CN115925495B - Composite burning rate catalyst of carbon nano tube filled metal carbonyl compound - Google Patents
Composite burning rate catalyst of carbon nano tube filled metal carbonyl compound Download PDFInfo
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- 239000003054 catalyst Substances 0.000 title claims abstract description 47
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- 125000002915 carbonyl group Chemical group [*:2]C([*:1])=O 0.000 claims description 9
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- HEDRZPFGACZZDS-UHFFFAOYSA-N Chloroform Chemical compound ClC(Cl)Cl HEDRZPFGACZZDS-UHFFFAOYSA-N 0.000 claims description 5
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 5
- GRYLNZFGIOXLOG-UHFFFAOYSA-N Nitric acid Chemical compound O[N+]([O-])=O GRYLNZFGIOXLOG-UHFFFAOYSA-N 0.000 claims description 5
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- 238000000967 suction filtration Methods 0.000 claims description 5
- QAOWNCQODCNURD-UHFFFAOYSA-N sulfuric acid Substances OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 claims description 5
- JUJWROOIHBZHMG-UHFFFAOYSA-N Pyridine Chemical compound C1=CC=NC=C1 JUJWROOIHBZHMG-UHFFFAOYSA-N 0.000 claims description 4
- 229910052799 carbon Inorganic materials 0.000 claims description 3
- 238000001914 filtration Methods 0.000 claims description 3
- UMJSCPRVCHMLSP-UHFFFAOYSA-N pyridine Natural products COC1=CC=CN=C1 UMJSCPRVCHMLSP-UHFFFAOYSA-N 0.000 claims description 2
- 238000004062 sedimentation Methods 0.000 claims description 2
- YLQBMQCUIZJEEH-UHFFFAOYSA-N tetrahydrofuran Natural products C=1C=COC=1 YLQBMQCUIZJEEH-UHFFFAOYSA-N 0.000 claims description 2
- 238000002485 combustion reaction Methods 0.000 abstract description 25
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- 230000003197 catalytic effect Effects 0.000 description 17
- ZOKXTWBITQBERF-UHFFFAOYSA-N Molybdenum Chemical compound [Mo] ZOKXTWBITQBERF-UHFFFAOYSA-N 0.000 description 14
- 229910052750 molybdenum Inorganic materials 0.000 description 14
- 239000011733 molybdenum Substances 0.000 description 14
- 238000000034 method Methods 0.000 description 9
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- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 4
- GDDNTTHUKVNJRA-UHFFFAOYSA-N 3-bromo-3,3-difluoroprop-1-ene Chemical compound FC(F)(Br)C=C GDDNTTHUKVNJRA-UHFFFAOYSA-N 0.000 description 3
- 239000008367 deionised water Substances 0.000 description 3
- 229910021641 deionized water Inorganic materials 0.000 description 3
- 238000011049 filling Methods 0.000 description 3
- XEEYBQQBJWHFJM-UHFFFAOYSA-N iron Substances [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 description 3
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- UGFAIRIUMAVXCW-UHFFFAOYSA-N Carbon monoxide Chemical compound [O+]#[C-] UGFAIRIUMAVXCW-UHFFFAOYSA-N 0.000 description 1
- VYZAMTAEIAYCRO-UHFFFAOYSA-N Chromium Chemical compound [Cr] VYZAMTAEIAYCRO-UHFFFAOYSA-N 0.000 description 1
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 description 1
- PWHULOQIROXLJO-UHFFFAOYSA-N Manganese Chemical compound [Mn] PWHULOQIROXLJO-UHFFFAOYSA-N 0.000 description 1
- QXZUUHYBWMWJHK-UHFFFAOYSA-N [Co].[Ni] Chemical compound [Co].[Ni] QXZUUHYBWMWJHK-UHFFFAOYSA-N 0.000 description 1
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- FQNHWXHRAUXLFU-UHFFFAOYSA-N carbon monoxide;tungsten Chemical group [W].[O+]#[C-].[O+]#[C-].[O+]#[C-].[O+]#[C-].[O+]#[C-].[O+]#[C-] FQNHWXHRAUXLFU-UHFFFAOYSA-N 0.000 description 1
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- 229960001701 chloroform Drugs 0.000 description 1
- 229910052804 chromium Inorganic materials 0.000 description 1
- NVIVJPRCKQTWLY-UHFFFAOYSA-N cobalt nickel Chemical compound [Co][Ni][Co] NVIVJPRCKQTWLY-UHFFFAOYSA-N 0.000 description 1
- 150000001875 compounds Chemical class 0.000 description 1
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Abstract
