CN112452329A - Synthesis method of reforming catalyst - Google Patents

Synthesis method of reforming catalyst Download PDF

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CN112452329A
CN112452329A CN202011230361.7A CN202011230361A CN112452329A CN 112452329 A CN112452329 A CN 112452329A CN 202011230361 A CN202011230361 A CN 202011230361A CN 112452329 A CN112452329 A CN 112452329A
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calixarene
chloroform
solution
precursor
reforming catalyst
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CN112452329B (en
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孙予罕
王慧
杜洋
马春辉
张磊
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Shanghai Cluster Rui Low Carbon Energy Technology Co ltd
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Abstract

The invention discloses a synthesis method of a reforming catalyst, which is characterized in that nickel nitrate, calixarene, chloroform and methanol are prepared into a solution, and the solution is vigorously stirred to fully dissolve the nickel nitrate; adding an alkaline substance into the obtained solution, and removing the solvent through rotary evaporation after reaction to obtain a precursor complex formed by calixarene and Ni; preparing a solution from the precursor complex, an auxiliary agent precursor, chloroform and methanol, performing equal-volume impregnation on the obtained solution and a carrier, and drying and roasting the obtained solid sample to obtain the catalyst. According to the invention, Ni and calixarene form small-size precursor complexes, other active metal elements are jointly impregnated on a carrier according to a certain proportion, and finally the catalyst is obtained after filtering, washing, drying and roasting.

Description

Synthesis method of reforming catalyst
Technical Field
The invention belongs to the technical field of petrochemical industry, and relates to a method for synthesizing a reforming catalyst by controlling synthesis of calixarene and application thereof.
Background
Methane and carbon dioxide are two greenhouse gases, and large amounts of emissions have an adverse effect on the environment. Since the first report of reforming and converting methane and carbon dioxide into synthesis gas in 1888, people have developed a great deal of research on the reaction, and the methane and carbon dioxide reforming reaction reduces the emission of methane and carbon dioxide and has environmental protection significance; and meanwhile, the generated synthesis gas can be used for further industrial application, and has economic benefit.
Catalysts for catalytic reforming of methane and carbon dioxide can be classified into two types: noble metals and non-noble metals. Among them, the noble metals Rh, Ru and Ir have the best catalytic activity. Although the noble metal catalyst has good catalytic activity and carbon deposit resistance, the industrial application of the noble metal catalyst is poor in economic benefit due to limited resources and high price. On the contrary, although the catalytic activity and the carbon deposit resistance of the non-noble metal are not as good as those of noble metals, the non-noble metal is low in price and rich in resources, so that the main research content is still the non-noble metal catalyst. Wherein the catalytic activity sequence of the non-noble metal is Ni & gt Co & gt Cu & gt Fe. Therefore, nickel-based catalysts have become the focus of research in methane and carbon dioxide reforming reactions.
Currently, the preparation methods for preparing reforming catalysts for methane and carbon dioxide include impregnation, sol-gel, and coprecipitation. Among them, the impregnation method and the coprecipitation method are relatively simple and easy to operate, and are the catalyst preparation methods mainly adopted at present.
Chinese patent CN102389801B discloses a nickel-based catalyst for reforming methane with carbon dioxide to obtain synthesis gas and a preparation method thereof, the method comprises the steps of preparing a mixed solution of metal salts in the first step, and treating treated gamma-Al in the second step under the condition of vacuumizing2O3Placing into the mixed solution for impregnationFinally, the catalyst is obtained by roasting. Although the method has good conversion rate, the preparation process has high requirement, and the method is not beneficial to popularization and application.
Chinese patent CN105413734B discloses a nickel-based catalyst for methane-carbon dioxide reforming to produce reducing gas and a preparation method thereof, wherein the first step is the preparation of a modified molecular sieve carrier, and the second step is the impregnation of an active component and an auxiliary agent, and then the catalyst is obtained by roasting. Although the method has good conversion rate, the preparation process is more complicated, and the carbon deposit amount is more, so that the method is not suitable for large-scale production.
