CN115672331A - Methanation catalyst and preparation method and application thereof - Google Patents
Methanation catalyst and preparation method and application thereof Download PDFInfo
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Abstract
The invention relates to the field of methanation catalysts, and discloses a methanation catalyst which contains Ni element and Al element 2 O 3 And a metal active component; the metal active component is selected from at least one element of Mn, co, mo, zr and In; wherein the methanation catalyst is a four-leaf striped agent, and the methanation catalyst is internally provided with a through partPore canal, the external surface area/framework volume of the methanation catalyst is 0.8-2.1mm 2 /mm 3 . The methanation catalyst has larger external specific surface area, can enhance the mass transfer and heat transfer efficiency, quickly transfer and release reaction heat generated by the internal pore passages of the catalyst and the surface of the catalyst, and improve the thermal stability of the catalyst. Meanwhile, since Ni element and Al element 2 O 3 And the metal active component is uniformly dispersed in the system space, so that the low-temperature activity (the CO conversion rate is up to 100%) and the methane selectivity (CH) of the catalyst are improved 4 Selectivity as high as 99%).
Description
Technical Field
The invention relates to the field of methanation catalysts, and particularly relates to a methanation catalyst, and a preparation method and application thereof.
Background
The process flow of the coal-based natural gas mainly comprises four parts of coal gasification, transformation, synthesis gas purification and synthesis gas methanation. The key of the technical route of coal-based natural gas is synthesis gas methanation technology, and the core of the synthesis gas methanation technology is a methanation catalyst and a methanation reactor. The traditional process usually adopts an indirect methanation process, takes Ni, co or noble metal Ru and the like as active components, wherein the Ni-based catalyst is widely applied to industrialization. The process route has the advantages of large treatment capacity, mature technical route, and adoption of indirect methanation process route in the commercialized and pilot-scale test processes at home and abroad.
The geometric shape and the geometric dimension of the catalyst have influence on fluid resistance, air flow velocity, bed temperature gradient distribution, concentration gradient distribution and the like, and are also related to the effective utilization rate of active metal of the catalyst, the carrying of reaction heat in the reaction process and the like. The methanation of the synthesis gas is to make the CO with the concentration of about 20 percent and a small amount of CO in the synthesis gas 2 And H 2 Carrying out methanation reaction. The methanation reaction is a strongly exothermic process, and every 1% conversion of CO in the reaction system will result in a 72 ℃ adiabatic temperature rise in the reactor. The traditional spherical or columnar catalyst particle bed layer is packed in a close-packed manner, heat is easy to gather and not easy to diffuse, and temperature rise is not beneficial to reaction, so that the activity and selectivity of the catalyst are influenced. To fully exploit the potential of the catalyst, an optimal outer catalyst should be selectedShape and size, which requires the most suitable shaping and preparation method.
CN105709794A discloses a heterotype methanation catalyst, a forming process and an application thereof, wherein nickel-based synthesis gas methanation catalyst powder is prepared into a catalyst with the diameter of a contour circumscribed circle of 3-22mm, the height of 3-12mm and the volume ratio of surface area to particle skeleton of 0.8-1.6mm in a tabletting or strip extruding mode 2 /mm 3 The radial maximum mass transfer distance is 1.4-4.0mm, and the geometrical shape is regular and symmetrical. The special-shaped methanation catalyst can improve the utilization efficiency of active components of the catalyst, reduce the resistance drop of a bed layer and improve the long-time running stability of the catalyst, but has the problems of low catalyst activity, poor crushing strength and easy pulverization of the catalyst.
CN211159813U discloses a clover-shaped catalyst for hydrogen production by methane cracking, which comprises: the catalyst comprises a catalyst body, wherein the cross section of the catalyst body is in a cloverleaf shape, three blades are formed by three 240-degree arcs, the radiuses of the three arcs are equal, and a pore channel which is concentrically distributed is arranged in each arc. The catalyst can improve the adsorption capacity and stability of the catalyst, and has the problems of low external surface area and low utilization rate of active components although the catalyst has low bulk density and high crushing strength.
Disclosure of Invention
The invention aims to solve the problems of low activity and selectivity of a methanation catalyst due to low mass transfer efficiency and heat transfer efficiency of the methanation catalyst in the prior art, and provides the methanation catalyst, and a preparation method and application of the methanation catalyst.
In order to achieve the above object, a first aspect of the present invention provides a methanation catalyst comprising an element Ni and Al 2 O 3 And a metal active component; the metal active component is selected from at least one element of Mn, co, mo, zr and In;
wherein the methanation catalyst is a four-leaf striped agent, a through pore canal is arranged in the methanation catalyst, and the external surface area/framework volume of the methanation catalyst is 0.8-2.1mm 2 /mm 3 。
In a second aspect the present invention provides a process for the preparation of a methanation catalyst, said process comprising the steps of:
(1) Preparing a mixed salt solution containing Ni salt, al salt and metal active component salt, and preparing a precipitator solution; wherein the metal active component is at least one element selected from the group consisting of Mn, co, mo, zr, and In;
(2) Carrying out coprecipitation reaction on the mixed salt solution and the precipitant solution by adopting a parallel-flow coprecipitation method;
(3) Carrying out solid-liquid separation on a product obtained by the coprecipitation reaction, then washing, drying and roasting the obtained solid, and crushing and screening to obtain methanation catalyst powder;
(4) Mixing the methanation catalyst powder with an optional forming agent and/or a lubricant to obtain a mixture, and sequentially forming and secondarily drying the mixture to obtain a methanation catalyst;
the methanation catalyst is a four-leaf striped agent by the molding, and a through pore channel is arranged in the methanation catalyst; the external surface area/framework volume of the methanation catalyst is 0.8-2.1mm 2 /mm 3 。
In a third aspect, the invention provides a methanation catalyst prepared by the method of the second aspect.
