CN110127627A - The method of the low-temperature plasma system and decomposing hydrogen sulfide of decomposing hydrogen sulfide - Google Patents

The method of the low-temperature plasma system and decomposing hydrogen sulfide of decomposing hydrogen sulfide Download PDF

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Publication number
CN110127627A
CN110127627A CN201810136800.4A CN201810136800A CN110127627A CN 110127627 A CN110127627 A CN 110127627A CN 201810136800 A CN201810136800 A CN 201810136800A CN 110127627 A CN110127627 A CN 110127627A
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hydrogen sulfide
temperature plasma
reaction
low
inner cylinder
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CN110127627B (en
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石宁
张婧
朱云峰
孙峰
任君朋
徐伟
张铁
李亚辉
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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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    • 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

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  • Chemical & Material Sciences (AREA)
  • Organic Chemistry (AREA)
  • Inorganic Chemistry (AREA)
  • Health & Medical Sciences (AREA)
  • General Health & Medical Sciences (AREA)
  • Engineering & Computer Science (AREA)
  • Combustion & Propulsion (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Physical Or Chemical Processes And Apparatus (AREA)

Abstract

The present invention relates to plasma chemistry fields, disclose the method for the low-temperature plasma system and decomposing hydrogen sulfide of decomposing hydrogen sulfide, contain the gas supply-distribution unit for passing sequentially through pipeline connection in the system, plasma reaction unit and product separative unit, contain reaction of low temperature plasma device and plasma electrical source in the plasma reaction unit, the reactor includes: inner cylinder, outer cylinder, central electrode in inner cylinder is set, it is circumferentially positioned at the side wall of inner cylinder or the outer surface of the centrally disposed electrode of package or forms the block media of the side wall of inner cylinder, grounding electrode, the thickness L of discharge air-gap1With the length L of region of discharge2Between proportionate relationship are as follows: L1: L2=1:(0.5~6000).The low-temperature plasma device of decomposing hydrogen sulfide provided by the invention and the method for decomposing hydrogen sulfide can be improved the conversion ratio of hydrogen sulfide.

