CN110124469A - The method of high-throughput plasma reaction device and decomposing hydrogen sulfide - Google Patents

The method of high-throughput plasma reaction device and decomposing hydrogen sulfide Download PDF

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Publication number
CN110124469A
CN110124469A CN201810135990.8A CN201810135990A CN110124469A CN 110124469 A CN110124469 A CN 110124469A CN 201810135990 A CN201810135990 A CN 201810135990A CN 110124469 A CN110124469 A CN 110124469A
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inner cylinder
reaction
hydrogen sulfide
reaction device
heat
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Inventor
张婧
姜春明
张铁
任君朋
孙峰
金满平
徐伟
石宁
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China Petroleum and Chemical Corp
Sinopec Qingdao Safety Engineering Institute
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China Petroleum and Chemical Corp
Sinopec Qingdao Safety Engineering Institute
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Application filed by China Petroleum and Chemical Corp, Sinopec Qingdao Safety Engineering Institute filed Critical China Petroleum and Chemical Corp
Priority to CN201810135990.8A priority Critical patent/CN110124469A/en
Priority to US16/968,785 priority patent/US11691119B2/en
Priority to CN201980004595.9A priority patent/CN111278766B/en
Priority to PCT/CN2019/074087 priority patent/WO2019154245A1/en
Priority to RU2020127670A priority patent/RU2753275C1/en
Publication of CN110124469A publication Critical patent/CN110124469A/en
Pending legal-status Critical Current

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    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01D—SEPARATION
    • B01D53/00—Separation of gases or vapours; Recovering vapours of volatile solvents from gases; Chemical or biological purification of waste gases, e.g. engine exhaust gases, smoke, fumes, flue gases, aerosols
    • B01D53/32—Separation of gases or vapours; Recovering vapours of volatile solvents from gases; Chemical or biological purification of waste gases, e.g. engine exhaust gases, smoke, fumes, flue gases, aerosols by electrical effects other than those provided for in group B01D61/00
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01D—SEPARATION
    • B01D53/00—Separation of gases or vapours; Recovering vapours of volatile solvents from gases; Chemical or biological purification of waste gases, e.g. engine exhaust gases, smoke, fumes, flue gases, aerosols
    • B01D53/32—Separation of gases or vapours; Recovering vapours of volatile solvents from gases; Chemical or biological purification of waste gases, e.g. engine exhaust gases, smoke, fumes, flue gases, aerosols by electrical effects other than those provided for in group B01D61/00
    • B01D53/323—Separation of gases or vapours; Recovering vapours of volatile solvents from gases; Chemical or biological purification of waste gases, e.g. engine exhaust gases, smoke, fumes, flue gases, aerosols by electrical effects other than those provided for in group B01D61/00 by electrostatic effects or by high-voltage electric fields
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01D—SEPARATION
    • B01D53/00—Separation of gases or vapours; Recovering vapours of volatile solvents from gases; Chemical or biological purification of waste gases, e.g. engine exhaust gases, smoke, fumes, flue gases, aerosols
    • B01D53/34—Chemical or biological purification of waste gases
    • B01D53/46—Removing components of defined structure
    • B01D53/48—Sulfur compounds
    • B01D53/52—Hydrogen sulfide
    • 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
    • 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
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01D—SEPARATION
    • B01D2256/00—Main component in the product gas stream after treatment
    • B01D2256/16—Hydrogen
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01D—SEPARATION
    • B01D2259/00—Type of treatment
    • B01D2259/80—Employing electric, magnetic, electromagnetic or wave energy, or particle radiation
    • B01D2259/818—Employing electrical discharges or the generation of a plasma
    • 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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  • Chemical & Material Sciences (AREA)
  • Engineering & Computer Science (AREA)
  • Organic Chemistry (AREA)
  • Oil, Petroleum & Natural Gas (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Analytical Chemistry (AREA)
  • General Chemical & Material Sciences (AREA)
  • Inorganic Chemistry (AREA)
  • Health & Medical Sciences (AREA)
  • Environmental & Geological Engineering (AREA)
  • Biomedical Technology (AREA)
  • General Health & Medical Sciences (AREA)
  • Combustion & Propulsion (AREA)
  • Physical Or Chemical Processes And Apparatus (AREA)

Abstract

The present invention relates to plasma chemistry fields, disclose the method for a kind of high-throughput plasma reaction device and decomposing hydrogen sulfide, comprising: the inner cylinder (1) containing reaction tube (14)；It is nested in the outer cylinder (2) of the outside of inner cylinder (1)；Central high pressure electrode (3)；The grounding electrode (4) of side wall is circumferentially positioned on the lateral wall of each reaction tube (14) or formed respectively；Block media (6) on at least partly outer surface of centrally disposed high-field electrode (3)；The distance between the inner sidewall of the lateral wall of block media and grounding electrode L1With the length L of region of discharge2Between proportionate relationship are as follows: L1: L2=1:(0.5~6000).High throughput plasma reaction device provided by the invention can realize the lasting of hydrogen sulfide decomposable process and be stablized under significantly higher hydrogen sulfide conversion ratio and be carried out, and device can be realized long-term operation.

Description

The method of high-throughput plasma reaction device and decomposing hydrogen sulfide
Technical field
The present invention relates to plasma chemistry fields, and in particular to a kind of high throughput plasma reaction device and a kind of point The method for solving hydrogen sulfide.
Background technique
Hydrogen sulfide (H2S it is) a kind of hypertoxic, stench sour gas, can not only causes the corrosion of the materials such as metal, but also It can be detrimental to health, pollute environment.The large and medium-sized oil plant in China is all made of traditional Claus method (Claus) processing and contains at present H2The tail gas of S, and Recovered sulphur.This method has only recycled the sulphur in hydrogen sulfide, but converts water for valuable hydrogen.From resource It comprehensively utilizes angle and considers that in traditional hydrogen sulfide recovery process, hydrogen resource is not effectively utilized.Therefore, will Hydrogen sulfide is decomposed into sulphur and hydrogen has been increasingly becoming the technical field that domestic and international researcher is paid close attention to.
Currently, hydrogen sulfide decomposition method specifically includes that high-temperature decomposition, electrochemical process, photocatalytic method and low-temperature plasma Body method etc..In aforementioned a variety of methods, high temperature thermal decomposition method relative maturity in industrial technology, but hydrogen sulfide thermal decomposition is consumingly Limited dependent on reaction temperature, and by thermodynamical equilibrium, though reaction temperature at 1000 DEG C or more, the conversion ratio of hydrogen sulfide Only 20%.In addition, hot conditions are to the more demanding of reactor material, this also will increase operating cost.Further, since vulcanization Hydrogen thermal decomposition conversion ratio is low, needs to separate a large amount of hydrogen sulfide gas from tail gas and recycle in systems, therefore also reduce Unit efficiency and energy consumption is increased, these bring difficulty to its large industrialized application.Although using membrane technology can be with Product is efficiently separated to break balance limitation, improves hydrogen sulfide conversion ratio, but thermal decomposition temperature tends to exceed the pole of film Heat resisting temperature is limited, membrane material structure is destroyed.Electrochemistry rule there are operating procedures more, equipment seriously corroded, reaction are steady The disadvantages of qualitative difference and low efficiency.Photocatalytic method decomposing hydrogen sulfide mainly uses for reference the research of photochemical catalyzing, research emphasis collection In in terms of developing high efficiency semiconductor.Using solar energy come decomposing hydrogen sulfide, with low energy consumption, reaction condition temperature It is relatively inexpensive method with simple operation and other advantages.But that there are treating capacities is small for this method, catalytic efficiency is low and is catalyzed Agent is easy the problems such as inactivation.
