CN103752315B - A metal-phase carrier-supported catalyst and its preparation method and application - Google Patents

Abstract

A metal phase carrier supported catalyst, a preparation method thereof and application thereof in catalyzing carbon monoxide or (and) carbon dioxide to prepare methane and methane to prepare synthesis gas. The metal phase carrier supported catalyst comprises an active component metal oxide and an auxiliary agent metal oxide which are supported on a metal phase carrier, and has the following general formula: xM₁O‑yM₂O/ZT, wherein M₁O represents an active component metal oxide, M₂O represents an auxiliary metal oxide, ZT represents a metal phase carrier, x represents the mass percent of the active component metal oxide in the catalyst, and y represents the mass percent of the auxiliary metal oxide in the catalyst. The catalyst has the advantages of high activity, high stability, excellent thermal conductivity, high permeability, convenient use, long service life, simple preparation and the like, can effectively solve the problem of heat effect in the strong emission/heat absorption reaction in the chemical field, and can be used as a catalyst for methanation process and reaction for preparing synthesis gas from methane.

Description

A metal-phase carrier-supported catalyst and its preparation method and application

technical field

The invention belongs to the technical field of catalysis, and relates to a catalyst and its preparation method and application, in particular to a catalyst supported by a metal phase and its preparation method and application. The catalyst can be used to catalyze the addition of carbon monoxide or (and) carbon dioxide Hydrogen reacts in the synthesis of methane and reforming of methane to synthesis gas.

Background technique

Natural gas is a safe, clean and high-quality energy source. The main component is methane (CH ₄ ). It has the advantages of high calorific value and low pollution. It is widely used in power generation, chemical industry and civil use. Since Sabatier and Senderens first used carbon monoxide and hydrogen to synthesize methane on a nickel-based catalyst in 1902, the methanation reaction has developed rapidly and has been widely used in gas purification processes.

The key to the methanation process is the development of new and efficient catalysts. The prior art teaches various methanation catalysts, such as Chinese patents 200610021836.5, 201010223996.4 and Chinese patent ZL88105142.x. In short, the methanation catalysts in the prior art basically use oxides as supports, such as alumina, silica, titania, zirconia, etc.

On the one hand, the methanation of carbon monoxide, methanation of carbon dioxide, and co-methanation of carbon monoxide and carbon dioxide are all strongly exothermic processes, and the thermal conductivity of oxide materials is poor, so it is easy to form "hot spots" or even runaway temperature in the reaction process. , thus leading to sintering deactivation of catalysts in the prior art and even production safety accidents. In actual production, the operation process of large reaction gas circulation ratio combined with multi-stage reaction and inter-stage cooling has to be adopted to solve the problem of reactor overheating, but it brings problems such as high energy consumption and low efficiency. On the other hand, in the prior art, in order to eliminate the limitation of gas in-diffusion and out-diffusion in the fixed bed reactor, it is necessary to use catalyst particles with smaller particle size and larger gas flow rate. However, these measures will cause an increase in the pressure drop at both ends of the bed, which will cause problems in energy consumption and safety, and will be detrimental to production.

In addition, methane to synthesis gas is one of the important ways to realize the chemical utilization of methane. At present, steam reforming, partial oxidation, carbon dioxide reforming and autothermal reforming have been developed to produce synthesis gas, but the above processes all have strong thermal effects. (Strong endothermic or strong exothermic) problem, according to their thermodynamic studies, it is easy to generate side reaction carbon deposition at low temperature. In fact, due to the generally low effective heat transfer coefficient in traditional fixed-bed reaction tubes, even if the tube wall temperature is as high as 800°C, there are still cold spots in the bed, and carbon deposition is unavoidable.

Due to the advantages of large specific surface area, good transfer performance, and low bed pressure, metal phase support structure catalysts have been applied in the fields of environmental catalysis and pollution control. Taking advantage of this excellent transfer performance, the application of metal phase support structure catalysts in strong exothermic/endothermic reactions in the chemical industry can greatly improve energy utilization efficiency, realize process integration, and achieve the purpose of process intensification. However, there are strong thermal effects in the methanation reaction and the methane-to-synthesis gas reaction. Therefore, there have been attempts in the prior art to try metal phase-supported methanation catalysts and methane-to-synthesis gas catalysts. However, these prior art catalysts have defects such as low melting point, high chemical activity, insufficient catalytic activity, complicated preparation, and serious pollution in the preparation process.

Contents of the invention

The purpose of the present invention is to provide a catalyst with the advantages of high catalytic activity, high stability, excellent thermal conductivity, convenient use, simple preparation and its preparation method and application, so as to be suitable for methane preparation reaction and methane production with strong thermal effect. Syngas reaction.

To achieve the purpose of the above invention, the present invention provides a metal-phase carrier-supported catalyst, which includes an active component metal oxide and an auxiliary metal oxide supported on a metal-phase carrier and has the general formula xM ₁ O-yM ₂ O/ ZT, where M ₁ O represents the active component metal oxide, M ₂ O represents the promoter metal oxide, ZT represents the metal phase support, x represents the mass percentage of the active component metal oxide in the catalyst, and y represents the promoter metal Oxides account for the mass percent of the catalyst.

As a further preferred solution, in the catalyst of the present invention, the active component metal oxide M ₁ O accounts for 1 to 15% by mass of the catalyst, and the promoter metal oxide M ₂ O accounts for 1 to 15% by mass of the catalyst. %, the rest is the metal phase carrier ZT. In different embodiments, the values of x and y can be 1, 3, 5, 6, 7.5, 9, 10, 13, 15, all of which can achieve the purpose of the present invention.

As a further preferred solution, the metal phase carrier is metallic nickel, metallic copper, metallic iron or metallic cupronickel.

As a further preferred solution, the metal phase support is a fiber with a diameter of 4 to 150 microns and a length of 2 to 10 mm, a three-dimensional porous structure monolithic metal fiber support or a three-dimensional porous structure monolithic metal fiber support formed by sintering the fibers. foam carrier.

As a further preferred solution, the active component metal oxide M ₁ O in the catalyst of the present invention is at least one of oxides of nickel and iron.

As a further preferred solution, the promoter metal oxide M ₂ O in the catalyst of the present invention is at least one of oxides of aluminum, cerium, lanthanum, molybdenum, manganese, tungsten, magnesium, calcium, sodium, and potassium.

