5 nm.
Example 5
The catalysts prepared in examples 1 to 4 were applied to CO methanation, and the specific steps are as follows: putting a proper amount of catalyst into a tabletting mold, placing the tabletting mold on a tabletting machine, increasing the pressure to 20 MPa, pressing for 20 min, taking out a pressed sample, crushing, and sieving to obtain a 40-60-mesh catalyst; the catalyst after 0.4. 0.4 g granulation was weighed and put into a reactor to evaluate the activity of CO methanation. First, H is introduced at a rate of 20 ml/min 2 Raising the temperature from room temperature to 550 ℃ at the speed of 2 ℃/min, keeping the temperature at 2H for in-situ reduction, then reducing the temperature to the reaction temperature, and switching to H 2 And (3) performing CO methanation reaction on the CO mixed gas. Reaction conditions: t=200 to 600 ℃, p=1 mpa, whsv=15000 mL h −1 g −1 The reaction results are shown in Table 2.
Figure SMS_2

Claims (6)

1. Ordered mesoporous Ni/MgGa 2 O 4 A methanation catalyst, characterized in that: ordered mesoporous MgGa with metal Ni as active component 2 O 4 The metal Ni is used as a carrier, and the loading capacity of the metal Ni is 10-30 wt%; the ordered mesoporous MgGa 2 O 4 Has a specific surface area of 300 to 500 m 2 /g, pore diameter is 4-10 nm;
the ordered mesoporous Ni/MgGa 2 O 4 The preparation method of the methanation catalyst comprises the following steps:
(1) Preparation of ordered mesoporous MgGa 2 O 4
Dissolving nonionic surfactant in solvent to obtain solution, and adding Ga (NO) 3 ) 3 •9H 2 O and magnesium salt react to obtain transparent viscous liquid, and then the transparent viscous liquid is aged, dried and roasted in inert gas atmosphere to obtain ordered mesoporous MgGa 2 O 4 ；
(2) Preparation of Ni/MgGa 2 O 4 Catalyst
Ni (NO) 3 ) 2 •6H 2 O is dissolved in deionized water, mgGa obtained in the step (1) is added 2 O 4 Stirring, ultrasonic drying, evaporating in water bath, and adding N 2 Roasting in atmosphere to obtain Ni/MgGa 2 O 4 A catalyst;
in the step (1), the magnesium salt is magnesium chloride or magnesium nitrate; the aging temperature is 30-50 ℃, and the aging time is 100-140 h; the drying temperature is 60-100 ℃ and the drying time is 8-12 h; the flow rate of inert gas in the roasting atmosphere is 60-100 mL/min, the roasting temperature is 500-800 ℃, and the roasting time is 4-6 h;
in the step (2), the water bath evaporation temperature is 60-90 ℃; roasting atmosphere N 2 The flow rate of the water is 60-100 mL/min; the roasting temperature is 400-600 ℃, and the roasting time is 1.5-3 h.
2. The ordered mesoporous Ni/MgGa according to claim 1 2 O 4 A methanation catalyst, characterized in that: the Ni/MgGa 2 O 4 The specific surface area of the methanation catalyst is 260-450 m 2 And/g, the pore diameter is 3.5-8 nm.
3. The ordered mesoporous Ni/MgGa according to claim 1 2 O 4 A methanation catalyst, characterized in that: the nonionic surfactant is at least one of P123 and F127.
4. The ordered mesoporous Ni/MgGa according to claim 1 2 O 4 A methanation catalyst, characterized in that: the solvent in the step (1) is at least one of deionized water, methanol, ethanol and acetone.
5. The ordered mesoporous Ni/MgGa according to claim 1 2 O 4 A methanation catalyst, characterized in that: the inert gas in the step (1) comprises at least one of argon and helium.
6. The ordered mesoporous Ni/MgGa2O4 methanation catalyst of claim 1, wherein: the molar ratio of the elemental gallium to the elemental magnesium in the step (1) is 1:2.
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