CN110127623B - Method for decomposing hydrogen sulfide by plasma - Google Patents
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- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
- C01B17/00—Sulfur; Compounds thereof
- C01B17/02—Preparation of sulfur; Purification
- C01B17/04—Preparation of sulfur; Purification from gaseous sulfur compounds including gaseous sulfides
- C01B17/0495—Preparation of sulfur; Purification from gaseous sulfur compounds including gaseous sulfides by dissociation of hydrogen sulfide into the elements
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
- C01B3/00—Hydrogen; Gaseous mixtures containing hydrogen; Separation of hydrogen from mixtures containing it; Purification of hydrogen
- C01B3/02—Production of hydrogen or of gaseous mixtures containing a substantial proportion of hydrogen
- C01B3/04—Production of hydrogen or of gaseous mixtures containing a substantial proportion of hydrogen by decomposition of inorganic compounds, e.g. ammonia
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- 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
- Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
- Y02E60/00—Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
- Y02E60/30—Hydrogen technology
- Y02E60/36—Hydrogen production from non-carbon containing sources, e.g. by water electrolysis
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- General Health & Medical Sciences (AREA)
- Engineering & Computer Science (AREA)
- Combustion & Propulsion (AREA)
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Abstract
The invention relates to the field of plasma chemistry, and discloses a method for decomposing hydrogen sulfide by using plasma, which comprises the following steps: introducing a feed gas containing hydrogen sulfide into a plasma system containing a plasma reactor to carry out a hydrogen sulfide decomposition reaction under a dielectric barrier discharge condition, wherein the dielectric barrier discharge condition comprises: the discharge voltage is 5-30 kV, and the discharge frequency is 200-30000 Hz; and the conditions of the hydrogen sulfide decomposition reaction include: the reaction temperature is 0-800 ℃, the reaction pressure is-0.06 MPa to 0.6MPa, and the residence time of reactants in the plasma reactor is 1 multiplied by 10‑5120 s. The method for decomposing hydrogen sulfide by using plasma provided by the invention can obtain higher hydrogen sulfide conversion rate under the dielectric barrier discharge condition by adopting the discharge condition of specific conditions and the hydrogen sulfide decomposition reaction condition.
Description
Technical Field
The invention relates to the field of plasma chemistry, in particular to a method for decomposing hydrogen sulfide by using plasma.
Background
Hydrogen sulfide (H)2S) is a highly toxic and malodorous acidic gas, which not only can cause corrosion of materials such as metal, but also can easily cause catalyst poisoning and inactivation in chemical production; in addition, hydrogen sulfide can also harm human health and cause environmental pollution. Therefore, in the case of performing a detoxification treatment of a large amount of hydrogen sulfide gas generated in industrial fields such as petroleum, natural gas, coal, and mineral processing, a solution is urgently needed in view of process requirements, equipment maintenance, environmental requirements, and the like.
Currently, the hydrogen sulfide is treated by the Claus process, which partially oxidizes hydrogen sulfide to produce sulfur and water. Although the method solves the problem of harmlessness of hydrogen sulfide, a large amount of hydrogen resources are lost.
With the increase of the processing amount of high-sulfur crude oil in China, the amount of the hydrogen sulfide-containing acidic tail gas which is a byproduct of an oil refining hydrofining unit is increased year by year, and the amount of hydrogen required by hydrofining is increased; in addition, hydrogen is used as a main raw material in chemical process such as oil hydrocracking, low-carbon alcohol synthesis, synthetic ammonia and the like, and the demand amount is also considerable. Therefore, the direct decomposition of the hydrogen sulfide is an ideal hydrogen sulfide resource utilization technical route, the hydrogen sulfide is harmless, the hydrogen and the elemental sulfur can be produced, the cyclic utilization of the hydrogen resource in the petroleum processing process can be realized, and the emission of a large amount of carbon dioxide brought by the conventional hydrocarbon reforming hydrogen production can be reduced.
At present, the hydrogen sulfide decomposition method mainly comprises the following steps: high temperature decomposition, electrochemical, photocatalytic, and low temperature plasma methods. Among the aforementioned methods, the pyrolysis method is relatively mature in industrial technology, but the thermal decomposition of hydrogen sulfide strongly depends on the reaction temperature and is limited by the thermodynamic equilibrium, and the conversion rate of hydrogen sulfide is only 20% even if the reaction temperature is 1000 ℃ or higher. In addition, the high temperature conditions place high demands on reactor materials, which also increases operating costs. In addition, since the thermal decomposition conversion of hydrogen sulfide is low, a large amount of hydrogen sulfide gas needs to be separated from the tail gas and circulated in the system, thereby reducing the efficiency of the apparatus and increasing the energy consumption, which all bring difficulties to large-scale industrial application thereof. Although the adoption of the membrane technology can effectively separate products, thereby breaking balance limitation and improving the conversion rate of hydrogen sulfide, the thermal decomposition temperature often exceeds the limit heat-resistant temperature of the membrane, so that the structure of the membrane material is damaged. The electrochemical method has the defects of multiple operation steps, serious equipment corrosion, poor reaction stability, low efficiency and the like. The photocatalytic method for decomposing hydrogen sulfide mainly refers to the research of photocatalytic water decomposition, and the research focuses on the aspects of developing high-efficiency semiconductor photocatalysts and the like. The method for decomposing the hydrogen sulfide by utilizing the solar energy has the advantages of low energy consumption, mild reaction conditions, simple operation and the like, and is a relatively economic method. However, this method has problems such as a small treatment amount, low catalytic efficiency, and easy deactivation of the catalyst.
Compared with other decomposition methods, the low-temperature plasma method has the advantages of simple operation, small device volume, high energy efficiency and the like, and the involved reaction has high controllability and can be flexibly applied under the conditions of small treatment capacity and difficult centralized treatment. In addition, the hydrogen sulfide decomposition device has the characteristics of high energy density and shortened reaction time, can realize effective decomposition of hydrogen sulfide at a lower temperature, and is suitable for occasions with different scales, dispersed layouts and variable production conditions. Besides, the low-temperature plasma method recovers hydrogen resources while recovering sulfur, and can realize resource utilization of hydrogen sulfide.
At present, researchers at home and abroad carry out extensive research on the technology of decomposing hydrogen sulfide by low-temperature plasma, and the used discharge forms mainly comprise glow discharge, corona discharge, sliding arc discharge, microwave plasma, radio frequency plasma, dielectric barrier discharge and the like.
Document International journal of hydrogen energy, 2012, 37: 1335-1347, decomposing hydrogen sulfide by contracting normal glow discharge, obtaining hydrogen sulfide with the lowest decomposition energy consumption of 2.35eV/H under the conditions of pressure of 0.02Mpa and temperature of 2000-4000K2And S. However, the reaction temperature is high, the pressure is low, and the conditions are harsh and are not easy to realize.
Document International journal of hydrogen energy, 2012, 37: 10010-.
Document "Chemical Engineering Science, 2009, 64 (23): 4826-4834 application of pulsed corona discharge to H2Research on hydrogen and sulfur preparation by S decomposition, a reactor adopts a wire tube structure, and pulse forming capacitance, discharge voltage and pulse frequency are considered to be H under the condition of fixed power of 100W2S conversion and decomposition energy efficiency. The result shows that under the condition of certain power, the low pulse forming capacitance, the low discharge voltage and the high pulse frequency are beneficial to obtaining high H2S, decomposing energy efficiency; in addition, with Ar and N2As equilibrium gas phase ratio, with Ar-N2Higher H can be obtained when the mixed gas is used as balance gas2Conversion of S in Ar/N2/H2H obtained when S volume fraction is 46%/46%/8%, discharge power is 60W, and pulse forming capacitance is 720pF2The minimum energy consumption for S decomposition is 4.9eV/H2S, but then H2The S conversion is only about 30%. In addition, the flow rate of the reaction system was only 1.18X 10-4SCMs-1The reaction effect of low flow, low concentration and low conversion rate has no practical significance in industrial production.