Another aspect of the present invention provides a kind of preparation method of catalyst, comprises the steps:

①Impregnate the metal phase carrier with an equal volume of a suspension containing aluminum powder (preferably ultrafine aluminum powder with a particle size between 1-10 microns) (“equal volume impregnation” means that the suspension containing aluminum powder and the suspension to be impregnated The volume of the metal phase carrier is the same), and then carry out drying treatment to disperse the aluminum powder particles on the surface of the metal phase carrier, and then perform a solid-solid alloying reaction between the aluminum powder particles and the surface layer of the metal phase carrier at 550-650°C (for example reaction for 1 to 10 hours) (for example, the reaction can be carried out in a high-purity protective atmosphere, such as nitrogen, hydrogen, argon or helium with a purity equal to or higher than 99.999%, or it can also be carried out in a vacuum) to obtain a metal phase carrier with alloyed surface (In different embodiments of the present invention, the temperature of solid-solid alloying reaction can be 550, 570, 600, 630, 650°C, and the reaction time can be 1, 2, 3, 5, 7, 8, 10 hours or shorter or longer, can achieve the purpose of the present invention);

② The product obtained in step ① is subjected to aluminum extraction treatment (for example, 1 to 6 hours) with hydrochloric acid or sodium hydroxide aqueous solution with a concentration of 5-20% at room temperature to 60 ° C, rinsed with distilled water, and dried in the air. After drying, the metal phase carrier with porous surface layer is obtained (in different embodiments of the present invention, the temperature of this step can be 20, 30, 40, 50, 60 °C, and the concentration of hydrochloric acid or sodium hydroxide aqueous solution can be 5, 5.5, 7, 10, 14, 18, 20%, the aluminum extraction treatment time can be 1, 2, 4, 5, 6 hours or shorter or longer, and the purpose of the present invention can be achieved);

③ The product obtained in step ② is immersed in equal volumes at room temperature or under equivalent conditions in an aqueous solution containing the salt of the active component M1 metal element and the salt of the auxiliary component M2 metal element (the immersion here can be the step ② The prepared product is immersed in the same solution containing both active components and auxiliary components, or the products obtained in step ② can be immersed in the first solution containing only one component, and then in the solution containing impregnated in the second solution of another component), and then baked at 300-600°C (for example, 0.5-2 hours) after drying to obtain the metal-phase-supported metal-phase-supported catalyst (in different embodiments Among them, the calcination temperature in this step can be 300, 350, 400, 500, 600°C, and the calcination time can be 0.5, 1, 1.5, 2 hours or shorter or longer, all of which can achieve the purpose of the present invention).

As a further preferred solution, the particle size of the aluminum powder used in the alloying process of the surface layer of the metal phase carrier is 1 to 3 microns, and the mass ratio of the aluminum powder/metal phase carrier is 0.5 to 10/100 (in different embodiments, the aluminum powder The mass ratio of /metal phase support can be 0.5/100, 1/100, 3/100, 5/100, 8/100, 10/100, all of which can achieve the purpose of the present invention).

Another aspect of the present invention is the use of the metal phase supported catalyst for the hydrogenation of carbon monoxide and/or carbon dioxide to produce methane.

Another aspect of the present invention is to use the metal-phase carrier-supported catalyst for preparing synthesis gas from methane, especially as a catalyst for preparing synthesis gas by methane-carbon dioxide reforming or methane autothermal reforming.

Compared with the prior art, the metal phase carrier-supported catalyst provided by the present invention has the advantages of stable structure, good thermal conductivity, high permeability, etc., and has the advantages of easy molding, easy filling, and easy storage in use, and its preparation method is simple , The raw material is easy to obtain, and the structure is controllable. Compared with the prior art of traditional oxide carrier-supported catalyst particles filling a fixed bed, the large porosity of the monolithic metal phase-supported catalyst of the present invention can greatly reduce the pressure drop at both ends of the bed, and its high thermal conductivity can make the bed The temperature in the layer is more uniform, which can fully meet the catalytic performance requirements of the synthesis gas methanation reaction.

Description of drawings

Fig. 1 is an optical photograph of the nickel oxide-alumina catalyst 10NiO-10Al ₂ O ₃ /8-Ni-SMF-450 prepared in Example 1 supported by sintered metal nickel fibers.

Fig. 2 is a SEM photo of the nickel oxide-alumina catalyst 10NiO-10Al ₂ O ₃ /8-Ni-SMF-450 prepared in Example 1 supported by sintered metal nickel fibers.

3 is the XRD spectrum of the nickel oxide-alumina catalyst 10NiO-10Al ₂ O ₃ /8-Ni-SMF-450 prepared in Example 1 supported by sintered metal nickel fibers.

Fig. 4 is an optical photograph of the iron oxide-alumina catalyst 10Fe ₂ O ₃ -5Al ₂ O ₃ /30-Cu-fiber-300 supported by metallic copper fibers prepared in Example 3.

Fig. 5 is a SEM photo of the metal copper fiber supported iron oxide-alumina catalyst 10Fe ₂ O ₃ -5Al ₂ O ₃ /30-Cu-fiber-300 prepared in Example 3.

Fig. 6 is an optical photo of the nickel oxide-alumina-cerium oxide catalyst 10NiO-5Al ₂ O ₃ -5CeO ₂ /Ni-foam-600 prepared in Example 8 on a metal foam nickel carrier.

Fig. 7 is a SEM photo of the nickel oxide-alumina-cerium oxide catalyst 10NiO-5Al ₂ O ₃ -5CeO ₂ /Ni-foam-600 prepared in Example 8 supported by a metal foam nickel carrier.

Figure 8 is the nickel oxide and magnesium oxide catalyst 8NiO-8Al ₂ O ₃ -2MgO/8-Ni-SMF-600 prepared in Example 6 supported by metal nickel fibers and the comparative particle catalyst 10NiO-5MgO/γ-Al ₂ Comparison of temperature distribution of O ₃ in the reactor.

Fig. 9 is the 1000-hour stability test results of the 5NiO-5Al ₂ O ₃ -2.5CeO ₂ /8-Ni-SMF-500 catalyst prepared in Example 5 for the methanation of carbon monoxide.

Fig. 10 is the test result of the 3000-hour stability test of the carbon monoxide methanation reaction catalyzed by the 5NiO-5Al ₂ O ₃ -2.5CeO ₂ /8-Ni-SMF-500 catalyst prepared in Example 5.

Fig. 11 is the 1000-hour stability test results of the carbon dioxide methanation reaction catalyzed by the 5NiO-5Al ₂ O ₃ -2.5CeO ₂ /8-Ni-SMF-500 catalyst prepared in Example 5.

detailed description

Below in conjunction with embodiment the present invention is further elaborated, and its purpose is for better understanding content of the present invention. Therefore, the examples cited do not limit the protection scope of the present invention.

Example 1

This example provides the preparation of a nickel oxide-alumina catalyst supported by sintered nickel metal fiber carrier.

① Weigh 15 grams of nickel metal fibers with a diameter of 8 microns and a length of 2 to 5 mm, 2.5 grams of cellulose fibers with a length of 0.1 to 1 mm and 1.5 liters of water, and add them to the mixer, fully stir to form a uniformly dispersed fiber slurry and then transfer In the paper machine, add water to 8.5 liters, stir, drain and shape; after drying, bake at 500°C in air for 1 hour; then sinter at 950°C in hydrogen for 1 hour, and the thickness of the product is controlled by pressing At 1 mm, a sintered metal nickel fiber support is obtained, expressed as 8-Ni-SMF;

② Cut the sintered metal nickel fiber carrier obtained in step ① into discs with a diameter of 16 mm, weigh 5 grams and place them in a 50 ml beaker. At room temperature, pipette the suspension containing 0.1 g of aluminum powder with a particle size of 1 to 3 microns (the mass ratio of aluminum powder/metal phase carrier is 2/100) to impregnate the metal phase carrier with equal volume and dry to make the aluminum powder particles After being dispersed on the surface of the metal phase carrier, the solid-solid alloying reaction between the aluminum powder particles and the surface layer of the metal phase carrier was carried out at 600°C in a high-purity protective atmosphere for 2 hours to obtain a metal phase carrier with an alloyed surface layer;