In a fourth aspect, the invention provides the use of a methanation catalyst as described in the first or third aspect in the preparation of synthetic natural gas by a methanation reaction.
Through the technical scheme, the methanation catalyst provided by the invention contains Ni element and Al 2 O 3 And a metal active component; the metal active component is selected from at least one element of Mn, co, mo, zr and In; wherein the methanation catalyst is a four-leaf bar-shaped agent, a through pore canal is arranged in the methanation catalyst, and the external surface area/framework volume of the methanation catalyst is 0.8-2.1mm 2 /mm 3 The structure ensures that the methanation catalyst has larger external specific surface area and can enhance the mass and heat transfer efficiencyThe catalyst can quickly transfer and release the reaction heat generated by the internal pore channels of the catalyst and the surface of the catalyst, and improve the thermal stability of the catalyst. Meanwhile, since Ni element and Al element 2 O 3 And the metal active component is uniformly dispersed in the system space, so that the low-temperature activity (the CO conversion rate is up to 100%) and the methane selectivity (CH) of the catalyst are improved 4 Selectivity as high as 99%).
Drawings
FIG. 1 is a top view and a perspective view of a methanation catalyst prepared in example 1;
FIG. 2 is a top view and a perspective view of a methanation catalyst prepared in example 2;
FIG. 3 is a top view and a perspective view of a methanation catalyst made in example 3;
FIG. 4 is a top view and a perspective view of a methanation catalyst made in example 4;
FIG. 5 is a top view and a perspective view of a methanation catalyst made in example 5;
FIG. 6 is a top view and a perspective view of a methanation catalyst made in example 6;
FIG. 7 is a top view and a perspective view of a methanation catalyst made in example 7;
FIG. 8 is a top view and a perspective view of a methanation catalyst prepared in comparative example 1;
FIG. 9 is a top view and a perspective view of a methanation catalyst prepared in comparative example 2;
FIG. 10 is a top view and a perspective view of a methanation catalyst prepared in comparative example 3;
FIG. 11 is a top view and a perspective view of a methanation catalyst prepared in comparative example 4.
Detailed Description
The endpoints of the ranges and any values disclosed herein are not limited to the precise range or value, and such ranges or values should be understood to encompass values close to those ranges or values. For ranges of values, between the endpoints of each of the ranges and the individual points, and between the individual points may be combined with each other to give one or more new ranges of values, and these ranges of values should be considered as specifically disclosed herein.
The first aspect of the present invention provides a methanation catalyst comprising Ni and Al 2 O 3 And a metal active component; the metal active component is selected from at least one element of Mn, co, mo, zr and In;
wherein the methanation catalyst is a four-leaf striped agent, a through pore canal is arranged in the methanation catalyst, and the external surface area/framework volume of the methanation catalyst is 0.8-2.1mm 2 /mm 3 。
According to some embodiments of the invention, the methanation catalyst has an external surface area/skeletal volume of from 0.8 to 2.1mm 2 /mm 3 The methanation catalyst with the structure has larger specific surface area, can enhance mass transfer and heat transfer efficiency, and quickly transfer and release reaction heat generated by the internal pore channels of the catalyst and the surface of the catalyst. In order to further enhance the mass and heat transfer efficiency and further improve the thermal stability of the catalyst, the external surface area/framework volume of the methanation catalyst is preferably 1.67-2.07mm 2 /mm 3 。
In the present invention, the term "four-leaf bar catalyst" means a bar catalyst in which the cross section of the catalyst is in the shape of four-leaf clover. The strip is a three-dimensional structure material which is prepared by extruding or tabletting and the like, and the length of the material is not less than 50% of the diameter of the circumscribed circle.
In the present invention, the term "external surface area/skeletal volume" is the ratio of the external surface area of the methanation catalyst to the skeletal volume of the methanation catalyst, wherein the external surface area of the methanation catalyst is: the side area of the catalyst + the side area of the channels +2 × (area of cross section of catalyst-area of cross section of channels); the skeleton volume of the methanation catalyst is as follows: the area of the cross section of the catalyst x the height of the catalyst-the volume of the channels.
The through hole refers to a hole channel existing in the methanation catalyst, so that the catalyst has a smooth shape, and the hole channel penetrates through the catalyst.
According to some embodiments of the present invention, the channels of the catalyst may be channels with a uniform cross section, or may be channels with a non-uniform cross section, preferably, the channels are channels with a uniform cross section, more preferably, the channels are cylindrical, and the channels have a circular uniform cross section; under the condition, the inner surface of the catalyst is more regular, the phenomenon of stress concentration caused by sharp hole walls in a hole structure is avoided, the collapse probability of the catalyst is reduced, and the catalyst has the characteristics of higher compactness and higher strength. In the present invention, the circular shape also includes a non-perfect circular shape. Further preferably, the diameter of the cylinder is 1-6mm. The catalyst preferably adopts the size and is internally provided with a through pore channel, so that the strength is high, and the utilization rate of the metal active component is improved.
According to some embodiments of the present invention, preferably, the cross section of the methanation catalyst is clover-shaped, and the pore channel extends along a central axis of a circumscribed circle where the clover-shaped blades are located and/or along a central axis of a circumscribed circle where the clover-shaped blades are located. Preferably, the diameter of the circumscribed circle of the clover shape is 6-12mm.
According to some embodiments of the present invention, preferably, the number of the channels is 1 to 5, preferably 1 or 4.
The invention has wide selection range of the specific positions of the pore channels, and the pore channels can penetrate through the catalyst. It should be noted that, when the number of the channels is greater than 1, there are no overlapping or contacting portions between the channels. When the number of the cell channels is 1, it is preferable that the cell channels extend along a central axis of a circumscribed circle on which a cross section of the catalyst is located, in which case, when the cross section of the catalyst is clover-shaped, the cell channels extend along a central axis of a circumscribed circle on which the clover-shaped is located.
