CN107537489B - Porous composite catalyst, preparation method and application thereof - Google Patents
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Abstract
The invention relates to a porous composite catalyst, a preparation method and application thereof, and mainly solves the problems of low activity, poor product selectivity and poor stability of the existing porous composite catalyst. The invention adopts a porous composite catalyst, which comprises the following components: (A) inert components: at least one of silica, alumina, magnesia, and zirconia; (B) active components: at least one of platinum, rhodium, palladium, ruthenium, nickel, iron, cobalt, and copper; (C) auxiliary agent: at least one of oxides of titanium, vanadium, chromium and manganese; the specific surface area of the porous composite catalyst is more than 2 square meters per gram, the pore volume is more than 0.006 cubic centimeter per gram, and the technical scheme of the preparation method thereof well solves the problems of low activity, poor stability and sintering resistance, easy carbon deposition and the like of the catalyst, and can be used in the catalytic industrial production processes of Fischer-Tropsch synthesis, synthesis gas methanation and methane reforming.
Description
Technical Field
The invention relates to a porous composite catalyst and a preparation method thereof, in particular to a porous composite catalyst which can be used for Fischer-Tropsch synthesis, synthesis gas methanation and methane reforming and a preparation method thereof.
Background
The conversion and utilization of the synthetic gas have important significance under the energy background of rich coal, oil and gas shortage in China. Both the Fischer-Tropsch synthesis and the methanation of synthesis gas are processes of synthesizing liquid fuel or methane by using the synthesis gas as a raw material under a catalyst and proper reaction conditions. On the other hand, along with the exploitation and development of unconventional natural gas, especially coal bed gas, shale gas and the like in China, the chemical utilization of natural gas is increasingly attracting attention, wherein methane reforming is an important process for the chemical utilization of natural gas, and methane reforming refers to a process for preparing methane into synthesis gas by using water vapor, carbon dioxide, oxygen and the like. The two technologies still have a lot of technical problems in large-scale industrial application, and the most important of them is how to design the catalyst in a targeted manner to improve the utilization efficiency of the catalyst, the yield of the target product and the selectivity. Therefore, the development of the high-performance catalyst has important significance for the development of processes such as Fischer-Tropsch synthesis, synthesis gas methanation, methane reforming and the like.
Currently, many porous composite catalysts have been used in the above process. For example, chinese patent No. ZL200410056853.3 discloses a ternary composite metal oxide catalyst and a preparation method thereof, wherein porous honeycomb ceramics are used as a carrier, an inner layer and an outer layer of oxides are respectively coated on the ceramic substrate, the inner layer comprises metal oxides and alumina, and the outer layer is a noble metal oxide, and the obtained catalyst is used for automobile exhaust purification treatment, so that a good effect is achieved. However, the coating process is complicated, and the particles of the active component in the catalyst are large and have a limited range of use. Chinese patent CN103143364A discloses a highly dispersed nano-composite catalyst, its preparation method and application, wherein a coprecipitation method is used to prepare a composite precipitate from a mixed salt solution and an alkaline precipitant, and the composite precipitate is refluxed, aged and calcined to obtain the nano-composite catalyst, which is used in methane reforming and has good performance. However, the preparation method of the nano composite catalyst must use the zirconia precursor, and the application range is limited. And the nanocomposite catalyst needs to be further processed for catalytic reaction. Chinese patent application No. 201010575387.5 discloses a method for preparing porous silica supported metal or oxide, in which porous silica/metal oxide composite material can be obtained through multiple steps of synthesis of porous silica and nonpolar solvent, impregnation of metal precursor with carrier silica, removal of nonpolar solvent, drying and roasting. In this patent, since a nonpolar solvent and an impregnation method are used, the preparation process is complicated, and the interaction between the metal oxide and the silicon oxide in the product is weak, resulting in a particle size of the metal oxide exceeding 200 nm. Chinese patent CN101005892 discloses a composite oxide catalyst comprising particles of Mo, V, an alkaline earth metal or a rare earth element and a silica support, which does not disclose the structural characteristics of the porous nature of the resulting catalyst particles, but since the preparation method is a precipitation-calcination method, it can be expected that the resulting catalyst particles are less porous. Moreover, the above patents all utilize impregnation methods with complicated steps, which not only increases the cost, but also makes the preparation process more complicated.
