KR102112030B1 - Supercritical semi-continuous flow type reactor, Method of manufacturing high heat resistant catalyst support using the same, and Method of recycling carbon fiber reinforced composites - Google Patents

Abstract

The supercritical fluid environment semi-continuous reactor includes a fluid container capable of injecting a solvent and an injection part including a carbon dioxide cylinder, a pump part for supplying the solvent at a uniform flow rate, and preheating the solvent supplied by the pump. Preheating unit, heating the solvent preheated by the preheater, a reaction unit for receiving a specimen therein, a cooling unit for cooling the solvent discharged from the reaction unit, and adjusting the solvent passed through the cooler to atmospheric pressure And a back pressure control part and a collection part for collecting the solvent that has passed through the back pressure regulator.

Description

Supercritical fluid environment semi-continuous reactor, a method of manufacturing a high heat resistance catalyst support using the same, and a method of recycling the carbon fiber reinforced composite using the same {Supercritical semi-continuous flow type reactor, Method of manufacturing high heat resistant catalyst support using the same, and Method of recycling carbon fiber reinforced composites}

The present invention relates to a supercritical fluid environment semi-continuous reactor, a method for manufacturing a high heat-resistant catalyst support using the supercritical fluid environment semi-continuous reactor, and a method for recycling a carbon fiber-reinforced composite material, and more specifically, to produce a high heat-resistant catalyst support and A supercritical fluid environment semi-continuous reactor capable of recycling carbon fiber reinforced composites, a method for manufacturing a high heat resistance catalyst support using the supercritical fluid environment semi-continuous reactors, and a method of recycling carbon fiber reinforced composites.

A single propellant thruster system is used to control posture and exercise ability of space vehicles such as satellites, and a single propellant thruster utilizing catalytic decomposition of a propellant as shown in Fig. 9 considering quick response characteristics and simplicity and stability of the system. Is used. Currently, a single-propellant thruster, which obtains thrust through catalytic decomposition of a hydrazine propellant, is mainly used. However, due to the toxicity of hydrazine, extra time and cost are consumed in handling, and research into high-performance, eco-friendly single propellant thrusters to replace them is actively underway.

Carbon fiber has superior properties compared to other fibers, such as strength and elasticity, and can be made of a composite material having high strength and high elasticity while being lightweight. The carbon fiber reinforced composite material is a composite material having a matrix of plastics, and a thermal curing matrix of an epoxy resin that is cured irreversibly is generally used. The above composite material is more expensive than the metal material, so its use is limited to the fields of automobile, machinery, aviation, aerospace, and sports, where weight is more important than cost. Carbon fiber-reinforced composites are discarded when errors occur in the manufacturing process or when the lifespan of parts is reached, and research is underway to process and recycle expensive carbon-fiber reinforced composites. Related references are as follows.

[1] N. Tanaka, T. Matsuo, K. Furukawa, M. Nishida, S. Suemori, A. Yasutake, The "Greening" of Spacecraft Reaction Control Systems, Mitsubishi Heavy Industries Technical Review, 48 (2011) 44-50 .

[2] Z.-M. Wang, Y.S. Lin, Sol-Gel Synthesis of Pure and Copper Oxide Coated Mesoporous Alumina Granular Particles, Journal of Catalysis, 174 (1998) 43-51.

[3] M. Tian, X.D. Wang, T. Zhang, Hexaaluminates: a review of the structure, synthesis and catalytic performance, Catalysis Science & Technology, 6 (2016) 1984-2004.

[4] E. Kiran, P.G. Debenedetti, C.J. Peters, Supercritical fluids: fundamentals and applications, Springer Science & Business Media, 2012.

[5] C.A. Garc ㅽ a-Gonz ㅱ lez, M.C. Camino-Rey, M. Alnaief, C. Zetzl, I. Smirnova, Supercritical drying of aerogels using CO2: Effect of extraction time on the end material textural properties, The Journal of Supercritical Fluids, 66 (2012) 297-306.

[6] C. Wang, S. Ying, Z. Xiao, Preparation of short carbon fiber / polypropylene fine-celled foams in supercritical CO2, Journal of Cellular Plastics, 49 (2012) 65-82.

[7] C.-C. Kuo, L.-C. Liu, W.-C. Liang, H.-C. Liu, C.-M. Chen, Preparation of polypropylene (PP) composite foams with high impact strengths by supercritical carbon dioxide and their feasible evaluation for electronic packages, Composites Part B: Engineering, 79 (2015) 1-5.

An object of the present invention is to provide a supercritical fluid environment semi-continuous reactor.

Another object to be achieved by the present invention is to provide a method for manufacturing a high heat-resistant catalyst support for a high performance eco-friendly single propellant thruster using the supercritical fluid environment semi-continuous reactor.

Another object to be achieved by the present invention is to provide a method for recycling a carbon fiber reinforced composite through solvation and decomposition of an epoxy bond by using the supercritical fluid environment semi-continuous reactor.

The supercritical fluid environment semi-continuous reactor according to an embodiment for realizing the object of the present invention for supplying the solvent at a uniform flow rate, an injection part including a fluid container capable of injecting a solvent and a carbon dioxide cylinder A pump unit, a preheating unit for preheating the solvent supplied by the pump, heating the solvent preheated by the preheater, a reaction unit accommodating a specimen therein, and cooling the solvent discharged from the reaction unit It includes a cooling unit, a back pressure control unit that adjusts the solvent that has passed through the cooler to atmospheric pressure, and a collection unit that collects the solvent that has passed through the back pressure regulator.

In one embodiment of the present invention, the solvent may be acetone (C ₃ H ₆ O), ethanol (C ₂ H ₆ O) and / or propanol (C ₃ H ₈ O).

In one embodiment of the present invention, the supercritical fluid environment semi-continuous reactor may further include a filter that filters out impurities and residues of the solvent that have passed through the cooling unit.

