Preparation method of catalyst Ni-Cu / N-MCHS@MS and its application in preparing hydrogenated rosin by rosin hydrogenation

Abstract

This invention belongs to the field of rosin hydrogenation to hydrogenated rosin technology, and discloses a method for preparing the catalyst Ni-Cu / N-MCHS@MS and its application in the preparation of hydrogenated rosin from rosin. Rosin is used as the raw material, and water and 200... # Using solvent oil as the solvent, a nickel-based bimetallic amphiphilic catalyst (Ni-Cu / N-MCHS@MS) doped with Cu is employed, and H2 is introduced to carry out a catalytic hydrogenation reaction to produce hydrogenated rosin. As can be seen from the above technical solution, the preparation method described in this invention can effectively improve the conversion rate of rosin, the obtained product tetrahydroabsicoic acid has high selectivity, the preparation method is simple, the reagents used are safe, and it is beneficial for industrial production.

Description

Technical Field

[0001] This invention belongs to the field of rosin hydrogenation to prepare hydrogenated rosin, and specifically relates to the preparation method of the catalyst Ni-Cu / N-MCHS@MS and its application in the preparation of hydrogenated rosin from rosin hydrogenation. Background Technology

[0002] China is a global leader in the production and export of forestry chemical products, particularly rosin. For a long time, China's rosin production and exports have consistently ranked among the world's top. Rosin is a natural resin extracted from pine wood. Its color ranges from light yellow to reddish-brown, and it has extremely high transparency and thermoplasticity. Rosin is composed of various components, primarily resin acids, along with small amounts of fatty acids and neutral substances. Analysis shows that in typical rosin, the content of resin acids ranges from 85.6% to 88.7%, fatty acids from 2.5% to 5.4%, and neutral substances from 5.2% to 7.6%. The acidic component, rosin acid, is also a mixture, mainly composed of isomeric rosin acid (40-60%) and piratic acid (9-27%). Rosin and its derivatives have traditionally been used in the production of adhesive pacifiers, facial tissues, and other products.

[0003] Because rosin molecules contain unsaturated conjugated double bonds, they are highly sensitive to oxygen and readily oxidize when exposed to oxygen-containing atmospheres, leading to a decline in material properties. Therefore, various methods, such as isomerization, disproportionation, hydrogenation, maleization, and esterification, are frequently used to modify rosin and create derivatives to increase its practical value. Among these derivatives, hydrogenated rosin is an important modifying material, produced through a hydrogenation reaction. Hydrogenated rosin possesses excellent antioxidant properties, low brittleness, and high thermal stability, and is non-toxic. Therefore, it has a wide range of industrial applications, including adhesives, synthetic rubber, coatings, inks, paper, electronics, food, welding, and pharmaceuticals.

[0004] To date, catalysts used in the hydrogenation of rosin to produce hydrogenated rosin are mainly classified into two categories based on their active sites: noble metal catalysts and non-noble metal catalysts. Catalysts with noble metals as the active component have made significant progress in rosin hydrogenation; however, noble metals also have some unavoidable drawbacks, such as high cost, relatively limited availability, and instability, which greatly increases their cost in industrial production. Non-noble metal catalysts, on the other hand, have drawbacks such as requiring sophisticated reaction equipment and demanding reaction conditions. Furthermore, the compatibility and synergy between the catalyst support and the active site play a crucial role in the rosin hydrogenation reaction, and the catalytic activity and product selectivity exhibited by catalysts obtained from different combinations of catalyst supports and active sites are unpredictable. Summary of the Invention

[0005] To improve rosin conversion rate and achieve highly selective preparation of tetrahydroabsic acid to obtain high-quality premium rosin, this invention provides a method for preparing the catalyst Ni-Cu / N-MCHS@MS and its application in the hydrogenation of rosin to prepare hydrogenated rosin.