Disclosure of Invention
The technical problems to be solved by the invention are that the catalyst in the prior art has complicated preparation steps, and has poor product selectivity and poor catalyst stability when being used for Fischer-Tropsch synthesis, synthesis gas methanation and methane reforming reactions; the porous composite catalyst is used for Fischer-Tropsch synthesis, synthesis gas methanation and methane reforming reaction, and has the advantages of high product selectivity and good catalyst stability.
The second technical problem to be solved by the present invention is to provide a method for preparing a porous composite catalyst to solve the first technical problem.
The present invention is also directed to a porous composite catalyst, which can solve the above problems.
In order to solve one of the above technical problems, the technical scheme adopted by the invention is as follows:
a porous composite catalyst comprises the following components in parts by weight:
a) 30-100 parts of at least one inert component selected from alumina, silica, magnesia and zirconia;
b) 0-20 parts of at least one element selected from platinum, ruthenium, rhodium and palladium;
c) 0-20 parts of at least one element selected from nickel, iron, cobalt and copper or an oxide thereof;
d) 0-5 parts of a compound selected from: at least one of oxides of titanium, vanadium, chromium and manganese;
wherein the contents of the component (b) and the component (c) are not all 0.
In the above technical solution, preferably, the component a) is one selected from alumina, silica, magnesia, zirconia and ceria; more preferably, component a) is selected from one of magnesium oxide, zirconium oxide and cerium oxide.
In the above technical solution, preferably, the component a) is a mixture of magnesium oxide and at least one selected from aluminum oxide and silicon oxide; more preferably, the ratio of the precursor of at least one of alumina and/or silica to the precursor of magnesium oxide is (50: 1) to (8: 1).
In the above technical scheme, preferably, the content of the component b) is 0.1-15 parts by weight.
In the above technical scheme, preferably, the content of the component c) is 0.1-15 parts by weight.
In the above technical scheme, preferably, the content of the component d) is 0.5-2 parts by weight.
In the above-mentioned technical solutions, preferably, component b) is ruthenium.
In the above technical solution, preferably, the component b) is nickel.
In the above-described embodiment, the ratio of the ruthenium-containing precursor to the nickel-containing precursor is preferably (1:4) to (4: 1).
In the above technical solution, preferably, the catalyst further comprises 0.1 to 1 part by weight of gallium and/or indium element or oxide thereof.
In the above technical solution, preferably, the porous composite catalyst has a microscopic particle size of 10 to 1000 nm, an average pore diameter of 2 to 200nm, a specific surface area of 2 to 400 m/g, and a pore volume of 0.006 to 1 cc/g; more preferably, the average pore diameter is 3-120 nm, the specific surface area is 50-330 m/g, and the pore volume is 0.05-0.6 cc/g.
In the above technical solution, preferably but not limited to: the microscopic particle size is 20-200 nm.
In the above technical scheme, the preparation method of the porous composite catalyst comprises the following steps:
a) uniformly mixing the inert component precursor and a surfactant in water, and then carrying out aging treatment at the temperature of 70-270 ℃ for 3-200 hours to prepare a precursor A of the porous composite catalyst;
b) uniformly mixing the precursors of the components B) to d) and the precursor A of the porous composite catalyst, and then carrying out aging treatment again at the temperature of 50-230 ℃ for 5-220 hours to obtain a precursor B of the porous composite catalyst, wherein the mass ratio of the substances in the precursor B is as follows: precursor A: precursors of components b) to c): the precursor of component d) is 1: (0.003-0.25): (0.001 to 0.15);
c) drying and roasting the precursor B of the porous composite catalyst to obtain a precursor C of the porous composite catalyst;
d) and (3) carrying out reduction treatment on the precursor C of the porous composite catalyst at 480-850 ℃ for 2-30 hours to obtain the porous composite catalyst.
