CN116173869A - Production system for chemical vapor deposition reaction - Google Patents

Production system for chemical vapor deposition reaction Download PDF

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Publication number
CN116173869A
CN116173869A CN202310189054.6A CN202310189054A CN116173869A CN 116173869 A CN116173869 A CN 116173869A CN 202310189054 A CN202310189054 A CN 202310189054A CN 116173869 A CN116173869 A CN 116173869A
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reactor
vapor deposition
chemical vapor
production system
gas
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赵社涛
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Yingna Material Technology Zhenjiang Co ltd
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Yingna Material Technology Zhenjiang Co ltd
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    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J19/00—Chemical, physical or physico-chemical processes in general; Their relevant apparatus
    • B01J19/18—Stationary reactors having moving elements inside
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01D—SEPARATION
    • B01D45/00—Separating dispersed particles from gases or vapours by gravity, inertia, or centrifugal forces
    • B01D45/02—Separating dispersed particles from gases or vapours by gravity, inertia, or centrifugal forces by utilising gravity
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01D—SEPARATION
    • B01D45/00—Separating dispersed particles from gases or vapours by gravity, inertia, or centrifugal forces
    • B01D45/12—Separating dispersed particles from gases or vapours by gravity, inertia, or centrifugal forces by centrifugal forces
    • B01D45/16—Separating dispersed particles from gases or vapours by gravity, inertia, or centrifugal forces by centrifugal forces generated by the winding course of the gas stream, the centrifugal forces being generated solely or partly by mechanical means, e.g. fixed swirl vanes
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01D—SEPARATION
    • B01D46/00—Filters or filtering processes specially modified for separating dispersed particles from gases or vapours
    • B01D46/02—Particle separators, e.g. dust precipitators, having hollow filters made of flexible material
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01D—SEPARATION
    • B01D46/00—Filters or filtering processes specially modified for separating dispersed particles from gases or vapours
    • B01D46/24—Particle separators, e.g. dust precipitators, using rigid hollow filter bodies
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J19/00—Chemical, physical or physico-chemical processes in general; Their relevant apparatus

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  • Chemical & Material Sciences (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Organic Chemistry (AREA)
  • Chemical Vapour Deposition (AREA)

Abstract

The invention relates to a production system for chemical vapor deposition reaction, which comprises a preheater, a reactor and dust removal equipment which are sequentially connected, wherein the outlet of the preheater is connected with a plurality of raw material gas inlets of the reactor and is used for inputting preheated raw material gas into the reactor; the tail gas outlet of the reactor is connected with the gas inlet of the dust removing device and is used for filtering particulate matters in the tail gas of the reactor; the reactor is a vertical reactor, a heating device is arranged outside the reactor, a stirrer is arranged inside the reactor, a plurality of stirring paddles are arranged in a reaction area of the reactor, a tail gas outlet is arranged at the upper part of the reactor, and a raw material gas inlet is arranged at the lower part of the reactor.