[0006] To achieve the above-mentioned objectives, the present invention adopts the following technical solution:

[0007] This invention provides the application of the catalyst Ni-Cu / N-MCHS@MS in the preparation of hydrogenated rosin from rosin hydrogenation, using rosin as raw material and water and 200 # Using solvent oil as the solvent, a nickel-based bimetallic amphiphilic catalyst Ni-Cu / N-MCHS@MS doped with Cu is used, and H2 is introduced to carry out a catalytic hydrogenation reaction to produce hydrogenated rosin.

[0008] Furthermore, the mass ratio of the rosin to the catalyst Ni-Cu / N-MCHS@MS is 10:1.

[0009] Furthermore, the reaction temperature of the catalytic hydrogenation reaction is 130–140°C, the reaction time is 4 h, and the H2 pressure during the reaction process is 3 MPa.

[0010] Furthermore, after the catalytic hydrogenation reaction is completed, the catalyst and product are separated by static aging and stratification.

[0011] In addition, this invention also provides a method for preparing the above-mentioned catalyst Ni-Cu / N-MCHS@MS, which uses polyether Pluronic F127 as a template agent, 1,3,5-trimethylbenzene (TMB) as a pore swelling and interface modifier, and dopamine as a carbon and nitrogen source to synthesize polydopamine spheres. Hydrophilicity is imparted by introducing a mesoporous silica shell externally, and amphiphilic hollow spherical nanomaterials N-MCHS@MS are prepared after high-temperature confined carbonization. Finally, Ni-Cu metal nanoparticles are loaded onto the amphiphilic hollow spherical nanomaterials through impregnation-hydrogen reduction to obtain Cu-doped nickel-based bimetallic amphiphilic catalyst Ni-Cu / N-MCHS@MS.

[0012] Furthermore, the preparation method of the catalyst Ni-Cu / N-MCHS@MS specifically includes the following steps:

[0013] 1) Preparation of amphiphilic hollow spherical nanomaterial N-MCHS@MS: Polyether F127 and dopamine hydrochloride were dispersed in a mixed solution containing ethanol and water. 1,3,5-trimethylbenzene (TMB) was added, and the solution was sonicated at room temperature. After sonication, the solution was made into a homogeneous emulsion. Concentrated ammonia solution was added dropwise and stirred magnetically. Then, hexadecyltrimethylammonium bromide (CTAB) was added and stirring continued. Tetraethyl orthosilicate (TEOS) was added and stirring continued. After the reaction was completed, the solution was centrifuged to obtain a black solid. The solid was processed and dried. The dried solid was calcined in stages at high temperature in a nitrogen atmosphere to finally form a black solid powder of amphiphilic hollow spherical nanomaterial N-MCHS@MS.

[0014] 2) Cu-doped nickel-based bimetallic amphiphilic catalyst Ni-Cu / N-MCHS@MS: The prepared nanomaterial N-MCHS@MS was dispersed in ethanol, and then nickel acetate tetrahydrate (NiC4H6O4·4H2O) and copper nitrate trihydrate (Cu(NO3)2·3H2O) were simultaneously added to dissolve them. The mixture was sonicated, then stirred, and the ethanol was removed by rotary evaporation. The dried solid was then reduced at high temperature in a hydrogen-argon mixed atmosphere to finally obtain the Cu-doped nickel-based bimetallic amphiphilic catalyst Ni-Cu / N-MCHS@MS. The molar ratio n of nickel to copper in the obtained Ni-Cu / N-MCHS@MS molecule is... 镍 :n 铜 The ratio is 5:1.

[0015] Furthermore, in step 1), after the ultrasound is completed, the solution is magnetically stirred at 600 rpm for 30 minutes at 30°C to form a uniform emulsion.

[0016] Further, in step 1), the segmented calcination involves grinding the dried solid and transferring it into a quartz boat, which is then placed in a tube furnace under a nitrogen atmosphere for high-temperature calcination. The temperature is increased to 550°C at a rate of 3°C / min and held for 2 hours to remove the template agent F127 and hexadecyltrimethylammonium bromide (CTAB). The temperature is then further increased from 550°C to 850°C at a rate of 3°C / min and held for another 2 hours, allowing the polydopamine spheres to decompose from the inside out under the protection of the outer silica shell, forming a hollow nitrogen-doped carbon layer embedded in the mesoporous silica shell. The resulting black solid powder is the amphiphilic nanomaterial N-MCHS@MS.