In the preparation method, preferably but not limited to, 1) the aging treatment temperature is 100-200 ℃, and the time is 5-90 hours; 2) the secondary aging treatment temperature is 70-130 ℃, the secondary aging treatment time is 8-120 hours, and the mass ratio of the substances in the precursor B is as follows: precursor A: precursor of active component: precursor of the auxiliary agent is 1: (0.03-0.15): (0.01 to 0.12); 3) the drying temperature is 60-120 ℃, and the drying time is 3-80 hours; the calcining treatment temperature is 500-700 ℃, and the time is 4-20 hours; 4) the reduction treatment temperature is 200 ℃ and 660 ℃, and the time is 4-15 hours.
In the preparation method, the types of the precursors are respectively as follows: the inert component precursor is selected from at least one of boehmite, diatomite, silica gel and silicate, aluminate, aluminum salt, magnesium oxide and zirconium salt; the active component precursor is selected from at least one of nitrate, sulfate, halide salt, acetate, carbonate and alkali salt; the auxiliary agent precursor is selected from at least one of halide salt, nitrate, acetate, sulfate and carbonate; the surfactant is at least one selected from alkyl benzene sulfonate, alkyl sulfonate, fatty acid salt, polyoxyethylene-polyoxypropylene copolymer, polyethylene glycol and polyvinyl alcohol.
In the above embodiment, preferably but not limited to, the inert component precursor is selected from at least one of boehmite, diatomaceous earth, silica gel and silicate, aluminate, aluminum salt, magnesium salt, oxide of magnesium, and cerium salt; the active component precursor is selected from at least one of nitrate, acetate, carbonate and basic salt; the auxiliary agent precursor is selected from at least one of nitrate, acetate and halide salt; the surfactant is at least one selected from fatty acid salt, polyoxyethylene-polyoxypropylene copolymer, polyethylene glycol and polyvinyl alcohol.
In the above technical solution, preferably, the inert component precursor is magnesium salt/magnesium oxide and at least one selected from boehmite and/or diatomaceous earth.
In the above technical solution, preferably, the inert component precursor is magnesium salt/magnesium oxide and one selected from boehmite and/or diatomaceous earth.
In the above technical scheme, preferably, the inert component precursor is magnesium oxide/magnesium carbonate and boehmite/diatomite.
In the above-described embodiment, the mass ratio of boehmite/diatomaceous earth to magnesium oxide/magnesium carbonate is more preferably (50: 1) to (8: 1).
A Fischer-Tropsch synthesis method for preparing C5-C20 hydrocarbon takes synthesis gas as a raw material, and the raw material is in contact reaction with the catalyst to obtain the C5-C20 hydrocarbon.
A method for methanation of synthesis gas takes synthesis gas as a raw material, and the raw material is in contact reaction with the catalyst to obtain methane.
The method for preparing synthetic gas by reforming methane takes methane and carbon dioxide as raw materials, and the raw materials react with the catalyst in a contact way to obtain the synthetic gas.
In the above technical scheme, the reaction conditions of the raw materials and the catalyst are those generally considered by those skilled in the art to achieve conversion.
According to the invention, firstly, the precursor of the inert component forms a stable open framework structure after aging treatment, the open framework structure can be used as a carrier for bearing the precursor of the active component and the auxiliary agent, and meanwhile, the stable open framework structure is not subjected to calcination treatment and has more hydroxyl groups on the surface, so that the active component and the auxiliary agent can form a stronger chemical bond when being loaded, thereby forming a stable compound. In addition, the precursor of the active component and the precursor of the auxiliary agent are mixed in situ, and the active component and the auxiliary agent can form a homogeneous compound after aging treatment; in addition, the inert component, the active component and the auxiliary agent precursor are added in situ in the preparation process, so that the post-loading process with complicated steps is avoided. Due to the existence of the surfactant, the specific surface area of the composite is improved, the active component can be more uniformly distributed in the inert component, and the pore content and the dispersity of the active component of the composite are improved.
The measures solve the problems of unstable compound structure, small interaction force between the carrier and the active component, easy sintering of the active component, low pore content, complicated preparation steps and the like in the traditional preparation method, and obtain the high-efficiency and stable porous compound, so that the activity, the stability and the service life of the catalyst are obviously improved when the porous compound is used in the catalytic industrial production processes of Fischer-Tropsch synthesis, synthesis gas methanation and methane reforming.
The present invention will be further illustrated by the following examples and comparative examples, but the porous composite and the preparation method are not limited to the following specific embodiments.
Description of the drawings:
FIG. 1 photograph of a transmission electron microscope of example 1.