Description

Production system for chemical vapor deposition reaction
Technical Field
The invention belongs to the technical field of chemical vapor deposition reaction equipment, and particularly relates to a production system for chemical vapor deposition reaction.
Background
For chemical vapor deposition reaction, the problem of mass and heat transfer between gas phase and solid phase is involved, and a reactor for chemical vapor deposition reaction is a difficult point in the chemical industry. For example, in the carbon nanotube reactor which has been industrialized at present, in order to obtain good mass and heat transfer performance due to the high temperature condition required for the reaction, a fluidized bed reactor with a large height-diameter ratio is generally adopted, the whole reactor is slender, and the raw material gas forms upward air flow in the reactor to drive the catalyst to fluidize and run in the reactor for reaction. However, the slender reactor has the advantages of large overall processing difficulty, narrow application range for materials and raw materials, small production capacity, difficult amplification, high height of plants and related matched equipment, and increased difficulty in installation and maintenance.
Disclosure of Invention
In view of the above problems, the present invention provides a production system for chemical vapor deposition reaction, comprising a preheater, a reactor and a dust removal device, which are sequentially connected, wherein an outlet of the preheater is connected with a plurality of raw material gas inlets of the reactor, and is used for inputting preheated raw material gas into the reactor; the tail gas outlet of the reactor is connected with the gas inlet of the dust removing device and is used for filtering particulate matters in the tail gas of the reactor;
the reactor is a vertical reactor, a heating device is arranged outside the reactor, a stirrer is arranged inside the reactor, a tail gas outlet is arranged at the upper part of the reactor, and a raw material gas inlet is arranged at the lower part of the reactor.
Optionally, the reactor comprises a reaction zone for performing chemical vapor deposition reaction, wherein the vertical height difference between the highest point and the lowest point of the reaction zone is h 1 The equivalent circle diameter of the maximum horizontal cross section of the reaction zone is h 2 The relationship between the two satisfies the following formula: h is a 1 /h 2 ≤5。
For vertical reactors, the top and partial bottom regions where the desired reaction temperature is not reached are not substantially reacted or the reaction efficiency is low.
As a specific embodiment, the reactor is cylindrical, and the ratio of the height to the diameter of the reaction zone in the reactor is h 1 /h 2 。
Optionally, the difference between the temperature of the mixed feed gases entering the reactor and the reaction temperature within the reactor is not greater than 100 ℃, preferably not greater than 50 ℃.
The reactor of the invention gives up the traditional slender fluidized bed reactor, adopts the reactor with the height-diameter ratio not more than 5, reduces the difficulty of processing, installing and maintaining the reactor, ensures lower equipment cost, and greatly improves the productivity of the reactor compared with the slender fluidized bed reactor on the premise of the same reactor height, thereby solving the problem that the chemical vapor deposition reactor is not easy to expand the production capacity. The stirrer is used for improving the mass and heat transfer problems caused by the overlarge diameter, and the preheater is matched for preheating the raw material gas, so that the raw material gas entering the reactor can quickly reach the reaction temperature, and the reactor can still maintain higher yield under the condition of not large height-diameter ratio.
Optionally, the preheater is selected from a tube heat exchanger, a plate heat exchanger or a coil heat exchanger.
Optionally, a feed inlet is arranged at the upper part of the reactor, and a discharge outlet is arranged at the lower part of the reactor and used for respectively inputting the catalyst and discharging the carbon nano tube products; the feed gas inlets are uniformly arranged at the bottom of the reactor around the axis of the reactor and are used for uniformly inputting feed gas into the reactor;
the bottom of the reactor is provided with a gas distribution plate, and the gas distribution plate is positioned between the discharge port and the raw material gas inlet.
Optionally, fins are uniformly arranged on the outer surface of the reactor, that is, fins are arranged between the reactor and the heating device, so that the heat exchange area of the reactor is increased.
The invention finds out a plurality of important keys affecting the mass transfer and the heat transfer of the reactor through practical engineering researchThe factors, namely the total heat exchange area of the preheater, the total heat exchange area of the reactor, the height of the reaction zone, the diameter of the reaction zone and the vertical length of the stirrer extending into the reaction zone, have certain matching relations, and can ensure that the reaction zone has good mass and heat transfer performance under the premise of low height-diameter ratio under the condition of meeting the matching relations. Further optionally, the total heat exchange area of the reactor, the total heat exchange area of the preheater and h of the reactor 1 、h 2 The following formula is satisfied:
Figure BDA0004104807200000021
wherein h is 1 And h 2 The unit of (2) is rice; s is S 1 For the total heat exchange area of the preheater, m 2 ；S 2 For the total heat exchange area of the reactor, m 2 The method comprises the steps of carrying out a first treatment on the surface of the h is the vertical length of the stirrer extending into the reaction zone, m.
The total heat exchange area of the preheater is the total heat exchange area marked on the nameplate of the preheater equipment. The total heat exchange area of the reactor is the sum of the surface area of the outer surface of the reactor surrounded by the heating device and the surface area of the fins.
When the length h of the stirrer extending into the reaction zone is increased, stirring and mass transfer in the reaction zone are enhanced, the conversion rate of raw materials is further increased, and the production weight of the carbon nano tube is increased.
Optionally, the top of dust collecting equipment is equipped with the gas vent, and inside is equipped with the cavity, has porous filter material in the cavity, and porous filter material plays the effect of the particulate matter in the filtration reaction tail gas, and the tail gas after the filtration is discharged by the gas vent. The porous filter material is a conventional dust-removing porous filter material.
Optionally, the top of dust collecting equipment is equipped with the gas vent, and the bottom is equipped with the collector, and the side at middle part is equipped with the air inlet, and follow reactor exhaust tail gas input dust collecting equipment, after filtering, solid material falls into the collector under the action of gravity, and the tail gas after filtering is discharged by the gas vent.
Optionally, the dust removing device is selected from a gravity dust removing device, a cloth bag dust removing device, a ceramic filter tube device, a metal sintering filter tube device or a cyclone dust remover.
Optionally, a cooling device may be further disposed between the reactor and the dust removing device, an inlet of the cooling device is connected with a tail gas outlet of the reactor, and an outlet of the cooling device is connected with an air inlet of the dust removing device, and is used for cooling tail gas exhausted from the reactor, so as to reduce the working temperature of the dust removing device.
Drawings
FIG. 1 is a schematic diagram of a production system for a chemical vapor deposition reaction;
FIG. 2 is a schematic structural view of the reactor.
In the drawing, a 1-preheater, a 2-reactor, a 3-dust removing device, a 4-raw material gas inlet, a 5-tail gas outlet, a 6-gas inlet, a 7-heating device, an 8-stirrer, a 9-feed inlet, a 10-discharge outlet, an 11-gas distribution plate, a 12-gas outlet and a 13-collector.
Detailed Description
Example 1
The embodiment provides a production system for chemical vapor deposition reaction, as shown in fig. 1-fig. and comprising a preheater 1, a reactor 2 and a dust removing device 3 which are sequentially connected, wherein the outlet of the preheater 1 is connected with four raw material gas inlets 4 of the reactor 2 and is used for inputting preheated raw material gas into the reactor 2; the tail gas outlet 5 of the reactor 2 is connected with the gas inlet 6 of the dust removing device 3 and is used for filtering particulate matters (such as a catalyst) in the tail gas of the reactor 2;
the reactor 2 is a vertical reactor, a heating device 7 is arranged outside the reactor, a stirrer 8 is arranged inside the reactor, a plurality of stirring paddles are arranged in a reaction zone of the reactor 2, a tail gas outlet 5 is arranged at the upper part of the reactor 2, and a raw material gas inlet 4 is arranged at the lower part of the reactor.
The reactor comprises a reaction zone for chemical vapor deposition reaction, the reaction zone is positioned in the middle of the reactor, and the vertical height difference between the highest point and the lowest point of the reaction zone is h 1 =1m, the equivalent circle diameter of the maximum horizontal cross section of the reaction zone is h 2 =0.8m, then h 1 /h 2 =1.25. The reaction zone is cylindrical.
The vertical length of the stirrer extending into the reaction zone was h=0.5 m, and the volume of the reaction zone was 0.5024m 3 The method comprises the steps of carrying out a first treatment on the surface of the The difference between the temperature of the feed gas entering the reactor 2 and the reaction temperature inside the reactor 2 was 100 ℃.
The preheater 1 is a tube-in-tube heat exchanger.
The top of the reactor 2 is provided with a feed inlet 9, and the bottom is provided with a discharge outlet 10 for respectively inputting catalyst and discharging carbon nanotube products; four raw material gas inlets 4 are uniformly arranged at the bottom of the reactor 2 around the axis of the reactor 2 and are used for uniformly inputting raw material gas into the reactor 2;
