Catalyst and application thereof in preparation of o-aminoanisole through hydrogenation

Abstract

The invention relates to the technical field of organic synthesis, in particular to a catalyst and application thereof in preparation of o-aminoanisole through hydrogenation, the catalyst adopts aluminum oxide as a carrier, the catalyst integrally has high active site density and excellent molecular transport performance, platinum and cobalt form a bimetallic synergistic system, and in the inactivation regeneration process, the catalyst has high catalytic activity and high catalytic activity. Dimethyl fumarate and azodiisobutyronitrile are introduced in the preparation process, an organic modified layer is formed on the surface of a carrier through the double-bond characteristic of dimethyl fumarate and azodiisobutyronitrile, and metal anchoring points are increased, so that metal nanoparticles are not easy to migrate and agglomerate in a high-temperature or regeneration environment; therefore, high dispersion is maintained, long-term stable operation can be realized even in an industrial reaction system with high space velocity or easy carbon deposition, the conversion rate of o-nitroanisole and the selectivity of o-aminoanisole are improved, and the product purity is high.

Description

TECHNICAL FIELD

[0001] The application relates to the technical field of organic synthesis, and particularly relates to a catalyst and application of the catalyst in hydrogenation preparation of o-aminoanisole. BACKGROUND

[0002] O-aminoanisole is an important organic intermediate and is widely applied in the fields of dyes, medicines, pesticides and polymer materials. At present, the methods for preparing o-aminoanisole in industry mainly include an iron powder reduction method, a sulfidized alkali reduction method and a catalytic hydrogenation method. The iron powder reduction method and the sulfidized alkali reduction method are relatively mature, but have defects of serious environmental pollution, low product purity and large raw material consumption, and thus cannot meet the requirements of green chemistry and sustainable development. In comparison, the catalytic hydrogenation method has advantages of high atom economy, environmental friendliness, high product purity and the like, and gradually becomes a key direction of research and application.

[0003] In the catalytic hydrogenation method, the activity and durability of the catalyst have a decisive role on the economy and stability of the o-aminoanisole hydrogenation process. If the catalyst activity is insufficient, the reaction efficiency is reduced and the energy consumption is increased; and if the catalyst durability is poor, the activity metal is aggregated under the requirement of multiple reactivation in long-period operation, the catalytic effect is reduced, and even the catalyst is seriously inactivated. Since the activity metal is usually a noble metal such as Pt and Pd, the catalyst is rapidly inactivated or has poor regeneration performance, which not only increases the catalyst supplement cost, but also affects the continuous stability of production. Therefore, development of a catalyst with high activity and long service life can significantly reduce the synthesis cost of o-aminoanisole. SUMMARY

[0004] The application aims to provide a catalyst and application of the catalyst in hydrogenation preparation of o-aminoanisole, so as to solve the problems of low production efficiency, large catalyst consumption and difficult control of reaction conditions in the prior art.

[0005] To achieve the above-mentioned purpose, the application provides a preparation method of a catalyst, which comprises the following steps: S1: mixing Al2O3 and a P123 solution, and drying to obtain a first carrier precursor; S2: configuring a mixed solution of P123 and F127, mixing the mixed solution with the first carrier precursor, and drying to obtain a second carrier precursor; S3: mixing an F127 solution, silicon dioxide and the second carrier precursor to obtain a third carrier precursor; S4: calcining the third carrier precursor under an air atmosphere to obtain an Al2O3 carrier; S5: mixing a cobalt salt, alcohol, dimethyl fumarate and azobisisobutyronitrile, and then adding the Al2O3 carrier and drying to obtain a dried carrier; S6: mixing the platinum salt and water, mixing with the carrier, drying to obtain an Al2O3 composite carrier containing a Pt and Co precursor; S7: performing temperature programmed reduction on the Al2O3 composite carrier containing the Pt and Co precursor under a mixed atmosphere of hydrogen and inert gas to obtain a Pt-Co / Al2O3 catalyst.

[0006] In some specific embodiments of the first aspect, in the S1 step, the Al2O3 is selected from any one or mixture of γ-Al2O3 or α-Al2O3.