FIG. 2 is a TEM photograph of comparative example 1.
Detailed Description
[ example 1 ]
Uniformly mixing 100 g of boehmite and 25 g of polyethylene glycol in 200 g of water, and then carrying out aging treatment at the treatment temperature of 120 ℃ for 15 hours to obtain a precursor A; uniformly mixing 13.6 g of platinum chloride (equivalent to 10g of platinum), 12.7 g of manganese nitrate (equivalent to 5g of manganese oxide) and the precursor A, then carrying out aging treatment again at 160 ℃ for 20 hours to obtain a precursor B, and then drying the precursor B at 120 ℃ for 20 hours; then calcining at 550 ℃ for 10 hours; obtaining a precursor C; and (3) carrying out reduction treatment on the precursor C at the temperature of 600 ℃ for 5 hours to obtain the porous composite catalyst, wherein the preparation process conditions are shown in Table 1, and the physical properties of the catalyst are shown in Table 2.
The catalyst is used for Fischer-Tropsch synthesis, the reaction temperature is 230 ℃, and the volume space velocity is 600h-1The pressure is 1.8MPa, the hydrogen-carbon ratio in the raw material is 2, the structural composition characteristics and the catalytic performance are shown in tables 1 and 2, and the stability (the conversion rate) is>90%) for 420 h.
The catalyst is used in methanation of catalyst synthesis gas, the reaction temperature is 350 ℃, and the volume space velocity is 2200h-1The pressure is 1.8MPa, the hydrogen-carbon ratio in the raw material is 2, the catalytic performance is shown in Table 2,
the catalyst is used for methane reforming reaction, the reaction temperature is 750 ℃, and the volume space velocity is 1400h-1The pressure is 0.2MPa, the molar ratio of methane to carbon dioxide in the raw material is 2, the catalytic performance is shown in Table 2, the conversion rate of methane is 87%, and the selectivity of hydrogen is 90%.
[ examples 2 to 5 ]
The porous composite catalyst of the present invention was synthesized by changing the kinds and the qualities of the inert component precursor, the active component precursor and the surfactant according to the synthesis procedure described in example 1, and adjusting the preparation conditions, the preparation process conditions are shown in table 1, and the physical properties of the catalyst are shown in table 2.
The catalyst was used for fischer-tropsch synthesis, synthesis gas methanation and methane reforming reactions, respectively, the reaction conditions were the same as in example 1, and the catalytic performance is shown in table 2.
[ example 6 ]
Uniformly mixing 98 g of boehmite, 2 g of magnesium oxide and 25 g of polyethylene glycol in 200 g of water, and then carrying out aging treatment at the treatment temperature of 120 ℃ for 15 hours to obtain a precursor A; uniformly mixing 13.6 g of platinum chloride (equivalent to 10g of platinum), 12.7 g of manganese nitrate (equivalent to 5g of manganese oxide) and the precursor A, then carrying out aging treatment again at 160 ℃ for 20 hours to obtain a precursor B, and then drying the precursor B at 120 ℃ for 20 hours; then calcining at 550 ℃ for 10 hours; obtaining a precursor C; and (3) carrying out reduction treatment on the precursor C at the temperature of 600 ℃ for 5 hours to obtain the porous composite catalyst, wherein the preparation process conditions are shown in Table 1.
The catalyst is used for Fischer-Tropsch synthesis, the reaction temperature is 230 ℃, and the volume space velocity is 600h-1The pressure is 1.8MPa, the hydrogen-carbon ratio in the raw material is 2, and the catalytic performance is shown in Table 2.
The catalyst is used in methanation of catalyst synthesis gas, the reaction temperature is 350 ℃, and the volume space velocity is 2200h-1The pressure is 1.8MPa, the hydrogen-carbon ratio in the raw material is 2, and the catalytic performance is shown in Table 2.
The catalyst is used for methane reforming reaction, the reaction temperature is 750 ℃, and the volume space velocity is 1400h-1The pressure is 0.2MPa, the molar ratio of methane to carbon dioxide in the raw material is 2, and the catalytic performance is shown in Table 2.
