CN110127621B - Grid type plasma system for decomposing hydrogen sulfide and method for decomposing hydrogen sulfide - Google Patents

Grid type plasma system for decomposing hydrogen sulfide and method for decomposing hydrogen sulfide Download PDF

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Publication number
CN110127621B
CN110127621B CN201810134906.0A CN201810134906A CN110127621B CN 110127621 B CN110127621 B CN 110127621B CN 201810134906 A CN201810134906 A CN 201810134906A CN 110127621 B CN110127621 B CN 110127621B
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hydrogen sulfide
grid
plasma
electrode
plasma reactor
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CN110127621A (en
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张婧
石宁
孙峰
任君朋
张铁
徐伟
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China Petroleum and Chemical Corp
Sinopec Safety Engineering Research Institute Co Ltd
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China Petroleum and Chemical Corp
Sinopec Safety Engineering Research Institute Co Ltd
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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
    • 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
    • C01B17/0404—Preparation of sulfur; Purification from gaseous sulfur compounds including gaseous sulfides by processes comprising a dry catalytic conversion of hydrogen sulfide-containing gases, e.g. the Claus process
    • 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
    • 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

Abstract

The invention relates to the field of plasma chemistry, and discloses a grid type plasma system for decomposing hydrogen sulfide and a method for decomposing hydrogen sulfide, wherein the system comprises a gas supply-distribution unit, a plasma reaction unit and a product separation unit, the plasma reaction unit comprises a grid type plasma reactor, and the method comprises the following steps: the device comprises an inner barrel (1), an outer barrel (2), a high-voltage electrode (3) and a grounding electrode (4) which are arranged in the inner barrel (1), and a blocking medium (6) which is arranged on the outer surface of the high-voltage electrode (3) and/or the grounding electrode (4), wherein the high-voltage electrode layers and the grounding electrode layers are alternately stacked, and gaps are reserved between the high-voltage electrode layers and the grounding electrode layers. The grid type plasma system for decomposing hydrogen sulfide and the method for decomposing hydrogen sulfide provided by the invention can improve the conversion rate of hydrogen sulfide.

Description

Grid type plasma system for decomposing hydrogen sulfide and method for decomposing hydrogen sulfide
Technical Field
The invention relates to the field of plasma chemistry, in particular to a grid type plasma system for decomposing hydrogen sulfide and a method for decomposing hydrogen sulfide.
Background
Hydrogen sulfide (H) 2 S) 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 method, electrochemical method, photocatalytic method, low temperature plasma method, and the like. 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 product can be effectively separated by adopting the membrane technology, so that the balance limit is broken and the hydrogen sulfide conversion rate is improved, the thermal decomposition temperature often exceeds the limit heat-resistant temperature of the membrane, and 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 can be effectively decomposed at a lower temperature due to the characteristics of high energy density and shortened reaction time, and the method 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.
The literature, international patent of Hydrogen energy, 2012,37:1335-1347 decomposing hydrogen sulfide by normal glow discharge shrinkage, under the conditions of 0.02Mpa and 2000-4000K, obtaining hydrogen sulfide with the lowest decomposition energy consumption of 2.35eV/H 2 And S. However, the reaction temperature is high, the pressure is low, and the conditions are harsh and difficult to realize.
The literature "International journal of hydrogen energy", 2012,37:10010-10019 adopts microwave plasma to decompose hydrogen sulfide, which can be completely decomposed under the conditions of atmospheric pressure and 2400K temperature, but the decomposed hydrogen and sulfur can be rapidly compounded at high temperature to regenerate hydrogen sulfide, and no corresponding quenching measure exists at present.
Document "Chemical Engineering Science, 2009, 64 (23): 4826-4834 pulsed corona discharge was used for H 2 Research 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 100W 2 Influence of S 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 H 2 S, decomposing energy efficiency; in addition, with Ar and N 2 As equilibrium gas phase ratio, with Ar-N 2 Higher H can be obtained when the mixed gas is used as balance gas 2 Conversion of S in Ar/N 2 /H 2 H obtained when S volume fraction is 46%/46%/8%, discharge power is 60W, and pulse forming capacitance is 720pF 2 The minimum energy consumption for S decomposition is 4.9eV/H 2 S, but then H 2 The S conversion is only about 30%. In addition, the flow rate of the reaction system was only 1.18X 10 -4 SCMs -1 The 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): 1215-1221 use sliding arc discharge pair H 2 S decomposition reaction was studied by reacting H 2 S is diluted by air to the concentration of 0-100 ppm, and the gas flow rate, the size of a reaction cavity and the frequency are examined to H under the condition that the total gas flow rate is 0-100L/min 2 Influence 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 H 2 S conversion, H obtained under optimized discharge conditions 2 S conversion rate can reach 75-80%, but H 2 The energy consumption of S decomposition is as high as 500eV/H 2 S, the concentration is low, the energy consumption is highThe effect has no industrial application prospect.
Dielectric barrier discharges can generally be generated at atmospheric pressure and the discharge temperature is low. In addition, the existence of the medium limits the increase of discharge current, thereby avoiding the gas from completely breaking down to form sparks or electric arcs, being beneficial to the generation of large-volume and stable plasmas, and having better industrial application prospect.
Literature "Plasma chemistry and Plasma processing", 1992, 12 (3): 275-285 investigation of H Using a modified ozone Generator 2 S is in the range of 130-560 ℃, and the reaction temperature and H are studied 2 S feed concentration, injection power and addition of H 2 、Ar、N 2 Pair H 2 The influence of S conversion rate and energy efficiency, and experiments show that the addition of Ar can promote H 2 Decomposition of S at a total flow rate of 50-100 mL/min, H 2 The 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 dielectric barrier discharge and photocatalyst to decompose hydrogen sulfide cooperatively, and the method is to fill a solid catalyst with photocatalytic activity in a plasma zone, however, this method has the disadvantage that sulfur generated by decomposition of hydrogen sulfide is deposited below a catalyst bed.
Document International Journal of Energy Research, 2013, 37 (11): 1280-1286, mixing Al 2 O 3 ，MoO x /Al 2 O 3 ，CoOx/Al 2 O 3 And NiO/Al 2 O 3 Catalyst is filled in discharge region, and H is carried out by using dielectric barrier discharge and catalyst 2 And (5) S decomposition research. The reaction result shows that MoOx/Al 2 O 3 And CoOx/Al 2 O 3 The catalyst has better effect; wherein when filled with MoOx/Al 2 O 3 Catalyst in H 2 Total S/Ar flow rate 150mL/min, H 2 H 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 layer 2 The highest conversion rate of S is about 48 percent. 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 apparatus and method, the apparatus is characterized in that the central electrode is metal, the grounding electrode is temperature-controllable circulating liquid, and the decomposition process of hydrogen sulfide can be continuously and stably performed by temperature control of the liquid grounding electrode. In addition, CN103204467A discloses a device and a method for preparing hydrogen by continuously and stably decomposing hydrogen sulfide, the prior art is characterized in that a central electrode is made of metal, a grounding electrode is used as temperature-controllable circulating liquid, temperature control is carried out through a liquid grounding electrode, the raw material is fed in a circumferential direction and reversely passes through a discharge region in a spiral mode along an axial direction, and the 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 hydrogen sulfide decomposition reaction is rather high, and the methods are not suitable for large-scale industrial application. Further, the methods disclosed in CN103204466A and CN103204467A have the drawback of very few kinds of available liquid grounding electrodes, and the disclosed salt solutions and the like can generally only maintain the temperature of the reactor below 100 ℃, while at below 100 ℃, elemental sulfur is generally in a solid state, which is easy to cause the blockage of the reactor.