[0007] In some specific embodiments of the first aspect, in the S1 step, the P123 solution is a P123 aqueous solution.

[0008] In some specific embodiments of the first aspect, in the S1 step, the mass concentration of the P123 aqueous solution is 3-5 wt%.

[0009] In some specific embodiments of the first aspect, in the S1 step, the mass of Al2O3 added per 1 L of P123 solution is 80-120 g.

[0010] In some specific embodiments of the first aspect, in the S1 step, the drying temperature is 50-70°C.

[0011] In some specific embodiments of the first aspect, in the S1 step, the drying time is 5-7 h.

[0012] In some specific embodiments of the first aspect, in the S2 step, the mass concentration of P123 in the mixed solution is 2-4 wt%.

[0013] In some specific embodiments of the first aspect, in the S2 step, the mass concentration of F127 in the mixed solution is 2-4 wt%.

[0014] In some specific embodiments of the first aspect, in the S2 step, the drying temperature is 50-70°C.

[0015] In some specific embodiments of the first aspect, in the S2 step, the drying time is 4-8 h.

[0016] In some specific embodiments of the first aspect, in the S3 step, the F127 solution is an F127 aqueous solution. In some specific embodiments of the first aspect, in the S3 step, the mass fraction of the F127 aqueous solution is 8-12 wt%.

[0017] In some embodiments of the first aspect, in the S3 step, the mass of the silica added to the 1 L F127 solution is 48-55 g.

[0018] In some embodiments of the first aspect, in the S4 step, the temperature of the calcination is 550-650 °C.

[0019] In some embodiments of the first aspect, the acid is selected from any one of hydrochloric acid, nitric acid, and sulfuric acid.

[0020] In some embodiments of the first aspect, the concentration of the acid is 0.8-1.2 M.

[0021] In some embodiments of the first aspect, in the S4 step, the drying temperature is 100-120 °C.

[0022] In some embodiments of the first aspect, in the S4 step, after the acid soaking, the Al2O3 carrier is obtained by washing with water.

[0023] In some embodiments of the first aspect, in the S5 step, the cobalt salt is selected from any one or mixture of cobalt chloride, cobalt nitrate, and cobalt acetate.

[0024] In some embodiments of the first aspect, in the S5 step, the molar amount of the cobalt salt added to the 1 L alcohol is 300-400 mmol.

[0025] In some embodiments of the first aspect, in the S5 step, the mass of the dimethyl fumarate added to the 1 L alcohol is 30-35 g.

[0026] In some embodiments of the first aspect, in the S5 step, the mass of the azobisisobutyronitrile added to the 1 L alcohol is 2-4 g.

[0027] In some embodiments of the first aspect, in the S5 step, the alcohol is selected from any one or mixture of methanol, ethanol, and isopropanol.

[0028] In some embodiments of the first aspect, in the S6 step, the mass of the platinum salt added to the 1 L water is 30-35 g.

[0029] In some embodiments of the first aspect, in the S6 step, the drying temperature is 60-80 °C.

[0030] In some specific embodiments of the preparation method of the first aspect, the platinum salt in the S6 step is selected from any one or mixture of platinum chloride, platinum nitrate and dichlorotetraamine platinum.

[0031] In some specific embodiments of the preparation method of the first aspect, in the S7 step, the mixed volume ratio of hydrogen and nitrogen is (1~3):20.

[0032] In some specific embodiments of the preparation method of the first aspect, in the S7 step, the temperature is raised at a rate of 2~4℃ / min to 270~360℃.

[0033] The second aspect of the present application provides a Pt-Co / Al2O3 catalyst prepared by any one of the methods of the first aspect.

[0034] The third aspect of the present application provides an application of the Pt-Co / Al2O3 catalyst of the second aspect in the preparation of o-aminoanisole by hydrogenation of o-nitroanisole.

[0035] In the present application, P123 is Pluronic P123, and F127 is Pluronic F127; Pluronic P123 and Pluronic F127 are purchased from BASF Company; In the present application, the specification of alumina is D50≤1μm, the purity of silica is 99.5%, and the particle size is 30±5nm (Beijing Woke of Sinopharm); "Room temperature" refers to the indoor ambient temperature, which can be 12℃~37℃, 20℃~30℃, 25℃~30℃, or about 25℃.