[ example 7 ]
The preparation process, the raw material amount and the treatment conditions were the same as those of example 6. Except that the mass of boehmite was adjusted to 89 g and the mass of magnesia was adjusted to 11 g, a porous composite catalyst was prepared under the process conditions shown in Table 1, and the physical properties of the catalyst are shown in Table 2.
The catalyst was used for fischer-tropsch synthesis, synthesis gas methanation and methane reforming reactions, respectively, the reaction conditions were the same as in example 6, and the catalytic performance is shown in table 2.
[ example 8 ]
The preparation process, the raw material amount and the treatment conditions were the same as those of example 6. Except that boehmite was adjusted to diatomaceous earth, the mass was still 98 g, and a porous composite catalyst was prepared under the preparation process conditions shown in table 1, and the catalyst physical properties shown in table 2.
The catalyst was used for fischer-tropsch synthesis, synthesis gas methanation and methane reforming reactions, respectively, the reaction conditions were the same as in example 6, and the catalytic performance is shown in table 2.
[ example 9 ]
The preparation process, the raw material amount and the treatment conditions were the same as those of example 6. Except that the mass of diatomaceous earth was adjusted to 89 g and the mass of magnesium oxide was adjusted to 11 g, a porous composite catalyst was prepared under the process conditions shown in Table 1 and the physical properties of the catalyst shown in Table 2.
The catalyst was used for fischer-tropsch synthesis, synthesis gas methanation and methane reforming reactions, respectively, the reaction conditions were the same as in example 6, and the catalytic performance is shown in table 2.
[ example 10 ]
Uniformly mixing 100 g of boehmite and 25 g of polyethylene glycol in 200 g of water, and then carrying out aging treatment at the treatment temperature of 120 ℃ for 15 hours to obtain a precursor A; uniformly mixing 13.6 g of platinum chloride (equivalent to 10g of platinum), 12.7 g of manganese nitrate (equivalent to 5g of manganese oxide), 0.55 g of gallium nitrate and the precursor A, then aging again at 160 ℃ for 20 hours to obtain a precursor B, and then drying the precursor B at 120 ℃ for 20 hours; then calcining at 550 ℃ for 10 hours; obtaining a precursor C; and (3) carrying out reduction treatment on the precursor C at the temperature of 600 ℃ for 5 hours to obtain the porous composite catalyst, wherein the preparation process conditions are shown in Table 1, and the physical properties of the catalyst are shown in Table 2.
The catalyst is used for Fischer-Tropsch synthesis, the reaction temperature is 230 ℃, and the volume space velocity is 600h-1The pressure is 1.8MPa, the hydrogen-carbon ratio in the raw material is 2, the structural composition characteristics and the catalytic performance are shown in tables 1 and 2, and the stability (the conversion rate) is>90%) for 420 h.
The catalyst is used in methanation of catalyst synthesis gas, the reaction temperature is 350 ℃, and the volume space velocity is 2200h-1The pressure is 1.8MPa, the hydrogen-carbon ratio in the raw material is 2, the catalytic performance is shown in Table 2,
the catalyst is used for methane reforming reaction, the reaction temperature is 750 ℃, and the volume space velocity is 1400h-1The pressure is 0.2MPa, the molar ratio of methane to carbon dioxide in the raw material is 2, the catalytic performance is shown in Table 2, the conversion rate of methane is 87%, and the selectivity of hydrogen is 90%.
[ example 11 ]
Uniformly mixing 100 g of boehmite and 25 g of polyethylene glycol in 200 g of water, and then carrying out aging treatment at the treatment temperature of 120 ℃ for 15 hours to obtain a precursor A; uniformly mixing 13.6 g of platinum chloride (equivalent to 10g of platinum), 12.7 g of manganese nitrate (equivalent to 5g of manganese oxide), 1.6 g of indium nitrate and the precursor A, then aging again at 160 ℃ for 20 hours to obtain a precursor B, and then drying the precursor B at 120 ℃ for 20 hours; then calcining at 550 ℃ for 10 hours; obtaining a precursor C; and (3) carrying out reduction treatment on the precursor C at the temperature of 600 ℃ for 5 hours to obtain the porous composite catalyst, wherein the preparation process conditions are shown in Table 1, and the physical properties of the catalyst are shown in Table 2.