In one embodiment of the present invention, the injection unit may further include a carbon dioxide regulator that injects liquid carbon dioxide at a constant flow rate by maintaining a constant pressure at the rear end from the high pressure carbon dioxide cylinder.

In one embodiment of the present invention, the pump unit is a pump, a manifold, and a pressure above a certain level is supplied to the manifold, and the pressure in the manifold is higher than a set pressure through the fluid supplied from the pump It may further include a back pressure regulator for discharging.

In one embodiment of the present invention, the reactor comprises a reactor including a cover, a cylindrical inconel accommodated in the cover, a flange portion formed at the front and rear ends of the inconel, and a flange coupling portion coupled to the flange portion. It can contain.

In one embodiment of the present invention, the reaction portion is coupled to the flange portion and the flange coupling portion using a plurality of bolts, and when separating the remaining bolts except one of the bolts, the flange coupling portion of the one It may further include a crane that rotates around the bolt and pulls it up.

The method for manufacturing a high heat-resistant catalyst support according to an embodiment for realizing another object of the present invention described above is a cylindrical inconel, a flange portion formed at the front and rear ends of the inconel, and a flange coupling coupled with the flange portion A supercritical fluid environment semi-continuous reactor including a reactor including a part may be used. The method for preparing the high heat-resistant catalyst support includes mounting a specimen to place the catalyst support in the reactor, fixing a reaction chamber to fix the flange coupling portion to the flange, and closing the reaction chamber in which the catalyst support is located, oxygen in the reactor A purging step of purging using nitrogen for removal, a reaction chamber heating step of heating the reactor in a carbon dioxide environment, and after stopping the carbon dioxide input to the reactor, a solvent input step of adding a solvent, and the pressure of the reactor Maintaining the temperature and the flow rate of the oil to maintain the reaction, after stopping and adding carbon dioxide to the reactor, stopping heating and cooling to cool, after cooling the reactor, lowering the pressure in the reaction chamber to atmospheric pressure The pressure drop in the chamber, and the flange coupling And, a step opening the reaction chamber to obtain the catalyst support with the reaction chaembeoeul open to dry.

In one embodiment of the present invention, the method for preparing the high heat-resistant catalyst support is separated from the flange portion of the supercritical fluid environment semi-continuous reactor from the flange portion before the specimen mounting step, and existing in the Inconel. Existing specimen removal step of removing the specimen, and using nitrogen or carbon dioxide, may further include a residue removal step of removing the existing experimental residue.

In one embodiment of the present invention, the solvent may be acetone (C ₃ H ₆ O), ethanol (C ₂ H ₆ O) and / or propanol (C ₃ H ₈ O).

Recycling method of the carbon fiber reinforced composite material according to an embodiment for realizing another object of the present invention described above is a cylindrical inconel, a flange portion formed at the front and rear ends of the inconel, and a flange coupled with the flange portion It is possible to use a supercritical fluid environment semi-continuous reactor including a reactor including a coupling portion. The method of recycling the carbon fiber-reinforced composite includes a specimen mounting step of positioning the carbon fiber-reinforced composite material to be recycled in the reactor, and fixing the flange coupling portion to the flange portion to close the reaction chamber in which the carbon fiber-reinforced composite material is located. Chamber fixing step, purging step of purging with nitrogen to remove oxygen in the reactor, heating of the reaction chamber to heat the reactor in a nitrogen environment, and stopping the introduction of carbon dioxide into the reactor, followed by solvent injection Injecting step, maintaining the pressure and temperature of the reactor, and maintaining the flow rate of vaginal oil, and then stopping and cooling the heating and cooling step of introducing and cooling the carbon dioxide after stopping and adding the solvent to the reactor. After cooling, the pressure in the reaction chamber is lowered to atmospheric pressure. The pressure in the chamber falling step, and a separation unit coupled to said flange, and a step of the reaction chaembeoeul opening.

In one embodiment of the present invention, the supercritical fluid environment semi-continuous reactor may further include a filter to filter out the impurities of the cooled solvent and residues after the experiment. The recycling method of the carbon fiber-reinforced composite material may further include a purging step of performing a purging operation using nitrogen in the reactor after the pressure drop step in the reaction chamber. The carbon fiber filtered by the filter can be recovered.

In one embodiment of the present invention, the solvent may be acetone (C ₃ H ₆ O), ethanol (C ₂ H ₆ O) and / or propanol (C ₃ H ₈ O).

Through the present invention, a supercritical fluid environment using carbon dioxide can be provided, and a high specific surface area high heat-resistant catalyst support for a high-performance eco-friendly single propellant thruster can be manufactured. When using a high specific surface area catalyst support, the amount of catalyst required for complete catalytic decomposition and catalytic combustion of the propellant is relatively small, which reduces the cost of catalyst production and fulfills the mission of spacecraft due to the reduction in volume and mass of the propulsion system. Can lead to improved skills. In addition, the core technology can be secured in the development of a high-performance, eco-friendly single-propellant thruster system, and the additional cost and time required for handling can be reduced by replacing the existing hydrazine thruster which is toxic.

Through the present invention, the composite material can be recycled through solvation and decomposition of an epoxy-based matrix constituting an expensive carbon fiber reinforced composite material, and a very advantageous recycling process can be provided in terms of unit cost. Therefore, due to the price problem, the application field of the carbon fiber reinforced composite material used in a limited field can be widened. In addition, through the present invention, a polypropylene-based plastic can be produced using a carbon dioxide in a supercritical fluid environment to produce a thermoplastic micro-foamed plastic composite, and can be applied to electronic equipment, aircraft, and physical shock protection equipment in a space environment.