Document Journal of applied physics, 1998, 84 (3): 1215-2S decomposition reaction was studied by reacting H2S is diluted by air to the concentration of 0-100 ppm, and the gas flow rate is examined under the condition that the total gas flow rate is 0-100L/minRatio, reaction chamber size and frequency pair H2Influence of S decomposition reaction. The experimental result shows that the low gas flow rate, the small disc space and the low frequency are beneficial to obtaining higher H2S conversion, H obtained under optimized discharge conditions2S conversion rate can reach 75-80%, but H2The energy consumption of S decomposition is as high as 500eV/H2S, the reaction effect with low concentration and high energy consumption has no industrial application prospect.
Dielectric barrier discharges can generally be generated at atmospheric pressure and the discharge temperature is low. In addition, the increase of the discharge current is limited due to the existence of the medium, so that the gas is prevented from being completely broken down to form sparks or electric arcs, the generation of large-size and stable plasmas is facilitated, and the method has a good industrial application prospect.
Literature "Plasma chemistry and Plasma processing", 1992, 12 (3): 275-285 investigated H using a modified ozone generator2S is in the range of 130-560 ℃, and the reaction temperature and H are studied2S feed concentration, injection power and addition of H2、Ar、N2Pair H2The influence of S conversion rate and energy efficiency, and experiments show that the addition of Ar can promote H2Decomposing S at a total flow rate of 50-100 mL/min and H2The conversion rate is 0.5-12% under the condition that the concentration of S is 20-100%, and the minimum energy consumption for producing hydrogen is about 0.75mol/kWh (50 eV/H)2) However, this process still has the disadvantages of low conversion and high energy consumption.
CN102408095A uses medium to block discharge and light catalyst to decompose hydrogen sulfide, and its method is to pack solid catalyst with light catalytic activity in plasma zone, however, this method has the disadvantage that sulfur produced by hydrogen sulfide decomposition will deposit under catalyst bed.
Document International Journal of Energy Research, 2013, 37 (11): 1280-1286-adding Al2O3，MoOx/Al2O3，CoOx/Al2O3And NiO/Al2O3Catalyst is filled in discharge region, and H is carried out by using dielectric barrier discharge and catalyst2And (5) S decomposition research. The reaction results show thatMoOx/Al2O3And CoOx/Al2O3The catalyst has better effect; wherein when filled with MoOx/Al2O3Catalyst in H2Total S/Ar flow rate 150mL/min, H2H is obtained when the S concentration is 5 volume percent, the injection specific energy SIE is 0.92kJ/L and the catalyst filling length is 10 percent of the bed layer2The highest conversion of S is about 48%. However, in the reaction process, the concentration of hydrogen sulfide is low, sulfur generated by decomposition is deposited in the reactor, and the activity of the catalyst is reduced and the discharge stability is reduced along with the prolonging of time, so that the conversion rate of the hydrogen sulfide is gradually reduced.
CN103204466A discloses a temperature-controlled hydrogen sulfide decomposition device and method, the device is characterized in that a central electrode is made of metal, a grounding electrode is made of temperature-controlled circulating liquid, and the hydrogen sulfide decomposition process can be continuously and stably carried out through temperature control of a liquid grounding electrode. In addition, CN103204467A discloses a device and a method for preparing hydrogen by continuously and stably decomposing hydrogen sulfide, which is characterized in that a central electrode is made of metal, a ground electrode is used as temperature-controllable circulating liquid, temperature control is performed through a liquid ground electrode, raw material is fed in a circumferential direction and reversely passes through a discharge area in a spiral mode along an axial direction, so that generated sulfur is timely and centrifugally separated. However, in order to ensure that the hydrogen sulfide is decomposed as sufficiently as possible in the methods disclosed in CN103204466A and CN103204467A, it is necessary to control the flow rate of the hydrogen sulfide so that the residence time of the hydrogen sulfide in the inner cylinder of the reactor is longer and to control the size of the inner cylinder so that more electric energy is obtained per unit volume of gas in the inner cylinder, and since the current prior art cannot provide a more powerful power source, the methods disclosed in CN103204466A and CN103204467A can only achieve the highest conversion rate of the hydrogen sulfide of about 20% even if the residence time of the hydrogen sulfide is longer and the size of the inner cylinder is controlled so that more electric energy is obtained per unit volume of gas in the inner cylinder, and when the highest conversion rate of the hydrogen sulfide reaches about 20%, the energy consumption of the decomposition reaction of the hydrogen sulfide is considerably high and is not suitable for large-scale industrial applications. Further, the methods disclosed in CN103204466A and CN103204467A have the drawback that the kinds of the liquid-applicable ground electrodes are very few, and the disclosed salt solutions and the like can generally only maintain the temperature of the reactor at 100 ℃ or lower, whereas elemental sulfur is generally solid at 100 ℃ or lower, which is likely to cause the reactor to be clogged.
Disclosure of Invention
The invention aims to overcome the defects of low hydrogen sulfide conversion rate and high decomposition energy consumption in the hydrogen sulfide decomposition reaction in the prior art, and provides a novel method for decomposing hydrogen sulfide by using plasma.
In order to achieve the above object, the present invention provides a method for decomposing hydrogen sulfide by plasma, comprising: introducing a raw material gas containing hydrogen sulfide into a plasma system containing a plasma reactor to carry out hydrogen sulfide decomposition reaction under a dielectric barrier discharge condition, wherein the plasma system sequentially contains a gas supply-distribution unit, a plasma reaction unit and a product separation unit according to a material flow direction, the plasma reaction unit contains a plasma power supply and the plasma reactor, and the dielectric barrier discharge condition comprises the following steps: the discharge voltage is 5-30 kV, and the discharge frequency is 200-30000 Hz; and the conditions of the hydrogen sulfide decomposition reaction include: the reaction temperature is 0-800 ℃, the reaction pressure is-0.06 MPa to 0.6MPa, and the residence time of reactants in the plasma reactor is 1 multiplied by 10-5～120s。
The method for decomposing hydrogen sulfide by using plasma provided by the invention can obtain higher hydrogen sulfide conversion rate under the dielectric barrier discharge condition by adopting the discharge condition of specific conditions and the hydrogen sulfide decomposition reaction condition.
In addition, the method of the invention also has the advantage of low energy consumption for decomposition.
Drawings
FIG. 1 is a schematic structural diagram of a preferred embodiment of a plasma reactor in a hydrogen sulfide decomposing plasma system provided by the present invention;
FIG. 2 is a schematic structural diagram of another preferred embodiment of a plasma reactor in a hydrogen sulfide decomposing plasma system provided by the present invention;
FIG. 3 is a flow diagram of a plasma system for decomposing hydrogen sulfide in accordance with the present invention.
Description of the reference numerals
1. Inner cylinder 2, outer cylinder
11. Reactor inlet 21, heat transfer medium inlet
12. Gas product outlet 22 and heat-conducting medium outlet
13. Liquid product outlet
14. Reaction tube
3. Central high-voltage electrode
4. Grounding electrode
5. Grounding wire
6. Barrier dielectric
A. Air supply-distribution unit A1 and mixer
B. Plasma reaction unit B1 and plasma reactor
C. Product separation unit and hydrogen sulfide recycle unit
C1, gas-liquid separator C2, particulate purifier
C3, amine liquid absorption tower C4 and analysis tower
C5, carrier-gas separator C6, sulfur storage
Detailed Description
The endpoints of the ranges and any values disclosed herein are not limited to the precise range or value, and such ranges or values should be understood to encompass values close to those ranges or values. For ranges of values, between the endpoints of each of the ranges and the individual points, and between the individual points may be combined with each other to give one or more new ranges of values, and these ranges of values should be considered as specifically disclosed herein.
