CN116272748B - System and method for supercritical thermal degradation of refrigerants - Google Patents
System and method for supercritical thermal degradation of refrigerants Download PDFInfo
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- CN116272748B CN116272748B CN202310457872.XA CN202310457872A CN116272748B CN 116272748 B CN116272748 B CN 116272748B CN 202310457872 A CN202310457872 A CN 202310457872A CN 116272748 B CN116272748 B CN 116272748B
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- 239000003507 refrigerant Substances 0.000 title claims abstract description 283
- 238000006731 degradation reaction Methods 0.000 title claims abstract description 47
- 230000015556 catabolic process Effects 0.000 title claims abstract description 45
- 238000000034 method Methods 0.000 title claims abstract description 30
- 239000007800 oxidant agent Substances 0.000 claims abstract description 164
- 230000001590 oxidative effect Effects 0.000 claims abstract description 141
- 239000001257 hydrogen Substances 0.000 claims description 78
- 229910052739 hydrogen Inorganic materials 0.000 claims description 78
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 claims description 77
- 150000001875 compounds Chemical class 0.000 claims description 74
- 239000007789 gas Substances 0.000 claims description 57
- 239000007788 liquid Substances 0.000 claims description 36
- 239000002994 raw material Substances 0.000 claims description 19
- 238000010438 heat treatment Methods 0.000 claims description 15
- 230000000593 degrading effect Effects 0.000 claims description 14
- 239000002826 coolant Substances 0.000 claims description 13
- 239000003054 catalyst Substances 0.000 claims description 11
- 238000003860 storage Methods 0.000 claims description 11
- 238000009413 insulation Methods 0.000 claims description 5
- OHMHBGPWCHTMQE-UHFFFAOYSA-N 2,2-dichloro-1,1,1-trifluoroethane Chemical compound FC(F)(F)C(Cl)Cl OHMHBGPWCHTMQE-UHFFFAOYSA-N 0.000 claims description 4
- 238000001816 cooling Methods 0.000 claims description 4
- 229910052751 metal Inorganic materials 0.000 claims description 3
- 239000002184 metal Substances 0.000 claims description 3
- 229910044991 metal oxide Inorganic materials 0.000 claims description 3
- 150000004706 metal oxides Chemical class 0.000 claims description 3
- 229910001463 metal phosphate Inorganic materials 0.000 claims description 3
- 238000012360 testing method Methods 0.000 claims description 3
- 230000009257 reactivity Effects 0.000 abstract description 6
- 238000012546 transfer Methods 0.000 abstract description 6
- 239000012530 fluid Substances 0.000 abstract description 2
- 239000003921 oil Substances 0.000 description 9
- 238000005516 engineering process Methods 0.000 description 6
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 5
- 230000000052 comparative effect Effects 0.000 description 5
- 238000012545 processing Methods 0.000 description 5
- 230000001105 regulatory effect Effects 0.000 description 5
- 238000009792 diffusion process Methods 0.000 description 4
- 238000005265 energy consumption Methods 0.000 description 4
- 230000009467 reduction Effects 0.000 description 4
- 238000000354 decomposition reaction Methods 0.000 description 3
- 239000000463 material Substances 0.000 description 3
- 230000006641 stabilisation Effects 0.000 description 3
- 238000011105 stabilization Methods 0.000 description 3
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 2
- 229910052799 carbon Inorganic materials 0.000 description 2
- 239000004568 cement Substances 0.000 description 2
- 230000001276 controlling effect Effects 0.000 description 2
- 238000011161 development Methods 0.000 description 2
- 230000000694 effects Effects 0.000 description 2
- 238000004519 manufacturing process Methods 0.000 description 2
- 238000002360 preparation method Methods 0.000 description 2
- 238000011084 recovery Methods 0.000 description 2
- 238000004064 recycling Methods 0.000 description 2
- 238000005057 refrigeration Methods 0.000 description 2
- 238000005245 sintering Methods 0.000 description 2
- 238000005979 thermal decomposition reaction Methods 0.000 description 2
- 229910017119 AlPO Inorganic materials 0.000 description 1
- ZAMOUSCENKQFHK-UHFFFAOYSA-N Chlorine atom Chemical compound [Cl] ZAMOUSCENKQFHK-UHFFFAOYSA-N 0.000 description 1
- PXGOKWXKJXAPGV-UHFFFAOYSA-N Fluorine Chemical compound FF PXGOKWXKJXAPGV-UHFFFAOYSA-N 0.000 description 1
- CBENFWSGALASAD-UHFFFAOYSA-N Ozone Chemical compound [O-][O+]=O CBENFWSGALASAD-UHFFFAOYSA-N 0.000 description 1
- 230000002411 adverse Effects 0.000 description 1
- 238000004378 air conditioning Methods 0.000 description 1
- 238000009835 boiling Methods 0.000 description 1
- 230000008859 change Effects 0.000 description 1
- 238000006243 chemical reaction Methods 0.000 description 1
- 239000000460 chlorine Substances 0.000 description 1
- 229910052801 chlorine Inorganic materials 0.000 description 1
- KYKAJFCTULSVSH-UHFFFAOYSA-N chloro(fluoro)methane Chemical compound F[C]Cl KYKAJFCTULSVSH-UHFFFAOYSA-N 0.000 description 1
- 125000004773 chlorofluoromethyl group Chemical group [H]C(F)(Cl)* 0.000 description 1
- 238000004891 communication Methods 0.000 description 1
- 238000010276 construction Methods 0.000 description 1
- 230000008030 elimination Effects 0.000 description 1
- 238000003379 elimination reaction Methods 0.000 description 1
- 238000004134 energy conservation Methods 0.000 description 1
- 230000007613 environmental effect Effects 0.000 description 1
- 238000011049 filling Methods 0.000 description 1
- 238000001914 filtration Methods 0.000 description 1
- 229910052731 fluorine Inorganic materials 0.000 description 1
- 239000011737 fluorine Substances 0.000 description 1
- 238000001165 gas chromatography-thermal conductivity detection Methods 0.000 description 1
- 150000002431 hydrogen Chemical class 0.000 description 1
- 230000003993 interaction Effects 0.000 description 1
- 239000010687 lubricating oil Substances 0.000 description 1
- 150000002739 metals Chemical class 0.000 description 1
- 238000002156 mixing Methods 0.000 description 1
- 239000000203 mixture Substances 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 229910052757 nitrogen Inorganic materials 0.000 description 1
- 230000002035 prolonged effect Effects 0.000 description 1
- 238000000746 purification Methods 0.000 description 1
- 238000000197 pyrolysis Methods 0.000 description 1
- 238000009834 vaporization Methods 0.000 description 1
- 230000008016 vaporization Effects 0.000 description 1
- 238000010792 warming Methods 0.000 description 1
Classifications
-
- 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
- B01J19/0006—Controlling or regulating processes
-
- 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
- B01J19/0006—Controlling or regulating processes
- B01J19/0013—Controlling the temperature of the process
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
- Y02P20/00—Technologies relating to chemical industry
- Y02P20/50—Improvements relating to the production of bulk chemicals
- Y02P20/54—Improvements relating to the production of bulk chemicals using solvents, e.g. supercritical solvents or ionic liquids
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- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Physical Or Chemical Processes And Apparatus (AREA)
Abstract
The invention discloses a system and a method for supercritical thermal degradation of a refrigerant. The system comprises: the device comprises a refrigerant supercharging device, an oxidant supercharging device, a preheater and a supercritical reactor, wherein the refrigerant supercharging device is provided with a refrigerant inlet and a high-pressure refrigerant outlet; the oxidant supercharging device is provided with an oxidant inlet and a high-pressure oxidant outlet; the preheater comprises a refrigerant heat exchange channel and an oxidant heat exchange channel, wherein the refrigerant heat exchange channel is provided with a high-pressure refrigerant inlet and a high-temperature refrigerant outlet, the high-pressure refrigerant inlet is connected with the high-pressure refrigerant outlet, the oxidant heat exchange channel is provided with a high-pressure oxidant inlet and a high-temperature oxidant outlet, and the high-pressure oxidant inlet is connected with the high-pressure oxidant outlet. The system for supercritical thermal degradation of the refrigerant utilizes the high reactivity and good mass transfer performance of the refrigerant in a supercritical fluid state, and realizes the effective degradation of the refrigerant under a low-temperature condition.
