Patent Application
20240098870
The present disclosure belongs to the technical field of gas degradation, and particularly relates to a thermal plasma treatment method for sulfur hexafluoride (SF6) degradation.
SF6 is a widely used insulating and arc extinguishing gas in a power system, but its potential greenhouse effect value is up to 23,500 times that of CO2, so use of SF6 has been restricted in many industries. Therefore, in the context of global efforts to reduce carbon emission, it is urgent to find a method that can efficiently degrade SF6.
However, SF6 has an extremely high self-recovery characteristic. Even if SF6 is ionized under an arc condition, SF6 molecules can also be quickly compounded, producing only a small amount of impurity gas. This allows SF6 to quickly restore the dielectric ability and have good arc extinguishing ability, so SF6 is widely used in the power system. However, in another aspect, this characteristic also makes it extremely difficult to degrade retired SF6 gas.
The effect of an existing high-temperature pyrolysis method is not satisfactory. On one hand, a heating process consumes a lot of energy; and on the other hand, the degradation rate is relatively low, and the purpose of harmless degradation of SF6 cannot be achieved.
In order to improve the energy efficiency of SF6 degradation and the degradation rate, a plasma waste gas treatment technology has been widely studied in recent years. Common methods include a radio frequency plasma method, a microwave plasma method, a dielectric barrier discharge plasma method, and the like. However, they are all cold plasma methods with low reaction temperature and low discharge power. On one hand, SF6 cannot be completely degraded into atoms, and on the other hand, SF6 with a low concentration and a low flow rate can be degraded only, which is not conducive to industrial application. This disclosure aims at solving the above problems.
The above-mentioned information disclosed in the background is only for enhancing the understanding of the background of the present disclosure, and therefore may contain information that does not form the prior art that is well-known to a person of ordinary skill in the art in this country.
For the problems in the prior art, the present disclosure provides a thermal plasma treatment method for sulfur hexafluoride (SF6) degradation. The degradation rate and the treatment capability are improved by using a thermal plasma generator; the self-recovery of SF6 is inhibited by using hydrogen-containing reaction gas, so that SF6 is completely degraded into elemental S; the SF6 treatment capability and the degradation rate are improved; and SF6 molecules are completely degraded.
The purposes of the present disclosure are achieved by the following technical solutions. A thermal plasma treatment method for SF6 degradation includes:
In the thermal plasma treatment method for SF6 degradation, a sulfur powder filtering device communicates with the arc plasma region to filter out sulfur powder in mixed gas after the reaction in the arc plasma region; and an alkali liquid spraying tower communicates with the sulfur powder filtering device and sprays acidic exhaust gas from the sulfur powder filtering device with alkali liquid.
In the thermal plasma treatment method for SF6 degradation, the predetermined ratio of H2 to SF6 is from a lower-limit ratio 3:1 to an upper-limit ratio, and the upper-limit ratio is limited by a harmful byproduct H2S.
In the thermal plasma treatment method for SF6 degradation, a predetermined ratio of Ar:H2:SF6 is 30 L/min:40 L/min:10 L/min.
In the thermal plasma treatment method for SF6 degradation, Ar, H2 and SF6 are respectively introduced into the thermal plasma generator via swirlers. The three swirlers are all made of a polytetrafluoroethylene material and are respectively clung to three annular electrodes. The swirlers can resist HF corrosion and play insulating and supporting roles between the electrodes.
In the thermal plasma treatment method for SF6 degradation, the thermal plasma generator includes a circulating water cooling interlayer which communicates with a water cooling system to drive a circulating water source in the water cooling interlayer, so that cooling water is in full contact with the electrodes and quickly brings away thermal loads on the electrodes.
In the thermal plasma treatment method for SF6 degradation, the thermal plasma generator includes three annular electrodes which are respectively a cathode, an arc strike anode and an arcing anode; a high-voltage alternating voltage is first applied between the cathode and the arc strike anode during discharge to strike an arc; after arcing succeeds, a stable direct current is applied between the cathode and the arcing anode to maintain the discharge of the thermal plasma generator.