③ The product obtained in step ② is subjected to aluminum extraction treatment with a 15% sodium hydroxide aqueous solution at room temperature to 60° C. for 1 hour, rinsed with distilled water, and dried in the air to obtain a metal phase carrier with a porous surface;

④ Weigh 3 grams of the carrier prepared in step ③, use an equal volume of an aqueous solution containing 1.528 grams and 1.305 grams of Ni(NO ₃ ) ₂ 6H ₂ O and Al(NO ₃ ) ₃ 9H ₂ O at room temperature Impregnate the carrier with equal volume, dry at 100°C and then bake at 450°C in the air for 2 hours to obtain the nickel oxide-alumina catalyst supported by the sintered nickel metal fiber carrier; In the catalyst prepared in the embodiment, the weight content of Al ₂ O ₃ is 10.4%; it is determined by the temperature-programmed reduction working curve method that in the catalyst prepared in the present embodiment, the weight content of NiO is 9.5%; the present embodiment The prepared catalyst is expressed as 10NiO-10Al ₂ O ₃ /8-Ni-SMF-450 (here the suffix "450" indicates that the calcination temperature of the catalyst in step ④ is 450°C, the same below).

The optical photo of 10NiO-10Al ₂ O ₃ /8-Ni-SMF-450 is shown in Figure 1, the scanning electron microscope (SEM) picture is shown in Figure 2, and the X-ray diffraction (XRD) picture is shown in Figure 3.

According to macroscopic measurement, in the monolithic catalyst 10NiO-10Al ₂ O ₃ /8-Ni-SMF-450 prepared in this implementation, the volume percentage of the sintered metal Ni fiber structured catalyst skeleton is 5%, and the porosity is 95%. %.

The diameter of the nickel metal fiber used in step ① of this embodiment can be 4 microns, and other conditions remain unchanged. The obtained catalyst is expressed as 10NiO-10Al ₂ O ₃ /4-Ni-SMF-450.

The mass of the aluminum powder in step ② of this embodiment can be 0.025-0.10 g or 0.10-0.50 g, and the other conditions remain unchanged.

In the second step of this embodiment, the solid-solid alloying reaction temperature can be 550-600°C or 600-650°C, the solid-solid alloying reaction time can be 1-2 hours or 2-10 hours, and the rest of the conditions remain unchanged.

In the third step of the present embodiment, the concentration of the sodium hydroxide solution can be 5-15% or 15-20%, and the other conditions remain unchanged.

In step ③ of the present embodiment, the aluminum extraction treatment time can be 1 to 6 hours, and the other conditions remain unchanged.

In step ④ of this embodiment, the calcination temperature can be 600°C, and other conditions remain unchanged. The obtained catalyst is expressed as 10NiO-10Al ₂ O ₃ /8-Ni-SMF-600.

The calcination time in step ④ of the present embodiment can be 0.5～2 hours, and other conditions remain unchanged.

In step ④ of this embodiment, the contents of Ni(NO ₃ ) ₂ 6H ₂ O and Al(NO ₃ ) ₃ 9H ₂ O in the aqueous solution used to impregnate 3 grams of carrier with equal volume can be 0.146 g and 1.864 g, Or 2.183 grams and 0.124 grams, or 0.719 grams and 1.228 grams, other conditions remain unchanged, the prepared catalyst is expressed as 1NiO-15Al ₂ O ₃ /8-Ni-SMF-450, 15NiO-1Al ₂ O ₃ /8- Ni-SMF-450, 5NiO-10Al ₂ O ₃ /8-Ni-SMF-450.

Example 2

This example provides the preparation of a nickel oxide-alumina catalyst supported by sintered red copper metal fiber carrier.

① Weigh 15 grams of copper metal fibers with a diameter of 8 microns and a length of 2 to 5 mm, 2.5 grams of cellulose fibers with a length of 0.1 to 1 mm, and 1.5 liters of water, and add them to the mixer, fully stir to form a uniformly dispersed fiber slurry and then transfer In the paper machine, add water to 8.5 liters, stir, drain and shape; after drying, bake at 250°C in air for 1 hour; then sinter at 900°C in hydrogen for 1 hour to obtain a sintered metal copper fiber carrier. Expressed as 8-Cu-SMF;

② Cut the sintered metal red copper fiber carrier obtained in step ① into discs with a diameter of 16 mm, weigh 5 grams and place them in a 50 ml beaker. At room temperature, pipette an equal volume of suspension containing 0.4 grams of aluminum powder with a particle size of 1 to 3 microns to impregnate the metal phase carrier and dry to disperse the aluminum powder particles on the surface of the metal phase carrier. Perform a solid-solid alloying reaction between the aluminum powder particles and the surface layer of the metal phase carrier at 600°C for 2 hours to obtain a metal phase carrier with an alloyed surface layer;

③ The product obtained in step ② is subjected to aluminum extraction treatment with a concentration of 20% hydrochloric acid aqueous solution at room temperature to 60 ° C for 6 hours, rinsed with distilled water, and dried in the air to obtain a metal phase carrier with a porous surface;

④ Weigh 3 grams of the carrier prepared in step ③, and use an equal volume of an aqueous solution containing 1.438 grams and 0.614 grams of Ni(NO ₃ ) ₂ 6H ₂ O and Al(NO ₃ ) ₃ 9H ₂ O at room temperature Impregnate the support with equal volume, dry at 100°C and then bake at 300°C in the air for 2 hours to obtain the nickel oxide-alumina catalyst supported by the sintered red copper metal fiber support.

According to the measurement of plasma inductively coupled atomic emission spectrometry, in the catalyst prepared in this example, the weight content of NiO is 9.6%, and the weight content of Al ₂ O ₃ is 5.3%; the catalyst prepared in this example is expressed as 10NiO- 5Al ₂ O ₃ /8-Cu-SMF-300.

According to macroscopic measurement, in the monolithic catalyst 10NiO-5Al ₂ O ₃ /8-Cu-SMF-300 prepared in this implementation, the volume percentage of the sintered metal Cu fiber structured catalyst skeleton is 38%, and the porosity is 62%. %.

In step ① of this embodiment, the diameter of the copper metal fiber can be 30 microns, and other conditions remain unchanged. The obtained catalyst is expressed as 10NiO-5Al ₂ O ₃ /30-Cu-SMF-300.

Example 3

This example provides the preparation of an iron oxide-alumina catalyst supported on a red copper fiber carrier.

① Weigh 15 grams of copper metal fiber (expressed as Cu-fiber) with a diameter of 30 microns and a length of 5-10 mm, and at room temperature, pipette the suspension containing 0.075 grams of aluminum powder with a particle size of 1-3 microns. After impregnating the metal phase carrier with equal volume of liquid and drying to disperse the aluminum powder particles on the surface of the metal phase carrier, the solid-solid alloying reaction between the aluminum powder particles and the surface layer of the metal phase carrier was carried out at 600°C in a high-purity protective atmosphere for 2 hours. Obtain a metal phase carrier with surface alloying;

② The product obtained in step ① is subjected to an aluminum extraction treatment with a 5% hydrochloric acid aqueous solution at room temperature to 60° C. for 1 hour, rinsed with distilled water, and dried in the air to obtain a metal phase carrier with a porous surface;

③ Weigh 3 grams of the carrier obtained in step ②, and use an equal volume of an aqueous solution containing 1.489 grams and 0.614 grams of Fe(NO ₃ ) ₃ 9H ₂ O and Al(NO ₃ ) ₃ 9H ₂ O at room temperature Impregnate the support with equal volume, dry at 100°C and then bake at 300°C in the air for 2 hours to obtain the iron oxide-alumina catalyst supported by the red copper metal fiber carrier.