Description
Technical Field
The invention relates to the technical field of refrigerant treatment, in particular to a system and a method for supercritical thermal degradation of a refrigerant.
Background
The construction of human production civilization has not been separated from the wide application of refrigeration and air conditioning technology. The core of refrigeration technology is the development of refrigerants. Currently, refrigerants have undergone four generations of development, in turn, chlorofluorocarbon (CFCs), hydrochlorofluorocarbon (HCFCs), hydrofluorocarbon (HFCs) and Hydrofluoroolefins (HFOs). At present, china is the world's largest producing country and consuming country of HCFCs refrigerant and HFCs refrigerant, and the annual production of the two types of refrigerant accounts for about 90% and 84% of the world. To avoid the damage of the refrigerant to the ozone layer and the influence on global warming, the reduction and elimination of the refrigerant of HCFCs and HFCs in China are already on schedule according to the basic plus amendment of Montreal protocol (formal effect of 1 month 1 day 2019).
While a great deal of refrigerant is needed for destroying in China, the refrigerant destroying technology is still immature. The prior refrigerant recovery processing technology is mostly from the purification point of view, so that the refrigerant with relatively high purity is obtained to realize recycling. In the related art, there are methods for separating a refrigerant from lubricating oil, so that the refrigerant can be purified and recovered to be reused, and methods for separating mixed components by using different boiling points of components in the mixed refrigerant through a multi-stage heat exchange assembly, so as to obtain a high-purity refrigerant, and further, recycling the refrigerant.
Along with the phase out of HCFCs and HFCs refrigerants, the treatment requirements of the two types of refrigerants are not only recovery, but also further degradation treatment so as to meet the environment protection requirements. In the next decades, china is faced with huge refrigerant degradation treatment pressure. In the related technology, the high-temperature sintering treatment method of the mixed system of CFCs and cement raw materials is adopted, the mass ratio of fluorine and chlorine elements in the system is lower than 0.04 percent and 0.5 percent of the total weight of CFCs refrigerant and cement raw materials, and the sintering treatment temperature is 1400-1600 ℃. The existing refrigerant treatment method is a pyrolysis method, has high energy consumption and high cost, and is contrary to the original purposes of energy conservation, emission reduction, low carbon and environmental protection in China. Thus, the current refrigerant degradation treatment technology remains to be improved.
Disclosure of Invention
The present invention aims to solve at least one of the technical problems in the related art to some extent. It is therefore an object of the present invention to provide a system and method for supercritical thermal degradation of a refrigerant that achieves efficient degradation of the refrigerant at low temperatures using high reactivity of the refrigerant in a supercritical fluid state and good mass transfer properties.
In a first aspect of the invention, the invention provides a system for supercritical thermal degradation of a refrigerant. According to an embodiment of the invention, the system comprises: a refrigerant pressurizing device having a refrigerant inlet and a high-pressure refrigerant outlet; an oxidant plenum having an oxidant inlet and a high pressure oxidant outlet; the device comprises a preheater, a heat exchange device and a heat exchange device, wherein the preheater comprises a refrigerant heat exchange channel and an oxidant heat exchange channel, the refrigerant heat exchange channel is provided with a high-pressure refrigerant inlet and a high-temperature refrigerant outlet, the high-pressure refrigerant inlet is connected with the high-pressure refrigerant outlet, the oxidant heat exchange channel is provided with a high-pressure oxidant inlet and a high-temperature oxidant outlet, and the high-pressure oxidant inlet is connected with the high-pressure oxidant outlet; the supercritical reactor is provided with a raw material inlet and a first tail gas outlet, and the raw material inlet is respectively connected with the high-temperature refrigerant outlet and the high-temperature oxidant outlet.
According to the supercritical thermal degradation refrigerant system disclosed by the embodiment of the invention, the refrigerant is pressurized by the refrigerant pressurizing device and then is supplied to the refrigerant heat exchange channel in the preheater for heating, the oxidant is pressurized by the oxidant pressurizing device and then is supplied to the oxidant heat exchange channel in the preheater for heating, the heated refrigerant and the oxidant enter the supercritical reactor from the raw material inlet, so that the refrigerant is thermally degraded in a supercritical state to generate tail gas, the generated tail gas is discharged from the first tail gas outlet, and in the supercritical reactor, the refrigerant is in the supercritical state, not only has high reactivity and good mass transfer performance, but also has high density, high solubility and strong convection diffusion capability, and the volume of the refrigerant with the same mass is smaller, thereby improving the processing capacity of the refrigerant, realizing the high concentration, high flow rate and rapid decomposition of the refrigerant, and further realizing the effective degradation of the refrigerant under the conditions of low temperature, low energy consumption, high flow rate and high rate under the high refrigerant component proportion. In addition, the refrigerant is heated through the refrigerant heat exchange channel, the oxidant is heated through the oxidant heat exchange channel, and the respectively heated refrigerant and oxidant enter the supercritical reactor from the raw material inlet to degrade, so that the problems of carbon powder generation and blockage caused by long-time heating after the refrigerant and the oxidant are mixed can be avoided.
In addition, the system for supercritical thermal degradation of a refrigerant according to the above embodiment of the present invention may have the following additional technical features:
in some embodiments of the invention, the supercritical reactor comprises a heater and/or a temperature controller, and/or the preheater comprises a heater and/or a temperature controller.
In some embodiments of the invention, the feed inlet and the first tail gas outlet are each independently provided with a pressure gauge.
In some embodiments of the invention, the first exhaust outlet is connected to a back pressure valve.
In some embodiments of the invention, a one-way valve is provided between the high pressure oxidant outlet and the high pressure oxidant inlet.
In some embodiments of the invention, a safety valve is provided between the high pressure oxidant outlet and the high pressure oxidant inlet and/or at the feedstock inlet.
In some embodiments of the present invention, the refrigerant pressurizing device includes a first liquid pump and a first flowmeter, the first liquid pump is connected to the first flowmeter, the first liquid pump is provided with the refrigerant inlet, and the first flowmeter is provided with the high-pressure refrigerant outlet.
In some embodiments of the present invention, the refrigerant pressurizing device further includes a refrigerant storage container, in which a refrigerant pre-pressurizing unit is disposed, the refrigerant storage container being connected to the refrigerant inlet.