1 is a schematic design diagram showing a supercritical fluid environment semi-continuous reactor according to an embodiment of the present invention.
FIG. 2 is a design diagram for explaining the components of the supercritical fluid environment semi-continuous reactor of FIG.
3 and 4 are detailed design drawings of the preheater and the reactor of FIG. 2.
5 is a view for explaining the operation of the reactor of FIG.
6 is a schematic diagram of a liquid single propellant thruster.
7 is a view for explaining a method for drying a high heat-resistant catalyst support utilizing a sol-gel method.
8 is a view for explaining the Oil-drop method in the sol-gel method.
9 is a flow chart showing a method of manufacturing a high heat-resistant catalyst support according to an embodiment of the present invention.
10 is a view for explaining the recycling process of the carbon fiber reinforced composite.
11 is a view for explaining the supercritical fluid environment according to the pressure, volume and temperature of the fluid.
12 is a flow chart showing a method for manufacturing a carbon fiber reinforced composite material according to recycling of the carbon fiber reinforced composite material according to an embodiment of the present invention.
13 is a scanning electron microscope photograph (b) of the polypropylene-based micro-foam plastic composite (a) and the composite.

With respect to the embodiments of the present invention disclosed in the text, specific structural or functional descriptions are exemplified only for the purpose of describing the embodiments of the present invention, and the embodiments of the present invention can be implemented in various forms and the text It should not be construed as being limited to the embodiments described in.

The present invention can be variously changed and can have various forms, and specific embodiments will be illustrated in the drawings and described in detail in the text. However, this is not intended to limit the present invention to a specific disclosure form, and it should be understood as including all modifications, equivalents, and substitutes included in the spirit and scope of the present invention.

Terms such as first and second may be used to describe various components, but the components should not be limited by the terms. The terms may be used for the purpose of distinguishing one component from other components. For example, without departing from the scope of the present invention, the first component may be referred to as the second component, and similarly, the second component may also be referred to as the first component.

When an element is said to be "connected" or "connected" to another component, it is understood that other components may be directly connected to or connected to the other component, but there may be other components in between. It should be. On the other hand, when a component is said to be "directly connected" or "directly connected" to another component, it should be understood that no other component exists in the middle. Other expressions that describe the relationship between the components, such as "between" and "immediately between" or "neighboring" and "directly neighboring to" should be interpreted as well.

The terms used in the present application are only used to describe specific embodiments, and are not intended to limit the present invention. Singular expressions include plural expressions unless the context clearly indicates otherwise. In this application, the terms “include” or “have” are intended to indicate the existence of a listed feature, number, step, operation, component, part, or combination thereof, one or more other features or numbers, It should be understood that the existence or addition possibilities of steps, actions, components, parts or combinations thereof are not excluded in advance.

Unless otherwise defined, all terms used herein, including technical or scientific terms, have the same meaning as commonly understood by a person skilled in the art to which the present invention pertains. Terms, such as those defined in the commonly used dictionary, should be interpreted as meanings consistent with meanings in the context of related technologies, and should not be interpreted as ideal or excessively formal meanings unless explicitly defined in the present application. .

On the other hand, when an embodiment can be implemented differently, a function or operation specified in a specific block may occur differently from the order specified in the flowchart. For example, two consecutive blocks may actually be executed substantially simultaneously, or the blocks may be performed backwards depending on related functions or operations.

Hereinafter, preferred embodiments of the present invention will be described in detail with reference to the accompanying drawings. The same reference numerals are used for the same components in the drawings, and duplicate descriptions for the same components are omitted.

6 is a view showing a supercritical fluid environment semi-continuous reactor according to an embodiment of the present invention.

Referring to FIG. 6, the supercritical fluid environment semi-continuous reactor includes an injection part 100, a pump part 200, a preheating part 300, a reaction part 400, a cooling part 500, and a filter part 600. , It may include a back pressure control unit 700 and the collection unit 800.

The injection unit 100 is acetone (C ₃ H ₆ O), ethanol (C ₂ H ₆ O), propanol (C ₃ H ₈ O) can be injected into a fluid container (see 67 in FIG. 2) and carbon dioxide cylinder (See 1 in FIG. 2). The injection unit 100 may further include a nitrogen cylinder (not shown). The carbon dioxide in the carbon dioxide cylinder is present as a liquid at room temperature and a high pressure condition of 50 bar or more, and in order to provide the pump unit 200 in a liquid state, the carbon dioxide cylinder may use a high pressure carbon dioxide cylinder. In addition, the nitrogen of the nitrogen cylinder is to remove the remnants of the front end of the pump unit 200, it can be used as an inert gas in the heating step of the reaction unit 400.

The pump unit 200 may supply a uniform flow of solvent to form a constant flow of solvent in the reactor (see 37 in FIG. 2). The flow rate of the supplied solvent can be controlled by the pump unit 200, and the supply pressure of the solvent is a back pressure regulator (see 20 in FIG. 2) and needle valves (19 in FIG. 2) in the pump unit 200. , 21). The pump unit 200 may pressurize and supply a solvent under various temperature ranges. The operation of the pump unit 200 starts after heating the interior of the preheating unit 300 and the reaction unit 400 with inert nitrogen gas, and operation may continue for the entire operating time.

The solvent supplied through the pump unit 200 passes through a spiral pipe in the preheater of the preheater 300 (see 30 in FIG. 2), and after being preheated to 250 ° C. through the heater of the preheater, It may be supplied to the reaction unit 400. The pressure is measured at the rear end of the preheater 300, and a relief valve (see 35 in FIG. 2) may be provided as a safety device in case of an emergency.