According to the measurement of plasma inductively coupled atomic emission spectrometry, in the catalyst prepared in this example, the weight content of _Fe2O3 is 10.6%, and the weight content _{of Al2O3} is 4.8% _; the catalyst prepared in this example shows It is 10Fe ₂ O ₃ -5Al ₂ O ₃ /30-Cu-fiber-300 (the suffix "300" here indicates that the calcination temperature of the catalyst in step ③ is 300°C, the same below).

The optical picture of 10Fe ₂ O ₃ -5Al ₂ O ₃ /30-Cu-fiber-300 is shown in Figure 4, and the scanning electron microscope (SEM) picture is shown in Figure 5.

In the first step of this example, the diameter of the copper metal fiber can be 150 microns (expressed as 150-Cu-fiber), and other conditions remain unchanged, and the obtained catalyst is expressed as 10Fe ₂ O ₃ -5Al ₂ O ₃ /150-Cu-fiber -300.

Example 4

This example provides the preparation of a nickel oxide-alumina catalyst supported on an iron metal fiber carrier.

① Weigh 5 grams of iron metal fiber (expressed as 80-Fe-fiber) with a diameter of 80 microns and a length of 5 to 10 mm. The suspension is impregnated with equal volumes of the metal phase carrier and dried to disperse the aluminum powder particles on the surface of the metal phase carrier, and the solid-solid alloying reaction between the aluminum powder particles and the surface layer of the metal phase carrier is carried out at 600°C in a high-purity protective atmosphere 2 Hour, obtain the metallic phase carrier of surface layer alloying;

② The product obtained in step ① is subjected to aluminum extraction treatment with 5% sodium hydroxide aqueous solution at room temperature to 60 ° C for 1 hour, rinsed with distilled water, and dried in the air to obtain a metal phase carrier with a porous surface ;

③ Weigh 3 grams of the carrier prepared in step ②, and use equal volumes of aqueous solutions containing 0.745 grams and 0.614 grams of Ni(NO ₃ ) ₂ 6H ₂ O and Al(NO ₃ ) ₃ 9H ₂ O at room temperature Impregnate the support with equal volume, dry at 100°C and then bake at 400°C in the air for 2 hours to obtain the nickel oxide-alumina catalyst supported by the metal iron fiber support.

According to the measurement of plasma inductively coupled atomic emission spectrometry, in the catalyst prepared in this embodiment, the weight content of NiO is 5.2%, and the weight content of Al ₂ O ₃ is 5.3%; the catalyst prepared in this embodiment is expressed as 5NiO- 5Al ₂ O ₃ /80-Fe-fiber-400.

The metal fibers used in this example may be 80 micron cupronickel fibers (represented as 80-BT-fiber), and the other conditions remain unchanged, and the obtained catalysts are respectively represented as 5NiO-5Al ₂ O ₃ /80-BT-fiber-400.

Example 5

This example provides the preparation of a nickel oxide-alumina-rare earth oxide catalyst supported on a sintered nickel metal fiber carrier.

① Weigh 15 grams of nickel metal fibers with a diameter of 8 microns and a length of 2 to 5 mm, 2.5 grams of cellulose fibers with a length of 0.1 to 1 mm and 1.5 liters of water, and add them to the mixer, fully stir to form a uniformly dispersed fiber slurry and then transfer In the paper machine, add water to 8.5 liters, stir, drain and shape; after drying, bake at 500°C in air for 1 hour; then sinter at 950°C in hydrogen for 1 hour, and the thickness of the product is controlled by pressing At 1 mm, a sintered metal nickel fiber support is obtained, expressed as 8-Ni-SMF;

② Cut the sintered metal nickel fiber carrier obtained in step ① into discs with a diameter of 16 mm, weigh 5 grams and place them in a 50 ml beaker. At room temperature, pipette the suspension containing 0.1 g of aluminum powder with a particle size of 1 to 3 microns (the mass ratio of aluminum powder/metal phase carrier is 2/100) to impregnate the metal phase carrier with equal volume and dry to make the aluminum powder particles After being dispersed on the surface of the metal phase carrier, the solid-solid alloying reaction between the aluminum powder particles and the surface layer of the metal phase carrier was carried out at 650°C in a high-purity protective atmosphere for 2 hours to obtain a metal phase carrier with an alloyed surface layer;

③ The product obtained in step ② is subjected to aluminum extraction treatment with 5% sodium hydroxide aqueous solution at room temperature to 60 °C for 6 hours, rinsed with distilled water, and dried in the air to obtain a metal phase carrier with a porous surface ;

④ Weigh 3 grams of the carrier prepared in step ③, and use equal volumes of Ni(NO ₃ ) ₂ 6H ₂ O, Al(NO ₃ ) ₃ 9H ₂ O and Ce( NO ₃ ) ₃ ·6H ₂ O aqueous solution, impregnating the support with equal volume at room temperature, drying at 100°C, and then calcining at 500°C in air for 2 hours to obtain the nickel oxide-alumina- Cerium oxide catalyst, wherein the weight content of NiO, Al ₂ O ₃ and CeO ₂ in the catalyst is 5%, 5% and 2.5% respectively, and the catalyst is expressed as 5NiO-5Al ₂ O ₃ -2.5CeO ₂ /8-Ni-SMF -500.

According to macroscopic measurement, in the monolithic catalyst 5NiO-5Al ₂ O ₃ -2.5CeO ₂ /8-Ni-SMF-500 prepared in this implementation, the metal nickel fiber structured catalyst skeleton accounts for 22% by volume, and the pores The rate is 78%.

In step ④ of this example, Ni(NO ₃ ) ₂ ·6H ₂ O, Al(NO ₃ ) ₃ ·9H ₂ O and Ce(NO ₃ ) ₃ ·6H ₂ The content of O can be 0.719 grams, 0.614 grams and 0.500 grams, or 1.528 grams, 0.652 grams and 0.510 grams, and the other conditions remain unchanged. The prepared catalyst is expressed as 5NiO-5Al ₂ O ₃ -5CeO ₂ /8-Ni- SMF-500, 10NiO-5Al ₂ O ₃ -5CeO ₂ /8-Ni-SMF-500.

In step ④ of this embodiment, the salt of the rare earth element in the aqueous solution used to impregnate 3 grams of the carrier in equal volume can be La(NO ₃ ) ₃ 6H ₂ O, and its content can be 0.120 g or 0.230 g, and the other conditions remain unchanged. , the prepared catalyst is expressed as 5NiO-5Al ₂ O ₃ -2.5La ₂ O ₃ /8-Ni-SMF-500, 5NiO-5Al ₂ O ₃ -5La ₂ O ₃ /8-Ni-SMF-500.

Example 6

This embodiment provides a preparation of a nickel metal fiber carrier loaded with different contents of nickel oxide-alumina-alkaline earth metal oxidizing agents.