Compared with other decomposition methods, low-temperature plasma body method has easy to operate, and device volume is small, and energy efficiency is high The advantages that, and the reaction being directed to has the controllability of height, and it can be when small treating capacity, being difficult to focus on flexibly It is applied on ground.Further, since it has the characteristics that high-energy density and can shorten the reaction time, can be realized at a lower temperature Hydrogen sulfide is effectively decomposed, the changeable occasion of different scales, scattered distribution, working condition is suitable for.Moreover, recycling While sulphur, hydrogen resource reclaim can be realized the utilization of hydrogen sulfide recycling by low-temperature plasma body method.
Currently, researchers at home and abroad conduct extensive research low temperature plasma decomposing hydrogen sulfide technology, use Discharge type mainly include glow discharge, corona discharge, sliding arc discharge, microwave plasma, radio frequency plasma and Dielectric barrier discharge etc..
Document " International journal of hydrogen energy ", 2012,37:1335-1347. use The method decomposing hydrogen sulfide for shrinking normal glow discharge, is vulcanized under the conditions of pressure 0.02Mpa, 2000~4000K of temperature The minimum decomposition energy consumption of hydrogen is 2.35eV/H2S.But this reaction temperature is high, pressure is low, and condition harshness is not easy to realize.
Document " International journal of hydrogen energy ", 2012,37:10010-10019 adopt With microwave plasma decomposition hydrogen sulfide, hydrogen sulfide can be decomposed completely under the conditions of atmospheric pressure, temperature 2400K, but after decomposition Hydrogen and sulphur can at high temperature rapidly it is compound regenerate hydrogen sulfide, there has been no corresponding quenching measures at present.
Document " Chemical Engineering Science ", 2009,64 (23): 4826-4834. uses impulse electric corona Electric discharge has carried out H2S decomposes the research of hydrogen making and sulphur, and reactor uses line tubular structure, in constant power 100W condition Under investigated pulse electric capacity, discharge voltage and pulse frequency to H2S conversion ratio and the influence for decomposing efficiency.As a result table Bright, under conditions of power is certain, low pulse electric capacity, low discharge voltage and high pulse frequencies help to obtain high H2S Decompose efficiency；In addition, with Ar and N2It is compared as Balance Air, with Ar-N2It is available higher when gaseous mixture is as Balance Air H2S conversion ratio, in Ar/N2/H2When S volume fraction is 46%/46%/8%, discharge power 60W, pulse electric capacity 720pF, The H of acquisition2The minimum decomposition energy consumption of S is 4.9eV/H2S, but H at this time2S conversion ratio is only 30% or so.In addition, this reaction system Flow is only 1.18 × 10-4SCMs-1, this low discharge, low concentration, low-conversion reaction effect do not have in the industrial production Practical significance.
Document " Journal of applied physics ", 1998,84 (3): 1215-1221 uses sliding arc discharge To H2S decomposition reaction is studied, and method is by H2S Dilution air to concentration is 0~100ppm, in gas overall flow rate To have investigated flow rate of gas, reaction cavity size and frequency under the conditions of 0~100L/min to H2The influence of S decomposition reaction. The experimental results showed that low gas flow rate, shallow bid spacing and low frequency help to obtain higher H2S conversion ratio, in the electric discharge of optimization Under the conditions of obtained H2S conversion ratio is up to 75~80%, but H2S decomposes energy consumption and is up to 500eV/H2S, this concentration is low, energy consumption is high Reaction effect is also without prospects for commercial application.
Dielectric barrier discharge can usually generate under atmospheric pressure, and discharge temp is lower.Further, since the presence of medium The growth of discharge current is limited, punctures completely so as to avoid gas and forms spark or electric arc, this is conducive to large volume, stabilization The generation of plasma has preferable prospects for commercial application.
Document " Plasma chemistry and plasma processing ", 1992,12 (3): 275-285 use changes Into ozone generator investigated H2Flash-over characteristic of the S within the scope of 130~560 DEG C, and have studied reaction temperature, H2S charging is dense Degree, injecting power and addition H2、Ar、N2Deng to H2The influence of S conversion ratio and energy efficiency, experiment discovery addition Ar can promote Into H2The decomposition of S, in 50~100mL/min of total flow, H2S concentration obtained under the conditions of being 20~100% conversion ratio be 0.5~ 12%, most low yield Hydrogen Energy consumption is about 0.75mol/kWh (50eV/H2), however, this process still remains, conversion ratio is low and energy consumption is high The shortcomings that.
CN102408095A cooperates with decomposing hydrogen sulfide using dielectric barrier discharge and photochemical catalyst, and method is that will have light The solid catalyst of catalytic activity is filled in plasma slab, however this method is decomposed the sulphur generated there are hydrogen sulfide and can be deposited The shortcomings that below catalyst bed.
Document " International Journal of Energy Research ", 2013,37 (11): 1280-1286. By Al2O3, MoOx/Al2O3, CoOx/Al2O3And NiO/Al2O3Catalyst is filled in region of discharge, using dielectric barrier discharge and urges Agent has carried out H2S decomposes research.Reaction result shows MoOx/Al2O3And CoOx/Al2O3Catalyst has better effects；Wherein As filling MoOx/Al2O3Catalyst, in H2S/Ar total flow 150mL/min, H25 volume % of S concentration, injection are than energy SIE When 0.92kJ/L, catalyst filling length are bed 10%, obtained H2S maximum conversion is about 48%.But this reaction process Concentration of hydrogen sulfide is lower, decomposes the sulfur deposition of generation in inside reactor, with the extension of time, catalyst activity reduction, Discharge stability reduces, and the conversion ratio of hydrogen sulfide is caused to gradually decrease.
