Rare earth doped multi-cation pillared modified double metal hydrogenation catalyst, its preparation method and application

Abstract

The application provides a rare earth doped multi-element anion pillared modified double metal hydrogenation catalyst and a preparation method and application thereof. The double doped pillared carrier of the application comprises Mg-Al hydrotalcite, a rare earth element and a transition metal element. By introducing the rare earth element into the carrier and the catalyst, the dispersion degree of the transition metal element in the catalyst is greatly improved, the coordination number between the transition metal elements is effectively reduced, more active centers of the transition metal elements are exposed, and better synergistic effect between the transition metal elements and noble metals is generated. Under the premise of guaranteeing efficient hydrogen oil production, the noble metal loading of the catalyst is greatly reduced, the noble metal consumption is as low as 0.05-0.15 wt% after optimization, the problems of high catalyst cost and large reactor load in the hydrogen oil production process are solved, and the concept of green chemistry is met.

Description

TECHNICAL FIELD

[0001] The present application relates to the technical field of organic liquid hydrogen storage, in particular to a rare earth doped multi-cation columnar modified bimetallic hydrogenation catalyst and a preparation method and application thereof. BACKGROUND

[0002] Hydrogen energy is considered to be the most potential energy in the 21st century due to its abundant source, renewable, high energy density and clean combustion. Hydrogen energy system mainly includes hydrogen production, hydrogen storage and transportation and hydrogen utilization technology, among which, hydrogen storage is the key to the effective utilization of hydrogen energy. Organic liquid hydrogen storage technology has attracted widespread attention due to its high hydrogen storage density, recyclability, liquid storage and transportation safety and convenience. This technology is expected to play an important role in future hydrogen energy storage. With the emergence of in-situ hydrogen production and hydrogenation station, the efficient, low-cost and low-energy production of hydrogen oil is one of the key problems to be solved for large-scale promotion of organic liquid hydrogen storage technology.

[0003] The current organic hydrogen storage carriers with large-scale application prospects are mainly aromatic hydrocarbon compounds such as toluene, benzene, naphthalene, quinoline, carbazole, benzyl toluene, dibenzyl toluene, and N-ethyl carbazole. The activation energy required for complete hydrogenation reaction of these compounds is high, and the catalysts required are generally noble metal catalysts. Patent CN112675842B discloses a high-activity and high-stability supported nickel catalyst and its preparation method. A non-noble metal hydrogenation catalyst with a Ni loading of 30-90wt% is prepared by a co-precipitation method, which reduces the agglomeration of nickel and ensures the dispersion of Ni. The hydrogenation catalyst prepared by this method has high activity, but the complete hydrogenation pressure in its application is above 7MPa, which has the problem of high device load and is difficult to meet the needs of efficient hydrogen-oil synthesis. Patent CN112675865B discloses a preparation method of a bimetallic catalyst for hydrogenation of organic liquid hydrogen storage. The hydrogen storage carrier can be completely hydrogenated under the conditions of a reaction temperature of 150-200℃ and a hydrogenation time of 1-2h, but the noble metal loading is 1.5-7.5wt%, which has the problem of high catalyst preparation cost. Patent CN114700084B discloses a sub-nanometer limited new Ru metal catalyst for hydrogenation of organic liquid hydrogen storage materials and its preparation method. The limited effect of the carrier greatly improves the dispersion of noble metal Ru. The Ru metal loading in the catalyst is 0.05-0.7%, and the Ru metal particle size is 0.2-2nm, which greatly reduces the amount of noble metal catalyst. However, the synthesis process of this method is complex and difficult to meet the needs of large-scale production. Patent CN115254141A discloses a synthesis method of a low-noble metal loading hydrogenation catalyst. The interaction of composite metal oxides is used to regulate the electron cloud density and defect degree of the carrier surface. A Ru nanocluster supported catalyst with small particle size is prepared by hydrogen reduction, which has high catalytic activity. However, this invention uses traditional hydrothermal synthesis method, which has the problems of high energy consumption and long synthesis process. At present, the development of high-efficiency and low-cost hydrogen-oil hydrogenation catalysts is still a problem that needs to be solved for large-scale promotion of organic liquid hydrogen storage technology. SUMMARY

[0004] In view of the above-mentioned deficiencies of the prior art, the purpose of the present application is to provide a rare earth doped multi-cationic pillar modified bimetallic hydrogenation catalyst and its preparation method and application.

[0005] To achieve the above object and other related objects, the present application provides a double-doped pillared support in the first aspect, comprising Mg-Al hydrotalcite, rare earth element and transition metal element; wherein the molar mass ratio of the rare earth element, the transition metal element, the Al element and the Mg element is 0.01:(0.1-0.3):(1-2):(2-3.5), such as 0.01:(0.1-0.2):(1-2):(2-3), 0.01:(0.1-0.15):(1-2):(2-3), 0.01:(0.15-0.2):(1-2):(2-3), 0.01:(0.15-0.3):(1-2):(2-3.5). Or the molar mass ratio of the rare earth metal ion and the Mg-Al hydrotalcite is 0.005-0.1:1, such as 0.005-0.01:1, 0.01-0.05:1, 0.05-0.1:1. The mass ratio of the transition metal ion and the Mg-Al hydrotalcite is 0.05-0.3:1, such as 0.05-0.1:1, 0.1-0.2:1 or 0.2-0.3:1.

[0006] In some possible embodiments, at least one of the following technical solutions is included, and the technical features in each technical solution can be combined as needed:

[0007] a1) the rare earth element is derived from a rare earth metal ion complex, and in the rare earth metal ion complex: the rare earth metal ion is selected from at least one of Ce, La, Y and Nd, and the ligand is selected from at least one of an organic complexing agent or an inorganic complexing agent;

[0008] a11) in technical feature a1, the ligand in the rare earth metal ion complex is selected from at least one of trimesic acid, pyromellitic acid, citric acid, phosphoric acid, hydrochloric acid, p-toluenesulfonic acid or benzene sulfonic acid; for example, selected from any one of the above, or a combination of two or three, such as trimesic acid / or pyromellitic acid and citric acid, trimesic acid / or pyromellitic acid and phosphoric acid, trimesic acid / or pyromellitic acid and hydrochloric acid, trimesic acid / or pyromellitic acid and p-toluenesulfonic acid, trimesic acid / or pyromellitic acid and benzene sulfonic acid.

[0009] a12) in technical feature a2, the ligand in the transition metal ion complex is selected from at least one of trimesic acid, pyromellitic acid, citric acid, phosphoric acid, hydrochloric acid, p-toluenesulfonic acid or benzene sulfonic acid; for example, selected from any one of the above, or a combination of two or three, such as trimesic acid / or pyromellitic acid and citric acid, trimesic acid / or pyromellitic acid and phosphoric acid, trimesic acid / or pyromellitic acid and hydrochloric acid, trimesic acid / or pyromellitic acid and p-toluenesulfonic acid, trimesic acid / or pyromellitic acid and benzene sulfonic acid.

[0010] a2) the rare earth element is derived from at least one of nitrate or chloride salt of rare earth metal ion;

[0011] a3) the transition metal element is derived from a transition metal ion complex, in which: the transition metal ion is selected from at least one of Ni, Co, Fe, Mn, Cu, Zn, and the ligand is selected from at least one of organic complexing agent or inorganic complexing agent;

[0012] a4) the transition metal element is derived from at least one of nitrate or chloride salt of transition metal ion.

[0013] It is worth noting that the key point of the double-doped pillared support of the present application lies in the introduction of the rare earth element, and the introduction of the rare earth element with rich defect sites effectively reduces the agglomeration of the transition metal element in the reduction process, reduces the particle size of the transition metal element, and improves the dispersion degree of the transition metal element, thereby obtaining a double-doped pillared support with excellent dispersion degree of metal elements. The above technical solutions are preferred embodiments obtained by the inventors of the present application through research.

[0014] The second aspect of the present application provides a preparation method of a double-doped pillared support, comprising the following steps:

[0015] 1) mixing an aqueous solution comprising rare earth metal ions and transition metal ions with a complexing agent to obtain a complex solution;

[0016] Preferably, at least one of the following technical solutions is included, and the technical features in each technical solution can be combined individually or as needed:

[0017] 1a) in step 1), the rare earth metal ion is selected from at least one of Ce, La, Y, and Nd;

[0018] 1b) in step 1), the rare earth metal ion is derived from at least one of nitrate or chloride salt of metal ion;

[0019] 1c) in step 1), the transition metal ion is selected from at least one of Ni, Co, Fe, Mn, Cu, and Zn;

[0020] 1d) in step 1), the transition metal ion is derived from at least one of nitrate or chloride salt of transition metal ion;

[0021] 1e) In step 1), the complexing agent is at least one selected from the group consisting of trimesic acid, pyromellitic acid, citric acid, phosphoric acid, hydrochloric acid, p-toluene sulfonic acid and benzene sulfonic acid; for example, at least one selected from the group consisting of any one of the above, or a combination of two or three, for example, trimesic acid / pyromellitic acid and citric acid, trimesic acid / pyromellitic acid and phosphoric acid, trimesic acid / pyromellitic acid and hydrochloric acid, trimesic acid / pyromellitic acid and p-toluene sulfonic acid, trimesic acid / pyromellitic acid and benzene sulfonic acid.

[0022] 1f) In step 1), the concentration of transition metal ions in the aqueous solution is 0.5-1.0 mol / L, such as 0.5-0.6 mol / L, 0.6-0.7 mol / L, 0.7-0.8 mol / L, 0.8-0.9 mol / L or 0.9-1.0 mol / L.