The invention discloses a nano composite burning rate catalyst of a carbon nano tube filled metal carbonyl compound, which is prepared by adding carbon oxide nano tubes into a metal carbonyl compound Mo (CO) 6 、Cr(CO) 6 、W(CO) 6 、Fe 2 (CO) 9 、Mn 2 (CO) 10 In the saturated solution of (2), the metal carbonyl compound is filled in the tube cavity of the oxidized carbon nano tube by ultrasonic treatment, so as to obtain the nano composite combustion speed catalyst of the metal carbonyl compound filled in the carbon nano tube. The preparation method is simple, the metal carbonyl compound is stably constrained in the carbon nano tube by utilizing the nano-scale pore canal of the carbon nano tube, the dispersity and the thermal stability of the metal carbonyl compound are greatly improved, the metal carbonyl compound and the carbon nano tube also have a synergistic catalysis effect, the metal carbonyl compound can be decomposed into nano metal oxides with extremely small particles during high-temperature decomposition, and the specific surface area of the composite combustion speed catalyst is improved, so that the combustion catalysis performance of each other is improved.
Description
Technical Field
The invention belongs to the technical field of solid propellants, and particularly relates to a series of carbon nano tube filled carbonyl metal compound composite combustion speed catalysts.
Background
The addition of a burn rate catalyst to a solid propellant is one of the main ways to adjust the combustion performance of the propellant, and the burn rate catalyst chemically alters the combustion process of the propellant. The burn rate catalyst is an important component for regulating and improving the ballistic performance of the propellant and is also a key functional material in the formulation of solid propellant. At present, the combustion rate catalysts commonly used in composite solid propellants are mainly: transition metal oxides, transition metals, carbon materials, organometallic compounds, and the like.
With the continued depth of research, an increasing number of catalysts have been studied and used in solid propellants, and Carbon Nanotubes (CNTs) have begun to move into the field of researchers and have been widely studied and used. The carbon nano tube has a larger cavity structure and a larger specific surface area, and can provide a large number of active sites for catalytic reaction, so that the carbon nano tube has excellent performance in the catalytic reaction. Yuan Zhifeng et Al have shown that adding carbon nanotubes to aluminum-containing modified dual-based propellants, the carbon nanotubes, when burned, introduce heat from the combustion face into the solid phase of the propellant, promoting thermal decomposition in the solid phase region, improving the burning rate of the propellant (Yuan Zhifeng, zhao Fengqi, song Xiuduo, etc. the influence of carbon nanotubes on the combustion performance and mechanical properties of Al-CMDB propellants. Energetic materials, 2018,26 (12): 1019-1024.). In addition, the carbon nanotubes have improved tensile strength and elongation of the propellant due to their high strength, high flexibility and entanglement with the binder.
The carbon nanotube is filled with metal, oxide and other matters, and the electromagnetic performance, the conduction performance, the mechanical performance, the catalytic performance and the like of the carbon nanotube can be improved, so that the carbon nanotube cavity filling metal and oxide thereof are widely used in the field of catalysts as catalytic materials. Meanwhile, the research shows that the transition metal and the transition metal oxide have good catalytic effect, and the aggregation phenomenon in the catalytic process affects the utilization of the active center. The carbon nano tube has a large specific surface area, and the problem that the nano catalytic active substance is easy to agglomerate and difficult to disperse in the preparation process can be solved by combining the carbon nano tube with nano metal particles.