Disclosure of Invention
The invention aims to overcome the defect of low hydrogen sulfide conversion rate in the hydrogen sulfide decomposition process provided by the prior art, and provides a novel grid type plasma system for decomposing hydrogen sulfide and a method for decomposing hydrogen sulfide.
In order to achieve the above object, a first aspect of the present invention provides a grid type plasma system for decomposing hydrogen sulfide, the system comprising a gas supply-distribution unit, a plasma reaction unit and a product separation unit which are connected in sequence by pipelines, the plasma reaction unit comprising a grid type plasma reactor and a plasma power supply, the reactor comprising:
the inner cylinder is provided with a reactant inlet and a product outlet respectively;
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 surround the periphery of the inner cylinder, and the heat-conducting medium can be led out from the heat-conducting medium outlet;
the high-voltage electrode is arranged in the inner barrel, and at least one layer of the high-voltage electrode is arranged in the inner barrel; in each high-voltage electrode layer, the number of the high-voltage electrodes is more than two, each high-voltage electrode is parallel to each other, a gap r1 is formed between every two adjacent high-voltage electrodes, and the r1 is more than 0;
the grounding electrode is made of a solid conductive material and is arranged in the inner barrel, and at least one layer of the grounding electrode is arranged in the inner barrel; in each grounding electrode layer, the number of the grounding electrodes is more than two, the grounding electrodes are parallel to each other, a gap r2 exists between every two adjacent grounding electrodes, and the r2 is larger than 0;
the blocking medium is arranged on the outer surface of the high-voltage electrode and/or the grounding electrode;
each high-voltage electrode layer and each ground electrode layer are alternately stacked, a gap r3 is reserved between the adjacent high-voltage electrode layers and the adjacent ground electrode layers, and the r3 is larger than 0.
A second aspect of the present invention provides a method for decomposing hydrogen sulfide, which is implemented in the grid plasma system for decomposing hydrogen sulfide according to the first aspect of the present invention, the method comprising:
raw material gas containing hydrogen sulfide from the gas supply-distribution unit enters the plasma reaction unit through a pipeline;
in the presence of a plasma discharge field generated by a grid type plasma reactor and a plasma power supply in the plasma reaction unit, the raw material gas enters an inner cylinder of the grid type plasma reactor through a reactant inlet to perform hydrogen sulfide decomposition reaction, and a product obtained after the reaction is led out of the grid type plasma reactor from a product outlet;
products from the grid type plasma reactor enter a product separation unit to be separated so as to respectively obtain elemental sulfur, hydrogen and tail gas containing hydrogen sulfide;
optionally introducing the hydrogen sulfide-containing tail gas obtained in the product separation unit into a hydrogen sulfide recycling unit for separation to obtain hydrogen sulfide recycled to the gas supply-distribution unit or the plasma reaction unit.
The grid type plasma system for decomposing hydrogen sulfide provided by the invention can be used for plasma decomposition of hydrogen sulfide, and the system can generate uniform and efficient dielectric barrier discharge, so that hydrogen sulfide is directly decomposed to generate hydrogen and sulfur.
The grid type plasma system for decomposing hydrogen sulfide and the method for decomposing hydrogen sulfide provided by the invention can obviously improve the conversion rate of hydrogen sulfide.
The grid type plasma reactor in the grid type plasma system for decomposing hydrogen sulfide provided by the invention is a sleeve type dielectric barrier discharge reaction system with a coaxial structure, the basic structure of the grid type plasma reactor mainly comprises a high-voltage electrode, a solid grounding electrode, a barrier medium and the like, and the sleeve type structure can enable a heat-conducting medium to circularly heat or cool a discharge reaction unit, so that the flexible temperature control of a discharge area is realized. In particular, the grid plasma system for decomposing hydrogen sulfide having the above-described specific structure of the present invention can significantly improve the conversion rate of hydrogen sulfide relative to the prior art.
In addition, the method for decomposing hydrogen sulfide provided by the invention can realize continuous and stable operation of the decomposition process of hydrogen sulfide under the condition of obviously higher hydrogen sulfide conversion rate, and the system can realize long-period operation. In addition, the method for decomposing the hydrogen sulfide provided by the invention can also be used for the treatment process of the hydrogen sulfide with high flow and high concentration.
Drawings
FIG. 1 is a schematic cross-sectional view of a preferred embodiment of a grid plasma reactor in a grid plasma system for decomposing hydrogen sulfide provided by the present invention;
FIG. 2 is a schematic cross-sectional view of another preferred embodiment of a grid plasma reactor in a grid plasma system for decomposing hydrogen sulfide provided in accordance with the present invention;
FIG. 3 is a schematic illustration of the inner barrel internal spatial structure of a preferred embodiment of a grated plasma reactor in a grated plasma system for decomposing hydrogen sulfide provided by the present invention;
FIG. 4 is a schematic structural diagram of a preferred embodiment of the barrier medium and the ground electrode or the high voltage electrode of the grid plasma reactor provided by the present invention;
FIG. 5 is a flow diagram of a grid plasma system for decomposing hydrogen sulfide in accordance with the present invention.
Description of the reference numerals
1. Inner cylinder 2, outer cylinder
11. Reactant inlet 21 and heat-conducting medium inlet
12. Product outlet 22 and heat-conducting medium outlet
3. 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 grid type plasma reactor
C. Product separation unit and hydrogen sulfide recycle unit
C1, gas-liquid separator C2, particle purifier
C3, amine liquid absorption tower C4 and desorption tower
C5, gas-carrying 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 these ranges or values should be understood to encompass values close to these 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 described above, a first aspect of the present invention provides a grid plasma system for decomposing hydrogen sulfide, the grid plasma system comprising a gas supply-distribution unit, a plasma reaction unit and a product separation unit which are connected in sequence by pipelines, the plasma reaction unit comprising a grid plasma reactor and a plasma power supply, the grid plasma reactor comprising:
the inner cylinder is provided with a reactant inlet and a product outlet respectively;
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 surround the periphery of the inner cylinder, and the heat-conducting medium can be led out from the heat-conducting medium outlet;
the high-voltage electrode is arranged in the inner barrel, and at least one layer of the high-voltage electrode is arranged in the inner barrel; in each high-voltage electrode layer, the number of the high-voltage electrodes is more than two, the high-voltage electrodes are parallel to each other, a gap r1 is reserved between every two adjacent high-voltage electrodes, and the r1 is larger than 0;
the grounding electrode is made of a solid conductive material and is arranged in the inner barrel, and at least one layer of the grounding electrode is arranged in the inner barrel; in each grounding electrode layer, the number of the grounding electrodes is more than two, the grounding electrodes are parallel to each other, a gap r2 is reserved between every two adjacent grounding electrodes, and the r2 is greater than 0;
the blocking medium is arranged on the outer surface of the high-voltage electrode and/or the grounding electrode;
each high-voltage electrode layer and each ground electrode layer are alternately stacked, a gap r3 is reserved between the adjacent high-voltage electrode layers and the adjacent ground electrode layers, and the r3 is larger than 0.