[0036] The reagents used in the present application are not further purified and are purchased from public legal markets, for example, Shanghai Aldrin Biochemical Technology Co., Ltd., Xilong Scientific Co., Ltd., Sinopharm Chemical Reagent Co., Ltd., and Shanghai Maikelin Biotechnology Co., Ltd.

[0037] Advantages of the present application: The catalyst uses γ-alumina as a carrier, forms a three-layer structure of gradient pores by layer-by-layer drop coating to control sol, provides a high specific surface area for loading active components, ensures smooth diffusion and reduces mass transfer limitations in the pores, the outer large pores are beneficial for the entry of reactants and the diffusion of products, and the whole has high active site density and excellent molecular transport performance, the active metal is platinum, the auxiliary metal is cobalt, and the two form a bimetallic synergistic system, The catalyst structure of the present application can significantly enhance the sintering resistance of the catalyst during the deactivation and regeneration process, improve the performance of the catalyst after regeneration, introduce dimethyl fumarate and azobisisobutyronitrile during the preparation process, form an organic modified layer on the surface of the carrier through the double bond characteristics, increase the metal anchoring point, and make the metal nanoparticles not easy to migrate and agglomerate under high temperature or regeneration environment, thereby maintaining high dispersion; the catalyst structure not only gives the catalyst very high activity and excellent selectivity, but also has excellent thermal stability and regeneration performance, and can be stably operated for a long time even in a high space velocity or an industrial reaction system prone to carbon deposition, and can maintain stable performance for more than 850h after first use and secondary activation, thereby improving the conversion rate of o-nitrophenyl methyl ether and the selectivity of o-aminophenyl methyl ether, and the product has high purity. DETAILED DESCRIPTION

[0038] The above content of the present application is further described in detail through the following examples, but this should not be understood as limiting the scope of the above subject matter of the present application to only the following examples, and any technology realized based on the above content of the present application belongs to the scope of the present application.

[0039] Example 1 Preparation steps of the carrier precursor PreCat-A: 10g of Al2O3 was dried in an oven at 120℃ for 2h, then uniformly spread on a 50cm 2 rotary disc (30rpm), and 100ml of P123 solution with a concentration of 3wt% was sprayed (10.0mL / min) to the Al2O3 by using a peristaltic pump; after the spraying was completed, it was placed in a 60℃ drying box for drying for 6h to obtain Al2O3 covered with P123, which was recorded as the carrier precursor PreCat-A.

[0040] Preparation steps of the carrier precursor PreCat-B: 3g of P123 and 3g of F127 were weighed according to a mass ratio of 1:1, added into 94g of deionized water, and stirred at 40℃ for 4h to obtain a 6wt% mixed solution, and the carrier precursor PreCat-A was uniformly spread on a 50cm 2 rotary disc (30rpm), and the 6wt% mixed sol was slowly sprayed (12.0mL / min) to the surface of the carrier precursor PreCat-A by using a peristaltic pump, and after the spraying was completed, it was placed in a 60℃ drying box for drying for 6h to obtain the carrier precursor PreCat-B.

[0041] Preparation steps of the carrier precursor PreCat-C: 10g of F127 was dissolved in 90g of deionized water, stirred at 50℃ for 3h, and then 5g of silicon dioxide was added under stirring at 600rpm to form a uniform mixed solution, and the carrier precursor PreCat-B was uniformly spread on a 50cm 2The uniform mixture was sprayed (11 mL / min) onto the surface of the support precursor PreCat-B using a peristaltic pump at a rotating disc (50 rpm), and after completion, dried at 50°C for 12 h to obtain a three-layer coated support precursor PreCat-C.

[0042] Al2O3 The preparation step of the support: the support precursor PreCat-C was calcined at 540°C for 3 h in an air atmosphere, and after calcination, immersed in 1M nitric acid, then washed with water until neutral, and dried at 110°C to obtain an Al2O3 support.

