CN110627606A - Application of carbon nano tube embedded metal particle catalyst in reaction of synthesizing cyclohexane by benzene selective catalytic hydrogenation - Google Patents

Application of carbon nano tube embedded metal particle catalyst in reaction of synthesizing cyclohexane by benzene selective catalytic hydrogenation Download PDF

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CN110627606A
CN110627606A CN201910799974.3A CN201910799974A CN110627606A CN 110627606 A CN110627606 A CN 110627606A CN 201910799974 A CN201910799974 A CN 201910799974A CN 110627606 A CN110627606 A CN 110627606A
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carbon
carbon nano
nano tube
metal
catalyst
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卢春山
张雪洁
聂娟娟
李小年
丰枫
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Zhejiang University of Technology ZJUT
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Abstract

The invention provides an application of a catalyst with metal particles embedded in carbon nano tubes in the reaction of synthesizing cyclohexane by selective catalytic hydrogenation of benzene, wherein the catalyst consists of carbon nano tubes, undoped carbon quantum dots and metal nano particles, the carbon nano tubes are single-wall or multi-wall carbon tubes with open pores, the carbon quantum dots are loaded on the outer walls of the carbon nano tubes, and the metal nano particles are embedded in the inner walls of the carbon nano tubes; the metal is one of palladium, platinum, gold, ruthenium, iridium, nickel and cobalt; the size of the carbon quantum dots is not more than 10 nm; in the carbon nanotube supported metal catalyst, the supported amount of the carbon quantum dots is 0.5-8.0 wt%, and the supported amount of the metal is 0.1-10.0 wt%. When the catalyst is applied to the reaction of synthesizing cyclohexane by benzene selective catalytic hydrogenation, high conversion rate, high selectivity and high stability are realized under the synergistic effect of the carbon quantum dots, the embedded metal particles and the confinement effect of the carbon nano tube, the catalytic efficiency is high, and the service life of the catalyst is long.

Description

Application of carbon nano tube embedded metal particle catalyst in reaction of synthesizing cyclohexane by benzene selective catalytic hydrogenation
(I) technical field
The invention relates to an application of a carbon nano tube embedded metal particle catalyst in a reaction for synthesizing cyclohexane by benzene selective catalytic hydrogenation.
(II) technical background
Carbon nanotubes have structural defects, curved surfaces, unique lumen structures, and electrical conductivity properties, and are excellent catalytic materials. Based on the collision theory of chemical reaction, the reaction space in the tube is obviously reduced, and the unique interaction of reactants and products with the inner wall of the carbon nano tube can influence the progress of the chemical reaction. Santis et al have learned through theoretical calculations that when the chemical reaction is confined to a small pore size, the reaction kinetics change significantly and the reaction rate can jump by orders of magnitude. Lu et al calculated the mechanism of the limited-domain reaction in carbon nanotubes using DFT theory, found that after the reaction limited-domain was inside the carbon nanotubes, the barrier affecting the reaction progress was significantly reduced, and the reactivity of the reactants in the tubes was enhanced with the reduction of the tube diameter of the carbon nanotubes. Therefore, the catalyst with the carbon nano tubes embedded with the metal particles can be used for preparing ethanol by converting synthesis gas, performing Fischer-Tropsch reaction, performing benzene hydrogenation reaction and performing NH reaction3The catalyst shows excellent catalytic performance in the decomposition reaction.
The preparation method of the prior metal catalyst loaded in the tube mainly comprises the following steps: in-situ filling methods, gas phase filling methods, and liquid phase filling methods. The in-situ filling method adopts the means of an electric arc method, a microwave method and the like to generate metal or compound in situ in the cavity channel and the shell layer of the carbon nano tube in the process of preparing the carbon nano tube. Generally, the in-situ filling method can fill a plurality of metals with higher melting points and higher surface tension, but the in-situ filling method has lower filling yield, and some metal carbides or metal particles are assembled into the carbon nanotube shell during the filling process. The gas phase filling method is a method of performing a high-temperature reaction in a gas phase. That is, the carbon nanotubes are mixed with the filler under a certain pressure and temperature, and the filler is vaporized by heating and introduced into the carbon nanotubes. The gas phase method has the advantages that only gas capable of reacting with the carbon nano tube is needed in the reaction, more reagents are not needed, the environment is not polluted, and other substances are not introduced into the system; the method has the disadvantages that the carbon nano tube has low opening rate, needs high temperature of 500-1000 ℃, is difficult to control proper reaction time and temperature, and is not easy to fill because amorphous carbon is accumulated in a tube cavity. The liquid phase filling method mixes and grinds the filler and the carbon nano tube to ensure that the filler and the carbon nano tube are fully contacted, then the temperature is raised to be higher than the melting point of the filler, and the melted filler enters the interior of the carbon nano tube under the capillary action. The filling of salts such as metal halides and oxides is usually carried out by melting the filling.