In the grid plasma reactor of the present invention, the high voltage electrode layers and the ground electrode layers are alternately stacked and represent: according to the material flow direction, when the first layer is the high-voltage electrode layer, the second layer is preferably the grounding electrode layer, and the subsequent possible layers are alternately arranged according to the arrangement mode of the first layer and the second layer; likewise, in terms of the direction of flow, when the first layer is the ground electrode layer, the second layer is preferably the high voltage electrode layer, and the subsequent layers, if present, are arranged alternately in the manner in which the first and second layers are arranged. In the above-described alternate stacking arrangement, the high-voltage electrode in the high-voltage electrode layer and the ground electrode in the adjacent ground electrode layer may be arranged in parallel or perpendicular to each other, or the high-voltage electrode in the high-voltage electrode layer and the ground electrode in the adjacent ground electrode layer may be arranged at a certain angle, as long as a uniform electric field can be generated in the inner tube. Particularly preferably, the high voltage electrode in the high voltage electrode layer and the ground electrode in the adjacent ground electrode layer of the present invention may be disposed parallel to each other or perpendicular to each other.
The invention defines that a gap r1 represents the shortest distance between the outer surfaces of two adjacent high-voltage electrodes; the present invention defines "gap r2" as the shortest distance between the outer surfaces of two adjacent ground electrodes; the invention defines that the gap r3 represents the shortest distance between the adjacent high-voltage electrode layer and the grounding electrode layer.
In the grid type plasma reactor, the number of the reactant inlets and the product outlets is preferably one.
The outer cylinder of the grid type plasma reactor disclosed by the invention surrounds the outer wall of the inner cylinder, so that the heat-conducting medium contained in the outer cylinder can maintain the temperature required by the inner cylinder. Specifically, the grid type plasma reactor has a sleeve type structural design, so that a heat-conducting medium can circularly flow in a shell layer, the whole discharge reaction unit can be maintained within a certain temperature range while the discharge strength is ensured, the generated sulfur flows out of the discharge reaction unit in a liquid state, the sulfur generated by the decomposition of 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.
In the present invention, in the grid type plasma reactor, in order to further improve the conversion rate of hydrogen sulfide, it is preferable that r1, r2 and r3 are each independently 100mm or less.
In particular, the inventors of the present invention found that, in a grid-type plasma reactor, the ratios of r1, r2, and r3 to the thickness D1 of the barrier medium are each independently controlled to be (0.1 to 150): 1, preferably (0.2 to 100): 1; more preferably (0.5 to 80): 1, the system of the invention is used for decomposing hydrogen sulfide, and can realize higher decomposition conversion rate of hydrogen sulfide under relatively lower decomposition energy consumption.
Particularly preferably, in a grid plasma reactor, r1, r2 and r3 are related to the length L of the discharge zone 1 The proportional relationship between each independently is 1: (2 to 1500), preferably 1: (20-500); length L of the discharge region 1 The reactants are initially brought into the discharge field created by the high voltage electrode and the ground electrode to a vertical distance from the discharge field. Controlling r1, r2 and r3 and the length L of the discharge region 1 Proportional relation betweenAre each independently 1: (2 to 1500), preferably 1: (20-500), the energy consumption for decomposing the hydrogen sulfide gas can be obviously reduced.
Particularly preferably, in the grid plasma reactor, r1, r2 and r3 are the same.
Preferably, in the grid plasma reactor, the high voltage electrodes are connected in parallel with each other.
Preferably, in the grid type plasma reactor, the respective ground electrodes are connected in parallel with each other.
According to a preferred embodiment 1, in a grid plasma reactor, the barrier medium is arranged on the outer surface of the high voltage electrode.
According to a preferred embodiment 2, in the grid plasma reactor, the blocking medium is provided on the outer surface of the ground electrode.
According to a preferred embodiment 3, in the grid plasma reactor, the blocking medium is provided on the outer surfaces of the high voltage electrode and the ground electrode.
In the foregoing embodiment mode 1 and embodiment mode 2 of the present invention, the discharge reaction unit (i.e., the plasma reaction unit) of the present invention can realize single dielectric barrier discharge. When the discharge is a single dielectric barrier discharge, the thickness D1 of the barrier medium is the thickness of the barrier medium on the corresponding high-voltage electrode or the corresponding ground electrode, and it should be further explained that, because an electric field exists between the ground electrode and the high-voltage electrode, the thickness herein indicates the thickness of the barrier medium on the corresponding one of the high-voltage electrode or the ground electrode.
In the foregoing embodiment 3 of the present invention, a double dielectric barrier discharge can be realized in the discharge reaction cell of the present invention. In the case of dual-dielectric barrier discharge, the thickness D1 of the barrier dielectric is the sum of the thicknesses of the barrier dielectric on the corresponding high-voltage electrode and the corresponding ground electrode, and since an electric field exists between the ground electrode and the high-voltage electrode, the sum of the thicknesses here represents the sum of the thicknesses of the barrier dielectric on the corresponding one of the high-voltage electrode and the corresponding one of the ground electrode.
In the grid type plasma reactor, the fixing form of the blocking medium and the high voltage electrode and/or the grounding electrode is not particularly limited in the invention, and the blocking medium can be fixed on the outer surface of the high voltage electrode and/or the grounding electrode in any fixing way, or the blocking medium can be coated on the outer surface of the high voltage electrode or the grounding electrode in the form of a coating.
Preferably, in the grid type plasma reactor, the material forming the barrier medium is an electrically insulating material, and more preferably, the material forming the barrier medium is selected from at least one of glass, ceramic, enamel, polytetrafluoroethylene, and mica. The glass can 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 grid type plasma reactor of the present invention further comprises a ground wire, wherein the ground wire is disposed on an outer side wall of the outer cylinder, and one end of the ground wire is electrically connected to the ground electrode.
Preferably, in the grid plasma reactor, the reactant inlet is disposed at an upper portion of the inner cylinder, and the product outlet is disposed at a bottom portion of the inner cylinder.
The dimensions of each of the high voltage electrodes of the present invention may be the same or different, and preferably, the dimensions of each of the high voltage electrodes are the same.