[0023] 1g) In step 1), the concentration of rare earth metal ions in the aqueous solution is 0.05-0.1 mol / L, such as 0.05-0.06 mol / L, 0.06-0.07 mol / L, 0.07-0.08 mol / L, 0.08-0.09 mol / L or 0.09-0.1 mol / L.

[0024] 1h) In step 1), the concentration of complexing agent in the complex solution is 0.5-1.0 mol / L, such as 0.5-0.6 mol / L, 0.6-0.7 mol / L, 0.7-0.8 mol / L, 0.8-0.9 mol / L or 0.9-1.0 mol / L.

[0025] 1i) In step 1), after mixing the aqueous solution of rare earth metal ions and transition metal ions with the complexing agent, the mixture is stirred vigorously to obtain a uniform transparent complex solution.

[0026] 1j) In step 1), the molar mass ratio of the rare earth element, the transition metal element, the Al element and the Mg element is 0.01:(0.1-0.3):(1-2):(2-3.5); for example, 0.01:(0.1-0.2):(1-2):(2-3), 0.01:(0.1-0.15):(1-2):(2-3), 0.01:(0.15-0.2):(1-2):(2-3), 0.01:(0.15-0.3):(1-2):(2-3.5).

[0027] 2) Provide Mg-Al hydrotalcite and prepare Mg-Al hydrotalcite colloid, and ion exchange the complex solution obtained in step 1) with the Mg-Al hydrotalcite colloid to obtain hydrotalcite-bimetallic ligand sol;

[0028] Preferably, at least one of the following technical solutions is included, and the technical features in each technical solution can be combined individually or as needed:

[0029] 2a) In step 2), the Mg-Al molar ratio of the Mg-Al hydrotalcite is 2-3:1, and a conventional commercially available Mg-Al hydrotalcite is generally selected.

[0030] 2b) In step 2), the particle size of the Mg-Al hydrotalcite is less than 1000 mesh; for example, 200-1000 mesh.

[0031] 2c) In step 2), the method for preparing the Mg-Al hydrotalcite colloid is adjusting the pH and temperature of the aqueous dispersion of the Mg-Al hydrotalcite, and stirring to obtain the Mg-Al hydrotalcite colloid; preferably, the pH is 5-7, such as 5-6 or 6-7; the temperature is 50-80°C, such as 50-60°C, 60-70°C, or 70-80°C.

[0032] 2d) In step 2), the complex solution of step 1) is added dropwise to the Mg-Al hydrotalcite colloid, and ion exchange is carried out at a certain pH and temperature; preferably, the pH is 5.5-6.5, such as 5.5-6.0 or 6.0-6.5, and the temperature is 50-80°C, such as 50-60°C, 60-70°C, or 70-80°C.

[0033] 3) The hydrotalcite-bimetallic ligand sol obtained in step 2) is reacted with a precipitating agent, and after the reaction, aging, drying is carried out to obtain a pillared support precursor;

[0034] Preferably, at least one of the following technical solutions is included, and the technical features in each technical solution can be combined individually or as needed:

[0035] 3a) In step 3), the precipitating agent is a mixture of sodium hydroxide and sodium carbonate; preferably, the molar ratio of sodium hydroxide to sodium carbonate is 2:1-1:1;

[0036] 3b) The precipitating agent solution is slowly added dropwise to the hydrotalcite-bimetallic ligand sol, and the flow rate is controlled at 0.2-1 mL / min, such as 0.2-0.5 mL / min or 0.5-1 mL / min;

[0037] 3c) In step 3), the aging time is 0.5-12 h, such as 0.5-2 h, 2-5 h, or 5-12 h; and the aging temperature is 60-80°C, such as 60-70°C or 70-80°C;

[0038] 3d) In step 3), the drying temperature is 70-90°C, such as 70-80°C or 80-90°C.

[0039] 4) the double-doped pillared support is obtained by mixing and grinding the pillared support precursor and the aqueous solution of the surfactant obtained in step 3).

[0040] Preferably, at least one of the following technical solutions is included, and the technical features in each technical solution can be combined individually or as needed:

[0041] 4a) in step 4), the surfactant is at least one selected from sodium dodecyl benzene sulfonate, cetyltrimethylammonium bromide, octadecyl trimethylammonium bromide, and stearic acid;

[0042] 4b) in step 4), the concentration of the surfactant in the aqueous solution is 0.5-1.0 mol / L;

[0043] 4c) in step 4), the mixing and grinding is performed in a ball mill with a frequency of 50-150 Hz, and the cycle grinding time is 2-6 h, and the cycle grinding impregnation temperature is 15-60℃.

[0044] It is worth noting that the present application takes hydrotalcite as a starting point for catalyst synthesis, and selects a metal coordination ion pillared modification synthesis method to obtain a composite metal oxide carrier with excellent metal element dispersion. Specifically, commercially available hydrotalcite is selected as a raw material, and an organic / inorganic metal coordination ion is selected as a precursor. A sol-gel-metal organic / inorganic coordination ion exchange method is used to prepare a multi-element pillared hydrotalcite carrier, which greatly simplifies the preparation process of the layered composite metal oxide carrier and ensures the safety of the preparation process. The double-doped pillared carrier prepared has good metal element dispersion and stability, thereby improving the overall performance of the catalyst. The above technical solutions are preferred embodiments obtained by the inventors of the present application. The third aspect of the present application provides the use of the double-doped pillared carrier in preparing a catalyst for organic liquid hydrogen storage technology. Specifically, it is used as a carrier for an organic liquid hydrogen storage catalyst, and is used for storing hydrogen in aromatic hydrocarbon organic liquids. Preferably, it is applied to the storage of dibenzyl toluene, toluene, naphthalene, or N-ethyl carbazole.

[0045] The fourth aspect of the present application provides a rare earth doped multi-element anion pillared modified double metal hydrogenation catalyst, which comprises the double-doped pillared carrier described above or prepared by the preparation method described above, and further comprises a noble metal active component and a transition metal active component; the precursor of the noble metal component is a noble metal salt, and the precursor of the transition metal component is a transition metal salt.

[0046] Preferably, at least one of the following technical solutions is included, and the technical features in each technical solution can be combined individually or as needed:

[0047] b1) the noble metal salt is selected from at least one nitrate and / or chloride salt of Au, Ru, Pt, Pd, Rh;

[0048] b2) the transition metal salt is selected from at least one nitrate and / or chloride salt of Ni, Co, Fe, Mn, Cu, Zn;

[0049] b3) the noble metal active component and the transition metal active component are present in the form of active component precursors, preferably in the form of a binary complex;

[0050] b4) the mass fraction of noble metal in the bimetallic hydrogenation catalyst is 0.05-0.15%, such as 0.05-0.08%, 0.08-0.1%, 0.1-0.12% or 0.12-0.15%;

[0051] b5) the mass fraction of transition metal in the bimetallic hydrogenation catalyst is 5-20%, such as 5-8%, 8-10%, 10-12%, 12-15% or 15-20%.

[0052] It is worth noting that the rare earth modified pillared bimetallic hydrogenation catalyst prepared by the present application effectively prevents the agglomeration of transition metal elements, reduces the particle size of transition metal elements, and improves the dispersity of transition metal elements due to the introduction of rare earth elements with abundant defect sites, greatly strengthens the synergistic effect between noble metal and transition metal, improves the atomic utilization rate, reduces the amount of noble metal under the premise of ensuring catalytic activity, and effectively reduces the cost of the catalyst. The rare earth doped multi-anion pillared modified bimetallic hydrogenation catalyst of the present application has an atomic level dispersity of noble metal active components. It has a lower transition metal particle size and can exhibit the synergistic effect of hydrogenation sites. And applied to the hydrogenation reaction process of organic hydrogen storage carriers, the catalyst has high activity and high selectivity, and can perform efficient hydrogenation at a lower temperature and pressure. The above technical solutions are preferred embodiments obtained by the inventors of the present application through research.

[0053] The fifth aspect of the present application provides a preparation method of a rare earth doped multi-anion pillared modified bimetallic hydrogenation catalyst, comprising the following steps:

[0054] 1) providing the double-doped pillared support described above or prepared by the preparation method;

[0055] 2) adding a complexing agent to the aqueous solution of noble metal precursors and transition metal precursors to prepare active component precursors;

[0056] Preferably, at least one of the following technical solutions is included, and the technical features in each technical solution can be combined as needed:

[0057] 2a) in step 2), the noble metal precursor is selected from nitrate and / or chloride salt of at least one of Au, Ru, Pt, Pd, Rh;

[0058] 2b) in step 2), the transition metal precursor is selected from nitrate and / or chloride salt of at least one of Ni, Co, Fe, Mn, Cu, Zn;

[0059] 2c) in step 2), the concentration of noble metal precursor in the aqueous solution is 0.05-0.10 mol / L, such as 0.05-0.08 mol / L or 0.08-0.10 mol / L;

[0060] 2d) in step 2), the concentration of transition metal precursor in the aqueous solution is 0.5-1.0 mol / L, such as 0.5-0.8 mol / L or 0.8-1.0 mol / L;

[0061] 2e) in step 2), the complexing agent is a basic complexing agent, the pH of the solution is adjusted to 9.0-11.5, such as 9.0-10.0 or 10.0-11.0 or 11.0-11.5; preferably, the basic complexing agent is selected from at least one of ammonia, triethylamine, triethanolamine, monoethanolamine;

[0062] 2f) in step 2), the molar ratio of noble metal precursor, transition metal precursor and water is 1:(5-20):(10-40), such as 1:(5-10):(10-40), 1:(10-15):(10-40), 1:(15-20):(10-40), 1:(5-10):(10-20), 1:(5-10):(20-30), 1:(5-10):(30-40).