① Weigh 15 grams of nickel metal fibers with a diameter of 8 microns and a length of 2 to 5 mm, 2.5 grams of cellulose fibers with a length of 0.1 to 1 mm and 1.5 liters of water, and add them to the mixer, fully stir to form a uniformly dispersed fiber slurry and then transfer In the paper machine, add water to 8.5 liters, stir, drain and shape; after drying, bake at 500°C in air for 1 hour; then sinter at 950°C in hydrogen for 1 hour, and the thickness of the product is controlled by pressing At 1 mm, a sintered metal nickel fiber support is obtained, expressed as 8-Ni-SMF;

② Cut the sintered metal nickel fiber carrier obtained in step ① into discs with a diameter of 16 mm, weigh 5 grams and place them in a 50 ml beaker. At room temperature, pipette the suspension containing 0.025 grams of aluminum powder with a particle size of 1 to 3 microns (the mass ratio of aluminum powder/metal phase carrier is 0.5/100) to impregnate the metal phase carrier with equal volume and dry to make the aluminum powder particles After being dispersed on the surface of the metal phase carrier, the solid-solid alloying reaction between the aluminum powder particles and the surface layer of the metal phase carrier was carried out at 500°C in a high-purity protective atmosphere for 2 hours to obtain a metal phase carrier with an alloyed surface layer;

③ The product obtained in step ② is subjected to aluminum extraction treatment with 5% sodium hydroxide aqueous solution at room temperature to 60 ° C for 1 hour, rinsed with distilled water, and dried in the air to obtain a metal phase carrier with a porous surface ;

④ Weigh 3 grams of the carrier prepared in step ③, and use equal volumes of Ni(NO ₃ ) ₂ 6H ₂ O, Al(NO ₃ ) ₃ 9H ₂ O and Mg( The aqueous solution of NO ₃ ) ₂ ·6H ₂ O is impregnated with an equal volume of the carrier at room temperature, dried at 100°C and then calcined at 600°C in air for 2 hours to obtain the nickel oxide-alumina- Magnesium oxide catalyst, wherein the weight content of NiO, Al ₂ O ₃ and MgO in the catalyst is 8%, 8% and 2% respectively, and the catalyst is expressed as 8NiO-8Al ₂ O ₃ -2MgO/8-Ni-SMF-600.

According to macroscopic measurements, in the monolithic catalyst 8NiO-8Al ₂ O ₃ -2MgO/8-Ni-SMF-600 prepared in this implementation, the volume percentage of the metal nickel fiber structured catalyst skeleton is 28%, and the porosity is 72%.

In step ④ of this embodiment, the salt of alkaline earth metal elements in the aqueous solution used to impregnate 5 grams of carrier in equal volume can be Ca(NO ₃ ) ₂ ·4H ₂ O, and its content is 0.519 grams. The other conditions remain unchanged, and the obtained The catalyst is expressed as 8NiO-8Al ₂ O ₃ -2CaO/8-Ni-SMF-600.

Example 7

This example provides the preparation of a nickel oxide-alumina-alkali metal oxide catalyst loaded on a sintered nickel metal fiber carrier.

① Weigh 15 grams of nickel metal fibers with a diameter of 8 microns and a length of 2 to 5 mm, 2.5 grams of cellulose fibers with a length of 0.1 to 1 mm and 1.5 liters of water, and add them to the mixer, fully stir to form a uniformly dispersed fiber slurry and then transfer In the paper machine, add water to 8.5 liters, stir, drain and shape; after drying, bake at 500°C in air for 1 hour; then sinter at 950°C in hydrogen for 1 hour, and the thickness of the product is controlled by pressing At 1 mm, a sintered metal nickel fiber support is obtained, expressed as 8-Ni-SMF;

② Cut the sintered metal nickel fiber carrier obtained in step ① into discs with a diameter of 16 mm, weigh 5 grams and place them in a 50 ml beaker. At room temperature, pipette the suspension containing 0.025 grams of aluminum powder with a particle size of 1 to 3 microns (the mass ratio of aluminum powder/metal phase carrier is 0.5/100) to impregnate the metal phase carrier with equal volume and dry to make the aluminum powder particles After being dispersed on the surface of the metal phase carrier, the solid-solid alloying reaction between the aluminum powder particles and the surface layer of the metal phase carrier was carried out at 550°C in a high-purity protective atmosphere for 2 hours to obtain a metal phase carrier with an alloyed surface layer;

③ The product obtained in step ② is subjected to aluminum extraction treatment with 5% sodium hydroxide aqueous solution at room temperature to 60 ° C for 1 hour, rinsed with distilled water, and dried in the air to obtain a metal phase carrier with a porous surface ;

④ Weigh 3 grams of the carrier prepared in step ③, and use equal volumes of Ni(NO ₃ ) ₂ 6H ₂ O, Al(NO ₃ ) ₃ 9H ₂ O and NaNO ₃ containing 1.222 grams, 1.043 grams and 0.110 grams impregnated carrier with an equal volume at room temperature, dried at 100°C and then calcined at 600°C in the air for 2 hours to obtain the nickel oxide-alumina-sodium oxide catalyst supported by nickel metal fiber carrier, wherein NiO, Al The weight contents of ₂ O ₃ and Na ₂ O in the catalyst were 8%, 8% and 2%, respectively, and the catalyst was expressed as 8NiO-8Al ₂ O ₃ -2Na ₂ O/8-Ni-SMF-600.

According to the macroscopic measurement, in the monolithic catalyst 8NiO-8Al ₂ O ₃ -2Na ₂ O/8-Ni-SMF-600 prepared in this implementation, the metal nickel fiber structure catalyst skeleton accounts for 28% by volume, and the pores The rate is 72%.

In step ④ of this embodiment, the salt of alkaline earth metal element in the aqueous solution used to impregnate 3 grams of support in equal volume can be KNO ₃ , its content is 0.090 g, and the other conditions remain unchanged. The prepared catalyst is expressed as 8NiO-8Al ₂ O ₃ -2K ₂ O/8-Ni-SMF-600.

Example 8

This example provides the preparation of a nickel oxide-alumina-cerium oxide catalyst supported on a metal foam nickel carrier.

①Weigh 5 grams of nickel foam metal (expressed as Ni-foam), and at room temperature, pipette the suspension containing 0.3 grams of aluminum powder with a particle size of 1 to 10 microns to impregnate the metal phase carrier with an equal volume and dry it to make the aluminum powder After the particles are dispersed on the surface of the metal phase carrier, the solid-solid alloying reaction between the aluminum powder particles and the surface layer of the metal phase carrier is carried out at 600°C in a high-purity protective atmosphere for 2 hours to obtain a metal phase carrier with an alloyed surface layer;

②The product obtained in step ① is subjected to aluminum extraction treatment with 15% sodium hydroxide aqueous solution at room temperature to 60°C for 1 hour, rinsed with distilled water, and dried in the air to obtain a porous metallic nickel foam carrier;

③ Weigh 3 grams of the carrier prepared in step ②, and use equal volumes of Ni(NO ₃ ) ₂ 6H ₂ O, Al(NO ₃ ) ₃ 9H ₂ O and Ce( NO ₃ ) ₃ ·6H ₂ O aqueous solution, impregnating the carrier with equal volume at room temperature, drying at 100°C and then calcining at 600°C in air for 2 hours to obtain the nickel oxide-alumina-cerium oxide supported on the nickel foam carrier The catalyst, wherein the weight content of NiO, Al ₂ O ₃ and CeO ₂ in the catalyst is 10%, 5% and 5% respectively, the catalyst is expressed as 10NiO-5Al ₂ O ₃ -5CeO ₂ /Ni-foam-600.