The characteristics of CN103204466A discloses a kind of controlling temp type hydrogen sulfide decomposer and method, the device is center height Piezoelectricity extremely metal, the circulating liquid that grounding electrode is temperature-controllable, are controlled by the temperature of liquid grounding electrode, so that vulcanization Hydrogen decomposable process is capable of the progress of continuous-stable.In addition, CN103204467A, which discloses a kind of hydrogen sulfide, continually and steadily decomposes system It is metal, grounding electrode for temperature-controllable that the characteristics of device and method for taking hydrogen, the prior art, which is using central high pressure electrode, Circulating liquid, temperature control is carried out by liquid grounding electrode, raw material airintake direction is circumferential air inlet and edge in a spiral mode It is axial inversely to pass through region of discharge, so that the sulphur generated is come out by timely centrifuge separation.However, CN103204466A and In order to guarantee that hydrogen sulfide is fully decomposed as far as possible in method disclosed in CN103204467A, need to control the flow velocity of hydrogen sulfide So that its residence time in reactor inner cylinder is longer and controls the gas that the size of inner cylinder makes unit volume in inner cylinder The electric energy of acquisition is more, also, since the current prior art can not provide more powerful power supply, so that using Method disclosed in CN103204466A and CN103204467A even control hydrogen sulfide residence time it is longer and control in The size of cylinder is so that the electric energy that the gas of unit volume obtains in inner cylinder is more also merely capable of so that the highest of hydrogen sulfide turns Rate reaches 20% or so, also, when the maximum conversion of hydrogen sulfide reaches 20% or so, vulcanizes the energy consumption of hydroperoxide decomposition reaction It is quite high, it is not suitable for large scale industry application.Further, in method disclosed in CN103204466A and CN103204467A There is also the few defect of the type of available liquid grounding electrode, disclosed in salting liquid etc. be generally only capable of maintaining reactor Temperature is 100 DEG C hereinafter, and be easy to causeing the blocking of reactor hereinafter, elemental sulfur is generally solid-state at 100 DEG C.
Summary of the invention
The purpose of the invention is to overcome the prior art existing sulphur when hydrogen sulfide is decomposed into hydrogen and elemental sulfur Change that hydrogen conversion ratio is low, energy consumption is high and cannot achieve the defect of big flow hydrogen sulfide treatment, provide a kind of new high throughput it is equal from The method of daughter reaction unit and application the high throughput plasma reaction device decomposing hydrogen sulfide.
To achieve the goals above, the first aspect of the present invention provides a kind of high-throughput plasma reaction device, this is anti- Answer device that there is collet core structure, and the reaction unit includes:
Inner cylinder is respectively arranged with reactor inlet and product exit on the inner cylinder, also, containing at least in the inner cylinder Two reaction tubes being set side by side are respectively corresponded at the top and bottom of each reaction tube and are communicated, so that by the reactor The raw material that entrance enters can have respectively entered in each reaction tube, and make the production generated in each reaction tube Object can be drawn by the product exit；
Outer cylinder, the outer cylinder is nested in the outside of the inner cylinder, and heat-conducting medium entrance is respectively arranged on the outer cylinder It is exported with heat-conducting medium, each described anti-of the inner cylinder can be distributed in by the heat-conducting medium that the heat-conducting medium entrance introduces Should be between pipe, and the heat-conducting medium is exported by the heat-conducting medium and is drawn；
Central high pressure electrode, the central high pressure electrode are separately positioned in each reaction tube of the inner cylinder；
Grounding electrode, the material for forming the grounding electrode is solid conductive material, and the grounding electrode surround set respectively It sets on the inner sidewall of each reaction tube or the grounding electrode is respectively formed each reaction tube at least partly Side wall；
Block media, the block media is arranged on at least partly outer surface of the central high pressure electrode, so that extremely The block media is enclosed on the outer surface for the central high pressure electrode that small part protrudes into the inner cylinder；
Wherein, in each reaction tube, the setting position of the block media make the central high pressure electrode and Region of discharge between the grounding electrode by the block media interval and the block media lateral wall and described connect The distance between inner sidewall of ground electrode L1With the length L of the region of discharge2Between proportionate relationship are as follows: L1: L2=1:(0.5 ~6000).
Second aspect, the present invention provide a kind of method of decomposing hydrogen sulfide, and this method is described in the first aspect present invention Implement in high-throughput plasma reaction device, this method comprises: under the conditions of dielectric barrier discharge, by the original containing hydrogen sulfide Material gas is introduced in the reaction tube of the inner cylinder of the high-throughput plasma reaction device from reactor inlet and carries out hydrogen sulfide Decomposition reaction, the logistics obtained after decomposition are drawn by the product exit, also, by continuing from heat-conducting medium entrance to described Heat-conducting medium is introduced in the outer cylinder of high-throughput plasma reaction device and the heat-conducting medium is drawn by heat-conducting medium outlet And temperature needed for maintaining the high-throughput plasma reaction device, the dielectric barrier discharge is by each reactor tank Grounding electrode, block media and central high pressure electrode formed.
Aforementioned high-throughput plasma reaction device provided by the invention is the jacket type dielectric impedance with coaxial configuration Discharge reactor, basic structure mainly include central high pressure electrode, solid grounding electrode and block media etc., this is telescopic Structure enables to heat-conducting medium to carry out circulating-heating or cooling to discharge reactor, to realize to the flexible of region of discharge Temperature control.Particularly, the present invention is by controlling between the lateral wall of the block media and the inner sidewall of the grounding electrode Distance L1With the length L of region of discharge2Between proportionate relationship are as follows: L1: L2=1:(0.5~6000) when, it can be relative to existing There is technology to improve the conversion ratio of hydrogen sulfide significantly.
It is provided by the invention high throughput plasma reaction device have hydrogen sulfide high conversion rate, low energy consumption and can be real The advantages of existing big flow hydrogen sulfide treatment.
Also, high throughput plasma reaction device provided by the invention can generate uniform, efficient dielectric impedance and put Electricity generates hydrogen and sulphur to expeditiously directly decompose hydrogen sulfide.
In addition, high throughput plasma reaction device provided by the invention can be under significantly higher hydrogen sulfide conversion ratio It realizes the lasting of hydrogen sulfide decomposable process and stablizes and carry out, and device can be realized long-term operation.Further, of the invention The high-throughput plasma reaction device of offer can also be used to big flow, the hydrogen sulfide treatment process of high concentration.
Detailed description of the invention
Fig. 1 is a kind of structure of preferred embodiment of high-throughput plasma reaction device provided by the invention Schematic diagram.
Description of symbols
1, inner cylinder 2, outer cylinder
11, reactor inlet 21, heat-conducting medium entrance
12, product gas outlet 22, heat-conducting medium outlet
13, liquid product outlet
14, reaction tube
3, central high pressure electrode
4, grounding electrode
5, it is grounded
6, block media
Specific embodiment
The endpoint of disclosed range and any value are not limited to the accurate range or value herein, these ranges or Value should be understood as comprising the value close to these ranges or value.For numberical range, between the endpoint value of each range, respectively It can be combined with each other between the endpoint value of a range and individual point value, and individually between point value and obtain one or more New numberical range, these numberical ranges should be considered as specific open herein.