When the number of the channels is 4, the relative arrangement positions of the channels are not particularly limited, and the channels are preferably uniformly distributed. The preferred embodiment is more beneficial to ensuring that the stress distribution of the catalyst is more balanced, and further optimizing the overall strength of the catalyst. Preferably, the uniform distribution means that the distances from the channels to the center of the circumscribed circle of the cross section of the catalyst are equal, more preferably, the distances between the channels are equal, and further preferably, the distance between each channel and the center of the circumscribed circle of the cross section of the catalyst is equal to the distance between each channel and the edge of the catalyst.
According to some embodiments of the present invention, preferably, the content of Ni element is 30 to 60 wt% in terms of oxide, and Al is based on the total amount of the methanation catalyst 2 O 3 Is 25 to 50 wt%, and the content of the metal active component is 1.5 to 10 wt%.
More preferably, the content of Ni element is 40-50 wt% calculated by oxide and Al element based on the total amount of the methanation catalyst 2 O 3 The content of (A) is 30-35 wt%, and the content of the metal active component is 2.5-7.5 wt%.
According to some embodiments of the present invention, the metal active component is at least one element selected from Mn, co, mo, zr, and In, preferably, the metal active component is Mn element and/or In element, more preferably, the metal active component is In element. The inventors of the present invention found that nickel (Ni) and Al are mixed in the course of their research 2 O 3 The catalyst is matched with indium (In) element for use, so that the utilization rate of active components, the catalytic activity of the catalyst and the methane selectivity can be further improved.
According to some embodiments of the present invention, preferably, the methanation catalyst further comprises a shaping agent and/or a lubricant; wherein the forming agent is selected from Al 2 O 3 、SiO 2 And amorphous silica-alumina, preferably Al 2 O 3 And/or amorphous silica-alumina, more preferably Al 2 O 3 (ii) a Further preferably, al 2 O 3 Is gamma-Al 2 O 3 (ii) a The lubricant is selected from at least one of graphite, stearic acid and sesbania powder, and is preferably graphite;
according to some embodiments of the present invention, preferably, the forming agent is present in an amount of 10 to 50 wt.%, preferably 12 to 25 wt.%, based on the total amount of methanation catalyst; and/or
The lubricant is present in an amount of 1 to 8 wt.%, preferably 3 to 5 wt.%, based on the total amount of methanation catalyst.
According to a particularly preferred embodiment of the present invention, the methanation catalyst contains Ni element and Al element 2 O 3 And a metal active component; the metal active component is In element; the methanation catalyst is a clover-shaped catalyst, the cross section of the methanation catalyst is clover-shaped, 1 or 4 through pore channels are arranged in the methanation catalyst, and the external surface area/framework volume is 1.67-2.07mm 2 /mm 3 (ii) a Based on the total amount of the methanation catalyst, the content of Ni element is 40-50 wt% and Al is calculated by oxide 2 O 3 The content of (A) is 30-35 wt%, the content of the metal active component is 2.5-7.5 wt%, the content of the forming agent is 12-25 wt%, and the content of the lubricant is 3-5 wt%, so that the mass transfer and heat transfer efficiency of the catalyst can be particularly enhanced, and the thermal stability of the catalyst, the low-temperature activity of the catalyst and the methane selectivity of the catalyst can be improved.
In the present invention, the forming agent is Al 2 O 3 In the case where the content of the molding agent is not counted in the above-mentioned Al 2 O 3 The content of (b). That is, based on the total amount of the methanation catalyst, al in the methanation catalyst 2 O 3 Is 25-50 wt%, preferably 30-35 wt%, when the methanation catalyst also contains a forming agent and the forming agent is Al 2 O 3 When it is Al 2 O 3 The content of (b) does not include the content of the molding agent, and the content of the molding agent is separately calculated.
In the invention, the content of each component in the methanation catalyst can be obtained by analyzing the components of the methanation catalyst, and can also be obtained by calculating the feeding amount of the raw materials in the preparation process.
In a second aspect the present invention provides a process for the preparation of a methanation catalyst, said process comprising the steps of:
(1) Preparing a mixed salt solution containing Ni salt, al salt and metal active component salt, and preparing a precipitator solution; wherein the metal active component is selected from at least one element of Mn, co, mo, zr and In;
(2) Carrying out coprecipitation reaction on the mixed salt solution and the precipitant solution by adopting a parallel-flow coprecipitation method;
(3) Carrying out solid-liquid separation on a product obtained by the coprecipitation reaction, then washing, drying and roasting the obtained solid, and crushing and screening to obtain methanation catalyst powder;
(4) Mixing the methanation catalyst powder with an optional forming agent and/or a lubricant to obtain a mixture, and sequentially forming and carrying out secondary drying on the mixture to obtain a methanation catalyst;
the methanation catalyst is a four-leaf striped agent by the molding, and a through pore channel is formed in the methanation catalyst; the external surface area/framework volume of the methanation catalyst is 0.8-2.1mm 2 /mm 3 。
According to some embodiments of the present invention, preferably, in step (1), the Ni salt is at least one selected from the group consisting of nickel nitrate, basic nickel carbonate, nickel chloride, and a hydrate containing nickel, and is preferably nickel nitrate.
According to some embodiments of the present invention, preferably, the Al salt is selected from at least one of aluminum nitrate, aluminum sulfate, aluminum chloride, and aluminum-containing hydrate, preferably aluminum nitrate.
According to some embodiments of the present invention, preferably, the metal active component salt is selected from at least one of a nitrate containing the metal active component, a chloride containing the metal active component, and a hydrate containing the metal active component, preferably a nitrate containing the metal active component, more preferably manganese nitrate and/or indium nitrate, and further preferably indium nitrate.