the bottom of the reactor 2 is provided with a gas distribution plate 11, and the gas distribution plate 11 is positioned between the discharge opening 10 and the raw material gas inlet 4, so that the entering raw material gas is uniformly distributed at the bottom of the reactor 2, and meanwhile, the discharged product is not hindered. The gas distribution plate 11 is of a conventional form in the art and has a surface with dense through holes.
Fins are uniformly arranged on the outer surface of the reactor, namely fins are arranged between the reactor and the heating device, so that the heat exchange area of the reactor is increased.
The top of dust collecting equipment 3 is equipped with gas vent 12, and the bottom is equipped with collector 13, and the side at middle part is equipped with air inlet 6, and follow reactor 2 exhaust tail gas input dust collecting equipment 3, after filtering, solid material falls into collector 13 under the action of gravity, and reuse catalyst and carbon nanotube wherein after waiting, the tail gas after filtering is discharged by gas vent 12, can discharge into outside air, also can collect the back and carry out subsequent specialty purification treatment.
The dust removing device 3 is a combination of a gravity dust removing device and a porous ceramic filter rod.
And a cooling device is further arranged between the reactor 2 and the dust removing equipment 3, an inlet of the cooling device is connected with a tail gas outlet 5 of the reactor 2, and an outlet of the cooling device is connected with an air inlet 6 of the dust removing equipment 3 and is used for cooling tail gas exhausted by the reactor 2 so as to reduce the working temperature of the dust removing equipment.
Raw gas of this exampleThe catalyst input by the feeding port 9 is powdery supported Fe-Ni bimetallic catalyst, and the flow rate of ethylene is 28.125m 3 And/h, the dosage of the catalyst is 3.287kg, the temperature of the preheated raw material gas is 550 ℃, the reaction temperature in the reactor is 650 ℃, and the stirring speed is 5r/min. At the end of the reaction, the bulk density of the carbon nanotubes was 60kg/m 3 The filling rate was 50% (the percentage of the total volume of carbon nanotube material accumulated to the volume of the reaction zone in a stationary state after the completion of the reaction), the reaction period of each batch was 1 hour, and the weight of carbon nanotubes produced per hour in the reactor was 15.072kg.
Total heat exchange area S of preheater 1 ＝15.0m 2 Total heat exchange area S of the reactor 2 ＝5.024m 2 。
Comparative example 1
The production system for chemical vapor deposition reaction provided in this comparative example was the same as that of example 1, the catalyst was also the same powder-supported Fe-Ni bimetallic catalyst, except that the reactor was a conventional fluidized bed reactor, no stirrer was provided inside, the catalyst was driven to perform fluidization reaction in the reactor by the upward flow rate of the reaction gas, the height of the reaction zone of the reactor was 1m, the inside diameter was 0.1m, the aspect ratio was 10, and the volume of the reaction zone was 0.00785m 3 1.56% of the volume of the reaction zone of example 1.
The reaction conditions were the same as in example 1, and the bulk density of the carbon nanotubes was 60kg/m after the completion of the reaction 3 The filling rate is 30% (the gas speed in the fluidized running reactor is relatively high, the expansion of the material bed layer is relatively high, so that the filling rate is relatively low after the reactor is stationary), the weight of the carbon nano tube produced by the reactor per hour is 0.141kg, and the productivity is obviously smaller than that of the embodiment 1.
Example 2
The production system for chemical vapor deposition reaction provided in this example was the same as that of example 1, except that the vertical length of the stirrer extending into the reaction zone was increased, h=0.8m, and the mass transfer and heat transfer properties of the reaction zone were improved.
Example 3
Provided by the embodimentThe production system for the chemical vapor deposition reaction was the same as in example 1, except that the reactor h 1 ＝5m，h 2 ＝1.2m，h 1 /h 2 = 4,h =4m, the volume of the reaction zone being 5.652m 3 . The bulk density of the carbon nanotube product was 30kg/m 3 The filling rate was 50%. Total heat exchange area S of preheater 1 ＝75.0m 2 Total heat exchange area S of the reactor 2 ＝43.5m 2 。
Example 4
The production system for chemical vapor deposition reaction provided in this example is the same as that in example 3, except that the reactor h 1 ＝5m，h 2 ＝0.98m，h 1 /h 2 =5.1, h=4m, the volume of the reaction zone is 3.77m 3 The bulk density of the carbon nanotube product was also 30kg/m 3 The filling rate was 35%. Total heat exchange area S of preheater 1 ＝50.5m 2 Total heat exchange area S of the reactor 2 ＝35.2m 2 。
Examples 1-3 all meet the following formulas, but example 4 does not meet the following formulas:
Figure BDA0004104807200000051
table 1 comparison of throughput for examples 1-4
Productivity (kg/h)
Example 1 15.07
Example 2 18.08
Example 3 84.78
Example 4 39.58
Comparative example 1 0.14
As can be seen from the above table, the production system for chemical vapor deposition reaction provided by the invention has a larger reaction area volume, greatly improves the productivity, and can obtain higher productivity by controlling the sizes of the preheater and the reactor so that the sizes of the preheater and the reactor meet a certain relation.