However, the existing preparation method of the carbon nanotube embedded metal particles has the defects of complex process, difficult regulation and control of the metal particle embedding process, low proportion of metal particles in the tube, low metal utilization rate and the like, and causes the use cost of the catalyst to be high. In the benzene hydrogenation reaction, the catalytic performance of the catalyst still has the problems of low activity, low selectivity and the like.
Disclosure of the invention
The invention aims to provide application of a carbon nano tube embedded metal particle catalyst with carbon quantum dots loaded on the outer wall of a tube in the reaction of synthesizing cyclohexane through selective catalytic hydrogenation of benzene, and the catalyst realizes high conversion rate, high selectivity and high stability, high catalytic efficiency and long service life of the catalyst under the synergistic effect of the carbon quantum dots, the embedded metal particles and the confinement effect of the carbon nano tube.
In order to achieve the purpose, the invention adopts the following technical scheme:
the invention provides an application of a catalyst with metal particles embedded in carbon nano tubes in the reaction of synthesizing cyclohexane by selective catalytic hydrogenation of benzene, wherein the catalyst consists of carbon nano tubes, undoped carbon quantum dots and metal nano particles, the carbon nano tubes are single-wall or multi-wall carbon tubes with open pores, the carbon quantum dots are loaded on the outer walls of the carbon nano tubes, and the metal nano particles are embedded in the inner walls of the carbon nano tubes; the metal is one of palladium, platinum, gold, ruthenium, iridium, nickel and cobalt; the size of the carbon quantum dots is not more than 10 nm; in the carbon nanotube-supported metal catalyst, the carbon quantum dot loading (mass ratio of the carbon quantum dot to the carbon nanotube) is 0.5-8.0 wt%, and the metal loading is 0.1-10.0 wt%.
Preferably, in the carbon nanotube embedded metal particle catalyst, the loading amount of the carbon quantum dots is 0.5-5.0 wt%. Preferably, the loading of metal in the catalyst is 0.5 to 5.0 wt%.
Preferably, the size of the carbon quantum dots is 2.5-5.5 nm.
Preferably, the carbon nanotube embedded metal particle catalyst can be prepared by the following method:
1) placing the carbon nano tube in concentrated nitric acid (65-68 wt%) for heating reflux treatment, cooling to room temperature after the reflux treatment is finished, washing with water until the filtrate is neutral, and drying to obtain the carbon nano tube subjected to acid treatment; because the freshly prepared carbon nano tube is a tube which grows out on metal particles and is usually closed, in order to utilize the space in the tube and remove the metal particles of the long carbon tube, concentrated nitric acid is adopted for pretreatment;
2) preparing an undoped carbon quantum dot solution and the carbon nano tube subjected to acid treatment obtained in the step 1) into a dispersion liquid, fully stirring to enable carbon quantum dots to be loaded on the outer wall of the carbon nano tube, and performing suction filtration and drying to obtain the carbon nano tube loaded with the carbon dots;
3) preparing the carbon nano tube loaded with the carbon dots obtained in the step 2) and deionized water into slurry, adding aqueous solution containing metal ions under the stirring state, forming complex anions by the metal ions and chloride ions in the aqueous solution, fully stirring, performing suction filtration, washing until the pH value of filtrate is neutral, and drying to obtain the carbon nano tube embedded metal particle catalyst.
According to the preparation method, the undoped carbon quantum dots and the carbon nano tubes are adsorbed on the outer walls of the carbon nano tubes through pi-pi conjugation, so that the carbon quantum dots are converted into excellent electron donating centers, and metal complex ions with negative charges are induced to spontaneously enter the tubes and deposit on the inner walls by utilizing the electron donating characteristics of the undoped carbon quantum dots, so that the small-particle-size and uniform distribution of metal active components in the carbon nano tubes is realized.