The size of each of the ground electrodes of the present invention may be the same or different, and preferably, the size of each of the ground electrodes is the same.
The same dimensions as described above in the present invention mean that the dimensions and shapes are all the same.
Preferably, in the grid plasma reactor, each of the high voltage electrodes and each of the ground electrodes have a cylindrical shape. It should be noted that the present invention is not particularly limited to the high voltage electrode and the ground electrode being cylindrical, and the high voltage electrode and the ground electrode may have any axisymmetrical shape.
In the grid type plasma reactor, when each of the high voltage electrodes and each of the ground electrodes are cylindrical, the diameters of the high voltage electrodes and the ground electrodes are each independently preferably 0.1 to 100mm, more preferably 0.5 to 50mm.
Preferably, in the grid plasma reactor, the ratio of the diameter of the high voltage electrode and the ground electrode to the length of the respective high voltage electrode and ground electrode is each independently 1: (10 to 600), preferably 1: (100-500).
Preferably, in the grid type 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.
The inner diameters of the present invention each represent a diameter.
In the grid plasma reactor, preferably, the material forming the ground electrode is selected from a graphite tube, a graphite rod, graphite powder, a metal tube, a metal rod, metal powder, or a mechanical mixture of conductive powders. 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 rod in the material for forming the grounding electrode may include an elemental metal tube, an elemental metal rod, an alloy metal tube, and an alloy metal rod, and the metal powder may include elemental metal powder and alloy metal powder. The inventor of the present invention finds that the use of a solid conductive material as the ground electrode of the discharge reaction unit of the present invention enables the conversion rate of hydrogen sulfide to be more significantly improved when the hydrogen sulfide decomposition reaction is performed using the system provided by the present invention.
In the grid type plasma reactor, the material forming the high voltage electrode is a conductive material, and preferably, the material forming the high voltage electrode is at least one selected from graphite tubes, graphite rods, graphite powder, metal rods, metal tubes, metal powder, and a mechanical mixture 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, and the metal powder can comprise elemental metal powder and alloy metal powder. The material forming the high voltage electrode of the present invention may be other rod-shaped or tubular materials having conductive properties.
The metal powder of the present invention means that when the outer surface of the ground electrode and/or the high voltage electrode is coated with the barrier medium, the barrier medium may be disposed in a hollow tubular form, and the metal powder is filled in the barrier medium to form the barrier medium coated ground electrode and/or high voltage electrode; the metal powder can be simple substance metal powder or alloy metal powder.
The invention can lead the temperature of the grid type plasma reactor with the sleeve structure to be maintained between 119 and 444.6 ℃ for example by introducing the heat-conducting medium into the area between the outer wall of the inner cylinder and the inner wall of the outer cylinder, thereby ensuring that the sulfur generated by the decomposition of the hydrogen sulfide flows out of the discharge area in a liquid state.
The grid type plasma reactor can also be filled with a catalyst capable of catalyzing hydrogen sulfide to be decomposed into elemental sulfur and hydrogen, and the catalyst is preferably filled in the inner cylinder of the reactor. The present invention has no particular requirement on the loading volume and the loading type of the catalyst, and as to the type of the catalyst, for example, one or more of the catalysts disclosed in CN102408095A, CN101590410A and CN103495427A may be mentioned.
The grid type plasma reactor provided by the invention has no particular limitation on the conditions of the decomposition reaction involved in the decomposition of hydrogen sulfide, and can be used for decomposing hydrogen sulfide by various conditions involved in a plasma decomposition method conventionally adopted in the field.
The grid type plasma reactor provided by the invention has no particular limitation on the concentration of hydrogen sulfide in the gas at the reactant inlet, and for example, the concentration of hydrogen sulfide in the gas may be 0.01 to 100 vol%.
The material forming the inner cylinder of the present invention may be, for example: an electrically conductive metallic material or an electrically insulating material, which is capable of serving as a structural support and is resistant to high temperatures, is preferred.
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 material forming the outer cylinder of the present invention may be, for example: an electrically conductive metallic material or an electrically insulating material, which is capable of serving as a structural support and is resistant to high temperatures, is preferred.
The following provides preferred embodiments of the grid plasma reactor for decomposing hydrogen sulfide according to the present invention:
nitrogen gas was passed into the inner cylinder of the grid plasma reactor from the reactant 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 grid type plasma reactor from the reactant inlet, 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 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 grid-type plasma system for decomposing hydrogen sulfide of 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 resulting hydrogen sulfide to the gas supply-distribution unit or the plasma reaction unit.
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, in the grid plasma system for decomposing hydrogen sulfide of the present invention, the product separation unit contains a gas-liquid separator, and optionally a particulate purifier and/or a carrier gas separator.
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 the products (gas-phase products and liquid-phase sulfur simple substance) from the plasma reaction unit can enter the gas-liquid separator to be separated so as to respectively obtain a first gas-state substance and liquid sulfur, the gas-state substance is optionally introduced into a particle purifier to be further separated so as to obtain residual solid sulfur and a second gas-state substance, and the liquid sulfur and the residual solid sulfur can both be led out of the grid type plasma system for decomposing hydrogen sulfide through pipelines. Further, the hydrogen sulfide circulating 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 circulating 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 used for the gas supply-distribution unit or the plasma reaction unit.
Preferably, the gas supply-distribution unit of the present invention includes a device capable of adjusting the volume ratio of the hydrogen sulfide-containing gas to the carrier gas, that is, the raw gas with a suitable gas type and hydrogen sulfide content can be obtained by the gas supply-distribution unit to enter the plasma reaction unit. For example, the gas supply and distribution unit may include a mixer, so that the gas containing hydrogen sulfide is mixed with the carrier gas and then enters the plasma reaction unit as a raw material gas.
The plasma reaction unit of the present invention may include one or more grid-type plasma reactors.
As previously mentioned, a second aspect of the present invention provides a method of decomposing hydrogen sulfide, the method being implemented in a grid plasma system of decomposing hydrogen sulfide as described in the first aspect of the present invention, the method comprising:
the raw gas containing hydrogen sulfide from the gas supply-distribution unit enters the plasma reaction unit through a pipeline;
in the presence of a plasma discharge field generated by a grid type plasma reactor and a plasma power supply in the plasma reaction unit, the raw material gas enters an inner cylinder of the grid type plasma reactor through a reactant inlet to perform hydrogen sulfide decomposition reaction, and a product obtained after the reaction is led out of the grid type plasma reactor from a product outlet;
products from the grid type plasma reactor enter a product separation unit to be separated so as to respectively obtain elemental sulfur, hydrogen and tail gas containing hydrogen sulfide;
optionally introducing the hydrogen sulfide-containing tail gas obtained in the product separation unit into a hydrogen sulfide recycling unit for separation to obtain hydrogen sulfide recycled to the gas supply-distribution unit or the plasma reaction unit.
