Preparation method of vegetable oil hydrodeoxygenation catalyst
阅读说明：本技术 一种植物油加氢脱氧催化剂的制备方法 (Preparation method of vegetable oil hydrodeoxygenation catalyst ) 是由 王东军 侯凯湖 董平 贾云刚 何玉莲 王斯晗 褚洪岭 李建忠 王伟众 袁宗胜 何 于 2018-07-26 设计创作，主要内容包括：本发明涉及一种植物油加氢脱氧催化剂的制备方法,包括以下步骤：(1)催化剂载体的制备：将MgAl<Sub>2</Sub>O<Sub>4</Sub>粉体、氢氧化铝干胶、田菁粉混合均匀,滴加稀硝酸挤条成型,焙烧,即得催化剂载体；(2)活性组分负载：将镍盐、钼盐、有机酸溶于去离子水中得到浸渍溶液,将上述载体放入上述浸渍溶液中进行等体积浸渍,15-30℃下静置8-12h,100-120℃下干燥10-12h,得到催化剂。通过该方法制备催化剂可实现植物油加氢脱氧路径的调控,从而降低生物柴油的生产成本。(The invention relates to a preparation method of a vegetable oil hydrodeoxygenation catalyst, which comprises the following steps: (1) preparation of catalyst carrier: MgAl is added 2 O 4 Uniformly mixing the powder, aluminum hydroxide dry glue and sesbania powder, dripping dilute nitric acid, extruding into strips, molding and roasting to obtain a catalyst carrier; (2) loading active components: dissolving nickel salt, molybdenum salt and organic acid in deionized water to obtain an impregnation solution, putting the carrier into the impregnation solution for isovolumetric impregnation, standing at 15-30 ℃ for 8-12h, and drying at 100-120 ℃ for 10-12h to obtain the catalyst. The catalyst prepared by the method can realize the regulation and control of the vegetable oil hydrodeoxygenation path, thereby reducing the production cost of the biodiesel.)
1. The preparation method of the vegetable oil hydrodeoxygenation catalyst is characterized by comprising the following steps of:
(1) preparation of catalyst support
MgAl is added2O4Uniformly mixing the powder, aluminum hydroxide dry glue and sesbania powder, dripping dilute nitric acid, extruding into strips, molding and roasting to obtain a catalyst carrier;
(2) active ingredient loading
Dissolving nickel salt, molybdenum salt and organic acid in deionized water to obtain an impregnation solution, putting the carrier into the impregnation solution for impregnation, standing at 15-30 ℃ for 8-12h, and drying at 100-120 ℃ for 10-12h to obtain a catalyst;
in the step (2), nickel salt and molybdenum salt are used as active components, and MoO is used as the active component3The mass of the + NiO accounts for 10-30 wt% of the mass of the carrier, and the mass of Mo in the active component is as follows: the molar ratio of Ni is 0.4-100, (Mo + Ni): the molar ratio of the organic acid is 0.3-3.0: 1.
2. the method of preparing a vegetable oil hydrodeoxygenation catalyst as claimed in claim 1, wherein the molar ratio of Mo: the molar ratio of Ni is 0.4-1.0 or 90-100.
3. The method of claim 2, wherein when Mo: when the molar ratio of Ni is 90-100, the preparation method also comprises the following steps:
(3) adjuvant loading
Putting the catalyst obtained in the step (2) into an auxiliary agent solution with the concentration of 0.50-1.5mol/L for isovolumetric impregnation, standing for 8-12h at 15-30 ℃, drying and roasting to obtain the catalyst;
the auxiliary agent is selected from one or more of Fe salt, Co salt and W salt.
4. The method for preparing a vegetable oil hydrodeoxygenation catalyst as claimed in claim 1, wherein in step (1), MgAl2O4Powder: aluminum hydroxide dry glue: the mass ratio of the sesbania powder is 5-8: 2-5: 0.3; MgAl per gram2O40.6-1.2mL of dilute nitric acid is dripped into the powder; the concentration of the dilute nitric acid is 0.2-0.5 wt%.
5. The method for preparing a vegetable oil hydrodeoxygenation catalyst as claimed in claim 1, wherein in step (2), the nickel salt is selected from Ni (NO)3)2·6H2O、NiSO4·6H2O、NiCl2·6H2O、C4H6O4Ni·4H2And one or more of O.