As previously mentioned, the present invention provides a method of plasma decomposing hydrogen sulfide, the method comprising: introducing raw material gas containing hydrogen sulfide into a reactor containing hydrogen sulfide under the condition of dielectric barrier dischargeThe hydrogen sulfide decomposition reaction is carried out in a plasma system of a plasma reactor, the plasma system sequentially comprises a gas supply-distribution unit, a plasma reaction unit and a product separation unit according to the material flow direction, the plasma reaction unit comprises a plasma power supply and the plasma reactor, and the dielectric barrier discharge condition comprises that: the discharge voltage is 5-30 kV, and the discharge frequency is 200-30000 Hz; and the conditions of the hydrogen sulfide decomposition reaction include: the reaction temperature is 0-800 ℃, the reaction pressure is-0.06 MPa to 0.6MPa, and the residence time of reactants in the plasma reactor is 1 multiplied by 10-5～120s。
More preferably, the dielectric barrier discharge condition includes: the discharge voltage is 5-20 kV, and the discharge frequency is 500-15000 Hz.
Preferably, the discharge current is 0.1 to 100A, preferably 0.5 to 10A.
Preferably, the conditions of the hydrogen sulfide decomposition reaction include: the reaction temperature is 40-500 ℃, the reaction pressure is-0.06 MPa to 0.3MPa, and the residence time of reactants in the plasma reactor is 2 multiplied by 10-5～60s。
Compared with the prior art, the method for decomposing the hydrogen sulfide can obviously improve the conversion rate of the hydrogen sulfide and reduce the energy consumption for decomposition.
Preferably, the hydrogen sulfide decomposition reaction is carried out in the presence of a carrier gas selected from at least one of nitrogen, hydrogen, helium, argon, water vapor, carbon monoxide, carbon dioxide, methane, ethane and propane; more preferably, the carrier gas is selected from at least one of hydrogen, argon, helium, and nitrogen.
In the present invention, the raw material gas does not include the aforementioned carrier gas of the present invention, the raw material gas is pure hydrogen sulfide gas or industrial waste gas containing hydrogen sulfide and other gases obtained in industrial production, and the carrier gas defined in the present invention is a gas that is actively added to be mixed with the raw material gas, although the raw material gas may contain the same kind of gas as the carrier gas defined in the present invention, and the method of the present invention can control the amount of the carrier gas added as needed.
Preferably, the content of the hydrogen sulfide gas in the feed gas is 0.1-100 vol% of the hydrogen sulfide gas at the reactor inlet of the plasma reactor; more preferably 10 to 50 vol%.
The structure of the plasma reactor is not particularly limited in the aforementioned method of the present invention, and the aforementioned method of the present invention can be performed using a plasma reactor that generates an electric field by dielectric barrier discharge, which is conventional in the art. However, the inventors of the present invention have found that when the hydrogen sulfide decomposition reaction of the present invention is carried out using a plasma reactor having the following structural features, the conversion rate of hydrogen sulfide can be further improved.
The plasma reactor includes:
the inner cylinder is provided with a reactor inlet and a product outlet respectively, and at least two parallel reaction tubes are arranged in the inner cylinder, the top and the bottom of each reaction tube are correspondingly communicated respectively, so that raw materials entering from the reactor inlet can enter each reaction tube respectively, and products generated in each reaction tube can be led out from the product outlet;
the outer cylinder is nested outside the inner cylinder, a heat-conducting medium inlet and a heat-conducting medium outlet are respectively arranged on the outer cylinder, the heat-conducting medium introduced from the heat-conducting medium inlet can be distributed among the reaction tubes of the inner cylinder, and the heat-conducting medium is led out from the heat-conducting medium outlet;
the central high-voltage electrodes are respectively arranged in the reaction tubes of the inner barrel;
the grounding electrode is made of a solid conductive material and forms at least part of the side wall of each reaction tube or is arranged on the side wall of each reaction tube in a surrounding mode;
a blocking dielectric forming at least a portion of the sidewall of each of the reaction tubes such that at least a portion of the blocking dielectric surrounds the central high voltage electrode; or the blocking medium is arranged on the inner side wall of each reaction tube in a surrounding manner; or the blocking medium is arranged on at least part of the outer surface of the central high-voltage electrode, so that the blocking medium is wrapped on the outer surface of the central high-voltage electrode at least partially extending into the inner barrel;
in each reaction tube, the barrier medium is arranged at a position such that a discharge area between the central high-voltage electrode and the grounding electrode is separated by the barrier medium;
and the feed gas containing hydrogen sulphide enters the plasma reactor from the reactor inlet.
The differences between the "side wall" and the "outer side wall" and the "inner side wall" of the present invention are: "outer sidewall" and "inner sidewall" refer to the "sidewall" outer and inner surfaces, respectively.
In the present invention, in order to further increase the conversion rate of hydrogen sulfide, it is preferable that in the plasma reactor, in each of the reaction tubes, the distance between the outer side wall of the center high voltage electrode and the inner side wall of the ground electrode is D1, and the thickness of the blocking medium is D1，L1＝d1-D1，L1And length L of discharge region2The proportion relation between the components is as follows: l is1：L21: (0.5 to 6000), more preferably L1：L2＝1：(2～3000)。
In particular, the inventors of the present invention found that L is controlled in each reaction tube1：L2Is in the aforementioned range of the present invention, and controls L1And the thickness D of the barrier medium1The proportion relation is as follows: l is1：D1(0.05-100): 1; more preferably L1：D1(0.1-30): 1, the system of the invention can realize higher decomposition conversion rate of the hydrogen sulfide under relatively lower decomposition energy consumption.
In the invention, a structure formed by the reaction tubes with the top and the bottom respectively communicated correspondingly is called an inner tube.
The reactor is characterized in that a central high-voltage electrode is respectively arranged in each reaction tube, and preferably, the central high-voltage electrode is arranged at the position of the shaft core of each reaction tube, so that the uniform discharge of the reactor is facilitated. The central high-voltage electrodes arranged in the reaction tubes at the positions of the shaft cores can be respectively connected with a power supply; the central high-voltage electrodes in the reaction tubes arranged at the positions of the shaft cores can also be connected in parallel in the inner cylinder of the reaction unit, and then the central high-voltage electrodes connected in parallel are connected with a power supply.
According to a first preferred embodiment, in the low-temperature plasma reactor, the barrier medium forms at least part of the side wall of each of the reaction tubes such that at least part of the barrier medium surrounds the central high-voltage electrode. More preferably, the side walls of each of the reaction tubes are all formed by the barrier medium.
According to another preferred embodiment, in the low-temperature plasma reactor, in each of the reaction tubes, the barrier medium is disposed on at least a part of an outer surface of the central high-voltage electrode such that the outer surface of the central high-voltage electrode at least partially protruding into the inner tube is coated with the barrier medium, and the ground electrode forms at least a part of a side wall of each of the reaction tubes.
In the plasma system, particularly, in the plasma reactor, the jacket cylinder type structure design can ensure that the heat-conducting medium circularly flows in the shell layer, the whole reactor can be maintained in a certain temperature range while the discharge intensity is ensured, the generated sulfur flows out of the reactor in a liquid state, the sulfur generated by the decomposition of the hydrogen sulfide can be effectively prevented from being solidified, and the decomposition process can be continuously and stably operated for a long period while the higher conversion rate is achieved.
The above-mentioned positions of the barrier dielectric and the ground electrode are advantageous for the high-power uniform discharge of the reaction system of the present invention. The fixing method of the barrier medium and the ground electrode to each other or the fixing method of the barrier medium, the ground electrode and the inner cylindrical wall is not particularly required in the present invention, and a person skilled in the art can select an appropriate fixing form according to the materials forming the barrier medium, the inner cylindrical wall and the ground electrode, and the present invention is not particularly limited thereto.
According to a preferred embodiment, the central high voltage electrodes in the individual reaction tubes are connected in parallel with one another.
Preferably, in the plasma reactor, the material forming the barrier medium is an electrically insulating material, more preferably the material forming the barrier medium is selected from at least one of glass, ceramic, enamel, polytetrafluoroethylene and mica. The glass may be quartz glass or hard glass. The material forming the barrier medium can also be other metal and non-metal composite materials with high-voltage electric insulation design, and the like. The ceramic may be an alumina ceramic.