In the step 1), the nitric acid treatment is a conventional treatment method for opening the carbon tube and removing residual metal. Preferably, in the acid treatment process of the carbon nano tube in the step 1), the ratio of the carbon nano tube to the nitric acid is 1-10 g: 20-100ml, the treatment temperature is 45-95 ℃, and the condensation reflux is carried out for 2-15 h. Preferably, the drying conditions are: drying at 50-100 deg.C for 1-10 hr. Preferably, the diameter distribution of the carbon nanotubes is 20-40nm, and the specific surface area is more than 150m2/g。
In the present invention, the undoped carbon quantum dots can be prepared by referring to the prior art. Preferably, the undoped carbon quantum dots are prepared by taking citric acid as a raw material and performing hydrothermal synthesis, and the specific process is as follows: taking citric acid and ethanol in a beaker in a ratio of 0.5-5.0g to 5-100mL, and mechanically stirring until the citric acid and the ethanol are uniformly mixed; then transferring the mixture into a hydrothermal kettle, carrying out hydrothermal treatment at the temperature of 120-; then, centrifugal treatment is carried out (organic matter particles which are not completely carbonized are removed) under the condition that the rotating speed is 20000r/min, supernatant is transferred into a two-layer dialysis bag with the molecular weight cutoff of 100-10000 Dalton for dialysis treatment, the carbon dot solution in the middle of the two layers is the carbon dot solution, and finally, the solution is concentrated to the concentration of 0.5-25.0mg/L under the condition of shading low temperature. Preferably, the two-layer dialysis bag has a molecular weight cut-off of 3000-7000 daltons.
Step 2) of the present invention is preferably carried out as follows: and feeding the non-doped carbon quantum dot solution and the carbon nano tube subjected to acid treatment according to the load capacity of the phosphorus-doped carbon quantum dots, stirring for 10-60min, and drying the filtered solid particles in a vacuum oven at the temperature of 50-100 ℃ for 2-15h to obtain the carbon nano tube loaded with the carbon dots.
Step 3) of the present invention is preferably carried out as follows: preparing the carbon nano tube loaded with the carbon dots obtained in the step 2) into slurry according to the feeding ratio of the carbon nano tube loaded with the carbon dots to water of 1 g: 5-35ml, adding the corresponding aqueous solution containing the metal ions according to the metal loading capacity at the temperature of 5-40 ℃ under the stirring state, wherein the dropping speed of the aqueous solution containing the metal ions is 1d/1-10s, continuously stirring for 2-6h after dropping, performing suction filtration, washing until the pH value is neutral, and drying for 3-15h at the temperature of 50-100 ℃ to obtain the catalyst.
Preferably, the application method comprises the following steps: uniformly mixing a carbon nanotube embedded metal particle catalyst with quartz sand particles, wherein the granularity of the quartz sand is 0.5-2mm, putting the quartz sand particles into a fixed bed reactor, introducing hydrogen for pretreatment for 0.5-2h at 50-150 ℃, then heating to 150 ℃ and 250 ℃, and keeping the temperature constant; setting the temperature of the container containing benzene at 20-50 deg.c, and flowing 1-10ml/min hydrogen gas through the container to bring benzene vapor into the reactor for benzene hydrogenating reaction to produce cyclohexane. The hydrogenation product was analyzed on-line by Agilent 7890A gas chromatography.
Compared with the prior art, the wood composite material has the beneficial effects that:
1) in the catalyst with embedded metal particles in the carbon nano tube, the catalyst structure is designed to load carbon quantum dots outside the tube, the metal particles are embedded in the tube, the electron donating characteristic of the carbon quantum dots, the domain limiting effect of the carbon tube on the metal particles and the carbon tube on reactant molecules, and the catalyst generates specific catalytic characteristic. When the catalyst is applied to the reaction of synthesizing cyclohexane by benzene selective catalytic hydrogenation, high conversion rate, high selectivity and high stability are realized under the synergistic effect of the carbon quantum dots, the embedded metal particles and the confinement effect of the carbon nano tube, the catalytic efficiency is high, and the service life of the catalyst is long.
2) In the preparation method of the catalyst, metal ions of anions are driven to the inner wall of the carbon tube through the electrostatic action by virtue of the electron-rich characteristic of the carbon quantum dots loaded on the outer wall of the carbon tube, so that the metal utilization rate is high. The method is simple, convenient and easy to control, and has low cost.
(IV) description of the drawings
A and b in fig. 1 are electron micrographs of the catalysts prepared in comparative example 1 and example 1, respectively.
Fig. 2 is a graph showing the percentage of metal particles in carbon nanotubes in the catalysts prepared in example 1, comparative example 1, and comparative example 3, where 1 is comparative example 1; 2 is comparative example 3; example 3 data from randomly selected 500 particles (TEM characterization) are obtained for example 1.