The square sea superand successfully prepares a series of nano composite materials of carbon nano tube embedded cobalt nickel compound by ultrasonic method, and researches show that the nano composite materials show better catalytic activity in ammonium perchlorate (ammonium perchlorate, AP) thermal decomposition, but only increase the heat release amount of the AP by 1742.72J/g (Fang H, xu R, yang L, et al, company fabrication of carbon nanotubes-encapsulated cobalt (nickel) salt nanocomposites and their highly efficient catalysis in the thermal degradation of ammonium perchlorate and hexagen. Journal of Alloys and Compounds,2022,928,167134); xu Ruizhe the copper-based nanocomposite is prepared by filling 12 copper salts into carbon nanotubes respectively, and catalytic testing is performed on AP, and the AP is found to have certain catalytic performance, but after the prepared composite combustion rate catalyst with the best effect is added into the AP, the heat release amount is only increased by 1448.06J/g (Xu R, yang L, fang H, et al, encoder complexes in carbon nanotubes as catalysts for thermal decomposition of energetic oxygenizers.ACS Applied Nano Materials,2022, 5:14942-14953.). The burning rate catalyst prepared by the two has a certain catalytic effect on the main component AP of the solid propellant, but has smaller change of heat release.
Metal carbonyl complexes are a class of complexes formed from transition metals and the ligand CO, also known as metal carbonyl compounds. Metal carbonyls are particularly important in modern organic chemistry, both in theoretical research and in practical use. In the chemical industry, olefins can be converted to commercially valuable products such as aldehydes, alcohols, and carboxylic acid derivatives, and carbonylation is one of the most important steps in the synthesis of olefins. It has been found that solid metal carbonyls can be used as carbonyl sources instead of carbon monoxide to directly interfere with carbonylation reactions, which have been a growing development in the field of organic chemistry. As the research is in progress, metal carbonyls have found wide application in contemporary organic synthesis reaction research, particularly in natural product synthesis, bio-organic chemistry and pharmaceutical chemistry.
In view of the above, the selection of the combustion rate catalyst is important in order to improve the combustion efficiency of the propellant. The carbon nano tube has unique catalytic activity, and the application of the carbonyl metal compound in other fields proves that the carbonyl metal compound has better potential catalytic activity, so that the novel composite combustion speed catalyst prepared by combining the carbonyl metal compound and the carbon nano tube becomes one of potential development directions in the field of catalytic materials.
Disclosure of Invention
The invention aims to provide a carbon nano tube filled metal carbonyl compound composite combustion speed catalyst which is simple to prepare, can be produced in a large scale and has good catalytic effect.
Aiming at the purposes, the invention adopts the technical scheme that: adding carbon oxide nanotubes into a saturated solution of a metal carbonyl compound, washing with a solvent corresponding to the saturated solution of the metal carbonyl compound after ultrasonic treatment, and carrying out suction filtration and drying to obtain the carbon nanotube-filled metal carbonyl compound composite burning rate catalyst; wherein the metal carbonyl compound is Mo (CO) 6 、Cr(CO) 6 、W(CO) 6 、Fe 2 (CO) 9 、Mn 2 (CO) 10 Any one of them.
Mo (CO) described above 6 The corresponding solvent of the saturated solution is benzene, cr (CO) 6 The corresponding solvent of the saturated solution is chloroform, W (CO) 6 The corresponding solvent of the saturated solution is tetrahydrofuran, fe 2 (CO) 9 The corresponding solvent of the saturated solution is pyridine, mn 2 (CO) 10 The corresponding solvent for the saturated solution is ethanol.
The addition ratio of the saturated solution of the carbon oxide nano tube and the carbonyl metal compound is 8-12 mg/mL.
The temperature of the ultrasonic treatment is 20-30 ℃, the ultrasonic time is 20-30 h, the ultrasonic power is 600-800W, the drying temperature is 50-60 ℃ and the time is 4-8 h.
The carbon oxide nanotubes are prepared by carrying out ultrasonic treatment on multi-wall carbon nanotubes by a mixed acid solution of concentrated sulfuric acid and concentrated nitric acid, and then settling, suction filtering, washing and drying the multi-wall carbon nanotubes. Wherein the pipe diameter of the multi-wall carbon nano-tube is 4-80 nm, the volume ratio of the concentrated sulfuric acid to the concentrated nitric acid in the mixed acid solution is 3:1, the ultrasonic treatment temperature of the mixed acid solution is 20-30 ℃, the ultrasonic power is 200-400W, the sedimentation time is 20-24 h, the drying temperature is 60-80 ℃, and the drying time is 20-24 h.