Therefore, the preparation of the methane and carbon dioxide reforming catalyst with high dispersity, small particle size and good stability is the key content of the current research. The addition of the auxiliary agent in the catalyst can improve the catalytic performance of the catalyst. The effect on the auxiliaries is currently roughly considered to be the following: changing the acidity and alkalinity of the surface of the catalyst, improving the dispersion degree of the active metal, modulating the interaction force between the active component and the carrier and changing the electron density of the active component to influence the catalyst on CH4And CO2Dissociation of (3). The assistant for the methane-carbon dioxide reforming catalyst is alkali metal (Na)2O、K2O), alkaline earth metal oxides (MgO, CaO), and rare earth oxides (CeO)2、La2O3) And the like. The calixarene serving as a macrocyclic ligand has a good threshold effect and strong coordination capacity with metal, and can effectively control the dispersion degree and particle size of the metal by coordinating with the metal.
Disclosure of Invention
The technical problem solved by the invention is as follows: the catalyst in the prior art has the defects of large particle size, easy Ni agglomeration and growth in the reaction process to inactivate, easy carbon accumulation and inactivation and the like.
In order to solve the above technical problem, the present invention provides a method for synthesizing a reforming catalyst, comprising the steps of:
step 1): preparing nickel nitrate, calixarene, chloroform and methanol into a solution, and violently stirring to fully dissolve the nickel nitrate;
step 2): adding an alkaline substance into the solution obtained in the step 1), and removing the solvent through rotary evaporation after reaction to obtain a precursor complex formed by calixarene and Ni;
step 3): preparing the precursor complex obtained in the step 2) with an auxiliary agent precursor, chloroform and methanol into a solution, performing equal-volume impregnation on the obtained solution and a carrier, and drying and roasting the obtained solid sample to obtain the catalyst.
Preferably, the structure of the calixarene in step 1) is as follows:
Figure BDA0002764997820000031
wherein n is 1, 3 or 5; r1～Rn+2is-H, C1-C5Alkyl radical, C1-C5Any one or more of alkoxy and nitro; all A are the same group and are-CH2or-S.
Preferably, the molar ratio of the calixarene to the nickel nitrate in the step 1) is 1: (1-15), preferably 1 (3-9); the volume ratio of chloroform to methanol is 1: (1-5); dissolving 0.01mol of calixarene in 5-20 mL of chloroform.
Preferably, in the step 2), the alkaline substance is any one of urea, ammonium bicarbonate, triethylamine and ammonia water, and the pH value of the solution is controlled to be 7-7.5.
Preferably, the reaction time in the step 2) is 4-24 h, and preferably 8-12 h; the rotary evaporation temperature is controlled to be 30-60 ℃;
preferably, the molar ratio of the precursor complex to the auxiliary agent precursor in the step 3) is 1 (5-20), and preferably 1 (8-15); the volume ratio of chloroform to methanol is 1: (1-10); dissolving every 0.01mol of precursor complex in 2-5 mL of chloroform; the precursor of the auxiliary agent is at least one of nitrates of Zn, La, Ce, Mg and Ca.
Preferably, the dipping temperature in the step 3) is 30-90 ℃, preferably 40-60 ℃, and the time is 12-48 hours, preferably 12-24 hours; the drying temperature is 70-120 ℃, preferably 80-100 ℃, and the drying time is 4-24 hours, preferably 6-12 hours; the roasting temperature is 400-700 ℃, preferably 500-650 ℃, and the roasting time is 2-12 hours, preferably 4-6 hours.
Preferably, the catalyst obtained in the step 3) comprises an active component Ni, an auxiliary agent and a carrier, wherein the mass content of Ni is 2-15%, the mass content of the auxiliary agent is 2-15%, and the balance is the carrier.
More preferably, the auxiliary agent is any one or more of Zn, La, Ce, Mg and Ca; the carrier is gamma-Al2O3And ZrO2Any one of them.
The catalyst preparation method provided by the invention can effectively control the size and dispersion degree of Ni, can avoid inactivation caused by rapid agglomeration and growth of Ni particles in the reaction process, and meanwhile, the small-sized Ni has higher specific surface area and better catalytic activity.
Compared with the prior art, the invention has the following advantages:
(1) by utilizing the threshold effect of calixarene and through coordination of a non-metal element and a Ni element, the removal of a calixarene framework in the roasting process is ensured, and meanwhile, the high dispersity, small size, large specific surface area and high catalytic activity of Ni particles can be effectively ensured, and meanwhile, Ni atoms are not easy to agglomerate in the reaction process to cause catalyst inactivation;
(2) the preparation process is simple, and the traditional impregnation method is adopted, so that the complexity of operation is reduced.