Preferably, the plasma reactor further comprises a grounding wire, the grounding wire is arranged on the outer side wall of the outer cylinder, and one end of the grounding wire is electrically connected with the grounding electrode on the side wall of each reaction tube.
Preferably, in the low-temperature plasma reactor, the reactor inlet is arranged at the upper part of the inner cylinder, and the product outlet is arranged at the lower part and/or the bottom of the inner cylinder.
According to a preferred embodiment, in the low-temperature plasma reactor, the product outlet includes a gaseous product outlet and a liquid product outlet, and the gaseous product outlet is disposed at a lower portion of the inner cylinder, and the liquid product outlet is disposed at a bottom portion of the inner cylinder.
According to a preferred embodiment, the dimensions of the individual reaction tubes are identical. The same dimension means that the reaction tubes are identical in size and shape. The arrangement of the reaction tubes of the present invention is not particularly limited, and the arrangement cross section thereof may be a regular triangle, a regular hexagon, a circle, or the like.
In each of the reaction tubes, a ratio of an inner diameter of the reaction tube to a pore diameter of the product outlet may be (0.1 to 100): 1.
the ratio of the pore size of the reactor inlet to the pore size of the product outlet may be (0.1 to 120): 1.
the ratio of the length of the reaction tube to the inner diameter of the reaction tube may be (0.5 to 500): 1.
preferably, in the plasma reactor, the gas product outlet is disposed below all the discharge regions, and the gas product outlet is disposed at a height H relative to the bottom of the inner cylinder1And the length L of the discharge region2The proportion relation between the components is as follows: h1：L21: (0.05 to 25000); preferably H1：L21: (0.1 to 10000); more preferably H1：L2＝1：(0.5～1000)。
Preferably, in the plasma reactor, the heat transfer medium inlet and the heat transfer medium outlet are disposed at a lower portion and an upper portion of the outer tub, respectively.
In the present invention, the inner cylinder is mainly used for the hydrogen sulfide decomposition reaction to occur, and the outer cylinder is mainly used for maintaining the desired temperature of the plasma reactor, and therefore, those skilled in the art can adjust and select an appropriate size ratio between the inner cylinder and the outer cylinder according to the purpose.
The reactor inlet of the present invention may be positioned such that the feed gas entering the inner drum is parallel to the inner diameter of the inner drum or at an angle, for example, may be tangentially positioned.
The inner diameters of the present invention each represent a diameter.
Preferably, the material forming the ground electrode is selected from a graphite tube, a metal foil or a metal mesh. The solid grounding electrode of the invention generates larger micro discharge current under the condition of certain injection power, and is more beneficial to the broken bond decomposition reaction of hydrogen sulfide. The metal tube and the metal foil in the material forming the ground electrode may include an elemental metal tube, an elemental metal foil, an alloy metal tube, and an alloy metal foil. The inventor of the invention finds that when a solid conductive material is adopted as a grounding electrode to be arranged on the side wall of the inner cylinder in a surrounding mode or at least part of the side wall of each reaction tube is formed, the conversion rate of hydrogen sulfide can be remarkably improved when the plasma system provided by the invention is adopted to carry out hydrogen sulfide decomposition reaction.
The material for forming the central high-voltage electrode is a conductive material, and preferably, the material for forming the central high-voltage electrode is at least one selected from graphite rods, graphite tubes, graphite powder, metal rods, metal tubes, metal powder and mechanical mixtures of conductive powder. The metal rod and the metal pipe can comprise an elemental metal rod, an alloy metal rod, an elemental metal pipe and an alloy metal pipe. The material forming the central high-voltage electrode can be other rod-shaped or tubular materials with conductive performance.
The invention can lead the heat-conducting medium to be introduced into the area between the outer side wall of the inner cylinder and the inner side wall of the outer cylinder of the plasma reactor, so that the temperature of the plasma reactor with a jacket structure is maintained between 119 and 444.6 ℃ for example, and the sulfur generated by the decomposition of the hydrogen sulfide can be ensured to flow out of a discharge area in a liquid state.
The plasma reactor of the present invention may further contain a catalyst capable of catalyzing the decomposition of hydrogen sulfide into elemental sulfur and hydrogen, and the catalyst is preferably contained in the inner cylinder of the plasma reactor. The present invention has no particular requirement on the loading volume and the loading type of the catalyst, and the type of the catalyst may be, for example, any one or more of the catalysts disclosed in CN102408095A, CN101590410A, and CN 103495427A.
In the present invention, the material forming the outer cylinder is not particularly limited as long as the material forming the outer cylinder can withstand the set temperature of the heat transfer medium.
The plasma reaction unit of the present invention may include 1 or more than 2 plasma reactors.
The following provides preferred embodiments of the plasma reactor of the present invention for decomposing hydrogen sulfide as described above:
nitrogen gas was passed into the inner barrel of the plasma reactor from the reactor inlet to purge the discharge zone of air, and the gas was withdrawn from the product outlet. Meanwhile, heat-conducting media are led into the outer barrel from the heat-conducting medium inlet, and the led-in heat-conducting media are led out from the heat-conducting medium outlet. The temperature of the heat transfer medium is maintained at the temperature required for the system reaction. Then introducing raw material gas containing hydrogen sulfide into the inner cylinder of the plasma reactor from the inlet of the reactor, filling the raw material gas into each reaction tube, switching on a high-voltage power supply after the raw material gas flow is stable, and forming a plasma discharge field between the central high-voltage electrode and the grounding electrode by adjusting voltage and frequency. The hydrogen sulfide gas is ionized in the discharge area and decomposed into hydrogen and elemental sulfur, and the elemental sulfur generated by discharge slowly flows down along the inner cylinder wall and flows out from the product outlet.
Preferably, the plasma system comprises a gas supply-distribution unit, a plasma reaction unit and a product separation unit in sequence according to the material flow direction, and the plasma reaction unit comprises a plasma power supply and the plasma reactor.
Preferably, the plasma system for decomposing hydrogen sulfide according to the present invention further comprises a hydrogen sulfide recycling unit for recovering hydrogen sulfide from the gas phase substance containing hydrogen sulfide obtained in the product separation unit and recycling the obtained hydrogen sulfide to the gas supply-distribution unit or the plasma reaction unit.
More preferably, the hydrogen sulfide circulation unit includes an amine liquid absorption tower for absorbing hydrogen sulfide and a desorption tower for desorbing hydrogen sulfide.
Preferably, the product separation unit comprises a gas-liquid separator for performing gas-liquid separation on gas-phase substances and liquid-phase substances from the plasma reaction unit, and optionally comprises a particle purifier and/or a gas-loaded separator; the particulate purifier is used for further separating the first gaseous substance separated by the gas-liquid separator to obtain a second gaseous substance and residual sulfur solids, and the carrier gas separator is used for separating carrier gas optionally contained in the first gaseous substance or the second gaseous substance from hydrogen.
Preferably, the gas supply-distribution unit comprises a gas distribution device and a mixer, the gas distribution device is used for distributing the raw gas and the carrier gas according to needs, and the mixer is used for mixing the raw gas from the gas distribution device and the carrier gas to obtain the reactant entering the plasma reactor of the plasma reaction unit.
In particular, the hydrogen sulfide recycling unit of the present invention may be attached to the product separation unit, and, preferably, the product separation unit and the hydrogen sulfide recycling unit are connected in a manner including: the gas-liquid separator in the product separation unit is connected with the plasma reaction unit through a pipeline, so that gas-phase products and liquid-phase sulfur elementary substances from the plasma reaction unit can enter the gas-liquid separator to be separated so as to obtain first gaseous substances and liquid sulfur respectively, the first gaseous substances are optionally introduced into a particle purifier to be further separated so as to obtain residual solid sulfur and second gaseous substances, and the liquid sulfur and the residual solid sulfur can both be led out of the plasma system of the invention through pipelines. Further, the hydrogen sulfide circulation unit is connected with the product separation unit through a pipeline, so that the second gaseous substance can enter an amine liquid absorption tower in the hydrogen sulfide circulation unit through a pipeline to respectively obtain hydrogen sulfide removing gas and hydrogen sulfide containing liquid, the hydrogen sulfide removing gas optionally enters a carrier gas separator through a pipeline to separate carrier gas possibly existing in the hydrogen sulfide removing gas, and a hydrogen-containing crude product is obtained, and the hydrogen-containing crude product can be further purified as required; and the liquid containing hydrogen sulfide is introduced into a desorption tower through a pipeline to desorb hydrogen sulfide gas so as to be circulated to the gas supply-distribution unit or the plasma reaction unit.