The beneficial effects of the invention are as follows:
the invention combines five carbonyl metal compounds with the carbon nano tube, and utilizes the nano pore canal of the carbon nano tube to ensure that the carbonyl metal compounds are stably restrained in the carbon nano tube, thereby obtaining a novel nano composite combustion speed catalyst. The composite combustion speed catalyst greatly improves the thermal stability of the metal carbonyl compound, and in addition, the dispersity of the metal carbonyl compound can be greatly improved by filling the metal carbonyl compound into the carbon nano tube due to the small pore diameter of the carbon nano tube. During high-temperature decomposition, the carbonyl metal compound can be decomposed into nano metal oxide with tiny particles, the specific surface area of the composite combustion speed catalyst is improved, the carbonyl metal compound and the carbon nano tube also have a synergistic catalysis effect, and the combustion catalysis performance of the carbonyl metal compound and the carbon nano tube can be improved by a direct effective and simple method.
Drawings
FIG. 1 is a transmission electron microscope image of a carbon nanotube-filled molybdenum hexacarbonyl composite burn rate catalyst prepared in example 1.
FIG. 2 is a differential scanning calorimetric analysis curve of a composite burn rate catalyst of a carbon nanotube-filled metal carbonyl compound prepared in examples 1 to 5, added to AP, and pure AP.
FIG. 3 is a differential scanning calorimetric analysis curve of pure AP and AP, respectively, with 5% of the carbon nanotube-filled molybdenum hexacarbonyl composite burn rate catalyst prepared in example 1, the carbon nanotube-supported molybdenum hexacarbonyl composite burn rate catalyst prepared in comparative example 1, carbon nanotube CNTs-1 with a pipe diameter of 4-6 nm, untreated carbon nanotube CNTs-2 with a pipe diameter of 4-6 nm, and pure molybdenum hexacarbonyl.
Detailed Description
The present invention will be described in further detail with reference to the drawings and examples, but the scope of the present invention is not limited to these examples.
Example 1
200mg of multiwall carbon nanotubes with the pipe diameter of 4-6 nm are added into 15mL of mixed acid solution with the volume ratio of concentrated sulfuric acid to concentrated nitric acid of 3:1, ultrasonic treatment is carried out for 4 hours at the temperature of 30 ℃ and the power of 300W, a black viscous solution is obtained, deionized water is added into the solution, after the solution is uniformly stirred by a glass rod, the solution is kept stand at room temperature and settled for 24 hours, obvious delamination is seen in a beaker, the upper transparent solution is poured out, deionized water is added again, and the black suspension is obtained after repeated times. Filtering the black suspension, separating, and deionizedRepeatedly washing with water until the pH value of the obtained black solid precipitate is neutral, transferring the black solid precipitate into a blast drying oven, drying at 80 ℃ for 24 hours, and grinding uniformly to obtain the carbon oxide nanotube with two open ends. 100mg of carbon oxide nanotubes was added to 10mL of Mo (CO) 6 In the saturated benzene solution of (2), after ultrasonic treatment for 30 hours at the temperature of 30 ℃ and the power of 800W, benzene is used for washing for 3 times, suction filtration is carried out, the product is placed in an oven for drying for 6 hours at the temperature of 60 ℃ and is taken out, and the obtained black powder is a carbon nano tube filled molybdenum hexacarbonyl composite burning rate catalyst, which is marked as Mo (CO) 6 @CNTs. As can be seen from fig. 1, molybdenum hexacarbonyl is filled in the carbon nanotubes, and a small amount of molybdenum hexacarbonyl is also present between the walls of the multi-wall carbon nanotubes.