[0063] 3) mixing, grinding and milling the active component precursor, the double-doped pillared support and water to obtain a mixed slurry;

[0064] Preferably, at least one of the following technical solutions is included, and the technical features in each technical solution can be combined individually or as needed:

[0065] 3a) in step 3), the mass ratio of active component precursor, double-doped pillared support and water is (1:10:50)-(1:20:50); such as (1:10:50)-(1:15:50) or (1:15:50)-(1:20:50).

[0066] 3b) in step 3), the active component precursor, the double-doped pillared support and water are mixed, ground and milled, and the pH of the system is 9.0-11.5, such as 9.0-10.0 or 10.0-11.0 or 11.0-11.5;

[0067] 3c) in step 3), the mixing and grinding is cyclic grinding in a ball mill, the ball mill frequency is 50-150 Hz, the cyclic grinding time is 2-6 h, and the cyclic grinding and impregnation temperature is 15-60℃

[0068] 4) After drying, calcination and reduction, the mixed slurry is obtained as a rare earth doped multi-cationic pillared modified bimetallic hydrogenation catalyst.

[0069] Preferably, at least one of the following technical solutions is included, and the technical features in each technical solution can be combined individually or as needed:

[0070] 4a) in step 4), the drying is performed under microwave conditions; preferably, the microwave power is 650-900 W, such as 650-700 W, 700-750 W, 750-800 W, 800-850 W, or 850-900 W; and the frequency is 1.75-2.65 GHz, such as 1.75-2.25 GHz or 2.25-2.65 GHz;

[0071] 4c) in step 4), the drying time is 1-4 h, such as 1-2 h, 2-3 h, or 3-4 h;

[0072] 4d) in step 4), the calcination temperature is 400-800℃, such as 400-500℃, 500-600℃, 600-700℃, or 700-800℃; and the calcination time is 4-16 h, such as 4-8 h, 8-10 h, or 10-16 h;

[0073] 4e) in step 4), the reduction uses hydrogen and argon mixed gas; preferably, the volume ratio of hydrogen is 5-50%, such as 5-10%, 10-20%, 20-30%, 30-40%, or 40-50%;

[0074] 4f) in step 4), the reduction temperature is 250-500℃, such as 250-300℃, 300-350℃, 350-400℃, 400-450℃, or 450-500℃; and the reduction time is 2-10 h, such as 2-5 h or 5-10 h;

[0075] 4g) in step 4), the reduction is performed in a tube furnace, and the flow rate of the hydrogen and argon mixed gas is 80-120 ml / min, such as 80-90 ml / min, 90-100 ml / min, 100-110 ml / min, or 110-120 ml / min.

[0076] It is worth mentioning that the preparation method of the rare earth doped multi-cationic pillared modified bimetallic hydrogenation catalyst of the application can obtain single-atom noble metal alloy hydrogenation active sites, greatly improve the reducibility of transition metal elements by relying on the hydrogen dissociation and hydrogen overflow effect of the highly dispersed noble metal surface, and the introduction of the rare earth element with rich defect sites effectively reduces the agglomeration of the transition metal elements in the reduction process, reduces the particle size of the transition metal elements, and improves the dispersion of the transition metal elements. The above improvements realize the coupling and strengthening of the step-by-step hydrogenation process of each benzene ring with different hydrogenation reaction steric hindances in the hydrogenation process of polycyclic aromatic hydrocarbon organic hydrogen storage carrier, greatly improve the atomic utilization rate and hydrogenation performance of the catalyst. Under the premise of ensuring efficient hydrogen production, the noble metal loading of the catalyst is greatly reduced, and the noble metal content is as low as 0.05-0.15wt% after optimization. By introducing the microwave-assisted synthesis method, the production time and reaction energy consumption of the catalyst are greatly reduced, and the disadvantages of the traditional co-precipitation-aging process and dynamic impregnation catalyst preparation process, such as gradient distribution of temperature distribution, uneven heating, long reaction time, etc. are avoided. The microwave-assisted synthesis method greatly shortens the preparation time of the catalyst and reduces the energy consumption. At the same time, the microwave-assisted synthesis method can obtain better catalyst particle size dispersion and activity component dispersion. The technical scheme of the application solves the problems of high catalyst cost and large reactor load in the hydrogen production process, and meets the concept of green chemistry.

[0077] The sixth aspect of the application provides the use of the rare earth doped multi-cationic pillared modified bimetallic hydrogenation catalyst in organic liquid hydrogen storage technology, specifically in the hydrogen storage of aromatic hydrocarbon organic liquid; preferably, in the hydrogen storage of dibenzyltoluene, toluene, naphthalene or N-ethylcarbazole. The catalyst has high activity and high selectivity, and can perform efficient hydrogenation at low temperature and pressure.

[0078] The seventh aspect of the application provides a method for storing organic liquid, wherein dibenzyltoluene and hydrogen are subjected to hydrogenation reaction under the catalysis of the rare earth doped multi-cationic pillared modified bimetallic hydrogenation catalyst, and efficient hydrogenation is performed at low temperature and pressure.

[0079] As described above, the application has at least one of the following beneficial effects:

[0080] 1) The double-doped pillared support of the application introduces rare earth elements, and the introduction of the rare earth element with rich defect sites effectively reduces the agglomeration of the transition metal elements in the reduction process, reduces the particle size of the transition metal elements, and improves the dispersion of the transition metal elements.

[0081] 2) The double-doped pillared support of the application has good metal element dispersion and stability, which helps to improve the overall performance of the catalyst. In the synthesis of the support, commercially available hydrotalcite is selected as the raw material, and organic / inorganic metal complex ions are selected as the precursor. The double-doped pillared support is prepared by a sol-gel-metal organic / inorganic ion exchange method, which greatly simplifies the preparation process of the layered composite metal oxide support, reduces the use of hazardous nitrate in the preparation process, and ensures the safety of the preparation process.

[0082] 3) The rare earth modified pillared bimetallic hydrogenation catalyst prepared by the application effectively prevents the agglomeration of transition metal elements, reduces the particle size of transition metal elements, improves the dispersion of transition metal elements, greatly strengthens the synergistic effect between noble metal-transition metal, improves the atomic utilization rate, and can reduce the amount of noble metal under the premise of ensuring the catalytic activity, effectively reducing the cost of the catalyst.

[0083] 4) The rare earth doped multi-anion pillared modified bimetallic hydrogenation catalyst has atomic level dispersion of noble metal active components, and has a lower transition metal particle size, which can reflect the synergistic effect of hydrogenation sites.

[0084] 5) The microwave-assisted synthesis method used in the active component loading step of the catalyst avoids the shortcomings of traditional co-precipitation-aging process and dynamic impregnation catalyst preparation process, such as gradient distribution of temperature distribution, uneven heating, long reaction time, etc. The microwave-assisted synthesis method greatly shortens the preparation time of the catalyst and reduces energy consumption. At the same time, the microwave-assisted synthesis method can obtain better catalyst particle size dispersion and active component dispersion.

[0085] 6) The rare earth doped multi-anion pillared modified bimetallic hydrogenation catalyst can be applied to the hydrogenation reaction process of organic hydrogen storage carriers, and has high activity and high selectivity, and can perform efficient hydrogenation at low temperature and pressure.

[0086] 7) The synthesis process used in the synthesis technology route of the support and catalyst is simple, safe and controllable, and is convenient for large-scale production. BRIEF DESCRIPTION OF DRAWINGS

[0087] Figure 1 The scanning electron microscope image of the catalyst described in Example 2.

[0088] Figure 2 The EDS mapping image of the catalyst described in Example 2.

[0089] Figure 3 The high-resolution transmission electron microscope characterization result image of the catalyst described in Example 2.

[0090] Figure 4 The catalyst of Example 2 was subjected to catalytic hydrogenation, and the relationship between the yield of the fully hydrogenated product H18-DBT and the time under different hydrogen pressures was plotted.

[0091] Figure 5 The catalysts of the related examples or comparative examples were all subjected to evaluation according to the catalyst evaluation method described in Example 3, and the relationship between the yield of the fully hydrogenated product and the time was plotted.

[0092] Figure 6 The TPR characterization graph of the related examples.

[0093] Figure 7 The XRD characterization graph of the related examples. DETAILED DESCRIPTION

[0094] The application will be further described in conjunction with the examples. It should be understood that these examples are only used to illustrate the application, and are not intended to limit the scope of the application. The experimental methods not specified in the following examples and the reagents not specified in the formulations are all prepared or configured according to the conventional conditions or the conditions recommended by the manufacturers.

[0095] Example 1 (pillar-supported carrier-1)

[0096] Step (1): 2.5054 g of lanthanum nitrate hexahydrate and 9.9094 g of nickel nitrate hexahydrate were weighed and dissolved in 200 ml of deionized water to prepare a metal salt solution, 5.6526 g of trimesic acid and 2.3521 g of phosphoric acid were slowly added and stirred vigorously, and after the solution was completely clear, a metal anion complex solution was prepared;

[0097] Step (2): 5 g of commercially available MgAl hydrotalcite after flotation was added to 300 mL of deionized water, uniformly mixed, and then transferred to a 1000 mL four-necked flask, the pH was adjusted to 6.5, and the mixture was refluxed and stirred at 70°C for 24 h to prepare a Mg-Al hydrotalcite colloid; the metal anion complex solution prepared in step (1) was slowly added dropwise into the four-necked flask, the pH in the flask was controlled at 5.5, and the temperature was controlled at 70°C, the total dropwise time was 5 h, and the mixture was stirred vigorously to form a hydrotalcite-bimetallic ligand sol;

[0098] Step (3): 3.3362 g of sodium hydroxide and 6.6936 g of sodium carbonate were dissolved in 50 ml of deionized water to prepare a precipitant solution; the precipitant solution was slowly added dropwise into the hydrotalcite-bimetallic ligand sol at a flow rate of 0.5 mL / min, and the mixture was stirred vigorously during the dropwise addition to perform ion exchange and pillar-support solidification. After the dropwise addition was completed, the mixture was aged statically at 70°C for 12 h, and then transferred to an oven for drying at 80°C until completely dehydrated to obtain a pillar-supported carrier precursor;

[0099] Step (4): After drying, the obtained pillared support precursor was mixed with 1.7295 g of cetyltrimethylammonium bromide and 500 mL of water, and then was put into a colloid mill for grinding at a frequency of 80 Hz and room temperature for 4 h. Then, the sample was transferred into a vacuum drying oven for complete drying at room temperature. Thus, a double-doped pillared support was obtained.