Preferably, in the method of the present invention, the gas-phase substance and the liquid-phase elemental sulfur from the grid plasma reactor enter the gas-liquid separator of the product separation unit to be separated to obtain a first gas-phase substance and liquid sulfur, respectively, and the gas-phase substance is optionally introduced into the particulate purifier optionally contained in the product separation unit to be further separated to obtain residual solid sulfur and a second gas-phase substance. 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, and optionally the hydrogen sulfide removing gas enters a carrier gas separator optionally contained in the product separation unit to separate carrier gas possibly existing in the hydrogen sulfide removing gas so as to obtain a crude product containing hydrogen. The hydrogen sulfide-containing liquid obtained in the invention is introduced into a desorption tower in the hydrogen sulfide circulation unit to desorb hydrogen sulfide gas, and the hydrogen sulfide obtained by desorption is circulated back to the gas supply-distribution unit or the plasma reaction unit.
In the present invention, the raw material gas preferably contains hydrogen sulfide and a carrier gas, and the type of the carrier gas is not particularly limited, and may be hydrogen, nitrogen, argon, helium, carbon dioxide, carbon monoxide, air, gaseous hydrocarbons, or the like. The source of the hydrogen sulfide gas in the raw material gas of the present invention may be pure hydrogen sulfide gas, or may be industrial waste gas obtained in industrial production and containing hydrogen sulfide and other gases, and when the raw material gas contains a carrier gas, it is preferable to control the volume content of the carrier gas in the raw material gas by using devices such as a valve and a flow meter.
The crude hydrogen-containing product of the present invention can be further purified as desired. The method for further purifying the hydrogen-containing crude product is not particularly limited in the present invention, and for example, the hydrogen-containing crude 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 are used for recovery.
The structure of a preferred embodiment of the grid plasma reactor of the present invention is provided below in conjunction with fig. 1 and 2, specifically:
the grid type plasma reactor has a sleeve type structure, and the grid type plasma reactor comprises:
the device comprises an inner cylinder 1, wherein a reactant inlet 11 and a product outlet 12 are respectively arranged on the inner cylinder 1;
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 surround the periphery of the inner cylinder 1, and the heat-conducting medium can be led out from the heat-conducting medium outlet 22;
the high-voltage electrode 3 is arranged in the inner barrel 1, and at least one layer of the high-voltage electrode 3 is arranged in the inner barrel 1; in each high-voltage electrode layer, the number of the high-voltage electrodes 3 is more than two, each high-voltage electrode 3 is parallel to each other, a gap r1 is formed between every two adjacent high-voltage electrodes 3, and the r1 is greater than 0;
a ground electrode 4, the material forming the ground electrode 4 being a solid conductive material, the ground electrode 4 being disposed in the inner tube 1, and the ground electrode 4 being disposed with at least one layer in the inner tube 1; in each ground electrode layer, the number of the ground electrodes 4 is two or more, the ground electrodes 4 are parallel to each other, a gap r2 is formed between every two adjacent ground electrodes 4, and the r2 is greater than 0;
the blocking medium 6 is arranged on the outer surface of the high-voltage electrode 3 and/or the grounding electrode 4;
each high-voltage electrode layer and each ground electrode layer are alternately stacked, a gap r3 is reserved between the adjacent high-voltage electrode layers and the adjacent ground electrode layers, and the r3 is larger than 0.
Specifically, the difference between fig. 1 and fig. 2 of the present invention is mainly that the relative positions of the high voltage electrode in each high voltage electrode layer and the ground electrode in the adjacent ground electrode layer are different, and the high voltage electrode in each high voltage electrode layer and the ground electrode in the adjacent ground electrode layer in fig. 1 are aligned and aligned in a flat arrangement manner, so that when the reactant enters the inner barrel 1, the main flowing direction is a straight line direction from top to bottom; in fig. 2, the high voltage electrodes in each high voltage electrode layer and the grounding electrodes in the adjacent grounding electrode layer are arranged in a hollow manner, so that the reactants enter the inner barrel 1 mainly in the flow direction of alternating from top to bottom and in the horizontal direction. As can be seen from fig. 1 and 2, the average residence time of the reactants in the reactor provided in fig. 2 is longer with a constant flow rate of the reactants.
Preferably, the ratios of r1, r2 and r3 to the thickness D1 of the blocking medium 6 are each independently (0.1 to 150): 1, preferably (0.2 to 100): 1; more preferably (0.5 to 80): 1.
preferably, the respective high voltage electrodes 3 are connected in parallel with each other.
Preferably, the respective ground electrodes 4 are connected in parallel with each other.
Preferably, the grid type plasma reactor further comprises a grounding wire 5, wherein the grounding wire 5 is arranged on the outer side wall of the outer cylinder 2, and one end of the grounding wire 5 is electrically connected with the grounding electrode 4.
Preferably, the reactant inlet 11 is disposed at an upper portion of the inner drum 1, and the product outlet 12 is disposed at a bottom portion of the inner drum 1.
Preferably, the high voltage electrodes 3 are the same size, the ground electrodes 4 are the same size, and the high voltage electrodes 3 and the ground electrodes 4 are cylindrical.
Preferably, the diameters of the high voltage electrode 3 and the ground electrode 4 are each independently 0.1 to 100mm, more preferably 0.5 to 50mm.
Preferably, the ratio of the diameter of the high voltage electrode 3 and the ground electrode 4 to the length of the respective high voltage electrode 3 and ground electrode 4 is each independently 1: (10 to 600), preferably 1: (100-500).
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.
In order to more intuitively describe the arrangement of the ground electrodes and the high voltage electrodes in the grid type plasma reactor of the present invention, the present invention provides a schematic perspective structure of the inner cylinder shown in fig. 3, in which a plurality of high voltage electrodes 3 are arranged in parallel to form a high voltage electrode layer, and a plurality of ground electrodes 4 are arranged in parallel to form a ground electrode layer on the adjacent upper layer and/or lower layer of the high voltage electrode layer.
Also, in fig. 4 of the present invention, the present invention provides a preferred relative position of the blocking medium 6 and the high voltage electrode or the ground electrode of the grid plasma reactor.
The flow of a preferred embodiment of the hydrogen sulfide decomposing grid plasma system of the present invention is provided below in conjunction with FIG. 5, specifically:
the grid type plasma system for decomposing hydrogen sulfide 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 grid type plasma reactor B1 and a plasma power supply (not shown). Preferably, the grid plasma reactor B1 has a structure as shown in fig. 1 or fig. 2. Preferably, the grid plasma reactor B includes a plurality of, for example, 4 grid plasma reactors B1.
