Nitrogen and fluorine co-doped titanium dioxide loaded palladium-zirconium bimetallic catalyst as well as preparation and application thereof

Abstract

The invention discloses a nitrogen-fluorine co-doped titanium dioxide loaded palladium-zirconium bimetallic catalyst as well as preparation and application of the nitrogen-fluorine co-doped titanium dioxide loaded palladium-zirconium bimetallic catalyst. The preparation method of the catalyst comprises the following steps: (1) preparing a fluorine-nitrogen co-doped titanium dioxide carrier; (2) preparing a precursor solution of palladium and zirconium; (3) mixing the fluorine-nitrogen co-doped titanium dioxide carrier with deionized water, stirring to form uniform slurry, sequentially adding the precursor solution of palladium and zirconium, adding a dispersing agent, stirring stably, heating and stirring, adjusting the pH value to be greater than 10.0, and continuously stirring for 1-2 hours; and carrying out suction filtration, washing and vacuum drying on the suspension, and reducing in an H2 atmosphere to obtain the catalyst. The invention provides the application of the nitrogen-fluorine co-doped titanium dioxide loaded palladium-zirconium bimetallic catalyst in synthesis of TAIW through HBIW continuous hydrogenolysis debenzylation reaction, the nitrogen-fluorine co-doped titanium dioxide loaded palladium-zirconium bimetallic catalyst has high reaction activity, yield and stability, meanwhile, the usage amount of precious metal palladium is reduced, and the production cost can be effectively reduced.

Description

(I) Technical field

[0001] The invention relates to a nitrogen-fluorine co-doped titanium dioxide-supported palladium-zirconium bimetallic catalyst, a preparation method thereof, and an application thereof in a CN hydrogenolysis reaction. (II) Background technology

[0002] The CN bond is one of the most common inert bonds in organic compounds. 2 The leaving ability of the group is poor, so the cleavage of the CN bond, especially the Csp 2 -N bonds remain one of the great challenges in chemical transformations. In the fields of organic synthesis, pharmaceuticals and the synthesis of energetic substances, benzyl groups are often used to protect heterocyclic nitrogen, which is then deprotected or debenzylated.

[0003] Catalytic hydrogenolysis is one of the most popular methods for removing benzyl groups from benzylamine compounds. It has the characteristics of mild conditions (room temperature and normal pressure), high conversion rate, and clean products, and has been widely used in the fine chemical industry. In the catalytic N-benzyl hydrogenolysis debenzylation reaction, heterogeneous supported palladium catalysts are the most widely used in the catalytic N-benzyl hydrogenolysis debenzylation reaction. However, some major problems often arise in practical applications, such as low yields of certain special debenzylation reactions, high precious metal loading and dosage, poor stability, and side reactions. In addition, the N-benzyl hydrogenolysis product is a strongly alkaline amine, which will deactivate the loaded precious metal catalyst, so it is necessary to increase the amount of catalyst or add acid to complete the reaction.

[0004] In recent years, many scientists have conducted extensive research on carrier modification and active component modification, such as forming a bimetallic, metal alloy or mixed metal oxide with the active phase. Using transition metals as metal promoters to modify palladium-based catalysts is an effective way to reduce the palladium content and improve catalytic performance. 2 Doping with nitrogen, sulfur, fluorine and carbon impurities has also been widely used to modify supported catalysts. However, there is little research on these for CN hydrogenolysis. (III) Summary of the invention

[0005] The first technical problem to be solved by the present invention is to provide a method for preparing a nitrogen-fluorine co-doped titanium dioxide-supported palladium-zirconium bimetallic catalyst.

[0006] The second technical problem to be solved by the present invention is to provide a nitrogen-fluorine co-doped titanium dioxide supported palladium-zirconium bimetallic catalyst.

[0007] The third technical problem of the present invention is to provide the application of the nitrogen-fluorine co-doped titanium dioxide supported palladium-zirconium bimetallic catalyst in CN hydrogenolysis reaction.

[0008] In order to solve the above technical problems, the present invention adopts the following technical solutions:

[0009] In a first aspect, the present invention provides a method for preparing a nitrogen-fluorine co-doped titanium dioxide-supported palladium-zirconium bimetallic catalyst, the preparation method being as follows:

[0010] (1) First, an appropriate amount of ammonium fluoride is added to a mixed solvent of ethanol and deionized water as a source of nitrogen and fluorine, and an appropriate amount of acidic solution is added to adjust the pH value of the solution to 4-5 to shorten the gelation time and generate a transparent solution. Under continuous magnetic stirring, an appropriate amount of titanium-containing organic matter is added to the solution, and the mixture is stirred for 2-4 hours to form a transparent and uniform mixture, which is then aged at room temperature for 12-24 hours until a transparent gel is formed. After that, the obtained gel is placed in a vacuum drying oven at 60-90° C. for 8-12 hours, and then ground with an agate mortar to obtain a dry gel powder. Finally, the dry gel powder is placed in a muffle furnace and calcined at 200-500° C. for 2-4 hours, and then cooled to room temperature to obtain a fluorine-nitrogen co-doped titanium dioxide carrier, which is denoted as TiO 2 -x%N,F, where x%=n 氟化铵 / n Ti ×100%=2-4%, where n Ti It refers to the number of moles of Ti contained in titanium-containing organic matter;

[0011] (2) Weighing a certain amount of a palladium-containing compound and a zirconium-containing compound and dissolving them in an appropriate amount of deionized water to prepare palladium and zirconium precursor solutions, respectively;

[0012] (3) taking a certain amount of the fluorine-nitrogen co-doped titanium dioxide carrier prepared in step (1) and mixing it with deionized water, stirring to form a uniform slurry, and then adding the palladium and zirconium precursor solutions obtained in step (2) in sequence, and adding a dispersant to stir stably, heating to 60-80° C. and stirring for 4-6 hours; slowly adding an aqueous solution of an alkaline substance to the above suspension, adjusting the pH value to greater than 10.0, and continuing to stir for 1-2 hours; filtering the above suspension, and washing with deionized water until the pH of the filtrate is neutral, and the obtained sample is vacuum dried, and then heated in H 2 Reduction under atmosphere can obtain the desired catalyst;

[0013] The theoretical loading amount of Pd in ​​the nitrogen-fluorine co-doped titanium dioxide supported palladium-zirconium bimetallic catalyst is 5-10%, and the theoretical loading amount of Pd is m Pd / (m Pd +m ZrO2 +m 氮氟改性二氧化钛载体 )×100%, theoretical loading of Zr=m Zr / (m Pd +m ZrO2 +m 氮氟改性二氧化钛载体)×100%, the molar ratio of palladium to zirconium is 7:(1~3), where m Pd Represents the mass of palladium contained in the palladium precursor solution, m ZrO2 Represents ZrO calculated based on the mass of Zr contained in the zirconium precursor solution 2 quality.

[0014] Preferably, in step (1), the titanium-containing organic matter is at least one of tetraethyl titanate, tetraisopropyl titanate, and tetrabutyl titanate.

[0015] Preferably, in step (1), the volume ratio of the titanium-containing organic matter to ethanol and water is 2-10:50:2-10.

[0016] Preferably, in step (1), the acidic solution is a 5-10 wt % acetic acid or hydrochloric acid solution.

