Tubular reactor device and method of using the same

Abstract

The present invention discloses a tubular reactor device and a method for using the same. The tubular reactor device comprises: a vertical tube, a horizontal tube, a storage device and a product collection box. The bottom end of the vertical tube is connected to the top end of the product collection box, and a tail gas outlet is formed on the product collection box. One end of the horizontal tube is connected to the side wall of the vertical tube, and the other end is formed with a second input port. A heating device is installed around the vertical tube and the horizontal tube for heating the vertical tube and the horizontal tube. The top end of the vertical tube is sealed and formed with a first input port. The storage device is a sealed tank body, and a first heating layer for heating the storage device is installed outside the storage device. The second input port is connected to the storage device through a pipeline, and a third input port is formed on the storage device. The tubular reactor device of the present invention and the method for preparing a carbon nanotube / oxide composite material based on the tubular reactor device can improve the uniformity of the carbon nanotube / oxide composite material.

Description

Technical Field

[0001] The invention belongs to the technical field of material preparation devices, and in particular relates to a tubular reactor device and a use method thereof. Background Art

[0002] Carbon nanotubes (CNTs) have high strength, high conductivity and multifunctional properties. Carbon tubes are compounded with oxides with functional properties to prepare composite materials with functional properties, which can be used as energy storage, optoelectronics, sensitive materials, etc. At present, carbon tube oxide compounding is to compound prepared carbon tubes with carbon tubes. Carbon tubes are difficult to disperse and difficult to achieve uniform compounding. There is an urgent need for a device that can improve the uniformity of compounding. Summary of the invention

[0003] In view of the deficiencies of the prior art, an object of the present invention is to provide a tubular reactor device.

[0004] Another object of the present invention is to provide a method for using the tubular reactor device.

[0005] Another object of the present invention is to provide a method for preparing carbon nanotube / oxide composite materials by a gas phase method. The preparation method adopts a tubular reactor device and is based on a floating catalytic method to perform a one-step composite method on carbon tubes grown floating in the gas phase, thereby achieving uniform composite. The preparation method has the characteristics of dispersing carbon tubes in one step without the need for subsequent treatment.

[0006] The purpose of the present invention is achieved through the following technical solutions.

[0007] A tubular reactor device, comprising: a vertical tube, a horizontal tube, a storage device and a product collection box, wherein the vertical tube is arranged vertically, the horizontal tube is arranged horizontally, the bottom end of the vertical tube is connected to the top end of the product collection box, an exhaust gas outlet is formed on the product collection box, one end of the horizontal tube is connected to the side wall of the vertical tube, and the other end is formed with a second input port, and heating devices are installed around the vertical tube and the horizontal tube for heating the vertical tube and the horizontal tube;

[0008] The top end of the vertical tube is sealed and formed with a first input port;

[0009] The storage device is a sealed tank, a first heating layer for heating the storage device is installed outside the storage device, the second input port is connected to the storage device through a pipeline, and a third input port is formed on the storage device.

[0010] In the above technical solution, it also includes: a first T-tube, which is composed of a first vertical tube and a first horizontal tube, one end of the first horizontal tube is connected to the side wall of the first vertical tube, so that the first T-tube has three ports connected to each other, and one port of the first T-tube is connected to the first input port.

[0011] The above technical solution also includes: a second T-tube having the same structure as the first T-tube, wherein one port of the second T-tube is connected to the third input port.

[0012] In the above technical solution, the heating device installed around the vertical pipe is the second heating layer.

[0013] In the above technical solution, the heating device installed around the horizontal pipe is the third heating layer.

[0014] The method for using the above-mentioned tubular reactor device comprises the following steps:

[0015] 1) placing a first reactant in a storage device, and heating a heating device to increase the temperature of the vertical tube and the horizontal tube respectively;

[0016] 2) opening the tail gas outlet, and simultaneously inputting the second reactant and the first carrier gas through the first input port; heating the storage device by heating the first heating layer, and inputting the second carrier gas into the storage device through the third input port.