As previously mentioned, the present invention provides a kind of high-throughput plasma reaction device, which has collet cylinder Formula structure, and the reaction unit includes:
Inner cylinder is respectively arranged with reactor inlet and product exit on the inner cylinder, also, containing at least in the inner cylinder Two reaction tubes being set side by side are respectively corresponded at the top and bottom of each reaction tube and are communicated, so that by the reactor The raw material that entrance enters can have respectively entered in each reaction tube, and make the production generated in each reaction tube Object can be drawn by the product exit；
Outer cylinder, the outer cylinder is nested in the outside of the inner cylinder, and heat-conducting medium entrance is respectively arranged on the outer cylinder It is exported with heat-conducting medium, each described anti-of the inner cylinder can be distributed in by the heat-conducting medium that the heat-conducting medium entrance introduces Should be between pipe, and the heat-conducting medium is exported by the heat-conducting medium and is drawn；
Central high pressure electrode, the central high pressure electrode are separately positioned in each reaction tube of the inner cylinder；
Grounding electrode, the material for forming the grounding electrode is solid conductive material, and the grounding electrode surround set respectively It sets on the inner sidewall of each reaction tube or the grounding electrode is respectively formed each reaction tube at least partly Side wall；
Block media, the block media is arranged on at least partly outer surface of the central high pressure electrode, so that extremely The block media is enclosed on the outer surface for the central high pressure electrode that small part protrudes into the inner cylinder；
Wherein, in each reaction tube, the setting position of the block media make the central high pressure electrode and Region of discharge between the grounding electrode by the block media interval and the block media lateral wall and described connect The distance between inner sidewall of ground electrode L1With the length L of the region of discharge2Between proportionate relationship are as follows: L1: L2=1:(0.5 ~6000).
Difference between " side wall " and " lateral wall " and " inner sidewall " of the invention are as follows: " lateral wall " and " inner sidewall " difference Indicate " side wall " outer surface and inner surface.
In the present invention, it is referred to as interior that top and bottom respectively correspond the structure that each reaction tube communicated is collectively formed Cylinder.
It is respectively arranged with central high pressure electrode in each reaction tube of the invention, the preferably described central high pressure electrode is set It is placed in the central spindle position of each reaction tube, to be conducive to the Uniform Discharge of reaction unit of the invention.
About the definition of region of discharge, the present invention is it should be understood that the region of discharge is the outer of the block media Region between side wall and the inner sidewall of the grounding electrode, and the upper edge of the region of discharge and lower edge terminate in described connect respectively Ground electrode is in the orthographic projection and orthographic projection of the block media on the central high pressure electrode on the central high pressure electrode Overlay segment upper edge and lower edge, thus the length L of the region of discharge2It is the grounding electrode in the central high pressure electrode On orthographic projection and orthographic projection of the block media on the central high pressure electrode overlap length.
Collet core structure design of the invention, enables to heat-conducting medium to circulate in shell, is guaranteeing to put Entire reaction unit can be made to maintain in certain temperature range while electric strength, flow out the sulphur generated in liquid form instead Device is answered, can effectively avoid hydrogen sulfide from decomposing the sulphur solidification generated, this point can be made while reaching higher conversion ratio Solution preocess continue, stable realization long-term operation.
In the present invention, in order to further increase the conversion ratio of hydrogen sulfide, preferably L1: L2=1:(2~3000).
Particularly, it was found by the inventors of the present invention that control L1: L2Proportionate relationship in aforementioned range of the invention, and Control the distance between the lateral wall of the block media and the inner sidewall of the grounding electrode L1With the thickness of the block media Spend D1Between proportionate relationship are as follows: L1: D1=(0.05~100): 1, particularly preferred L1: D1=(0.1~30): when 1, this hair is utilized When bright high-throughput plasma reaction device carries out the decomposition of hydrogen sulfide, it can be realized more under relatively lower decomposition energy consumption High hydrogen sulfide rates of decomposing and transforming.
The block media of the invention is arranged on at least partly outer surface of the central high pressure electrode, the blocking Medium can be fixed on the outer surface of the central high pressure electrode in a manner of any be capable of fixing, alternatively, the blocking is situated between Matter can also be coated on the outer surface of the central high pressure electrode in the form of coating.
According to a kind of preferred embodiment, the central high pressure electrode in each reaction tube is connected in parallel to each other company It connects.
Preferably, the material for forming the block media is electrically insulating material, more preferably forms the material of the block media Material is selected from least one of glass, ceramics, enamel, polytetrafluoroethylene (PTFE) and mica.The glass can be quartz glass or hard Matter glass；The material for forming the block media can also be other metals and nonmetallic compound with high voltage electrical isolation design Material etc..The ceramics can be aluminium oxide ceramics.
Preferably, which further includes ground line, and the ground line is arranged on the lateral wall of the outer cylinder, and one End is electrically connected with the grounding electrode in each reaction tube.
Preferably, the top of the inner cylinder is arranged in the reactor inlet, and the product exit is arranged in the inner cylinder Lower part and/or bottom.
According to a kind of preferred embodiment, the product exit includes that product gas outlet and product liquid go out Mouthful, and the lower part of the inner cylinder is arranged in for the product gas outlet and the liquid product outlet is arranged in the inner cylinder Bottom.
According to a kind of preferred embodiment, the size of each reaction tube is identical.The identical expression of the size The size and shape of each reaction tube are identical.The arrangement mode of the reaction tube of the invention does not limit particularly System, arrangement cross section can be equilateral triangle, regular hexagon, circle etc..
In each reaction tube, the ratio between aperture of the internal diameter of the reaction tube and the product exit can be (0.1 ~100): 1.
The aperture of the reactor inlet and the ratio between the aperture of the product gas outlet can be (0.1~120): 1.
Ratio between the length of each reaction tube of the invention and the internal diameter of each reaction tube can be (0.5~500): 1.
Under preferable case, the lower section of all region of discharges is arranged in the product gas outlet, and the gas produces Height H of the setting position of object outlet relative to the inner cylinder bottom1With the length L of the region of discharge2Between proportionate relationship Are as follows: H1: L2=1:(0.05~25000)；Preferably H1: L2=1:(0.1~10000)；More preferably H1: L2=1:(0.5~ 1000)。
Preferably, the heat-conducting medium entrance and heat-conducting medium outlet are separately positioned on the lower part of the outer cylinder and upper Portion.
In the present invention, be mainly used in the inner cylinder occur vulcanization hydroperoxide decomposition reaction, and the outer cylinder be mainly used for for Decomposition reaction in inner cylinder provides required temperature, and therefore, those skilled in the art can adjust according to the purposes and select properly Inner barrel and outer barrel between size ratio.
The reactor inlet of the invention is arranged to the unstripped gas entered in the inner cylinder and the inner cylinder Internal diameter it is parallel or at an angle, such as can be tangentially-arranged.
The internal diameter of the invention indicates diameter.
Preferably, the material for forming the grounding electrode is selected from graphite-pipe, metal tube, metal foil or metal mesh.The present invention Solid grounding electrode, the micro discharge electric current generated under conditions of injecting power is certain is bigger, is more advantageous to the disconnected of hydrogen sulfide Key decomposition reaction.The metal tube and metal foil formed in the material of the grounding electrode may include elemental metals pipe, elemental gold Belong to foil, alloying metal pipe, alloying metal foil.It was found by the inventors of the present invention that using solid conductive material as grounding electrode ring Around the inner sidewall that the reaction tube is arranged in or when forming the side wall of the reaction tube, enable to using provided by the invention When high-throughput plasma reaction device carries out vulcanization hydroperoxide decomposition reaction, the conversion ratio of hydrogen sulfide improves more significantly.
