CN113210000A - Pd/g-C3N4Application of NS catalyst in HBIW hydrogenolysis reaction - Google Patents
Pd/g-C3N4Application of NS catalyst in HBIW hydrogenolysis reaction Download PDFInfo
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Abstract
The invention relates to Pd/g-C3N4An application of NS catalyst in HBIW hydrogenolysis reaction, belonging to the technical field of noble metal catalysis. The invention relates to a nano carbon nitride (g-C)3N4NS) as a support to support metallic palladium for HBIW hydrogenolysis. The catalyst has stable structure, and the metal palladium is not easy to fall off, so that the catalyst has higher stability; meanwhile, compared with the traditional carrier porous structure, the flaky structure of the catalyst has a larger specific surface for noble metal loading, and can avoid the phenomenon that the reaction is stopped in advance due to the blockage of catalyst pores caused by the separation of hydrogenolysis products compared with the porous structure, thereby effectively reducing the material transfer efficiency, improving the catalytic efficiency and the yield, and effectively reducing the consumption of noble metal palladium in the HBIW hydrogenolysis process. Can realize the high-efficiency hydrogenolysis of HBIW under the lower usage amount of metal palladium, and effectively reduces the noble metal palladium content in CL-20, greatly reduces the production cost of CL-20 and has very good application prospect.
Description
Technical Field
The invention relates to palladium (Pd/g-C) loaded by graphite phase carbon nitride nanosheets3N4NS) catalyst in the hydrogenolysis reaction of Hexabenzylhexaazaisowurtzitane (HBIW), belonging to the technical field of noble metal catalysis.
Background
At present, the hydrogenolysis and nitration processes of hexa-benzyl hexa-aza-isowurtzitane (HBIW) are widely adopted in various countries for the production of a main explosive, namely hexa-nitro-hexa-aza-isowurtzitane (CL-20), wherein the nitration process adopts cheap nitrating agents such as nitric acid and sulfuric acid, an expensive palladium noble metal catalyst is used in the hydrogenolysis process, and the production cost is increased due to the large use of the noble metal catalyst, so that the price of the CL-20 is far higher than that of explosives such as hexogen, therefore, the search for a new catalyst or the reduction of the use amount of the catalyst becomes a research hotspot of various countries, and the method has great significance for reducing the cost of the CL-20 and promoting.
Research on hydrogenolysis of HBIW mainly focuses on hydrogenolysis under the condition that hydrogen pressure is about 4bar, and research shows that palladium metal has excellent effect on hydrogenolysis of HBIW, so that widely used catalysts are mainly Pd/C and Pd (OH)2The catalyst has two types (US 6147209A, WO9720785A1), and palladium-based bimetallic prepared by combining palladium and non-noble metal can be applied to HBIW hydrogenolysis, so that the consumption of noble metal palladium is reduced to reduce the CL-20 production cost (CN 106946894A).
In order to improve the catalytic effect of palladium, palladium is widely loaded on materials such as porous activated carbon, SiO2 and Al2O3, and although a porous material provides a large specific surface area, the porous structure of the catalyst carrier often causes obstruction to substance transfer of HBIW in the reaction process and reduces the reaction rate because the macromolecular three-dimensional structure of HBIW needs to remove four benzyl groups at a time. Graphite phase carbon nitride nanosheets are used as carriers of the noble metal palladium, the nanosheets are nanometer in thickness and small and can be well dispersed in a reaction system, and meanwhile, the flaky structure can effectively reduce the material transfer resistance and greatly improve the reaction efficiency. At present, the application of the HBIW hydrogenolysis has not been reported.
Disclosure of Invention
The invention aims to solve the problem of low reaction rate of HBIW hydrogenolysis catalyzed by a porous carrier loaded with noble metal, and provides Pd/g-C3N4An application method of an NS catalyst in HBIW hydrogenolysis.
The purpose of the invention is realized by the following technical scheme.
The invention adopts graphite phase carbon nitride nanosheets (g-C)3N4NS) is used as a carrier of metal palladium (Pd), the carrier has the characteristics of simple preparation, sheet shape and nano-scale thickness, and simultaneously, a nitrogen ring consisting of nitrogen atoms exists on the surface, so that the carrier can generate strong coordination with the metal Pd, and the metal is stably and uniformly loaded on a carbon nitride nano-sheet; meanwhile, due to the special structure of the nanosheet, HBIW with a larger three-dimensional structure can be easily adsorbed on the nanosheet and reacts with H atoms dissociated from the noble metal, so that the hydrogen is smoothly desorbed after hydrogenolysis. Compared with carriers such as alumina, silicon dioxide, activated carbon and the like, the carrier has the advantages of acid resistance, alkali resistance, stable structure, high burning point, simple synthesis and the like, and can efficiently realize the normal pressure hydrogenolysis of HBIW.