Preferably, the gas supply-distribution unit a includes a mixer A1, the mixer A1 is configured to mix a gas containing hydrogen sulfide with, for example, a carrier gas as needed to form a raw material gas, and introduce the obtained raw material gas into a grid-type plasma reactor B1 in the 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 may also enter the 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 crude hydrogen-containing 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 grid type plasma system for decomposing hydrogen sulfide provided by the invention has the following specific advantages:
(1) Because the grid type plasma reactor is adopted to decompose the hydrogen sulfide, and the reactor uses metal, alloy or other conductive solid materials as a grounding electrode, compared with a liquid grounding electrode, the grounding electrode has the advantages that micro discharge current generated by discharge is larger when the grounding electrode is matched with the structure of the invention, and the discharge decomposition reaction of hydrogen sulfide molecules is more facilitated.
(2) Because the grid type plasma reactor is adopted to decompose the hydrogen sulfide, and the jacket structure is arranged on the outer side of the grounding electrode of the reactor, the temperature of the reactor can be controlled by controlling the temperature of the heat-conducting medium in the jacket, so that sulfur generated by the discharge decomposition of the hydrogen sulfide can smoothly flow out of a discharge area, the sulfur is prevented from solidifying and blocking the reactor, and the discharge is continuously and stably carried out.
(3) Since the decomposition of hydrogen sulfide is carried out by using a grid type plasma reactor, the reactor is preferably controlled by controlling the ratio of r1, r2 and r3 to the thickness D1 of the barrier medium to be each independently (0.1 to 150): 1, preferably (0.2 to 100): 1; more preferably (0.5 to 80): 1, the conversion rate of the hydrogen sulfide can be obviously improved and the decomposition energy consumption can be reduced by matching with the structure of the reaction device.
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 conversion of hydrogen sulfide in the following examples was calculated according to the following formula:
% conversion of hydrogen sulfide = moles of hydrogen sulfide converted/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.
Example 1
The hydrogen sulfide decomposition reaction was carried out by using a grid plasma system for decomposing hydrogen sulfide having the flow chart shown in fig. 5, and the grid plasma reactor in this example had the structure shown in fig. 1.
The process flow of the present embodiment is as shown in the foregoing specific embodiments, and the structural parameters of the grid type plasma reactor are as follows:
the grid type plasma reactor comprises:
the inner cylinder is provided with a reactant inlet and a product outlet respectively;
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 surround the periphery of the inner cylinder, and the heat-conducting medium can be led out from the heat-conducting medium outlet;
the high-voltage electrode is arranged in the inner barrel, and 5 layers of the high-voltage electrode are arranged in the inner barrel; in each high-voltage electrode layer, the number of the high-voltage electrodes is 7, the high-voltage electrodes are parallel to each other, a gap r1 is reserved between every two adjacent high-voltage electrodes, the high-voltage electrodes are made of stainless steel metal rods, and the high-voltage electrodes are the same in size;
a ground electrode disposed in the inner tube, the ground electrode having 5 layers disposed in the inner tube; in each grounding electrode layer, the number of the grounding electrodes is 7, the grounding electrodes are parallel to each other, a gap r2 is reserved between every two adjacent grounding electrodes, the grounding electrodes are made of stainless steel metal rods, and the grounding electrodes are the same in size;
the blocking medium is wrapped on each high-voltage electrode, and the material for forming the blocking medium is hard glass;
a gap r3 is formed between the high voltage electrode layer and the ground electrode layer.
In the embodiment, reactants enter the inner cylinder from the upper part of the inner cylinder, and products are led out from a product outlet positioned at the lower part of the inner cylinder; the heat-conducting medium of the embodiment is introduced from the lower part of the outer barrel and is led out from the upper part of the outer barrel;
wherein r1= r2= r3, and the ratios of r1, r2 and r3 to the thickness D1 of the blocking medium are all 50:1;
the size of each high-voltage electrode is the same as that of each grounding electrode, and the ratio of the diameter to the length is 1:240;
r1, r2 and r3 and the length L of the discharge region 1 Ratio therebetweenIs 1:50;
the volume of the inner cylinder of the grid plasma reaction apparatus of this example was 1.6L.
The operation steps of the grid plasma system for decomposing hydrogen sulfide are as follows:
nitrogen gas is introduced from the gas supply-distribution unit into the grid plasma reactor of the plasma reaction unit, the nitrogen gas enters the inner cylinder of the grid plasma reactor from the reactant inlet to purge air in the discharge region, and the gas is withdrawn from the product outlet. Meanwhile, a heat-conducting medium (specifically hydrogenated terphenyl) 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 145 ℃.
Then hydrogen sulfide gas and carrier gas (N) 2 ) Sequentially mixing the raw materials by a gas distribution system and a mixer to obtain a raw material gas and H in the raw material gas 2 The volume fraction of S is 30%, raw material gas enters an inner cylinder of the grid type plasma reactor from a reactant inlet, and the flow rate of the raw material gas is controlled so that the average retention time of the gas in a discharge area is 18.5S. And (3) after the raw material gas is 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 high-voltage electrode and the grounding electrode. Wherein the discharge conditions are as follows: the voltage was 21.3kV, the frequency was 3.6kHz, and the current was 1.43A. The hydrogen sulfide gas is ionized in the discharge area and decomposed into hydrogen and elemental sulfur, the elemental sulfur generated by discharge slowly flows down along the inner cylinder wall and flows out from the product outlet, and the gas after reaction is led out from the product outlet.
And the obtained products 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 20min 2 The S conversion was 76.9%; and the discharge state and H are not abnormal even after the continuous discharge for 100H 2 The S conversion rate is kept stable. And the decomposition energy consumption of the embodiment is 13.8eV/H 2 S molecule (1 molecule of H per molecule decomposed) 2 The energy required for S is 13.8 eV).
Example 2
The hydrogen sulfide decomposition reaction was carried out by using a grid type plasma system for decomposing hydrogen sulfide having a flow chart shown in fig. 5, and the grid type plasma reactor in the present embodiment had a structure shown in fig. 2.
The process flow of this embodiment is as shown in the foregoing specific embodiment, and the structural parameters of the grid type plasma reactor are as follows:
the grid type plasma reactor comprises:
the inner cylinder is provided with a reactant inlet and a product outlet respectively;
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 surround the periphery of the inner cylinder, and the heat-conducting medium can be led out from the heat-conducting medium outlet;
the high-voltage electrode is arranged in the inner barrel, and 5 layers of the high-voltage electrode are arranged in the inner barrel; in each high-voltage electrode layer, the number of the high-voltage electrodes is 7, the high-voltage electrodes are parallel to each other, a gap r1 is formed between every two adjacent high-voltage electrodes, the high-voltage electrodes are made of graphite rods, and the high-voltage electrodes are the same in size;
a ground electrode disposed in the inner tube, the ground electrode having 5 layers disposed in the inner tube; in each grounding electrode layer, the number of the grounding electrodes is 7, the grounding electrodes are parallel to each other, a gap r2 is reserved between every two adjacent grounding electrodes, the grounding electrodes are made of graphite rods, and the grounding electrodes are the same in size;
the blocking dielectric is wrapped on each grounding electrode, and the material for forming the blocking dielectric is polytetrafluoroethylene;
a gap r3 is formed between the high voltage electrode layer and the ground electrode layer.