The material for forming the central high pressure electrode is conductive material, it is preferable that forms the material of the central high pressure electrode Material is selected from least one of graphite-pipe, metal bar, metal tube, graphite rod, metal powder and graphite powder.The metal bar, metal Pipe may include elemental metals stick, alloying metal stick, elemental metals pipe, alloying metal pipe, and the metal powder may include simple substance Metal powder, alloying metal powder, elemental metals powder and/or the mechanical impurity or metal powder of alloying metal powder and mixing for graphite powder Close object.The material of the formation central high pressure electrode of the invention, which has, to be the rodlike and tubulose material of other conductive energy Material.
The present invention can be introduced thermally conductive by the region between the lateral wall of the inner cylinder and the inner sidewall of the outer cylinder Medium and the temperature for the reaction unit for having jacket structured is maintained between such as 119~444.6 DEG C, to guarantee hydrogen sulfide It decomposes the sulphur generated and flows out region of discharge in liquid form.
Can also be loaded in the of the invention high-throughput plasma reaction device can catalysed curing hydrogen resolve into list The catalyst of matter sulphur and hydrogen, the catalyst are preferably seated in the inner cylinder of the reaction unit.The present invention is to the catalysis The admission space and filling type of agent do not require particularly, about the type of catalyst, such as can be In catalyst disclosed in CN102408095A, CN101590410A and CN103495427A any one or it is a variety of.
As previously mentioned, the second aspect of the present invention provides a kind of method of decomposing hydrogen sulfide, this method is in the present invention the Implement in high-throughput plasma reaction device described in one side, this method comprises: will contain under the conditions of dielectric barrier discharge There is the unstripped gas of hydrogen sulfide to be introduced in the reaction tube of the inner cylinder of the high-throughput plasma reaction device from reactor inlet The decomposition reaction of hydrogen sulfide is carried out, the logistics obtained after decomposition is drawn by the product exit, also, by continuing by thermally conductive Jie Matter entrance introduces heat-conducting medium and is exported by heat-conducting medium and draws into the outer cylinder of the high-throughput plasma reaction device The heat-conducting medium and temperature needed for maintaining the high-throughput plasma reaction device, the dielectric barrier discharge is by each Grounding electrode, block media and central high pressure electrode in the reactor tank are formed.
The high-throughput plasma reaction device provided by the invention is to decomposition reaction involved in decomposing hydrogen sulfide Condition is not particularly limited, and can be each involved in the plasma decomposing hydrogen sulfide method in the art routinely used Kind of condition is decomposed, and the condition of decomposing hydrogen sulfide, art technology are listed to the embodiment of the present invention exemplary partial Personnel should not be construed as limiting the invention.
In the present invention, to the material of the formation outer cylinder, there is no particular limitation, as long as forming the material of the outer cylinder It is able to bear the set temperature of heat-conducting medium.
The high-throughput plasma reaction device provided by the invention is to the hydrogen sulfide in the gas at reactor inlet Concentration there is no particular limitation, such as the concentration of hydrogen sulfide can be 0.01~100 volume % in gas.
A kind of preferred embodiment of high-throughput plasma reaction device of the invention is provided below in conjunction with Fig. 1 Structure, specifically:
The reaction unit has collet core structure, and the reaction unit includes:
Inner cylinder 1 is respectively arranged with reactor inlet 11 and product exit 13 on the inner cylinder 1, also, in the inner cylinder 1 The reaction tube 14 being set side by side containing at least two, the top and bottom of each reaction tube 14, which respectively correspond, to be communicated, so that It can be had respectively entered in each reaction tube 14, and made each described by the raw material that the reactor inlet 11 enters The product generated in reaction tube 14 can be drawn by the product exit；
Outer cylinder 2, the outer cylinder 2 is nested in the outside of the inner cylinder 1, and is respectively arranged with heat-conducting medium on the outer cylinder 2 Entrance 21 and heat-conducting medium outlet 22, can be distributed in the inner cylinder 1 by the heat-conducting medium that the heat-conducting medium entrance 21 introduces Each reaction tube 14 between, and the heat-conducting medium by the heat-conducting medium outlet 22 draw；
Central high pressure electrode 3, the central high pressure electrode 3 are separately positioned on each reaction tube 14 of the inner cylinder 1 In；
Grounding electrode 4, the material for forming the grounding electrode 4 is solid conductive material, and the grounding electrode 4 is surround respectively It is arranged on the inner sidewall of each reaction tube 14 or the grounding electrode 4 is respectively formed each reaction tube 14 At least partly side wall；
Block media 6, the block media 6 are arranged on at least partly outer surface of the central high pressure electrode 3, so that The block media 6 is enclosed on the outer surface for the central high pressure electrode 3 being extending at least partially into the inner cylinder 1；
Wherein, in each reaction tube 14, the setting position of the block media 6 makes the central high pressure electrode Region of discharge between the grounding electrode by the block media interval and the block media 6 lateral wall and institute State the distance between the inner sidewall of grounding electrode L1With the length L of the region of discharge2Between proportionate relationship are as follows: L1: L2=1: (0.5~6000), more preferable L1: L2=1:(2~3000).
Under preferable case, in each reaction tube 14, the lateral wall and the grounding electrode 4 of the block media 6 The distance between inner sidewall L1With the thickness D of the block media 61Proportionate relationship are as follows: L1: D1=(0.05~100): 1； More preferable L1: D1=(0.1~30): 1.
Preferably, the central high pressure electrode 3 in each reaction tube 14 is connected in parallel with each other.
Under preferable case, which further includes ground line 5, and the lateral wall of the outer cylinder 2 is arranged in the ground line 5 On, and one end is electrically connected with the grounding electrode 4 in each reaction tube 14.
Preferably, the top of the inner cylinder 1 is arranged in the reactor inlet 11, and the product exit is arranged described interior The lower part and/or bottom of cylinder 1.
Under preferable case, the product exit includes product gas outlet 12 and liquid product outlet 13, and the gas The lower part of the inner cylinder 1 is arranged in product exit 12 and the bottom of the inner cylinder 1 is arranged in the liquid product outlet 13.
Under preferable case, the size of each reaction tube 14 is identical.
Preferably, the lower section of all region of discharges, and the gaseous product is arranged in the product gas outlet 12 Height H of the setting position of outlet 12 relative to 1 bottom of inner cylinder1With the length L of the region of discharge2Between ratio close System are as follows: H1: L2=1:(0.05~25000)；Preferably H1: L2=1:(0.1~10000)；More preferably H1: L2=1:(0.5~ 1000)。
It is preferred that the heat-conducting medium entrance 21 and the heat-conducting medium outlet 22 be separately positioned on the outer cylinder 2 lower part and Top.