The optical photos and scanning electron microscope (SEM) photos of the 10NiO-5Al ₂ O ₃ -5CeO ₂ /Ni-foam-600 catalyst prepared in this example are shown in Figure 6 and Figure 7, respectively.

According to macroscopic measurement, in the monolithic catalyst 10NiO-5Al ₂ O ₃ -5CeO ₂ /Ni-foam-600 prepared in this practice, the metal nickel foam skeleton accounts for 20% by volume, and the porosity is 80%.

In this example, the metal foam material can be copper foam (expressed as BT-foam), copper foam (expressed as Cu-foam), and iron foam (expressed as Fe-foam), and the other conditions remain unchanged. The prepared catalysts are respectively Expressed as 10NiO-5Al ₂ O ₃ -5CeO ₂ /BT-foam-600, 10NiO-5Al ₂ O ₃ -5CeO ₂ /Cu-foam-600, 10NiO-5Al ₂ O ₃ -5CeO ₂ /Fe-foam-600.

Example 9

This example provides the preparation of a nickel oxide-alumina-manganese oxide catalyst supported on a metal foam nickel carrier.

① Weigh 5 grams of nickel foam (expressed as Ni-foam) metal, at room temperature, pipette the suspension containing 0.3 grams of aluminum powder with a particle size of 1 to 10 microns to impregnate the metal phase carrier with equal volume and dry to make the aluminum powder After the particles are dispersed on the surface of the metal phase carrier, the solid-solid alloying reaction between the aluminum powder particles and the surface layer of the metal phase carrier is carried out at 600°C in a high-purity protective atmosphere for 2 hours to obtain a metal phase carrier with an alloyed surface layer;

②The product obtained in step ① is subjected to aluminum extraction treatment with 15% sodium hydroxide aqueous solution at room temperature to 60°C for 1 hour, rinsed with distilled water, and dried in the air to obtain a porous metallic nickel foam carrier;

③ Weigh 3 grams of the carrier prepared in step ②, and use equal volumes of Ni(NO ₃ ) ₂ 6H ₂ O, Al(NO ₃ ) ₃ 9H ₂ O and Mn( NO ₃ ) ₂ ·4H ₂ O aqueous solution, impregnating the carrier with equal volume at room temperature, drying at 100°C and then roasting at 600°C in air for 2 hours to obtain the nickel oxide-alumina-manganese oxide supported on the nickel foam carrier The catalyst, wherein the weight content of NiO, Al ₂ O ₃ and MnO ₂ in the catalyst is 10%, 5% and 5% respectively, and the catalyst is expressed as 10NiO-5Al ₂ O ₃ -5MnO ₂ /Ni-foam-600.

In step ③ of this embodiment, the aqueous solution used to impregnate 3 grams of support in equal volume may contain 1.528 grams, 0.652 grams and 0.250 grams of Ni(NO ₃ ) ₂ ·6H ₂ O, Al(NO ₃ ) ₃ ·9H ₂ Aqueous solution of O and Mo(NO ₃ ) ₃ .5H ₂ O, impregnating the carrier with equal volume at room temperature, drying at 100°C and then roasting at 600°C in the air for 2 hours, keeping the other conditions unchanged, the nickel foam carrier supported Nickel oxide-alumina-molybdenum oxide catalyst, wherein the weight content of NiO, Al ₂ O ₃ and MoO ₃ in the catalyst is 10%, 5% and 5% respectively, the catalyst is expressed as 10NiO-5Al ₂ O ₃ -5MoO ₃ /Ni-foam-600.

In step ③ of this embodiment, first use an equal volume of an aqueous solution containing 1.528 g and 0.652 g of Ni(NO ₃ ) ₂ 6H ₂ O and Al(NO ₃ ) ₃ 9H ₂ O to impregnate 3 After drying at 100°C, impregnate again with an equal volume of an aqueous solution containing 0.230 g of Na ₂ WO ₄ 2H ₂ O, then dry at 100°C and bake at 600°C in air for 2 hours, and the rest of the conditions remain unchanged. , to obtain the nickel oxide-alumina-tungsten oxide-sodium oxide catalyst supported by the nickel foam carrier, wherein the weight contents of NiO, Al ₂ O ₃ , WO ₃ and Na ₂ O in the catalyst are 10%, 5%, respectively. %, 4% and 1%, the catalyst is expressed as 10NiO-5Al ₂ O ₃ -4WO ₃ -1Na ₂ O/Ni-foam-600.

The inventors of the present application found that the catalyst obtained by loading NiO on a porous metal phase carrier in the present invention is significantly better than NiO-based catalysts supported on an oxide carrier such as Al ₂ O ₃ in terms of catalytic performance and thermal conductivity. The following are the catalysts used in comparative experiments made by the inventors of the present application.

Comparative example 1

Weigh 1.438g of Ni(NO ₃ ) ₂ 6H ₂ O and 1.198g of Mg(NO ₃ ) ₂ 6H ₂ O and dissolve them in 4 ml of water to form an aqueous solution, and dry 3.0 g of γ-Al ₂ O at room temperature ₃ Immerse in the prepared mixed aqueous solution of nickel nitrate and magnesium nitrate for 12 hours by equal-volume impregnation method, dry at 120°C, and bake at 550°C for 2 hours in an air atmosphere to obtain MgO-modified alumina-supported oxide Nickel catalyst, wherein the weight content of NiO and MgO in the catalyst is 10% and 5% respectively, expressed as 10NiO-5MgO/γ-Al ₂ O ₃ .

Application example 1

The catalytic performance of the catalyst of the present invention for carbon monoxide methanation under different reaction conditions was investigated in a fixed-bed reactor. The reaction raw materials were carbon monoxide and hydrogen, and the molar ratio of carbon monoxide and hydrogen was 1:3. The fixed bed reactor is a quartz tube with an inner diameter of 16 mm. Carbon monoxide and hydrogen are mixed before entering the reaction tube, and after mixing evenly, enter the catalyst bed for reaction. After the reaction product is condensed by the cold trap, the gas phase product enters the chromatogram and is analyzed by a thermal conductivity cell detector (TCD).

This application example is carried out on the 10NiO-10Al ₂ O ₃ /8-Ni-SMF-450 catalyst prepared in Example 1. The catalyst dosage is 0.482 grams and the volume is about 1.25 milliliters. The reaction conditions, conversion rate and selection are listed in Table 1 respectively.