In the thermal plasma treatment method for SF6 degradation, a negative electrode of the direct current power supply is connected to the cathode; a positive electrode of the direct current power supply is connected to the arc strike anode and the arcing anode; the direct current power supply generates an overvoltage for arc striking; after arcing, a constant current is provided; and the direct current power supply has an adjustable output power.
In the thermal plasma treatment method for SF6 degradation, a working voltage of the direct current power supply is 150 V, and a working current of the direct current power supply is 100 A.
In the thermal plasma treatment method for SF6 degradation, the alkali liquid spraying tower uses 5% Ca(OH)2 alkali liquid.
Compared with the prior art, the present disclosure has the following advantages: are action temperature in the present disclosure is high; the temperature of thermal plasma exceeds the reaction temperature for completely degrading SF6, so that the reaction rate is extremely high, and the SF6 degradation rate exceeds 99%; composite reactions are weak; since F radicals are all captured by H radicals, basically no composite reactions will occur; degradation products mainly include HF which can be absorbed by alkali liquid and is convenient to treat; gas flows are uniformly mixed; under the action of the swirlers, inlet gases are mixed uniformly, so that the degradation effect can be improved, and the use amount of H2 can be saved at the same time.
By reading the detailed description in the preferred specific implementation modes below, various other advantages and benefits of the present disclosure will become clear to those of ordinary skill in the art. The accompanying drawings in the description are only used for the purpose of illustrating the preferred implementation modes, and are not considered as a limitation to the present disclosure. Obviously, the drawings described below are only some embodiments of the present disclosure. For those of ordinary skill in the art, other drawings can be obtained based on these drawings without creative work. Furthermore, throughout the drawings, the same reference signs are used to denote the same components.
In the drawings:
The present disclosure is further explained below in combination with the accompanying drawings and the embodiments.
Specific embodiments of the present disclosure will be described in more detail below with reference to
It should be noted that certain words are used in the specification and claims to refer to specific components. Those skilled in the art should understand that they may use different terms to refer to a same component. This specification and claims do not use differences in terms as a way to distinguish components, but use differences in functions of components as a criterion for distinguishing. If “comprise” or “include” mentioned in the entire specification and claims is an open term, it should be interpreted as “including but not limited to”. The following description of the specification is a preferred implementation mode for implementing the present disclosure. However, the description is based on the general principles of the specification and is not intended to limit the scope of the present disclosure. The protection scope of the present disclosure shall be subject to those defined by the appended claims.
In order to facilitate the understanding of the embodiments of the present disclosure, specific embodiments will be used as an example for further explanation and description in conjunction with the accompanying drawings, and the drawings do not constitute a limitation to the embodiments of the present disclosure.
For better understanding, a thermal plasma treatment method for SF6 degradation includes:
Ar is input into athermal plasma generator as a carrier gas, and annular electrodes are electrically connected to a direct current power supply to generate an arc plasma region in the presence of the carrier gas Ar.
In this example, a reaction gas is H2. To-be-reacted SF6 and to-be-reacted H2 in a predetermined ratio are input into the arc plasma region to generate hydrogen radicals and fluorine radicals which are bonded with each other to generate HF to inhibit the self-recovery reaction of SF6, and final products include HF and elemental S. A reaction temperature in the arc plasma region is 6000K-15000K.
In a preferable implementation of the thermal plasma treatment method for SF6 degradation, a sulfur powder filtering device communicates with the arc plasma region to filter out sulfur powder in mixed gas after the reaction in the arc plasma region. An alkali liquid spraying tower communicates with the sulfur powder filtering device and sprays acidic exhaust gas from the sulfur powder filtering device with alkali liquid.
In one embodiment, as shown in
In a preferable embodiment of the SF6 degrading device based on the thermal plasma, the carrier gas Ar has a flow rate of 30 L/min; the reaction gas H2 has a flow rate of 40 L/min; and SF6 has a flow rate of 10 L/min.