[0043] The loading step of the auxiliary metal and the active metal: 10.9 mmol of cobalt acetate was added to 30 mL of ethanol, 1.0 g of dimethyl fumarate was added, and 80 mg of azobisisobutyronitrile (AIBN) was added, and a light blue complex solution was obtained after stirring at 40°C for 2 h. The Al2O3 support was added by the equal-volume impregnation method, and after standing for 1 h, the light blue complex was formed into an organic film on the support by vacuum spin-drying at 70°C for 60 min, and then dried at 110°C for 3 h to obtain a dry support.

[0044] 0.50 g of [Pt(NH3)4]Cl2 was added to 15 mL of water, and the dry support from the previous step was contacted at 40°C for 2 h, and after suction filtration, dried at 70°C to obtain an Al2O3 composite support containing Pt and Co precursors.

[0045] Hydrogen and nitrogen mixed gas (V H2 :V N2 =1:20) was introduced, and the Al2O3 composite support containing Pt and Co precursors was reduced in a mixed gas atmosphere at a temperature increase rate of 3°C / min to a target temperature of 280°C for 1 h to obtain a Pt-Co / Al2O3 catalyst Cat-1 Example 2 The preparation step of the support precursor PreCat-A-1: 10 g of Al2O3 was dried in an oven at 120°C for 2 h, and then uniformly spread on a 50 cm 2 The 100 mL of P123 solution with a concentration of 5 wt% was sprayed (10 mL / min) onto the Al2O3 using a peristaltic pump at a rotating disc (30 rpm); after spraying was completed, dried in a 60°C drying oven for 6 h to obtain Al2O3 covered with P123, denoted as the support precursor PreCat-A-1.

[0046] The preparation step of the support precursor PreCat-B-1: 3 g of P123 and 3 g of F127 were weighed according to a mass ratio of 1:1, added to 94 g of deionized water, and stirred at 45°C for 3 h to obtain a 6 wt% mixture, and the support precursor PreCat-A-1 was uniformly spread on a 50 cm 2The 6wt% mixed sol was slowly sprayed (12 mL / min) onto the surface of the support precursor PreCat-A-1 using a peristaltic pump under a rotating disk (30 rpm), and after completion, it was dried in a 70°C drying oven for 6 h to obtain the support precursor PreCat-B-1.

[0047] Preparation steps of the support precursor PreCat-C-1: 15 g of F127 was dissolved in 90 g of deionized water at 70°C, stirred for 3 h, and then 7 g of silica was added under stirring at 600 rpm to form a uniform mixture. The PreCat-B-1 was evenly spread on a 50 cm 2 The uniform mixture was sprayed (11 mL / min) onto the surface of the support precursor PreCat-B-1 using a peristaltic pump under a rotating disk (50 rpm), and after completion, it was dried at 50°C for 12 h to obtain the three-layer coated support precursor PreCat-C-1.

[0048] Al2O3 Preparation steps of the support-1: The support precursor PreCat-C-1 was calcined at 600°C for 3 h in an air atmosphere, and after calcination, it was quickly immersed in 1M nitric acid and then washed with water until neutral. After drying at 120°C, the Al2O3 support-1 was obtained.

[0049] Supporting steps of the auxiliary metal and the active metal: 15.1 mmol of cobalt acetate was added to 30 mL of ethanol, 1.0 g of dimethyl fumarate was added, and 80 mg of azobisisobutyronitrile (AIBN) was added. A light blue complex solution was obtained after stirring at 40°C for 2 h. The Al2O3 support-1 was added by the equal-volume impregnation method, and after standing for 1 h, the light blue complex was formed into an organic film in the support by vacuum rotary evaporation at 70°C for 60 min. Then, the dried support was obtained after drying at 110°C for 3 h.

[0050] 0.45 g of [Pt(NH3)4]Cl2 was added to 15 mL of water, and the dried support from the previous step was contacted at 40°C for 2 h. After suction filtration, the Al2O3 composite support-1 containing Pt and Co precursors was dried at 80°C to obtain the Al2O3 composite support-1 containing Pt and Co precursors.