In the reactor of the reaction unit 400, the temperature inside the reactor 37 may be increased to around 400 degrees C through a separate heating wire. In addition, to maintain the pressure of up to 180 bar, it is designed to maintain a supercritical fluid environment by using an inconel in a cylindrical shape of 8 cm or more in diameter (see 37c in FIG. 3). The reactor front and rear ends included a flange shape capable of fixing 8 bolts. Specimens for the purpose of the present invention can be inserted by lifting the flange through a separate crane after removing the 7 bolts at the rear end of the reactor. After the reactor is fastened, a solvent in a supercritical fluid environment in a high temperature and high pressure state passes through the reactor and can perform the object of the present invention. Paraffin and ammonia, or a mixture of matrix and solvent, can be passed through the reactor in a supercritical fluid state and transferred to a cooler (see 40 in FIG. 2).

The solvent flow in the supercritical fluid state discharged from the reactor is cooled while flowing a spiral tube embedded in a cylindrical heat exchanger through which water in the cooler of the cooling part 500 passes. When drying the catalyst support using carbon dioxide, it is possible to prevent the formation of dry ice in the back pressure regulating part 700 at the rear end, and in the subcritical and liquid state while passing through the cooler in the experiment of carbon fiber reinforced composite using an organic solvent. Can be cooled.

The fluid that has passed through the cooler is supplied to the filter (see 48 of FIG. 2) of the filter unit 600 and can pass through a porous material to recover fibers in the fluid. In addition, the filter may be designed to serve to prevent impurities other than the solvent fluid from flowing into the back pressure regulating unit 700 at the rear stage to cause failure. In the case of the production of a catalyst support using carbon dioxide, since a flow flowing toward the back pressure regulating part 700 does not contain impurities, a separate flow path may be installed around the filter for smooth flow and operation of the fluid.

The back pressure regulating part 700 may serve to adjust the pressure of the solvent in the liquid state or gaseous state located at the front end of the regulator to atmospheric pressure as it passes through the back pressure regulator. According to the expansion phenomenon through the pressure drop, the temperature of the solvent is lowered, thereby preventing the combustion of the solvent. The fluid that has passed through the back pressure regulator may be collected in the collection unit 800.

In the case of a solvation decomposition reaction using ethanol, acetone, and propanol, it may be collected in a small tank in the collection unit 800 for further analysis of the epoxy compound dissolved in the solvent. In the case of drying using carbon dioxide as a solvent, carbon dioxide can be exhausted to the outside of the present invention.

FIG. 2 is a design diagram for explaining the components of the supercritical fluid environment semi-continuous reactor of FIG. 1.

2, the supercritical fluid environment semi-continuous reactor includes a carbon dioxide cylinder (1), a pressure gauge (2), a pressure gauge (3), a needle valve (4), a carbon dioxide regulator (5), and a carbon dioxide supply line (6). ), Supply pipe (7), needle valve (8), needle valve (9), filter (10), ball valve (11), needle valve (12), pump (13), needle valve (14), bypass (15) ), Electrical components 16, manifold system 17, pressure gauge 18, needle valve 19, back pressure regulator 20, needle valve 21, bypass 22, needle valve 23, Flowmeter 24, flow gauge 25, needle valve 26, bypass 27, check valve 28, needle valve 29, preheater 30, heater 31, temperature sensor 32, Regulator 33, pressure gauge 34, relief valve 35, electronic heater 36, reactor 37, regulator 38, temperature gauge 39, cooler 40, coolant inlet 41, Cooling water outlet (42), pressure gauge (43), ball valve (44), temperature gauge (45), ball valve (46), ball valve (47), filter (48), discharge Ball valve 49, bypass 50, pressure sensor 51, regulator 52, check valve 53, needle valve 54, back pressure regulator 55, needle valve 56, bypass (57) ), Pressure regulating valve 58, ball valve 59, drive unit 60, ball valve 61, bypass 62, ball valve 63, ball valve 64, fluid collection container 65, Carbon dioxide collection vessel 66 and fluid vessel 67.

According to this embodiment, it is possible to use both a high pressure carbon dioxide cylinder for supplying liquid carbon dioxide, liquid carbon dioxide at a low temperature, and a carbon dioxide cylinder 1 in the form of a siphon.

The pressure gauge 2 can grasp the amount of carbon dioxide inside the carbon dioxide cylinder.

The pressure gauge 3 may indicate the pressure of the wake adjusted through the carbon dioxide regulator 5.

The needle valve 5 can control the flow of carbon dioxide injected into a separate supply pipe for purging the semi-continuous reactor system using carbon dioxide.

The carbon dioxide regulator 5 may inject liquid carbon dioxide at a constant flow rate by maintaining a constant pressure at the rear end from a high pressure carbon dioxide cylinder. In the case of using a siphon-type carbon dioxide, it is necessary to maintain a rear pressure of at least 50 bar or higher at room temperature to supply liquid carbon dioxide.

The carbon dioxide supply line 6 may be sealed with an insulating material in preparation for injection using low temperature liquid carbon dioxide.

The supply pipe 7 may be a separate supply pipe for purging the semi-continuous reactor system using carbon dioxide.

The needle valve 8 may control the flow rate of the carbon dioxide supply pipe for injecting high pressure liquid carbon dioxide.

The needle valve 9 may control the supply of fluids such as methanol, propanol, acetone, and the carbon dioxide supply flow rate for system purge.

The filter 10 may remove impurities in the supply fluid such as carbon dioxide, methanol, propanol, and acetone.

The ball valve 11 may drain the fluid located in the supply pipe before the pump after the end of the experiment.

The needle valve 12 can control the flow to the pump to supply the fluid.

The pump 13 may be selected as a material that does not react with the fluid in addition to the pressure and temperature conditions of the fluid and the material for preventing internal leakage in order to satisfy the conditions for using both liquid carbon dioxide and acetone, methanol, and propanol. .

The needle valve 14 may control the flow rate of the rear end of the pump for fluid supply.

The detour 15 is a detour of flow for proceeding purge of the system without using a pump, and is equipped with a separate ball valve.