The hydrogen-containing crude product of the present invention can be further purified as necessary. The method for further purifying the crude hydrogen-containing product is not particularly limited in the present invention, and for example, the crude hydrogen-containing product may be introduced into an alkaline solution containing sodium hydroxide.
The liquid sulfur and the residual solid sulfur obtained in the process of the present invention can be recovered.
The structure of a preferred embodiment of the plasma reactor of the invention is provided below in connection with fig. 1, in particular:
the reactor has a coaxial jacket-type structure, and the reactor comprises:
the reactor comprises an inner cylinder 1, wherein a reactor inlet 11 and a product outlet are respectively arranged on the inner cylinder 1, at least two reaction tubes 14 which are arranged in parallel are arranged in the inner cylinder 1, the top and the bottom of each reaction tube 14 are respectively and correspondingly communicated, so that raw materials entering from the reactor inlet 11 can respectively enter each reaction tube 14, and products generated in each reaction tube 14 can be led out from the product outlet;
the outer cylinder 2 is nested outside the inner cylinder 1, a heat-conducting medium inlet 21 and a heat-conducting medium outlet 22 are respectively arranged on the outer cylinder 2, the heat-conducting medium introduced from the heat-conducting medium inlet 21 can be distributed among the reaction tubes 14 of the inner cylinder 1, and the heat-conducting medium is led out from the heat-conducting medium outlet 22;
the central high-voltage electrodes 3 are respectively arranged in the reaction tubes 14 of the inner barrel 1;
a grounding electrode 4, wherein the material forming the grounding electrode 4 is a solid conductive material, and the grounding electrode 4 forms at least part of the side wall of each reaction tube 14 or the grounding electrode 4 is respectively arranged on the side wall of each reaction tube 14 in a surrounding manner;
a barrier dielectric forming at least part of the side wall of each of said reaction tubes 14 such that at least part of said barrier dielectric surrounds said central high voltage electrode 3; or the barrier medium is arranged on the inner side wall of each reaction tube 14 in a surrounding manner;
in each of the reaction tubes 14, the barrier medium is disposed at a position such that a discharge region between the center high voltage electrode and the ground electrode is spaced by the barrier medium.
The structure of another preferred embodiment of the plasma reactor of the present invention is provided below in conjunction with fig. 2, in particular:
the reactor has a coaxial jacket-type structure, and the reactor comprises:
the reactor comprises an inner cylinder 1, wherein a reactor inlet 11 and a product outlet are respectively arranged on the inner cylinder 1, at least two reaction tubes 14 which are arranged in parallel are arranged in the inner cylinder 1, the top and the bottom of each reaction tube 14 are respectively and correspondingly communicated, so that raw materials entering from the reactor inlet 11 can respectively enter each reaction tube 14, and products generated in each reaction tube 14 can be led out from the product outlet;
the outer cylinder 2 is nested outside the inner cylinder 1, a heat-conducting medium inlet 21 and a heat-conducting medium outlet 22 are respectively arranged on the outer cylinder 2, the heat-conducting medium introduced from the heat-conducting medium inlet 21 can be distributed among the reaction tubes 14 of the inner cylinder 1, and the heat-conducting medium is led out from the heat-conducting medium outlet 22;
the central high-voltage electrodes 3 are respectively arranged in the reaction tubes 14 of the inner barrel 1;
a ground electrode 4, the material forming the ground electrode 4 is a solid conductive material, and the ground electrode 4 forms at least a part of the side wall of each of the reaction tubes 14;
the barrier medium 6 is arranged on at least part of the outer surface of the central high-voltage electrode 3, so that the barrier medium 6 is wrapped on the outer surface of the central high-voltage electrode 3 at least partially extending into the inner barrel 1;
in each of the reaction tubes 14, the barrier medium is disposed at a position such that a discharge region between the center high voltage electrode and the ground electrode is spaced by the barrier medium.
In fig. 1 and 2, it is preferable that the plasma reactor of the present invention further has the following features:
preferably, in each of the reaction tubes 14, a distance between an outer side wall of the center high voltage electrode 3 and an inner side wall of the ground electrode is D1, and a thickness of the blocking medium 6 is D1，L1＝d1-D1，L1And length L of discharge region2Has a proportional relation of L1：L21: (0.5 to 6000), more preferably L1：L2＝1：(2～3000)。
Preferably, in each of said reaction tubes 14, L1And the thickness D of the barrier medium 61The proportion relation is as follows: l is1：D1(0.05-100): 1; more preferably L1：D1＝(0.1～30)：1。
Preferably, the central high voltage electrodes 3 in each of the reaction tubes 14 are connected in parallel with each other.
Preferably, the plasma reactor further comprises a ground wire 5, wherein the ground wire 5 is disposed on the outer sidewall of the outer tube 2, and one end of the ground wire is electrically connected to the ground electrode 4 on the sidewall of each of the reaction tubes 14.
Preferably, the reactor inlet 11 is disposed at the upper portion of the inner drum 1, and the product outlet is disposed at the lower portion and/or bottom of the inner drum 1. More preferably, the product outlets include a gaseous product outlet 12 and a liquid product outlet 13, and the gaseous product outlet 12 is disposed at a lower portion of the inner drum 1, and the liquid product outlet 13 is disposed at a bottom portion of the inner drum 1.
Preferably, the reaction tubes 14 are the same size.
Preferably, the gas product outlet 12 is disposed below all the discharge regions, and the gas product outlet 12 is disposed at a height H relative to the bottom of the inner cylinder 11And the length L of the discharge region2The proportion relation between the components is as follows: h1：L21: (0.05 to 25000); preferably H1：L21: (0.1 to 10000); more preferably H1：L2＝1：(0.5～1000)。
Preferably, the heat transfer medium inlet 21 and the heat transfer medium outlet 22 are disposed at a lower portion and an upper portion of the outer tub 2, respectively.
The flow of a preferred embodiment of the plasma system of the present invention is provided below in conjunction with fig. 3, specifically:
the plasma system comprises a gas supply-distribution unit A, a plasma reaction unit B, a product separation unit and a hydrogen sulfide circulation unit C which are sequentially connected through pipelines, wherein the plasma reaction unit comprises a plasma reactor B1 and a plasma power supply (not shown). Preferably, the plasma reactor B1 has the structure shown in fig. 1 or fig. 2. Preferably, the plasma reaction unit B includes a plurality of plasma reactors B1.
Preferably, the gas supply-distribution unit a includes a mixer a1, the mixer a1 is configured to mix hydrogen sulfide gas with, for example, carrier gas to form a raw material gas as required, and introduce the obtained raw material gas into a plasma reactor B1 in a plasma reaction unit B to perform a hydrogen sulfide decomposition reaction, the reacted product enters a product separation unit and a hydrogen sulfide circulation unit C, for example, the reacted product enters a gas-liquid separator C1 to perform gas-liquid separation, liquid sulfur obtained after the gas-liquid separation enters a sulfur storage C6, the first gaseous substance obtained after the gas-liquid separation enters a particulate purifier C2 to perform further separation, and solid sulfur obtained by the further separation also can enter a sulfur storage C6. The second gaseous substance obtained from the particulate purifier C2 is introduced into an amine liquid absorption tower C3 to obtain a hydrogen sulfide removal gas and a hydrogen sulfide containing liquid (amine liquid), respectively, and preferably the hydrogen sulfide removal gas is introduced into a carrier gas separator C5 to separate carrier gases that may be present therein, thereby obtaining a hydrogen-containing crude product containing a large amount of hydrogen. Preferably, the amine solution is introduced into a desorption tower C4 to desorb hydrogen sulfide gas (referred to as desorption hydrogen sulfide), and the desorbed hydrogen sulfide gas is recycled to the gas supply/distribution unit A1 through a pipeline.