[0017] Furthermore, in step 1), the volume ratio of ethanol to water in the ethanol-water mixture is 1:1.

[0018] Furthermore, in step 2), the hydrogen volume ratio of the hydrogen-argon mixed atmosphere is 15%; the high-temperature reduction process is to raise the temperature to 550℃ at a heating rate of 2℃ / min and hold it for 4h.

[0019] First, in an ethanol medium, the present invention uses the prepared amphiphilic nanomaterial N-MCHS@MS nanoparticles as a stabilizer, and impregnates and reduces them with hydrogen to load nickel-copper nanoparticles onto the amphiphilic nanomaterial, forming a stable Ni-Cu / N-MCHS@MS nanocatalyst. Second, the Ni-Cu / N-MCHS@MS catalyst provided by the present invention exhibits excellent catalytic activity and product selectivity for the hydrogenation reaction of rosin phase. This excellent catalytic performance is jointly achieved by the amphiphilic support material N-MCHS@MS and the bimetallic active centers. On the one hand, the high nitrogen content of the nanosphere support provides more effective metal coordination anchoring sites, which is beneficial to improving the dispersibility of metal nanoparticles and increasing the number of active components; in addition, the high edge enrichment of nitrogen (pyridine nitrogen) in N-MCHS@MS can generate abundant defect sites to improve the electron donor / acceptor effect, thereby enabling the metal nanoparticles to be rapidly and firmly anchored on the support material; and the lipophilicity of the support is beneficial to the mass transfer and enrichment of reactants, while the introduction of the hydrophilic layer improves the dispersibility of the catalyst in an aqueous medium. On the other hand, compared with single nickel catalysts, doping with an appropriate proportion of copper not only effectively improves the disadvantage of nickel's tendency to aggregate, but also forms a synergistic effect with nickel, resulting in a smaller and more dispersed active component, thus further enhancing catalytic activity. Furthermore, experimental data demonstrate that the specific interplay and synergy between Ni-Cu particles as bimetallic active centers and the support N-MCHS@MS in this invention endows the catalyst with high activity and high selectivity for the product tetrahydroabsic acid.

[0020] In the catalytic hydrogenation reaction, the Ni-Cu / N-MCHS@MS solid catalyst provided by this invention forms a three-phase interface between the rosin oil phase and hydrogen, which reduces mass transfer resistance and facilitates the reaction. This allows the catalytic hydrogenation reaction to proceed under mild conditions, and the mild reaction conditions enable the catalyst to have higher catalytic efficiency and product selectivity for rosin.

[0021] Experimental results show that the catalyst provided by this invention effectively improves the rosin conversion rate during rosin hydrogenation, achieving a conversion rate of over 98%. It also enables the highly selective preparation of tetrahydroabietic acid, with a selectivity exceeding 32%, reaching the level of high-quality premium rosin. As can be seen from the above technical solution, the preparation method described in this invention effectively improves the rosin conversion rate, yields a highly selective tetrahydroabietic acid product, has a simple preparation method, uses safe reagents, and is beneficial for industrial production. Attached Figure Description

[0022] Figure 1 Scanning electron microscope (SEM) image of N-MCHS@MS, the amphiphilic nanoporous material provided by this invention;

[0023] Figure 2 Transmission electron microscope (TEM) image of N-MCHS@MS, the amphiphilic nanoporous material provided by this invention;

[0024] Figure 3 High-resolution transmission electron microscopy (TEM) image of the amphiphilic bimetallic catalyst Ni-Cu / N-MCHS@MS provided by this invention. Detailed Implementation

[0025] This invention discloses a method for preparing the catalyst Ni-Cu / N-MCHS@MS and its application in the hydrogenation of rosin to prepare hydrogenated rosin. Those skilled in the art can refer to the content of this document and appropriately modify the process parameters to achieve the desired result. It should be particularly noted that all similar substitutions and modifications are obvious to those skilled in the art and are considered to be included in this invention. The methods and applications of this invention have been described through preferred embodiments. Those skilled in the art can obviously make modifications or appropriate alterations and combinations to the methods and applications described herein without departing from the content, spirit, and scope of this invention to realize and apply the technology of this invention.