6. The method for preparing the vegetable oil hydrodeoxygenation catalyst as claimed in claim 1, wherein in step (2), the molybdenum salt is selected from (NH)4)6Mo7O24·4H2O、Mo(NO3)3·5H2O、H2MoO4·H2And one or more of O.
7. The method for preparing the vegetable oil hydrodeoxygenation catalyst as claimed in claim 1, wherein in the step (2), the organic acid is one or more selected from citric acid, oxalic acid, glycolic acid and malic acid.
8. The method for preparing the vegetable oil hydrodeoxygenation catalyst according to claim 3, characterized in that in step (3), the Fe salt is ferric nitrate, the Co salt is cobalt nitrate, and the W salt is tungsten nitrate.
9. The method for preparing a vegetable oil hydrodeoxygenation catalyst as claimed in claim 1, wherein in step (1), the MgAl is present2O4The particle size of the powder is 10-20 nm.
10. The method for preparing the vegetable oil hydrodeoxygenation catalyst according to claim 1, characterized in that in step (1), the roasting conditions are as follows: the temperature is 400 ℃ and 800 ℃, and the time is 2-6 h.
11. The method for preparing a vegetable oil hydrodeoxygenation catalyst according to claim 1, characterized in that in step (2), the drying conditions are: the temperature is 100 ℃ and 120 ℃, and the time is 10-12 h.
12. The method for preparing the vegetable oil hydrodeoxygenation catalyst according to claim 3, characterized in that in the step (3), the drying and roasting processes are as follows: drying at 105-120 deg.C for 3-5h, and calcining at 480-650 deg.C for 3-5 h.
Technical Field
The invention relates to a preparation method of a hydrodeoxygenation catalyst, in particular to a preparation method of a vegetable oil hydrodeoxygenation catalyst.
Background
With the continuous progress of society, the rapid development of economy and the increasingly prominent contradiction between supply and demand of global petroleum resources, on one hand, the demand of people for petroleum resources is increased, and on the other hand, the supply of petroleum resources is deficient day by day. As the consumption of oil resources increases, many environmental problems are caused. Therefore, the search for an environmentally friendly and renewable energy source has attracted a high degree of attention in many countries. Among various renewable energy sources, biomass energy sources have the characteristics of wide distribution, low pollution, renewability and the like, and are increasingly paid more attention by people.
The biodiesel is a diesel substitute fuel prepared from animal and vegetable oil, has excellent combustion performance and environmental protection performance compared with petroleum diesel, and only generates little SO during combustion2And NO2Is an ideal clean energy source. In the rapid development of biodiesel as a petrochemical fuel substitute with a promising future, a hydrodeoxygenation catalyst is the key for preparing second-generation biodiesel. The main component of the vegetable oil is higher fatty acid ester, which has higher relative molecular weight and higher oxygen content. The vegetable oil hydrodeoxygenation reaction mainly comprises two paths which are carried out simultaneously: route 1 is a direct hydrodehydration reaction, the product of which is predominantly C16、C18Isovalent hydrocarbons and C3H8、H2O, the yield of the diesel oil fraction is high, but the hydrogen consumption is high; route 2 is a hydrodecarbonylation reaction and a hydrodedecarboxylation reaction, the products of which are mainly C15、C17Iso-odd number of carbon atoms and C3H8、CO、CO2The yield of diesel oil fraction is low, but the hydrogen consumption is less.
In NiMo/La-Al2O3In the research of catalyzing the hydrodeoxygenation of the soybean oil to prepare the second-generation biodiesel, the university of the great continental engineering is used for smoothly investigating the influence of reaction conditions on the hydrodeoxygenation result of the soybean oil. At the temperature of 360 ℃, the pressure of 5MPa and the liquid hourly space velocity of 1h-1Under the condition of MoNi/La-Al2O3(Mo/Ni ═ 1: 1) the hydrodeoxygenation of soybean oil was 94.3%, the selectivity for direct hydrodehydration was 31.4%, and the hydrodecarbonylation and hydrodedecarboxylation selectivity was 68.6%.
With Mo-Ni/Al2O3As a catalyst, the aviation kerosene is prepared by taking palm oil as a raw material through hydrodeoxygenation reaction in medium and petrochemical department, Zhang-Shuang-super and the like. The result shows that the temperature is 360 ℃, the pressure is 6.4MPa, and the liquid hourly space velocity is 2h-1Under the conditions, the deoxidation rate of the palm oil is 100%, the selectivity of direct hydro-dehydration is 53.9%, the selectivity of hydro-decarbonylation is 20.7%, and the selectivity of hydro-decarboxylation is 25.4%.