(V) detailed description of the preferred embodiments
The technical solution of the present invention is specifically described below with specific examples, but the scope of the present invention is not limited thereto:
in the examples, the activated carbon used was Norit 800, the carbon tubes were obtained from Nanjing Xiancheng nanomaterial science and technology Co., Ltd, and the graphene was obtained from Chengdu organic chemistry Co., Ltd, academy of sciences of China.
Example 1
1) Citric acid and ethanol are taken in a beaker, the proportion is 0.5 g: 15mL, and the mixture is mechanically stirred until the mixture is uniformly mixed. Then transferred to a hydrothermal kettle, hydrothermal for 15 hours at 160 ℃, and then naturally cooled. Then carrying out centrifugal treatment (removing organic particles which are not completely carbonized) at the rotation speed of 20000r/min, transferring the supernatant into a two-layer dialysis bag with the molecular weight cutoff of 3500-.
2) Weighing 10g of carbon nano-tube (diameter distribution is 20-40nm, specific surface area is more than 150 m)2Put into a round-bottom flask, then concentrated nitric acid (65-68 wt%) is measured and added into the flask, the ratio of the carbon nano tube to the nitric acid is 5 g: 50ml, and then the flask is put into a hydrothermal pot for heating and refluxing for 5 hours at 90 ℃. And after the reflux is finished, taking out the flask, cooling to a room temperature state, transferring to a funnel, adding deionized water, continuously washing, performing suction filtration until the filtrate is neutral, and then putting the filter cake into an oven to dry for 10 hours at the temperature of 80 ℃. Obtaining the carbon nano tube treated by acid for standby.
3) Preparing a mixed solution of the carbon quantum dot solution prepared in the step 1) and the carbon nano tube treated by acid, wherein the mass ratio of the carbon dots to the carbon nano tube is 5.0 wt%, then placing the solution on a magnetic stirrer for stirring, carrying out suction filtration after 30min, and then placing the obtained solid particles into a vacuum oven for drying for 5h at 100 ℃ to obtain the carbon nano tube loaded with the carbon dots.
4) Preparing the solid obtained in the step 3) and deionized water into slurry, wherein the ratio of the solid to the water is 1g to 5ml, and palladium ions [ PdCl ] with the corresponding load of 5.0 wt% are added in the slurry under the stirring state at the temperature of 40 DEG C4]2-The dropping rate of the aqueous solution of (4) was 1 d/5S. Stirring for 6 hours, carrying out suction filtration, washing until the pH value is neutral, and drying for 15 hours at 100 ℃ to obtain the catalyst.
Examples 2 to 15
The catalyst was prepared according to example 1, with specific parameters as shown in Table 1.
TABLE 1
Note: metal ion form in the impregnation: [ PdCl4]2-，[PtCl4]2-，[IrCl4]2-，[AuCl4]2-，[NiCl4]2-，[CoCl4]2-，[RuCl4]2-。
Comparative example 1
The preparation method is the same as that of example 1 except that carbon quantum dots are not added.
Comparative example 2
Graphene was used instead of carbon nanotubes, and the other preparation methods were the same as in example 1. Graphene is a polymer made of carbon atoms in sp2The hybrid tracks form hexagonal honeycomb lattice two-dimensional carbon nano-materials without tubular structures.
Comparative example 3
The following documents Journal of Molecular Catalysis A were used: carbon tube embedded metal particle Pd/CNT (5%) catalyst prepared by the preparation method reported in Chemical 323(2010) 33-39.
Comparative example 4
The dialysis was performed using a dialysis membrane having a molecular weight of 1000-.
Example 16
The catalyst of example 1 and quartz sand particles with the particle size of 0.5-2mm are uniformly mixed, put into a fixed bed reactor, pretreated by introducing hydrogen at 150 ℃ for 0.5h, and then heated to 160 ℃ and kept at constant temperature. The temperature of the vessel containing benzene was set at 30 ℃ and 6ml/min of hydrogen gas was passed through the vessel to carry benzene vapor into the reactor for the hydrogenation of benzene. The hydrogenation product was analyzed on-line by Agilent 7890A gas chromatography. Benzene conversion was 82% after 5 hours, 82% after 20 hours and cyclohexane selectivity was 100%.