The electrical components 16 can set the temperature and pressure of the reactor system and the supply flow rate of the fluid, and obtain data by grasping the temperature and pressure of the reactor and the preheater in real time.

The manifold system 17 can be a 500 ml volume manifold system for smooth supply of fluid. A needle valve for discharging fluid in the manifold after the end of the experiment is attached.

The pressure gauge 18 can check the pressure in the manifold system 17 and the set pressure of the back pressure regulator 20. A ball valve is attached so that it can be used only for experimentation.

The needle valve 19 may control fluid flow to the back pressure regulator 20 for supplying fluid.

The reverse pressure regulator 20 is for supplying fluid, and a pressure above a certain level is supplied to the manifold 17, and the pressure in the manifold is greater than the set pressure of the regulator through the fluid supplied from the pump 130. When it becomes high, the supply proceeds by discharging the fluid.

The needle valve 21 may control the fluid flow at the rear end of the reverse pressure regulator 20.

The bypass 22 is a bypass for use when the reverse pressure regulator 20 is not used, and a needle valve is attached to not be used when experimenting.

The needle valve 23 is a needle valve for controlling the flow of fluid to the flow meter 24.

The flow meter 24 may be an electronic flow meter capable of measuring the flow rate of the supplied carbon dioxide. Liquid carbon dioxide, acetone, ethanol, and propanol are all used. Seals can be used, and impurities can be removed through the filter at the front of the flow meter.

The flow gauge 25 may display the flow rate measured by the flow meter 24 on the system electrical component 16.

The needle valve 26 may control the flow of fluid passing through the flow meter 24.

The bypass 27 is a bypass for the case where the flow meter 24 is not used, and a needle valve for flow control is attached. In the case of acetone, ethanol, and propanol, the flow rate can be measured with the naked eye without using an electronic flow meter.

The check valve 28 may control the flow rate from the preheater 30 at the rear end, and maintain the flow of fluid passing through the flowmeter 24 in a constant direction.

The needle valve 29 can control the flow to the preheater.

The preheater 30 may perform preheating to smoothly form a desired supercritical fluid environment. The fluid can be preheated using a coiled 1/4 "pipe.

The heater 31 is for preheating the preheater 30 and may be an electronic heater. A mechanism for controlling the amount of heat according to the set temperature of the electrical appliance 16 is included.

The temperature sensor 32 may measure the temperature inside the preheater 30.

The regulator 33 may adjust the heater 31 of the preheater 30 by comparing the temperature measured from the temperature sensor 32 with the temperature input from the electrical appliance 16.

The pressure gauge 34 can check the pressure after the preheater 30.

The relief valve 35 may prepare for a case when the pressure of the preheater 30 and the reactor 37 is locally increased due to an unexpected emergency.

The electronic heater 36 is an electronic heater of a reactor that forms a supercritical fluid environment, and includes a mechanism for controlling the amount of heat according to a set temperature of the electrical appliance 16.

The reactor 37 may form a supercritical fluid environment. The temperature is measured at three parts of the front end, middle end, and rear end of the reactor 37, and the temperature is adjusted through the regulator 38 in the electrical appliance 16 using the measured temperature. In addition, the internal pressure is regulated through the pressure regulating valve 58 at the rear end.

The regulator 38 may measure the temperature of the front, middle, and rear stages of the reactor 37, and control the heat amount of the heater by comparing with the input value of the electrical equipment 16.

When a sufficient pressure is supplied to the reactor through the pump 13, the pressure is adjusted through the pressure regulating valve 58 or the reverse pressure regulator 55 to generate a semi-continuous flow, and the temperature gauge 39 Can measure the temperature of the flow of the resulting semi-continuous flow.

The cooler 40 may protect the pressure regulating valve 55 and the back pressure regulator 55 at a rear stage from high temperature.

The coolant inlet 41 is an inlet of the coolant of the cooler 40, and a ball valve for flow control is installed.

The cooling water outlet 42 is an outlet of the cooling water of the cooler 40, and a ball valve for flow control is installed.

The pressure gauge 43 may measure pressure after the cooler 40.

The ball valve 44 may control flow depending on whether the pressure gauge 43 is used.

The temperature gauge 45 may measure the temperature after the cooler 40.

The ball valve 46 may control the flow of fluid after the cooler 40 with the filter 48.

The ball valve 47 may allow flow to flow to a bypass installed for the case where the filter 48 is not used.

The filter 48 may filter impurities in the flow of the flow after the cooler 40 and remnants after the experiment.

The discharge ball valve 49 may discharge fluid in the filter after the end of the experiment.

The bypass 50 may be a bypass for the case where the filter 48 is not used.

The pressure sensor 51 may be an electronic pressure sensor for measuring pressure after the filter 48. It is the same as the pressure inside the reactor 37, and the pressure regulating valve 58 is driven using the pressure data of the pressure sensor 51.

The regulator 52 may drive the pressure regulating valve 58 by comparing pressure data received from the pressure sensor 51 with a required pressure value.

The check valve 53 may induce the flow of the flow after the filter 48 in one direction.

The needle valve 54 may control the flow of flow to the reverse pressure regulator 55 after the filter 48.

The back pressure regulator 55 may adjust the pressure in the reactor 37. The main adjustment is performed by the pressure regulating valve 58, and when the driving of the pressure regulating valve 58 is not smoothly performed, the pressure regulating is performed using the reverse pressure regulator 55. A specific pressure is set through the pressure gauge 43 after the cooler 40.

The needle valve 56 may control the flow of fluid after the filter 48 and after the back pressure regulator 55.

The bypass (57) is a bypass for proceeding pressure control using the pressure regulating valve (58) without using the back pressure regulator (55) after the filter (48), and a needle valve to control the flow Installed.