Example 2
In this example, an equal volume of Cr (CO) was used 6 Substitution of Mo (CO) in example 1 with saturated trichloromethane solution 6 The procedure of example 1 was repeated except that the black powder obtained was a carbon nanotube-filled chromium hexacarbonyl composite burn rate catalyst, denoted Cr (CO) 6 @CNTs。
Example 3
In this example, an equal volume W (CO) is used 6 Replacement of Mo (CO) in example 1 with saturated tetrahydrofuran solution 6 The procedure of example 1 was repeated except that the black powder obtained was a carbon nanotube-filled tungsten hexacarbonyl composite burn-in catalyst, denoted as W (CO) 6 @CNTs。
Example 4
In this example, an equal volume of Fe is used 2 (CO) 9 Replacement of Mo (CO) in example 1 with a saturated pyridine solution 6 The same procedure as in example 1 was repeated except that the black powder obtained was a carbon nanotube-filled iron carbonyl composite burn-in catalyst, denoted as Fe 2 (CO) 9 @CNTs。
Example 5
In this example, an equal volume of Mn is used 2 (CO) 10 Replacement of Mo (CO) in example 1 with saturated ethanol solution 6 The same procedure as in example 1 was repeated except that the black powder obtained was carbon nanotube-filled manganese decacarbonylComposite burn rate catalyst, designated Mn 2 (CO) 10 @CNTs。
Comparative example 1
Adding 100mg of untreated carbon nano tube with the tube diameter of 4-6 nm into 10mL of deionized water, performing ultrasonic treatment for 30 hours at the temperature of 30 ℃ and the power of 800W, performing suction filtration, adding 10mL of saturated benzene solution of molybdenum hexacarbonyl into the product, stirring for 24 hours at room temperature, performing suction filtration, and drying for 6 hours at the temperature of 60 ℃ in an oven to obtain black powder which is the carbon nano tube supported molybdenum hexacarbonyl composite combustion catalyst and is marked as Mo (CO) 6 /CNTs。
In order to prove the beneficial effects of the invention, 5% of the carbon nano tube filled metal carbonyl compound composite combustion speed catalyst prepared in examples 1-5 is respectively added into AP for combustion catalysis performance test, and the results are shown in figure 2. Meanwhile, 5% of carbon nano tube loaded hexacarbonyl molybdenum composite combustion speed catalyst (Mo (CO) of comparative example 1 is added into AP respectively 6 CNTs), 5% of carbon nanotube CNTs-1 with the diameter of 4-6 nm, 5% of carbon nanotube CNTs-2 with the diameter of 4-6 nm which is untreated, and 5% of pure molybdenum hexacarbonyl are subjected to comparative experiments, and the results are shown in figure 3.
As can be seen from FIG. 2, under the same conditions, after 5% of the carbon nanotube-filled metal carbonyl compound composite burn-rate catalyst prepared in examples 1-5 is added into the main component AP of the solid propellant, the peak temperature of the high-temperature decomposition stage of the AP is respectively reduced from 420.4 ℃ to 339.8 ℃, 331.1 ℃, 334.9 ℃, 309.3 ℃, 334.8 ℃, 80.6 ℃, 89.3 ℃, 85.5 ℃, 111.1 ℃ and 85.6 ℃ from 976.42J/g to 3881.05J/g, 3305.25J/g, 3559.30J/g, 3119.01J/g and 3226.15J/g, respectively increased by 2904.63J/g, 2328.83J/g, 2582.88J/g, 2142.59J/g and 2249.73J/g, wherein the apparent decomposition heat of the AP is respectively increased from 976.42J/g to 3881.05J/g, 3535J/g, 3226.15J/g and the heat release of the carbon nanotube-filled molybdenum hexacarbonyl to the thermal decomposition catalysis of the AP is highest. After adding 5% of the carbon nano tube filled metal carbonyl compound composite combustion speed catalyst prepared in examples 1-5, the peak temperature of AP is greatly reduced, and the concentrated heat release phenomenon is shown in the high-temperature decomposition stage, and the heat release amount is obviously increased, which shows that the carbon nano tube filled molybdenum hexacarbonyl composite prepared in example 1 has better combustion catalysis effect on the thermal decomposition of the APBurning-rate catalyst Mo (CO) 6 The catalyst has the best effect on the thermal decomposition of the AP, and when 5% of the carbon nano tube filled molybdenum hexacarbonyl composite combustion speed catalyst prepared in the embodiment 1 is added into the main component AP of the solid propellant, the heat release amount of the catalyst is obviously improved to be nearly 4 times of that of the pure AP, and other embodiments are also better improved than that of the pure AP.