[0017] A method for preparing a carbon nanotube / oxide composite material comprises the following steps:

[0018] 1) placing an oxide precursor in a storage device of a tubular reactor device, and heating the heating device to raise the temperature of the vertical tube to 1100-1350° C. and the temperature of the horizontal tube to 800-900° C., wherein the oxide precursor is a mixture of a precursor reactant and water, and the ratio of the precursor reactant to water is (0.1-8):1 by volume;

[0019] In the step 1), the precursor reactant is titanium tetrachloride and / or tin tetrachloride.

[0020] In the step 1), when the precursor reactant is a mixture of titanium tetrachloride and tin tetrachloride, the ratio of titanium tetrachloride to tin tetrachloride is 1:1 by volume.

[0021] In the step 1), the precursor reactant is manganese nitrate.

[0022] 2) opening the tail gas outlet of the tubular reactor device, and simultaneously inputting carbon tube reactants, water and a first carrier gas through the first input port, wherein the input rate of the carbon tube reactants is 3 to 20 ml / h, the input rate of the water is 1 to 10 ml / h, and the input rate of the first carrier gas is 50 to 2000 sccm, wherein the carbon tube reactants are a mixture of a carbon source, a catalyst and an additive, wherein the carbon source is a liquid or gaseous hydrocarbon, the catalyst is an organic salt or an inorganic salt of a transition metal family, and the additive is thiophene and / or water;

[0023] The first heating layer is heated to heat the storage device to 50-120° C., and a second carrier gas is input into the storage device through the third input port. The input speed of the second carrier gas is 50-2000 sccm.

[0024] In the step 2), the ratio of the carbon source, the catalyst and the additive is (80-96): (1-3): (0.5-50) by mass.

[0025] In the step 2), the carbon tube reactant is a mixture obtained by uniformly mixing ethanol, ferrocene and thiophene, and the ratio of ethanol, ferrocene and thiophene is 93.75:3:0.5 by weight;

[0026] In the step 2), the ethanol, ferrocene and thiophene are uniformly mixed by mixing the ethanol, ferrocene and thiophene and then ultrasonicating them for at least 10 minutes.

[0027] In the above technical solution, the first carrier gas and the second carrier gas are argon, nitrogen and / or helium.

[0028] The carbon nanotube / oxide composite material obtained by the above preparation method.

[0029] Compared with the prior art, the tubular reactor device of the present invention and the preparation method of the carbon nanotube / oxide composite material based on the tubular reactor device can improve the uniformity of the carbon nanotube / oxide composite material. The preparation method of the present invention is based on the floating catalytic preparation process, and the carbon nanotubes grown floating in the gas phase are compounded in one step to achieve uniform compounding. The preparation method has the advantage of being one-step and not requiring subsequent treatment to disperse the carbon nanotubes. BRIEF DESCRIPTION OF THE DRAWINGS

[0030] Figure 1 It is a schematic structural diagram of a tubular reactor device of the present invention;

[0031] Figure 2 Optical photograph of carbon nanotube / oxide composite material obtained in Example 2 of the present invention;

[0032] Figure 3This is a scanning electron microscope image of a carbon nanotube / oxide composite material obtained in Example 2 of the present invention;

[0033] Figure 4 The transmission electron microscope image of the carbon nanotube / oxide composite material obtained in Example 2 of the present invention;

[0034] Figure 5 The transmission electron microscope image of the carbon nanotube / oxide composite material obtained in Example 3 of the present invention;

[0035] Figure 6 This is an optical photograph of the carbon nanotube / oxide composite material obtained in Example 4 of the present invention.

[0036] Among them, 1 is a product collecting box, 2 is a third heating layer, 3 is a horizontal pipe, 4 is a pipeline, 5 is a storage device, 6 is a first heating layer, 7 is a second T-tube, 7-1 is a second horizontal pipe, 7-2 is a second vertical pipe, 8 is a first T-tube, 8-1 is a first horizontal pipe, 8-2 is a first vertical pipe, 9 is a vertical pipe, 10 is a second heating layer, and 11 is an exhaust gas outlet. DETAILED DESCRIPTION

[0037] The technical solution of the present invention is further described below in conjunction with specific embodiments.