In some embodiments of the present invention, the oxidant pressurizing device includes an oxidant booster pump and a second flowmeter, where the oxidant booster pump is connected to the second flowmeter, the oxidant booster pump is provided with the oxidant inlet, and the second flowmeter is provided with the high-pressure oxidant outlet.
In some embodiments of the present invention, the oxidant booster device further includes a buffer tank and a pressure reducing valve, the oxidant booster pump is connected to the buffer tank, and the buffer tank is connected to the second flowmeter through the pressure reducing valve.
In some embodiments of the invention, the system for supercritical thermal degradation of a refrigerant further comprises: a hydrogen-containing compound pressurizing device having a hydrogen-containing compound inlet and a high-pressure hydrogen-containing compound outlet; the preheater further comprises a hydrogen-containing compound heat exchange channel, wherein the hydrogen-containing compound heat exchange channel is provided with a high-pressure hydrogen-containing compound inlet and a high-temperature hydrogen-containing compound outlet, the high-pressure hydrogen-containing compound inlet is connected with the high-pressure hydrogen-containing compound outlet, and the raw material inlet is connected with the high-temperature hydrogen-containing compound outlet.
In some embodiments of the invention, the feedstock inlet is connected to the high temperature refrigerant outlet, the high temperature oxidant outlet, and the high temperature hydrogen-containing compound outlet, respectively, by a thermal insulation pipe.
In some embodiments of the present invention, the hydrogen-containing compound pressurizing device includes a second liquid pump and a third flowmeter, where the second liquid pump is connected to the third flowmeter, the second liquid pump is provided with the hydrogen-containing compound inlet, and the third flowmeter is provided with the high-pressure hydrogen-containing compound outlet.
In some embodiments of the invention, the system for supercritical thermal degradation of a refrigerant further comprises: the tail gas treatment device is provided with a tail gas inlet and a second tail gas outlet, the tail gas inlet is connected with the first tail gas outlet, and the second tail gas outlet is connected with the back pressure valve.
In some embodiments of the invention, the exhaust treatment device includes a condenser having the exhaust inlet and a low temperature gas outlet, the low temperature gas outlet being connected to the filter, and the filter having the second exhaust outlet.
In some embodiments of the invention, the tail gas treatment device further comprises a constant temperature oil bath, and the condenser further comprises a cooling medium inlet and a cooling medium outlet, wherein the cooling medium inlet and the cooling medium outlet are respectively connected with the constant temperature oil bath.
In some embodiments of the invention, a catalyst is disposed within the supercritical reactor.
In some embodiments of the invention, the catalyst comprises at least one of a metal, a metal oxide, and a metal phosphate.
In a second aspect of the invention, the invention provides a method for degrading a refrigerant using the supercritical thermal degradation refrigerant system of the above embodiment. According to an embodiment of the invention, the method comprises:
(1) Pressurizing the refrigerant by adopting a refrigerant pressurizing device, and pressurizing the oxidant by adopting an oxidant pressurizing device;
(2) Heating the pressurized refrigerant and the pressurized oxidant respectively by adopting a preheater;
(3) And sending the heated refrigerant and the oxidant into a supercritical reactor, controlling the pressure in the supercritical reactor not to be lower than the critical pressure of the refrigerant, and controlling the temperature in the supercritical reactor not to be lower than the critical temperature of the refrigerant so as to degrade the refrigerant in a supercritical state.
According to the method for degrading the refrigerant, the refrigerant is pressurized by adopting the refrigerant pressurizing device, the oxidant is pressurized by adopting the oxidant pressurizing device, so that the pressure of the refrigerant and the oxidant is not lower than the critical pressure of the refrigerant, the pressurized refrigerant and the pressurized oxidant are respectively heated by adopting the preheater, the temperature of the refrigerant and the temperature of the oxidant are not lower than the critical temperature of the refrigerant, the heated refrigerant and the heated oxidant are sent into the supercritical reactor, the pressure in the supercritical reactor is controlled to be not lower than the critical pressure of the refrigerant, the temperature in the supercritical reactor is controlled to be not lower than the critical temperature of the refrigerant, the refrigerant can be thermally degraded in a supercritical state to generate tail gas, and in the supercritical reactor, the refrigerant not only has high reactivity and good mass transfer performance, but also has high density, high solubility and strong convection diffusion capacity, and smaller volume of the refrigerant with the same mass, thereby improving the processing capacity of the refrigerant, realizing high concentration, high decomposition rate, high efficiency, high flow rate, high refrigerant flow rate, high refrigerant consumption, high refrigerant flow rate and high degradation ratio. In addition, the pre-heater is adopted to heat the pressurized refrigerant and the oxidant respectively, and the heated refrigerant and the heated oxidant are sent into the supercritical reactor for degradation, so that the problems of carbon powder generation and blockage caused by long-time heating after the refrigerant and the oxidant are mixed can be avoided.
In addition, the method for degrading a refrigerant according to the above embodiment of the present invention may have the following additional technical features:
in some embodiments of the present invention, step (2) further comprises heating the pressurized hydrogen-containing compound with a preheater; step (3) further comprises feeding the heated hydrogen-containing compound into the supercritical reactor.
In some embodiments of the invention, prior to step (1), a tightness test is performed on the system of supercritical thermally degraded refrigerant.
In some embodiments of the invention, prior to step (1), a catalyst is loaded into the supercritical reactor.
In some embodiments of the invention, the refrigerant comprises at least one of a hydrochlorofluorocarbon, a hydrofluorocarbon, and a hydrofluoroolefin.
In some embodiments of the invention, the oxidizing agent comprises O 2 And/or H 2 O 2 。
In some embodiments of the invention, the hydrogen-containing compound comprises H 2 O、CH 3 OH、CH 3 CH 2 At least one of OH.
In some embodiments of the present invention, the method of degrading a refrigerant using the supercritical thermal degradation refrigerant system of the above embodiment further comprises: (4) And cooling and/or purifying tail gas generated by degrading the refrigerant in a supercritical state.
In some embodiments of the invention, the temperature within the supercritical reactor is no greater than 600 ℃, and the pressure within the supercritical reactor is no greater than 20MPa.
Additional aspects and advantages of the invention will be set forth in part in the description which follows, and in part will be obvious from the description, or may be learned by practice of the invention.
Drawings
The foregoing and/or additional aspects and advantages of the invention will become apparent and may be better understood from the following description of embodiments taken in conjunction with the accompanying drawings in which:
fig. 1 is a schematic structural view of a system for supercritical thermal degradation of a refrigerant according to an embodiment of the present invention.
Reference numerals: 10. the refrigerant pressurizing device 11, the refrigerant inlet 12, the high-pressure refrigerant outlet 13, the first liquid pump 14, the first flow meter 15, the refrigerant storage container 20, the oxidant pressurizing device 21, the oxidant inlet 22, the high-pressure oxidant outlet 23, the oxidant booster pump 24, the second flow meter 25, the buffer tank 26, the pressure reducing valve 30, the preheater 31, the refrigerant heat exchange channel 311, the high-pressure refrigerant inlet 312, the high-temperature refrigerant outlet 32, the oxidant heat exchange channel 321, the high-pressure oxidant inlet 322, the high-temperature oxidant outlet 33, the hydrogen-containing compound heat exchange channel 331, the high-pressure hydrogen-containing compound inlet 332, the high-temperature hydrogen-containing compound outlet 40, the supercritical reactor 41, the raw material inlet 42, the first tail gas outlet 43, the pressure meter 44, the heat insulation pipe 50, the back pressure valve 60, the check valve 70, the safety valve 80, the hydrogen-containing compound pressurizing device 81, the hydrogen-containing compound inlet 82, the high-containing compound outlet 83, the second liquid pump 84, the third flow meter 90, the constant temperature gas inlet 92, the constant temperature filter 93, the constant temperature medium outlet 93, the constant temperature exhaust gas outlet 93, the constant temperature device 93, the constant temperature medium outlet 93, the constant temperature exhaust gas inlet 93, the constant temperature device 93, the constant temperature exhaust gas outlet 93, the constant temperature medium.