[0017] Preferably, in step (1), the calcination temperature is 300-400°C, more preferably 400°C.

[0018] Preferably, in step (2), the palladium compound is at least one of palladium chloride, sodium tetrachloropalladate, palladium acetate and palladium nitrate.

[0019] Preferably, in step (2), the zirconium compound is at least one of zirconium chloride, zirconium nitrate, zirconium oxychloride, zirconium acetate and zirconium n-propoxide.

[0020] Preferably, in step (2), the dispersant is at least one of polyethylene glycol, polyvinyl pyrrolidone and ethylenediamine. The amount of the dispersant is 5-20% of the mass of the catalyst, the mass of the catalyst = m Pd +m ZrO2 +m 氮氟改性二氧化钛载体 .

[0021] Preferably, in step (3), the aqueous solution of the alkaline substance is 5-10 wt % ammonia water or NaOH solution.

[0022] Preferably, in step (3), the vacuum drying temperature is 80-110° C., and the vacuum drying time is 8-24 h.

[0023] Preferably, in step (3), the reduction condition is 100-400° C. for 1-4 h in a hydrogen atmosphere.

[0024] In a second aspect, the present invention provides a nitrogen-fluorine co-doped titanium dioxide-supported palladium-zirconium bimetallic catalyst prepared according to the preparation method described in the first aspect.

[0025] In a third aspect, the present invention provides an application of the nitrogen-fluorine co-doped titanium dioxide-supported palladium-zirconium bimetallic catalyst in the continuous hydrogenolysis debenzylation reaction of hexabenzylhexaazaisowurtzitane (HBIW) to synthesize TAIW.

[0026] The application comprises the following specific steps:

[0027] (1) The first step of hydrogenolysis reaction uses HBIW as raw material (hereinafter referred to as HBIW hydrogenolysis reaction), and the specific operation process is as follows: HBIW, DMF, PhBr, nitrogen-fluorine co-doped titanium dioxide supported palladium-zirconium bimetallic catalyst and Ac 2 O are sequentially added into a reactor, and a continuous hydrogenation reaction is first carried out at 25-40° C., 0.4-0.6 MPa hydrogen pressure and stirring conditions for 12-24 hours, the obtained reaction liquid is filtered to remove the filtrate, and the filter cake is dried to obtain a solid containing the target product TADBIW and the catalyst; wherein, in the calculation of the yield of the first step, the yield = (mass of gray-white solid-amount of catalyst) / amount of HBIW input;

[0028] (2) The second step hydrogenolysis reaction uses TADBIW as a raw material (hereinafter referred to as TADBIW hydrogenolysis reaction), and the specific steps are as follows: the solid containing TADBIW and the catalyst obtained by the first step hydrogenolysis reaction is added to the reactor together with an appropriate amount of acetic acid, and after acid washing at 60-70°C for 1-4 hours, nitrogen-fluorine co-doped titanium dioxide supported palladium-zirconium bimetallic catalyst and deionized water are added in sequence, and then continuously hydrogenated for 12-24 hours at 40-70°C, 1.5-3MPa hydrogen pressure and stirring conditions, and then filtered and washed with acetic acid. The obtained black solid is the catalyst, and the desired product TAIW is dissolved in the filtrate. The second step hydrogenation product is quantitatively analyzed by liquid chromatography.

[0029] Preferably, in step (1), HBIW, DMF, PhBr, nitrogen-fluorine co-doped titanium dioxide supported palladium-zirconium bimetallic catalyst and Ac 2 The feed ratio of O is 15g:127mL:0.3mL:0.2g:20mL.

[0030] Preferably, in step (2), the feed ratio of the solid containing TADBIW and the catalyst, acetic acid, nitrogen-fluorine co-doped titanium dioxide supported palladium-zirconium bimetallic catalyst, and deionized water is 15 g:127 mL:0.2 g:18 mL, and the mass of the solid containing TADBIW and the catalyst is based on the mass of HBIW required for its preparation.

[0031] Compared with the prior art, the beneficial effects of the present invention are as follows:

[0032] (1) The catalyst prepared in the present invention is in TiO 2The N and F dopants doped in the lattice play a synergistic role, including a larger surface area, higher anatase crystallinity, and enhanced acidic sites, which are beneficial to increase the catalytic activity.

[0033] (2) The catalyst prepared by the present invention introduces transition metal zirconium. The addition of Zr can form small-sized, electron-rich palladium nanoparticles (Pd NPs). The formation of well-dispersed and small-volume PdNPs and the electronic effect between Pd and Zr jointly promote the enhancement of the hydrogenolysis activity of the two-component catalyst. At the same time, a dispersant is added during the preparation process to enhance the interaction between palladium and zirconium, so that the active component palladium after reduction can be evenly dispersed on the surface, making the synergistic effect between the metals stronger and improving the activity of the catalyst.

[0034] (3) The catalyst used in the present invention is easy to prepare.

[0035] (4) The present invention applies the prepared catalyst to the continuous hydrogenolysis debenzylation reaction of hexabenzylhexaazaisowurtzitane (HBIW), which has high reaction activity, yield and stability, while reducing the use of precious metal palladium, which can effectively reduce production costs. (IV) Description of the drawings

[0036] Figure 1 Preparation of Pd for Example 2 7 Zr 2 / TiO 2 -XRD pattern of 3%N,F catalyst.

[0037] Figure 2 Preparation of Pd for Example 2 7 Zr 2 / TiO 2 -3% N,F catalyst H 2 -TPR diagram. (V) Specific implementation methods

[0038] The present invention is further described below by means of specific embodiments, but the protection scope of the present invention is not limited thereto.

[0039] The raw materials and reagents used in the present invention are commercially available.

[0040] Example 1

[0041] Preparation method of nitrogen-fluorine co-doped titanium dioxide supported palladium-zirconium bimetallic catalyst:

[0042] (1) First, 0.0163 g of ammonium fluoride was added to a mixture of 50 mL of ethanol and 5 mL of deionized water, and an appropriate amount of acetic acid solution was added to adjust the pH value of the solution to 4-5. Then, 5 mL of tetrabutyl titanate was added to the solution under continuous magnetic stirring, and the mixture was stirred for 2 h to form a transparent and uniform mixture, which was aged at room temperature for 12 h until a transparent gel was formed. After that, the obtained gel was placed in a vacuum drying oven at 80 ° C for 12 h, and then ground with an agate mortar to obtain a dry gel powder; finally, the dry gel powder was placed in a muffle furnace and calcined at 400 ° C for 2 h, and cooled to room temperature to obtain a fluorine-nitrogen co-doped titanium dioxide carrier, which was recorded as TiO 2 -3%N,F;

[0043] (2) Weighing 0.2666 g of palladium chloride and 0.0922 g of zirconium nitrate pentahydrate, respectively, and dissolving them in an appropriate amount of deionized water to prepare palladium and zirconium precursor solutions, respectively;

[0044] (3) Weigh 1.8135 g of titanium dioxide carrier and 80 mL of deionized water, mix, stir to form a uniform slurry, then add the palladium and zirconium precursor solutions obtained in step (1) in sequence, and add 0.2000 g of polyvinyl pyrrolidone to stir stably, heat to 70° C. and keep stirring for 4 h; slowly add 5% sodium hydroxide solution to the above suspension, adjust the solution pH to greater than 10.0, and continue stirring for 2 h; filter the above suspension, and wash with deionized water until the pH of the filtrate is neutral. The obtained sample is vacuum dried at 110° C. for 12 h, and then heated to 70° C. for 4 h. 2 8% Pd-1% Zr / TiO was obtained by reduction at 150℃ for 2h under atmosphere. 2 -3% N, F two-component catalyst.