The method for decomposing hydrogen sulfide by using plasma provided by the invention has the following specific advantages:
(1) the specific discharge condition and the specific hydrogen sulfide decomposition reaction condition provided by the invention can obviously improve the conversion rate of the hydrogen sulfide;
(2) preferably, since the decomposition of hydrogen sulfide is carried out by using a plasma reactor using a metal, alloy or other conductive solid material as a ground electrode, the ground electrode generates a larger micro discharge current by discharge when it is matched with the specific conditions and reactor structure of the present invention, as compared with a liquid ground electrode, and is more favorable for the discharge decomposition reaction of hydrogen sulfide molecules.
(3) Preferably, the plasma reactor is used for decomposing hydrogen sulfide, and the jacket structure is arranged on the outer side of the grounding electrode of the reactor, so that the temperature of the reactor can be controlled by controlling the temperature of the heat-conducting medium in the jacket, sulfur generated by the discharge decomposition of the hydrogen sulfide can smoothly flow out of a discharge area, the reactor is prevented from being blocked by the solidification of the sulfur, and the discharge is continuously and stably carried out.
(4) Preferably, since the decomposition of hydrogen sulfide is carried out by using a plasma reactor, the reactor is preferably controlled to L1And L2The proportion relation between the components is as follows: l is1：L21: (0.5 to 6000), more preferably L1：L21: (2-3000), the structure of the reactor, specific discharge conditions and decomposition conditions are matched, so that the conversion rate of the hydrogen sulfide can be obviously improved, and the energy consumption for decomposition is reduced.
The present invention will be described in detail below by way of examples. In the following examples, various raw materials used were commercially available unless otherwise specified.
The thickness of the barrier dielectric is the same in the following examples and comparative examples.
The hydrogen sulfide conversion in the following examples was calculated according to the following formula:
percent conversion of hydrogen sulfide ═ moles of converted hydrogen sulfide/moles of initial hydrogen sulfide × 100%
The energy consumption for decomposing hydrogen sulfide in the following examples was measured by an oscilloscope and calculated using lissajous figures.
The volume of the inner cylinder of the reaction apparatus in example 1 below was 1L, and the volume of the inner cylinder of the reaction apparatus in the remaining examples was calculated from the corresponding data.
Example 1
The method for decomposing hydrogen sulfide by plasma of the present invention was carried out using a hydrogen sulfide decomposing plasma system having a flow chart shown in fig. 3, and the plasma reactor in this example had a structure shown in fig. 1.
The process flow of this example is as shown in the previous embodiment, and the structural parameters of the plasma reactor are as follows:
the plasma reactor comprises:
the reactor comprises an inner cylinder, wherein a reactor inlet, a gas product outlet and a liquid product outlet are respectively arranged on the inner cylinder, 4 reaction tubes arranged in parallel are contained in the inner cylinder, the top and the bottom of each reaction tube are respectively and correspondingly communicated, so that raw materials entering from the reactor inlet can respectively enter each reaction tube, gaseous products generated in each reaction tube can be led out from the gas product outlet, liquid products generated in each reaction tube can be led out from the liquid product outlet, the sizes of the 4 reaction tubes are completely the same, all side walls of the reaction tubes are formed by blocking media, and the material forming the blocking media is hard glass;
the outer cylinder is nested outside the inner cylinder, a heat-conducting medium inlet and a heat-conducting medium outlet are respectively arranged on the outer cylinder, the heat-conducting medium introduced from the heat-conducting medium inlet can be distributed among the reaction tubes of the inner cylinder, and the heat-conducting medium is led out from the heat-conducting medium outlet;
the central high-voltage electrodes are arranged on the central axis of each reaction tube, the materials for forming the central high-voltage electrodes are stainless steel metal rods, and the central high-voltage electrodes in the reaction tubes are connected in parallel;
the grounding electrodes are respectively arranged on the outer side walls of the reaction tubes in a surrounding mode, the grounding electrodes are made of stainless steel metal foils, and the lower edge of the central high-voltage electrode is flush with the lower edge of the grounding electrode.
In each reaction tube, L1：L2＝1：1700；
H1：L2＝1：48；
L1And the thickness D of the barrier medium1The ratio of (A) to (B) is 6: 1;
operating the plasma system for decomposing hydrogen sulfide:
nitrogen gas is introduced from a gas supply-distribution unit into the plasma reactor of the plasma reaction unit, the nitrogen gas enters from the reactor inlet into the inner cylinder of the plasma reactor to purge air in the discharge region, and the gas is led out from the gas product outlet and the liquid product outlet. Meanwhile, a heat-conducting medium (specifically, dimethyl silicone oil) is introduced into the outer cylinder from the heat-conducting medium inlet, the introduced heat-conducting medium is led out from the heat-conducting medium outlet, and the temperature of the heat-conducting medium is kept at 120 ℃. Then mixing the hydrogen sulfide gas and the Ar carrier gas sequentially through a gas distribution system and a mixer to obtain a reactant, wherein H in the reactant2The volume fraction of S is 30%, reactants enter the inner cylinder of the plasma reactor from the inlet of the reactor, the flow rate of the reactants is controlled so that the average residence time of gas in a discharge area is 7.5S, and the reaction pressure in the inner cylinder of the reactor is kept to be 0.05MPa in the embodiment. And after the reactants are introduced into the reactor for 30min, switching on an alternating-current high-voltage power supply, and adjusting the voltage and the frequency to form a plasma discharge field between the central high-voltage electrode and the grounding electrode. Wherein the discharge conditions are as follows: the voltage was 16.5kV, the frequency was 7.0kHz, and the current was 0.75A. The hydrogen sulfide gas is ionized in the discharge area and decomposed into hydrogen and elemental sulfur, and the elemental sulfur generated by discharge slowly flows down along the inner cylinder wall and flows out from the liquid product outlet. The gas after reaction mainly flows out from the gas product outlet.
And the obtained gas product and the liquid product both enter a gas-liquid separator of a product separation unit for gas-liquid separation to respectively obtain a first gaseous substance and liquid sulfur, the first gaseous substance enters a particle purifier for further separation to obtain residual solid sulfur and a second gaseous substance, and the liquid sulfur and the residual solid sulfur both enter a sulfur storage. And further, the second gaseous substance enters an amine liquid absorption tower in the hydrogen sulfide circulation unit to respectively obtain hydrogen sulfide removing gas and hydrogen sulfide containing liquid, the hydrogen sulfide removing gas enters a gas carrier separator to separate carrier gas so as to obtain a hydrogen-containing crude product, the hydrogen sulfide containing liquid enters an analysis tower to analyze the hydrogen sulfide gas, and the hydrogen sulfide gas obtained by analysis is circulated back to the gas supply-distribution unit. The hydrogen-containing crude product is introduced into a solution containing sodium hydroxide for further purification to obtain hydrogen gas.
As a result: in this example, H was measured after the hydrogen sulfide decomposition reaction was continued for 20min2The S conversion was 75.2%; and the discharge state and H are not abnormal after the discharge lasts for 100H2The S conversion rate is kept stable. And the decomposition energy consumption of the embodiment is 14.1eV/H2S molecule (1 molecule of H per decomposition)2S requires 14.1eV as energy).
Example 2
The method for decomposing hydrogen sulfide by plasma of the present invention was carried out using a hydrogen sulfide decomposing plasma system having the flow chart shown in fig. 3, and the plasma reactor in this example had the structure shown in fig. 2.