According to some embodiments of the invention, preferably, the precipitating agent is selected from NaOH and/or Na 2 CO 3 Preferably NaOH.
According to some embodiments of the invention, preferably, the forming agent is selected from Al 2 O 3 、SiO 2 And amorphous silica-alumina, and a method for producing the same,preferably Al 2 O 3 And/or amorphous silica-alumina, more preferably Al 2 O 3 (ii) a Further preferably, al 2 O 3 Is gamma-Al 2 O 3 。
According to some embodiments of the present invention, preferably, the shaping agent is used in an amount of 10 to 50 wt%, preferably 12 to 25 wt%, based on the total amount of the methanation catalyst.
According to some embodiments of the present invention, preferably, the lubricant is selected from at least one of graphite, stearic acid, and sesbania powder, preferably graphite.
According to some embodiments of the present invention, the lubricant is preferably used in an amount of 1-8 wt.%, preferably 3-5 wt.%, based on the total amount of methanation catalyst.
According to some embodiments of the present invention, in the step (2), a co-current co-precipitation method is adopted, and the dropping speed of the mixed salt solution and the precipitant solution is adjusted so that the pH of the mixed solution system formed by the mixed salt solution and the precipitant solution is 8 to 12, preferably 9 to 10; meanwhile, the temperature of coprecipitation is controlled to be 90-110 ℃, and preferably 100-110 ℃; the time for the coprecipitation is controlled to 6 to 32 hours, preferably 12 to 24 hours.
According to some embodiments of the present invention, in step (3), the solid-liquid separation method is not particularly limited, and the product obtained by the coprecipitation reaction may be separated by a solid-liquid separation method known in the art, for example, by filtration. Preferably, after filtering the product obtained by the coprecipitation reaction, taking out the filter cake, and washing the filter cake with deionized water, wherein the volume ratio of the deionized water to the filter cake in each washing is preferably 2-20:1, preferably 5 to 15:1, washing times are 1-10 times, preferably 2-6 times, based on the final filtrate conductivity being less than 50 muS/cm.
According to some embodiments of the present invention, preferably, in the step (3), the conditions of the first drying include: the temperature is 100-110 ℃, and the time is 12-24 hours.
According to some embodiments of the invention, preferably, the conditions of the firing comprise: the temperature is 350-400 ℃, and the time is 4-5 hours.
According to some embodiments of the present invention, preferably, the methanation catalyst powder has an average particle size of less than 0.1mm.
According to some embodiments of the present invention, preferably, in the step (4), the mixing time is 30 to 60 minutes; preferably, the conditions of the second drying include: the temperature is 100-110 deg.C, and the time is 12-24 hr.
According to some embodiments of the present invention, preferably, the methanation catalyst has an external surface area/skeletal volume of 1.67-2.07mm 2 /mm 3 。
According to some embodiments of the present invention, the Ni salt, the Al salt and the metal active component salt are preferably used in amounts such that the resultant methanation catalyst contains Ni element in an amount of 30 to 60 wt% in terms of oxide and Al in an amount of 30 to 60 wt% in terms of oxide, based on the total amount of the methanation catalyst 2 O 3 The content of (A) is 25-50 wt%, and the content of the metal active component is 1.5-10 wt%.
More preferably, the Ni salt, the Al salt and the metal active component salt are used in such amounts that the prepared methanation catalyst contains 40-50 wt% of Ni element and Al element in terms of oxide based on the total amount of the methanation catalyst 2 O 3 The content of (A) is 30-35 wt%, and the content of the metal active component is 2.5-7.5 wt%.
In a third aspect, the invention provides a methanation catalyst prepared by the method of the second aspect.
In a fourth aspect, the invention provides the use of a methanation catalyst as described in the first or third aspect in the preparation of synthetic natural gas by a methanation reaction.
The methanation catalyst provided by the invention or the methanation catalyst prepared by the method provided by the invention needs to be subjected to reduction activation in the presence of hydrogen before being used for methanation reaction, and the activation conditions can be, for example: the pressure is 0-5MPa, preferably 2-5MPa; the temperature is 200-300 deg.C, preferably 250-300 deg.C(ii) a For a period of 0.5 to 10 hours, preferably 1 to 5 hours; the activation can be carried out in pure hydrogen or in a gas mixture of hydrogen and an inert gas, for example in a gas mixture of hydrogen with nitrogen and/or argon, preferably at 95% by volume N 2 And 5 vol% H 2 In the mixed gas of (3).
According to some embodiments of the invention, preferably, the contacting conditions of the methanation reaction comprise: the volume composition of the feed gas is as follows: 8-8.5 vol.% CO,50-55 vol.% H 2 25-26% by volume CH 4 2-2.5 vol.% CO 2 10-11 vol% N 2 (ii) a The pressure is 2-5MPa, the temperature is 200-300 ℃, and the air volume space velocity is 10000-40000h -1 。
In the present invention, "Φ" represents the size of the diameter.
In the present invention, the pressure is measured as gauge pressure.
The present invention will be described in detail below by way of examples.
In the following examples and comparative examples, all the raw materials used are commercially available ones unless otherwise specified.
In the following examples and comparative examples, the content of each component in the methanation catalyst is calculated by the charging amount of the raw material in the preparation process.
Examples 1 to 9 serve to illustrate methanation catalysts and methods for their preparation.