[0045] Application of catalyst in continuous hydrogenolysis of benzylhexaazaisowurtzitane (HBIW):

[0046] (1) HBIW hydrogenolysis reaction: 15.00 g HBIW, 127 mL DMF, 0.3 mL PhBr, 0.2 g catalyst, 20 mL Ac 2 O were added into the reactor in sequence, and the continuous hydrogenation reaction was first carried out at 25°C, 0.5MPa hydrogen pressure and stirring conditions for 8h, and then the temperature was raised to 40°C and the reaction was continued for 16h. The obtained reaction liquid was filtered to remove the filtrate, and the filter cake was placed in a blast oven at 110°C and dried for 2h to obtain an off-white solid containing the target product TADBIW and the catalyst. The TADBIW yield after the first step HBIW hydrogenolysis reaction was calculated using the weighed mass;

[0047] (2) TADBIW hydrogenolysis reaction: The dried filter cake from the first step of hydrogenolysis reaction was weighed and added to the reactor together with 127 mL of acetic acid. After acid washing at 60°C for 2 h to fully dissolve the solid product from the first step, 0.20 g of catalyst and 18 ml of deionized water were added in sequence. Then, continuous hydrogenation reaction was carried out at 60°C, 1.5 MPa hydrogen pressure and stirring for 24 h. After suction filtration and washing with acetic acid, the obtained black solid was the catalyst, and the desired product TAIW was dissolved in the filtrate. The second step hydrogenation product was quantitatively analyzed by liquid chromatography.

[0048] Example 2

[0049] Preparation method of nitrogen-fluorine co-doped titanium dioxide supported palladium-zirconium bimetallic catalyst:

[0050] (1) First, 0.0163 g of ammonium fluoride was added to a mixture of 50 mL of ethanol and 5 mL of deionized water, and an appropriate amount of acetic acid solution was added to adjust the pH value of the solution to 4-5. Then, 5 mL of tetrabutyl titanate was added to the solution under continuous magnetic stirring, and the mixture was stirred for 2 h to form a transparent and uniform mixture, which was aged at room temperature for 12 h until a transparent gel was formed. After that, the obtained gel was placed in a vacuum drying oven at 80 ° C for 12 h, and then ground with an agate mortar to obtain a dry gel powder; finally, the dry gel powder was placed in a muffle furnace and calcined at 400 ° C for 2 h, and cooled to room temperature to obtain a fluorine-nitrogen co-doped titanium dioxide carrier, which was recorded as TiO 2 -3%N,F;

[0051] (2) Weighing 0.2666 g of palladium chloride and 0.1844 g of zirconium nitrate pentahydrate, respectively, and dissolving them in an appropriate amount of deionized water to prepare palladium and zirconium precursor solutions, respectively;

[0052] (3) Weigh 1.7870 g of titanium dioxide carrier and 80 mL of deionized water, mix, stir to form a uniform slurry, then add the palladium and zirconium precursor solutions obtained in step (1) in sequence, and add 0.2000 g of polyvinyl pyrrolidone to stir stably, heat to 70° C. and keep stirring for 4 h; slowly add 5% sodium hydroxide solution to the above suspension, adjust the solution pH to greater than 10.0, and continue stirring for 2 h; filter the above suspension, and wash with deionized water until the pH of the filtrate is neutral. The obtained sample is vacuum dried at 110° C. for 12 h, and then heated to 70° C. for 4 h. 2 Pd was obtained by reduction at 150℃ for 2h under atmosphere. 7 Zr 2 / TiO 2 -3% N, F two-component catalyst.

[0053] The operation and parameters of the continuous hydrogenolysis debenzylation reaction of hexabenzylhexaazaisowurtzitane (HBIW) in this example are the same as those in Example 1.

[0054] Example 3

[0055] Preparation method of nitrogen-fluorine co-doped titanium dioxide supported palladium-zirconium bimetallic catalyst:

[0056] (1) First, 0.0163 g of ammonium fluoride was added to a mixture of 50 mL of ethanol and 5 mL of deionized water, and an appropriate amount of acetic acid solution was added to adjust the pH value of the solution to 4-5. Then, 5 mL of tetrabutyl titanate was added to the solution under continuous magnetic stirring, and the mixture was stirred for 2 h to form a transparent and uniform mixture, which was aged at room temperature for 12 h until a transparent gel was formed. After that, the obtained gel was placed in a vacuum drying oven at 80 ° C for 12 h, and then ground with an agate mortar to obtain a dry gel powder; finally, the dry gel powder was placed in a muffle furnace and calcined at 400 ° C for 2 h, and cooled to room temperature to obtain a fluorine-nitrogen co-doped titanium dioxide carrier, which was recorded as TiO 2 -3%N,F;

[0057] (2) Weighing 0.2666 g of palladium chloride and 0.2767 g of zirconium nitrate pentahydrate, respectively, and dissolving them in an appropriate amount of deionized water to prepare palladium and zirconium precursor solutions, respectively;

[0058] (3) Weigh 1.7606 g of titanium dioxide carrier and 80 mL of deionized water, mix, stir to form a uniform slurry, add the palladium and zirconium precursor solutions obtained in step (1) in sequence, and add 0.2000 g of polyvinyl pyrrolidone to stir stably, heat to 70° C. and keep stirring for 4 h; slowly add 5% sodium hydroxide solution to the above suspension, adjust the solution pH to greater than 10.0, and continue stirring for 2 h; filter the above suspension, and wash with deionized water until the pH of the filtrate is neutral. The obtained sample is vacuum dried at 110° C. for 12 h, and then heated to 70° C. for 4 h. 2 Pd was obtained by reduction at 150℃ for 2h under atmosphere. 7 Zr 3 / TiO 2 -3% N, F two-component catalyst.

[0059] The operation and parameters of the continuous hydrogenolysis debenzylation reaction of hexabenzylhexaazaisowurtzitane (HBIW) in this example are the same as those in Example 1.