The pressure regulating valve 58 may maintain the pressure inside the reactor 37 equal to a set value. It is driven according to the signal of the regulator 52 in the electrical appliance 16 for pressure adjustment.

The ball valve 59 can control the flow of fluid to the pressure regulating valve 58.

The driving unit 60 is an actual actuator of the pressure regulating valve 58, and a seal for using carbon dioxide, ethanol, propanol, acetone, and the like is applied.

The ball valve 61 may control the flow of fluid after the pressure regulating valve 58.

The bypass 62 proceeds to adjust the pressure in the reactor 37 using the back pressure regulator 55 after the filter 48 without using the pressure regulating valve 58 and the driving unit 60. This is a detour for the ball valve, and a ball valve is installed to control the flow.

The ball valve 63 may control the flow of fluid in order to collect fluid when a fluid such as acetone, ethanol, or propanol passes through the reactor.

The ball valve 64 may control the flow of fluid to collect fluid when liquid carbon dioxide passes through the reactor 37.

The fluid collection container 65 may collect fluid when fluids such as acetone, ethanol, and propanol pass through the reactor 37.

The carbon dioxide collection container 66 may collect fluid when the carbon dioxide fluid passes through the reactor 37.

The fluid container 67 is a container for supplying fluid such as acetone, ethanol, and propanol, which corresponds to a fluid injection unit, and the fluid is supplied to the system through the pump 13, and a ball valve is provided for flow control. Installed.

3 and 4 are detailed design drawings of the preheater and the reactor of FIG. 2. 5 is a view for explaining the operation of the reactor of FIG.

3 to 5, the reactor 37 has an upper cover 37a, a lower cover 37b, an inconel 37c, a flange portion 37d, a flange coupling portion 37e, a wire 37f, and a winch (37g), may include a frame (37h).

The upper cover 37a and the lower cover 37b may accommodate the inconel 37c, and the upper cover 37a may be opened. The upper cover 37a and the lower cover 37b may surround the inconel 37c, and a heating wire for heating the inconel 37c may be provided.

The inconel 37c may have a cylindrical shape of 8 cm or more in diameter to maintain a maximum pressure of 180 bar. The flange portion 37d may be formed at the front end and the rear end of the inconel 37c to be coupled with the flange coupling portion 37e. The flange portion 37d and the flange coupling portion 37e may be coupled to each other using eight bolts, and after removing the seven bolts at the rear end, the wire 37f connected to the flange coupling portion 37e ) And lifting the flange coupling part 37e through a crane including the winch 37g that pulls up the wire 37f to insert a specimen therein.

6 is a schematic diagram of a liquid single propellant thruster. 7 is a view for explaining a method of drying a high heat-resistant catalyst support utilizing a sol-gel method. 8 is a view for explaining the Oil-drop method in the sol-gel method.

Referring to Figures 6 to 8, a single propellant thruster system is used to control posture and exercise ability of a space vehicle such as an artificial satellite, and a catalyst of a propellant as shown in FIG. 9 in consideration of quick response characteristics and simplicity and stability of the system A single propellant thruster using decomposition is used. Currently, a single-propellant thruster, which obtains thrust through catalytic decomposition of a hydrazine propellant, is mainly used. However, due to the toxicity of hydrazine, extra time and cost are consumed in handling, and research into high-performance, eco-friendly single propellant thrusters to replace them is actively underway. As a propellant of a typical high-performance eco-friendly single propellant thruster, a pre-mixed propellant in which fuel and an oxidant are mixed is mainly used, and when the catalyst is burned, a high-temperature environment reaching 1,800 degrees C is formed. In order to maintain the performance of a high-performance eco-friendly single propellant thruster, research and development related to a high heat-resistant catalyst capable of maintaining a high specific surface area in a high-temperature environment should be accompanied.

A sol-gel method for producing a porous alumina support is known as a method for producing a high heat-resistant catalyst. The sol of the support is produced through the hydrolysis reaction of the alumina precursor, and the catalyst support in the form of a gel is produced through a pelletization process. Subsequently, the catalyst is prepared through drying and active material loading. The active material may be supported in the sol state, and the pellet and the process may use an oil-drop method or a mechanical compression method. In addition, drying methods include drying in a room temperature environment, drying in a cryogenic environment, and drying in a supercritical fluid environment. The catalyst support produced in the above manner was named Xerogel, Cryogel, Aerogel. The specific surface area of the support is formed differently depending on the drying environment of the support, and in the case of the Aerogel method of drying in a supercritical fluid environment, as shown in Fig. 10, when drying the support, it is the least affected by gravity and the interaction between the surrounding supports. It has a specific surface area. When preparing the catalyst support through the sol-gel method, the pelletization process maintains the shape of the gel-like catalyst support through an aqueous ammonia solution after passing the alumina in the sol state through the paraffin layer as shown in FIG. A high specific surface area Aerogel catalyst support can be produced by drying the supercritical fluid environment of the gel-shaped catalyst support, and in the present invention, liquid carbon dioxide is used as an initial solvent to form a supercritical fluid environment, and FIGS. The catalyst support can be easily made by using a supercritical fluid environment semi-continuous reactor of 5.

9 is a flow chart showing a method of manufacturing a high heat-resistant catalyst support according to an embodiment of the present invention.

1, 2 and 9, the method for preparing the high heat-resistant catalyst support may include a sample preparation step (S100), an experiment step (S200), and a sample separation step (S300). The method for preparing the high heat-resistant catalyst support may be performed using the supercritical fluid environment semi-continuous reactor of FIGS. 1 and 2.

The sample preparation step (S100) may include an existing specimen removal step (S110), a residue removal step (S120), a specimen mounting step (S130), and a reaction chamber fixing step (S140).

In the step of removing the existing specimen (S110), the flange coupling portion 37e of the reactor 37 of the supercritical fluid environment semi-continuous reactor is separated from the flange portion 37d, and the existing specimen existing inside the Inconel 37c. Can be removed.