[0026] To enable those skilled in the art to better understand the present invention, the present invention will be further described in detail below with reference to specific embodiments.

[0027] Example 1: Preparation of Ni-Cu / N-MCHS@MS catalyst

[0028] 1) Preparation of amphiphilic hollow spherical nanomaterial N-MCHS@MS: 0.1 g of polyether F127 and 0.12 g of dopamine hydrochloride were weighed and dispersed in a round-bottom flask containing a mixture of 5 mL anhydrous ethanol and 5 mL deionized water. 0.1 mL of 1,3,5-trimethylbenzene (TMB) was added, and the solution was sonicated at room temperature for 30 min. After sonication, the solution was magnetically stirred at 600 rpm for 30 min at 30 °C to form a homogeneous emulsion. 0.08 mL of concentrated ammonia solution (AR) was then added dropwise, and magnetic stirring was continued for 8 h. 0.1 g of hexadecyltrimethylammonium bromide (CTAB) was then weighed and added, and stirring was continued for 20 min. 0.6 mL of tetraethyl orthosilicate (TEOS) was added, and stirring was continued for 4 h. After the reaction, the solution was transferred to a centrifuge tube and centrifuged to obtain a black solid. The solid was washed twice each with deionized water and anhydrous ethanol, and then allowed to stand at room temperature until completely dry. The dried solid was ground and transferred to a quartz boat, which was then placed in a tube furnace under a nitrogen atmosphere for high-temperature calcination. The temperature was increased to 550°C at a rate of 3°C / min and held for 2 hours to remove the template agent F127 and CTAB. The temperature was further increased from 550°C to 850°C at a rate of 3°C / min and held for another 2 hours, allowing the polydopamine spheres to decompose from the inside out under the protection of the outer silica shell, forming a hollow nitrogen-doped carbon layer embedded in the mesoporous silica shell. The resulting black solid powder is the amphiphilic nanomaterial N-MCHS@MS.

[0029] 2) Preparation of Cu-doped nickel-based bimetallic amphiphilic catalyst Ni-Cu / N-MCHS@MS: 0.1 g of amphiphilic nanomaterial N-MCHS@MS was dispersed in 25 mL of anhydrous ethanol. Then, 49 mg of nickel acetate tetrahydrate (NiC4H6O4·4H2O) and 10 mg of copper nitrate trihydrate (Cu(NO3)2·3H2O) were accurately weighed and added to the solution to dissolve them. The mixture was sonicated at room temperature for 20 min. After sonication, the mixture was magnetically stirred at 600 rpm for 4 h at room temperature (25 °C). The liquid mixture was rotary evaporated at 55°C to remove ethanol. The dried solid was ground and transferred to a quartz boat, then placed in a tube furnace under a hydrogen (15% by volume) and argon (85% by volume) mixed atmosphere for high-temperature reduction. The temperature was increased to 550°C at a rate of 2°C / min and held for 4 hours, finally yielding the amphiphilic bimetallic catalyst Ni-Cu / N-MCHS@MS(n 镍 :n 铜 =5:1).

[0030] Figure 1 and Figure 2The images show scanning electron microscope (SEM) and transmission electron microscope (TEM) images of the synthesized amphiphilic nanomaterial N-MCHS@MS. As can be seen from the images, the catalyst support has uniform particle size and a large specific surface area, which can increase the contact area between the substrate and the catalyst and promote the reaction. Figure 3 High-resolution transmission electron microscopy (TEM) image of the synthesized amphiphilic nanocatalyst Ni-Cu / N-MCHS@MS. Figure 3 It can be observed that the Ni-Cu alloy is loaded on the support with a small particle size.