The catalyst is used for Fischer-Tropsch synthesis, the reaction temperature is 230 ℃, and the volume space velocity is 600h-1The pressure is 1.8MPa, the hydrogen-carbon ratio in the raw material is 2, the structural composition characteristics and the catalytic performance are shown in tables 1 and 2, and the stability (the conversion rate) is>90%) for 420 h.
The catalyst is used in methanation of catalyst synthesis gas, the reaction temperature is 350 ℃, and the volume space velocity is 2200h-1The pressure is 1.8MPa, the hydrogen-carbon ratio in the raw material is 2, the catalytic performance is shown in Table 2,
applying the catalyst to AReforming alkane at 750 deg.c and volume space velocity of 1400 hr-1The pressure is 0.2MPa, the molar ratio of methane to carbon dioxide in the raw material is 2, the catalytic performance is shown in Table 2, the conversion rate of methane is 87%, and the selectivity of hydrogen is 90%.
[ example 12 ]
Uniformly mixing 100 g of boehmite and 25 g of polyethylene glycol in 200 g of water, and then carrying out aging treatment at the treatment temperature of 120 ℃ for 15 hours to obtain a precursor A; uniformly mixing 13.6 g of platinum chloride (equivalent to 10g of platinum), 12.7 g of manganese nitrate (equivalent to 5g of manganese oxide), 0.25 g of gallium nitrate, 0.3 g of indium nitrate and the precursor A, then carrying out aging treatment again at 160 ℃ for 20 hours to obtain a precursor B, and then drying the precursor B at 120 ℃ for 20 hours; then calcining at 550 ℃ for 10 hours; obtaining a precursor C; and (3) carrying out reduction treatment on the precursor C at the temperature of 600 ℃ for 5 hours to obtain the porous composite catalyst, wherein the preparation process conditions are shown in Table 1, and the physical properties of the catalyst are shown in Table 2.
The catalyst is used for Fischer-Tropsch synthesis, the reaction temperature is 230 ℃, and the volume space velocity is 600h-1The pressure is 1.8MPa, the hydrogen-carbon ratio in the raw material is 2, the structural composition characteristics and the catalytic performance are shown in tables 1 and 2, and the stability (the conversion rate) is>90%) for 420 h.
The catalyst is used in methanation of catalyst synthesis gas, the reaction temperature is 350 ℃, and the volume space velocity is 2200h-1The pressure is 1.8MPa, the hydrogen-carbon ratio in the raw material is 2, the catalytic performance is shown in Table 2,
the catalyst is used for methane reforming reaction, the reaction temperature is 750 ℃, and the volume space velocity is 1400h-1The pressure is 0.2MPa, the molar ratio of methane to carbon dioxide in the raw material is 2, the catalytic performance is shown in Table 2, the conversion rate of methane is 87%, and the selectivity of hydrogen is 90%.
[ COMPARATIVE EXAMPLES 1 to 4 ]
The composites were prepared using an impregnation method. Firstly, 100 g of boehmite and 25 g of polyethylene glycol are mixed and added into 200 g of water, the mixture is uniformly stirred to form a homogeneous solution, then the product is aged at the treatment temperature of 120 ℃ for 15 hours, and then the product is dried at the temperature of 100 ℃ for 10 hours and calcined at the temperature of 550 ℃ for 10 hours in the air atmosphere, so that the carrier can be obtained. After 13.6 g of platinum chloride (equivalent to 10g of platinum), 12.7 g of manganese nitrate (equivalent to 5g of manganese oxide) and 20g of water were mixed to prepare a mixed solution, the mixed solution was loaded on the carrier by an equal volume impregnation method, and the carrier was calcined again at 550 ℃ for 10 hours in an air atmosphere and then subjected to reduction treatment at 600 ℃ for 5 hours, thereby obtaining the porous composite catalyst in comparative example 1. The porous composite catalyst can be obtained by changing the composition proportion of the raw materials, the preparation process, the types and the quality of the inert component precursor, the active component precursor and the surfactant, and the structural composition characteristics and the catalytic performance of the porous composite catalyst are shown in tables 3 and 4.