The process flow of this example is as shown in the previous embodiment, and the structural parameters of the plasma reactor are as follows:
the plasma reactor comprises:
the reactor comprises an inner cylinder, wherein a reactor inlet, a gas product outlet and a liquid product outlet are respectively arranged on the inner cylinder, 4 reaction tubes arranged in parallel are contained in the inner cylinder, the top and the bottom of each reaction tube are respectively and correspondingly communicated, so that raw materials entering from the reactor inlet can respectively enter each reaction tube, gaseous products generated in each reaction tube can be led out from the gas product outlet, liquid products generated in each reaction tube can be led out from the liquid product outlet, and the sizes of the 4 reaction tubes are completely the same;
the outer cylinder is nested outside the inner cylinder, a heat-conducting medium inlet and a heat-conducting medium outlet are respectively arranged on the outer cylinder, the heat-conducting medium introduced from the heat-conducting medium inlet can be distributed among the reaction tubes of the inner cylinder, and the heat-conducting medium is led out from the heat-conducting medium outlet;
the central high-voltage electrodes are arranged on the central axis of each reaction tube, the materials for forming the central high-voltage electrodes are stainless steel metal rods, and the central high-voltage electrodes in the reaction tubes are connected in parallel;
the lower edge of the center high-voltage electrode is flush with the lower edge of the grounding electrode;
the blocking medium is arranged on the outer surface of the part of the central high-voltage electrode extending into the reaction tube, the upper edge of the blocking medium is higher than that of the grounding electrode, and the material forming the blocking medium is quartz glass;
in each reaction tube, L1And L2The ratio of (1): 3000A;
H1：L2＝1：250；
L1and the thickness D of the barrier medium1The proportion relation between the components is as follows: l is1：D1＝15：1；
The operation procedure of the plasma system for decomposing hydrogen sulfide was similar to that of example 1, except that the dielectric barrier discharge conditions in this example included: the discharge voltage is 17.5kV, the discharge frequency is 7.8kHz, and the current is 0.8A; and the conditions of the hydrogen sulfide decomposition reaction include: the reaction temperature is 140 ℃ (i.e. the temperature maintained by the heat-conducting medium), the reaction pressure is 0.02MPa, and the residence time of the reactants in the plasma reactor is 8.3 s.
As a result: in this example, H was measured after the hydrogen sulfide decomposition reaction was continued for 20min2The S conversion was 75.6%; and the discharge state and H are not abnormal after the discharge lasts for 100H2The S conversion rate is kept stable. And the decomposition energy consumption of the embodiment is 14.5eV/H2And (3) an S molecule.
Example 3
This example uses a similar process and system to that of example 1 for the hydrogen sulfide decomposition reaction, except that:
the dielectric barrier discharge conditions of the present embodiment include: the discharge voltage is 12.5kV, the discharge frequency is 12kHz, and the current is 2.5A; and the conditions of the hydrogen sulfide decomposition reaction include: the reaction temperature is 180 ℃ (the temperature for keeping the heat-conducting medium), the reaction pressure is 0.1MPa, and the residence time of the reactants in the plasma reactor is 9.2 s.
The rest is the same as in example 1.
As a result: in this example, H was measured after the hydrogen sulfide decomposition reaction was continued for 20min2The S conversion was 74.2%; and the discharge state and H are not abnormal after the discharge lasts for 100H2The S conversion rate is kept stable. And the decomposition energy consumption of the embodiment is 15.2eV/H2And (3) an S molecule.
Example 4
This example uses a similar process and system to that of example 2 for the hydrogen sulfide decomposition reaction, except that:
the dielectric barrier discharge conditions of the present embodiment include: the discharge voltage is 25kV, the discharge frequency is 7.9kHz, and the current is 0.85A; and the conditions of the hydrogen sulfide decomposition reaction include: the reaction temperature is 140 ℃ (i.e. the temperature maintained by the heat-conducting medium), the reaction pressure is 0.02MPa, and the residence time of the reactants in the plasma reactor is 8.3 s.
The rest is the same as in example 2.
As a result: in this example, H was measured after the hydrogen sulfide decomposition reaction was continued for 20min2The S conversion was 74.6%; and the discharge state and H are not abnormal after the discharge lasts for 100H2The S conversion rate is kept stable. And the decomposition energy consumption of the embodiment is 21.3eV/H2And (3) an S molecule.
Example 5
This example uses a similar process and system to that of example 1 for the hydrogen sulfide decomposition reaction, except that:
l of the present embodiment1：L2＝1：3500。
The rest is the same as in example 1.
As a result: in this example, H was measured after the hydrogen sulfide decomposition reaction was continued for 20min2The S conversion rate was 71.9%; and the discharge state and H are not abnormal after the discharge lasts for 100H2The S conversion rate is kept stable. And the decomposition energy consumption of the embodiment is 23.9eV/H2And (3) an S molecule.
Example 6
This example uses a similar process and system to that of example 2 for the hydrogen sulfide decomposition reaction, except that:
l in the present embodiment1：D1＝35：1。
The rest is the same as in example 2.
As a result: in this example, H was measured after the hydrogen sulfide decomposition reaction was continued for 20min2The S conversion rate is 70.8%; and the discharge state and H are not abnormal after the discharge lasts for 100H2The S conversion rate is kept stable. And the decomposition energy consumption of the embodiment is 24.5eV/H2And (3) an S molecule.
From the above results, it can be seen that the hydrogen sulfide decomposition using the method for decomposing hydrogen sulfide by plasma according to the present invention can significantly improve the hydrogen sulfide conversion rate compared to the prior art, and the method for decomposing hydrogen sulfide by plasma according to the present invention can maintain a high hydrogen sulfide conversion rate for a long period of time with low decomposition energy consumption.
The preferred embodiments of the present invention have been described above in detail, but the present invention is not limited thereto. Within the scope of the technical idea of the invention, many simple modifications can be made to the technical solution of the invention, including combinations of various technical features in any other suitable way, and these simple modifications and combinations should also be regarded as the disclosure of the invention, and all fall within the scope of the invention.
Claims (33)
1. A method of plasma decomposing hydrogen sulfide, the method comprising: introducing a raw material gas containing hydrogen sulfide into a plasma system containing a plasma reactor to carry out hydrogen sulfide decomposition reaction under the condition of dielectric barrier discharge, wherein the plasma system is arranged according to the flow directionThe plasma reactor comprises an air supply-air distribution unit, a plasma reaction unit and a product separation unit, wherein the plasma reaction unit comprises a plasma power supply and the plasma reactor, and the dielectric barrier discharge condition comprises that: the discharge voltage is 5-30 kV, and the discharge frequency is 200-30000 Hz; and the conditions of the hydrogen sulfide decomposition reaction include: the reaction temperature is 0-800 ℃, the reaction pressure is-0.06 MPa to 0.6MPa, and the residence time of reactants in the plasma reactor is 1 multiplied by 10-5~120s；
Wherein the plasma reactor comprises:
the reactor comprises an inner cylinder (1), wherein a reactor inlet (11) and a product outlet are respectively arranged on the inner cylinder (1), at least two reaction tubes (14) which are arranged in parallel are contained in the inner cylinder (1), the top and the bottom of each reaction tube (14) are respectively and correspondingly communicated, so that raw materials entering from the reactor inlet (11) can respectively enter each reaction tube (14), and products generated in each reaction tube (14) can be led out from the product outlet;
the outer cylinder (2) is nested outside the inner cylinder (1), a heat-conducting medium inlet (21) and a heat-conducting medium outlet (22) are respectively arranged on the outer cylinder (2), a heat-conducting medium introduced from the heat-conducting medium inlet (21) can be distributed among the reaction tubes (14) of the inner cylinder (1), and the heat-conducting medium is led out from the heat-conducting medium outlet (22);
the central high-voltage electrodes (3) are respectively arranged in the reaction tubes (14) of the inner barrel (1);
the material forming the grounding electrode (4) is a solid conductive material, and the grounding electrode (4) forms at least part of the side wall of each reaction tube (14) or the grounding electrode (4) is respectively arranged on the outer side wall of each reaction tube (14) in a surrounding manner;
a barrier medium (6), said barrier medium (6) forming at least part of the side wall of each of said reaction tubes (14) such that at least part of said barrier medium surrounds said central high voltage electrode (3); or the barrier medium (6) is arranged on the inner side wall of each reaction tube (14) in a surrounding way; or the blocking medium (6) is arranged on at least part of the outer surface of the central high-voltage electrode (3), so that the blocking medium (6) is wrapped on the outer surface of the central high-voltage electrode (3) at least part of which extends into the inner barrel (1);
in each reaction tube (14), the barrier medium is arranged at a position such that a discharge area between the central high voltage electrode and the ground electrode is separated by the barrier medium;
and the feed gas comprising hydrogen sulphide enters the plasma reactor from the reactor inlet (11).