It is presented below another using the preferred of the present invention high-throughput plasma reaction device decomposing hydrogen sulfide above-mentioned Specific embodiment:
It is passed through nitrogen into the inner cylinder of high-throughput plasma reaction device from reactor inlet, to remove in region of discharge Air, and gas from product exit draw.Meanwhile heat-conducting medium is introduced into outer cylinder from heat-conducting medium entrance, introducing Heat-conducting medium is exported from heat-conducting medium and is drawn.The temperature of heat-conducting medium remains the temperature of system response needs.Then from reaction Device entrance is passed through the unstripped gas containing hydrogen sulfide into the inner cylinder of high-throughput plasma reaction device, and unstripped gas is full of each anti- Ying Guanzhong steadily connects high voltage power supply to flow of feed gas later, makes central high pressure electrode and ground connection by adjusting voltage and frequency Plasma discharge field is formed between electrode.Hydrogen sulfide gas is ionized in region of discharge, is decomposed into hydrogen and elemental sulfur, is put The elemental sulfur that electricity generates slowly is flowed down along inner tube wall, and is flowed out from product exit.
High throughput plasma reaction device provided by the invention also has the advantages that following specific:
(1) the high throughput plasma reaction device uses conductive solids material as grounding electrode, is grounded electricity with liquid Pole is compared, and the structure of high-throughput plasma reaction device provided by the invention is cooperated, so that the electric discharge of such grounding electrode generates Micro discharge electric current it is bigger, be more advantageous to the electric discharge decomposition reaction of hydrogen sulfide molecule.
(2) setting is jacket structured on the outside of the grounding electrode of the high throughput plasma reaction device, can be by controlling collet Middle heat-conducting medium temperature to carry out temperature control to reaction unit, and the sulphur that hydrogen sulfide electric discharge decomposition can be made to generate, which smoothly flows out, to be put Electric area avoids sulphur frozen plug reaction unit, makes continual and steady progress of discharging.
(3) lateral wall and the grounding electrode that the high throughput plasma reaction device passes through the control block media The distance between inner sidewall L1With the length L of region of discharge2Between proportionate relationship are as follows: L1: L2=1:(0.5~6000)；More It is preferred that L1: L2=1:(2~3000), the structure of complex reaction device enables to the conversion ratio of hydrogen sulfide to significantly improve and decomposes Energy consumption reduces.
The present invention will be described in detail by way of examples below.In following embodiment, in the feelings being not particularly illustrated Under condition, the various raw materials used are all from commercially available.
The thickness of block media in following embodiment and comparative example is all the same.
The conversion ratio of hydrogen sulfide is calculated according to the following formula in following instance:
Molal quantity/premature cure hydrogen molal quantity × 100% of the hydrogen sulfide of the conversion ratio %=conversion of hydrogen sulfide
The energy consumption of decomposing hydrogen sulfide is detected by oscillograph and is calculated using Lissajou's figure and obtained in following instance.
The volume of reaction unit inner cylinder in following example 1 is 1L, in the reaction unit of remaining embodiment and comparative example The volume of cylinder can be calculated according to corresponding data and be obtained.
Embodiment 1
Vulcanization hydroperoxide decomposition reaction, high-throughput plasma are carried out using high-throughput plasma reaction device shown in FIG. 1 The specific structure and structural parameters of reaction unit are as follows:
Reaction unit includes:
Inner cylinder is respectively arranged with reactor inlet, product gas outlet and liquid product outlet on the inner cylinder, also, The reaction tube being set side by side in the inner cylinder containing 4 is respectively corresponded at the top and bottom of each reaction tube and is communicated, so that The raw material entered by the reactor inlet can have respectively entered in each reaction tube, and make each reaction The gaseous products generated in pipe can be drawn by the product gas outlet, and make the liquid generated in each reaction tube State product can be drawn by the liquid product outlet, and the size of 4 reaction tubes is identical；
Outer cylinder, the outer cylinder is nested in the outside of the inner cylinder, and heat-conducting medium entrance is respectively arranged on the outer cylinder It is exported with heat-conducting medium, each described anti-of the inner cylinder can be distributed in by the heat-conducting medium that the heat-conducting medium entrance introduces Should be between pipe, and the heat-conducting medium is exported by the heat-conducting medium and is drawn；
The axial centerline of each reaction tube is arranged in central high pressure electrode, the central high pressure electrode, is formed The material of the central high pressure electrode is stainless steel metal stick, and the central high pressure electrode in each reaction tube is connected in parallel；
Grounding electrode, the grounding electrode is circumferentially positioned at respectively on the inner sidewall of each reaction tube, described in formation The material of grounding electrode is stainless steel metal foil, and the lower edge of the central high pressure electrode in the present embodiment and the grounding electrode Lower edge flushes；
The part that the central high pressure electrode stretches in the reaction tube is arranged in block media, the block media Outer surface on, and the upper edge of block media be higher than grounding electrode upper edge, formed the block media material be hard glass Glass.
In each reaction tube, the distance between inner sidewall of the lateral wall of the block media and grounding electrode L1 With the length L of region of discharge2Ratio be 1:1700；
Height H of the setting position of product gas outlet relative to the inner cylinder bottom1Described in each reaction tube The length L of region of discharge2Between proportionate relationship are as follows: H1: L2=1:48；
L1With the thickness D of the block media1Between proportionate relationship are as follows: L1: D1=6:1；
Gaseous mixture enters in reaction unit inner cylinder from the top of reaction unit inner cylinder in the present embodiment, and fills from reaction is located at The product gas outlet for setting inner cylinder lower part draws gaseous product, and elemental sulfur draws from the liquid product outlet for being located at reaction unit bottom Out；And the heat-conducting medium of the present embodiment is introduced from the lower part of the outer cylinder of reaction unit, and the top of the outer cylinder from reaction unit It draws.
The operating procedure of high-throughput plasma reaction device:
It is passed through nitrogen into the inner cylinder of plasma reaction device from reactor inlet, to remove the sky in region of discharge Gas, and gas is drawn from product gas outlet and liquid product outlet.Meanwhile it introducing and leading into outer cylinder from heat-conducting medium entrance Thermal medium (specially dimethicone), the heat-conducting medium of introducing is exported from heat-conducting medium draws, and the temperature of heat-conducting medium is kept It is 145 DEG C.
Then H is passed through into the inner cylinder of high-throughput plasma reaction device from reactor inlet2S/Ar gaseous mixture, wherein H2S volume fraction be 20%, control gaseous mixture flow velocity make gas region of discharge mean residence time be 8.8s.H2S/Ar is mixed After conjunction gas is passed through reaction unit 30min, ac high voltage source is connected, makes central high pressure electrode by adjusting voltage and frequency and connects Plasma discharge field is formed between ground electrode.Wherein discharging condition are as follows: voltage 18.2kV, frequency 3.3kHz, electric current are 1.8A.Hydrogen sulfide gas is ionized in region of discharge, is decomposed into hydrogen and elemental sulfur, and the elemental sulfur for generation of discharging is along inner tube wall It slowly flows down, and is flowed out from liquid product outlet.Gas is flowed out from product gas outlet after reaction.