Example 1
(1) Dissolving 9.39 moles of nickel nitrate, 5.16 moles of aluminum nitrate and 0.41 mole of indium nitrate in 40L of deionized water to obtain a mixed salt solution; dissolving 15.75 mol of sodium hydroxide in 40L of deionized water to obtain a precipitator solution;
(2) Respectively carrying out parallel-flow coprecipitation on a mixed salt solution and a precipitator solution at certain flow rates, controlling the pH of the formed mixed solution to be 9, then placing the obtained mixed solution in a hydrothermal reaction kettle, and reacting for 24 hours at 100 ℃;
(3) Filtering suspension obtained by the hydrothermal reaction, washing the product obtained by filtering with deionized water until the conductivity of the filtrate is less than 50 mu S/cm, drying the washed product at 110 ℃ for 12 hours, roasting at 350 ℃ for 4 hours, and crushing and screening to obtain methanation catalyst powder with the particle size of less than 0.1 mm;
(4) 1000g of methanation catalyst powder and 200g of gamma-Al 2 O 3 40g of graphite to obtain mixed powder, putting the mixed powder into a mixer, and then adding 200mL of 2% HNO 3 Spraying the water solution onto the surface of the mixed powder in a mist form, continuously carrying out wet mixing for 30 minutes after all the liquid is sprayed, granulating the obtained mixed wet material by using a granulator, forming by using a flaker, and drying at 110 ℃ for 12 hours to obtain the methanation catalyst, wherein the composition and the content of the methanation catalyst are shown in table 1.
As shown in fig. 1, the methanation catalyst is a tetrafoil stripe agent, 1 through cylindrical pore canal (the diameter phi is 2.5 mm) is arranged in the catalyst, the cross section of the catalyst is a tetrafoil shape, the pore canal extends along the central axis of a circumscribed circle (the diameter phi is 6 mm) where the tetrafoil shape is located, the diameter phi of the circumscribed circle where the tetrafoil-shaped blades are located is 3.5mm, the diagonal length of a square formed by the centers of the circumscribed circles where the four blades are respectively located is 2.5mm, and the height of the catalyst is 6mm; the external surface area/framework volume of the methanation catalyst is 1.67mm 2 /mm 3 The lateral pressure strength was 161N/cm.
Example 2
(1) Dissolving 9.39 moles of nickel nitrate, 5.16 moles of aluminum nitrate and 0.41 mole of manganese nitrate in 40L of deionized water to obtain a mixed salt solution; dissolving 15.75 mol of sodium hydroxide in 40L of deionized water to obtain a precipitant solution;
(2) Respectively carrying out parallel-flow co-precipitation on the mixed salt solution and the precipitant solution at certain flow rates, controlling the pH of the formed mixed solution to be 9, then placing the obtained mixed solution into a hydrothermal reaction kettle, and reacting for 24 hours at 100 ℃;
(3) Filtering a suspension obtained by the hydrothermal reaction, washing a product obtained by filtering with deionized water until the conductivity of the filtrate is less than 50 mu S/cm, drying the washed product at 110 ℃ for 12 hours, roasting at 350 ℃ for 4 hours, and crushing and screening to obtain methanation catalyst powder with the particle size of less than 0.1 mm;
(4) 1000g of methanation catalyst powder and 150g of gamma-Al 2 O 3 60g of graphite to obtain mixed powder, putting the mixed powder into a mixer, and then adding 200mL of 2% HNO 3 Spraying the water solution on the surface of the mixed powder in a mist form, continuously carrying out wet mixing for 30 minutes after all the liquid is sprayed, granulating the obtained mixed wet material by using a granulator, forming by using a tabletting machine, and drying at 110 ℃ for 12 hours to obtain the methanation catalyst, wherein the composition and the content of the methanation catalyst are shown in table 1.
As shown in fig. 2, the methanation catalyst is a tetrafoil stripe agent, 1 through cylindrical pore canal (the diameter phi is 5 mm) is arranged in the catalyst, the cross section of the catalyst is in a tetrafoil shape, the pore canal extends along the central axis of a circumscribed circle (the diameter phi is 12 mm) where the tetrafoil shape is located, the diameter phi of the circumscribed circle where the tetrafoil-shaped blades are located is 6mm, the diagonal length of a square formed by the centers of the circumscribed circles where the four blades are respectively located is 6mm, and the height of the catalyst is 12mm; the external surface area/framework volume of the methanation catalyst is 0.9mm 2 /mm 3 The lateral pressure strength was 153N/cm.
Example 3
The methanation catalyst powder is prepared according to the steps (1) to (3) of the example 2, except that in the step (4), 1000g of the methanation catalyst powder is uniformly mixed with 150g of amorphous silica-alumina and 50g of sesbania powder to obtain mixed powder, the mixed powder is put into a mixer, and 200mL of HNO with the mass concentration of 2 percent is added 3 Spraying the water solution on the surface of the mixed powder in a mist form, continuously carrying out wet mixing for 30 minutes after all the liquid is sprayed, granulating the obtained mixed wet material by using a granulator, forming by using a tabletting machine, and drying at 110 ℃ for 12 hours to obtain the methanation catalyst, wherein the composition and the content of the methanation catalyst are shown in table 1.
As shown in figure 3, the methanation catalyst is a clover-shaped catalyst, 1 through cylindrical pore canal (the diameter phi is 4 mm) is arranged in the catalyst, the cross section of the catalyst is clover-shaped, the pore canal extends along the central axis of a circumscribed circle (the diameter phi is 12 mm) where the clover-shaped is positioned,the diameter phi of a circumscribed circle where the four-leaf-shaped blades are located is 5.5mm, the diagonal length of a square formed by the centers of the circumscribed circles where the four blades are respectively located is 6.5mm, and the height of the catalyst is 12mm; the external surface area/framework volume of the methanation catalyst is 0.84mm 2 /mm 3 The lateral pressure strength was 145N/cm.