[0051] Hydrogen and nitrogen mixed gas (V H2 :V N2 =1:10) was introduced, and the Al2O3 composite support-1 containing Pt and Co precursors was reduced at a temperature rising rate of 6°C / min to a target temperature of 320°C for 1 h to obtain the Pt–Co / Al2O3 catalyst Cat-2 Comparative Example 1 The difference between the preparation method of the catalyst Cat-1 in Comparative Example 1 and Example 1 is that the preparation step of the support precursor PreCat-B is not performed, and the remaining steps are the same. Specifically: A carrier precursor PreCat-A was prepared in the same manner as in Example 1.

[0052] The preparation steps of the carrier precursor PreCat-C: 10 g of F127 was weighed and dissolved in 90 g of deionized water, stirred at 70°C for 3 h, and then 5 g of silica was added under stirring at 600 rpm to form a uniform mixture. The dried carrier precursor PreCat-A was uniformly spread on a 50 cm 2 The uniform mixture was sprayed (11 mL / min) onto the surface of the carrier precursor PreCat-A on a rotating disc (50 rpm) using a peristaltic pump, and after completion, dried at 50°C for 12 h to obtain the carrier precursor PreCat-C-2.

[0053] Next, the carrier precursor PreCat-C-2 was subjected to the preparation of the Al2O3 carrier, the loading of the promoter metal and the active metal in the same processing steps as in Example 1 to obtain the catalyst Cat-3.

[0054] Comparative Example 2: Comparative Example 2 differs from Example 1 in that no silica was added in the preparation step of the carrier precursor PreCat-C, and the remaining steps were the same, to obtain the catalyst Cat-4.

[0055] Comparative Example 3: Comparative Example 3 differs from Example 1 in that no preparation step of the carrier precursor PreCat-C was performed, and the remaining steps were the same, specifically: A carrier precursor PreCat-B was prepared in the same manner as in Example 1.

[0056] The carrier precursor PreCat-B was calcined at 540°C for 3 h under air atmosphere, and after calcination, was rapidly immersed in 1M nitric acid and then washed with water until neutral, and dried at 110°C to obtain the Al2O3 carrier. Next, the Al2O3 carrier was subjected to the loading of the promoter metal and the active metal in the same processing steps as in the preparation of the catalyst Cat-1 in Example 1 to obtain the catalyst Cat-5.

[0057] Comparative Example 4: Comparative Example 4 differs from Example 1 in that no dimethyl fumarate was added in the loading step of the promoter metal and the active metal, and the remaining steps were the same, to obtain the catalyst Cat-6.

[0058] Comparative Example 5: Comparative Example 5 differs from Example 1 in that no azobisisobutyronitrile was added in the loading step of the promoter metal and the active metal, and the remaining steps were the same, to obtain the catalyst Cat-7.

[0059] Comparative Example 6: The difference between Comparative Example 6 and Example 1 is that no cobalt acetate is added in the step of loading the promoter metal and the active metal, and the rest of the steps are the same, to obtain the catalyst Cat-8.

[0060] Comparative Example 7: The difference between Comparative Example 7 and Example 1 is that cobalt acetate is replaced by an equimolar amount of copper acetate in the step of loading the promoter metal and the active metal, and the rest of the steps are the same, to obtain the catalyst Cat-9.

[0061] Example 3 Fill 10 g of any one of the Pt-Co / Al2O3 catalysts Cat 1-9 in a 30 ml fixed bed, add 10% of the methanol to the raw material mass of o-nitroanisole to configure a raw material liquid, pump the raw material liquid into the fixed bed, replace three times with nitrogen, and then replace once with hydrogen. After the hydrogen replaces the gas therein, adjust the hydrogen pressure to 1.8-2 MPa. The reaction conditions are as follows: mass space velocity 1.2 g / g*hr (raw material mass flow rate / catalyst mass), hydrogen ratio 30 (volume ratio), and temperature 80°C. The hydrogenated liquid at the outlet of the fixed bed is subjected to rectification to obtain o-anisidine. HPLC detection is performed, and the o-nitroanisole conversion rate A1% and the o-anisidine yield B1% are recorded for a continuous operation of 72 h. The results are shown in Table 1: Table 1