[0038] Example 1

[0039] like Figure 1 As shown, the tubular reactor device of the present invention includes: a vertical tube 9, a horizontal tube 3, a storage device 5, a first T-tube 8, a second T-tube 7 and a product collecting box 1, the vertical tube 9 is vertically arranged, the horizontal tube 3 is horizontally arranged, the bottom end of the vertical tube 9 is connected with the top end of the product collecting box 1, an exhaust gas outlet 11 is formed on the product collecting box 1, one end of the horizontal tube 3 is connected with the side wall of the vertical tube 9, and the other end is formed with a second input port, heating devices are installed around the vertical tube 9 and the horizontal tube 3 for heating the vertical tube 9 and the horizontal tube 3, wherein the heating device installed around the vertical tube 9 is a second heating layer 10, and the heating device installed around the horizontal tube 3 is a third heating layer 2.

[0040] The storage device 5 is a sealed tank, and a first heating layer 6 for heating the storage device 5 is installed outside the storage device 5 . The second input port is connected to the storage device 5 through a pipeline 4 , and a third input port is formed on the storage device 5 .

[0041] The top end of the vertical pipe 9 is sealed and formed with a first input port;

[0042] The first T-tube 8 is composed of a first vertical tube 8-2 and a first transverse tube 8-1. One end of the first transverse tube 8-1 is connected to the side wall of the first vertical tube 8-2 so that the first T-tube 8 has three ports connected to each other. One port of the first vertical tube 8-2 is connected to the first input port.

[0043] The second T-tube 7 has the same structure as the first T-tube 8, that is, the second T-tube 7 consists of a second vertical tube 7-2 and a second horizontal tube 7-1, one end of the second horizontal tube 7-1 is connected to the side wall of the second vertical tube 7-2, so that the second T-tube 7 has three ports connected to each other, and one port of the second vertical tube 7-2 is connected to the third input port.

[0044] The experimental operation of the following examples was carried out based on the tubular reactor apparatus in Example 1.

[0045] In the following embodiments, both the first carrier gas and the second carrier gas are argon.

[0046] Example 2

[0047] A method for preparing a carbon nanotube / oxide composite material comprises the following steps:

[0048] 1) An oxide precursor is injected into the storage device 5 through the upper port of the second vertical pipe 7-2. The oxide precursor is a mixture of a precursor reactant and water. The ratio of the precursor reactant to water is 0.2:1 by volume. The precursor reactant is titanium tetrachloride. The second heating layer 10 and the third heating layer 2 are heated separately so that the temperature of the vertical pipe 9 is raised to 1170°C and the temperature of the horizontal pipe 3 is raised to 800°C.

[0049] 2) Open the tail gas outlet 11, and simultaneously input the carbon tube reactant, water and the first carrier gas through the first input port, wherein the carbon tube reactant and water are input through the upper port of the first vertical tube 8-2, and the first carrier gas is input through the port of the first horizontal tube 8-1, the input rate of the carbon tube reactant is 9ml / h, the input rate of water is 6ml / h, and the input rate of the first carrier gas is 200sccm. The carbon tube reactant is a mixture (yellow liquid) obtained by mixing ethanol (carbon source), ferrocene (catalyst) and thiophene (additive) with ultrasound for 10 minutes, and the ratio of ethanol, ferrocene and thiophene is 93.75:3:0.5 by mass. Driven by the first carrier gas, the carbon tube reactant enters the vertical tube 9 and is pyrolyzed in the airflow of the vertical tube 9 to form carbon tubes.

[0050] The first heating layer 6 is heated to heat the storage device 5 to 80°C, the oxide precursor is bubbled, and the second carrier gas is input into the storage device 5 through the port of the second horizontal tube 7-1. The input speed of the second carrier gas is 200sccm. The second carrier gas drives the vapor of the oxide precursor into the horizontal tube 3.

[0051] At high temperature, titanium tetrachloride reacts with water vapor to form titanium oxide in the gas phase, which directly compounds with the carbon tubes in the airflow to form a carbon nanotube / oxide composite material. Then, driven by the airflow, the carbon nanotube / oxide composite material enters the product collection box 1, and the exhaust gas formed by the reaction is discharged through the exhaust gas outlet 11.

[0052] The carbon nanotube / oxide composite material obtained in Example 2 is white and fluffy like cotton. The optical photograph is as follows: Figure 2 Scanning electron microscopy and transmission electron microscopy showed that titanium oxide was uniformly wrapped on the surface of carbon nanotubes, as shown in Figure 3 and Figure 4 As shown. This shows that the carbon tubes are dispersed in the airflow and are uniformly compounded with the titanium oxide formed by the reaction in the airflow. The complex carbon tube dispersion process in the traditional compounding process is avoided. One-step, efficient and uniform compounding is achieved. The carbon tube / titanium oxide coaxial nanostructure is obtained.