Example 17
The catalyst of example 2 and quartz sand particles with the granularity of 0.5-2mm are uniformly mixed, put into a fixed bed reactor, pretreated by introducing hydrogen at 100 ℃ for 1.5h, and then heated to 150 ℃ and kept at constant temperature. The temperature of the vessel containing benzene was set at 20 ℃ and 5ml/min of hydrogen gas was passed through the vessel to carry benzene vapor into the reactor for the hydrogenation of benzene. The hydrogenation product was analyzed on-line by Agilent 7890A gas chromatography. Benzene conversion was 83% after 5 hours, 83% after 20 hours and cyclohexane selectivity was 100%.
Example 18
The catalyst of example 3 and quartz sand particles with the granularity of 0.5-2mm are uniformly mixed, put into a fixed bed reactor, pretreated for 2 hours by introducing hydrogen at 50 ℃, and then heated to 250 ℃ and kept at constant temperature. The temperature of the vessel containing benzene was set at 50 ℃ and 10ml/min of hydrogen gas was passed through the vessel to carry benzene vapor into the reactor for the hydrogenation of benzene. The hydrogenation product was analyzed on-line by Agilent 7890A gas chromatography. Benzene conversion was 81% after 5 hours, 82% after 20 hours and 100% cyclohexane selectivity.
Example 19
The catalyst of example 4 and quartz sand particles with the particle size of 0.5-2mm are uniformly mixed, put into a fixed bed reactor, pretreated by introducing hydrogen at 120 ℃ for 1.0h, and then heated to 220 ℃ and kept at constant temperature. The temperature of the vessel containing benzene was set at 40 ℃ and 8ml/min of hydrogen gas was passed through the vessel to carry benzene vapor into the reactor for the hydrogenation of benzene. The hydrogenation product was analyzed on-line by Agilent 7890A gas chromatography. Benzene conversion was 85% after 5 hours, 86% after 20 hours and 100% cyclohexane selectivity.
Example 20
The catalyst of example 5 and quartz sand particles with the particle size of 0.5-2mm are uniformly mixed, put into a fixed bed reactor, pretreated by introducing hydrogen at 80 ℃ for 1.5h, and then heated to 200 ℃ and kept at constant temperature. The temperature of the vessel containing benzene was set at 20 ℃ and 1ml/min of hydrogen gas was passed through the vessel to carry benzene vapor into the reactor for the hydrogenation of benzene. The hydrogenation product was analyzed on-line by Agilent 7890A gas chromatography. Benzene conversion was 84% after 5 hours, 86% after 20 hours and 100% cyclohexane selectivity.
Example 21
The catalyst of example 6 was mixed uniformly with quartz sand particles of 0.5-2mm particle size, placed in a fixed bed reactor, pretreated with hydrogen at 60 ℃ for 2.0h, then heated to 180 ℃ and held at constant temperature. The temperature of the vessel containing benzene was set at 20 ℃ and 4ml/min of hydrogen gas was passed through the vessel to carry benzene vapor into the reactor for the hydrogenation of benzene. The hydrogenation product was analyzed on-line by Agilent 7890A gas chromatography. Benzene conversion was 86% after 5 hours, 85% after 20 hours and 100% cyclohexane selectivity.
Example 22
The catalyst of example 7 was mixed uniformly with quartz sand particles of 0.5-2mm particle size, placed in a fixed bed reactor, pretreated with hydrogen at 80 ℃ for 1.5h, then heated to 200 ℃ and held at constant temperature. The temperature of the vessel containing benzene was set at 20 ℃ and 3ml/min of hydrogen gas was passed through the vessel to carry benzene vapor into the reactor for the hydrogenation of benzene. The hydrogenation product was analyzed on-line by Agilent 7890A gas chromatography. Benzene conversion was measured at 84% after 5 hours, 84% after 20 hours and 100% cyclohexane selectivity.
Example 23
The catalyst of example 8 and quartz sand particles with a particle size of 0.5-2mm were mixed uniformly, put into a fixed bed reactor, pretreated with hydrogen at 120 ℃ for 1.5h, then heated to 210 ℃ and kept at constant temperature. The temperature of the vessel containing benzene was set at 30 ℃ and 4ml/min of hydrogen gas was passed through the vessel to carry benzene vapor into the reactor for the hydrogenation of benzene. The hydrogenation product was analyzed on-line by Agilent 7890A gas chromatography. Benzene conversion was 85% after 5 hours, 85% after 20 hours and 100% cyclohexane selectivity.