[0060] Example 4

[0061] Preparation method of nitrogen-fluorine co-doped titanium dioxide supported palladium-zirconium bimetallic catalyst:

[0062] (1) First, 0.0163 g of ammonium fluoride was added to a mixture of 50 mL of ethanol and 5 mL of deionized water, and an appropriate amount of acetic acid solution was added to adjust the pH value of the solution to 4-5. Then, 5 mL of tetrabutyl titanate was added to the solution under continuous magnetic stirring, and the mixture was stirred for 2 h to form a transparent and uniform mixture, which was aged at room temperature for 12 h until a transparent gel was formed. After that, the obtained gel was placed in a vacuum drying oven at 80 ° C for 12 h, and then ground with an agate mortar to obtain a dry gel powder; finally, the dry gel powder was placed in a muffle furnace and calcined at 400 ° C for 2 h, and cooled to room temperature to obtain a fluorine-nitrogen co-doped titanium dioxide carrier, which was recorded as TiO 2 -3%N,F;

[0063] (1) Weighing 0.2666 g of palladium chloride and 0.3690 g of zirconium nitrate pentahydrate, respectively, and dissolving them in an appropriate amount of deionized water to prepare palladium and zirconium precursor solutions, respectively;

[0064] (2) Weigh 1.7341 g of titanium dioxide carrier and 80 mL of deionized water, mix, stir to form a uniform slurry, add the palladium and zirconium precursor solutions obtained in step (1) in sequence, and add 0.2000 g of polyvinyl pyrrolidone to stir stably, heat to 70° C. and keep stirring for 4 h; slowly add 5% sodium hydroxide solution to the above suspension, adjust the solution pH to greater than 10.0, and continue stirring for 2 h; filter the above suspension, and wash with deionized water until the pH of the filtrate is neutral. The obtained sample is vacuum dried at 110° C. for 12 h, and then heated to 70° C. for 4 h. 2 Pd was obtained by reduction at 150℃ for 2h under atmosphere. 7 Zr 4 / 3%N,F two-component catalyst.

[0065] The operation and parameters of the continuous hydrogenolysis debenzylation reaction of hexabenzylhexaazaisowurtzitane (HBIW) in this example are the same as those in Example 1.

[0066] Example 5

[0067] Preparation method of nitrogen-fluorine co-doped titanium dioxide supported palladium-zirconium bimetallic catalyst:

[0068] (1) First, 0.0163 g of ammonium fluoride was added to a mixture of 50 mL of ethanol and 5 mL of deionized water, and an appropriate amount of acetic acid solution was added to adjust the pH value of the solution to 4-5. Then, 5 mL of tetrabutyl titanate was added to the solution under continuous magnetic stirring, and the mixture was stirred for 2 h to form a transparent and uniform mixture, which was aged at room temperature for 12 h until a transparent gel was formed. After that, the obtained gel was placed in a vacuum drying oven at 80 ° C for 12 h, and then ground with an agate mortar to obtain a dry gel powder; finally, the dry gel powder was placed in a muffle furnace and calcined at 400 ° C for 2 h, and cooled to room temperature to obtain a fluorine-nitrogen co-doped titanium dioxide carrier, which was recorded as TiO 2 -3%N,F;

[0069] (2) Weighing 0.2666 g of palladium chloride and 0.4612 g of zirconium nitrate pentahydrate, respectively, and dissolving them in an appropriate amount of deionized water to prepare palladium and zirconium precursor solutions, respectively;

[0070] (3) Weigh 1.7076 g of titanium dioxide carrier and 80 mL of deionized water, mix, stir to form a uniform slurry, add the palladium and zirconium precursor solutions obtained in step (1) in sequence, and add 0.2000 g of polyvinyl pyrrolidone to stir stably, heat to 70° C. and keep stirring for 4 h; slowly add 5% sodium hydroxide solution to the above suspension, adjust the solution pH to greater than 10.0, and continue stirring for 2 h; filter the above suspension, and wash with deionized water until the pH of the filtrate is neutral. The obtained sample is vacuum dried at 110° C. for 12 h, and then heated to 70° C. for 4 h. 2 Pd was obtained by reduction at 150℃ for 2h under atmosphere. 7 Zr 5 / TiO 2 -3% N, F two-component catalyst.

[0071] The operation and parameters of the continuous hydrogenolysis debenzylation reaction of hexabenzylhexaazaisowurtzitane (HBIW) in this example are the same as those in Example 1.

[0072] Example 6

[0073] Preparation method of nitrogen-fluorine co-doped titanium dioxide supported palladium-zirconium bimetallic catalyst:

[0074] (1) First, 0.0054 g of ammonium fluoride was added to a mixture of 50 mL of ethanol and 5 mL of deionized water, and an appropriate amount of acetic acid solution was added to adjust the pH value of the solution to 4-5. Then, 5 mL of tetrabutyl titanate was added to the solution under continuous magnetic stirring, and the mixture was stirred for 2 h to form a transparent and uniform mixture, which was aged at room temperature for 12 h until a transparent gel was formed. After that, the obtained gel was placed in a vacuum drying oven at 80 ° C for 12 h, and then ground with an agate mortar to obtain a dry gel powder; finally, the dry gel powder was placed in a muffle furnace and calcined at 400 ° C for 2 h, and cooled to room temperature to obtain a fluorine-nitrogen co-doped titanium dioxide carrier, which was recorded as TiO 2 -1%N,F;

[0075] (2) Weighing 0.2666 g of palladium chloride and 0.1844 g of zirconium nitrate pentahydrate, respectively, and dissolving them in an appropriate amount of deionized water to prepare palladium and zirconium precursor solutions, respectively;

[0076] (3) Weigh 1.7870 g of titanium dioxide carrier and 80 mL of deionized water, mix, stir to form a uniform slurry, then add the palladium and zirconium precursor solutions obtained in step (1) in sequence, and add 0.2000 g of polyvinyl pyrrolidone to stir stably, heat to 70° C. and keep stirring for 4 h; slowly add 5% sodium hydroxide solution to the above suspension, adjust the solution pH to greater than 10.0, and continue stirring for 2 h; filter the above suspension, and wash with deionized water until the pH of the filtrate is neutral. The obtained sample is vacuum dried at 110° C. for 12 h, and then heated to 70° C. for 4 h. 2 Pd was obtained by reduction at 150℃ for 2h under atmosphere. 7 Zr 2 / TiO 2 -1% N, F two-component catalyst.

[0077] The operation and parameters of the continuous hydrogenolysis debenzylation of hexabenzylhexaazaisowurtzitane (HBIW) in this example are the same as those in Example 1.

[0078] Example 7

[0079] Preparation method of nitrogen-fluorine co-doped titanium dioxide supported palladium-zirconium bimetallic catalyst:

[0080] (1) First, 0.0109 g of ammonium fluoride was added to a mixture of 50 mL of ethanol and 5 mL of deionized water, and an appropriate amount of acetic acid solution was added to adjust the pH value of the solution to 4-5. Then, 5 mL of tetrabutyl titanate was added to the solution under continuous magnetic stirring, and the mixture was stirred for 2 h to form a transparent and uniform mixture, which was aged at room temperature for 12 h until a transparent gel was formed. After that, the obtained gel was placed in a vacuum drying oven at 80 ° C for 12 h, and then ground with an agate mortar to obtain a dry gel powder; finally, the dry gel powder was placed in a muffle furnace and calcined at 400 ° C for 2 h, and cooled to room temperature to obtain a fluorine-nitrogen co-doped titanium dioxide carrier, which was recorded as TiO 2 -2%N,F;

[0081] (2) Weighing 0.2666 g of palladium chloride and 0.1844 g of zirconium nitrate pentahydrate, respectively, and dissolving them in an appropriate amount of deionized water to prepare palladium and zirconium precursor solutions, respectively;

[0082] (3) Weigh 1.7870 g of titanium dioxide carrier and 80 mL of deionized water, mix, stir to form a uniform slurry, then add the palladium and zirconium precursor solutions obtained in step (1) in sequence, and add 0.2000 g of polyvinyl pyrrolidone to stir stably, heat to 70° C. and keep stirring for 4 h; slowly add 5% sodium hydroxide solution to the above suspension, adjust the solution pH to greater than 10.0, and continue stirring for 2 h; filter the above suspension, and wash with deionized water until the pH of the filtrate is neutral. The obtained sample is vacuum dried at 110° C. for 12 h, and then heated to 70° C. for 4 h. 2 Pd was obtained by reduction at 150℃ for 2h under atmosphere. 7 Zr 2 / TiO 2 -2% N, F two-component catalyst.