[0053] Example 3

[0054] A method for preparing a carbon nanotube / oxide composite material comprises the following steps:

[0055] 1) An oxide precursor is injected into the storage device 5 through the upper port of the second vertical pipe 7-2. The oxide precursor is a mixture of a precursor reactant and water. The ratio of the precursor reactant to water is 0.5:1 by volume. The precursor reactant is tin tetrachloride. The second heating layer 10 and the third heating layer 2 are heated separately so that the temperature of the vertical pipe 9 is raised to 1170°C and the temperature of the horizontal pipe 3 is raised to 800°C.

[0056] 2) Open the tail gas outlet 11, and simultaneously input the carbon tube reactant, water and the first carrier gas through the first input port, wherein the carbon tube reactant and water are input through the upper port of the first vertical tube 8-2, and the first carrier gas is input through the port of the first horizontal tube 8-1, the input rate of the carbon tube reactant is 9ml / h, the input rate of water is 6ml / h, and the input rate of the first carrier gas is 200sccm. The carbon tube reactant is a mixture (yellow liquid) obtained by mixing ethanol (carbon source), ferrocene (catalyst) and thiophene (additive) with ultrasound for 10 minutes, and the ratio of ethanol, ferrocene and thiophene is 93.75:3:0.5 by mass. Driven by the first carrier gas, the carbon tube reactant enters the vertical tube 9 and is pyrolyzed in the airflow of the vertical tube 9 to form carbon tubes.

[0057] The first heating layer 6 is heated to heat the storage device 5 to 80°C, the oxide precursor is bubbled, and the second carrier gas is input into the storage device 5 through the port of the second horizontal tube 7-1. The input speed of the second carrier gas is 200sccm. The second carrier gas drives the vapor of the oxide precursor into the horizontal tube 3.

[0058] At high temperature, tin tetrachloride reacts with water vapor to form tin oxide in the gas phase, which directly compounds with the carbon tubes in the airflow to form a carbon nanotube / oxide composite material. Then, driven by the airflow, the carbon nanotube / oxide composite material enters the product collection box 1, and the exhaust gas formed by the reaction is discharged through the exhaust gas outlet 11.

[0059] Transmission electron microscopy showed that tin oxide was uniformly loaded on the surface of carbon nanotubes ( Figure 5 ). This shows that the gas phase recombination process realized based on this process can directly recombine carbon nanotubes in the gas phase. The carbon nanotubes grown in the gas phase are in a dispersed state, which is conducive to the loading of tin oxide on the surface of the carbon nanotubes. Compared with the subsequent tin oxide recombination, the dispersion process of the carbon nanotubes is avoided.

[0060] Example 4

[0061] A method for preparing a carbon nanotube / oxide composite material comprises the following steps:

[0062] 1) Inject an oxide precursor into the storage device 5 through the upper port of the second vertical pipe 7-2. The oxide precursor is a mixture of a precursor reactant and water. The ratio of the precursor reactant to water is 0.3:1 by volume. The precursor reactant is a mixture of tin tetrachloride and titanium tetrachloride. The ratio of tin tetrachloride to titanium tetrachloride is 1:1 by volume. The second heating layer 10 and the third heating layer 2 are heated respectively so that the temperature of the vertical pipe 9 is raised to 1170°C and the temperature of the horizontal pipe 3 is raised to 800°C.

[0063] 2) Open the tail gas outlet 11, and simultaneously input the carbon tube reactant, water and the first carrier gas through the first input port, wherein the carbon tube reactant and water are input through the upper port of the first vertical tube 8-2, and the first carrier gas is input through the port of the first horizontal tube 8-1, the input rate of the carbon tube reactant is 9ml / h, the input rate of water is 6ml / h, and the input rate of the first carrier gas is 200sccm. The carbon tube reactant is a mixture (yellow liquid) obtained by mixing ethanol (carbon source), ferrocene (catalyst) and thiophene (additive) with ultrasound for 10 minutes, and the ratio of ethanol, ferrocene and thiophene is 93.75:3:0.5 by mass. Driven by the first carrier gas, the carbon tube reactant enters the vertical tube 9 and is pyrolyzed in the airflow of the vertical tube 9 to form carbon tubes.