Example 24
The catalyst of example 9 was mixed uniformly with quartz sand particles of 0.5-2mm particle size, placed in a fixed bed reactor, pretreated with hydrogen at 140 ℃ for 0.5h, then heated to 180 ℃ and held at constant temperature. The temperature of the vessel containing benzene was set at 20 ℃ and 5ml/min of hydrogen gas was passed through the vessel to carry benzene vapor into the reactor for the hydrogenation of benzene. The hydrogenation product was analyzed on-line by Agilent 7890A gas chromatography. Benzene conversion was 83% after 5 hours, 84% after 20 hours and 100% cyclohexane selectivity.
Example 25
The catalyst of example 10 was mixed uniformly with quartz sand particles of 0.5-2mm particle size, placed in a fixed bed reactor, pretreated with hydrogen at 120 ℃ for 1.5h, then heated to 160 ℃ and held at constant temperature. The temperature of the vessel containing benzene was set at 30 ℃ and 6ml/min of hydrogen gas was passed through the vessel to carry benzene vapor into the reactor for the hydrogenation of benzene. The hydrogenation product was analyzed on-line by Agilent 7890A gas chromatography. Benzene conversion was 83% after 5 hours, 84% after 20 hours and 100% cyclohexane selectivity.
Example 26
The catalyst of example 11 was mixed uniformly with quartz sand particles of 0.5-2mm particle size, placed in a fixed bed reactor, pretreated with hydrogen at 110 ℃ for 2.0h, then heated to 200 ℃ and held at constant temperature. The temperature of the vessel containing benzene was set at 25 ℃ and 7ml/min of hydrogen gas was passed through the vessel to carry benzene vapor into the reactor for the hydrogenation of benzene. The hydrogenation product was analyzed on-line by Agilent 7890A gas chromatography. Benzene conversion was 82% after 5 hours, 83% after 20 hours and cyclohexane selectivity was 100%.
Example 27
The catalyst of example 12 was mixed uniformly with quartz sand particles of 0.5-2mm particle size, placed in a fixed bed reactor, pretreated with hydrogen at 130 ℃ for 1.5h, then heated to 190 ℃ and held at constant temperature. The temperature of the vessel containing benzene was set at 20 ℃ and 2ml/min of hydrogen gas was passed through the vessel to carry benzene vapor into the reactor for the hydrogenation of benzene. The hydrogenation product was analyzed on-line by Agilent 7890A gas chromatography. Benzene conversion was 82% after 5 hours, 82% after 20 hours and cyclohexane selectivity was 100%.
Example 28
The catalyst of example 13 was mixed uniformly with quartz sand particles of 0.5-2mm particle size, placed in a fixed bed reactor, pretreated with hydrogen at 100 ℃ for 1.5h, then heated to 190 ℃ and held at constant temperature. The temperature of the vessel containing benzene was set at 30 ℃ and 8ml/min of hydrogen gas was passed through the vessel to carry benzene vapor into the reactor for the hydrogenation of benzene. The hydrogenation product was analyzed on-line by Agilent 7890A gas chromatography. Benzene conversion was 84% after 5 hours, 85% after 20 hours and 100% cyclohexane selectivity.
Example 29
The catalyst of example 14 was mixed uniformly with quartz sand particles of 0.5-2mm particle size, placed in a fixed bed reactor, pretreated with hydrogen at 120 ℃ for 1.5h, then heated to 210 ℃ and held at constant temperature. The temperature of the vessel containing benzene was set at 35 ℃ and 5ml/min of hydrogen gas was passed through the vessel to carry benzene vapor into the reactor for the hydrogenation of benzene. The hydrogenation product was analyzed on-line by Agilent 7890A gas chromatography. Benzene conversion was 86% after 5 hours, 86% after 20 hours and 100% cyclohexane selectivity.
Example 30
The catalyst of example 15 was mixed uniformly with quartz sand particles of 0.5-2mm particle size, placed in a fixed bed reactor, pretreated with hydrogen at 150 ℃ for 0.5h, then heated to 200 ℃ and held at constant temperature. The temperature of the vessel containing benzene was set at 20 ℃ and 5ml/min of hydrogen gas was passed through the vessel to carry benzene vapor into the reactor for the hydrogenation of benzene. The hydrogenation product was analyzed on-line by Agilent 7890A gas chromatography. Benzene conversion was 84% after 5 hours, 86% after 20 hours and 100% cyclohexane selectivity.