As a result: the vulcanization hydroperoxide decomposition reaction of the present embodiment measures H after persistently carrying out 20min2S conversion ratio is 73.5%；And Continuous discharge 100h has not yet to see exception, discharge condition and H2S conversion ratio keeps stable.And the decomposition energy consumption of the present embodiment is 13.8eV/H2S molecule (1 molecule H of every decomposition2The energy that S needs is 13.8eV).
Comparative example 1
This comparative example carries out hydrogen sulfide using high-throughput reaction of low temperature plasma device similar to Example 1 and decomposes instead It answers, except that:
Grounding electrode in this comparative example is liquid grounding electrode, and be molten condition molar ratio be 1:1 LiCl with AlCl3, which is also heat-conducting medium, and keeping temperature is 145 DEG C, and is placed in reactor outer cylinder.
Control gaseous mixture flow velocity make gas region of discharge mean residence time be 19.2s.
Remaining is in the same manner as in Example 1.
And this comparative example carries out vulcanization hydroperoxide decomposition reaction using operating method same as Example 1.
As a result: the vulcanization hydroperoxide decomposition reaction of this comparative example measures H after persistently carrying out 20min2S conversion ratio is 15.6%, is held H after continuous electric discharge 1.5h2S conversion ratio is reduced to 5.1%.
The decomposition energy consumption of this comparative example is 115eV/H2S molecule.
Comparative example 2
This comparative example is carried out using reaction of low temperature plasma device similar with comparative example 1, except that:
L in each reaction tube, in this comparative example1With the length L of region of discharge2Ratio be 1:6500；
Control gaseous mixture flow velocity make gas region of discharge mean residence time be 19.2s.
Remaining is identical with comparative example 1.
As a result: the vulcanization hydroperoxide decomposition reaction of this comparative example measures H after persistently carrying out 20min2S conversion ratio is 4.8%, is continued H after electric discharge 1.5h2S conversion ratio is reduced to 1.4%.
The decomposition energy consumption of this comparative example is 140eV/H2S molecule.
Embodiment 2
The present embodiment is anti-using the decomposition that high-throughput low-temperature plasma reactor similar to Example 1 carries out hydrogen sulfide It answers, the difference is that in the present embodiment:
Whole side walls of reaction tube are formed by grounding electrode, and the material for forming the grounding electrode is stainless steel metal Foil；
In each reaction tube, the distance between inner sidewall of the lateral wall of the block media and grounding electrode L1 With the length L of region of discharge2Ratio be 1:3000；
Height H of the setting position of product gas outlet relative to the inner cylinder bottom1Described in each reaction tube The length L of region of discharge2Between proportionate relationship are as follows: H1: L2=1:250；
L1With the thickness D of the block media1Between proportionate relationship are as follows: L1: D1=15:1；
H is passed through into the inner cylinder of high-throughput reaction of low temperature plasma device from reactor inlet in the present embodiment2S/Ar is mixed Gas is closed, wherein H2S volume fraction is 20%, and control gaseous mixture flow velocity makes the gas to be in the mean residence time of region of discharge 7.8s。H2After S/Ar gaseous mixture is passed through reactor 30min, ac high voltage source is connected, makes center by adjusting voltage and frequency Plasma discharge field is formed between high-field electrode and grounding electrode.Wherein discharging condition are as follows: voltage 21.3kV, frequency are 0.9kHz, electric current 2.3A.
Remaining is in the same manner as in Example 1.
As a result: the vulcanization hydroperoxide decomposition reaction of the present embodiment measures H after persistently carrying out 20min2S conversion ratio is 72.7%；And Continuous discharge 100h has not yet to see exception, discharge condition and H2S conversion ratio keeps stable.And the decomposition energy consumption of the present embodiment is 14.0eV/H2S molecule.
Embodiment 3
The present embodiment is anti-using the decomposition that high-throughput low-temperature plasma reactor similar to Example 1 carries out hydrogen sulfide It answers, the difference is that in the present embodiment:
Whole side walls of reaction tube are formed by grounding electrode, and the material for forming the grounding electrode is copper foil；
In each reaction tube, the distance between inner sidewall of the lateral wall of the block media and grounding electrode L1 With the length L of region of discharge2Ratio be 1:300；
Height H of the setting position of product gas outlet relative to the inner cylinder bottom1Described in each reaction tube The length L of region of discharge2Between proportionate relationship are as follows: H1: L2=1:100；
L1With the thickness D of the block media1Between proportionate relationship are as follows: L1: D1=0.5:1；
H is passed through into the inner cylinder of high-throughput reaction of low temperature plasma device from reactor inlet in the present embodiment2S/Ar is mixed Gas is closed, wherein H2S volume fraction is 20%, and control gaseous mixture flow velocity makes the gas to be in the mean residence time of region of discharge 10.5s。H2After S/Ar gaseous mixture is passed through reactor 30min, ac high voltage source is connected, makes center by adjusting voltage and frequency Plasma discharge field is formed between high-field electrode and grounding electrode.Wherein discharging condition are as follows: voltage 13.7kV, frequency are 4.2kHz, electric current 2.5A.
Remaining is in the same manner as in Example 1.
As a result: the vulcanization hydroperoxide decomposition reaction of the present embodiment measures H after persistently carrying out 20min2S conversion ratio is 74.2%；And Continuous discharge 100h has not yet to see exception, discharge condition and H2S conversion ratio keeps stable.And the decomposition energy consumption of the present embodiment is 14.3eV/H2S molecule.
Embodiment 4
The present embodiment carries out the decomposition reaction of hydrogen sulfide using plasma reactor similar to Example 1, different It is, in the present embodiment:
L1With the thickness D of block media1Ratio be 37:1.
Remaining is in the same manner as in Example 1.
As a result: the vulcanization hydroperoxide decomposition reaction of the present embodiment measures H after persistently carrying out 20min2S conversion ratio is 66.6%；And Continuous discharge 100h has not yet to see exception, discharge condition and H2S conversion ratio keeps stable.And the decomposition energy consumption of the present embodiment is 24.1eV/H2S molecule.
Embodiment 5
The present embodiment carries out the decomposition reaction of hydrogen sulfide using plasma reactor similar to Example 2, different It is, in the present embodiment:
L1With the length L of region of discharge2Ratio be 1:3500；
Remaining is in the same manner as in Example 2.
As a result: the vulcanization hydroperoxide decomposition reaction of the present embodiment measures H after persistently carrying out 20min2S conversion ratio is 65.8%；And Continuous discharge 100h has not yet to see exception, discharge condition and H2S conversion ratio keeps stable.And the decomposition energy consumption of the present embodiment is 23.7eV/H2S molecule.
Hydrogen sulfide is carried out using high-throughput plasma reaction device provided by the invention it can be seen from the above results The conversion ratio of hydrogen sulfide can be improved compared with the existing technology significantly when decomposition and reaction unit provided by the invention can High hydrogen sulfide conversion ratio is kept to long period under low decomposition energy consumption.