[0062] Example 4 When the continuous operation in the manner of Example 3 is performed for 800 h, the o-nitroanisole conversion rate A2% and the o-anisidine yield B2% are detected, and the results are shown in Table 2: Table 2

[0063] Example 5 In the same manner as in Example 3, 10 g of any one of the Pt-Co / Al2O3 catalysts Cat 1-9 is filled in a 30 ml fixed bed, 10% of the methanol is added to the raw material mass of o-nitroanisole to configure a raw material liquid, the raw material liquid is pumped into the fixed bed, three times of replacement with nitrogen are performed, and then one time of replacement with hydrogen is performed. After the hydrogen replaces the gas therein, the hydrogen pressure is adjusted to 1.8-2 MPa. The reaction conditions are as follows: mass space velocity 1.2 g / g*hr (raw material mass flow rate / catalyst mass), hydrogen ratio 30 (volume ratio), and temperature 80°C. The hydrogenated liquid at the outlet of the fixed bed is subjected to rectification to obtain o-anisidine. HPLC detection is performed, and when the o-anisidine yield % is less than 80% of the o-anisidine yield (i.e., B1) when the operation is performed for 72 h, the deactivated catalyst is recorded, and the deactivated catalyst numbers are Cat-1D-Cat-9D.

[0064] The deactivated catalysts Cat-1D~Cat-9D were heated to 380℃ under air atmosphere for 2h, cooled to 40℃, and then replaced by hydrogen and nitrogen mixed gas (V H2 :V N2 =1:9) for 2h to perform secondary activation, to obtain the activated catalysts Cat-1R~Cat-9R, as shown in Table 3: Table 3

[0065] Example 6 In the manner of Example 3, but the catalyst was replaced by any of the catalysts Cat1R~9R, and the continuous operation was performed for 800h, and the conversion rate of o-nitroanisole A3%, and the yield of o-aminophenyl methyl ether B3% were detected, as shown in Table 4: Table 4

[0066] The catalysts of the present application are constructed by layer-by-layer coating of P123, F127 and silica to form a multi-layer organic-inorganic composite interface, and after calcination and acid treatment, a surface functionalized Al2O3 carrier is formed. This hierarchical construction can improve the structural stability and metal dispersion of the carrier, especially beneficial to the dispersion of the metal in the process of high-temperature secondary activation. In the process of loading the auxiliary metal Co, the ligand-assisted organic complex film regulation strategy is adopted to anchor Co and Pt on the surface of the carrier in a highly dispersed state, effectively avoiding sintering and agglomeration at high temperature. In the high-temperature air atmosphere and high-temperature hydrogen atmosphere, the agglomeration of the auxiliary metal and the active metal can be prevented, and the particle size is prevented from becoming large.

[0067] Therefore, as shown in Table 4, the Pt-Co / Al2O3 catalysts obtained in Example 1 and Example 2 of the present application can still maintain good metal dispersion and pore structure stability after secondary activation, thereby ensuring their catalytic activity and cycle stability in subsequent reactions. In the case of continuous operation for up to 850h, the yield of o-aminophenyl methyl ether is still higher than 98%, and the overall process not only improves the initial performance, but also ensures that the performance after secondary activation remains good. The catalysts of the present application have excellent durability and regenerability.

[0068] The methods of the present application have been described by way of preferred embodiments, and modifications or suitable variations and adaptations of the methods and applications described herein can be made by those skilled in the art in the light of the content, spirit and scope of the present application, to implement and apply the present technology. Those skilled in the art can make appropriate modifications to the process parameters based on the content herein to implement. It is particularly important to note that all such obvious substitutions and modifications are within the scope of the present application.