As can be seen from FIG. 3, under the same conditions, when 5% of Mo (CO) prepared in comparative example 1 was added to the solid propellant main component AP 6 When CNTs are used as the catalyst, the peak temperature of the AP pyrolysis stage is reduced from 420.4 ℃ to 338.7 ℃, and the apparent decomposition heat of the AP is increased from 976.42J/g to 3270.10J/g. In addition, the catalytic performance evaluation is carried out by directly adding the metal carbonyl compound and the pure AP, and the pure metal carbonyl compound is found to not show obvious catalytic effect on the AP; the AP thermal decomposition process is catalyzed by adding 5% of carbon nano tubes, the peak temperature of the AP high-temperature decomposition stage is reduced from 420.4 ℃ to 331.4 ℃, the apparent decomposition heat of AP is increased from 976.42J/g to 3211.89J/g, the AP thermal decomposition process is catalyzed by adding 5% of untreated carbon nano tubes CNTs-2, the peak temperature of the AP high-temperature decomposition stage is reduced from 420.4 ℃ to 311.5 ℃, the apparent decomposition heat of AP is increased from 976.42J/g to 2600.74J/g, although the peak temperature can be obviously reduced, the heat release is smaller, compared with the catalytic effects of two carbon nano tubes, and the catalytic effect of the carbon nano tubes is obviously better than that of the untreated carbon nano tubes.
Claims (5)
1. A carbon nano tube filled metal carbonyl compound composite burning rate catalyst is characterized in that: adding carbon oxide nanotubes into a saturated solution of a metal carbonyl compound, washing with a solvent corresponding to the saturated solution of the metal carbonyl compound after ultrasonic treatment, and carrying out suction filtration and drying to obtain the carbon nanotube-filled metal carbonyl compound composite burning rate catalyst; wherein the metal carbonyl compound is Mo (CO) 6 、Cr(CO) 6 、W(CO) 6 、Fe 2 (CO) 9 、Mn 2 (CO) 10 Any one of them;
the temperature of the ultrasonic treatment is 20-30 o C. The ultrasonic time is 20-30 h, the ultrasonic power is 600-800W, and the drying temperature is highThe degree is 50-60 o C. The time is 4-8 h;
the addition proportion of the saturated solution of the carbon oxide nano tube and the carbonyl metal compound is 8-12 mg/mL.
2. The carbon nanotube-filled metal carbonyl composite burn rate catalyst of claim 1, wherein: the carbon oxide nanotubes are prepared by carrying out ultrasonic treatment on multi-wall carbon nanotubes by a mixed acid solution of concentrated sulfuric acid and concentrated nitric acid, and then settling, suction filtering, washing and drying the multi-wall carbon nanotubes.
3. The carbon nanotube-filled metal carbonyl composite burn rate catalyst of claim 2, wherein: the pipe diameter of the multi-wall carbon nano-tube is 4-80 nm, and the volume ratio of the concentrated sulfuric acid to the concentrated nitric acid in the mixed acid solution is 3:1.
4. The carbon nanotube-filled metal carbonyl composite burn rate catalyst of claim 2, wherein: the ultrasonic treatment temperature of the mixed acid solution is 20-30 DEG C o C. The time is 4-6 h, the ultrasonic power is 200-400W, the sedimentation time is 20-24 h, and the drying temperature is 60-80 o And C, drying time is 20-24 h.
5. The carbon nanotube-filled metal carbonyl composite burn rate catalyst of claim 1, wherein: the Mo (CO) 6 The corresponding solvent of the saturated solution is benzene, cr (CO) 6 The corresponding solvent of the saturated solution is chloroform, W (CO) 6 The corresponding solvent of the saturated solution is tetrahydrofuran, fe 2 (CO) 9 The corresponding solvent of the saturated solution is pyridine, mn 2 (CO) 10 The corresponding solvent for the saturated solution is ethanol.
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| CN108114713A (en) * | 2016-11-28 | 2018-06-05 | 中国科学院大连化学物理研究所 | Carbon nanometer tube loaded type catalyst for oxidizing atmosphere and preparation method thereof |
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