The preferred embodiment of the present invention has been described above in detail, and still, the present invention is not limited thereto.In skill of the invention In art conception range, can with various simple variants of the technical solution of the present invention are made, including each technical characteristic with it is any its Its suitable method is combined, and it should also be regarded as the disclosure of the present invention for these simple variants and combination, is belonged to Protection scope of the present invention.

Claims (13)

1. a kind of high throughput plasma reaction device, which has collet core structure, and the reaction unit includes:
Inner cylinder (1) is respectively arranged with reactor inlet (11) and product exit (13), also, the inner cylinder on the inner cylinder (1) (1) reaction tube (14) being set side by side in containing at least two respectively corresponds at the top and bottom of each reaction tube (14) It communicates, the raw material entered by the reactor inlet (11) is had respectively entered in each reaction tube (14), with And the middle product generated of each reaction tube (14) is drawn by the product exit；
Outer cylinder (2), the outer cylinder (2) are nested in the outside of the inner cylinder (1), and are respectively arranged on the outer cylinder (2) thermally conductive Medium inlet (21) and heat-conducting medium outlet (22), can be distributed in by the heat-conducting medium that the heat-conducting medium entrance (21) introduces Between each reaction tube (14) of the inner cylinder (1), and the heat-conducting medium exports (22) by the heat-conducting medium and draws Out；
Central high pressure electrode (3), the central high pressure electrode (3) are separately positioned on each reaction tube of the inner cylinder (1) (14) in；
Grounding electrode (4), the material for forming the grounding electrode (4) is solid conductive material, grounding electrode (4) the difference ring Around setting is on the inner sidewall of each reaction tube (14) or the grounding electrode (4) is respectively formed each reaction Manage at least partly side wall of (14)；
Block media (6), the block media (6) are arranged on at least partly outer surface of the central high pressure electrode (3), make The block media (6) are enclosed on the outer surface for the central high pressure electrode (3) that must be extending at least partially into the inner cylinder (1)；
Wherein, in each reaction tube (14), the setting position of the block media (6) makes the central high pressure electrode Region of discharge between the grounding electrode by the lateral wall of the block media interval and the block media (6) and The distance between the inner sidewall of grounding electrode L1With the length L of the region of discharge2Between proportionate relationship are as follows: L1: L2= 1:(0.5~6000).
2. high throughput plasma reaction device according to claim 1, wherein L1: L2=1:(2~3000).
3. high throughput plasma reaction device according to claim 1 or 2, wherein the outside of the block media (6) The distance between the inner sidewall of wall and grounding electrode L1With the thickness D of the block media1Between proportionate relationship are as follows: L1: D1=(0.05~100): 1, preferably L1: D1=(0.1~30): 1.
4. high-throughput plasma reaction device described in any one of -3 according to claim 1, wherein each reaction Central high pressure electrode (3) in pipe (14) is connected in parallel with each other.
5. high-throughput plasma reaction device described in any one of -3 according to claim 1, wherein form the blocking The material of medium is electrically insulating material；Preferably,
Form at least one of the material of the block media in glass, quartz, ceramics, enamel, polytetrafluoroethylene (PTFE) and mica Kind.
6. high-throughput plasma reaction device described in any one of -3 according to claim 1, wherein the reaction unit is also Including ground line (5), the ground line is arranged on the lateral wall of the outer cylinder (2), and one end and each reaction tube (14) grounding electrode (4) electrical connection in.
7. high-throughput plasma reaction device described in any one of -3 according to claim 1, wherein the reactor enters Mouth (11) setting is arranged in the top of the inner cylinder (1), the product exit in the lower part and/or bottom of the inner cylinder (1)；It is excellent Selection of land,
The product exit includes product gas outlet (12) and liquid product outlet (13), and the product gas outlet (12) It is arranged and is arranged in the lower part of the inner cylinder (1) and the liquid product outlet (13) in the bottom of the inner cylinder (1).
8. high-throughput plasma reaction device described in any one of -3 according to claim 1, wherein each reaction The size for managing (14) is identical.
9. high throughput plasma reaction device according to claim 7, wherein product gas outlet (12) setting In the lower section of all region of discharges, and the setting position of the product gas outlet (12) is relative to the inner cylinder (1) bottom The height H in portion1With the length L of the region of discharge2Between proportionate relationship are as follows: H1: L2=1:(0.05~25000)；Preferably H1: L2=1:(0.1~10000)；More preferably H1: L2=1:(0.5~1000).
10. high-throughput plasma reaction device described in any one of -3 according to claim 1, wherein thermally conductive Jie Matter entrance (21) and heat-conducting medium outlet (22) are separately positioned on the lower part and top of the outer cylinder (2).
11. high throughput plasma reaction device according to claim 1, wherein form the material of the grounding electrode (4) Material is selected from graphite-pipe, metal tube, metal foil or metal mesh.
12. high throughput plasma reaction device according to claim 1, wherein form the central high pressure electrode (3) Material be selected from least one of graphite-pipe, metal bar, metal tube, graphite powder, metal powder and graphite rod.
13. a kind of method of decomposing hydrogen sulfide, high-throughput plasma of this method described in any one of claim 1-11 Implement in precursor reactant device, this method comprises: under the conditions of dielectric barrier discharge, by the unstripped gas containing hydrogen sulfide from reactor Entrance is introduced to the decomposition reaction that hydrogen sulfide is carried out in the reaction tube of the inner cylinder of the high-throughput plasma reaction device, decomposes The logistics obtained afterwards is drawn by the product exit, also, by continuing from heat-conducting medium entrance to the high-throughput plasma Heat-conducting medium is introduced in the outer cylinder of precursor reactant device and the heat-conducting medium is drawn by heat-conducting medium outlet and maintains the height Temperature needed for flux plasma reaction device, the dielectric barrier discharge by each reactor tank grounding electrode, Block media and central high pressure electrode are formed.
CN201810135990.8A 2018-02-09 2018-02-09 The method of high-throughput plasma reaction device and decomposing hydrogen sulfide Pending CN110124469A (en)

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Application Number Priority Date Filing Date Title
CN201810135990.8A CN110124469A (en) 2018-02-09 2018-02-09 The method of high-throughput plasma reaction device and decomposing hydrogen sulfide
US16/968,785 US11691119B2 (en) 2018-02-09 2019-01-31 Low temperature plasma reaction device and hydrogen sulfide decomposition method
CN201980004595.9A CN111278766B (en) 2018-02-09 2019-01-31 Low temperature plasma reaction apparatus and method for decomposing hydrogen sulfide
PCT/CN2019/074087 WO2019154245A1 (en) 2018-02-09 2019-01-31 Low temperature plasma reaction device and hydrogen sulphide decomposition method
RU2020127670A RU2753275C1 (en) 2018-02-09 2019-01-31 Apparatus for executing low-temperature plasma reaction and method for decomposing hydrogen sulphide

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