[ COMPARATIVE EXAMPLES 5 to 8 ]
Uniformly mixing 100 g of boehmite and 25 g of polyethylene glycol in 200 g of water, and then carrying out aging treatment at the treatment temperature of 120 ℃ for 15 hours to obtain a precursor A; uniformly mixing 12.7 g of manganese nitrate (equivalent to 5g of manganese oxide) and the precursor A, then carrying out aging treatment again at 160 ℃ for 20 hours to obtain a precursor B, and then drying the precursor B at 120 ℃ for 20 hours; then calcining at 550 ℃ for 10 hours; obtaining a precursor C; and (3) carrying out reduction treatment on the precursor C at the temperature of 600 ℃ for 5 hours to obtain the porous composite catalyst.
The catalyst is used for methane reforming reaction, the reaction temperature is 750 ℃, and the volume space velocity is 1400h-1The pressure is 0.2MPa, and the molar ratio of methane to carbon dioxide in the raw material is 2.
Comparative example 6 is obtained by adjusting boehmite to diatomaceous earth under the same conditions as in comparative example 6.
Comparative example 7 is where boehmite is adjusted to magnesium oxide and other conditions are the same as in comparative example 6.
Comparative example 8 is a boehmite/magnesia mixture adjusted to a boehmite/magnesia mixture (where boehmite has a mass of 89 grams and magnesia has a mass of 11 grams) with the same other conditions as in comparative example 6.
The structural composition characteristics and catalytic performance of comparative examples 6-9 are shown in tables 3 and 4.
TABLE 1
TABLE 2
TABLE 3
TABLE 4
Claims (6)
1. A porous composite catalyst comprises the following components in parts by weight:
a) 30-100 parts of at least one inert component selected from alumina, zirconia, magnesia and silica;
b)0.1 to 15 parts of at least one element selected from platinum, ruthenium, rhodium and palladium;
c) 0.1-15 parts of at least one element selected from nickel, iron, cobalt and copper or an oxide thereof;
d) 0.5-2 parts of at least one of oxides of titanium, vanadium, chromium and manganese; the preparation method of the porous composite catalyst comprises the following steps:
a) uniformly mixing the inert component precursor and a surfactant in water, and then carrying out aging treatment at the temperature of 70-270 ℃ for 3-200 hours to prepare a precursor A of the porous composite catalyst;
b) uniformly mixing the precursors of the components B) to d) and the precursor A of the porous composite catalyst, and then carrying out aging treatment again at the temperature of 50-230 ℃ for 5-220 hours to obtain a precursor B of the porous composite catalyst, wherein the mass ratio of the substances in the precursor B is as follows: precursor A: precursors of components b) to c): the precursor of component d) is 1: (0.003-0.25): (0.001 to 0.15);
c) drying and roasting the precursor B of the porous composite catalyst to obtain a precursor C of the porous composite catalyst;
d) and (3) carrying out reduction treatment on the precursor C of the porous composite catalyst at 480-850 ℃ for 2-30 hours to obtain the porous composite catalyst.
2. The porous composite catalyst according to claim 1, wherein component a) is selected from one of alumina, magnesia, zirconia and silica.
3. The porous composite catalyst according to claim 1, wherein the porous composite catalyst has a microscopic particle size of 10 to 1000 nm, an average pore diameter of 2 to 200nm, a specific surface area of 2 to 400 m/g, and a pore volume of 0.006 to 1 cm/g.
4. The porous composite catalyst as claimed in claim 3, wherein the average pore diameter is 3 to 120 nm, the specific surface area is 50 to 330 m/g, and the pore volume is 0.05 to 0.6 cm/g.
5. A Fischer-Tropsch synthesis method for preparing C5-C20 hydrocarbons, which takes synthesis gas as a raw material, and the raw material is in contact reaction with the catalyst of any one of claims 1-4 to obtain the C5-C20 hydrocarbons.
6. A synthetic gas methanation method, which takes synthetic gas as a raw material, and the raw material is in contact reaction with the catalyst of any one of claims 1 to 4 to obtain methane.
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| CN104226327A (en) * | 2013-06-17 | 2014-12-24 | 中国石油化工股份有限公司 | Catalyst for alkene preparation from synthesis gas and preparation method thereof |
| CN104923221A (en) * | 2014-03-17 | 2015-09-23 | 中国石油化工股份有限公司 | Silicon-based composite metal oxide and preparation method thereof |
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