[0100] Example 2 (catalyst-1)

[0101] Step (1): The double-doped pillared support prepared in Example 1 was provided.

[0102] Step (2): 0.0340 g of ruthenium trichloride and 1.3590 g of nickel nitrate hexahydrate were weighed, dissolved in 50 mL of deionized water, and adjusted to a pH of 11.0±0.2 with monoethanolamine. After mixing, an active component precursor was prepared.

[0103] Step (3): The active component precursor was transferred into a colloid mill together with 10 g of the hydrotalcite support and 200 mL of deionized water, and was ground at a frequency of 80 Hz and room temperature for 4 h. Then, the slurry was placed into a microwave drying oven for drying at a frequency of 800 W and 2.24 GHz until the sample was completely dried. The sample was transferred into a muffle furnace, heated to 550 degrees Celsius, and calcined for 6 h. After cooling, the sample was taken out of the furnace, placed into a tube furnace, and was heated to 500 degrees Celsius at a rate of 5 degrees Celsius per minute in a hydrogen and argon mixed gas (10% hydrogen and 90% argon) with a flow rate of 100 mL / min. After maintaining for 5 h, the sample was ground to obtain a rare earth doped multi-element anion pillared modified bimetallic hydrogenation catalyst.

[0104] The scanning electron microscope, EDS mapping and high-resolution transmission electron microscope characterization results of the obtained catalyst are shown in Figure 1 、 Figure 2 and Figure 3 . As can be seen from Figures 1-3 , the rare earth doped bimetallic hydrogenation catalyst prepared by the method has good dispersion of each element, and Ru is highly distributed on the surface of the support in a state close to a single atom (particle size of 0.200±0.0002 nm).

[0105] Example 3 (dibenzyltoluene hydrogenation-1)

[0106] The catalyst obtained in Example 2 was applied to the hydrogenation reaction of dibenzyl toluene, 0.5 g of the catalyst and 5 g of dibenzyl toluene were weighed into a high-pressure reactor, and hydrogen was replaced for 3 times. The hydrogen pressure was adjusted to 5 MPa, the reaction temperature was raised to 170°C, and the reaction was carried out for 1 h. After the reaction was completed, the composition of the residual liquid phase and the generated gas was analyzed by GC-MS and gas chromatography, respectively. The analysis results are as follows: the conversion rate of the hydrogenation product dibenzyl toluene (DBT) is 100%, and the yield of the complete hydrogenation product H18-DBT is 100%. Only the hydrogen pressure during the hydrogenation reaction was changed, and the rest of the conditions were maintained unchanged. The relationship between the yield of the complete hydrogenation product H18-DBT and the time under different hydrogen pressures is shown in Table 1. It can be seen from Table 1 that when the hydrogen pressure is 4 MPa, the reaction time is 1 h, and the yield of H18-DBT is more than 95%; when the hydrogen pressure is ≥5 MPa and the reaction time is ≤1 h, the hydrogen storage carrier can be completely hydrogenated, indicating that the catalyst can realize the efficient hydrogenation process of the organic hydrogen storage carrier under low reaction load (temperature, pressure). Figure 4 Figure 4 It can be seen from Table 1 that when the hydrogen pressure is 4 MPa, the reaction time is 1 h, and the yield of H18-DBT is more than 95%; when the hydrogen pressure is ≥5 MPa and the reaction time is ≤1 h, the hydrogen storage carrier can be completely hydrogenated, indicating that the catalyst can realize the efficient hydrogenation process of the organic hydrogen storage carrier under low reaction load (temperature, pressure).

[0107] Example 4 (pillar-supported carrier-2)

[0108] Step (1): 1.2026 g of cerium nitrate hexahydrate and 9.9094 g of nickel nitrate hexahydrate were dissolved in 200 ml of deionized water to prepare a metal salt solution, 5.6526 g of trimesic acid and 2.3521 g of phosphoric acid were slowly added and stirred vigorously, and after the solution was completely clear, a metal anion complex solution was prepared;

[0109] Step (2): 5 g of commercially available MgAl hydrotalcite after flotation was added to 300 mL of deionized water, uniformly mixed, and then transferred to a 1000 mL four-necked flask. The pH was adjusted to 6.5, and the mixture was refluxed and stirred at 70°C for 24 h to obtain Mg-Al hydrotalcite colloid. The prepared metal anion complex solution was slowly added to the four-necked flask, the pH in the flask was controlled at 5.5, and the temperature was controlled at 70°C. The total dropping time was 5 h, and the mixture was stirred vigorously to form a hydrotalcite-bimetallic ligand sol.

[0110] Step (3): 3.3362 g of sodium hydroxide and 6.6936 g of sodium carbonate were dissolved in 50 ml of deionized water to prepare a precipitant solution. The precipitant solution was slowly added to the hydrotalcite-bimetallic ligand sol at a flow rate of 0.5 mL / min, and the mixture was stirred vigorously during the addition to carry out ion exchange and pillar support solidification. After the addition was completed, the mixture was aged at 70°C for 12 h, and then transferred to an oven for drying at 80°C until completely dehydrated to obtain a pillar-supported carrier precursor.

[0111] ​Step (4): After drying, the obtained pillared support precursor was mixed with 1.7295 g of cetyltrimethylammonium bromide and 500 mL of water, and then was put into a colloid mill for grinding at a frequency of 80 Hz and room temperature for 4 h. Then, the sample was transferred into a vacuum drying oven for complete drying at room temperature. Thus, a double-doped pillared support was obtained.

[0112] Example 5 (catalyst-2)

[0113] Step (1): The double-doped pillared support prepared in Example 4 was provided.

[0114] Step (2): 0.0340 g of ruthenium trichloride and 1.3590 g of nickel nitrate hexahydrate were weighed, dissolved in 50 mL of deionized water, and adjusted to a pH of 11.0 ± 0.2 with monoethanolamine. After mixing uniformly under rapid stirring, an active component precursor was prepared.

[0115] Step (3): The active component precursor was transferred into a colloid mill together with 10 g of the hydrotalcite support and 200 mL of deionized water, and was ground at a frequency of 80 Hz and room temperature for 4 h. Then, the slurry was placed into a microwave drying oven for drying at a frequency of 800 W and 2.24 GHz until the sample was completely dried. The sample was transferred into a muffle furnace, heated to 550 degrees Celsius, and calcined for 6 h. After cooling, the sample was taken out, placed into a tube furnace, and purged with a hydrogen-argon mixed gas (10% hydrogen + 90% argon) at a flow rate of 100 mL / min. The tube furnace was heated to 500 degrees Celsius at a rate of 5 degrees Celsius / min, and maintained for 5 h. After cooling, the sample was ground to obtain a rare earth-doped multi-anion pillared modified double-metal hydrogenation catalyst.

[0116] Comparative Example 1-1 (without rare earth elements in the pillared support)

[0117] Step (1): 9.9094 g of nickel nitrate hexahydrate was weighed, dissolved in 200 mL of deionized water to prepare a metal salt solution, and 5.6526 g of trimesic acid and 2.3521 g of phosphoric acid were slowly added and stirred vigorously. After the solution was completely clear, a metal anion complex solution was prepared.

[0118] Step (2): 5 g of commercially available Mg-Al hydrotalcite after flotation was added to 300 mL of deionized water, uniformly mixed, and then transferred into a 1000 mL four-necked flask. The pH was adjusted to 6.5, and the Mg-Al hydrotalcite colloid was refluxed and stirred at 70 degrees Celsius for 24 h. The prepared metal anion complex solution was slowly dropped into the four-necked flask, the pH in the flask was controlled at 5.5, the temperature was controlled at 70 degrees Celsius, and the total dropping time was 5 h. The hydrotalcite-double metal ligand sol was formed under vigorous stirring.

[0119] Step (3): A precipitant solution was prepared by dissolving 3.3362 g of sodium hydroxide and 6.6936 g of sodium carbonate in 50 mL of deionized water. The hydrotalcite-bimetallic ligand sol was slowly added to the precipitant solution, and the flow rate was controlled at 0.5 mL / min. The ion exchange and pillaring process was carried out with vigorous stirring. After the addition was completed, the sample was statically aged at 70°C for 12 h, and then transferred to an oven for drying at 80°C until completely dehydrated to obtain the pillared support precursor.

[0120] Step (4): After drying, the obtained precursor was mixed with 1.7295 g of cetyltrimethylammonium bromide and 500 mL of water, and then transferred to a colloid mill for grinding at a frequency of 80 Hz and room temperature for 4 h. The sample was then completely dried in a vacuum drying oven at room temperature to obtain the pillared support.

[0121] Comparative Example 1-2 (catalyst)

[0122] Step (1): The pillared support prepared in Comparative Example 1-1 was provided.

[0123] Step (2): 0.0340 g of ruthenium trichloride and 1.3590 g of nickel nitrate hexahydrate were dissolved in 50 mL of deionized water, and the pH was adjusted to 11.0 ± 0.2 with monoethanolamine. After rapid stirring and mixing, an active component precursor was prepared.