In a preferable embodiment of the SF6 degrading device based on the thermal plasma, a negative electrode and a positive electrode of the direct current power supply 8 are respectively connected to the annular electrodes to first generate an overvoltage between the cathode 4.1 and the arc strike anode 4.2 for arc striking; after arcing, a constant current is provided between the cathode 4.1 and the arcing anode 4.3; and the direct current power supply 8 has an adjustable output power.
In a preferable embodiment of the SF6 degrading device based on the thermal plasma, a working voltage of the direct current power supply 8 is 150 V, and a working current of the direct current power supply 8 is 100 A.
In a preferable embodiment of the SF6 degrading device based on the thermal plasma, each swirler 5 internally includes a rotating gas path, as shown in
In a preferable embodiment of the SF6 degrading device based on the thermal plasma, the water cooling interlayer 6 adopts a split type once-through water cooling structure; a surface of a water path is provided with a concave-convex structure to enlarge a heat exchange area, as shown in
In a preferable embodiment of the SF6 degrading device based on the thermal plasma, the alkali liquid spraying tower 10 is provided with a stainless steel pore plate used for placing a PE plastic fragment packing.
In a preferable embodiment of the SF6 degrading device based on the thermal plasma, the alkali liquid spraying tower 10 uses 5% Ca(OH)2 alkali liquid.
In a preferable embodiment of the SF6 degrading device based on the thermal plasma, the waste gas detection device includes an X-ray diffraction analyzer, a chromatographic analyzer and a spectrum analyzer.
In a preferable embodiment of the SF6 degrading device based on the thermal plasma, within the predetermined ratio, a flow rate ratio of H2 to SF6 is greater than 3.
In one embodiment, the SF6 degrading device based on the thermal plasma includes a gas inlet control system, a thermal plasma generator and a harmless treatment system. The gas inlet control system includes input lines for three gases: SF6, a carrier gas and a reaction gas; each gas input line includes a gas source, a gas valve and a mass flow meter; the mass flow meters control the flow rates of the three gases to be adjustable; a typical working state is as follows: the carrier gas Ar has a flow rate of 30 L/min; the reaction gas H2 has a flow rate of 40 L/min; and SF6 has a flow rate of 10 L/min. In addition, there is a vacuum pump 3 between the SF6 gas source and the mass flow meter and the vacuum pump 3 can be used for directly pumping gas in equipment such as a retired SF6 circuit breaker for degradation.
In one embodiment, the thermal plasma generator includes a direct current power supply 8, a reaction cavity 7 and a circulating water cooling system; a negative electrode and a positive electrode of the high-power direct current power supply 8 are respectively connected to a cathode and anodes of the thermal plasma generator. During working, the direct current power supply 8 will first generate an overvoltage for arc striking; after arcing, a stable current is then provided; and the power supply has an adjustable output power. A typical working state is at a voltage of 150 V and a current of 100 A. The reaction cavity 7 is used for accommodating the thermal plasma jet flow generated by discharge and degrading the input SF6 here. A wall of the reaction cavity 7 adopts a high-temperature-resistant and corrosion-resistant material, and the reaction cavity is provided with a sulfur powder cleaning device; meanwhile, a front surface of the reaction cavity is provided with an observation window which is made of organic glass; the device is cooled by the circulating water cooling system using a circulating water source in a wall interlayer of the reaction cavity 7, and the cooling is driven by the water pump which has a lift of 45 m.
In one embodiment, the harmless treatment system includes a sulfur powder filtering device 9, an alkali liquid spraying tower 10, a waste gas detection device and a waste residue detection device. The sulfur powder filtering device 9 uses a bag collector, which requires the device to be sealed as a whole; and sulfur powder collected at the bottom can be recycled. The alkali liquid spraying tower 10 uses 5% Ca(OH)2 alkali liquid, and a mortar pump is used to cyclically pump alkali liquid into air to form two layers of sprays which are in full contact with and absorb acidic exhaust gas to finally achieve a discharge standard. CaF2 sediments collected at the bottom can be recycled. The waste gas detection device can adopt a chromatographic analyzer and a spectrum analyzer. After waste gas is discharged from the alkali liquid spraying tower 10, a sampling bag is used to collect the waste gas and the waste gas is detected. After it is detected that the waste gas meets the standard, the waste gas can be directly discharged into the atmosphere. The waste residue detection device can use an X-ray diffraction analyzer. Waste residues collected at the bottom of the alkali liquid spraying tower 10 need to be detected. The waste residues are treated after it is confirmed that no nontoxic byproducts are contained.