Example 4
A methanation catalyst powder was produced in accordance with the procedures (1) to (3) of example 1 except that in the procedure (4), 1000g of the methanation catalyst powder was mixed with 150g of γ -Al 2 O 3 And 50g of graphite are uniformly mixed to obtain mixed powder, the mixed powder is placed into a mixer, and then 200mL of HNO with the mass concentration of 2 percent is added 3 Spraying the water solution on the surface of the mixed powder in a mist form, continuously carrying out wet mixing for 30 minutes after all the liquid is sprayed, granulating the obtained mixed wet material by using a granulator, forming by using a tabletting machine, and drying at 110 ℃ for 12 hours to obtain the methanation catalyst, wherein the composition and the content of the methanation catalyst are shown in table 1.
As shown in fig. 4, the methanation catalyst is a tetrafoil stripe agent, 4 through cylindrical pore canals (the diameters phi are all 1.25 mm) are arranged in the catalyst, the cross section of the catalyst is in a tetrafoil shape, the diameter phi of a circumscribed circle where the tetrafoil shape is located is 6mm, the pore canals extend along the central axis of a circumscribed circle (the diameter phi is 3.5 mm) where the tetrafoil-shaped blades are located, the diagonal length of a square formed by the centers of the circumscribed circles where the four blades are respectively located is 2.5mm, and the height of the catalyst is 6mm; the external surface area/framework volume of the methanation catalyst is 2.07mm 2 /mm 3 The lateral pressure strength was 132N/cm.
Example 5
Methanation catalyst powder was prepared according to the steps (1) to (3) of example 2, except that in the step (4), 1000g of methanation catalyst powder was mixed with 200g of γ -Al 2 O 3 And 60g of stearic acid are uniformly mixed to obtain mixed powder, the mixed powder is placed into a mixer, and then 200mL of HNO with the mass concentration of 2 percent is added 3 Spraying the water solution onto the surface of the mixed powder in the form of mist, continuously wet-mixing for 30 min after all the liquid is sprayed, and granulating the obtained wet mixtureAfter granulation, the pellets were formed with a tablet machine and dried at 110 ℃ for 12 hours to obtain a methanation catalyst, the composition and content of which are shown in table 1.
As shown in fig. 5, the methanation catalyst is a tetrafoil stripe agent, 4 through cylindrical pore canals (the diameter phi is 2.5 mm) are arranged in the catalyst, the cross section of the catalyst is in a tetrafoil shape, the diameter phi of a circumscribed circle where the tetrafoil shape is located is 12mm, the pore canals extend along the central axis of a circumscribed circle (the diameter phi is 6 mm) where the tetrafoil-shaped blades are located, the diagonal length of a square formed by the centers of the circumscribed circles where the four blades are located respectively is 6mm, and the height of the catalyst is 12mm; the external surface area/framework volume of the methanation catalyst is 1.11mm 2 /mm 3 The lateral pressure strength was 124N/cm.
Example 6
Methanation catalyst powder was prepared according to the steps (1) to (3) of example 2 except that in the step (4), 1000g of methanation catalyst powder was uniformly mixed with 300g of amorphous silica-alumina and 60g of graphite to obtain mixed powder, the mixed powder was put into a blender, and 200mL of HNO having a mass concentration of 2% 3 Spraying the water solution on the surface of the mixed powder in a mist form, continuously carrying out wet mixing for 30 minutes after all the liquid is sprayed, granulating the obtained mixed wet material by using a granulator, forming by using a tabletting machine, and drying at 110 ℃ for 12 hours to obtain the methanation catalyst, wherein the composition and the content of the methanation catalyst are shown in table 1.
As shown in fig. 6, the methanation catalyst is a tetrafoil stripe agent, 4 through cylindrical pore passages (the diameters phi are all 2.5 mm) are arranged inside the catalyst, the cross section of the catalyst is in a tetrafoil shape, the diameter phi of a circumscribed circle where the tetrafoil shape is located is 12mm, the pore passages extend along the direction of a central axis of a circumscribed circle (the diameter phi is 6 mm) where the tetrafoil-shaped blades are located, but the centers of the cross sections of the 4 pore passages are not overlapped with the centers of the circumscribed circles where the four blades are respectively located; the diagonal line length of a square formed by the centers of the circumscribed circles where the four blades are respectively located is 6mm; the length of a diagonal line of a square formed by the centers of the circular sections of the 4 pore canals is 4.5mm, the center of the square is superposed with the center of a circumscribed circle where the clover shape is positioned, and the height of the catalyst is 12mm; the methaneThe external surface area/framework volume of the catalyst is 1.11mm 2 /mm 3 The lateral pressure strength was 118N/cm.
Example 7
Methanation catalyst powder was prepared according to the steps (1) to (3) of example 2, except that in the step (4), 1000g of methanation catalyst powder and 200g of SiO 2 And 40g of stearic acid are uniformly mixed to obtain mixed powder, the mixed powder is placed into a mixer, and then 200mL of HNO with the mass concentration of 2 percent is added 3 Spraying the water solution onto the surface of the mixed powder in a mist form, continuously carrying out wet mixing for 30 minutes after all the liquid is sprayed, granulating the obtained mixed wet material by using a granulator, forming by using a flaker, and drying for 12 hours at 110 ℃ to obtain the methanation catalyst, wherein the composition and the content of the methanation catalyst are shown in table 1.
As shown in fig. 7, the methanation catalyst is a tetrafoil stripe agent, 4 through cylindrical pore canals (the diameter phi is 2 mm) are arranged in the catalyst, the cross section of the catalyst is in a tetrafoil shape, the diameter phi of a circumscribed circle where the tetrafoil shape is located is 12mm, the pore canals extend along the central axis of a circumscribed circle (the diameter phi is 5.5 mm) where the tetrafoil-shaped blades are located, the diagonal length of a square formed by the centers of the circumscribed circles where the four blades are located respectively is 6.5mm, and the height of the catalyst is 12mm; the external surface area/framework volume of the methanation catalyst is 1.04mm 2 /mm 3 The lateral pressure intensity was 127N/cm.