Detailed Description
In order to make the invention more comprehensible, preferred embodiments are described in detail below.
The evaluation procedure for the reforming reaction using the catalyst prepared in the example was as follows:
mixing the oxidation precursor catalyst (0.1g, 80-100 mesh) with analytically pure quartz sand (0.9g, 80-100 mesh), and adding into H2/N2Atmosphere (50% each by volume, flow rate 120mL/min), 700 ℃ pre-reduction for 1 h. After reduction is complete, at 50% H2/N2Raising the reaction temperature to 850 ℃ in the atmosphere, and switching to CO after raising the temperature to 850 DEG C2/CH4The mixed gas (molar ratio 1:1, GHSV: 30000 mL/g.h) undergoes the reforming reaction. Stable reactionAfter determination, the composition of the product was measured on-line by gas chromatography.
Example 1
The calixarene is selected from p-tert-butyl thiacalix [6 ]]Aromatic hydrocarbons (n ═ 3, R)1～R4T-butyl, a ═ S);
calixarene (0.01mol, 7.44g) was weighed and dissolved in 15mL of chloroform, nickel nitrate hexahydrate (0.15mol, 43.62g) was weighed and dissolved in 45mL of a mixed solution of methanol, the chloroform solution of calixarene was added with vigorous stirring while adding 50. mu.L of ammonia water, the reaction was carried out for 18h, and all the solution was removed by rotary evaporation (50 ℃) to obtain a precursor complex solid formed by calixarene and Ni. This solid, lanthanum nitrate (0.1mol, 32.49g), was dissolved in a mixed solution of 5mL of chloroform and 40mL of methanol, and then mixed with γ -Al2O3(0.66mol, 67.32g), soaking at the temperature of 60 ℃ for 36h, taking out, drying at the temperature of 100 ℃ for 12h, taking out the dried solid, roasting at the roasting temperature of 600 ℃ for 4h, and obtaining the oxidized precursor catalyst after roasting.
Calculating to obtain CO2Conversion 81.27%, CH4Conversion rate 85.61%, H in output2The ratio of/CO is 0.84, the reaction lasts for 300h, CO2、CH4Conversion and H2the/CO ratio remains substantially unchanged.
Example 2
The calixarene is selected from p-tert-butyl thiacalix [4 ]]Aromatic hydrocarbons (n ═ 1, R)1～R4T-butyl, a ═ S);
calixarene (0.01mol, 7.21g) was weighed and dissolved in 10mL of chloroform, nickel nitrate hexahydrate (0.1mol, 29.08g) was weighed and dissolved in 30mL of a mixed solution of methanol, the chloroform solution of calixarene was added while stirring vigorously and 100. mu.L of triethylamine was added, the reaction was carried out for 12h, and all the solution was removed by rotary evaporation (50 ℃) to obtain a precursor complex solid formed by calixarene and Ni. This solid, magnesium nitrate hexahydrate (0.2mol, 51.28g) was dissolved in a mixed solution of 5mL of chloroform and 30mL of methanol and then mixed with gamma-Al2O3(0.3mol, 30.59g) soaking, keeping the temperature at 50 ℃ for 12h, taking out, drying at 100 ℃ for 12h, taking out the dried solidAnd roasting at 650 ℃ for 4h to obtain the oxide precursor catalyst after roasting.
Calculating to obtain CO2Conversion 82.77%, CH4Conversion of 87.25%, H in the output2The ratio of/CO is 0.85, the reaction lasts for 300h, CO2、CH4Conversion and H2the/CO ratio remains substantially unchanged.
Example 3
The calixarene is selected from p-tert-butyl thiacalix [4 ]]Aromatic hydrocarbons (n ═ 1, R)1～R4T-butyl, a ═ S);
calixarene (0.01mol, 7.21g) was weighed and dissolved in 10mL of chloroform, nickel nitrate hexahydrate (0.05mol, 14.54g) was weighed and dissolved in 30mL of a mixed solution of methanol, the chloroform solution of calixarene was added while stirring vigorously and 100. mu.L of triethylamine was added, the reaction was carried out for 12h, and all the solution was removed by rotary evaporation (50 ℃) to obtain a precursor complex solid formed by calixarene and Ni. This solid, magnesium nitrate hexahydrate (0.1mol, 25.64g) was dissolved in a mixed solution of 5mL of chloroform and 25mL of methanol and then mixed with gamma-Al2O3(0.012mol, 12.24g) is soaked, the temperature is kept at 50 ℃ for 24h, the mixture is taken out and dried at 90 ℃ for 12h, the dried solid is taken out and roasted, the roasting temperature is 650 ℃, the roasting time is 4h, and the oxidized precursor catalyst is obtained after the roasting is finished.