In the embodiment, reactants enter the inner cylinder from the upper part of the inner cylinder, and products are led out from a product outlet positioned at the lower part of the inner cylinder; the heat-conducting medium of the embodiment is introduced from the lower part of the outer barrel and is led out from the upper part of the outer barrel;
wherein r1= r2= r3, and the ratio of r1, r2 and r3 to the thickness D1 of the blocking medium is 68:1;
the size of each high-voltage electrode is the same as that of each grounding electrode, and the ratio of the diameter to the length is 1:320;
r1, r2 and r3 and the length L of the discharge region 1 The ratio between is 1:150;
the volume of the inner cylinder of the grid plasma reaction apparatus of this example was 1.6L.
The operation procedure of the grid plasma system for decomposing hydrogen sulfide was the same as in example 1.
The difference is that:
introducing H-containing gas into the inner cylinder of the reactor from the reactant inlet 2 Mixed gas of S and carrier gas (He), wherein H 2 The S volume fraction was 95%, and the reactant flow rate was controlled so that the average residence time of the gas in the discharge zone was 19.2. And (3) introducing the mixed gas into the reactor for 30min, then switching on an alternating-current high-voltage power supply, and adjusting voltage and frequency to form a plasma discharge field between the high-voltage electrode and the grounding electrode. Wherein the discharge conditions are as follows: the voltage was 17.2kV, the frequency was 1.5kHz, and the current was 1.2A. The hydrogen sulfide gas is ionized in the discharge area and decomposed into hydrogen and elemental sulfur, and the elemental sulfur generated by discharge flows along the inner cylinderThe wall slowly flows down and out of the product outlet, and the reacted gas is drawn off from the product outlet.
As a result: in this example, H was measured after the hydrogen sulfide decomposition reaction was continued for 20min 2 The S conversion was 76.6%; and the discharge state and H are not abnormal after the discharge lasts for 100H 2 The S conversion rate is kept stable. In addition, the decomposition energy consumption of the embodiment is 14.2eV/H 2 And (3) an S molecule.
Example 3
This example was carried out using a system similar to that of example 1, except that the blocking dielectric in the grid plasma reactor of this example was disposed on the outer surfaces of the high voltage electrode and the ground electrode, i.e., a double dielectric barrier discharge.
And r1= r2, and r3=1.2r1, the ratio of r1 and r2 to the thickness D1 of the blocking medium being 15:1;
the size of each high-voltage electrode is the same as that of each grounding electrode, and the ratio of the diameter to the length is 1:130, 130;
r1 and r2 and length L of discharge region 1 The ratio between is 1:300, respectively;
the volume of the inner cylinder of the grid plasma reaction apparatus of this example was 1.6L.
Introducing H-containing gas into the inner cylinder of the reactor from the reactant inlet 2 Mixed gas of S and carrier gas (Ar), wherein H 2 The S volume fraction was 20%, and the reactant flow rate was controlled so that the average residence time of the gas in the discharge zone was 16.2S. And (3) after the mixed gas is 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 high-voltage electrode and the grounding electrode. Wherein the discharge conditions are: the voltage was 15.7kV, the frequency was 7.5kHz, and the current was 1.8A. The hydrogen sulfide gas is ionized in the discharge area and decomposed into hydrogen and elemental sulfur, the elemental sulfur generated by discharge slowly flows down along the inner cylinder wall and flows out from the product outlet, and the gas after reaction is led out from the product outlet.
The rest is the same as in example 1.
As a result: the hydrogen sulfide decomposition reaction of this example was continuedH is measured after 20min 2 The S conversion was 76.1%; and the discharge state and H are not abnormal after the discharge lasts for 100H 2 The S conversion rate is kept stable. And the decomposition energy consumption of the embodiment is 14.5eV/H 2 And (3) an S molecule.
Example 4
This example uses a grid plasma system for decomposing hydrogen sulfide similar to that of example 1, except that in this example:
r1= r2= r3, and the ratios of r1, r2, and r3 to the thickness D1 of the blocking medium are all 95:1;
the rest is the same as in example 1.
And this example carried out the hydrogen sulfide decomposition reaction in the same manner as in example 1.
As a result: in this example, H was measured after the hydrogen sulfide decomposition reaction was continued for 20min 2 The S conversion was 68.7%; and the discharge state and H are not abnormal after the discharge lasts for 100H 2 The S conversion rate is kept stable. And the decomposition energy consumption of the embodiment is 23.9eV/H 2 And (3) an S molecule.
Example 5
This example uses a grid plasma system for decomposing hydrogen sulfide similar to that of example 1, except that in this example:
r1= r2= r3, and the ratio of r1, r2 and r3 to the thickness D1 of the blocking medium is 135:1;
the rest is the same as in example 1.
And this example carried out the hydrogen sulfide decomposition reaction in the same manner as in example 1.
As a result: in this example, the decomposition reaction of hydrogen sulfide was continued for 20min and then H was measured 2 The S conversion was 61.4%; and the discharge state and H are not abnormal even after the continuous discharge for 100H 2 The S conversion rate is kept stable. And the decomposition energy consumption of the embodiment is 27.8eV/H 2 And (3) an S molecule.
Example 6
This example uses a grid plasma system for decomposing hydrogen sulfide similar to that of example 3, except that in this example:
r1 and r2 and length L of discharge region 1 The ratio between is 1:700 of the base material;
the rest is the same as in example 3.
And this example carried out the hydrogen sulfide decomposition reaction in the same manner as in example 3.
As a result: in this example, H was measured after the hydrogen sulfide decomposition reaction was continued for 20min 2 The S conversion rate is 70.9%; and the discharge state and H are not abnormal after the discharge lasts for 100H 2 The S conversion rate is kept stable. And the decomposition energy consumption of the embodiment is 26.4eV/H 2 And (3) an S molecule.
From the above results, it can be seen that the present invention provides a system that can achieve high hydrogen sulfide conversion and that can stably maintain the hydrogen sulfide conversion at a high level for a long period of time.