Detailed Description
Embodiments of the present invention are described in detail below, examples of which are illustrated in the accompanying drawings, wherein like or similar reference numerals refer to like or similar elements or elements having like or similar functions throughout. The embodiments described below by referring to the drawings are illustrative and intended to explain the present invention and should not be construed as limiting the invention.
In the description of the present invention, it should be understood that the terms "center", "longitudinal", "lateral", "length", "width", "thickness", "upper", "lower", "front", "rear", "left", "right", "vertical", "horizontal", "top", "bottom", "inner", "outer", "clockwise", "counterclockwise", "axial", "radial", "circumferential", etc. indicate orientations or positional relationships based on the orientations or positional relationships shown in the drawings are merely for convenience in describing the present invention and simplifying the description, and do not indicate or imply that the device or element being referred to must have a specific orientation, be configured and operated in a specific orientation, and therefore should not be construed as limiting the present invention.
Furthermore, the terms "first," "second," and the like, are used for descriptive purposes only and are not to be construed as indicating or implying a relative importance or implicitly indicating the number of technical features indicated. Thus, a feature defining "a first" or "a second" may explicitly or implicitly include at least one such feature. In the description of the present invention, the meaning of "plurality" means at least two, for example, two, three, etc., unless specifically defined otherwise.
In the present invention, unless explicitly specified and limited otherwise, the terms "mounted," "connected," "secured," and the like are to be construed broadly, and may be, for example, fixedly connected, detachably connected, or integrally formed; can be mechanically or electrically connected; either directly or indirectly, through intermediaries, or both, may be in communication with each other or in interaction with each other, unless expressly defined otherwise. The specific meaning of the above terms in the present invention can be understood by those of ordinary skill in the art according to the specific circumstances.
In the present invention, unless expressly stated or limited otherwise, a first feature "up" or "down" a second feature may be the first and second features in direct contact, or the first and second features in indirect contact via an intervening medium. Moreover, a first feature being "above," "over" and "on" a second feature may be a first feature being directly above or obliquely above the second feature, or simply indicating that the first feature is level higher than the second feature. The first feature being "under", "below" and "beneath" the second feature may be the first feature being directly under or obliquely below the second feature, or simply indicating that the first feature is less level than the second feature.
In a first aspect of the invention, the invention provides a system for supercritical thermal degradation of a refrigerant. Referring to fig. 1, according to an embodiment of the present invention, the system includes: a refrigerant pressurizing device 10, an oxidant pressurizing device 20, a preheater 30 and a supercritical reactor 40, the refrigerant pressurizing device 10 having a refrigerant inlet 11 and a high-pressure refrigerant outlet 12; the oxidant plenum 20 has an oxidant inlet 21 and a high pressure oxidant outlet 22; the preheater 30 includes a refrigerant heat exchange passage 31 and an oxidant heat exchange passage 32, the refrigerant heat exchange passage 31 having a high pressure refrigerant inlet 311 and a high temperature refrigerant outlet 312, the high pressure refrigerant inlet 311 being connected to the high pressure refrigerant outlet 12, the oxidant heat exchange passage 32 having a high pressure oxidant inlet 321 and a high temperature oxidant outlet 322, the high pressure oxidant inlet 321 being connected to the high pressure oxidant outlet 22; the supercritical reactor 40 has a raw material inlet 41 and a first off-gas outlet 42, the raw material inlet 41 being connected to the high-temperature refrigerant outlet 312 and the high-temperature oxidant outlet 322, respectively.
According to the system for supercritical thermal degradation of refrigerant in the above embodiment of the present invention, the refrigerant is pressurized by the refrigerant pressurizing device 10 and then is supplied to the refrigerant heat exchange channel 31 in the preheater 30 for heating, the oxidant is pressurized by the oxidant pressurizing device 20 and then is supplied to the oxidant heat exchange channel 32 in the preheater 30 for heating, the heated refrigerant and oxidant enter the supercritical reactor 40 from the raw material inlet 41, so that the refrigerant is thermally degraded in the supercritical state to generate tail gas, the generated tail gas is discharged from the first tail gas outlet 42, and the refrigerant is in the supercritical state in the supercritical reactor 40, so that the refrigerant not only has high reactivity and good mass transfer performance, but also can be effectively degraded in low temperature conditions, and also has high density, high solubility and strong convective diffusion capability, and the volume of the refrigerant with the same mass is smaller, thereby improving the processing capability of the refrigerant, realizing high concentration, high flow and fast rate decomposition of the refrigerant, and further realizing the effective degradation of the refrigerant under the conditions of low temperature, low energy consumption, high flow rate and high refrigerant component proportion. In addition, the refrigerant is heated through the refrigerant heat exchange channel 31, the oxidant is heated through the oxidant heat exchange channel 32, and the respectively heated refrigerant and oxidant enter the supercritical reactor 40 from the raw material inlet 41 for degradation, so that the problems of carbon powder generation and blockage caused by long-time heating after the refrigerant and the oxidant are mixed can be avoided.
In an embodiment of the present invention, the refrigerant comprises a hydrochlorofluorocarbon (e.g., CCl 3 F) Hydrochlorofluorocarbons (e.g. CHClF) 2 ) Hydrofluorocarbons (e.g. C 2 H 2 F 4 ) And hydrofluoroolefins (e.g. C 3 H 2 F 4 ) At least one of them.
According to some embodiments of the present invention, the refrigerant pressure boosting device 10 may be used to boost the pressure of the refrigerant above its critical pressure, the refrigerant pressure boosting device 10 may include a first liquid pump 13 and a first flow meter 14, the first liquid pump 13 is adapted to pressurize and supply the refrigerant to the preheater 30, the first liquid pump 13 is connected to the first flow meter 14, the first liquid pump 13 is provided with a refrigerant inlet 11, the first flow meter 14 is provided with a high pressure refrigerant outlet 12, the first flow meter 14 may have a first regulating valve (not shown), and the first regulating valve may regulate the flow of the refrigerant. Thereby, the refrigerant can be pressurized to above the critical pressure of the refrigerant by the first liquid pump 13, and the flow rate of the refrigerant is controlled by the first flow meter 14. The type of the first liquid pump 13 is not particularly limited, and may be selected by those skilled in the art according to actual needs. As a specific example, the first liquid pump 13 may be a liquid booster pump having a liquid delivery function.