In the residue removal step (S120), existing experimental residues may be removed using nitrogen or carbon dioxide.

In the specimen mounting step (S130), the catalyst support may be placed in the reactor 37. At this time, the catalyst support may be a catalyst support that has undergone a pelletization process after the sol-gel method, as described above.

In the fixing of the reaction chamber (S140), the flange coupling portion 37e may be fixed to the flange portion 37d to close the reaction chamber in which the catalyst support is located.

The experiment step (S200) may include a purging step (S210), a reaction chamber heating step (S220), a solvent input step (S230), a holding step (S330), and a heating stop and cooling step (S340).

In the purging step (S210), a purging operation using nitrogen may be performed to remove oxygen in the reactor 37.

In the reaction chamber heating step (S220), the reactor 37 may be heated. At this time, the reactor 37 may be heated in a carbon dioxide environment.

In the step of introducing the solvent (S230), after stopping the input of carbon dioxide into the reactor 37, a solvent may be introduced. The solvent may be a fluid such as acetone, ethanol, or propanol.

In the holding step (S330), the reaction may be maintained by maintaining the pressure, temperature, and the amount of vaginal flow of the reactor 37.

In the step of stopping heating and cooling (S340), carbon dioxide is introduced into the reactor 37 and heating is stopped, followed by cooling.

The sample separation step (S300) may include a pressure drop step (S310) and a reaction chamber opening step (S320) in the reaction chamber.

In the step of dropping the pressure in the reaction chamber (S310), after the reactor 37 is cooled, the pressure in the reaction chamber may be reduced to atmospheric pressure.

In the opening of the reaction chamber (S320), the flange coupling portion 37e of the reactor 37 is separated to open the reaction chamber.

Thereafter, a dried catalyst support can be obtained to obtain a highly heat-resistant catalyst support.

10 is a view for explaining the recycling process of the carbon fiber reinforced composite. 11 is a view for explaining the supercritical fluid environment according to the pressure, volume and temperature of the fluid.

Referring to FIGS. 10 and 11, carbon fibers have superior properties compared to other fibers, such as strength and elasticity, and can make a composite material having high strength and high elasticity while being lightweight. The carbon fiber reinforced composite material is a composite material having a matrix of plastics, and a thermal curing matrix of an epoxy resin that is cured irreversibly is generally used. The above composite material is more expensive than the metal material, so its use is limited to the fields of automobile, machinery, aviation, aerospace, and sports, where weight is more important than cost. Carbon fiber-reinforced composites are discarded when an error occurs during the manufacturing process or when the parts have reached the end of their life. Research is underway to process and recycle expensive carbon fiber-reinforced composites. Same as 4.

The matrix using the epoxy resin in the carbon fiber reinforced composite is solvated and decomposed through an environmentally friendly solvent such as methanol, propanol, acetone, etc. in a supercritical fluid environment. Through the present invention, it is possible to form a supercritical fluid environment for the recycling of carbon fiber reinforced composites, and carbon fibers can be recovered and recycled when manufacturing new composite parts because they do not affect the mechanical properties of carbon fibers. In addition, the chemically decomposed epoxy resin-based matrix can be reused for other purposes depending on the conditions of the supercritical fluid environment used in the present invention, and the solvent used in the present invention can also be recycled through a distillation process to be economically feasible. Recycling process can be provided.

12 is a flow chart showing a method of manufacturing a carbon fiber reinforced composite according to recycling of the carbon fiber reinforced composite according to an embodiment of the present invention.

1, 2 and 12, the method for preparing the high heat-resistant catalyst support may include a sample preparation step (S100), an experimental step (S200), and a sample separation step (S300). The method for preparing the high heat-resistant catalyst support may be performed using the supercritical fluid environment semi-continuous reactor of FIGS. 1 and 2.

The sample preparation step (S100) may include an existing specimen removal step (S110), a residue removal step (S120), a specimen mounting step (S130), and a reaction chamber fixing step (S140).

In the step of removing the existing specimen (S110), the flange coupling portion 37e of the reactor 37 of the supercritical fluid environment semi-continuous reactor is separated from the flange portion 37d, and the existing specimen existing inside the Inconel 37c. Can be removed.

In the residue removal step (S120), existing experimental residues may be removed using nitrogen or carbon dioxide.

In the specimen mounting step (S130), the carbon fiber-reinforced composite material to be recycled may be located in the reactor 37. At this time, the carbon fiber-reinforced composite material, as described above, is a carbon fiber composite material having a matrix of plastics, and may be a thermal curing matrix of an epoxy resin that is generally irreversibly cured.

In the step of fixing the reaction chamber (S140), the flange coupling portion 37e may be fixed to the flange portion 37d to close the reaction chamber in which the carbon fiber reinforced composite material is located.

The experiment step (S200) may include a purging step (S210), a reaction chamber heating step (S220), a solvent input step (S230), a holding step (S330), and a heating stop and cooling step (S340).

In the purging step (S210), a purging operation using nitrogen may be performed to remove oxygen in the reactor 37.

In the reaction chamber heating step (S220), the reactor 37 may be heated. At this time, the reactor 37 may be heated in a nitrogen (N2) environment.

In the solvent input step (S230), after the nitrogen input is stopped in the reactor 37, a solvent may be added. The solvent may be a fluid such as acetone, ethanol, or propanol.

In the holding step (S330), the reaction may be maintained by maintaining the pressure, temperature, and the amount of vaginal flow of the reactor 37.

In the heating interruption and cooling step (S340), after the solvent input and heating are stopped in the reactor 37, carbon dioxide may be introduced and cooled.

The sample separation step (S300) may include a pressure drop in the reaction chamber (S310), a drain filter connection step (S312), a purging step (S314), and a reaction chamber opening step (S320).