[0124] Step (3): The active component precursor was transferred to a colloid mill together with 10 g of hydrotalcite support and 200 mL of deionized water, and the grinding was carried out at a frequency of 80 Hz and room temperature for 4 h. Then the slurry was placed in a microwave drying oven and dried at a frequency of 800 W and 2.24 GHz until the sample was completely dry. The sample was transferred to a muffle furnace and heated to 550°C for 6 h. After cooling, the sample was taken out and placed in a tube furnace, and a mixture of hydrogen and argon gas (10% hydrogen and 90% argon) was introduced at a flow rate of 100 mL / min. The tube furnace was heated to 500°C at a rate of 5°C / min and maintained for 5 h. After cooling, the sample was ground to obtain a multi-anion pillared modified bimetallic hydrogenation catalyst.

[0125] Comparative Example 2-1 (without rare earth elements in the pillared support)

[0126] Step (1): 9.9094 g of nickel nitrate hexahydrate was dissolved in 200 mL of deionized water to prepare a metal salt solution. 5.6526 g of trimesic acid and 2.3521 g of phosphoric acid were slowly added and stirred vigorously. After the solution was completely clear, a metal anion complex solution was prepared.

[0127] Step (2): 5 g of the commercial MgAl hydrotalcite after flotation was weighed, added to 300 mL of deionized water, uniformly mixed, and then transferred to a 1000 mL four-necked flask. The pH was adjusted to 6.5, and the mixture was stirred at 70°C for 24 h to obtain Mg-Al hydrotalcite colloid. The prepared metal anion complex solution was slowly added dropwise into the four-necked flask, the pH in the flask was controlled at 5.5, the temperature was controlled at 70°C, and the total dropping time was 5 h. The mixture was stirred vigorously to form a hydrotalcite-bimetallic ligand sol.

[0128] Step (3): 3.3362 g of sodium hydroxide and 6.6936 g of sodium carbonate were dissolved in 50 mL of deionized water to prepare a precipitant solution. The precipitant solution was slowly added dropwise into the hydrotalcite-bimetallic ligand sol. The flow rate was controlled at 0.5 mL / min, and the mixture was stirred vigorously during the dropping process to perform ion exchange and pillar support solidification. After the dropping was completed, the mixture was aged at 70°C for 12 h. After the aging was completed, the mixture was transferred to an oven and dried at 80°C until completely dehydrated to obtain a pillar support precursor.

[0129] Step (4): After the drying was completed, the obtained precursor was mixed with 1.7295 g of cetyltrimethylammonium bromide and 500 mL of water, and then was put into a colloid mill. The mixture was ground at a frequency of 80 Hz and room temperature for 4 h, and then was transferred to a vacuum drying box and completely dried at room temperature to obtain a double-doped pillar support.

[0130] Comparative Example 2-2 (catalyst)

[0131] Step (1): A double-doped pillar support prepared in Comparative Example 2-1 was provided.

[0132] Step (2): 0.0121 g of ruthenium trichloride and 1.3590 g of nickel nitrate hexahydrate were dissolved in 50 mL of deionized water, and the pH was adjusted to 11.0±0.2 with monoethanolamine. The mixture was uniformly mixed by rapid stirring to prepare an active component precursor.

[0133] Step (3): The active component precursor was transferred to a colloid mill together with 10 g of the hydrotalcite support and 200 mL of deionized water. The mixture was ground at a frequency of 80 Hz and room temperature for 4 h. Then, the slurry was placed in a microwave drying box and dried at a frequency of 2.24 GHz and 800 W until the sample was completely dry. The sample was transferred to a muffle furnace, heated to 550°C, and calcined for 6 h. After cooling, the sample was taken out and placed in a tube furnace. Hydrogen and argon mixed gas (10% hydrogen and 90% argon) was introduced at a flow rate of 100 mL / min. The tube furnace was heated to 500°C at a rate of 5°C / min and maintained for 5 h. After cooling, the mixture was ground to obtain a multi-anion pillar support modified bimetallic hydrogenation catalyst.

[0134] The catalysts obtained in Example 2, Example 5, Comparative Example 1-2 and Comparative Example 2-2 were evaluated according to the catalyst evaluation method described in Example 3, and the relationship between the yield of the complete hydrogenation product and time is shown in Table 1. Figure 5 The results show that: the rare earth doped bimetallic hydrogenation catalysts (Example 2, Example 5) have higher reaction activity and reaction rate.

[0135] Comparative Example 3-1 (without rare earth elements in the pillared support)

[0136] Step (1): 9.9094 g of nickel nitrate hexahydrate was weighed and dissolved in 200 ml of deionized water to prepare a metal salt solution, 5.6526 g of trimesic acid, 2.3521 g of phosphoric acid were slowly added and stirred vigorously, and after the solution was completely clear, a metal anion complex solution was prepared;

[0137] Step (2): 5 g of commercially available MgAl hydrotalcite after flotation was weighed and added to 300 mL of deionized water, and after uniform mixing, it was transferred to a 1000 mL four-necked flask, the pH was adjusted to 6.5, and it was refluxed and stirred at 70°C for 24 h to obtain Mg-Al hydrotalcite colloid. The prepared metal anion complex solution was slowly added dropwise into the four-necked flask, the pH in the bottle was controlled at 5.5, the temperature was 70°C, and the total dropwise time was 5 h, and the solution was stirred vigorously to form a hydrotalcite-bimetallic ligand sol.

[0138] Step (3): 3.3362 g of sodium hydroxide and 6.6936 g of sodium carbonate were dissolved in 50 ml of deionized water to prepare a precipitant solution. The precipitant solution was slowly added dropwise into the hydrotalcite-bimetallic ligand sol, and the flow rate was controlled at 0.5 mL / min, and the ion exchange and pillared support solidification process were carried out during the dropwise addition. After the dropwise addition was completed, it was aged at 70°C for 12 h, and after the aging was completed, it was transferred to an oven and dried at 80°C until completely dehydrated to obtain a pillared support precursor.

[0139] Step (4): After drying, the obtained precursor was mixed with 1.7295 g of cetyltrimethylammonium bromide and 500 mL of water, and then put into a colloid mill for grinding at a frequency of 80 Hz and room temperature for 4 h, and then transferred to a vacuum drying oven for complete drying at room temperature to obtain a double-doped pillared support.

[0140] Comparative Example 3-2 (without loading noble metal)

[0141] Step (1): The pillared support prepared in Comparative Example 3-1 was provided;

[0142] Step (2): 1.3590 g of nickel nitrate hexahydrate was weighed and dissolved in 50 mL of deionized water, and the pH was adjusted to 11.0±0.2 with monoethanolamine, and after rapid stirring and mixing, an active component precursor was obtained;

[0143] Step (3): The active component precursor and 10 g of hydrotalcite support, 200 mL of deionized water were transferred to a colloid mill and ground at a frequency of 80 Hz and room temperature for 4 h. Then the slurry was placed in a microwave drying oven and dried at a frequency of 800 W and 2.24 GHz until the sample was completely dry. The sample was transferred to a muffle furnace and heated to 550 degrees Celsius and calcined for 6 h. After cooling, the sample was taken out and placed in a tube furnace. Hydrogen and argon mixed gas (10% hydrogen and 90% argon) was introduced at a flow rate of 100 ml / min. The tube furnace was heated to 500 degrees Celsius at a rate of 5 degrees Celsius per minute and maintained for 5 h. After cooling, the catalyst was ground.

[0144] According to the TPR characterization of Comparative Example 1-2, Comparative Example 2-2 and Comparative Example 3-2 without loading noble metal, Figure 6 It can be known from the TPR characterization of Comparative Example 1-2, Comparative Example 2-2 and Comparative Example 3-2 without loading noble metal that the active sites of the bimetallic catalyst can exhibit a synergistic effect, and the hydrogen overflow effect on the surface of the bimetallic catalyst can reduce NiO at a lower temperature, thereby improving the low-temperature activity of the hydrogenation catalyst.

[0145] Example 6 (Pillared Support-3)

[0146] Step (1): 4.3458 g of cerium nitrate hexahydrate and 9.9094 g of nickel nitrate hexahydrate were dissolved in 200 ml of deionized water to prepare a metal salt solution. 5.6526 g of trimesic acid and 2.3521 g of phosphoric acid were slowly added and stirred vigorously. After the solution was completely clear, a metal anion complex solution was prepared.

[0147] Step (2): 5 g of commercially available MgAl hydrotalcite after flotation was added to 300 mL of deionized water and uniformly mixed. Then it was transferred to a 1000 mL four-necked flask, the pH was adjusted to 6.5, and it was refluxed and stirred at 70 degrees Celsius for 24 h to obtain a Mg-Al hydrotalcite colloid. The prepared metal anion complex solution was slowly added to the four-necked flask, the pH in the bottle was controlled at 5.5, the temperature was 70 degrees Celsius, and the total dropping time was 5 h. Vigorous stirring was performed to form a hydrotalcite-bimetallic ligand sol.

[0148] Step (3): 3.3362 g of sodium hydroxide and 6.6936 g of sodium carbonate were dissolved in 50 ml of deionized water to prepare a precipitant solution. The precipitant solution was slowly added to the hydrotalcite-bimetallic ligand sol at a flow rate of 0.5 mL / min, and vigorous stirring was performed during the dropping process to perform ion exchange and column support solidification. After the dropping was completed, it was statically aged at 70 degrees Celsius for 12 h. After aging, it was transferred to an oven and dried at 80 degrees Celsius until completely dehydrated to obtain a pillared support precursor.

[0149] Step (4): After drying, the obtained precursor was mixed with 1.7295 g of cetyltrimethylammonium bromide and 500 mL of water, and then was put into a colloid mill for grinding at a frequency of 80 Hz and room temperature for 4 h. Then, the slurry was transferred into a vacuum drying oven for complete drying at room temperature to obtain the double-doped pillared support.