[0083] The operation and parameters of the continuous hydrogenolysis debenzylation reaction of hexabenzylhexaazaisowurtzitane (HBIW) in this example are the same as those in Example 1.

[0084] Example 8

[0085] Preparation method of nitrogen-fluorine co-doped titanium dioxide supported palladium-zirconium bimetallic catalyst:

[0086] (1) First, 0.0218 g of ammonium fluoride was added to a mixture of 50 mL of ethanol and 5 mL of deionized water, and an appropriate amount of acetic acid solution was added to adjust the pH value of the solution to 4-5. Then, 5 mL of tetrabutyl titanate was added to the solution under continuous magnetic stirring, and the mixture was stirred for 2 h to form a transparent and uniform mixture, which was aged at room temperature for 12 h until a transparent gel was formed. After that, the obtained gel was placed in a vacuum drying oven at 80 ° C for 12 h, and then ground with an agate mortar to obtain a dry gel powder; finally, the dry gel powder was placed in a muffle furnace and calcined at 400 ° C for 2 h, and cooled to room temperature to obtain a fluorine-nitrogen co-doped titanium dioxide carrier, which was recorded as TiO 2 -4%N,F;

[0087] (2) Weighing 0.2666 g of palladium chloride and 0.1844 g of zirconium nitrate pentahydrate, respectively, and dissolving them in an appropriate amount of deionized water to prepare palladium and zirconium precursor solutions, respectively;

[0088] (3) Weigh 1.7870 g of titanium dioxide carrier and 80 mL of deionized water, mix, stir to form a uniform slurry, then add the palladium and zirconium precursor solutions obtained in step (1) in sequence, and add 0.2000 g of polyvinyl pyrrolidone to stir stably, heat to 70° C. and keep stirring for 4 h; slowly add 5% sodium hydroxide solution to the above suspension, adjust the solution pH to greater than 10.0, and continue stirring for 2 h; filter the above suspension, and wash with deionized water until the pH of the filtrate is neutral. The obtained sample is vacuum dried at 110° C. for 12 h, and then heated to 70° C. for 4 h. 2 Pd was obtained by reduction at 150℃ for 2h under atmosphere. 7 Zr 2 / TiO 2 -4% N, F two-component catalyst.

[0089] The operation and parameters of the continuous hydrogenolysis debenzylation reaction of hexabenzylhexaazaisowurtzitane (HBIW) in this example are the same as those in Example 1.

[0090] Example 9

[0091] Preparation method of nitrogen-fluorine co-doped titanium dioxide supported palladium-zirconium bimetallic catalyst:

[0092] (1) First, 0.0272 g of ammonium fluoride was added to a mixture of 50 mL of ethanol and 5 mL of deionized water, and an appropriate amount of acetic acid solution was added to adjust the pH value of the solution to 4-5. Then, 5 mL of tetrabutyl titanate was added to the solution under continuous magnetic stirring, and the mixture was stirred for 2 h to form a transparent and uniform mixture, which was aged at room temperature for 12 h until a transparent gel was formed. After that, the obtained gel was placed in a vacuum drying oven at 80 ° C for 12 h, and then ground with an agate mortar to obtain a dry gel powder; finally, the dry gel powder was placed in a muffle furnace and calcined at 400 ° C for 2 h, and cooled to room temperature to obtain a fluorine-nitrogen co-doped titanium dioxide carrier, which was recorded as TiO 2 -5%N,F;

[0093] (2) Weighing 0.2666 g of palladium chloride and 0.1844 g of zirconium nitrate pentahydrate, respectively, and dissolving them in an appropriate amount of deionized water to prepare palladium and zirconium precursor solutions, respectively;

[0094] (3) Weigh 1.7870 g of titanium dioxide carrier and 80 mL of deionized water, mix, stir to form a uniform slurry, then add the palladium and zirconium precursor solutions obtained in step (1) in sequence, and add 0.2000 g of polyvinyl pyrrolidone to stir stably, heat to 70° C. and keep stirring for 4 h; slowly add 5% sodium hydroxide solution to the above suspension, adjust the solution pH to greater than 10.0, and continue stirring for 2 h; filter the above suspension, and wash with deionized water until the pH of the filtrate is neutral. The obtained sample is vacuum dried at 110° C. for 12 h, and then heated to 70° C. for 4 h. 2 Pd was obtained by reduction at 150℃ for 2h under atmosphere. 7 Zr 2 / TiO 2 -5% N, F two-component catalyst.

[0095] The operation and parameters of the continuous hydrogenolysis debenzylation reaction of hexabenzylhexaazaisowurtzitane (HBIW) in this example are the same as those in Example 1.

[0096] Example 10

[0097] Preparation method of nitrogen-fluorine co-doped titanium dioxide supported palladium-zirconium bimetallic catalyst:

[0098] (1) First, 0.0163 g of ammonium fluoride was added to a mixture of 50 mL of ethanol and 5 mL of deionized water, and an appropriate amount of acetic acid solution was added to adjust the pH value of the solution to 4-5. Then, 5 mL of tetrabutyl titanate was added to the solution under continuous magnetic stirring, and the mixture was stirred for 2 h to form a transparent and uniform mixture, which was aged at room temperature for 12 h until a transparent gel was formed. After that, the obtained gel was placed in a vacuum drying oven at 80 ° C for 12 h, and then ground with an agate mortar to obtain a dry gel powder; finally, the dry gel powder was placed in a muffle furnace and calcined at 400 ° C for 2 h, and cooled to room temperature to obtain a fluorine-nitrogen co-doped titanium dioxide carrier, which was recorded as TiO 2 -3%N,F;

[0099] (2) Weighing 0.2666 g of palladium chloride and 0.1844 g of zirconium nitrate pentahydrate, respectively, and dissolving them in an appropriate amount of deionized water to prepare palladium and zirconium precursor solutions, respectively;

[0100] (3) Weigh 1.7870 g of titanium dioxide carrier and 80 mL of deionized water, mix, stir to form a uniform slurry, add the palladium and zirconium precursor solutions obtained in step (1) in sequence, and add 0.2000 g of polyethylene glycol at the same time, stir to stabilize, heat to 70° C. and keep stirring for 4 h; slowly add 5% sodium hydroxide solution to the above suspension, adjust the pH value of the solution to 10.0, and continue stirring for 2 h; filter the above suspension, and wash with deionized water until the pH of the filtrate is neutral. The obtained sample is vacuum dried at 110° C. for 12 h, and then heated to 70° C. for 4 h. 2 The desired catalyst was obtained by reduction at 150 °C for 2 h under a carbonyl atmosphere.

[0101] The operation and parameters of the continuous hydrogenolysis debenzylation reaction of hexabenzylhexaazaisowurtzitane (HBIW) in this example are the same as those in Example 1.