Example 31
The catalyst of comparative example 1 was uniformly mixed with quartz sand particles having a particle size of 0.5 to 2mm, put into a fixed bed reactor, pretreated with hydrogen at 150 ℃ for 0.5h, then heated to 160 ℃ and maintained at constant temperature. The temperature of the vessel containing benzene was set at 30 ℃ and 6ml/min of hydrogen gas was passed through the vessel to carry benzene vapor into the reactor for the hydrogenation of benzene. The hydrogenation product was analyzed on-line by Agilent 7890A gas chromatography. Benzene conversion was 65% after 5 hours, 66% after 20 hours and cyclohexane selectivity was 100%.
Example 32
The catalyst of comparative example 2 was uniformly mixed with quartz sand particles having a particle size of 0.5 to 2mm, put into a fixed bed reactor, pretreated with hydrogen at 150 ℃ for 0.5h, then heated to 160 ℃ and maintained at constant temperature. The temperature of the vessel containing benzene was set at 30 ℃ and 6ml/min of hydrogen gas was passed through the vessel to carry benzene vapor into the reactor for the hydrogenation of benzene. The hydrogenation product was analyzed on-line by Agilent 7890A gas chromatography. Benzene conversion was 45% after 5 hours, 46% after 20 hours and 100% cyclohexane selectivity.
Example 33
The catalyst of comparative example 3 was uniformly mixed with quartz sand particles having a particle size of 0.5 to 2mm, put into a fixed bed reactor, pretreated with hydrogen at 150 ℃ for 0.5h, then heated to 160 ℃ and maintained at constant temperature. The temperature of the vessel containing benzene was set at 30 ℃ and 6ml/min of hydrogen gas was passed through the vessel to carry benzene vapor into the reactor for the hydrogenation of benzene. The hydrogenation product was analyzed on-line by Agilent 7890A gas chromatography. Benzene conversion was 55% after 5 hours, 56% after 20 hours and 100% cyclohexane selectivity.
Example 34
The catalyst of comparative example 4 was uniformly mixed with quartz sand particles having a particle size of 0.5 to 2mm, put into a fixed bed reactor, pretreated with hydrogen at 150 ℃ for 0.5h, then heated to 160 ℃ and maintained at constant temperature. The temperature of the vessel containing benzene was set at 30 ℃ and 6ml/min of hydrogen gas was passed through the vessel to carry benzene vapor into the reactor for the hydrogenation of benzene. The hydrogenation product was analyzed on-line by Agilent 7890A gas chromatography. Benzene conversion was measured at 78% after 5 hours, 78% after 20 hours and 100% cyclohexane selectivity.
Example 35
Example 23 a catalyst stability test was conducted and the results showed that the average conversion was 85.5% and the average selectivity for C ═ C double bond hydrogenation was 100% over 100 hours.

Claims (8)

1. The application of the catalyst with the metal particles embedded in the carbon nano tube in the reaction of synthesizing cyclohexane by selective catalytic hydrogenation of benzene is characterized in that: the catalyst consists of a carbon nano tube, undoped carbon quantum dots and metal nano particles, wherein the carbon nano tube is a single-walled or multi-walled carbon tube with an opening, the carbon quantum dots are loaded on the outer wall of the carbon nano tube, and the metal nano particles are embedded in the inner wall of the carbon nano tube; the metal is one of palladium, platinum, gold, ruthenium, iridium, nickel and cobalt; the size of the carbon quantum dots is not more than 10 nm; in the carbon nanotube supported metal catalyst, the supported amount of the carbon quantum dots is 0.5-8.0 wt%, and the supported amount of the metal is 0.1-10.0 wt%.
2. The use of claim 1, wherein: the size of the carbon quantum dots is 2.5-5.5 nm.
3. The use of claim 1, wherein: the carbon nano tube embedded metal particle catalyst is prepared by the following method:
1) placing the carbon nano tube in concentrated nitric acid, heating and refluxing, cooling to room temperature after the heating and refluxing treatment, washing with water until filtrate is neutral, and drying to obtain the carbon nano tube subjected to acid treatment;
2) preparing an undoped carbon quantum dot solution and the carbon nano tube subjected to acid treatment obtained in the step 1) into a dispersion liquid, fully stirring to enable carbon quantum dots to be loaded on the outer wall of the carbon nano tube, and performing suction filtration and drying to obtain the carbon nano tube loaded with the carbon dots;
3) preparing the carbon nano tube loaded with the carbon dots obtained in the step 2) and deionized water into slurry, adding aqueous solution containing metal ions under the stirring state, forming complex anions by the metal ions and chloride ions in the aqueous solution, fully stirring, performing suction filtration, washing until the pH value of filtrate is neutral, and drying to obtain the carbon nano tube embedded metal particle catalyst.