[0150] Example 7 (catalyst-3)

[0151] Step (1): The double-doped pillared support prepared in Example 6 was provided.

[0152] Step (2): 0.0340 g of ruthenium trichloride and 1.3590 g of nickel nitrate hexahydrate were dissolved in 50 mL of deionized water, and the pH was adjusted to 11.0±0.2 with monoethanolamine. After mixing uniformly under rapid stirring, an active component precursor was prepared.

[0153] Step (3): The active component precursor was transferred into a colloid mill together with 10 g of hydrotalcite support and 200 mL of deionized water for grinding at a frequency of 80 Hz and room temperature for 4 h. Then, the slurry was placed into a microwave drying oven for drying at a frequency of 800 W and 2.24 GHz until the sample was completely dried. The sample was transferred into a muffle furnace, and the temperature was increased to 550 °C at a rate of 5 °C / min. The sample was calcined for 6 h. After cooling, the sample was ground and placed into a tube furnace. Hydrogen and argon mixed gas (10% hydrogen and 90% argon) was introduced at a flow rate of 100 mL / min. The temperature of the tube furnace was increased to 500 °C at a rate of 5 °C / min, and the temperature was maintained for 5 h. After cooling, a rare earth doped multi-anion pillared modified double-metal hydrogenation catalyst was obtained.

[0154] The catalyst was applied to the hydrogenation reaction of toluene. 0.5 g of the catalyst and 5 g of toluene were transferred into a high-pressure reaction kettle. Hydrogen was used for replacement for 3 times. The hydrogen pressure was adjusted to 5 MPa. The reaction temperature was increased to 180 °C. The reaction was carried out for 1 h. After the reaction was completed, the composition of the residual liquid phase and the generated gas was analyzed by GC-MS and gas chromatography, respectively. The analysis results were as follows: the conversion rate of toluene was 100%, and the yield of the complete hydrogenation product methylcyclohexane was 99.3%.

[0155] Example 8 (pillared support-4)

[0156] Step (1): 1.2527 g of lanthanum nitrate hexahydrate and 9.9094 g of nickel nitrate hexahydrate were dissolved in 200 mL of deionized water to prepare a metal salt solution. 5.6526 g of trimesic acid and 2.3521 g of phosphoric acid were slowly added and stirred vigorously. After the solution was completely clear, a metal anion complex solution was prepared.

[0157] Step (2): Take 5g of the commercial MgAl hydrotalcite after flotation, add 300mL of deionized water, mix uniformly, then transfer to a 1000mL four-necked flask, adjust the pH to 6.5, and reflux and stir at 70°C for 24h to obtain Mg-Al hydrotalcite colloid. Slowly drop the prepared metal anion complex solution into the four-necked flask, control the pH in the flask to be 5.5 and the temperature to be 70°C, and the total dropping time is 5h, and the stirring is violent to form a hydrotalcite-bimetallic ligand sol;

[0158] Step (3): Dissolve 3.3362g of sodium hydroxide and 6.6936g of sodium carbonate in 50ml of deionized water to prepare a precipitant solution; slowly add the precipitant solution to the hydrotalcite-bimetallic ligand sol, and the flow rate is controlled at 0.5mL / min. Stir vigorously during the dropping process to carry out ion exchange and column support solidification. After the dropping is completed, it is aged at 70°C for 12h, and then transferred to an oven for drying at 80°C until completely dehydrated to obtain a column support precursor;

[0159] Step (4): After drying, the obtained precursor is mixed with 1.7295g of cetyltrimethylammonium bromide and 500mL of water, and then put into a colloid mill for grinding at a frequency of 80Hz and room temperature for 4h. Then it is transferred to a vacuum drying box for complete drying at room temperature to obtain a double-doped column support.

[0160] Example 9 (catalyst-4)

[0161] Step (1): Provide the double-doped column support prepared in Example 8;

[0162] Step (2): Take 0.0340g of ruthenium trichloride and 1.3590g of nickel nitrate hexahydrate, dissolve them in 50mL of deionized water, adjust the pH to 11.0±0.2 with monoethanolamine, mix uniformly under rapid stirring to prepare an active component precursor;

[0163] Step (3): Transfer the active component precursor and 10g of hydrotalcite support, 200mL of deionized water to a colloid mill, and grind at a frequency of 80Hz and room temperature for 4h. Then put the slurry into a microwave drying box and dry at a frequency of 800W and 2.24GHz until the sample is completely dry. Transfer the sample to a muffle furnace, heat to 550°C and calcine for 6h. After cooling, take out the sample and put it into a tube furnace, pass in a hydrogen-argon mixed gas (10% hydrogen+90% argon) at a flow rate of 100ml / min, and heat the tube furnace to 500°C at a rate of 5°C / min, keep for 5h, and then grind to obtain a rare earth-doped multi-anion column-modified bimetallic hydrogenation catalyst.

[0164] The catalysts prepared in Example 9, Example 5, Comparative Example 1-2 were evaluated for activity according to the evaluation method described in Example 3, in combination with the XRD results of Example 9, Example 5, Comparative Example 1-2 (see Figure 7 ), and the relationship between the particle size of the transition metal Ni of the catalyst and the yield of the complete hydrogenation product H18-DBT was calculated by half-peak width and is shown in Table 1.

[0165] Table 1 Particle size and reaction activity of rare earth modified series of catalysts

[0166] Catalyst Reduction temperature (°C) Ru (wt%) Ni particle size (nm) H18-DBT yield (1 h) Example 9 550 0.05 21.05 95.4％ Example 5 550 0.05 12.14 99.8％ Comparative Examples 1-2 550 0.05 95.28 92.9％

[0167] As can be seen from Table 1, the preparation method of the rare earth in-situ co-precipitation doped of the present application can effectively reduce the particle size of Ni in the bimetallic hydrogenation catalyst, and the hydrogenation activity of the catalyst is inversely proportional to the particle size of Ni, and smaller particle size of Ni can produce a better synergistic effect with the noble metal Ru.

[0168] Comparative Example 4

[0169] 2.5054 g of lanthanum nitrate hexahydrate, 9.9094 g of nickel nitrate hexahydrate, 77.3252 g of magnesium nitrate hexahydrate, and 40.6282 g of aluminum nitrate nonahydrate were weighed out and dissolved in 200 ml of deionized water to prepare a metal salt solution, and then 33.3624 g of sodium hydroxide and 66.9364 g of sodium carbonate were dissolved in 150 ml of deionized water to prepare a precipitate solution. The prepared metal salt solution and the precipitate solution were dropped into a four-necked flask at a rate of 4:3 in terms of volume flow rate, and the pH in the flask was controlled at 7.5 and the temperature was controlled at 70°C. After co-precipitation was completed, dynamic aging was continued at 70°C for 2 h. After aging was completed, the sample was washed by suction filtration until it was neutral, and then was transferred to an oven for drying at 80°C for 12 h, and then was ground to obtain a catalyst carrier.

[0170] 0.0340 g of ruthenium trichloride was weighed out and dissolved in 50 ml of deionized water, and then 10 g of the carrier was stirred at room temperature for 4 h, and then the sample was transferred to a vacuum drying oven for drying for 2 h. After the sample was completely dried, the sample was transferred to a muffle furnace and was heated to 550°C for calcination for 6 h. After cooling, the sample was taken out and was placed in a tube furnace, and a hydrogen-argon mixed gas (10% hydrogen + 90% argon) was introduced at a flow rate of 100 ml / min. The tube furnace was heated to 500°C at a rate of 5°C / min and was maintained for 5 h, and then was cooled and ground to obtain an organic hydrogen storage material hydrogenation bimetallic catalyst.

[0171] Comparative Example 4 is a traditional co-precipitation-impregnation preparation process of the catalyst, and other conditions are the same as those of Example 1 and Example 2, except that the preparation method is different. The catalysts obtained in Example 2 and Comparative Example 4 were evaluated for activity according to the evaluation method described in Example 3, and the evaluation results are shown in Table 2.

[0172] Table 2 Effect of catalyst preparation method on reaction

[0173]

[0174]

[0175] From Table 2, it can be seen that the catalyst obtained in Example 21 has higher hydrogenation activity, which indicates that the catalyst prepared by the method of metal anion pillared-microwave assisted complex impregnation forms more catalyst active centers compared with the catalyst prepared by the traditional co-precipitation-impregnation synthesis method. Therefore, it can be seen that the method of binary metal anion pillared modification-microwave assisted complex impregnation has great application advantages.

[0176] Example 10 (pillared support-5)

[0177] Step (1): 1.2527 g of lanthanum nitrate nonahydrate and 8.8086 g of iron nitrate nonahydrate were dissolved in 200 ml of deionized water to prepare a metal salt solution, 5.6526 g of trimesic acid and 2.3521 g of phosphoric acid were slowly added and stirred vigorously, and after the solution was completely clear, a metal anion complex solution was prepared;

[0178] Step (2): 5 g of commercially available MgAl hydrotalcite after flotation was added to 300 mL of deionized water, uniformly mixed, and then transferred to a 1000 mL four-necked flask, the pH was adjusted to 6.5, and the mixture was stirred at 70°C for 24 h to prepare a Mg-Al hydrotalcite colloid; the metal anion complex solution prepared in step (1) was slowly added dropwise into the four-necked flask, the pH in the flask was controlled at 5.5, the temperature was 70°C, and the total dropwise time was 5 h, and the mixture was stirred vigorously to form a hydrotalcite-bimetallic ligand sol;

[0179] Step (3): 3.3362 g of sodium hydroxide and 6.6936 g of sodium carbonate were dissolved in 50 ml of deionized water to prepare a precipitant solution; the precipitant solution was slowly added dropwise into the hydrotalcite-bimetallic ligand sol, the flow rate was controlled at 0.5 mL / min, and the mixture was stirred vigorously during the dropwise addition to perform ion exchange and pillared body solidification. After the dropwise addition was completed, the mixture was aged at 70°C for 12 h, and then transferred to an oven and dried at 80°C until completely dehydrated to obtain a pillared support precursor;

[0180] Step (4): After drying, the obtained pillared support precursor was mixed with 1.7295 g of cetyltrimethylammonium bromide and 500 mL of water, and then put into a colloid mill for grinding at a frequency of 80 Hz and room temperature for 4 h, and then transferred to a vacuum drying oven and completely dried at room temperature to obtain a double-doped pillared support.