[0102] Embodiment 11

[0103] Preparation method of nitrogen-fluorine co-doped titanium dioxide supported palladium-zirconium bimetallic catalyst:

[0104] (1) First, 0.0163 g of ammonium fluoride was added to a mixture of 50 mL of ethanol and 5 mL of deionized water, and an appropriate amount of acetic acid solution was added to adjust the pH value of the solution to 4-5. Then, 5 mL of tetrabutyl titanate was added to the solution under continuous magnetic stirring, and the mixture was stirred for 2 h to form a transparent and uniform mixture, which was aged at room temperature for 12 h until a transparent gel was formed. After that, the obtained gel was placed in a vacuum drying oven at 80 ° C for 12 h, and then ground with an agate mortar to obtain a dry gel powder; finally, the dry gel powder was placed in a muffle furnace and calcined at 400 ° C for 2 h, and cooled to room temperature to obtain a fluorine-nitrogen co-doped titanium dioxide carrier, which was recorded as TiO 2 -3%N,F;

[0105] (2) Weighing 0.2666 g of palladium chloride and 0.1844 g of zirconium nitrate pentahydrate, respectively, and dissolving them in an appropriate amount of deionized water to prepare palladium and zirconium precursor solutions, respectively;

[0106] (3) Weigh 1.7870 g of titanium dioxide carrier and 80 mL of deionized water, mix, stir to form a uniform slurry, add the palladium and zirconium precursor solutions obtained in step (1) in sequence, and add 0.2000 g of ethylenediamine at the same time, stir to stabilize, heat to 70° C. and keep stirring for 4 h; slowly add 5% sodium hydroxide solution to the above suspension, adjust the pH value of the solution to 10.0, and continue stirring for 2 h; filter the above suspension, and wash with deionized water until the pH of the filtrate is neutral. The obtained sample is vacuum dried at 110° C. for 12 h, and then heated to 70° C. for 4 h. 2 The desired two-component catalyst was obtained by reduction at 150 °C for 2 h under a carbonyl atmosphere.

[0107] The operation and parameters of the continuous hydrogenolysis debenzylation reaction of hexabenzylhexaazaisowurtzitane (HBIW) in this example are the same as those in Example 1.

[0108] Example 12

[0109] Preparation method of nitrogen-fluorine co-doped titanium dioxide supported palladium-zirconium bimetallic catalyst:

[0110] (1) First, 0.0163 g of ammonium fluoride was added to a mixture of 50 mL of ethanol and 5 mL of deionized water, and an appropriate amount of acetic acid solution was added to adjust the pH value of the solution to 4-5. Then, 5 mL of tetrabutyl titanate was added to the solution under continuous magnetic stirring, and the mixture was stirred for 2 h to form a transparent and uniform mixture, which was aged at room temperature for 12 h until a transparent gel was formed. After that, the obtained gel was placed in a vacuum drying oven at 80 ° C for 12 h, and then ground with an agate mortar to obtain a dry gel powder; finally, the dry gel powder was placed in a muffle furnace and calcined at 200 ° C for 2 h, and cooled to room temperature to obtain a fluorine-nitrogen co-doped titanium dioxide carrier, which was recorded as TiO 2 -3%N,F;

[0111] (2) Weighing 0.2666 g of palladium chloride and 0.1844 g of zirconium nitrate pentahydrate, respectively, and dissolving them in an appropriate amount of deionized water to prepare palladium and zirconium precursor solutions, respectively;

[0112] (3) Weigh 1.7870 g of titanium dioxide carrier and 80 mL of deionized water, mix, stir to form a uniform slurry, then add the palladium and zirconium precursor solutions obtained in step (1) in sequence, and add 0.2000 g of polyvinyl pyrrolidone to stir stably, heat to 70° C. and keep stirring for 4 h; slowly add 5% sodium hydroxide solution to the above suspension, adjust the solution pH to greater than 10.0, and continue stirring for 2 h; filter the above suspension, and wash with deionized water until the pH of the filtrate is neutral. The obtained sample is vacuum dried at 110° C. for 12 h, and then heated to 70° C. for 4 h. 2 Pd was obtained by reduction at 150℃ for 2h under atmosphere. 7 Zr 2 / TiO 2 -3% N, F two-component catalyst.

[0113] The operation and parameters of the continuous hydrogenolysis debenzylation of hexabenzylhexaazaisowurtzitane (HBIW) in this example are the same as those in Example 1.

[0114] Embodiment 13

[0115] Preparation method of nitrogen-fluorine co-doped titanium dioxide supported palladium-zirconium bimetallic catalyst:

[0116] (1) First, 0.0163 g of ammonium fluoride was added to a mixture of 50 mL of ethanol and 5 mL of deionized water, and an appropriate amount of acetic acid solution was added to adjust the pH value of the solution to 4-5. Then, 5 mL of tetrabutyl titanate was added to the solution under continuous magnetic stirring, and the mixture was stirred for 2 h to form a transparent and uniform mixture, which was aged at room temperature for 12 h until a transparent gel was formed. After that, the obtained gel was placed in a vacuum drying oven at 80 ° C for 12 h, and then ground with an agate mortar to obtain a dry gel powder; finally, the dry gel powder was placed in a muffle furnace and calcined at 300 ° C for 2 h, and cooled to room temperature to obtain a fluorine-nitrogen co-doped titanium dioxide carrier, which was recorded as TiO 2 -3%N,F;

[0117] (2) Weighing 0.2666 g of palladium chloride and 0.1844 g of zirconium nitrate pentahydrate, respectively, and dissolving them in an appropriate amount of deionized water to prepare palladium and zirconium precursor solutions, respectively;

[0118] (3) Weigh 1.7870 g of titanium dioxide carrier and 80 mL of deionized water, mix, stir to form a uniform slurry, then add the palladium and zirconium precursor solutions obtained in step (1) in sequence, and add 0.2000 g of polyvinyl pyrrolidone to stir stably, heat to 70° C. and keep stirring for 4 h; slowly add 5% sodium hydroxide solution to the above suspension, adjust the solution pH to greater than 10.0, and continue stirring for 2 h; filter the above suspension, and wash with deionized water until the pH of the filtrate is neutral. The obtained sample is vacuum dried at 110° C. for 12 h, and then heated to 70° C. for 4 h.2 Pd was obtained by reduction at 150℃ for 2h under atmosphere. 7 Zr 2 / TiO 2 -3% N, F two-component catalyst.

[0119] The operation and parameters of the continuous hydrogenolysis debenzylation reaction of hexabenzylhexaazaisowurtzitane (HBIW) in this example are the same as those in Example 1.