According to further embodiments of the present invention, the refrigerant pressurizing device 10 may further include a refrigerant storage container 15, a refrigerant pre-pressurizing unit (not shown) being provided in the refrigerant storage container 15, the refrigerant storage container 15 being connected to the refrigerant inlet 11. Thus, the refrigerant in the refrigerant storage container 15 can be pressurized by the refrigerant pre-pressurizing means, and adverse effects on the life of the first liquid pump 13 after vaporization of the refrigerant can be avoided. The type of the refrigerant pre-pressurizing unit is not particularly limited, and a person skilled in the art may select according to actual needs, and as a specific example, the refrigerant pre-pressurizing unit may include an air bag that is inflated by a pneumatic pump to inflate the air bag, thereby pressurizing the refrigerant in the refrigerant storage container 15.
According to further embodiments of the present invention, the pressure of the oxidant may be brought above the critical pressure of the refrigerant by the oxidant booster device 20, the oxidant booster device 20 may include an oxidant booster pump 23 and a second flow meter 24, the oxidant booster pump 23 and the second flow meter 24 being connected, the oxidant booster pump 23 being provided with an oxidant inlet 21, the second flow meter 24 being provided with a high pressure oxidant outlet 22, the second flow meter 24 may be provided with a second regulating valve (not shown), and the second regulating valve may regulate the flow of the oxidant. Thereby, the oxidizer can be pressurized to above the critical pressure of the refrigerant by the oxidizer booster pump 23, and the flow rate of the oxidizer can be controlled by the second flow meter 24. The types of the oxidizing agent and the oxidizing agent booster pump 23 are not particularly limited, and may be selected by those skilled in the art according to actual needs. For example, the oxidizing agent may include O 2 And/or H 2 O 2 For the oxidant in gaseous form, a gas booster pump may be employed; for the oxidant in liquid form, a liquid booster pump may be employed. Further, for the oxidizer in the form of gas, the oxidizer pressurizing device 20 may further include a buffer tank 25 and a pressure reducing valve 26, the oxidizer pressurizing pump 23 being connected to the buffer tank 25, the buffer tank 25 being connected to the second flowmeter 24 through the pressure reducing valve 26. Pressurization and stabilization of the oxidant can thereby be achieved so that the oxidant can stably enter the supercritical reactor 40.
According to further embodiments of the present invention, the supercritical reactor 40 may include a heater (not shown) and/or a temperature controller (not shown), the temperature within the supercritical reactor 40 may be heated above the critical temperature of the refrigerant using the heater, and stabilization of the temperature field within the supercritical reactor 40 may be controlled using the temperature controller. Specifically, the temperature controller may have a temperature sensing element (such as a thermocouple or a temperature sensor) through which the temperature in the supercritical reactor 40 can be detected, and may be connected to a heater, and when the temperature in the supercritical reactor 40 reaches a temperature value preset by the temperature controller, the temperature controller may stop the heater. Similarly, the preheater 30 may also include a heater and/or a temperature controller, which may be used to heat the material entering the preheater 30 above the critical temperature of the refrigerant, and which may be used to control the stabilization of the temperature field within the preheater 30. Specifically, the temperature controller may have a temperature sensing element (such as a thermocouple or a temperature sensor) through which the temperature in the preheater 30 may be detected, and may be connected to the heater, and the temperature controller may stop the heater when the temperature in the preheater 30 reaches a temperature value preset by the temperature controller. The type of heater and the type of temperature controller are not particularly limited, and those skilled in the art may select according to actual needs, and as a specific example, an electric heater and a PID temperature controller may be employed.
According to further embodiments of the present invention, a catalyst may also be disposed within the supercritical reactor, the catalyst being adapted to catalyze the degradation of the refrigerant. Whereby the rate of refrigerant degradation can be increased. The kind of the catalyst is not particularly limited, and may be selected according to practical needs by those skilled in the art, and may include, for example, metals (e.g., pt, pb), metal oxides (e.g., al 2 O 3 MgO) and metal phosphates (e.g. AlPO 4 、Mg 3 (PO 4 ) 2 ) At least one of them.
According to further embodiments of the invention, a pressure gauge 43 may be provided at the raw material inlet 41 and at the first tail gas outlet 42, each independently. Whereby the pressure change of the supercritical reactor 40 can be observed by the pressure gauge 43. Further, the first exhaust outlet 42 may be connected to a back pressure valve 50. The total pressure of the system of supercritical thermally degraded refrigerant can thus be controlled by the back pressure valve 50.
According to further embodiments of the present invention, for oxidants in gaseous form, a one-way valve 60 may be provided between the high pressure oxidant outlet 22 and the high pressure oxidant inlet 321. The oxidizer flowing out of the high-pressure oxidizer outlet 22 can flow into the oxidizer heat exchanging channel 32 through the high-pressure oxidizer inlet 321 through the check valve 60, whereby the oxidizer can be prevented from flowing back. Further, a safety valve 70 may be provided between the high pressure oxidant outlet 22 and the high pressure oxidant inlet 321 and/or at the raw material inlet 41. Thereby protecting the system of supercritical thermally degrading refrigerant.
According to still further embodiments of the present invention, the system for supercritical thermal degradation of a refrigerant may further comprise: the hydrogen-containing compound pressurizing device 80 may be configured such that the pressure of the hydrogen-containing compound is equal to or higher than the critical pressure of the refrigerant by the hydrogen-containing compound pressurizing device 80, and the hydrogen-containing compound pressurizing device 80 has a hydrogen-containing compound inlet 81 and a high-pressure hydrogen-containing compound outlet 82. Thus, the hydrogen element can be supplied to the degradation system of the refrigerant having a shortage of hydrogen by the hydrogen-containing compound pressurizing device 80, and the refrigerant is subjected to thermal decomposition in the supercritical state in combination with the oxidizing agent and the hydrogen-containing compound. The type of the hydrogen-containing compound is not particularly limited, and may be selected according to actual needs by those skilled in the art, for example, H 2 O、CH 3 OH、CH 3 CH 2 At least one of OH. Further, the hydrogen-containing compound pressurizing device 80 may include a second liquid pump 83 and a third flow meter 84, the second liquid pump 83 being adapted to pressurize and supply the hydrogen-containing compound to the preheater 30, the second liquid pump 83 being connected to the third flow meter 84, the second liquid pump 83 being provided with a hydrogen-containing compound inlet 81, the third flow meter 84 being provided with a high pressure hydrogen-containing compound outlet 82, the third flow meter 84 may be provided with a third regulating valve (not shown) which may regulate the flow rate of the hydrogen-containing compound. Thereby, the hydrogen-containing compound can be pressurized to above the critical pressure of the refrigerant by the second liquid pump 83 and passed through the first liquid pump The flow meter 84 controls the flow of the hydrogen-containing compound. The type of the second liquid pump 83 is not particularly limited, and may be selected by those skilled in the art according to actual needs. As a specific example, the second liquid pump 83 may be a liquid booster pump having a liquid delivery function.
According to still further embodiments of the present invention, the preheater 30 may further comprise a hydrogen-containing compound heat exchange channel 33, the hydrogen-containing compound heat exchange channel 33 having a high pressure hydrogen-containing compound inlet 331 and a high temperature hydrogen-containing compound outlet 332, the high pressure hydrogen-containing compound inlet 331 being connected to the high pressure hydrogen-containing compound outlet 82, the feedstock inlet 41 being connected to the high temperature hydrogen-containing compound outlet 332. Thereby, the hydrogen-containing compound can be heated to a temperature higher than the critical temperature of the refrigerant.