2. The method of claim 1, wherein the dielectric barrier discharge condition comprises: the discharge voltage is 5-20 kV, and the discharge frequency is 500-15000 Hz.
3. The method of claim 1, wherein the dielectric barrier discharge condition comprises: the discharge current is 0.1 to 100A.
4. The method of claim 1, wherein the dielectric barrier discharge condition comprises: the discharge current is 0.5-10A.
5. The method of claim 1, wherein the conditions of the hydrogen sulfide decomposition reaction include: the reaction temperature is 40-500 ℃, the reaction pressure is-0.06 MPa to 0.3MPa, and the residence time of reactants in the plasma reactor is 2 multiplied by 10-5~60s。
6. The method according to any one of claims 1 to 5, wherein the hydrogen sulfide decomposition reaction is carried out in the presence of a carrier gas selected from at least one of nitrogen, hydrogen, helium, argon, water vapor, carbon monoxide, carbon dioxide, methane, ethane and propane.
7. The method of claim 6, wherein the carrier gas is selected from at least one of hydrogen, argon, helium, and nitrogen.
8. The method according to any one of claims 1 to 5, wherein the content of the hydrogen sulfide gas in the feed gas is such that the content of the hydrogen sulfide gas at the reactor inlet of the plasma reactor is 0.1 to 100 vol%.
9. The method according to claim 8, wherein the content of the hydrogen sulfide gas in the feed gas is such that the content of the hydrogen sulfide gas at the reactor inlet of the plasma reactor is 10-50 vol%.
10. The method according to claim 1, wherein in the plasma reactor, in each of the reaction tubes (14), the distance between the outer side wall of the central high voltage electrode (3) and the inner side wall of the ground electrode is D1, and the thickness of the blocking medium (6) is D11，L1=d1-D1，L1And the length L of the discharge region2The proportion relation between the components is as follows: l is1：L2=1：（0.5~6000）。
11. The method according to claim 10, wherein in the plasma reactor, in each of the reaction tubes (14), L1And the length L of the discharge region2The proportion relation between the components is as follows: l is1：L2=1：（2~3000）。
12. The method according to claim 10, wherein in the plasma reactor, in each of the reaction tubes (14), L1And D1The proportion relation is as follows: l is1：D1=（0.05~100）：1。
13. According to claimThe method according to claim 10, wherein, in said plasma reactor, in each of said reaction tubes (14), L1And D1The proportion relation is as follows: l is1：D1=（0.1~30）：1。
14. A method according to claim 1, wherein in the plasma reactor the barrier medium (6) forms at least part of the side wall of each of the reaction tubes (14) such that at least part of the barrier medium surrounds the central high voltage electrode (3).
15. The method according to claim 1, wherein in the plasma reactor the side walls of each of the reaction tubes (14) are all formed by the barrier medium.
16. A method according to claim 1, wherein in the plasma reactor, in each of the reaction tubes (14), the barrier medium (6) is provided on at least part of the outer surface of the central high voltage electrode (3) such that the outer surface of the central high voltage electrode (3) at least partly protruding into the inner vessel (1) is coated with the barrier medium (6), and the ground electrode (4) forms at least part of the side wall of each of the reaction tubes (14).
17. The method of claim 1, wherein, in the plasma reactor, the material forming the blocking dielectric is an electrically insulating material.
18. The method of claim 1, wherein, in the plasma reactor, the material forming the barrier medium is selected from at least one of glass, quartz, ceramic, enamel, polytetrafluoroethylene, and mica.
19. The method according to claim 1, wherein the plasma reactor further comprises a ground wire (5) disposed on an outer sidewall of the outer tub (2) and having one end electrically connected to the ground electrode (4) on the sidewall of each of the reaction tubes (14).
20. A method according to claim 1, wherein in the plasma reactor the reactor inlet (11) is provided in the upper part of the inner barrel (1) and the product outlet is provided in the lower part and/or bottom of the inner barrel (1).
21. A method according to claim 1, wherein in the plasma reactor the product outlets comprise a gaseous product outlet (12) and a liquid product outlet (13), and the gaseous product outlet (12) is provided in a lower portion of the inner barrel (1), and the liquid product outlet (13) is provided in a bottom portion of the inner barrel (1).
22. The method according to claim 1, wherein in the plasma reactor the dimensions of each of the reaction tubes (14) are the same.
23. A method according to claim 21, wherein in the plasma reactor the gaseous product outlets (12) are arranged below all the discharge zones and the gaseous product outlets (12) are arranged at a height H relative to the bottom of the inner vessel (1)1And the length L of the discharge region2The proportion relation between the components is as follows: h1：L2=1：（0.05~25000）。
24. A method according to claim 23, wherein in the plasma reactor the gaseous product outlet (12) is arranged at a height H relative to the bottom of the inner barrel (1)1And the length L of the discharge region2The proportion relation between the components is as follows: h1：L2=1：（0.1~10000）。
25. The method of claim 23Wherein, in the plasma reactor, the gas product outlet (12) is arranged at a position corresponding to the height H of the bottom of the inner cylinder (1)1And the length L of the discharge region2The proportion relation between the components is as follows: h1：L2=1：（0.5~1000）。
26. The method according to claim 1, wherein in the plasma reactor the heat transfer medium inlet (21) and the heat transfer medium outlet (22) are arranged in a lower part and an upper part of the outer tub (2), respectively.
27. The method according to claim 1, wherein in the plasma reactor the material forming the ground electrode (4) is selected from a graphite tube, a metal foil or a metal mesh.
28. The method according to claim 1, wherein in the plasma reactor the material forming the central high voltage electrode (3) is selected from at least one of a graphite tube, a graphite rod, graphite powder, a metal rod, a metal tube, metal powder.
29. The method according to claim 1, wherein in the plasma reactor the material forming the central high voltage electrode (3) is selected from electrically conductive powders.
30. The method as claimed in claim 1, wherein the plasma system further comprises a hydrogen sulfide recycling unit for recovering hydrogen sulfide from the gas phase substance containing hydrogen sulfide obtained in the product separation unit and recycling the resulting hydrogen sulfide to the gas supply-distribution unit or the plasma reaction unit.
31. The method according to claim 30, wherein the hydrogen sulfide circulation unit comprises an amine liquid absorption tower for absorbing hydrogen sulfide and a desorption tower for desorbing hydrogen sulfide.
32. The method according to claim 1, wherein the product separation unit comprises a gas-liquid separator for gas-liquid separation of gas-phase substances and liquid-phase substances from the plasma reaction unit, and optionally comprises a particulate purifier and/or a gas-loaded separator; the particulate purifier is used for further separating the first gaseous substance separated by the gas-liquid separator to obtain a second gaseous substance and residual sulfur solids, and the carrier gas separator is used for separating carrier gas optionally contained in the first gaseous substance or the second gaseous substance from hydrogen.
33. The method of claim 1, wherein the gas supply-distribution unit comprises a gas distribution device and a mixer, wherein the gas distribution device is used for distributing the raw gas and the carrier gas according to needs, and the mixer is used for mixing the raw gas from the gas distribution device and the carrier gas to obtain reactants entering the plasma reactor of the plasma reaction unit.
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