[0031] Example 2: Preparation of hydrogenated rosin by hydrogenation of rosin phase

[0032] Weigh 0.5 g of rosin and 50 mg of the Cu-doped nickel-based bimetallic amphiphilic catalyst Ni-Cu / N-MCHS@MS prepared in Example 1, and add them to a 100 mL magnetically coupled mechanically stirred reactor. Add 15 mL of solvent (which may include 10 mL of 200# solvent oil and 5 mL of water). Seal the reactor and connect the hydrogenation device. First, purge the air in the reactor four times with 1 MPa of H2. Then, charge the reactor with 3 MPa of H2. Repeatedly check the reactor for leaks. After confirming that there are no leaks, place the reactor in an external electric heating mantle and connect the circulating cooling water, temperature sensing probe, and power supply. Turn on the switch, set the program, raise the temperature to 130 °C, turn on the mechanical stirrer, maintain the speed at 350 rpm, and react for 4 hours. After the reaction is complete, cool the reactor, open the reactor, and transfer all the liquid inside to centrifuge tubes. Let it stand to allow it to separate into layers. Take the upper light yellow transparent oil phase, treat it with methyl esterification, and perform component analysis on gas chromatography. The total conversion rate of rosin is 98.1%, the selectivity of tetrahydroabietic acid reaches 32.1%, the selectivity of dehydroabietic acid is 6.6%, and the content of tetrahydroabietic acid is greater than 30%, which can reach the level of premium hydrogenated rosin.

[0033] Example 3: Preparation of Hydrogenated Rosin by Hydrogenation of Rosin Fluid Phase

[0034] Weigh 0.5 g of rosin and 50 mg of the Cu-doped nickel-based bimetallic amphiphilic catalyst Ni-Cu / N-MCHS@MS prepared in Example 1, and add them to a 100 mL magnetically coupled mechanically stirred reactor. Add 15 mL of solvent (which may include 10 mL of 200# solvent oil and 5 mL of water). Seal the reactor and connect the hydrogenation device. First, purge the air in the reactor four times with 1 MPa of H2. Then, charge the reactor with 3 MPa of H2. Repeatedly check the reactor for leaks. After confirming that there are no leaks, place the reactor in an external electric heating mantle and connect the circulating cooling water, temperature sensing probe, and power supply. Turn on the switch, set the program, raise the temperature to 140 °C, turn on the mechanical stirrer, maintain the speed at 350 rpm, and react for 4 hours. After the reaction is complete, cool the reactor, open the reactor, and transfer all the liquid inside to centrifuge tubes. Let it stand to allow it to separate into layers. Take the upper light yellow transparent oil phase, treat it with methyl esterification, and perform component analysis on gas chromatography. The total conversion rate of rosin was 98.9%, the selectivity of tetrahydroabsic acid was 37.8%, and the selectivity of dehydroabsic acid was 2.2%. The hydrogenated rosin product obtained in this example reached the premium level of highly hydrogenated rosin.

[0035] Example 4: Reuse of Catalyst

[0036] Weigh 0.5 g of rosin and 50 mg of the Ni-Cu / N-MCHS@MS catalyst obtained in Example 1, and add them to a 100 mL magnetically coupled mechanically stirred reactor. Add 15 mL of solvent (which may include 10 mL of 200# solvent oil and 5 mL of water). Seal the reactor and connect the hydrogenation device. First, purge the air from the reactor four times with 1 MPa of H2. Then, charge the reactor with 3 MPa of H2. Repeatedly check the reactor for leaks. After confirming that there are no leaks, place the reactor in an external electric heating mantle and connect the circulating cooling water, temperature sensing probe, and power supply. After turning on the switch and setting the program, raise the temperature to 130 °C, turn on the mechanical stirrer, maintain the speed at 350 rpm, and react for 4 hours. After the reaction was completed, the catalyst was separated from the product. The separated catalyst was reused, and the above experimental steps were repeated. The catalyst was recycled 8 times, and the total conversion rate of rosin was 90.3%. The selectivity of tetrahydroabsic acid reached 30.1%, and the selectivity of dehydroabsic acid was 7.9%, still reaching the premium level of highly hydrogenated rosin. This indicates that the catalyst has excellent stability.