According to further embodiments of the present invention, the feedstock inlet 41 may be connected to the high temperature refrigerant outlet 312, the high temperature oxidant outlet 322, and the high temperature hydrogen-containing compound 332 outlet, respectively, via a thermal insulation pipe 44. Thereby, heat loss of the system of supercritical thermally degrading refrigerant can be reduced. Further, the thermal insulation pipe 44 may include a main pipe and three parallel branch pipes connected to the main pipe, the raw material inlet 41 is connected to the three parallel branch pipes through the main pipe, and the three parallel branch pipes are respectively connected to the high temperature refrigerant outlet 312, the high temperature oxidizer outlet 322, and the high temperature hydrogen-containing compound outlet 332, thereby sufficiently mixing the refrigerant, the oxidizer, and the hydrogen-containing compound, thereby facilitating efficient degradation of the refrigerant.
According to still further embodiments of the present invention, the system for supercritical thermal degradation of a refrigerant may further comprise: the exhaust gas treatment device 90, the exhaust gas treatment device 90 has an exhaust gas inlet 91 and a second exhaust gas outlet 92, the exhaust gas inlet 91 being connected to the first exhaust gas outlet 42, the second exhaust gas outlet 92 being connected to the back pressure valve 50. Thereby can degrade the tail gas (such as CO) generated by the refrigerant under the supercritical state 2 HF, HCl, etc.).
According to further embodiments of the present invention, the exhaust treatment device 90 may include a condenser 93 and a filter 94, the condenser 93 having an exhaust inlet 91 and a low temperature gas outlet 931, the low temperature gas outlet 931 being coupled to the filter 94, the filter 94 having a second exhaust outlet 92. Therefore, the tail gas generated by the degradation of the refrigerant in the supercritical state can be cooled and ash can be filtered, so that the back pressure valve 50 can safely work for a long time in the temperature resistant range, the running stability of the system is improved, and the service life of the system is prolonged.
According to further embodiments of the present invention, the tail gas treatment device 90 further comprises a constant temperature oil bath 95, the constant temperature oil bath 95 having a constant temperature oil inlet and a constant temperature oil outlet, the condenser 93 further having a cooling medium inlet 932 and a cooling medium outlet 933, the cooling medium inlet 932 being connected to the constant temperature oil outlet, the cooling medium outlet 933 being connected to the constant temperature oil inlet. Thereby, an external circulation can be formed, providing the cooling medium to the condenser 93. Further, the temperature of the constant temperature oil bath 95 may range from room temperature to 150 ℃.
In a second aspect of the invention, the invention provides a method for degrading a refrigerant using the supercritical thermal degradation refrigerant system of the above embodiment. According to an embodiment of the invention, the method comprises:
(1) The refrigerant is pressurized by the refrigerant pressurizing device 10, and the oxidant is pressurized by the oxidant pressurizing device 20;
(2) The pre-heater 30 is adopted to heat the pressurized refrigerant and the oxidant respectively;
(3) The heated refrigerant and oxidant are fed into the supercritical reactor 40, the pressure in the supercritical reactor 40 is controlled not to be lower than the critical pressure of the refrigerant, and the temperature in the supercritical reactor 40 is controlled not to be lower than the critical temperature of the refrigerant, so that the refrigerant is degraded in a supercritical state.
According to the method for degrading the refrigerant in the above embodiment of the present invention, the refrigerant pressurizing device 10 is used to pressurize the refrigerant, the oxidant pressurizing device 20 is used to pressurize the oxidant, so that the pressures of the refrigerant and the oxidant are not lower than the critical pressure of the refrigerant, the pre-heater 30 is used to heat the pressurized refrigerant and the oxidant respectively, so that the temperatures of the refrigerant and the oxidant are not lower than the critical temperature of the refrigerant, the heated refrigerant and the oxidant are sent into the supercritical reactor 40, the pressure in the supercritical reactor 40 is controlled to be not lower than the critical pressure of the refrigerant, the temperature in the supercritical reactor 40 is controlled to be not lower than the critical temperature of the refrigerant, the refrigerant is thermally degraded in the supercritical state to generate tail gas, and in the supercritical reactor 40, the refrigerant has high reactivity and good mass transfer performance, can be effectively degraded under the low temperature condition, and also has high density, high solubility and strong convection diffusion capacity, the volume of the refrigerant with the same mass is smaller, thereby the refrigerant can be processed more efficiently, the refrigerant has high processing capacity, the high concentration, the high degradation rate, the high refrigerant flow rate and the high degradation rate, and the high flow rate and the high degradation rate are realized. In addition, the pre-heater 30 is used for heating the pressurized refrigerant and the oxidant respectively, and the heated refrigerant and the heated oxidant are sent into the supercritical reactor 40 for degradation, so that the problems of carbon powder generation and blockage caused by long-time heating after the refrigerant and the oxidant are mixed can be avoided.
In embodiments of the present invention, the temperature within supercritical reactor 40 may be no higher than 600 ℃, and the pressure within supercritical reactor 40 may be no higher than 20MPa. Thereby reducing the energy consumption and the equipment cost.
According to some embodiments of the present invention, for the refrigerant having a low hydrogen content, the step (2) further includes heating the pressurized hydrogen-containing compound using a preheater 30; in step (3), the heated hydrogen-containing compound may be fed to the supercritical reactor 40 at the same time as the heated refrigerant and the oxidizing agent are fed to the supercritical reactor 40. Thus, the hydrogen element can be provided for the degradation system of the refrigerant with insufficient hydrogen, so that the refrigerant is matched with the oxidant and the hydrogen-containing compound to complete thermal decomposition under the supercritical state. The proportions of the refrigerant, the oxidizing agent, and the hydrogen-containing compound are not particularly limited, and may be selected as desired by those skilled in the art. As a specific example, the refrigerant may be C 2 H 2 F 4 The oxidant can be O 2 The hydrogen-containing compound can be H 2 O，C 2 H 2 F 4 、O 2 And H is 2 The molar ratio of O may be 1:1.5:1. Further, the oxidizing agent and the hydrogen-containing compound may be slightly excessive, whereby the refrigerant may be sufficiently degraded.
According to still other embodiments of the present invention, prior to step (1), a tightness test is performed on the system of supercritical thermally degraded refrigerant. Thereby, the tightness of the system can be ensured. After the tightness of the system is ensured, the system is vacuumized by using a vacuum pump, and the preparation work before the degradation reaction is completed. To further increase the reaction rate, a catalyst may be loaded into the supercritical reactor 40 prior to step (1). The kind of the catalyst is described in detail above and will not be described here.
Further, the method for degrading the refrigerant by using the supercritical thermal degradation refrigerant system of the above embodiment may further include: (4) And cooling and/or purifying tail gas generated by degrading the refrigerant in the supercritical state. Thereby cooling and/or filtering ash from the tail gas generated by the degradation of the refrigerant in the supercritical state. The cooled and/or purified tail gas may be further recovered or treated harmlessly.
The invention will now be described with reference to specific examples, which are intended to be illustrative only and not limiting in any way.
Example 1
And (3) filling high-pressure nitrogen into the system to check the tightness of the system, and vacuumizing the system by using a vacuum pump after the tightness of the system is ensured, so as to finish the preparation work before the degradation reaction.