In one embodiment, electrodes of the plasma generator are annular electrodes which are made of copper tungsten and are respectively clung to the three swirlers 5 to achieve electrical insulation. Each swirler 5 internally includes a rotating gas path, so that a gas flow field of input gas converges towards a center of the corresponding electrode, so that arcing is kept in the center of the electrode to reduce ablation, and a stable thermal plasma jet flow is generated.
The reaction cavity 7 is used for accommodating the thermal plasma jet flow generated by discharge and degrading the input SF6 here. The reaction cavity is made of stainless steel and is provided with a sulfur powder collection and cleaning device. The cavity can be opened to pull out a sulfur powder collection box. Meanwhile, a front surface of the reaction cavity 7 is provided with an observation window which is made of organic glass.
The harmless treatment system includes a sulfur powder filtering device 9, an alkali liquid spraying tower 10, a waste gas collection and detection outlet W1 and a waste residue collection and detection outlet W2.
The sulfur powder filtering device 9 uses a bag collector, which requires the device to be sealed as a whole, and sulfur powder collected at the bottom can be recycled.
Since Ca(OH)2 can absorb HF and remove fluorine from waste liquid, the alkali liquid spraying tower 10 uses 5% Ca(OH)2 alkali liquid which is added from a feed port 11; and a stainless steel pore plate 13 is added in the alkali liquid spraying tower 10 and is used for placing a PE fragment packing 12 to avoid production of large air bubbles in the alkali liquid. Exhaust gas is introduced from the bottom of an absorption tank and is in full contact with and absorbed by a Ca(OH)2 suspension, so that the exhaust gas finally meets the discharge standard. The CaF2 sediments collected at the bottom can be recycled.
The waste gas collection and detection outlet W1 can adopt a chromatographic analyzer and a spectrum analyzer. After waste gas is discharged from the alkali liquid spraying tower, a sampling bag is used to collect the waste gas and the waste gas is detected. After it is detected that the waste gas meets the standard, the waste gas can be directly discharged into the atmosphere. The waste residue collection and detection outlet W2 can use an X-ray diffraction analyzer. Waste residues collected at the bottom of the alkali liquid spraying tower 10 need to be detected. The waste residues are treated after it is confirmed that no nontoxic byproducts are contained.
The device in this example can work stably for a long time under an atmospheric pressure. In the implementation process, the water cooling system is first turned on to drive the circulating water source in the water cooling interlayer 6; and the gas valves, the vacuum pump and the mass flow meters are then turned on. After gas flow parameters are set, the thermal plasma generator is powered by the direct current power supply 8 to generate a thermal plasma jet flow; SF6 reacts with H2 in a high-temperature region and elemental S and HF gas are generated in the reaction cavity 7. The elemental S is removed by the sulfur powder filtering device 9, and the HF gas is removed by the alkali liquid spraying tower 10; the waste gas can be discharged after the finally obtained waste gas has been tested to meet the standard at the waste gas collection and detection outlet W1, and the waste residues can be discharged after waste residues have been tested to meet the standard at the waste residue collection and detection outlet W2.
When Ar serves as the carrier gas, arcing is more stable, power required to maintain the discharge is low, and Ar is not bonded with H or F to generate byproducts. As the reaction gas, H2 reacts with SF6 to only generate HF and S, which is convenient for harmless treatment.
Optionally, N2 can be used as the carrier gas, so that the raw material is cheaper and readily available. However, N radicals and F radicals will be bonded with each other in the cooling process to generate NF3 which is a greenhouse gas.