Li in Ni of Tianjin university2P/SiO2In the research of the hydrodeoxygenation performance of the catalyst for catalyzing methyl laurate, the hydrodeoxygenation performance of different metal phosphide catalysts is investigated, and the influence between the structure and the performance of the catalyst is discussed. At the temperature of 300 ℃, the pressure of 2MPa and the liquid hourly space velocity of 5.2h-1Under the conditions, the deoxidation rate of the methyl laurate is 99.48 percent, the selectivity of the direct hydro-dehydration is 12.7 percent, and the selectivity of the hydro-decarbonylation and the hydro-decarboxylation is 87.3 percent.
The above-mentioned research on the hydrodeoxygenation of the catalyst and the vegetable oil only focuses on the comprehensive hydrodeoxygenation performance of the catalyst and the total removal rate of oxygen in the vegetable oil, and it is not possible to select which route is the main route in the hydrodeoxygenation depending on the local or current hydrogen resource or price status.
The vegetable oil is used as raw material to prepare the biodiesel, and the hydrodeoxygenation process is the key. Hydrodeoxygenation needs to be carried out in the presence of hydrogen. If the catalyst with the dominant performance of the path 2 is adopted in the place where the hydrogen resource is scarce, the oxygen in the vegetable oil is removed mainly in a mode of hydrogenation decarbonylation or hydrogenation decarboxylation so as to reduce the hydrogen consumption; and in the place where hydrogen is cheap and easy to obtain, the catalyst with the dominant performance of the path 1 is adopted to remove oxygen in the vegetable oil in a hydro-dehydration mode so as to increase the yield of the target product.
Therefore, the catalyst with proper performance and two different selective catalytic performances is developed, and a hydrogenation path can be selected according to the local and current hydrogen resource conditions, which has great significance for reasonably utilizing resources and reducing the production cost of biodiesel.
Disclosure of Invention
The invention aims to provide a preparation method of a vegetable oil hydrodeoxygenation catalyst aiming at the defect that a hydrodeoxygenation catalyst developed in the prior art cannot select a hydrodeoxygenation path.
In order to achieve the aim, the invention provides a preparation method of a vegetable oil hydrodeoxygenation catalyst, which comprises the following steps:
(1) preparation of catalyst support
MgAl is added2O4Uniformly mixing the powder, aluminum hydroxide dry glue and sesbania powder, dripping dilute nitric acid, extruding into strips, molding and roasting to obtain a catalyst carrier;
(2) active ingredient loading
Dissolving nickel salt, molybdenum salt and organic acid in deionized water to obtain an impregnation solution, putting the carrier into the impregnation solution for impregnation (such as equal-volume impregnation), standing at 15-30 ℃ for 8-12h, and drying at 100-120 ℃ for 10-12h to obtain the catalyst.
In the preparation method of the vegetable oil hydrodeoxygenation catalyst, in the step (2), preferably, nickel salt and molybdenum salt are used as active components, and MoO is used as the active component3The mass of the + NiO accounts for 10-30 wt% of the mass of the carrier, and the mass of Mo in the active component is as follows: the molar ratio of Ni is 0.4-100, (Mo + Ni): organic compoundsThe molar ratio of the acid is 0.3-3.0: 1.
according to the preparation method of the vegetable oil hydrodeoxygenation catalyst, in the step (2), Mo: the molar ratio of Ni is preferably 0.4-1.0 or 90-100.
When Mo in the active component: when the molar ratio of Ni is 90-100, the preparation method also comprises the following steps:
(3) adjuvant loading
Putting the catalyst obtained in the step (2) into an auxiliary agent solution with the concentration of 0.50-1.5mol/L for isovolumetric impregnation, standing for 8-12h at 15-30 ℃, drying and roasting to obtain the catalyst;
the auxiliary agent is selected from one or more of Fe salt, Co salt and W salt.
The preparation method of the vegetable oil hydrodeoxygenation catalyst comprises the step (1) of MgAl2O4Powder: aluminum hydroxide dry glue: the mass ratio of the sesbania powder is preferably 5-8: 2-5: 0.3; MgAl per gram2O4Preferably, 0.6-1.2mL of dilute nitric acid is dripped into the powder, and the concentration of the dilute nitric acid is preferably 0.2-0.5 wt%.