Opening the refrigerant booster pair C 2 H 2 F 4 Pressurizing and starting the oxidant pressurizing device to perform pressurizing on O 2 Pressurizing, and starting the hydrogen-containing compound pressurizing device to pressurize H 2 Pressurizing O and adjusting C by a flowmeter respectively 2 H 2 F 4 、O 2 、H 2 The feed rate of O is such that C 2 H 2 F 4 、O 2 And H is 2 The molar ratio of O is 1:1.5:1; starting the preheater to enable C 2 H 2 F 4 、O 2 、H 2 O reaches 300 ℃ before entering the supercritical reactor; c after heating 2 H 2 F 4 、O 2 And H is 2 O is sent into a supercritical reactor, the furnace temperature of the supercritical reactor is controlled to 300 ℃, and the pressure in the supercritical reactor is controlled to 15MPa, so that C is realized 2 H 2 F 4 Degradation under supercritical conditions (partial pressure 4.29 MPa).
Comparative example 1
C 2 H 2 F 4 、O 2 、H 2 The temperature reached before the mixture of O enters the supercritical reactor is 300 ℃, the furnace temperature of the supercritical reactor is controlled to be 300 ℃, the pressure in the supercritical reactor is controlled to be low pressure (0.35 MPa), and C 2 H 2 F 4 The partial pressure was 0.1MPa, and the rest was the same as in example 1.
Comparative example 2
C 2 H 2 F 4 、O 2 、H 2 The temperature reached before O enters the supercritical reactor is 300 ℃, the furnace temperature of the supercritical reactor is controlled to be 300 ℃, the pressure in the supercritical reactor is controlled to be medium pressure (3.5 MPa), and C 2 H 2 F 4 The partial pressure was 1MPa, and the rest was the same as in example 1.
C in example 1 and comparative examples 1 to 2 was carried out by GC-TCD method 2 H 2 F 4 Degradation of the generated tail gas C in supercritical state 2 H 2 F 4 Analyzing the content and calculating C 2 H 2 F 4 The reduction rate of the content and the result are shown in Table 1.
TABLE 1
| Reactor temperature (. Degree. C.) | Reactor pressure (MPa) | C 2 H 2 F 4 Reduction of content (%) | |
| Example 1 | 300 | 15 | 99.8 |
| Comparative example 1 | 300 | 0.35 | 26.3 |
| Comparative example 2 | 300 | 3.5 | 14.9 |
As can be seen from example 1, the method for degrading a refrigerant using the above-described example of the present invention can effectively degrade a refrigerant under supercritical conditions.
In the description of the present specification, a description referring to terms "one embodiment," "some embodiments," "examples," "specific examples," or "some examples," etc., means that a particular feature, structure, material, or characteristic described in connection with the embodiment or example is included in at least one embodiment or example of the present invention. In this specification, schematic representations of the above terms are not necessarily directed to the same embodiment or example. Furthermore, the particular features, structures, materials, or characteristics described may be combined in any suitable manner in any one or more embodiments or examples. Furthermore, the different embodiments or examples described in this specification and the features of the different embodiments or examples may be combined and combined by those skilled in the art without contradiction.
While embodiments of the present invention have been shown and described above, it will be understood that the above embodiments are illustrative and not to be construed as limiting the invention, and that variations, modifications, alternatives and variations may be made to the above embodiments by one of ordinary skill in the art within the scope of the invention.
Claims (25)
1. A system for supercritical thermal degradation of a refrigerant, comprising:
the refrigerant pressurizing device is provided with a refrigerant inlet and a high-pressure refrigerant outlet, the refrigerant pressurizing device comprises a first liquid pump and a first flowmeter, the first liquid pump is connected with the first flowmeter, the first liquid pump is provided with the refrigerant inlet, the first flowmeter is provided with the high-pressure refrigerant outlet, the refrigerant pressurizing device further comprises a refrigerant storage container, a refrigerant pre-pressurizing unit is arranged in the refrigerant storage container, the refrigerant storage container is connected with the refrigerant inlet, and the refrigerant pressurizing device is used for pressurizing the refrigerant to enable the pressure of the refrigerant to be above the critical pressure of the refrigerant;
an oxidant plenum having an oxidant inlet and a high pressure oxidant outlet;
the device comprises a preheater, a heat exchange device and a heat exchange device, wherein the preheater comprises a refrigerant heat exchange channel and an oxidant heat exchange channel, the refrigerant heat exchange channel is provided with a high-pressure refrigerant inlet and a high-temperature refrigerant outlet, the high-pressure refrigerant inlet is connected with the high-pressure refrigerant outlet, the oxidant heat exchange channel is provided with a high-pressure oxidant inlet and a high-temperature oxidant outlet, and the high-pressure oxidant inlet is connected with the high-pressure oxidant outlet;
The supercritical reactor is provided with a raw material inlet and a first tail gas outlet, and the raw material inlet is respectively connected with the high-temperature refrigerant outlet and the high-temperature oxidant outlet.
2. The system of claim 1, wherein the supercritical reactor comprises a heater and/or a temperature controller, and/or the preheater comprises a heater and/or a temperature controller.
3. The system of claim 1, wherein the feed inlet and the first tail gas outlet are each independently provided with a pressure gauge.
4. The system of claim 1, wherein the first exhaust outlet is connected to a back pressure valve.
5. The system of claim 1, wherein a one-way valve is disposed between the high pressure oxidant outlet and the high pressure oxidant inlet.
6. The system according to claim 1, characterized in that a safety valve is provided between the high pressure oxidant outlet and the high pressure oxidant inlet and/or at the raw material inlet.
7. The system of claim 2, wherein the oxidant booster means comprises an oxidant booster pump and a second flow meter, the oxidant booster pump and the second flow meter being connected, the oxidant booster pump being provided with the oxidant inlet and the second flow meter being provided with the high pressure oxidant outlet.
8. The system of claim 7, wherein the oxidant booster device further comprises a buffer tank and a pressure relief valve, the oxidant booster pump being coupled to the buffer tank, the buffer tank being coupled to the second flow meter through the pressure relief valve.
9. The system according to claim 1 or 2, further comprising:
a hydrogen-containing compound pressurizing device having a hydrogen-containing compound inlet and a high-pressure hydrogen-containing compound outlet;
the preheater further comprises a hydrogen-containing compound heat exchange channel, wherein the hydrogen-containing compound heat exchange channel is provided with a high-pressure hydrogen-containing compound inlet and a high-temperature hydrogen-containing compound outlet, the high-pressure hydrogen-containing compound inlet is connected with the high-pressure hydrogen-containing compound outlet, and the raw material inlet is connected with the high-temperature hydrogen-containing compound outlet.
10. The system of claim 9, wherein the feedstock inlet is connected to the high temperature refrigerant outlet, the high temperature oxidant outlet, and the high temperature hydrogen-containing compound outlet, respectively, by a thermal insulation pipe.
11. The system of claim 9, wherein the hydrogen-containing compound pressurizing device comprises a second liquid pump and a third flowmeter, the second liquid pump is connected with the third flowmeter, the second liquid pump is provided with the hydrogen-containing compound inlet, and the third flowmeter is provided with the high-pressure hydrogen-containing compound outlet.
12. The system as recited in claim 4, further comprising:
the tail gas treatment device is provided with a tail gas inlet and a second tail gas outlet, the tail gas inlet is connected with the first tail gas outlet, and the second tail gas outlet is connected with the back pressure valve.