Pd/g-C3N4The application of the NS catalyst in HBIW hydrogenolysis reaction comprises the following steps: sequentially adding HBIW, DMF and Pd/g-C at room temperature3N4Adding NS catalyst, bromobenzene and acetic anhydride into a reactor, sealing, replacing gas in a reaction bottle with nitrogen for three times, replacing gas in the reaction bottle with hydrogen for three times, heating to a specific temperature for reaction for a certain time, continuously blowing hydrogen into a hydrogen balloon in the reaction process, filtering after the reaction, extracting a filtrate solvent, carrying out rotary evaporation on an extracting solution, and drying to obtain a target product.
Wherein the reaction formula of the catalytic hydrogenolysis of HBIW is shown as follows:
the mass ratio of palladium to HBIW is preferably 0.004-0.02, more preferably 0.004-0.01, and most preferably 0.004.
The hydrogen pressure is normal pressure;
the temperature is preferably 18 to 50 ℃, more preferably 25 to 45 ℃, and most preferably 45 ℃.
The time is preferably 6 to 15 hours, more preferably 6 to 10 hours, and most preferably 8 hours.
The Pd/g-C3N4The preparation method of the NS catalyst comprises the following steps: g to C3N4NS is ultrasonically dispersed in water solution, palladium salt is added into the water solution, a reducing agent solution is added after the palladium salt is heated and stirred for a certain time, and the Pd/g-C is obtained after the palladium salt is filtered, washed and dried after the palladium salt is stirred for a certain time3N4And (3) an NS catalyst.
The palladium and g-C3N4The mass ratio of NS is 5-20%;
said g-C3N4The proportion of NS and water is 1g (80-100) ml;
the ultrasonic time is preferably 2-6h, more preferably 1.5-4 h, and most preferably 2.5 h;
the palladium salt comprises palladium chloride, palladium perchlorate and palladium nitrate;
the stirring time after the palladium salt solution is added is preferably 5-8 hours, and most preferably 7 hours;
the reducing agent comprises sodium borohydride and hydrazine hydrate.
The concentration of the reducing agent solution is 2 mg/ml;
the stirring time after the reducing agent is added is preferably 7-15 hours, and most preferably 12 hours.
The drying is preferably vacuum drying at 60 ℃ for 4 h.
The solvent used for solvent extraction is chloroform.
Advantageous effects
1. Pd/g-C of the invention3N4Application of NS catalyst in HBIW hydrogenolysis, Pd/g-C3N4The NS catalyst realizes the high-efficiency catalytic hydrogenolysis of HBIW under the normal pressure of hydrogen. The catalyst is mixed with conventional catalyst (Pd/C, Pd (OH)2/C、Pd/Al2O3And the like), a larger specific surface can be used for loading noble metals, and meanwhile, compared with a porous structure, the sheet structure can avoid the phenomenon that the reaction is stopped in advance due to the blockage of catalyst pores caused by the separation of hydrogenolysis products, can effectively reduce the substance transfer efficiency and improve the catalytic efficiency and yield, can realize the high-efficiency hydrogenation of HBIW under the lower palladium consumption, has great significance for further reducing the production cost of CL-20, and has good application prospect.
2. Pd/g-C of the invention3N4Application of NS catalyst in HBIW hydrogenolysis, Pd/g-C3N4The NS has the characteristics of stable structure, simple production and high-efficiency catalysis, greatly reduces the production cost and has good application prospect.
Detailed Description
The present invention will be further described with reference to the following examples.
Example 1
Pd/g-C3N4Preparation of NS catalyst
1g g-C3N4Dispersing NS in 300ml deionized water, performing ultrasonic treatment for 150min, and adding 167mg PdCl2Heating to 90 deg.C, stirring at constant temperature for 7h, and adding 89ml NaBH4The solution (2mg/ml) was stirred for 12h, filtered, washed with water to neutrality and dried under vacuum at 60 ℃ for 4h to give Pd (6.3%)/g-C with a palladium content of 6.3%3N4And (3) an NS catalyst.
Hydrogenolysis of HBIW
1g of HBIW, 158mg of Pd (6.3%)/mpg-C3N4Catalyst, 3ml DMF, 0.018ml bromobenzene and 1.5ml acetic anhydride were added to the reaction flask, the gas in the reaction flask was replaced with nitrogen three times, then with hydrogen three times, and hydrogen was bubbled continuously through the hydrogen balloon. Heating to 45 ℃ for reaction for 8h, cooling to room temperature after the reaction is finished, filtering to obtain a solid, drying, extracting the solid with trichloromethane, and carrying out rotary evaporation and drying on the extracting solution to obtain a hydrogenolysis product.