4. Use according to claim 3, characterized in that: the carbon quantum dots without impurity doping are prepared by taking citric acid as a raw material and performing hydrothermal synthesis, and the specific process is as follows: taking citric acid and ethanol in a beaker, wherein the proportion is 0.5-5.0 g: 5-100mL, mechanically stirring until the mixture is uniformly mixed; then transferring the mixture into a hydrothermal kettle, carrying out hydrothermal treatment at the temperature of 120-; then carrying out centrifugal treatment under the condition that the rotating speed is 20000r/min, transferring the supernatant into a two-layer dialysis bag with the molecular weight cutoff of 100-10000 Dalton for dialysis treatment, wherein the carbon dot solution between the two layers is the carbon dot solution, and finally concentrating under the condition of shading low temperature until the concentration is 0.5-25.0 mg/L.
5. The use of claim 4, wherein: the cut-off molecular weight of the two-layer dialysis bag is 3000-7000 dalton.
6. Use according to one of claims 3 to 5, characterized in that: step 2) is carried out as follows: and feeding the non-doped carbon quantum dot solution and the carbon nano tube subjected to acid treatment according to the load capacity of the phosphorus-doped carbon quantum dots, stirring for 10-60min, and drying the filtered solid particles in a vacuum oven at the temperature of 50-100 ℃ for 2-15h to obtain the carbon nano tube loaded with the carbon dots.
7. The use of claim 1, wherein: step 3) is carried out as follows: the carbon nano tube loaded with the carbon dots obtained in the step 2) is mixed with water according to the feeding ratio of the carbon nano tube loaded with the carbon dots to the water of 1 g: preparing 5-35ml of prepared slurry, adding corresponding aqueous solution containing metal ions according to the metal loading capacity at the temperature of 5-40 ℃ under the stirring state, wherein the dropping speed of the aqueous solution containing the metal ions is 1d/1-10s, continuing stirring for 2-6h after the dropping is finished, performing suction filtration, washing until the pH value is neutral, and drying for 3-15h at the temperature of 50-100 ℃ to obtain the catalyst.
8. Use according to claim 1 or 2, characterized in that: the application method comprises the following steps: uniformly mixing a carbon nanotube embedded metal particle catalyst with quartz sand particles, wherein the granularity of the quartz sand is 0.5-2mm, putting the quartz sand particles into a fixed bed reactor, introducing hydrogen for pretreatment for 0.5-2h at 50-150 ℃, then heating to 150 ℃ and 250 ℃, and keeping the temperature constant; setting the temperature of the container containing benzene at 20-50 deg.c, and flowing 1-10ml/min hydrogen gas through the container to bring benzene vapor into the reactor for benzene hydrogenating reaction to produce cyclohexane.
CN201910799974.3A 2019-08-27 2019-08-27 Application of carbon nano tube embedded metal particle catalyst in reaction of synthesizing cyclohexane by benzene selective catalytic hydrogenation Pending CN110627606A (en)

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Cited By (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN111644206A (en) * 2020-06-28 2020-09-11 云南中烟工业有限责任公司 CQDs-loaded Fe-MIL-101 material, preparation method thereof and application thereof in catalytic oxidation of cyclohexane

Citations (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN108722459A (en) * 2017-06-30 2018-11-02 福州大学 The preparation method and applications of functionalized carbon nano-tube Pt-supported catalyst
CN109420510A (en) * 2017-08-24 2019-03-05 中国石油化工股份有限公司 A kind of preparing cyclohexane by hydrogenating benzene catalyst and preparation method thereof

Patent Citations (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN108722459A (en) * 2017-06-30 2018-11-02 福州大学 The preparation method and applications of functionalized carbon nano-tube Pt-supported catalyst
CN109420510A (en) * 2017-08-24 2019-03-05 中国石油化工股份有限公司 A kind of preparing cyclohexane by hydrogenating benzene catalyst and preparation method thereof

Cited By (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN111644206A (en) * 2020-06-28 2020-09-11 云南中烟工业有限责任公司 CQDs-loaded Fe-MIL-101 material, preparation method thereof and application thereof in catalytic oxidation of cyclohexane
CN111644206B (en) * 2020-06-28 2023-05-26 云南中烟工业有限责任公司 CQDs-loaded Fe-MIL-101 material, preparation method thereof and application thereof in catalytic oxidation of cyclohexane

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