Table 1 Effects of reaction temperature and gas hourly space velocity on the CO methanation performance of the catalyst 10NiO-10Al ₂ O ₃ /8-Ni-SMF-450 prepared in Example 1

Reaction temperature (°C) Raw gas space velocity (h ^-1 ) CO conversion rate (%) CH ₄ selectivity (%) 250 2500 85.9 91.5 250 5000 91.9 86.8 250 10000 96.7 84.3 400 2500 99.3 92.8 400 5000 99.1 90.7 400 10000 98.2 86.8 550 2500 84.1 80.8 550 5000 83.6 82.5 550 10000 75.3 78.4

Application example 2

The catalytic performance of the catalyst of the present invention for carbon dioxide methanation under different reaction conditions was investigated in a fixed-bed reactor. The reaction raw materials were carbon dioxide and hydrogen, and the molar ratio of carbon dioxide and hydrogen was 1:4. The fixed bed reactor is a quartz tube with an inner diameter of 16 mm. Carbon dioxide and hydrogen are mixed before entering the reaction tube, and after mixing evenly, enter the catalyst bed for reaction. After the reaction product is condensed by the cold trap, the gas phase product enters the chromatogram and is analyzed by a thermal conductivity cell detector (TCD).

This application example is carried out on the 10NiO-10Al ₂ O ₃ /8-Ni-SMF-450 catalyst prepared in Example 1. The catalyst dosage is 0.482 grams and the volume is about 1.25 milliliters. The reaction conditions, conversion rate and selection are listed in Table 2 respectively.

Table 2 Effect of reaction temperature and gas hourly space velocity on the catalytic performance of the catalyst 10NiO-10Al ₂ O ₃ /8-Ni-SMF-450 prepared in Example 1 for CO ₂ methanation

Reaction temperature (°C) Raw gas space velocity (h ^-1 ) _CO2 conversion rate (%) CH ₄ selectivity (%) 250 2500 52.7 99.65 250 5000 46.2 99.85 250 10000 35.5 99.92 400 2500 91.3 99.6 400 5000 81.8 99.0 400 10000 76.5 97.4 550 2500 72.6 82.1 550 5000 67.2 75.6 550 10000 64.6 69.5

Application example 3

Reaction device, reaction raw material, catalyst consumption are the same as application example 1.

In this application example, under the conditions of gas hourly space velocity of 5000 h ^-1 and reaction temperature of 350°C, the catalytic performance of the catalyst of the example for methanation of carbon monoxide was investigated, and the results are listed in Table 3.

The carbon monoxide methanation catalytic performance of each embodiment of table 3 and comparative example catalyst

Application example 4

The catalytic performance of the catalyst of the present invention to the co-methanation reaction of carbon monoxide and carbon dioxide was investigated on a fixed-bed reactor. The molar ratio is 17:20:10:53. The fixed bed reactor is a quartz tube with an inner diameter of 16 mm. Carbon monoxide, carbon dioxide, methane and hydrogen are mixed before entering the reaction tube, and after mixing evenly, enter the catalyst bed for reaction. After the reaction product is condensed by the cold trap, the gas phase product enters the chromatogram and is analyzed by a thermal conductivity cell detector (TCD).

This application example is carried out on the 10NiO-5Al ₂ O ₃ /8-Cu-SMF-300 catalyst prepared in Example 2. The amount of the catalyst is 1.053 grams, and the volume is about 1.61 milliliters. The reaction conditions and conversion rates used are listed respectively in Table 4. A negative value for the conversion rate of carbon dioxide indicates that the carbon dioxide has not been converted and some carbon dioxide is newly formed.

Table 4 Effect of reaction temperature and gas hourly space velocity on the catalytic performance of the catalyst 10NiO-5Al ₂ O ₃ /8-Cu-SMF-300 prepared in Example 2

Reaction temperature (°C) Raw gas space velocity (h ^-1 ) CO conversion rate (%) _CO2 conversion rate (%) 350 5000 95.4 -8.9 350 10000 91.8 -7.8 350 15000 87.4 -6.0 450 5000 82.8 -4.0 450 10000 75.2 -2.0 450 15000 66.5 1.7 550 5000 33.5 9.0 550 10000 24.3 14.1 550 15000 17.0 18.4

Application example 5

The catalytic performance of the catalyst of the present invention on the reforming reaction of methane and carbon dioxide under different conditions was investigated in a fixed bed reactor. The reaction raw material was a mixture of carbon dioxide and methane, and the molar ratio of methane and carbon dioxide was 1:1. The fixed-bed reactor is a quartz tube with an inner diameter of 16 mm. Methane and carbon dioxide are mixed before entering the reaction tube, and after mixing evenly, enter the catalyst bed for reaction. After the reaction product is condensed by the cold trap, the gas phase product enters the chromatogram and is analyzed by a thermal conductivity cell detector (TCD).

This application example is carried out on the 5NiO-5Al ₂ O ₃ -2.5CeO ₂ /8-Ni-SMF-500 catalyst prepared in Example 5. The catalyst dosage is 1.216 grams, and the volume is about 1.92 milliliters. The reaction conditions and The conversion rates are listed in Table 5, respectively.

Table 5 Effect of reaction temperature and gas hourly space velocity on catalytic performance of catalyst 5NiO-5Al ₂ O ₃ -2.5CeO ₂ /8-Ni-SMF-500 in Example 5

Reaction temperature (°C) Raw gas space velocity (h ^-1 ) CH ₄ conversion rate (%) _CO2 conversion rate (%) 750 3000 72.0 74.3 750 6000 59.9 72.6 750 9000 42.8 62.2 800 3000 87.0 91.8 800 6000 84.8 86.7 800 9000 68.9 80.7 850 3000 93.6 95.4 850 6000 93.2 94.4 850 9000 88.5 92.1

Application example 6

On the fixed-bed reactor, the catalytic performance of the catalyst of the present invention to methane autothermal reforming reaction under different conditions has been investigated. The reaction raw material is a mixed gas of methane, water vapor and oxygen, and the mol ratio of methane, water vapor and oxygen is 3:10:2. The fixed bed reactor is a quartz tube with an inner diameter of 16 mm. Methane, water vapor and oxygen are mixed before entering the reaction tube, and after mixing evenly, enter the catalyst bed for reaction. After the reaction product is condensed by the cold trap, the gas phase product enters the chromatogram and is analyzed by a thermal conductivity cell detector (TCD).

This application example is carried out on the 8NiO-8Al ₂ O ₃ -2MgO/8-Ni-fiber-600 catalyst prepared in Example 6. The catalyst dosage is 1.139 grams, and the volume is about 1.76 milliliters. The reaction conditions and conversion rate used are and selectivity are listed in Table 6, respectively. Table 6 Effect of reaction temperature and gas hourly space velocity on catalytic performance of catalyst 8NiO-8Al ₂ O ₃ -2MgO/8-Ni-fiber-600 in Example 6

Reaction temperature (°C) Raw gas space velocity (h ^-1 ) CH ₄ conversion rate (%) CO selectivity (%) 650 3000 74.3 93.6 650 6000 70.6 92.9 650 9000 64.8 92.4 750 3000 88.2 95.2 750 6000 85.3 94.9 750 9000 81.9 95.1 850 3000 96.8 97.8 850 6000 94.3 97.2 850 9000 92.4 96.4

Application example 7

This example illustrates the excellent effect of the high thermal conductivity of the catalyst of the present invention on strengthening reaction heat transfer and eliminating high-temperature hot spots through CFD simulation comparison.

Reaction device, reaction raw material, catalyst consumption are the same as application example 1.