Example 2
Example Pd (6.3%)/g-C3N4The operation and parameters for the preparation of the NS catalyst were the same as in example 1.
Hydrogenolysis of hexabenzylhexaazaisowurtzitane
1g of HBIW, 127mg of Pd (6.3%)/mpg-C3N4Catalyst, 3ml DMF, 0.018ml bromobenzene and 1.5ml acetic anhydride were added to the reaction flask, the gas in the reaction flask was replaced with nitrogen three times, then with hydrogen three times, and hydrogen was bubbled continuously through the hydrogen balloon. Heating the mixture from room temperature to 45 ℃ for reaction for 8h, cooling the mixture to room temperature after the reaction is finished, filtering the mixture to obtain a solid, drying the solid, extracting the solid with trichloromethane, and carrying out rotary evaporation and drying on the extracting solution to obtain a hydrogenolysis product.
Example 3
Example Pd (6.3%)/g-C3N4The operation and parameters for the preparation of the NS catalyst were the same as in example 1.
Hydrogenolysis of hexabenzylhexaazaisowurtzitane
1g of HBIW, 95mg of Pd (6.3%)/mpg-C3N4Catalyst, 3ml DMF, 0.018ml bromobenzene and 1.5ml acetic anhydride were added to the reaction flask, the gas in the reaction flask was replaced with nitrogen three times, then with hydrogen three times, and hydrogen was bubbled continuously through the hydrogen balloon. Heating the mixture from room temperature to 45 ℃ for reaction for 8h, cooling the mixture to room temperature after the reaction is finished, filtering the mixture to obtain a solid, drying the solid, extracting the solid with trichloromethane, and carrying out rotary evaporation and drying on the extracting solution to obtain a hydrogenolysis product.
Example 4
Example Pd (6.3%)/g-C3N4 NS4The catalyst preparation operation and parameters were the same as in example 1.
Hydrogenolysis of hexabenzylhexaazaisowurtzitane
1g of HBIW, 63mg of Pd (6.3%)/mpg-C3N4Catalyst, 3ml DMF, 0.018ml bromobenzene and 1.5ml acetic anhydride were added to the reaction flask, the gas in the reaction flask was replaced with nitrogen three times, then with hydrogen three times, and hydrogen was bubbled continuously through the hydrogen balloon. Heating the mixture from room temperature to 45 ℃ for reaction for 8 hours, and finishing the reactionCooling to room temperature after the hydrogenolysis reaction is finished, filtering to obtain a solid, drying, extracting the solid with trichloromethane, and carrying out rotary evaporation and drying on the extracting solution to obtain the hydrogenolysis product.
Comparative example 1
The catalyst used in this comparative example was purchased as Pd (10%)/C.
Hydrogenolysis of hexabenzylhexaazaisowurtzitane
1g of HBIW, 100mg of Pd (10%)/C catalyst, 3ml of DMF, 0.018ml of bromobenzene and 1.5ml of acetic anhydride were charged into a reaction flask, the gas in the reaction flask was replaced three times with nitrogen and then three times with hydrogen, and the hydrogen balloon was continuously bubbled with hydrogen. Firstly reacting at 18 ℃ for 1h, then heating to 45 ℃ for reacting for 8h, cooling to room temperature after the reaction is finished, filtering to obtain a solid, drying, extracting the solid with trichloromethane, and carrying out rotary evaporation and drying on an extracting solution to obtain a hydrogenolysis product.
Comparative example 2
The catalyst used in this comparative example was purchased as Pd (5%)/C.
Hydrogenolysis of hexabenzylhexaazaisowurtzitane
1g of HBIW, 200mg of Pd (5%)/C catalyst, 3ml of DMF, 0.018ml of bromobenzene and 1.5ml of acetic anhydride were charged into a reaction flask, the gas in the reaction flask was replaced three times with nitrogen and then three times with hydrogen, and hydrogen was continuously bubbled through a hydrogen balloon. Firstly reacting at 18 ℃ for 1h, then heating to 45 ℃ for reacting for 8h, cooling to room temperature after the reaction is finished, filtering to obtain a solid, drying, extracting the solid with trichloromethane, and carrying out rotary evaporation and drying on an extracting solution to obtain a hydrogenolysis product.
The yields of the HBIW hydrogenolysis products in the examples and comparative examples are shown in Table 1:
TABLE 1
The above detailed description is intended to illustrate the objects, aspects and advantages of the present invention, and it should be understood that the above detailed description is only exemplary of the present invention and is not intended to limit the scope of the present invention, and any modifications, equivalents, improvements and the like made within the spirit and principle of the present invention should be included in the scope of the present invention.