[0181] Example 11 (catalyst-5)

[0182] Step (1): providing the double-doped pillared support prepared in Example 10;

[0183] Step (2): taking 0.0468 g of chloroplatinic acid, dissolving it in 50 mL of deionized water, adjusting the pH to 11.0 ± 0.2 with monoethanolamine, and preparing an active component precursor after mixing uniformly under rapid stirring;

[0184] Step (3): transferring the active component precursor and 10 g of the hydrotalcite support, 200 mL of deionized water to a colloid mill, and grinding at a frequency of 80 Hz and room temperature for 4 h, then placing the slurry in a microwave drying oven and drying at a frequency of 800 W and 2.24 GHz until the sample is completely dry. The sample is transferred to a muffle furnace and heated to 550 degrees Celsius and calcined for 6 h. After cooling, the sample is placed in a tube furnace, and a hydrogen argon mixed gas (10% hydrogen + 90% argon) is introduced at a flow rate of 100 ml / min. The tube furnace is heated to 500 degrees Celsius at a rate of 5 degrees Celsius per minute and maintained for 5 h. After cooling, the rare earth doped multi-anion pillared modified double metal hydrogenation catalyst is obtained by grinding.

[0185] The catalyst is applied to the hydrogenation reaction of naphthalene. 0.5 g of the catalyst and 5 g of naphthalene are transferred to a high-pressure reaction kettle. Hydrogen is used to replace the reaction kettle three times. The hydrogen pressure is adjusted to 6 MPa, the reaction temperature is raised to 180 degrees Celsius, and the reaction is carried out for 1 h. After the reaction is completed, the composition of the residual liquid phase and the generated gas is analyzed qualitatively and quantitatively by GC-MS and gas chromatography. The analysis results are as follows: the conversion rate of the reactant naphthalene after hydrogenation is 100%, and the yield of the complete hydrogenation product decalin is 98.6%.

[0186] Example 12 (pillared support-6)

[0187] Step (1): taking 4.3458 g of cerium nitrate hexahydrate and 8.2364 g of cobalt nitrate hexahydrate, dissolving them in 200 mL of deionized water to prepare a metal salt solution, slowly adding 5.6526 g of trimesic acid and 2.3521 g of phosphoric acid, and stirring vigorously. After the solution is completely clear, a metal anion complex solution is prepared;

[0188] Step (2): taking 5 g of the floated commercial MgAl hydrotalcite, adding 300 mL of deionized water, mixing uniformly, and then transferring it to a 1000 mL four-necked flask. The pH is adjusted to 6.5, and the Mg-Al hydrotalcite colloid is refluxed and stirred at 70 degrees Celsius for 24 h. The prepared metal anion complex solution is slowly added to the four-necked flask, the pH in the bottle is controlled at 5.5, the temperature is 70 degrees Celsius, and the total drop time is 5 h. Vigorous stirring is performed to form a hydrotalcite-double metal ligand sol;

[0189] Step (3): A precipitant solution was prepared by dissolving 3.3362 g of sodium hydroxide and 6.6936 g of sodium carbonate in 50 mL of deionized water. The hydrotalcite-bimetallic ligand sol was slowly added with the precipitant solution at a flow rate of 0.5 mL / min, and the ion exchange and pillar support solidification process was carried out with vigorous stirring. After the addition was completed, the sample was statically aged at 70°C for 12 h, and then transferred to an oven for drying at 80°C until completely dehydrated to obtain the pillar support precursor.

[0190] Step (4): After drying, the obtained pillar support precursor was mixed with 1.7295 g of cetyltrimethylammonium bromide and 500 mL of water, and then transferred to a colloid mill for grinding at a frequency of 80 Hz and room temperature for 4 h. After that, the sample was completely dried in a vacuum drying oven at room temperature to obtain the double-doped pillar support.

[0191] Example 13 (Catalyst-6)

[0192] Step (1): The double-doped pillar support prepared in Example 12 was provided.

[0193] Step (2): 0.0252 g of ruthenium trichloride was dissolved in 50 mL of deionized water, and the pH was adjusted to 11.0 ± 0.2 with monoethanolamine. After mixing well under rapid stirring, the active component precursor was prepared.

[0194] Step (3): The active component precursor was transferred to a colloid mill with 10 g of hydrotalcite support and 200 mL of deionized water for grinding at a frequency of 80 Hz and room temperature for 4 h. Then, the slurry was placed in a microwave drying oven for drying at a frequency of 800 W and 2.24 GHz until the sample was completely dry. The sample was transferred to a muffle furnace and heated to 550°C for calcination for 6 h. After cooling, the sample was taken out and placed in a tube furnace, and a hydrogen-argon mixed gas (10% hydrogen + 90% argon) was introduced at a flow rate of 100 mL / min. The tube furnace was heated to 500°C at a rate of 5°C / min and maintained for 5 h. After cooling, the sample was ground to obtain a rare earth-doped multi-anion pillar support modified bimetallic hydrogenation catalyst.

[0195] The catalyst was applied to the hydrogenation reaction of N-ethylcarbazole. 0.5 g of the catalyst and 5 g of N-ethylcarbazole were transferred to a high-pressure reaction kettle. Hydrogen was replaced three times, and the hydrogen pressure was adjusted to 4 MPa. The reaction temperature was raised to 180°C, and the reaction was carried out for 1 h. After the reaction was completed, the composition of the residual liquid phase and the generated gas was analyzed qualitatively and quantitatively by GC-MS and gas chromatography, respectively. The conversion rate of the hydrogenated reaction product N-ethylcarbazole was 92.1%, and the yield of the completely hydrogenated product was 89.2%.

[0196] Example 14 (Pillar Support-7)

[0197] Step (1): Take 10.7075 g of nickel nitrate hexahydrate and dissolve it in 200 ml of deionized water to prepare a metal salt solution, slowly add 5.6526 g of pyromellitic acid, and stir vigorously. After the solution is completely clear, a metal anion complex solution is prepared.

[0198] Step (2): Take 5 g of commercially available MgAl hydrotalcite after flotation, add 300 mL of deionized water, mix uniformly, and then transfer to a 1000 mL four-necked flask. Adjust the pH to 6.5 and reflux at 70°C for 24 h to obtain a Mg-Al hydrotalcite colloid. Slowly drop the prepared metal anion complex solution into the four-necked flask, control the pH in the bottle to be 5.5 and the temperature to be 70°C, and the total dropping time is 5 h. Stir vigorously to form a hydrotalcite-bimetallic ligand sol.

[0199] Step (3): Dissolve 3.3362 g of sodium hydroxide and 6.6936 g of sodium carbonate in 50 ml of deionized water to prepare a precipitant solution. Slowly add the precipitant solution to the hydrotalcite-bimetallic ligand sol at a flow rate of 0.5 mL / min, and stir vigorously during the dropping process to perform ion exchange and pillar support solidification. After the dropping is completed, 70°C static aging is carried out for 12 h. After aging, it is transferred to an oven for drying at 80°C until completely dehydrated to obtain a pillar support precursor.

[0200] Example 15 (Catalyst-7)

[0201] Step (1): Provide the pillar support prepared in Example 14;

[0202] Step (2): Take 0.0682 g of ruthenium trichloride, dissolve it in 50 mL of deionized water, and adjust the pH to 11.0±0.2 with monoethanolamine. After rapid stirring and mixing, an active component precursor is prepared;

[0203] Step (3): Transfer the active component precursor and 10 g of hydrotalcite support, 200 mL of deionized water to a colloid mill, and grind at a frequency of 80 Hz and room temperature for 4 h. Then the slurry is placed in a microwave drying oven and dried at a frequency of 800 W and 2.24 GHz until the sample is completely dry. The sample is transferred to a muffle furnace and heated to 550°C for 6 h. After cooling, the sample is taken out and placed in a tube furnace, and a mixture of hydrogen and argon gas (10% hydrogen and 90% argon) is introduced at a flow rate of 100 ml / min. The tube furnace is heated to 500°C at a rate of 5°C / min and maintained for 5 h. After cooling, the rare earth doped multi-anion pillar modified bimetallic hydrogenation catalyst is obtained by grinding.

[0204] The catalyst was applied to the hydrogenation reaction of naphthalene, 0.5 g of the catalyst and 5 g of naphthalene were weighed into a high-pressure reactor, hydrogen was replaced for 3 times, the hydrogen pressure was adjusted to 4 MPa, the reaction temperature was raised to 180°C, and the reaction was carried out for 1 h. After the reaction was completed, the composition of the residual liquid phase and the generated gas was analyzed by GC-MS and gas chromatography, respectively. The conversion rate of the reaction material naphthalene after hydrogenation was 100%, and the yield of the complete hydrogenation product decahydronaphthalene was 94.3%.

[0205] The above examples are intended to illustrate the embodiments disclosed in the present application and should not be understood to limit the present application. In addition, various modifications listed herein and changes in the method and composition of the application are obvious to those skilled in the art without departing from the scope and spirit of the present application. Although the present application has been specifically described in conjunction with various preferred embodiments thereof, it should be understood that the present application should not be limited to these specific embodiments. In fact, various modifications such as those described above which are obvious to those skilled in the art to obtain the application should be included within the scope of the present application.