In the preparation method of the vegetable oil hydrodeoxygenation catalyst, in the step (2), the nickel salt is preferably selected from Ni (NO)3)2·6H2O、NiSO4·6H2O、NiCl2·6H2O、C4H6O4Ni·4H2And one or more of O.
In the preparation method of the vegetable oil hydrodeoxygenation catalyst, in the step (2), the molybdenum salt is preferably selected from (NH)4)6Mo7O24·4H2O、Mo(NO3)3·5H2O、H2MoO4·H2And one or more of O.
In the preparation method of the vegetable oil hydrodeoxygenation catalyst, in the step (2), the organic acid is preferably selected from one or more of citric acid, oxalic acid, glycolic acid and malic acid.
In the preparation method of the vegetable oil hydrodeoxygenation catalyst, in the step (3), the Fe salt is preferably ferric nitrate, the Co salt is preferably cobalt nitrate, and the W salt is preferably tungsten nitrate.
The preparation method of the vegetable oil hydrodeoxygenation catalyst comprises the step (1) of preparing the MgAl2O4The particle size of the powder is preferably 10 to 20 nm.
In the preparation method of the vegetable oil hydrodeoxygenation catalyst, in the step (1), the roasting conditions are preferably as follows: the temperature is 400 ℃ and 800 ℃, and the time is 2-6 h.
In the preparation method of the vegetable oil hydrodeoxygenation catalyst, in the step (2), the drying conditions are preferably as follows: the temperature is 100 ℃ and 120 ℃, and the time is 10-12 h.
In the preparation method of the vegetable oil hydrodeoxygenation catalyst, in the step (3), the drying and roasting processes are preferably as follows: drying at 105-120 deg.C for 3-5h, and calcining at 480-650 deg.C for 3-5 h.
The technical scheme of one embodiment of the invention is as follows:
s1, preparation of a catalyst carrier: MgAl is added2O4Uniformly mixing the powder, the aluminum hydroxide dry glue and the sesbania powder, dripping dilute nitric acid to extrude the mixture into strips for molding, and roasting the strips in a muffle furnace at the temperature of 400 ℃ and 800 ℃ for 2 to 6 hours to obtain a catalyst carrier;
wherein the mass ratio is MgAl2O4Powder: aluminum hydroxide dry glue: sesbania powder 5-8: 2-5: 0.3; MgAl per gram2O40.6-1.2mL of dilute nitric acid is dripped into the powder, wherein the concentration of the dilute nitric acid is 2-5%;
(2) loading active components: dissolving nickel salt, molybdenum salt and organic acid in deionized water, wherein the mass ratio of the solution to the carrier is 0.7:1.0, impregnating with active components, standing for 8-12h at 15-30 ℃, and drying for 10-12h at 120 ℃ in an oven 100-;
wherein the active component is MoO3The mass of + NiO is 10 to 30 wt% of the mass of the support, Mo: ni molar ratio of 0.4-1.0 or 90-100, (Mo + Ni): the organic acid molar ratio is 0.3-3.0: 1;
the nickel salt is Ni (NO)3)2·6H2O、NiSO4·6H2O、NiCl2·6H2O、C4H6O4Ni·4H2One or more of O;
the molybdenum salt is (NH)4)6Mo7O24·4H2O、Mo(NO3)3·5H2O、H2MoO4·H2One or more of O;
the organic acid is one or more of citric acid, oxalic acid, glycolic acid and malic acid;
the MgAl2O4The particle size of the powder is preferably 10 to 20 nm.