[0064] The first heating layer 6 is heated to heat the storage device 5 to 80°C, the oxide precursor is bubbled, and the second carrier gas is input into the storage device 5 through the port of the second horizontal tube 7-1. The input speed of the second carrier gas is 200sccm. The second carrier gas drives the vapor of the oxide precursor into the horizontal tube 3.

[0065] At high temperature, tin tetrachloride reacts with water vapor to form tin oxide in the gas phase, and titanium tetrachloride reacts with water vapor to form titanium oxide in the gas phase. Tin oxide and titanium oxide directly compound with carbon tubes in the gas flow to form a carbon nanotube / oxide composite material. Then, driven by the gas flow, the carbon nanotube / oxide composite material enters the product collection box 1, and the exhaust gas formed by the reaction is discharged through the exhaust gas outlet 11.

[0066] The optical photograph of the carbon nanotube / oxide composite material obtained in Example 4 is as follows Figure 6 As shown, it is light yellow and fluffy cotton-like. Compared with Example 1, the carbon nanotube / oxide composite material obtained in Example 4 is light yellow due to the addition of tin oxide, which is different from the white color of the carbon nanotube / oxide composite material obtained in Example 1. The overall product has a uniform color, indicating that the carbon nanotubes and tin oxide are uniformly composited.

[0067] In the technical solution of the present invention, by changing the oxide precursor, the carbon tube reactant, the first carrier gas and the second carrier gas input speed, the carbon tube reactant input speed, the water input speed and the heating temperature, the technical effects consistent with the above embodiments can be achieved. The above is an exemplary description of the present invention. It should be noted that, without departing from the core of the present invention, any simple deformation, modification or equivalent replacement that can be made by other technicians in this field without spending creative labor falls within the protection scope of the present invention.

Claims

1. A method for using a tubular reactor device, characterized in that: The tubular reactor device comprises: a vertical tube (9), a horizontal tube (3), a storage device (5) and a product collection box (1); the vertical tube (9) is arranged vertically, the horizontal tube (3) is arranged horizontally, the bottom end of the vertical tube (9) is connected to the top end of the product collection box (1), an exhaust gas outlet (11) is formed on the product collection box (1), one end of the horizontal tube (3) is connected to the side wall of the vertical tube (9), and the other end is formed with a second input port, and heating devices are installed around the vertical tube (9) and the horizontal tube (3) for heating the vertical tube (9) and the horizontal tube (3); The top end of the vertical pipe (9) is sealed and formed with a first input port; The storage device (5) is a sealed tank, a first heating layer (6) for heating the storage device (5) is installed outside the storage device (5), the second input port is connected to the storage device (5) through a pipeline (4), and a third input port is formed on the storage device (5); The method of use comprises the following steps: 1) placing a first reactant in a storage device (5) and raising the temperature of a heating device so that the temperature of the vertical tube (9) and the temperature of the horizontal tube (3) are respectively raised; 2) opening the tail gas outlet (11), and simultaneously inputting the second reactant and the first carrier gas through the first input port; heating the storage device (5) by the first heating layer (6), and inputting the second carrier gas into the storage device (5) through the third input port.

2. The method for using the tubular reactor device according to claim 1, characterized in that: Also includes: A first T-tube (8), the first T-tube (8) being composed of a first vertical tube (8-2) and a first horizontal tube (8-1), one end of the first horizontal tube (8-1) being connected to the side wall of the first vertical tube (8-2), so that the first T-tube (8) has three ports connected to each other, and one port of the first T-tube (8) being connected to the first input port.

3. The method for using the tubular reactor device according to claim 2, characterized in that: Also includes: A second T-tube (7) having the same structure as the first T-tube (8), one port of the second T-tube (7) being in communication with the third input port.

4. The method for using the tubular reactor device according to claim 3, characterized in that: The heating device installed around the vertical pipe (9) is a second heating layer (10).

5. The method for using the tubular reactor device according to claim 4, characterized in that: The heating device installed around the horizontal pipe (3) is the third heating layer (2).

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