Calculating to obtain CO2Conversion 86.02%, CH4Conversion rate of 90.16%, H in output2The ratio of/CO is 0.9, the reaction lasts for 300h, CO2、CH4Conversion and H2the/CO ratio remains substantially unchanged.
Example 4
The calixarene is selected from p-nitrothiacalix [4 ]]Aromatic hydrocarbons (n ═ 1, R)1～R4＝-NO2，A＝-S)；
Calixarene (0.01mol, 6.04g) was weighed out and dissolved in 20mL of chloroform, nickel nitrate hexahydrate (0.15mol, 43.62g) was weighed out and dissolved in 100mL of a mixed solution of methanol, the calixarene solution in chloroform was added with vigorous stirring while 100. mu.L of triethylamine was added, the reaction was carried out for 24h, and all dissolved solvents were removed by rotary evaporation (60 ℃ C.)And (4) obtaining precursor complex solid formed by calixarene and Ni. This solid, magnesium nitrate hexahydrate (0.2mol, 51.28g) was dissolved in a mixed solution of 5mL of chloroform and 50mL of methanol and then mixed with gamma-Al2O3(0.4mol, 40.81g) soaking, keeping the temperature at 80 ℃ for 48h, taking out, drying at 120 ℃ for 12h, taking out the dried solid, roasting at 650 ℃, roasting for 12h, and obtaining the oxidized precursor catalyst after roasting.
Calculating to obtain CO2Conversion 74.41%, CH4Conversion of 79.86%, H in the effluent2The ratio of/CO is 0.82, the reaction lasts for 300h, CO2、CH4Conversion and H2the/CO ratio remains substantially unchanged.
Example 5
The calixarene is selected from p-tert-butyl thiacalix [4 ]]Aromatic hydrocarbons (n ═ 1, R)1～R4T-butyl, a ═ S);
calixarene (0.01mol, 7.21g) was weighed and dissolved in 5mL of chloroform, nickel nitrate hexahydrate (0.01mol, 2.91g) was weighed and dissolved in 5mL of a mixed solution of methanol, the chloroform solution of calixarene was added while stirring vigorously and 100. mu.L of triethylamine was added, the reaction was carried out for 4h, and all the solution was removed by rotary evaporation (40 ℃) to obtain a precursor complex solid formed by calixarene and Ni. This solid, lanthanum nitrate (0.05mol, 16.25g), was dissolved in a mixed solution of 2mL of chloroform and 2mL of methanol, and then mixed with ZrO2(0.15mol, 18.48g) soaking, keeping the temperature at 60 ℃ for 24h, taking out, drying at 80 ℃ for 12h, taking out the dried solid, roasting at 700 ℃, roasting for 6h, and obtaining the oxidized precursor catalyst after roasting.
Calculating to obtain CO2Conversion 75.44%, CH4Conversion of 81.94%, H in the output2The ratio of/CO is 0.82, the reaction lasts for 300h, CO2、CH4Conversion and H2the/CO ratio remains substantially unchanged.
Example 6
The calixarene is selected from p-tert-butyl calix [8 ]]Aromatic hydrocarbons (n ═ 5, R)1～R4Is tert-butyl, A is-CH2)；
Calixarene (0.01mol, 12.98g) was weighed and dissolved in 5mL of chloroform, nickel nitrate hexahydrate (0.05mol, 14.54g) was weighed and dissolved in 10mL of a mixed solution of methanol, the chloroform solution of calixarene was added with vigorous stirring while adding 50. mu.L of ammonia water, the reaction was carried out for 10h, and all the solution was removed by rotary evaporation (60 ℃) to obtain a precursor complex solid formed by calixarene and Ni. This solid, cerium nitrate (0.1mol, 43.42g), was dissolved in a mixed solution of 3mL of chloroform and 15mL of methanol, and then mixed with ZrO2(0.6mol, 73.93g), soaking at 70 ℃ for 12h, taking out, drying at 120 ℃ for 24h, taking out the dried solid, roasting at 600 ℃ for 4h, and obtaining the oxidized precursor catalyst after roasting.