Optionally, the reaction gas can be other hydrogen-containing gases, which can also provide H radicals and F radicals which are bonded to generate HF. However, when CH4 and NH3 are used as the reaction gas, byproducts such as CF4 and NF3 will be generated, which are also greenhouse gases.
Optionally, the reaction gas can be oxygen-containing gas. The principle of the oxygen-containing gas for degrading SF6 is slightly different from that of the hydrogen-containing gas. In the cooling process, instead of bonding with F radicals, O radicals are provided to be bonded with S to form a sulfur-oxygen double bond, and SO2F2, SOF2, SOF4, SO2 and other compounds are generated, thereby inhibiting the self-recovery characteristic of SF6. When O2 is used as the reaction gas, the advantage is that no solid products are generated, but the disadvantage is that harmful byproducts such as SO2F2 are generated. When H2O is used as the reaction gas, a main product is still HF, but harmful byproducts such as SO2F2 are also generated. Particularly, the simultaneous presence of HF and H2O is highly corrosive and will reduce the service life of the device.
More preferably, the alkali liquid spraying tower can use a mortar pump to cyclically pump the alkali liquid into air to form two layers of sprays which are in full contact with and absorb acidic exhaust gas; the absorption effect is better; and relevant national standards can be met.
More preferably, a flow rate ratio of the introduced H2 to SF6 is slightly greater than 3, which can further improve the degrading effect of SF6.
In one embodiment, Ar is used as the carrier gas to generate a stable direct current arc under a working condition of the thermal plasma generator, and to-be-reacted SF6 and to-be-reacted H2 are uniformly mixed and input through the swirlers; and a high temperature generated in the arc plasma region reaches a temperature for thoroughly decomposing the reaction gas, thus releasing a large number of hydrogen radicals and fluorine radicals. Since the bonding of the two radicals to generate HF has a smallest Gibbs free energy, most of the fluorine radicals are captured and no longer react with sulfur radicals to generate SF6; and the final products after the reaction gas passes through the thermal plasma region include HF and elemental S. When the hydrogen is excessive, the degradation rate of SF6 treated by this method can reach 99.6% or above, and the concentration of SF6 in the exhaust gas can be less than 0.07%. A calculation method of the degradation rate is to divide a difference between the concentrations of input SF6 and output SF6 by the concentration of the input SF6.
In one embodiment, the thermal plasma generator is powered by a high-power direct current power supply to generate a high-temperature arc plasma region by discharge; a reaction temperature in the arc plasma region can reach 6000K-15000K; the reaction temperature can also reach 3500K or more even if it is at a tail end of a thermal plasma jet flow outside an electric field region; and when the reaction temperature increases, the movement rate of gas molecules increases, which not only increases the number of collisions of the gas molecules within unit time. More importantly, the energy of the gas molecules increases, so that the percentage of activated molecules increases, thereby accelerating a SF6 degradation reaction. The hydrogen-containing reaction gas includes H2, NH3, CH4, H2S, etc., generating H radicals which are bonded with F radicals released by SF6 in the thermal plasma region to inhibit the self-recovery characteristic of SF6; when the reaction temperature is sufficient High, assuming that all the gas molecules are decomposed into S, F, H radicals, since the generation of elemental S and HF has a lower Gibbs free energy than the self-recovery generation of SF6 and H2, the final products are more likely to be HF rather than SF6 according to the principle of a minimum Gibbs free energy; and at the same time, according to a calculation result of Gibbs free energy change, when the reaction temperature is higher than 2534K, an activation energy required for complete degradation of SF6 into S radicals and F radicals can be provided. The resulting overall reaction is as follows:
SF6+3H2→S+6HF ΔH=−419.3 kJ/mol, ΔS=697 J/(mol·K)
At this time, the numerical value of ΔH−TΔS is much less than 0, and the reaction can proceed rapidly and spontaneously. The reaction principle is as shown in