[0120] Comparative Example 1

[0121] Preparation method of nitrogen-fluorine co-doped titanium dioxide supported palladium catalyst:

[0122] (1) First, 0.0163 g of ammonium fluoride was added to a mixture of 50 mL of ethanol and 5 mL of deionized water, and an appropriate amount of acetic acid solution was added to adjust the pH value of the solution to 4-5. Then, 5 mL of tetrabutyl titanate was added to the solution under continuous magnetic stirring, and the mixture was stirred for 2 h to form a transparent and uniform mixture, which was aged at room temperature for 12 h until a transparent gel was formed. After that, the obtained gel was placed in a vacuum drying oven at 80 ° C for 12 h, and then ground with an agate mortar to obtain a dry gel powder; finally, the dry gel powder was placed in a muffle furnace and calcined at 400 ° C for 2 h, and cooled to room temperature to obtain a fluorine-nitrogen co-doped titanium dioxide carrier, which was recorded as TiO 2 -3%N,F;

[0123] (2) Weighing 0.2666 g of palladium chloride and dissolving it in an appropriate amount of deionized water to prepare a palladium precursor solution;

[0124] (3) Weigh 1.8400 g of titanium dioxide carrier and 80 mL of deionized water, mix, stir to form a uniform slurry, add the palladium and zirconium precursor solutions obtained in step (1) in sequence, and add 0.2000 g of polyvinyl pyrrolidone at the same time, stir to stabilize, heat to 70° C. and keep stirring for 4 h; slowly add 5% sodium hydroxide solution to the above suspension, adjust the pH value of the solution to 10.0, and continue stirring for 2 h; filter the above suspension, and wash with deionized water until the pH of the filtrate is neutral. The obtained sample is vacuum dried at 110° C. for 12 h, and then heated to 70° C. for 4 h. 2 The desired catalyst was obtained by reduction at 150 °C for 2 h under a carbonyl atmosphere.

[0125] The operation and parameters of the continuous hydrogenolysis debenzylation reaction of hexabenzylhexaazaisowurtzitane (HBIW) in this comparative example are the same as those in Example 1.

[0126] Table 1 Effect of the content of metal additive zirconium on the catalyst

[0127]

[0128] Comparative Example 2

[0129] Preparation method of titanium dioxide supported palladium catalyst:

[0130] (1) First, an appropriate amount of acetic acid solution was added to a mixture of 50 mL of ethanol and 5 mL of deionized water to adjust the pH value of the solution to 4-5. Then, 5 mL of tetrabutyl titanate was added to the solution under continuous magnetic stirring, and the mixture was stirred for 2 h to form a transparent and uniform mixture, which was aged at room temperature for 12 h until a transparent gel was formed. After that, the obtained gel was placed in a vacuum drying oven at 80 ° C for 12 h, and then ground with an agate mortar to obtain a dry gel powder; finally, the dry gel powder was placed in a muffle furnace and calcined at 400 ° C for 2 h, and cooled to room temperature to obtain a fluorine-nitrogen co-doped titanium dioxide carrier, which was recorded as TiO 2 ;

[0131] (2) Weighing 0.2666 g of palladium chloride and dissolving it in an appropriate amount of deionized water to prepare a palladium precursor solution;

[0132] (3) Weigh 1.8400 g of titanium dioxide carrier and 80 mL of deionized water, mix, stir to form a uniform slurry, add the palladium and zirconium precursor solutions obtained in step (1) in sequence, and add 0.2000 g of polyvinyl pyrrolidone at the same time, stir to stabilize, heat to 70° C. and keep stirring for 4 h; slowly add 5% sodium hydroxide solution to the above suspension, adjust the pH value of the solution to 10.0, and continue stirring for 2 h; filter the above suspension, and wash with deionized water until the pH of the filtrate is neutral. The obtained sample is vacuum dried at 110° C. for 12 h, and then heated to 70° C. for 4 h. 2 The desired catalyst was obtained by reduction at 150 °C for 2 h under a carbonyl atmosphere.

[0133] The operation and parameters of the continuous hydrogenolysis debenzylation reaction of hexabenzylhexaazaisowurtzitane (HBIW) in this comparative example are the same as those in Example 1.

[0134] Table 2 Effect of nitrogen and fluorine doping on catalyst

[0135]

[0136]

[0137] Comparative Example 3

[0138] Preparation method of nitrogen-fluorine co-doped titanium dioxide supported palladium-zirconium bimetallic catalyst:

[0139] (1) First, 0.0163 g of ammonium fluoride was added to a mixture of 50 mL of ethanol and 5 mL of deionized water, and an appropriate amount of acetic acid solution was added to adjust the pH value of the solution to 4-5. Then, 5 mL of tetrabutyl titanate was added to the solution under continuous magnetic stirring, and the mixture was stirred for 2 h to form a transparent and uniform mixture, which was aged at room temperature for 12 h until a transparent gel was formed. After that, the obtained gel was placed in a vacuum drying oven at 80 ° C for 12 h, and then ground with an agate mortar to obtain a dry gel powder; finally, the dry gel powder was placed in a muffle furnace and calcined at 400 ° C for 2 h, and cooled to room temperature to obtain a fluorine-nitrogen co-doped titanium dioxide carrier, which was recorded as TiO 2 -3%N,F;

[0140] (2) Weighing 0.2666 g of palladium chloride and 0.1844 g of zirconium nitrate pentahydrate, respectively, and dissolving them in an appropriate amount of deionized water to prepare palladium and zirconium precursor solutions, respectively;

[0141] (3) Weigh 1.7870 g of titanium dioxide carrier and 80 mL of deionized water, mix, stir to form a uniform slurry, add the palladium and zirconium precursor solutions obtained in step (1) in sequence, heat to 70° C. and keep stirring for 4 h; slowly add 5% sodium hydroxide solution dropwise to the above suspension, adjust the pH value of the solution to 10.0, and continue stirring for 2 h; filter the above suspension, and wash with deionized water until the pH of the filtrate is neutral. The obtained sample is vacuum dried at 110° C. for 12 h, and then heated to 40° C. for 2 h. 2 The desired catalyst was obtained by reduction at 150 °C for 2 h under a carbonyl atmosphere.

[0142] The operation and parameters of the continuous hydrogenolysis debenzylation reaction of hexabenzylhexaazaisowurtzitane (HBIW) in this comparative example are the same as those in Example 1.

[0143] Table 3 Effect of dispersant type on catalyst

[0144]

[0145] Comparative Example 4

[0146] Preparation method of nitrogen-fluorine co-doped titanium dioxide supported palladium-zirconium bimetallic catalyst:

[0147] (1) First, 0.0163 g of ammonium fluoride was added to a mixture of 50 mL of ethanol and 5 mL of deionized water, and an appropriate amount of acetic acid solution was added to adjust the pH value of the solution to 4-5. Then, 5 mL of tetrabutyl titanate was added to the solution under continuous magnetic stirring, and the mixture was stirred for 2 h to form a transparent and uniform mixture, which was aged at room temperature for 12 h until a transparent gel was formed. After that, the obtained gel was placed in a vacuum drying oven at 80 ° C for 12 h, and then ground with an agate mortar to obtain a dry gel powder; finally, the dry gel powder was placed in a muffle furnace and calcined at 500 ° C for 2 h, and cooled to room temperature to obtain a fluorine-nitrogen co-doped titanium dioxide carrier, which was recorded as TiO 2 -3%N,F;

[0148] (2) Weighing 0.2666 g of palladium chloride and 0.1844 g of zirconium nitrate pentahydrate, respectively, and dissolving them in an appropriate amount of deionized water to prepare palladium and zirconium precursor solutions, respectively;

[0149] (3) Weigh 1.7870 g of titanium dioxide carrier and 80 mL of deionized water, mix, stir to form a uniform slurry, then add the palladium and zirconium precursor solutions obtained in step (1) in sequence, and add 0.2000 g of polyvinyl pyrrolidone to stir stably, heat to 70° C. and keep stirring for 4 h; slowly add 5% sodium hydroxide solution to the above suspension, adjust the solution pH to greater than 10.0, and continue stirring for 2 h; filter the above suspension, and wash with deionized water until the pH of the filtrate is neutral. The obtained sample is vacuum dried at 110° C. for 12 h, and then heated to 70° C. for 4 h. 2 Pd was obtained by reduction at 150℃ for 2h under atmosphere. 7 Zr 2 / TiO 2 -3% N, F two-component catalyst.