Calculating to obtain CO2Conversion 83.28%, CH4Conversion rate is 87.65%, and H in output2The ratio of/CO is 0.86, the reaction lasts for 300h, CO2、CH4Conversion and H2the/CO ratio remains substantially unchanged.
Example 7
The calixarene adopts p-isopropyl cup [8 ]]Aromatic hydrocarbons (n ═ 5, R)1～R4Is isopropyl, A is-CH2)；
Calixarene (0.01mol, 11.86g) was weighed and dissolved in 20mL of chloroform, nickel nitrate hexahydrate (0.12mol, 34.90g) was weighed and dissolved in 80mL of a mixed solution of methanol, the chloroform solution of calixarene was added while stirring vigorously and 100. mu.L of triethylamine was added, the reaction was carried out for 4h, and all the solution was removed by rotary evaporation (60 ℃) to obtain a precursor complex solid formed by calixarene and Ni. This solid, magnesium nitrate hexahydrate (0.15mol, 38.46g) was dissolved in a mixed solution of 4mL of chloroform and 40mL of methanol and then mixed with gamma-Al2O3(0.45mol, 45.90g) soaking, keeping the temperature at 30 ℃ for 48h, taking out, drying at 100 ℃ for 8h, taking out the dried solid, roasting at 550 ℃, and roasting for 12h to obtain the oxidized precursor catalyst after roasting.
Calculating to obtain CO2Conversion 74.62%, CH4Conversion of 76.51%, H in the output2The ratio of/CO is 0.81, the reaction lasts for 300 hours,CO2、CH4conversion and H2the/CO ratio remains substantially unchanged.
Example 8
The calixarene is selected from p-tert-butyl calix [6 ]]Aromatic hydrocarbons (n ═ 3, R)1～R4Is tert-butyl, A is-CH2)；
Calixarene (0.01mol, 9.73g) was weighed and dissolved in 10mL of chloroform, nickel nitrate hexahydrate (0.08mol, 23.26g) was weighed and dissolved in 30mL of a mixed solution of methanol, the chloroform solution of calixarene was added while stirring vigorously and 100. mu.L of triethylamine was added, the reaction was carried out for 24h, and all the solution was removed by rotary evaporation (30 ℃) to obtain a precursor complex solid formed by calixarene and Ni. This solid, magnesium nitrate hexahydrate (0.1mol, 25.64g) was dissolved in a mixed solution of 2mL of chloroform and 20mL of methanol and then mixed with ZrO2(0.35mol, 43.13g) soaking, keeping the temperature at 90 ℃ for 12h, taking out, drying at 70 ℃ for 4h, taking out the dried solid, roasting at 400 ℃, roasting for 2h, and obtaining the oxidized precursor catalyst after roasting.
Calculating to obtain CO2Conversion 79.52%, CH4Conversion of 82.46%, H in the effluent2The ratio of/CO is 0.85, the reaction lasts for 300h, CO2、CH4Conversion and H2the/CO ratio remains substantially unchanged.
Comparative example 1
Nickel nitrate hexahydrate (0.05mol, 14.54g) and magnesium nitrate hexahydrate (0.1mol, 25.64g) were weighed, dissolved in 30mL of aqueous solution, and mixed with gamma-Al2O3(0.012mol, 12.24g) is soaked, the temperature is kept at 50 ℃ for 24h, the mixture is taken out and dried at 90 ℃ for 12h, the dried solid is taken out and roasted, the roasting temperature is 650 ℃, the roasting time is 4h, and the oxidized precursor catalyst is obtained after the roasting is finished.
Calculating to obtain CO2Conversion 62.02%, CH4Conversion of 64.16%, H in the output2The ratio of/CO is 0.72, the obvious inactivation phenomenon appears after the reaction is carried out for 300h, and the carbon deposition is serious in the thermogravimetric analysis of the catalyst.