The technical scheme of another embodiment of the invention is as follows:
s1, preparation of a catalyst carrier: MgAl is added2O4Uniformly mixing the powder, the aluminum hydroxide dry glue and the sesbania powder, dripping dilute nitric acid to extrude the mixture into strips for molding, and roasting the strips in a muffle furnace at the temperature of 400 ℃ and 800 ℃ for 2 to 6 hours to obtain a catalyst carrier;
wherein, MgAl2O4Powder: aluminum hydroxide dry glue: the sesbania powder mass ratio is 5-8: 2-5: 0.3; MgAl per gram2O40.6-1.2mL of dilute nitric acid is dripped into the powder, wherein the concentration of the dilute nitric acid is 2-5%;
(2) loading active components: dissolving nickel salt, molybdenum salt and organic acid in deionized water, wherein the mass ratio of the solution to a carrier is 0.7:1.0, impregnating with an active component, standing for 8-12h at 15-30 ℃, and drying for 10-12h at 120 ℃ in an oven 100 ℃ to obtain a main catalyst;
wherein the active component is MoO3The mass of the + NiO accounts for 10-30 wt% of the mass of the carrier, and the molar ratio is Mo: and Ni is 90-100, and the molar ratio is (Mo + Ni): organic acid 0.3-3.0: 1;
the nickel salt is Ni (NO)3)2·6H2O、NiSO4·6H2O、NiCl2·6H2O、C4H6O4Ni·4H2One or more of O;
the molybdenum salt is (NH)4)6Mo7O24·4H2O、Mo(NO3)3·5H2O、H2MoO4·H2One or more of O;
the organic acid is one or more of citric acid, oxalic acid, glycolic acid and malic acid;
(3) auxiliary agent loading: dipping an auxiliary agent solution with the concentration of 0.50-1.5mol/L onto the main catalyst obtained in the step (2), wherein the ratio of the solution to the main catalyst of the carrier is 0.5:1.0, standing for 8-12h at 15-30 ℃, drying for 3-5h at 105-120 ℃ in a muffle furnace and roasting for 3-5h at 480-650 ℃ to obtain the required catalyst;
the auxiliary agent is one or two of Fe salt, Co salt and W salt.
The Fe salt is ferric nitrate; the Co salt is specifically cobalt nitrate; the W salt is tungsten nitrate;
the MgAl2O4The particle size of the powder is preferably 10 to 20 nm.
The catalyst obtained by the invention can realize the regulation and control of the vegetable oil hydrodeoxygenation path through the preparation method, thereby reducing the production cost of the biodiesel.
According to the preparation method of the vegetable oil hydrodeoxygenation catalyst, the vegetable oil hydrodeoxygenation path can be regulated and controlled by the catalyst prepared through the method. Specifically, a hydrogenation path is selected according to the local and current hydrogen resource conditions, and the ratio of the hydrogenation and deoxidation paths of the prepared catalyst vegetable oil is selected and regulated by adjusting the molybdenum-nickel ratio and adding an auxiliary agent, so that the method has great significance for reasonably utilizing resources and reducing the production cost of the biodiesel, and simultaneously can reduce the production cost of the biodiesel.
The invention specifically comprises the following beneficial effects:
1. according to the invention, the hydrodeoxygenation catalyst prepared by twice impregnation is impregnated with the loaded active component firstly, then the loaded auxiliary agent is impregnated, and the catalytic performance of the catalyst is adjusted through the modification effect of the auxiliary agent, so that the regulation and control of the vegetable oil hydrodeoxygenation path are realized; and two catalysts with respectively superior path performance can be obtained by adjusting the molybdenum-nickel ratio or/and adding an auxiliary agent.
2. At a reaction temperature of 370 ℃ and a pressure of 2.0MPa, airspeed of 1h-1Hydrogen-oil volume ratio 200: 1, the hydrodeoxygenation performance of the catalyst is evaluated on a continuous flow fixed bed reaction device by taking an n-octane solution containing 20 percent of jatropha curcas oil as a raw material. The result shows that the selectivity of the direct hydrogenation dehydration of the jatropha curcas oil can be adjusted according to the requirement, and the adjustable range is 9.8-91.8%.
3. The catalyst can realize effective regulation and control of the vegetable oil hydrodeoxygenation path, namely, the catalyst with the dominant performance of the path 1 is selected in a place with sufficient hydrogen, namely, the molybdenum-nickel ratio is increased (the molar ratio of Mo to Ni is 90-100, preferably 100), the diesel oil yield can be increased by more than 4 percent, and the diesel oil yield can be increased by 4.96 percent to the maximum extent; the catalyst with the dominant performance of route 2 is selected in the place where hydrogen is scarce, i.e. the molybdenum-nickel ratio (molar ratio of Mo: Ni is 0.4-1.0, preferably 0.4) is reduced, so that the hydrogen consumption can be reduced by more than 40.0%.
Detailed Description
The following examples illustrate the invention in detail: the present example is carried out on the premise of the technical scheme of the present invention, and detailed embodiments and processes are given, but the scope of the present invention is not limited to the following examples, and the experimental methods without specific conditions noted in the following examples are generally performed according to conventional conditions.