[0150] The operation and parameters of the continuous hydrogenolysis debenzylation reaction of hexabenzylhexaazaisowurtzitane (HBIW) in this example are the same as those in Example 1.

[0151] Table 4 Effect of different calcination temperatures of fluorine-nitrogen co-doped titanium dioxide carrier on catalyst

[0152]

[0153] Comparative Example 5

[0154] The preparation and reaction conditions of the catalyst in this comparative example are the same as those in Example 2. The catalyst after the reaction is recycled, and the amount of catalyst added in the second round of reaction and thereafter is reduced to 0.15 g for the first step HBIW hydrogenolysis reaction and to 0.02 g for the second step TADBIW hydrogenolysis reaction.

[0155] Application of catalyst in continuous hydrogenolysis of benzylhexaazaisowurtzitane (HBIW):

[0156] (1) HBIW hydrogenolysis reaction: 15.00 g HBIW, 127 mL DMF, 0.3 mL PhBr, 0.2 g catalyst, 20 mL Ac 2 O were added into the reactor in sequence, and the hydrogenation reaction was carried out continuously for 8 hours at 25°C, 0.5MPa hydrogen pressure and stirring conditions, and then the temperature was raised to 40°C and the reaction was continued for 16 hours. The obtained reaction liquid was filtered to remove the filtrate, and the filter cake was placed in a blast oven at 110°C and dried for 2 hours to obtain an off-white solid containing the target product TADBIW and the catalyst. The TADBIW yield after the first step HBIW hydrogenolysis reaction was calculated after weighing;

[0157] (2) TADBIW hydrogenolysis reaction: The dried filter cake from the first step of hydrogenolysis reaction was weighed and added to the reactor together with 127 mL of acetic acid. After acid washing at 60°C for 2 h, 0.20 g of catalyst and 18 ml of deionized water were added in sequence. Then, continuous hydrogenation reaction was carried out at 60°C, 1.5 MPa hydrogen pressure and stirring for 24 h. After suction filtration and washing with acetic acid, the obtained black solid was the catalyst, and the desired product TAIW was dissolved in the filtrate. The second step hydrogenation product was quantitatively analyzed by gas chromatography.

[0158] Table 5 Stability evaluation of catalyst

[0159]

[0160]

Claims

1. A method for preparing a nitrogen-fluorine co-doped titanium dioxide-supported palladium-zirconium bimetallic catalyst, characterized in that: The preparation method is as follows: (1) First, an appropriate amount of ammonium fluoride is added to a mixed solvent of ethanol and deionized water as a source of nitrogen and fluorine, and an appropriate amount of acidic solution is added to adjust the pH value of the solution to 4-5 to shorten the gelation time and generate a transparent solution. Under continuous magnetic stirring, an appropriate amount of titanium-containing organic matter is added to the solution, and the mixture is stirred for 2-4 hours to form a transparent and uniform mixture, which is then aged at room temperature for 12-24 hours until a transparent gel is formed. After that, the obtained gel is placed in a vacuum drying oven at 60-90° C. for 8-12 hours, and then ground with an agate mortar to obtain a dry gel powder. Finally, the dry gel powder is placed in a muffle furnace and calcined at 200-500° C. for 2-4 hours, and then cooled to room temperature to obtain a fluorine-nitrogen co-doped titanium dioxide carrier, which is recorded as TiO2-x%N,F, where x%=n 氟化铵 / n Ti ×100%=2~4%, where n Ti It refers to the number of moles of Ti contained in titanium-containing organic matter; (2) Weighing a certain amount of a palladium-containing compound and a zirconium-containing compound and dissolving them in an appropriate amount of deionized water to prepare palladium and zirconium precursor solutions, respectively; (3) taking a certain amount of the fluorine-nitrogen co-doped titanium dioxide carrier prepared in step (1) and mixing it with deionized water, stirring to form a uniform slurry, and then adding the palladium and zirconium precursor solutions obtained in step (2) in sequence, and adding a dispersant to stir stably, heating to 60-80° C. and maintaining stirring for 4-6 hours; slowly adding an aqueous solution of an alkaline substance to the above suspension, adjusting the pH value to greater than 10.0, and continuing to stir for 1-2 hours; filtering the above suspension, and washing with deionized water until the pH of the filtrate is neutral, and after vacuum drying the obtained sample, reducing it under a H2 atmosphere to obtain a nitrogen-fluorine co-doped titanium dioxide-supported palladium-zirconium bimetallic catalyst; The theoretical loading amount of Pd in ​​the nitrogen-fluorine co-doped titanium dioxide supported palladium-zirconium bimetallic catalyst is 5-10%, and the theoretical loading amount of Pd = m Pd / (m Pd +m ZrO2 +m 氮氟改性二氧化钛载体 )×100%, the molar ratio of palladium to zirconium is 7:(1~3), where m Pd Represents the mass of palladium contained in the palladium precursor solution, m ZrO2 It represents the mass of ZrO2 converted from the mass of Zr contained in the zirconium precursor solution.

2. The preparation method according to claim 1, characterized in that: In step (1), the titanium-containing organic matter is at least one of tetraethyl titanate, tetraisopropyl titanate, and tetrabutyl titanate.

3. The preparation method according to claim 1 or 2, characterized in that: In step (1), the volume ratio of the titanium-containing organic matter to ethanol and water is 2-10:50:2-10.

4. The preparation method according to claim 1, characterized in that: In step (1), the acidic solution is a 5-10wt% acetic acid or hydrochloric acid solution; in step (3), the aqueous solution of the alkaline substance is a 5-10wt% ammonia or NaOH solution.

5. The preparation method according to claim 1, characterized in that: In step (1), the calcination temperature is 300-400°C, preferably 400°C.

6. The preparation method according to claim 1, characterized in that: In step (2), the palladium compound is at least one of palladium chloride, sodium tetrachloropalladate, palladium acetate, and palladium nitrate, and the zirconium compound is at least one of zirconium chloride, zirconium nitrate, zirconium oxychloride, zirconium acetate, and zirconium n-propoxide.

7. The preparation method according to claim 1, characterized in that: In step (2), the dispersant is at least one of polyethylene glycol, polyvinyl pyrrolidone and ethylenediamine, and the amount of the dispersant is 5-20% of the mass of the catalyst, and the mass of the catalyst = m Pd +m ZrO2 +m 氮氟改性二氧化钛载体 .

8. The preparation method according to claim 1, characterized in that: In step (3), the reduction condition is 100-400° C. for 1-4 h in a hydrogen atmosphere.

9. A nitrogen-fluorine co-doped titanium dioxide-supported palladium-zirconium bimetallic catalyst prepared according to the preparation method of any one of claims 1 to 8.

10. Use of the nitrogen-fluorine co-doped titanium dioxide-supported palladium-zirconium bimetallic catalyst as claimed in claim 9 in the continuous hydrogenolysis-debenzylation reaction of hexabenzylhexaazaisowurtzitane to synthesize TAIW.

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