This application example is carried out on the 8NiO-8Al ₂ O ₃ -2MgO/8-Ni-fiber-600 catalyst prepared in Example 6, the reaction temperature is 350°C, the gas hourly space velocity is 10000h ^-1 , and the molar ratio of carbon monoxide to hydrogen is 1 :3, the carbon monoxide conversion rate is 95%, and the methane selectivity is 91%. Under the same reaction conditions, on the catalyst 10NiO-5MgO/γ-Al ₂ O ₃ prepared in Comparative Example 1, the conversion rate of carbon monoxide was 98%, and the methane selectivity was 85%. CFD software fluent was used to numerically simulate the temperature distribution in the reactor, the particle bed (10NiO-5MgO/γ-Al ₂ O ₃ ) and the metal fiber structured catalyst (8NiO-8Al ₂ O ₃ -2MgO/8-Ni-fiber -600) The temperature distribution in the reactor is shown in Figure 8. It can be seen from Fig. 8 that the hot spot temperature at the center of the catalyst bed is only 110°C due to the good thermal conductivity of the catalyst of the present invention; however, the hot spot temperature at the center of the traditional oxide-supported catalyst bed is as high as 400°C.

Application example 8

Reaction device, reaction raw material, catalyst consumption are the same as application example 1.

In this application example, on the 5NiO-5Al ₂ O ₃ -2.5CeO ₂ /8-Ni-SMF-500 catalyst prepared in Example 5, the mixed gas with a molar ratio of carbon monoxide and hydrogen of 1:3 was used as a raw material to investigate The 1000-hour stability of the catalytic carbon monoxide methanation reaction, the results are shown in Figure 9.

Application example 9

The reaction device and reaction raw materials are the same as in Application Example 1, and the catalyst consumption is 10.4 milliliters.

In this application example, on the 5NiO-5Al ₂ O ₃ -2.5CeO ₂ /8-Ni-SMF-500 catalyst prepared in Example 5, the mixed gas with a molar ratio of carbon monoxide and hydrogen of 1:3 was used as the raw material, at 330 Under the reaction temperature of ℃ and the gas hourly space velocity of 5000h ^-1 , the stability of the catalytic carbon monoxide methanation reaction was investigated for 3000 hours, and the results are shown in Fig. 10 . It can be seen from Fig. 10 that the catalyst of the present invention has excellent reaction stability, activity and selectivity for carbon monoxide methanation.

Application Example 10

The reaction device and reaction raw materials are the same as in Application Example 1, and the catalyst consumption is 10.2 milliliters.

This application example is carried out on the 5NiO-5Al ₂ O ₃ -2.5CeO ₂ /8-Ni-SMF-500 catalyst prepared in Example 5, using the mixed gas with the molar ratio of carbon dioxide and hydrogen as 1:4 as raw material, in At a reaction temperature of 320°C and a gas hourly space velocity of 5000 h ^-1 , the 1000-hour stability of the catalytic carbon dioxide methanation was investigated, and the results are shown in Figure 11. It can be seen from Fig. 11 that the catalyst of the present invention has excellent reaction stability, activity and selectivity for carbon dioxide methanation.

Claims (10)

1. a metal phase carrier load type catalyst, including be carried on metal phase carrier activity component metal oxide and Auxiliary agent metal oxides also has formula xM₁O-yM₂O/ZT, wherein M₁O represents activity component metal oxide, M₂O Representing auxiliary agent metal oxides, ZT represents metal phase carrier, and x represents the quality of catalyst shared by activity component metal oxide Percent, y represents that auxiliary agent metal oxides accounts for the mass percent of catalyst；It is characterized in that:

Activity component metal oxide M₁O is at least one in the oxide of nickel and ferrum；

Auxiliary agent metal oxides M₂O be aluminum, cerium, lanthanum, molybdenum, manganese, tungsten, magnesium, calcium, sodium, potassium oxide in extremely Few one；

The method preparing described metal phase carrier load type catalyst comprises the steps:

1. with the suspension incipient impregnation metal phase carrier containing aluminium powder and be dried make aluminum particle be dispersed in metal phase carrier table Behind face, make aluminum particle carry out solid-solid alloying reaction with metal phase carrier top layer at 550～650 DEG C, obtain table Layer alloyed metal (AM) phase carrier；

2. the top layer alloyed metal (AM) phase carrier 1. step prepared, below 60 DEG C at a temperature of be 5～20% by concentration Hydrochloric acid or sodium hydrate aqueous solution carry out taking out aluminum and process, through rinsing, drying, the metal obtaining top layer porous carries mutually Body；

The metal phase carrier of the top layer porous 3. step 2. prepared, incipient impregnation is in containing active component M₁Metallic element Salt and adjuvant component M₂The aqueous solution of the salt of metallic element, roasting at 300～600 DEG C after drying, i.e. obtain described Metal phase carrier load type catalyst.

Catalyst the most according to claim 1, it is characterised in that: described mass percent x is 1～15%, described Mass percent y is 1～15%, and remaining composition of described catalyst is described metal phase carrier.

Catalyst the most according to claim 1, it is characterised in that: described metal phase carrier ZT is metallic nickel, metal Copper, metallic iron or metal copper-nickel alloy.

Catalyst the most according to claim 1, it is characterised in that: described metal phase carrier is a diameter of 4～150 micro- Rice, the fiber of a length of 2～10 millimeters or by the three-dimensional porous structure monoblock type metal fiber carrier of this fiber sintering Or three-dimensional porous structure monoblock type metallic foam support.

Catalyst the most according to claim 4, it is characterised in that: the metallic framework of described metal phase carrier accounts for described The percent by volume of metal phase carrier is 5～40%, remaining for porosity.

6. for the method preparing the metal phase carrier load type catalyst as according to any one of claim 1-5, Described method comprises the steps:

1. with the suspension incipient impregnation metal phase carrier containing aluminium powder and be dried make aluminum particle be dispersed in metal phase carrier table Behind face, make aluminum particle carry out solid-solid alloying reaction with metal phase carrier top layer at 550～650 DEG C, obtain table Layer alloyed metal (AM) phase carrier；

2. the top layer alloyed metal (AM) phase carrier 1. step prepared, below 60 DEG C at a temperature of be 5～20% by concentration Hydrochloric acid or sodium hydrate aqueous solution carry out taking out aluminum and process, through rinsing, drying, the metal obtaining top layer porous carries mutually Body；

The metal phase carrier of the top layer porous 3. step 2. prepared, incipient impregnation is in containing active component M₁Metallic element Salt and adjuvant component M₂The aqueous solution of the salt of metallic element, after drying, roasting at 300～600 DEG C, i.e. obtains Described metal phase carrier load type catalyst.

Catalyst method the most according to claim 6, it is characterised in that in described metal phase carrier top layer alloying During, the particle diameter of described aluminium powder is 1～10 micron, and the mass ratio of aluminium powder/metal phase carrier is 0.5～10/100.

8. by described in claim 1 or that according to claim 6 prepared by method metal phase carrier load type catalyst It is used as the purposes of the catalyst of the reaction of carbon monoxide and/or hydrogenation of carbon dioxide synthesizing methane.

9. by described in claim 1 or metal phase carrier load type catalyst that according to claim 6 prepared by method It is used as the methane purposes for the catalyst of the reaction of synthesis gas.

Purposes the most according to claim 9, it is characterised in that: described methane for the reaction of synthesis gas be methane- CO 2 reformation or methane self-heating recapitalization prepare the reaction of synthesis gas.