Claims (12)
1. Pd/g-C3N4The application of the NS catalyst in HBIW hydrogenolysis reaction is characterized in that: sequentially adding HBIW, DMF and Pd/g-C at room temperature3N4Adding NS catalyst, bromobenzene and acetic anhydride into a reactor, sealing, replacing gas in a reaction bottle with nitrogen for three times, replacing gas in the reaction bottle with hydrogen for three times, heating to a specific temperature for reacting for a certain time, continuously blowing hydrogen into a hydrogen balloon in the reaction process, filtering after the reaction, extracting filtrate solvent, carrying out rotary evaporation on the extracting solution, and drying to obtain a target product; compared with the traditional carrier porous structure, the flaky structure of the catalyst has a larger specific surface for noble metal loading, and meanwhile, compared with the porous structure, the flaky structure can avoid the phenomenon that the reaction is stopped in advance due to the blockage of catalyst pores caused by the separation of hydrogenolysis products, can effectively reduce the substance transfer efficiency, improve the catalytic efficiency and the yield, and effectively reduce the consumption of noble metal palladium in the HBIW hydrogenolysis process.
2. The method of claim 1, wherein: the mass ratio of the palladium to the HBIW is 0.004-0.02.
3. The method of claim 2, wherein: the mass ratio of the palladium to the HBIW is 0.004-0.01.
4. A method according to claim 2 or 3, characterized by: the mass ratio of palladium to HBIW was 0.004.
5. The method of claim 1, wherein: the hydrogen pressure is normal pressure, and the temperature is preferably 18 to 50 ℃, more preferably 25 to 45 ℃, and most preferably 45 ℃.
6. The method of claim 1, wherein the method further comprises the step of applying a pressure to the substrateIn the following steps: the Pd/g-C3N4The preparation method of the NS catalyst comprises the following steps: g to C3N4NS is uniformly dispersed in water solution by ultrasonic, palladium salt solution is added into carrier solution, reducing agent solution is added after stirring, and Pd/g-C is obtained by stirring, filtering, washing and drying3N4An NS catalyst; the mass ratio of the palladium to the carrier is 5-20%.
7. The method of claim 6, wherein: the palladium salt comprises palladium chloride, palladium perchlorate and palladium nitrate; the reducing agent comprises sodium borohydride and hydrazine hydrate; the solvent used for solvent extraction is chloroform.
8. The method of claim 6, wherein: g-C3N4The ratio of NS to water is preferably 1g (80-100) ml.
9. The method of claim 6 or 8, wherein: g-C3N4The ultrasonic time after the NS is added into the water solution is preferably 2-6 h.
10. The method of claim 6, wherein: the stirring time after adding the palladium salt solution is preferably 5-8 h; the stirring time after the reducing agent is added is preferably 7-15 h.
11. The method of claim 6, wherein: the concentration of the reducing agent solution is 2 mg/ml.
12. The method of claim 6, wherein: the drying is preferably vacuum drying at 60 ℃ for 4 h.
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Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN113680362A (en) * | 2021-08-18 | 2021-11-23 | 北京工业大学 | Preparation method of palladium hydroxide carbon catalyst for removing N-benzyl |
| CN113731465A (en) * | 2021-08-31 | 2021-12-03 | 浙江工业大学 | Pd/N-CNTs catalyst, and preparation method and application thereof |
| CN114573596A (en) * | 2022-03-15 | 2022-06-03 | 西安近代化学研究所 | Method for realizing HBIW one-step continuous synthesis of HAIW by acoustic resonance enhancement |
| CN115611905A (en) * | 2022-09-09 | 2023-01-17 | 南京铁鸣能源科技有限公司 | Method for efficiently synthesizing CL-20 high-energy-content cage-shaped compound based on monoatomic catalyst |
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Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN113680362A (en) * | 2021-08-18 | 2021-11-23 | 北京工业大学 | Preparation method of palladium hydroxide carbon catalyst for removing N-benzyl |
| CN113731465A (en) * | 2021-08-31 | 2021-12-03 | 浙江工业大学 | Pd/N-CNTs catalyst, and preparation method and application thereof |
| CN114573596A (en) * | 2022-03-15 | 2022-06-03 | 西安近代化学研究所 | Method for realizing HBIW one-step continuous synthesis of HAIW by acoustic resonance enhancement |
| CN115611905A (en) * | 2022-09-09 | 2023-01-17 | 南京铁鸣能源科技有限公司 | Method for efficiently synthesizing CL-20 high-energy-content cage-shaped compound based on monoatomic catalyst |
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Application publication date: 20210806 |