In one embodiment, regulation and control of a gas flow field have two main functions. One function is to generate a rotating gas flow through the swirler, so that an arc root of the arc continuously moves on the surfaces of the electrodes to reduce local electrode ablation and prolong the service life of the electrodes. Meanwhile, multiple symmetrical rotating gas inlets make the reaction gas fully mixed to reduce the use amount of H2 and improve the degradation effect of SF6. The other function is to enable the gas flow to generate a downward velocity component through the swirler, which can make the arcing more stable and concentrated and make the gas flow field of the input gas more converge to the high-temperature region in the center of the arc, so as to improve the degradation effect. Each swirler 5 includes four symmetrical clockwise rotating gas inlets, as shown in
In one embodiment, the closed shell includes a reaction cavity 7 such as a pneumatic cooling expansion cavity and a water cooling interlayer 6. When a gas flow after SF6 degradation enters the pneumatic cooling expansion cavity from a narrow reaction gas path, due to the sudden expansion of a gas volume, a flow velocity decreases rapidly, which achieves a cooling effect; and in combination with circulating water cooling heat exchange in the water cooling interlayer 6 on the cavity wall, rapid cooling of the reaction gas is achieved. The device in this example can work stably for a long time under an atmospheric pressure. In the implementation process, the device is characterized in that firstly, the water cooling system is turned on to drive the circulating water source in the water cooling interlayer 6; the reaction gas is then introduced from the swirler 5; the power supply of the thermal plasma generator is finally turned on to generate the thermal plasma jet flow; and SF6 reacts with H2 in the high-temperature region and elemental S and HF gas are generated. After the reaction ends, the power supply of the plasma generator is turned off first; the three gas inlets are then closed; and the cooling water source is turned off at last. In this example, when the hydrogen is excessive, the degradation rate of SF6 can reach 99.6% or above, and the concentration of SF6 in the exhaust gas can be less than 0.07%. The calculation method of the degradation rate is to divide a difference between the concentrations of input SF6 and output SF6 by the concentration of the input SF6. In addition, in this example, the SF6 treatment capability can reach 10 L/min or more.
Optionally, the carrier gas can be replaced by gas such as N2, and the reaction gas can be replaced by hydrogen-containing gas such as CH4, NH3 and H2S.
Optionally, the three-annular-electrode structure can be replaced by a double-electrode structure, but the double-electrode structure will lead to narrowing of the thermal plasma region and put forward higher requirements on the power supply of the thermal plasma generator.
Optionally, the three gas inlets can be replaced by two gas inlets or a single gas inlet, which can make the reaction gas mixed more uniformly, but also lead to problems such as the adhesion of sulfur powder on the surface of the electrode to reduce the service life of the electrode.
More preferably, an electrode material can be replaced by a material with better conductivity and higher corrosion resistance, such as silver tungsten.
More preferably, the material of the reaction cavity of the thermal plasma generator can be replaced by Hastelloy C-2000, which is more resistant to HF gas corrosion than ordinary stainless steel.
When an enough amount of H2 is used as the reaction gas, degradation products only include HF and elemental S which is solid powder. The elemental S is separated and stored in a sulfur powder collection device, and HF can be absorbed by the Ca(OH)2 solution in the alkali liquid tower to generate harmless CaF2 sediments. When there is a little H2, degradation products will also include sulfur fluoride compounds such as SF4 and SF2 in addition to HF and elemental S. These acidic gases can also be absorbed by Ca(OH)2 to generate harmless CaSO4 sediments. When O2 is used as the reaction gas, degradation products include acidic gas such as SO2F2, SOF2, SOF4 and SO2. They can also be absorbed by Ca(OH)2 to generate harmless CaSO4 sediments.
Although the embodiments of the present disclosure are described above with reference to the accompanying drawings, the present disclosure is not limited to the above specific embodiments and application fields. The above specific embodiments are only illustrative and instructive, but not restrictive. Under the enlightenment of this specification and without departing from the scope of protection of the claims of the present disclosure, those of ordinary skill in the art can also make many forms, which all fall within the protection of the present disclosure.