Claims

1. A double doped pillared support characterized in that, The application relates to a double-doped pillared support, which comprises Mg-Al hydrotalcite, rare earth elements and transition metal elements; wherein the molar mass ratio of the rare earth elements, the transition metal elements, Al elements and Mg elements is 0.01: (0.1-0.3): (1-2): (2-3.5); and the preparation method comprises the following steps: 1) mixing an aqueous solution containing rare earth metal ions and transition metal ions with a complexing agent to obtain a complex solution; the complexing agent is uniformly substituted benzenetricarboxylic acid and phosphoric acid; or the complexing agent is uniformly substituted benzenetricarboxylic acid and citric acid; or the complexing agent is uniformly substituted benzenetetracarboxylic acid and phosphoric acid; or the complexing agent is uniformly substituted benzenetetracarboxylic acid and citric acid; 2) providing Mg-Al hydrotalcite to prepare Mg-Al hydrotalcite colloid, and ion exchanging the complex solution obtained in the step 1) with the Mg-Al hydrotalcite colloid to obtain a hydrotalcite-bimetallic ligand sol; 3) reacting the hydrotalcite-bimetallic ligand sol obtained in the step 2) with a precipitating agent, and then performing standing aging and drying to obtain a pillared support precursor; and 4) mixing and grinding the pillared support precursor obtained in the step 3) and an aqueous solution of a surfactant to obtain the double-doped pillared support. At least one of the following technical features is included: a1) the rare earth metal ions are selected from at least one of Ce, La, Y and Nd; a2) the rare earth elements are derived from at least one of nitrate or chloride of the rare earth metal ions; 2. The double doped pillared support of claim 1, wherein, a3) the transition metal ions are selected from at least one of Ni, Co, Fe, Mn, Cu and Zn; a4) the transition metal elements are derived from at least one of nitrate or chloride of the transition metal ions. At least one of the following technical features is further included: 1f) in the step 1), the concentration of the transition metal ions in the aqueous solution is 0.5-1.0 mol / L; 1g) in the step 1), the concentration of the rare earth metal ions in the aqueous solution is 0.05-0.1 mol / L; 3. The dual doped pillared support of claim 1, wherein, 1h) in the step 1), the concentration of the complexing agent in the complex solution is 0.5-1.0 mol / L; 1i) in the step 1), after the aqueous solution containing the rare earth metal ions and the transition metal ions is mixed with the complexing agent, the mixture is stirred to obtain a uniform transparent complex solution; 2a) in the step 2), the Mg-Al molar mass ratio of the Mg-Al hydrotalcite is 2-3:1; 2b) in the step 2), the particle size of the Mg-Al hydrotalcite is less than 1000 mesh; 2c) in the step 2), the method for preparing the Mg-Al hydrotalcite colloid is adjusting the pH and temperature of the water dispersion of the Mg-Al hydrotalcite and stirring to obtain the Mg-Al hydrotalcite colloid; 2d) in the step 2), the complex solution of the step 1) is added dropwise into the Mg-Al hydrotalcite colloid, and ion exchange is performed under a certain pH and temperature; 3a) in the step 3), the precipitating agent is a mixture of sodium hydroxide and sodium carbonate; 3b) the precipitating agent solution is slowly added dropwise into the hydrotalcite-bimetallic ligand sol, and the flow rate is controlled to be 0.2-1 mL / min; 3c) in the step 3), the standing aging time is 0.5-12 h, and the aging temperature is 60-80 DEG C; 3d) in the step 3), the drying temperature is 70-90 DEG C; ​ ​ ​ 4a) in step 4), the surfactant is at least one selected from sodium dodecyl benzene sulfonate, cetyl trimethyl ammonium bromide, octadecyl trimethyl ammonium bromide, stearic acid; 4b) in step 4), the concentration of the surfactant in the aqueous solution is 0.5-1.0 mol / L; 4c) in step 4), the mixed grinding is circular grinding in a ball mill, the frequency of the ball mill is 50-150 Hz, the circular grinding time is 2-6 h, and the circular grinding immersion temperature is 15-60℃.

4. The dual doped pillared support of claim 3, wherein, In step 2), the method for preparing the Mg-Al hydrotalcite colloid is adjusting the pH and temperature of the aqueous dispersion of the Mg-Al hydrotalcite, and stirring to obtain the Mg-Al hydrotalcite colloid; the pH is 5-7, and the temperature is 50-80℃.

5. The dual doped pillared support of claim 3, wherein, In step 2), the complex solution of step 1) is added dropwise into the Mg-Al hydrotalcite colloid, and ion exchange is carried out by maintaining a certain pH and temperature; the pH is 5.5-6.5, and the temperature is 50-80℃.

6. The dual doped pillared support of claim 3, wherein, In step 3), the precipitant is a mixture of sodium hydroxide and sodium carbonate; the molar ratio of sodium hydroxide to sodium carbonate is 2:1-1:

1.

7. Use of the double-doped pillared support according to any one of claims 1-6 in the preparation of a catalyst for organic liquid hydrogen storage technology.

8. A rare earth doped polyanion pillared modified double metal hydrocatalyst characterized by, The double-doped pillared support according to any one of claims 1-6, further comprising a noble metal active component and a transition metal active component; the precursor of the noble metal component is a noble metal salt, and the precursor of the transition metal component is a transition metal salt.

9. The rare earth doped multi-cation pillared modified double metal hydrocatalyst of claim 8, wherein, At least one of the following technical features is included: b1) the noble metal salt is at least one nitrate and / or chloride salt selected from Au, Ru, Pt, Pd, Rh; b2) the transition metal salt is at least one nitrate and / or chloride salt selected from Ni, Co, Fe, Mn, Cu, Zn; b4) the mass proportion of the noble metal in the bimetallic hydrogenation catalyst is 0.05-0.15%; b5) the mass proportion of the transition metal in the bimetallic hydrogenation catalyst is 5-20%.

10. A process for the preparation of a rare earth doped multi-cation pillared modified double metal hydrocatalyst according to any one of claims 8-9, characterized in that, The following steps are included: 1) providing the double-doped pillared support according to any one of claims 1-6; 2) adding a complexing agent to an aqueous solution of a noble metal precursor and a transition metal precursor to prepare an active component precursor; 3) mixing and grinding the active component precursor, the double-doped pillared support, and water to obtain a mixed slurry; 4) obtaining a rare earth-doped multi-element anion pillared modified bimetallic hydrogenation catalyst after drying, calcination, and reduction of the mixed slurry.

11. The method of making a rare earth doped multi-cation pillared modified double metal hydrocatalyst of claim 10, wherein, At least one of the following technical features is included: 2c) in step 2), the concentration of the noble metal precursor in the aqueous solution is 0.05-0.10 mol / L; 2d) in step 2), the concentration of the transition metal precursor in the aqueous solution is 0.5-1.0 mol / L; 2e) in step 2), the complexing agent is an alkaline complexing agent, and the pH of the solution is adjusted to 9.0-11.5; 2f) in step 2), the molar ratio of the noble metal precursor, the transition metal precursor, and water is 1:(5-20):(10-40). 3a) in step 3), the mass ratio of active component precursor, double-doped pillared support and water is (1:10:50)~(1:20:50); 3b) in step 3), the active component precursor, double-doped pillared support and water are mixed and ground, and the pH of the system is 9.0~11.5; 3c) in step 3), the mixing and grinding is cyclic grinding in a ball mill, the ball mill frequency is 50~150Hz, the cyclic grinding time is 2~6h, and the cyclic grinding impregnation temperature is 15~60℃; 4a) in step 4), the drying is carried out under microwave conditions; 4c) in step 4), the drying time is 1~4h; 4d) in step 4), the calcination temperature is 400-800℃, and the calcination time is 4~16 h; 4e) in step 4), the reduction uses hydrogen and argon mixed gas; 4f) in step 4), the reduction temperature is 250~500℃, and the reduction time is 2~10 h; 4g) in step 4), the reduction is carried out in a tube furnace, and the flow rate of hydrogen and argon mixed gas is 80~120mL / min.

12. The method of making a rare earth doped multi-cation pillared modified double metal hydrocatalyst of claim 11, wherein, In step 2), the complexing agent is an alkaline complexing agent, and the pH of the solution is adjusted to 9.0~11.5; the alkaline complexing agent is at least one selected from the group consisting of ammonia, triethylamine, triethanolamine, and monoethanolamine.

13. The method of making a rare earth doped multi-cation pillared modified double metal hydrocatalyst of claim 11, wherein, In step 4), the drying is carried out under microwave conditions; the microwave power is 650~900W, and the frequency is 1.75~2.65GHz.

14. The method of making a rare earth doped multi-cation pillared modified double metal hydrocatalyst of claim 11, wherein, In step 4), the reduction uses hydrogen and argon mixed gas; the volume ratio of hydrogen is 5~50%.

15. Use of the rare earth doped multi-anion pillared modified bimetallic hydrogenation catalyst according to any one of claims 8-9 in organic liquid hydrogen storage technology.

16. The use according to claim 15, characterized in that, Applied to hydrogen storage of aromatic hydrocarbon organic liquids.

17. The use according to claim 16, characterized in that, Applied to hydrogen storage of dibenzyltoluene, hydrogen storage of toluene, hydrogen storage of naphthalene, or hydrogen storage of N-ethylcarbazole.

18. A method of hydrogen storage for an organic liquid, characterized by, Dibenzyltoluene and hydrogen gas are subjected to hydrogenation reaction under the catalysis of the rare earth doped multi-anion pillared modified bimetallic hydrogenation catalyst according to any one of claims 8-9.

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