[0037] Example 5: Preparation of Hydrogenated Rosin by Hydrogenation of Rosin Fluid Phase - Temperature Selection

[0038] Weigh 0.5 g of rosin and 50 mg of the Ni-Cu / N-MCHS@MS catalyst prepared in Example 1, and add them to a 100 mL magnetically coupled mechanically stirred reactor. Add 15 mL of solvent (which may include 10 mL of 200# solvent oil and 5 mL of water). Seal the reactor and connect the hydrogenation device. First, purge the air from the reactor four times with 1 MPa of H2. Then, charge the reactor with 3 MPa of H2. Repeatedly check the reactor for leaks. After confirming that there are no leaks, place the reactor in an external electric heating mantle and connect the circulating cooling water, temperature sensing probe, and power supply. After turning on the switch and setting the program, raise the temperature above 150°C, maintain the rotation speed at 350 rpm, and react for 4 hours. After the reaction is complete, open the reactor and transfer all the liquid inside to centrifuge tubes. Let it stand to allow it to separate into layers. Take the upper pale yellow transparent oil phase, treat it with methyl esterification, and perform component analysis on gas chromatography. The overall conversion rate of rosin was 99.1%, with a selectivity of 32.8% for tetrahydroabsic acid and 5.7% for dehydroabsic acid, reaching the premium level for highly hydrogenated rosin. The catalytic efficiency remained essentially unchanged at excessively high temperatures. Considering safety and cost savings in actual production, the effective catalytic temperature for this catalyst was selected as 130–140℃.

[0039] Effects of different catalysts on the hydrogenation reaction of rosin (Example)

[0040] 0.5 g of rosin, 50 mg of the different catalysts mentioned in Table 1, and 15 mL of solvent (including 10 mL of 200# solvent oil and 5 mL of water) were added to a magnetically coupled mechanically stirred reactor. The mixture was stirred evenly, and the air in the reactor was purged by replacing the rosin with 1 MPa H2 four times. Then, 3 MPa H2 was introduced into the reactor, and the reactor was mechanically stirred at 130 °C for 4 h. After the reaction was completed, the reactor was allowed to stand to separate into layers. The upper light yellow transparent oil phase was subjected to methyl esterification and then analyzed by gas chromatography. The total conversion of rosin and the selectivity of tetrahydroabsic acid and dehydroabsic acid are shown in Table 1.

[0041] Table 1 Results of rosin hydrogenation catalyzed by different types of catalysts

[0042]

[0043] Table 1 shows that the total conversion rate of rosin and the content of tetrahydroabsic acid, dihydroabsic acid and dehydroabsic acid vary depending on the type of catalyst. In view of the requirements of this invention, this invention pays special attention to the total conversion rate of rosin and the content of dihydroabsic acid and tetrahydroabsic acid in the product, especially the content of tetrahydroabsic acid, which exceeds the level of extra-grade hydrogenated rosin.

[0044] Table 1 shows that, under the same conditions, the catalyst Ni-Cu / N-MCHS@MS provided by this invention exhibits significantly better catalytic performance for the hydrogenation reaction of aqueous rosin than catalysts supported on single metals Ni and Cu, as well as Pd / C and Ru / C catalysts, while achieving catalytic effects similar to those achieved with Pd and Ru. Furthermore, under the same conditions, the catalyst provided by this invention also shows significantly better overall rosin conversion and higher levels of dihydroabietic acid and tetrahydroabietic acid in the products compared to the catalyst Ni-Cu / mSiO2 (which lacks a hollow structure) and the hollow catalyst Ni-Cu / CxNy@mSiO2 synthesized using resorcinol and formaldehyde as carbon sources and ethylenediamine as a nitrogen source.

[0045] Therefore, it can be seen that the catalysts used in the rosin hydrogenation catalytic reaction, the catalysts obtained by combining different catalyst supports and catalytic active centers, exhibit unpredictable catalytic activity and product selectivity in the rosin hydrogenation reaction. The catalyst prepared by this invention has a specific mutual matching and synergy between Ni-Cu particles as bimetallic active centers and the support N-MCHS@MS, which makes the catalyst unexpectedly exhibit high catalytic activity and product selectivity.