Claims

1. A method for preparing a catalyst, comprising: S1: mixing Al2O3 and a P123 solution, drying to obtain a first carrier precursor; S2: configuring a mixed solution of P123 and F127, mixing with the first carrier precursor, and drying to obtain a second carrier precursor; S3: mixing a F127 solution, silica, and the second carrier precursor to obtain a third carrier precursor; S4: calcining the third carrier precursor under an air atmosphere to obtain an Al2O3 carrier; S5: mixing a cobalt salt, an alcohol, dimethyl fumarate, and azobisisobutyronitrile, adding the Al2O3 carrier, and drying to obtain a dried carrier; S6: mixing a platinum salt and water, mixing with the carrier, and drying to obtain an Al2O3 composite carrier containing a Pt and Co precursor; S7: reducing the Al2O3 composite carrier containing the Pt and Co precursor under a mixed atmosphere of hydrogen and an inert gas by programmed temperature rising to obtain a Pt-Co / Al2O3 catalyst.

2. The process for the preparation of the catalyst according to claim 1, characterized in that, In the S1 step, the Al2O3 is selected from any one or mixture of γ-Al2O3 or α-Al2O3; and / or, in the S1 step, the P123 solution is a P123 aqueous solution; and / or, in the S1 step, the mass concentration of the P123 aqueous solution is 3-5 wt%; and / or, in the S1 step, the mass of Al2O3 added per 1 L of P123 solution is 80-120 g; and / or, in the S1 step, the drying temperature is 50-70°C; and / or, in the S1 step, the drying time is 5-7 h.

3. A process for the preparation of a catalyst according to any one of claims 1 or 2, characterized in that, In the S2 step, the mass concentration of P123 in the mixed solution is 2-4 wt%; and / or, in the S2 step, the mass concentration of F127 in the mixed solution is 2-4 wt%; and / or, in the S2 step, the drying temperature is 50-70°C; and / or, in the S2 step, the drying time is 4-8 h.

4. Process for the preparation of a catalyst according to any one of claims 1 to 3, characterized in that, In the S3 step, the F127 solution is a F127 aqueous solution; and / or, in the S3 step, the mass fraction of the F127 aqueous solution is 8-12 wt%; and / or, in the S3 step, the mass of silica added per 1 L of F127 solution is 48-55 g.

5. A process for the preparation of the catalyst according to any one of claims 1 to 4, characterized in that, In the S4 step, the calcination temperature is 550-650°C; and / or, in the S4 step, after calcination, the Al2O3 carrier is obtained by further acid soaking; and / or, the acid is selected from any one of hydrochloric acid, nitric acid, and sulfuric acid; and / or, the concentration of the acid is 0.8-1.2 M; and / or, in the S4 step, the drying temperature is 100-120°C; and / or, in the S4 step, after acid soaking, the Al2O3 carrier is obtained by further water washing.

6. A process for the preparation of the catalyst according to any one of claims 1 to 5, characterized in that, The cobalt salt in the S5 step is selected from any one or mixture of cobalt chloride, cobalt nitrate, and cobalt acetate; and / or, the molar amount of the cobalt salt added in the S5 step is 300-400 mmol per 1 L of alcohol; and / or, the mass of dimethyl fumarate added in the S5 step is 30-35 g per 1 L of alcohol; and / or, the mass of azobisisobutyronitrile added in the S5 step is 2-4 g per 1 L of alcohol; and / or, the alcohol in the S5 step is selected from any one or mixture of methanol, ethanol, and isopropanol.

7. A process for the preparation of the catalyst according to any one of claims 1 to 6, characterized in that, The mass of the platinum salt added in the S6 step is 30-35 g per 1 L of water; and / or, the drying temperature in the S6 step is 60-80℃; and / or, the platinum salt in the S6 step is selected from any one or mixture of platinum chloride, platinum nitrate, and dichlorotetraamine platinum.

8. A process for the preparation of the catalyst according to any one of claims 1 to 7, characterized in that, In the S7 step, the mixed volume ratio of hydrogen and nitrogen is (1-3):20; and / or, the temperature programming mode in the S7 step is to increase the temperature to 270-360℃ at a rate of 2-4℃ / min.

9. A Pt-Co / Al2O3 catalyst prepared by the method of any one of claims 1-8.

10. Use of the Pt-Co / Al2O3 catalyst of claim 9 in the hydrogenation of o-nitroanisole to prepare o-aminophenyl methyl ether.

Images