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 various technical features being combined 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 (17)

1. A grid type plasma system for decomposing hydrogen sulfide comprises a gas supply-distribution unit, a plasma reaction unit, a product separation unit and a hydrogen sulfide circulation unit which are sequentially connected through pipelines, wherein the plasma reaction unit comprises a grid type plasma reactor and a plasma power supply, and the grid type plasma reactor comprises:
the device comprises an inner cylinder (1), wherein a reactant inlet (11) and a product outlet (12) are respectively arranged on the inner cylinder (1);
the outer cylinder (2) is nested outside the inner cylinder (1), the outer cylinder (2) is respectively provided with a heat-conducting medium inlet (21) and a heat-conducting medium outlet (22), the heat-conducting medium introduced from the heat-conducting medium inlet (21) can surround the periphery of the inner cylinder (1), and the heat-conducting medium can be led out from the heat-conducting medium outlet (22);
the high-voltage electrode (3) is arranged in the inner barrel (1), and at least one layer of the high-voltage electrode (3) is arranged in the inner barrel (1); in each high-voltage electrode layer, the number of the high-voltage electrodes (3) is more than two, the high-voltage electrodes (3) are parallel to each other, a gap r1 is reserved between every two adjacent high-voltage electrodes (3), and the r1 is greater than 0;
the grounding electrode (4) is made of a solid conductive material, the grounding electrode (4) is arranged in the inner cylinder (1), and at least one layer of the grounding electrode (4) is arranged in the inner cylinder (1); in each grounding electrode layer, the number of the grounding electrodes (4) is more than two, the grounding electrodes (4) are parallel to each other, a gap r2 is reserved between every two adjacent grounding electrodes (4), and the r2 is larger than 0;
a blocking medium (6), wherein the blocking medium (6) is arranged on the outer surface of the high-voltage electrode (3) and/or the grounding electrode (4);
each high-voltage electrode layer and each ground electrode layer are alternately stacked, a gap r3 is reserved between the adjacent high-voltage electrode layers and the adjacent ground electrode layers, and the r3 is greater than 0;
in the grid plasma reactor, r1, r2 and r3 are each independently less than or equal to 100mm;
in the grid-type plasma reactor, the ratios of r1, r2 and r3 to the thickness D1 of the barrier medium (6) are each independently (0.1 to 150): 1;
in the grid type plasma reactor, r1, r2 and r3 are related to the length L of the discharge area 1 The proportional relationship between each is independently 1: (2-1500);
in the grid plasma reactor, the ratio of the diameter of the high voltage electrode (3) and the ground electrode (4) to the length of the respective high voltage electrode (3) and ground electrode (4) is each independently 1: (10-600);
the product separation unit comprises a gas-liquid separator and optionally a particle purifier and/or a gas-loaded separator;
the hydrogen sulfide circulating unit is used for recovering hydrogen sulfide in the gas phase substance containing the hydrogen sulfide obtained from the product separating unit and circulating the obtained hydrogen sulfide to the gas supply-distribution unit or the plasma reaction unit;
the hydrogen sulfide circulation unit includes an amine liquid absorption tower for absorbing hydrogen sulfide and a desorption tower for desorbing hydrogen sulfide.
2. The grid plasma system as claimed in claim 1, wherein in the grid plasma reactor the ratio of r1, r2 and r3 to the thickness D1 of the blocking medium (6) is each independently (0.2 to 100): 1.
3. the grid plasma system as claimed in claim 1 or 2, wherein in the grid plasma reactor the ratios of r1, r2 and r3 to the thickness D1 of the barrier medium (6) are each independently (0.5 to 80): 1.
4. the grid plasma system as claimed in claim 1 or 2, wherein in the grid plasma reactor r1, r2 and r3 are related to the length L of the discharge area 1 The proportional relationship between each independently is 1: (20 to 500); length L of the discharge region 1 The reactants are initially brought into the discharge field generated by the high voltage electrode and the ground electrode to a vertical distance from the discharge field.
5. Grid plasma system according to claim 1 or 2, wherein in the grid plasma reactor the individual high voltage electrodes (3) are connected in parallel with each other.
6. Grid plasma system according to claim 1 or 2, wherein in the grid plasma reactor the respective ground electrodes (4) are connected in parallel to each other.
7. Grid plasma system according to claim 1 or 2, wherein in the grid plasma reactor the material forming the blocking medium (6) is an electrically insulating material.
8. The grid plasma system according to claim 1 or 2, wherein in the grid plasma reactor, the material forming the barrier medium is selected from at least one of glass, quartz, ceramic, enamel, polytetrafluoroethylene, and mica.
9. The grid plasma system as claimed in claim 1 or 2, wherein the grid plasma reactor further comprises a grounding wire (5) disposed on an outer sidewall of the outer cylindrical housing (2) and having one end electrically connected to the grounding electrode (4).
10. Grid plasma system according to claim 1 or 2, wherein the reactant inlet (11) is arranged at the upper part of the inner drum (1) and the product outlet (12) is arranged at the bottom of the inner drum (1).
11. Grid plasma system according to claim 1 or 2, wherein the high voltage electrodes (3) are of the same size and the ground electrodes (4) are of the same size, and each high voltage electrode (3) and each ground electrode (4) is cylindrical.
12. The grid plasma system as claimed in claim 11, wherein the dimensions of each of the high voltage electrodes (3) are the same and the dimensions of each of the ground electrodes (4) are the same, and each of the high voltage electrodes (3) and each of the ground electrodes (4) are cylindrical, the diameters of the high voltage electrodes (3) and the ground electrodes (4) being each independently 0.1 to 100mm.
13. The grid plasma system as claimed in claim 11, wherein the high voltage electrodes (3) are of the same size and the ground electrodes (4) are of the same size, and each high voltage electrode (3) and each ground electrode (4) are cylindrical, the high voltage electrode (3) and the ground electrode (4) each independently having a diameter of 0.5 to 50mm.
14. Grid plasma system according to claim 11, wherein in the grid plasma reactor the ratio of the diameter of the high voltage electrode (3) and the ground electrode (4) to the length of the respective high voltage electrode (3) and ground electrode (4) is each independently 1: (100-500).
15. The grid plasma system as claimed in claim 1 or 2, wherein in the grid plasma reactor, the heat conducting medium inlet (21) and the heat conducting medium outlet (22) are provided at a lower portion and an upper portion of the outer tub (2), respectively.
16. The grid plasma system according to claim 1 or 2, wherein in the grid plasma reactor, the material forming the ground electrode (4) and the material forming the high voltage electrode (3) are each independently selected from the group consisting of graphite tubes, graphite rods, graphite powder, metal tubes, metal rods, metal powder, alloy tubes, alloy rods and alloy powder.
17. A method of decomposing hydrogen sulfide, the method being implemented in the grid plasma system of decomposing hydrogen sulfide of any one of claims 1-16, the method comprising:
raw material gas containing hydrogen sulfide from the gas supply-distribution unit enters the plasma reaction unit through a pipeline;
in the presence of a plasma discharge field generated by a grid type plasma reactor and a plasma power supply in the plasma reaction unit, the raw material gas enters an inner cylinder of the grid type plasma reactor through a reactant inlet to perform hydrogen sulfide decomposition reaction, and a product obtained after the reaction is led out of the grid type plasma reactor from a product outlet;
products from the grid type plasma reactor enter a product separation unit to be separated so as to respectively obtain elemental sulfur, hydrogen and tail gas containing hydrogen sulfide;
introducing the tail gas containing hydrogen sulfide obtained in the product separation unit into a hydrogen sulfide circulation unit for separation so as to obtain hydrogen sulfide which is circulated to the gas supply-distribution unit or the plasma reaction unit.
CN201810134906.0A 2018-02-09 2018-02-09 Grid type plasma system for decomposing hydrogen sulfide and method for decomposing hydrogen sulfide Active CN110127621B (en)

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