[0046] The above description is only a preferred embodiment of the present invention. It should be noted that for those skilled in the art, several improvements and modifications can be made without departing from the principle of the present invention, and these improvements and modifications should also be considered within the scope of protection of the present invention.

Claims

1. The application of Ni-Cu / N-MCHS@MS catalyst in the preparation of hydrogenated rosin by rosin hydrogenation, characterized in that, Using rosin as the raw material, and water and 200 # Using solvent oil as the solvent, a nickel-based bimetallic amphiphilic catalyst Ni-Cu / N-MCHS@MS doped with Cu is used, and H2 is introduced to carry out a catalytic hydrogenation reaction to produce hydrogenated rosin; The preparation method of the catalyst Ni-Cu / N-MCHS@MS specifically includes the following steps: 1) Preparation of amphiphilic hollow spherical nanomaterial N-MCHS@MS: Polyether F127 and dopamine hydrochloride were dispersed in a mixed solution containing ethanol and water. 1,3,5-trimethylbenzene was added, and the solution was sonicated at room temperature. After sonication, the solution was made into a uniform emulsion. Concentrated ammonia solution was then added dropwise while magnetically stirring. Hexadecyltrimethylammonium bromide was then added and stirring continued. Tetraethyl orthosilicate was added and stirring continued. After the reaction was completed, the solution was centrifuged to obtain a black solid. The solid was then dried. The dried solid was calcined in stages at high temperature in a nitrogen atmosphere to finally form a black solid powder of amphiphilic hollow spherical nanomaterial N-MCHS@MS. 2) Preparation of Cu-doped nickel-based bimetallic amphiphilic catalyst Ni-Cu / N-MCHS@MS: The prepared nanomaterial N-MCHS@MS was dispersed in ethanol, and then nickel acetate tetrahydrate and copper nitrate trihydrate were added to dissolve them. The mixed solution was sonicated, and then stirred. The liquid mixture was rotary evaporated to remove the ethanol. The dried solid was reduced at high temperature in a hydrogen-argon mixed atmosphere to finally obtain the Cu-doped nickel-based bimetallic amphiphilic catalyst Ni-Cu / N-MCHS@MS.

2. The application as described in claim 1, characterized in that: The mass ratio of the rosin to the catalyst Ni-Cu / N-MCHS@MS is 10:

1.

3. The application as described in claim 1, characterized in that: The catalytic hydrogenation reaction is carried out at a temperature of 130-140°C for 4 hours, with an H2 pressure of 3 MPa.

4. The application as described in claim 1, characterized in that: After the catalytic hydrogenation reaction is completed, the catalyst and product are separated by static aging and stratification.

5. The application as described in claim 1, characterized in that, In step 1), after the ultrasound is completed, the solution is magnetically stirred at 600 rpm for 30 min at 30 ℃ to form a uniform emulsion.

6. The application as described in claim 1, characterized in that, In step 1), the segmented high-temperature calcination involves grinding the dried solid and transferring it into a quartz boat, which is then placed in a tube furnace under a nitrogen atmosphere for high-temperature calcination. The temperature is increased to 550 °C at a rate of 3 °C / min and held for 2 h to remove the template agent F127 and hexadecyltrimethylammonium bromide. The temperature is further increased from 550 °C to 850 °C at a rate of 3 °C / min and held for another 2 h, allowing the polydopamine spheres to decompose from the inside out under the protection of the outer silica shell, forming a hollow nitrogen-doped carbon layer embedded in the mesoporous silica shell. The resulting black solid powder is the amphiphilic nanomaterial N-MCHS@MS.

7. The application as described in claim 1, characterized in that, In step 1), the volume ratio of ethanol to water in the mixed solution of ethanol and water is 1:

1.

8. The application as described in claim 1, characterized in that, In step 2), the hydrogen accounts for 15% of the volume of the hydrogen-argon mixed atmosphere; the high-temperature reduction process is carried out by heating to 550 ℃ at a rate of 2 ℃ / min and holding for 4 h.

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