Example 8
Following the procedure of example 2, except that in step (1), manganese nitrate was replaced with an equimolar amount of indium nitrate, a methanation catalyst was obtained, the composition and content of which are shown in Table 1.
Example 9
The procedure of example 2 was followed, except that in step (1), manganese nitrate was replaced with an equimolar amount of cobalt nitrate to obtain a methanation catalyst whose composition and content are shown in Table 1.
Comparative example 1
The process according to example 2 is followed, except that the methanation catalyst is a cylinder with a diameter Φ of 6mm and a height of 6mm, as shown in FIG. 8; external surface area/framework of the methanation catalystVolume of 1mm 2 /mm 3 The lateral pressure strength was 182N/cm.
Comparative example 2
The process according to example 2 is followed, except that the methanation catalyst is a cylinder with a diameter Φ of 12mm and a height of 12mm, as shown in FIG. 9; the external surface area/framework volume of the methanation catalyst is 0.5mm 2 /mm 3 The lateral pressure strength was 196N/cm.
Comparative example 3
According to the method of example 2, except that the methanation catalyst is a cylinder with a diameter phi of 12mm and a height of 12mm, the catalyst has 1 through cylindrical hole channel (with a diameter phi of 5 mm) inside, and the hole channel extends along the central axis of the cylinder, as shown in fig. 10; the external surface area/framework volume of the methanation catalyst is 0.738mm 2 /mm 3 The lateral pressure intensity was 177N/cm.
Comparative example 4
According to the method of example 2, except that the methanation catalyst is a cylinder with a diameter phi of 12mm and a height of 12mm, the interior of the catalyst is provided with 4 through cylindrical hole channels (with a diameter phi of 2.5 mm), the hole channels extend along the cylinder, the diagonal length of a square formed by the centers of the four hole channels is 6mm, and the center of the square coincides with the center of the circular cross section of the methanation catalyst, as shown in fig. 11; the external surface area/framework volume of the methanation catalyst is 0.906mm 2 /mm 3 The lateral pressure intensity was 177N/cm.
TABLE 1
Note: the forming agent is Al 2 O 3 Of (i) is Al 2 O 3 In an amount excluding the content of the molding agent
Test example
The test example is used for testing the performance of the methanation catalyst in the methanation reaction
(1) Activation of methanation catalyst
Respectively adding 100g of riceThe methanation catalysts prepared in the examples and the comparative examples are filled into a microchannel reactor, nitrogen-containing hydrogen is adopted to activate the methanation catalyst, and the gas volume composition is as follows: 95 volume% N 2 5% by volume of H 2 The temperature is raised to 300 ℃ at the speed of 2 ℃/min under the pressure of 2MPa, and then the temperature is kept constant for 4 hours.
(2) Evaluation of methanation Activity of methanation catalyst
After activation, cooling to room temperature in a pure nitrogen atmosphere, then switching the pure nitrogen atmosphere into a feed gas, and performing methanation reaction, wherein the volume of the feed gas at the inlet comprises: 8.18 vol.% CO,53.59 vol.% H 2 25.22 vol.% CH 4 2.03% by volume CO 2 10.62 vol% N 2 (ii) a The pressure is 2MPa, the temperature is 240 ℃, 270 ℃ and 300 ℃ respectively, and the gas volume space velocity is 40000h -1 And sampling after 8 hours of reaction. And detecting the components of the reacted gas sample by using an online gas chromatography, and calculating to obtain the catalytic activity data of the methanation catalyst at different temperatures.
Wherein the conversion rate of the CO component in the gas sample is calculated by the following formula:
CH in sample gas 4 The selectivity of the components is calculated by the following formula:
wherein n is the number of moles of the corresponding gas detected at the inlet or outlet end of the reactor.
The activity of the methanation catalyst is expressed in terms of the amount of methane in the product, and the results are shown in Table 2.
TABLE 2
From the above results, it can be seen that the methanation catalyst provided by the present invention has a higher external surface area/skeletal volume ratio, and exhibits higher CO conversion and CH conversion under the same methanation reaction conditions, compared to the conventional cylindrical catalyst of the same dimensions 4 Selectivity; compared with the conventional cylindrical catalyst with through-hole channels inside the same size, the methanation catalyst provided by the invention has higher external surface area/framework volume ratio and also shows higher CO conversion rate and CH (carbon monoxide) under the same methanation reaction conditions 4 And (4) selectivity.
The methanation catalyst provided by the invention is a four-leaf strip agent, a through pore canal is arranged in the methanation catalyst, and the external surface area/framework volume of the methanation catalyst is 0.8-2.1mm 2 /mm 3 The structure enhances the mass transfer and heat transfer of the methanation catalyst, improves the utilization rate of the catalyst and avoids the aggregation of reaction heat; meanwhile, ni element and Al which are uniformly dispersed in the methanation catalyst are combined 2 O 3 And metal active components, and improves the catalytic activity (CO conversion rate is up to 100%) and methane selectivity (CH) of the catalyst 4 Selectivity as high as 99%). Preferably, when the metal active component is In element, the external surface area/skeleton volume is 1.67-2.07mm 2 /mm 3 In addition, the methanation catalyst provided by the invention has higher CO conversion rate and CH 4 And (4) selectivity.
The preferred embodiments of the present invention have been described above in detail, but the present invention is not limited thereto. Within the scope of the technical idea of the invention, many simple modifications can be made to the technical solution of the invention, including combinations of various technical features in any other suitable way, and these simple modifications and combinations should also be regarded as the disclosure of the invention, and all fall within the scope of the invention.