In the step of lowering the pressure in the reaction chamber (S310), after the reactor 37 is cooled, the pressure in the reaction chamber may be reduced to atmospheric pressure.

In the drain filter connection step S312, the filter 48 may be connected.

In the purging step (S314), a purging operation may be performed using nitrogen in the reactor 37.

In the opening of the reaction chamber (S320), the flange coupling portion 37e of the reactor 37 may be separated to open the reaction chamber.

Thereafter, the carbon fiber filtered by the filter 48 may be recovered. Accordingly, the matrix using the epoxy resin in the carbon fiber reinforced composite material can be separated and the carbon fiber can be recovered.

13 is a scanning electron microscope photograph (b) of the polypropylene-based micro-foam plastic composite (a) and the composite.

Through the present invention, a supercritical fluid environment using carbon dioxide can be provided, and a high specific surface area high heat-resistant catalyst support for a high-performance eco-friendly single propellant thruster can be manufactured. When using a high specific surface area catalyst support, the amount of catalyst required for complete catalytic decomposition and catalytic combustion of the propellant is relatively small, which reduces the cost of catalyst production and fulfills the mission of spacecraft due to the reduction in volume and mass of the propulsion system. Can lead to improved skills. In addition, the core technology can be secured in the development of a high-performance, eco-friendly single-propellant thruster system, and the additional cost and time required for handling can be reduced by replacing the existing hydrazine thruster which is toxic.

Through the present invention, the composite material can be recycled through solvation and decomposition of an epoxy-based matrix constituting an expensive carbon fiber reinforced composite material, and a very advantageous recycling process can be provided in terms of unit cost. Therefore, due to the price problem, the application field of the carbon fiber reinforced composite material used in a limited field can be widened. In addition, through the present invention, a polypropylene-based plastic can be produced by using carbon dioxide in a supercritical fluid environment to produce a thermoplastic microfoam plastic composite as shown in FIG. 13, and can be applied to electronic equipment, aircraft, and physical shock protection equipment in space environments. have.

Although described above with reference to the preferred embodiment of the present invention, those skilled in the art may variously modify and change the present invention without departing from the spirit and scope of the present invention as set forth in the claims below. You will understand that you can.

100: injection unit 200: pump unit
300: preheating unit 400: reaction unit
500: cooling unit 600: filter unit
700: back pressure control unit 800: collection unit

Claims (13)

delete delete delete delete delete delete delete Using a supercritical fluid environment semi-continuous reactor comprising a reactor comprising a cylindrical inconel, a flange portion formed at the front and rear ends of the inconel, and a flange coupling portion coupled to the flange portion,
A specimen mounting step of positioning the catalyst support in the reactor;
A reaction chamber fixing step of fixing the flange coupling portion to the flange portion and closing the reaction chamber in which the catalyst support is located;
A purging step of purging with nitrogen to remove oxygen in the reactor;
A reaction chamber heating step of heating the reactor in a carbon dioxide environment;
After stopping the carbon dioxide input to the reactor, a solvent input step of introducing a solvent;
A maintenance step of maintaining the pressure, temperature, and vaginal flow of the reactor to continue the reaction;
After stopping the carbon dioxide input and heating to the reactor, the heating stops and cooling to cool;
After cooling the reactor, the pressure drop in the reaction chamber to lower the pressure in the reaction chamber to atmospheric pressure; And
And separating the flange coupling portion to open the reaction chamber to obtain the dried catalyst support. The method of claim 8,
Before the specimen mounting step,
An existing specimen removal step of separating the flange coupling portion of the supercritical fluid environment semi-continuous reactor from the flange portion and removing an existing specimen existing inside the inconel; And
Method for producing a high heat-resistant catalyst support, characterized in that it further comprises a residue removal step of removing the existing experimental residues using nitrogen or carbon dioxide. The method of claim 9,
The solvent is acetone (C ₃ H ₆ O), ethanol (C ₂ H ₆ O) and propanol (C ₃ H ₈ O) any one or more of the method for producing a high-temperature catalyst support characterized in that it comprises. Using a supercritical fluid environment semi-continuous reactor comprising a reactor comprising a cylindrical inconel, a flange portion formed at the front and rear ends of the inconel, and a flange coupling portion coupled to the flange portion,
A specimen mounting step of positioning the carbon fiber-reinforced composite material to be recycled in the reactor;
A reaction chamber fixing step of fixing the flange coupling portion to the flange portion and closing the reaction chamber in which the carbon fiber reinforced composite material is located;
A purging step of purging with nitrogen to remove oxygen in the reactor;
A reaction chamber heating step of heating the reactor in a nitrogen environment;
After stopping the nitrogen input to the reactor, a solvent input step of introducing a solvent;
A maintenance step of maintaining the pressure, temperature, and vaginal flow of the reactor to continue the reaction;
After stopping the solvent input and heating to the reactor, the heating and cooling step of introducing and cooling the carbon dioxide;
After cooling the reactor, the pressure drop in the reaction chamber to lower the pressure in the reaction chamber to atmospheric pressure; And
A method of recycling a carbon fiber reinforced composite comprising separating the flange coupling portion and opening the reaction chamber. The method of claim 11,
The supercritical fluid environment semi-continuous reactor further includes a filter that filters out the impurities of the cooled solvent and residues after the experiment,
After the pressure drop step in the reaction chamber, further comprising a purging step of performing a purging operation using nitrogen in the reactor, the method of recycling carbon fiber reinforced composite, characterized in that to recover the filtered carbon fibers in the filter. The method of claim 11,
The solvent is acetone (C ₃ H ₆ O), ethanol (C ₂ H ₆ O) and propanol (C ₃ H ₈ O) at least one of the carbon fiber-reinforced composite recycling method characterized in that it comprises at least one.

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