The technical scheme of one embodiment of the invention is as follows:
s1, preparation of a catalyst carrier: MgAl is added2O4Uniformly mixing the powder, the aluminum hydroxide dry glue and the sesbania powder, dripping dilute nitric acid to extrude the mixture into strips for molding, and roasting the strips in a muffle furnace at the temperature of 400 ℃ and 800 ℃ for 2 to 6 hours to obtain a catalyst carrier;
wherein the mass ratio is MgAl2O4Powder: aluminum hydroxide dry glue: sesbania powder 5-8: 2-5: 0.3; MgAl per gram2O40.6-1.2mL of dilute nitric acid is dripped into the powder, wherein the concentration of the dilute nitric acid is 2-5%;
(2) loading active components: dissolving nickel salt, molybdenum salt and organic acid in deionized water, wherein the mass ratio of the solution to the carrier is 0.7:1.0, impregnating with active components, standing for 8-12h at 15-30 ℃, and drying for 10-12h at 120 ℃ in an oven 100-;
wherein the active component is MoO3The mass of + NiO is 10 to 30 wt% of the mass of the support, Mo: ni molar ratio of 0.4-1.0 or 90-100, (Mo + Ni): the organic acid molar ratio is 0.3-3.0: 1;
the nickel salt is Ni (NO)3)2·6H2O、NiSO4·6H2O、NiCl2·6H2O、C4H6O4Ni·4H2One or more of O;
the molybdenum salt is (NH)4)6Mo7O24·4H2O、Mo(NO3)3·5H2O、H2MoO4·H2One or more of O;
the organic acid is one or more of citric acid, oxalic acid, glycolic acid and malic acid;
the MgAl2O4The particle size of the powder is preferably 10 to 20 nm.
See, in particular, examples 1-2 and 6.
The technical scheme of another embodiment of the invention is as follows:
s1, preparation of a catalyst carrier: MgAl is added2O4Uniformly mixing the powder, the aluminum hydroxide dry glue and the sesbania powder, dripping dilute nitric acid to extrude the mixture into strips for molding, and roasting the strips in a muffle furnace at the temperature of 400 ℃ and 800 ℃ for 2 to 6 hours to obtain a catalyst carrier;
wherein, MgAl2O4Powder: aluminum hydroxide dry glue: the sesbania powder mass ratio is 5-8: 2-5: 0.3; MgAl per gram2O40.6-1.2mL of dilute nitric acid is dripped into the powder, wherein the concentration of the dilute nitric acid is 2-5%;
(2) loading active components: dissolving nickel salt, molybdenum salt and organic acid in deionized water, wherein the mass ratio of the solution to a carrier is 0.7:1.0, impregnating with an active component, standing for 8-12h at 15-30 ℃, and drying for 10-12h at 120 ℃ in an oven 100 ℃ to obtain a main catalyst;
wherein the active component is MoO3The mass of the + NiO accounts for 10-30 wt% of the mass of the carrier, and the molar ratio is Mo: and Ni is 90-100, and the molar ratio is (Mo + Ni): organic acid 0.3-3.0: 1;
the nickel salt is Ni (NO)3)2·6H2O、NiSO4·6H2O、NiCl2·6H2O、C4H6O4Ni·4H2One or more of O;
the molybdenum salt is (NH)4)6Mo7O24·4H2O、Mo(NO3)3·5H2O、H2MoO4·H2One or more of O;
the organic acid is one or more of citric acid, oxalic acid, glycolic acid and malic acid;
(3) auxiliary agent loading: dipping an auxiliary agent solution with the concentration of 0.50-1.5mol/L onto the main catalyst obtained in the step (2), wherein the ratio of the solution to the main catalyst of the carrier is 0.5:1.0, standing for 8-12h at 15-30 ℃, drying for 3-5h at 105-120 ℃ in a muffle furnace and roasting for 3-5h at 480-650 ℃ to obtain the required catalyst;
the auxiliary agent is one or two of Fe salt, Co salt and W salt.
The Fe salt is ferric nitrate; the Co salt is specifically cobalt nitrate; the W salt is tungsten nitrate;
the MgAl2O4The particle size of the powder is preferably 10 to 20 nm.
See, in particular, examples 3-5.
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