Claims (12)
1. A methanation catalyst is characterized by containing Ni element and Al element 2 O 3 And a metal active component; the metal active component is selected from at least one element of Mn, co, mo, zr and In;
wherein the methanation catalyst is a four-leaf striped agent, a through pore canal is arranged in the methanation catalyst, and the external surface area/framework volume of the methanation catalyst is 0.8-2.1mm 2 /mm 3 。
2. Methanation catalyst according to claim 1, wherein the external surface area/skeletal volume of the methanation catalyst is 1.67-2.07mm 2 /mm 3 ；
Preferably, the duct is a channel with a uniform cross section, and more preferably, the duct is cylindrical;
further preferably, the diameter of the cylinder is 1-6mm.
3. Methanation catalyst according to claim 1 or 2, wherein the cross-section of the methanation catalyst is clover-shaped, the pore channel extends along the central axis of the circumscribed circle on which the clover-shaped blades lie and/or along the central axis of the circumscribed circle on which the clover-shaped blades lie;
preferably, the number of said channels is 1-5, preferably 1 or 4.
4. Methanation catalyst according to any of claims 1 to 3, wherein the content of Ni element is 30 to 60% by weight, calculated as oxide, based on the total amount of the methanation catalyst, al 2 O 3 The content of (A) is 25-50 wt%, and the content of the metal active component is 1.5-10 wt%;
preferably, the content of Ni element is 40-50 wt% calculated by oxide and Al element based on the total amount of the methanation catalyst 2 O 3 The content of (A) is 30-35 wt%, and the content of the metal active component is 2.5-7.5 wt%;
preferably, the metal active component is an Mn element and/or an In element, more preferably an In element.
5. Methanation catalyst according to any of claims 1 to 4, wherein the methanation catalyst further comprises a shaping agent and/or a lubricant;
wherein the forming agent is selected from Al 2 O 3 、SiO 2 And amorphous silica-alumina, preferably Al 2 O 3 And/or amorphous silica-alumina, more preferably Al 2 O 3 (ii) a Further preferably, al 2 O 3 Is gamma-Al 2 O 3 (ii) a The lubricant is selected from at least one of graphite, stearic acid and sesbania powder, and is preferably graphite;
preferably, the content of the forming agent is 10-50 wt%, preferably 12-25 wt% based on the total amount of the methanation catalyst; and/or
The lubricant is present in an amount of 1 to 8 wt.%, preferably 3 to 5 wt.%, based on the total amount of methanation catalyst.
6. A process for preparing a methanation catalyst, the process comprising the steps of:
(1) Preparing a mixed salt solution containing Ni salt, al salt and metal active component salt, and preparing a precipitator solution; wherein the metal active component is selected from at least one element of Mn, co, mo, zr and In;
(2) Carrying out coprecipitation reaction on the mixed salt solution and the precipitant solution by adopting a parallel-flow coprecipitation method;
(3) Carrying out solid-liquid separation on a product obtained by the coprecipitation reaction, then washing, drying and roasting the obtained solid, and crushing and screening to obtain methanation catalyst powder;
(4) Mixing the methanation catalyst powder with an optional forming agent and/or a lubricant to obtain a mixture, and sequentially forming and carrying out secondary drying on the mixture to obtain a methanation catalyst;
the methanation catalyst is a four-leaf striped agent by the molding, and a through pore channel is arranged in the methanation catalyst; the external surface area/framework volume of the methanation catalyst is 0.8-2.1mm 2 /mm 3 。
7. The method according to claim 6, wherein in step (1), the Ni salt is selected from at least one of nickel nitrate, basic nickel carbonate, nickel chloride and a nickel-containing hydrate, preferably nickel nitrate; and/or
The Al salt is selected from at least one of aluminum nitrate, aluminum sulfate, aluminum chloride and aluminum-containing hydrate, and is preferably aluminum nitrate; and/or
The metal active component salt is at least one selected from a nitrate containing a metal active component, a chloride containing a metal active component and a hydrate containing a metal active component, preferably a nitrate containing a metal active component, more preferably manganese nitrate and/or indium nitrate, and further preferably indium nitrate; and/or
The precipitant is selected from NaOH and/or Na 2 CO 3 Preferably NaOH; and/or
The forming agent is selected from Al 2 O 3 、SiO 2 And amorphous silica-alumina, preferably Al 2 O 3 And/or amorphous silica-alumina, more preferably Al 2 O 3 (ii) a Further preferably, al 2 O 3 Is gamma-Al 2 O 3 ；
Preferably, the forming agent is used in an amount of 10-50 wt%, preferably 12-25 wt%, based on the total amount of the methanation catalyst; and/or
The lubricant is selected from at least one of graphite, stearic acid and sesbania powder, and is preferably graphite;
preferably, the lubricant is used in an amount of 1-8 wt.%, preferably 3-5 wt.%, based on the total amount of methanation catalyst.
8. The method according to claim 6 or 7, wherein in step (2), the conditions of the coprecipitation reaction include: the pH is 8-12, preferably 9-10; the temperature is 90-110 ℃, preferably 100-110 ℃; the time is 6 to 32 hours, preferably 12 to 24 hours.
9. The method according to any one of claims 6 to 8, wherein in step (3), the conditions of the first drying comprise: the temperature is 100-110 ℃, and the time is 12-24 hours;
preferably, the conditions of the calcination include: the temperature is 350-400 ℃, and the time is 4-5 hours;
preferably, the average particle size of the methanation catalyst powder is less than 0.1mm.
10. The method according to any one of claims 6 to 9, wherein in step (4), the mixing time is 30 to 60 minutes;
preferably, the conditions of the second drying include: the temperature is 100-110 ℃, and the time is 12-24 hours;
preferably, the methanation catalyst has an external surface area/skeletal volume of 1.67-2.07mm 2 /mm 3 。
11. A methanation catalyst prepared by the process of any one of claims 6 to 10.
12. Use of a methanation catalyst as claimed in any of claims 1 to 5 and 11 in the preparation of synthetic natural gas by methanation.
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