Table 1 shows a comparison of the performance of the catalysts of examples 1 to 8 and comparative example 1. As can be seen from Table 1Examples 1-8 the addition of calixarene ligand during the synthesis of the precursor complex effectively reduced the particle size of the final shaped oxidic precursor catalyst, with an average particle size of 6.4nm and a larger specific surface area of 151.24m2In g, CO with higher catalytic activity, catalysts of examples 1 to 82The conversion rate is 74.41-86.02%, CH4The conversion rate is 76.51% -90.16%, and the catalyst can stably run for more than 300H, the activity of the catalyst is maintained stable, and H is2The ratio of/CO is 0.81 to 0.9. In contrast, in comparative example 1, no calixarene is added in the synthesis process, the particle size of the finally formed oxidation precursor catalyst is 2.2 times of the average particle size of examples 1-8, and the specific surface area is reduced to 71.6% of the average specific surface area of the oxidation precursor catalysts of examples 1-8, when the reforming catalytic reaction is carried out, the initial 24h catalytic activity is similar to that of the catalysts of examples 1-8, but after the continuous operation for 300h, the catalytic activity is greatly reduced, CO is greatly reduced, and2the conversion rate is reduced to 62.02 percent, and CH4The conversion rate is reduced to 64.16%, H2the/CO was reduced to 0.72. Therefore, the precursor complex is controlled and synthesized by calixarene, the dispersion degree of metal Ni in the precursor complex can be effectively controlled, the precursor oxidation state catalyst is obtained by impregnation, drying and roasting, the particle size of the catalyst can be effectively reduced, and the high-CO catalyst is obtained2And CH4The reforming catalyst with high conversion rate and high stability has simple and easy operation in the synthesis process and industrial application prospect.
The performance versus ratio for the catalysts of examples 1-8 and comparative example 1 run for 300h is shown in table 1.
TABLE 1
Figure BDA0002764997820000091

Claims (9)

1. A method of synthesizing a reforming catalyst, comprising the steps of:
step 1): preparing nickel nitrate, calixarene, chloroform and methanol into a solution, and violently stirring to fully dissolve the nickel nitrate;
step 2): adding an alkaline substance into the solution obtained in the step 1), and removing the solvent through rotary evaporation after reaction to obtain a precursor complex formed by calixarene and Ni;
step 3): preparing the precursor complex obtained in the step 2) with an auxiliary agent precursor, chloroform and methanol into a solution, performing equal-volume impregnation on the obtained solution and a carrier, and drying and roasting the obtained solid sample to obtain the catalyst.
2. The method for synthesizing a reforming catalyst according to claim 1, wherein the calixarene in the step 1) has the following structure:
Figure FDA0002764997810000011
wherein n is 1, 3 or 5; r1～Rn+2is-H, C1-C5Alkyl radical, C1-C5Any one or more of alkoxy and nitro; all A are the same group and are-CH2or-S.
3. The method for synthesizing a reforming catalyst according to claim 1, wherein the molar ratio of calixarene to nickel nitrate in step 1) is 1: (1-15); the volume ratio of chloroform to methanol is 1: (1-5); dissolving 0.01mol of calixarene in 5-20 mL of chloroform.
4. The method for synthesizing a reforming catalyst according to claim 1, wherein the basic substance in the step 2) is any one of urea, ammonium bicarbonate, triethylamine and ammonia water, and the pH value of the solution is controlled to be 7-7.5.
5. The method for synthesizing a reforming catalyst according to claim 1, wherein the reaction time in the step 2) is 4-24 hours, preferably 8-12 hours; the rotary evaporation temperature is controlled to be 30-60 ℃.
6. The synthesis method of the reforming catalyst according to claim 1, wherein the molar ratio of the precursor complex to the auxiliary precursor in the step 3) is 1 (5-20); the volume ratio of chloroform to methanol is 1: (1-10); dissolving every 0.01mol of precursor complex in 2-5 mL of chloroform; the precursor of the auxiliary agent is at least one of nitrates of Zn, La, Ce, Mg and Ca.
7. The method for synthesizing the reforming catalyst according to claim 1, wherein the temperature for impregnation in the step 3) is 30 to 90 ℃ and the time is 12 to 48 hours; the drying temperature is 70-120 ℃, and the drying time is 4-24 hours; the roasting temperature is 400-700 ℃, and the roasting time is 2-12 h.
8. The synthesis method of the reforming catalyst according to claim 1, wherein the catalyst obtained in step 3) comprises an active component Ni, an auxiliary agent and a carrier, wherein the mass content of Ni is 2-15%, the mass content of the auxiliary agent is 2-15%, and the balance is the carrier.
9. The method for synthesizing the reforming catalyst according to claim 8, wherein the auxiliary agent is any one or more of Zn, La, Ce, Mg and Ca; the carrier is gamma-Al2O3And ZrO2Any one of them.
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