13. The system of claim 12, wherein the exhaust treatment device comprises a condenser having the exhaust inlet and a low temperature gas outlet, the low temperature gas outlet being connected to the filter, and a filter having the second exhaust outlet.
14. The system of claim 13, wherein the tail gas treatment device further comprises a constant temperature oil bath, the condenser further having a cooling medium inlet and a cooling medium outlet, the cooling medium inlet and the cooling medium outlet being respectively connected to the constant temperature oil bath.
15. The system of claim 1 or 2, wherein a catalyst is disposed within the supercritical reactor.
16. The system of claim 15, wherein the catalyst comprises at least one of a metal, a metal oxide, and a metal phosphate.
17. A method of degrading a refrigerant using the supercritical thermal degradation refrigerant system of any one of claims 1-16, comprising:
(1) Pressurizing the refrigerant by adopting a refrigerant pressurizing device, and pressurizing the oxidant by adopting an oxidant pressurizing device;
(2) Heating the pressurized refrigerant and the pressurized oxidant respectively by adopting a preheater;
(3) And sending the heated refrigerant and the oxidant into a supercritical reactor, controlling the pressure in the supercritical reactor not to be lower than the critical pressure of the refrigerant, and controlling the temperature in the supercritical reactor not to be lower than the critical temperature of the refrigerant so as to degrade the refrigerant in a supercritical state.
18. The method of claim 17 wherein step (2) further comprises heating the pressurized hydrogen-containing compound with a preheater; step (3) further comprises feeding the heated hydrogen-containing compound into the supercritical reactor.
19. The method of claim 17, wherein prior to step (1), a tightness test is performed on the system of supercritical thermally degraded refrigerant.
20. The method of claim 17, wherein prior to step (1), a catalyst is loaded into the supercritical reactor.
21. The method of claim 17, wherein the refrigerant comprises at least one of a hydrochlorofluorocarbon, a hydrofluorocarbon, and a hydrofluoroolefin.
22. The method of claim 17, wherein the oxidizing agent comprises O 2 And/or H 2 O 2 。
23. The method of claim 18 wherein the hydrogen-containing compound comprises H 2 O、CH 3 OH、CH 3 CH 2 At least one of OH.
24. The method according to claim 17 or 18, further comprising:
(4) And cooling and/or purifying tail gas generated by degrading the refrigerant in a supercritical state.
25. The method according to claim 17 or 18, wherein the temperature in the supercritical reactor is not higher than 600 ℃, and the pressure in the supercritical reactor is not higher than 20MPa.
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Citations (13)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPH02274269A (en) * | 1989-04-14 | 1990-11-08 | Agency Of Ind Science & Technol | Method of decomposing fluorocarbon |
| CA2020610A1 (en) * | 1989-07-07 | 1991-01-08 | Yoshinori Imoto | Method of decomposing flon |
| JPH07275871A (en) * | 1994-04-08 | 1995-10-24 | Kobe Steel Ltd | Supercritical water oxidation treatment method of harmful substance and apparatus therefor |
| JPH07313987A (en) * | 1994-03-30 | 1995-12-05 | Kobe Steel Ltd | High pressure reaction container apparatus |
| JPH0924242A (en) * | 1996-07-05 | 1997-01-28 | Dowa Mining Co Ltd | Chlorofluorocarbon(cfc) decomposition apparatus |
| JPH11276860A (en) * | 1998-03-27 | 1999-10-12 | Japan Pionics Co Ltd | Treatment of fluorocarbon by decomposition and decomposition treatment device |
| JP2001272142A (en) * | 2000-03-27 | 2001-10-05 | Sanyo Electric Co Ltd | Method for regenerating recovered refrigerant |
| KR20020016705A (en) * | 2000-08-26 | 2002-03-06 | 박재경 | Freon gas decomposition apparatus used high temperature plasma |
| JP2002248334A (en) * | 2001-02-27 | 2002-09-03 | Toshiba Eng Co Ltd | Steam plant provided with facility for treating organic matter with supercritical water |
| CN1625437A (en) * | 2001-03-07 | 2005-06-08 | 洋马株式会社 | Reaction system of organic substance employing supercritical fluid or sub-critical fluid |
| CN101275806A (en) * | 2007-03-28 | 2008-10-01 | 中国科学院微电子研究所 | Carbon dioxide supercritical drying device |
| CN101993143A (en) * | 2010-10-27 | 2011-03-30 | 南京工业大学 | System and method for treating caustic sludge wastewater by using supercritical water oxidation method |
| CN107803107A (en) * | 2016-09-09 | 2018-03-16 | 云南民族大学 | Solid base MgO/ZrO2The method of catalyzing hydrolysis freon |
-
2023
- 2023-04-25 CN CN202310457872.XA patent/CN116272748B/en active Active
Patent Citations (13)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPH02274269A (en) * | 1989-04-14 | 1990-11-08 | Agency Of Ind Science & Technol | Method of decomposing fluorocarbon |
| CA2020610A1 (en) * | 1989-07-07 | 1991-01-08 | Yoshinori Imoto | Method of decomposing flon |
| JPH07313987A (en) * | 1994-03-30 | 1995-12-05 | Kobe Steel Ltd | High pressure reaction container apparatus |
| JPH07275871A (en) * | 1994-04-08 | 1995-10-24 | Kobe Steel Ltd | Supercritical water oxidation treatment method of harmful substance and apparatus therefor |
| JPH0924242A (en) * | 1996-07-05 | 1997-01-28 | Dowa Mining Co Ltd | Chlorofluorocarbon(cfc) decomposition apparatus |
| JPH11276860A (en) * | 1998-03-27 | 1999-10-12 | Japan Pionics Co Ltd | Treatment of fluorocarbon by decomposition and decomposition treatment device |
| JP2001272142A (en) * | 2000-03-27 | 2001-10-05 | Sanyo Electric Co Ltd | Method for regenerating recovered refrigerant |
| KR20020016705A (en) * | 2000-08-26 | 2002-03-06 | 박재경 | Freon gas decomposition apparatus used high temperature plasma |
| JP2002248334A (en) * | 2001-02-27 | 2002-09-03 | Toshiba Eng Co Ltd | Steam plant provided with facility for treating organic matter with supercritical water |
| CN1625437A (en) * | 2001-03-07 | 2005-06-08 | 洋马株式会社 | Reaction system of organic substance employing supercritical fluid or sub-critical fluid |
| CN101275806A (en) * | 2007-03-28 | 2008-10-01 | 中国科学院微电子研究所 | Carbon dioxide supercritical drying device |
| CN101993143A (en) * | 2010-10-27 | 2011-03-30 | 南京工业大学 | System and method for treating caustic sludge wastewater by using supercritical water oxidation method |
| CN107803107A (en) * | 2016-09-09 | 2018-03-16 | 云南民族大学 | Solid base MgO/ZrO2The method of catalyzing hydrolysis freon |
Non-Patent Citations (3)
| Title |
|---|
| 李广平编著.皮革化工材料的生产及应用.轻工业出版社,1979,第17页. * |
| 氟里昂催化分解研究进展;马臻, 华伟明, 高滋;化学通报(06);全文 * |
| 超临界甲醇中PBT的分解行为研究;孟令辉, 黄玉东, 梁志华, 柴田充弘, 四十宫龙德;材料科学与工艺(03);全文 * |
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