Claims (9)

1. The production system for the chemical vapor deposition reaction is characterized by comprising a preheater, a reactor and dust removal equipment which are sequentially connected, wherein the outlet of the preheater is connected with a plurality of raw material gas inlets of the reactor and is used for inputting the preheated raw material gas into the reactor; the tail gas outlet of the reactor is connected with the gas inlet of the dust removing device and is used for filtering particulate matters in the tail gas of the reactor;
the reactor is a vertical reactor, a heating device is arranged outside the reactor, a stirrer is arranged inside the reactor, a tail gas outlet is arranged at the upper part of the reactor, and a raw material gas inlet is arranged at the lower part of the reactor.
2. The production system for chemical vapor deposition according to claim 1, wherein the reactor comprises a reaction zone for performing chemical vapor deposition, and the vertical height difference between the highest point and the lowest point of the reaction zone is h 1 The equivalent circle diameter of the maximum horizontal cross section of the reaction zone is h 2 The relationship between the two satisfies the following formula: h is a 1 /h 2 ≤5。
3. The production system for chemical vapor deposition reaction according to claim 2, wherein the total heat exchange area of the preheater, the total heat exchange area of the reactor, and the h of the reactor 1 、h 2 The following formula is satisfied:
Figure FDA0004104807190000011
wherein h is 1 And h 2 The unit of (2) is rice; s is S 1 For the total heat exchange area of the preheater, m 2 ；S 2 For the total heat exchange area of the reactor, m 2 The method comprises the steps of carrying out a first treatment on the surface of the h is the vertical length of the stirrer extending into the reaction zone, m.
4. The production system for chemical vapor deposition reaction according to claim 1, wherein the reactor is provided with a feed inlet at an upper portion thereof and a discharge outlet at a lower portion thereof for feeding a catalyst and discharging a carbon nanotube product, respectively; the feed gas inlets are arranged at the bottom of the reactor and are used for uniformly inputting feed gas into the reactor.
5. The production system for chemical vapor deposition reactions according to claim 1 wherein the bottom of the reactor is provided with a gas distribution plate located between the discharge port and the feed gas inlet.
6. The production system for chemical vapor deposition reaction according to claim 1, wherein the outer surface of the reactor is provided with fins to increase a heat exchange area of the reactor.
7. The production system for chemical vapor deposition reaction according to claim 1, wherein the top of the dust removing device is provided with an exhaust port, a cavity is arranged in the dust removing device, a porous filtering material is arranged in the cavity, the porous filtering material plays a role in filtering particulate matters in reaction tail gas, and the filtered tail gas is discharged from the exhaust port.
8. The production system for chemical vapor deposition reaction according to claim 1, wherein the dust removing device has an exhaust port at the top, a collector at the bottom, an air inlet at the side of the middle, and the exhaust gas discharged from the reactor is introduced into the dust removing device, and after being filtered, the solid material enters the collector, and the filtered exhaust gas is discharged through the exhaust port.
9. The production system for chemical vapor deposition reaction according to claim 1, wherein a cooling device is further disposed between the reactor and the dust removing apparatus, an inlet of the cooling device is connected to a tail gas outlet of the reactor, and an outlet of the cooling device is connected to an air inlet of the dust removing apparatus, for cooling the tail gas discharged from the reactor, so as to reduce an operating temperature of the dust removing apparatus.
CN202310189054.6A 2023-03-02 2023-03-02 Production system for chemical vapor deposition reaction Pending CN116173869A (en)

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