Description

The method of the low-temperature plasma system and decomposing hydrogen sulfide of decomposing hydrogen sulfide
Technical field
The present invention relates to plasma chemistry fields, and in particular to a kind of low-temperature plasma system of decomposing hydrogen sulfide and A kind of method of decomposing 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 is also easy to that catalyst poisoning is caused to inactivate in Chemical Manufacture；In addition, hydrogen sulfide can also be detrimental to health, cause environment dirty Dye.Therefore, a large amount of hydrogen sulfide gas generated in the industrial circles such as petroleum, natural gas, coal and mineral products processing are carried out innoxious When processing, no matter consider from process requirement, plant maintenance or environmental requirement etc., it is urgently to be resolved.
Crouse's (Claus) method processing hydrogen sulfide is industrially generallyd use at present, and method is by hydrogen sulfide partial oxidation Obtain sulphur and water.Although the method solves the problems, such as the innoxious of hydrogen sulfide, but have lost a large amount of hydrogen resources.
With increasing for China's high sulfur bauxite amount, the sulfide hydrogen acid tail gas of hydrofinishing unit by-product is refined oil Amount increases year by year, and amounts of hydrogen needed for hydrofinishing is consequently increased；In addition, hydrogen, as oil hydrogenation cracking, low-carbon alcohols are closed At the primary raw material of, synthesis chemical engineering process such as ammonia, demand is also considerable.Therefore, hydrogen sulfide is directly decomposed is One ideal hydrogen sulfide application technology as the second resource route, not only can make its innoxious, but also can produce hydrogen and elemental sulfur, no Hydrogen resource recycling in petroleum refining process only may be implemented, it is a large amount of that conventional hydrocarbon-based reformation hydrogen production bring can also be reduced CO2 emission.
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 middle electrocardio Extremely metal, the circulating liquid that grounding electrode is temperature-controllable, are controlled by the temperature of liquid grounding electrode, so that hydrogen sulfide point Solution preocess is capable of the progress of continuous-stable.In addition, CN103204467A, which discloses a kind of hydrogen sulfide, continually and steadily decomposes preparing hydrogen The characteristics of device and method of gas, the prior art is the circulation fluid using central electrode as metal, grounding electrode for temperature-controllable Body carries out temperature control by liquid grounding electrode, and raw material airintake direction is for circumferential air inlet and in a spiral mode along axial reverse By region of discharge, so that the sulphur generated is come out by timely centrifuge separation.However, CN103204466A and CN103204467A is public In order to guarantee that hydrogen sulfide is fully decomposed as far as possible in the method opened, the flow velocity for needing to control hydrogen sulfide makes it in reactor Residence time in inner cylinder is longer and the size electric energy that the gas of unit volume in inner cylinder is obtained of control inner cylinder is more, Also, since the current prior art can not provide more powerful power supply so that using CN103204466A and Method disclosed in CN103204467A even control hydrogen sulfide residence time it is longer and control inner cylinder size so that The electric energy that the gas of unit volume obtains in inner cylinder is more also merely capable of so that the maximum conversion of hydrogen sulfide reaches 20% left side The right side, also, when the maximum conversion of hydrogen sulfide reaches 20% or so, the energy consumption for vulcanizing hydroperoxide decomposition reaction is quite high, and uncomfortable Together in large scale industry application.Further, there is also available liquid in method disclosed in CN103204466A and CN103204467A The few defect of the type of body grounding electrode, disclosed in salting liquid etc. to be generally only capable of maintaining the temperature of reactor be 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 the conversions of hydrogen sulfide present in the hydrogen sulfide decomposition technique for overcoming the prior art to provide The defect that rate is not high and conversion ratio is unstable provides low-temperature plasma system and the decomposition of the new decomposing hydrogen sulfide of one kind The method of hydrogen sulfide.
To achieve the goals above, the first aspect of the present invention provides a kind of low-temperature plasma system of decomposing hydrogen sulfide It unites, it is single containing gas supply-distribution unit, plasma reaction unit and the product separation for passing sequentially through pipeline connection in the system Member, reaction of low temperature plasma device and plasma electrical source are contained in the plasma reaction unit, which includes:
Inner cylinder is respectively arranged with reactor inlet and product exit on the inner cylinder；
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；
Central electrode, the central electrode are arranged in the inner cylinder；
Block media, the block media are circumferentially positioned on the inner sidewall of the inner cylinder or wrap up setting in described On the outer surface of heart electrode or the block media forms at least partly side wall of the inner cylinder and makes at least partly described resistance Dielectric ring is kept off around the central electrode；
Grounding electrode, the material for forming the grounding electrode is solid conductive material, and the grounding electrode is circumferentially positioned at On the lateral wall of the inner cylinder or the grounding electrode forms at least partly side wall of the inner cylinder, and the block media Setting position make the region of discharge between the central electrode and the grounding electrode by the block media interval；
Wherein, the distance between inner sidewall of the lateral wall of the central electrode and the grounding electrode is d1, Yi Jisuo State block media with a thickness of D1, and L1=d1-D1, L1With the length L of region of discharge2Between proportionate relationship are as follows: L1: L2=1: (0.5~6000).
The second aspect of the present invention provides a kind of method of decomposing hydrogen sulfide, and this method is described in the first aspect present invention Implement in low-temperature plasma system, this method comprises:
Entered in plasma reaction unit from unstripped gas of the gas supply-distribution unit containing hydrogen sulfide by pipeline；
By in the plasma reaction unit reaction of low temperature plasma device and plasma electrical source generate etc. In the presence of ionic discharge field, the unstripped gas is entered by reactor inlet carries out sulphur in the inner cylinder of reaction of low temperature plasma device Change hydroperoxide decomposition reaction, it is anti-that the gaseous substance obtained after reaction and liquid phase sulphur simple substance by product exit draw the low temperature plasma Answer device；
Gaseous substance and liquid phase sulphur simple substance from the reaction of low temperature plasma device enter in product separative unit and divide From to obtain elemental sulfur, hydrogen and hydrogen sulfide containing tail gas respectively；
Optionally the hydrogen sulfide containing tail gas obtained in the product separative unit is introduced in hydrogen sulfide cycling element It is separated to obtain the hydrogen sulfide for being recycled to the gas supply-distribution unit or the plasma reaction unit.
The low-temperature plasma system of aforementioned decomposing hydrogen sulfide provided by the invention can be used in the plasma of hydrogen sulfide It decomposes, which can generate uniform, efficient dielectric barrier discharge, generate hydrogen and sulphur so that hydrogen sulfide directly be decomposed Sulphur.
The low-temperature plasma system of decomposing hydrogen sulfide provided by the invention and the method for decomposing hydrogen sulfide can obtain height The hydrogen of purity, and the high conversion rate of hydrogen sulfide.
The low-temperature plasma body unit of aforementioned decomposing hydrogen sulfide provided by the invention is that the jacket type with coaxial configuration is situated between Matter barrier discharge consersion unit, basic structure mainly include central electrode, solid grounding electrode and block media etc., the sleeve Formula 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 passes through control L1With L2Proportionate relationship are as follows: L1: L2=1:(0.5~6000) (d1 is described The distance between the inner sidewall of the lateral wall of central electrode and the grounding electrode, D1For the thickness of the block media, and L1= d1-D1) when, the device of the invention can improve the conversion ratio of hydrogen sulfide compared with the existing technology significantly and reduce resolution Consumption.
In addition, the method for decomposing hydrogen sulfide provided by the invention can realize sulphur under significantly higher hydrogen sulfide conversion ratio Change the lasting of hydrogen decomposable process and stablize and carry out, and system can be realized long-term operation.In addition, decomposition provided by the invention The method of hydrogen sulfide can also be used to big flow, the hydrogen sulfide treatment process of various concentration.
Detailed description of the invention
Fig. 1 is the reaction of low temperature plasma device in the low-temperature plasma system of decomposing hydrogen sulfide provided by the invention A kind of structural schematic diagram of preferred embodiment；
Fig. 2 is the reaction of low temperature plasma device in the low-temperature plasma system of decomposing hydrogen sulfide provided by the invention Another structural schematic diagram of preferred embodiment；
Fig. 3 is the flow chart of the low-temperature plasma system of decomposing hydrogen sulfide provided by the invention.
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
3, central electrode
4, grounding electrode
5, it is grounded
6, block media
A, gas supply-distribution unit A1, mixer
B, plasma reaction unit B 1, reaction of low temperature plasma device
C, product separative unit and hydrogen sulfide cycling element
C1, gas-liquid separator C2, particle clarifier
C3, amine absorption tower C4, Analytic Tower
C5, carrier-gas separator C6, sulphur memory
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 first aspect of the present invention provides a kind of low-temperature plasma system of decomposing hydrogen sulfide, this is It is described etc. containing gas supply-distribution unit, plasma reaction unit and the product separative unit for passing sequentially through pipeline connection in system Contain reaction of low temperature plasma device and plasma electrical source in gas ions reaction member, which includes:
Inner cylinder is respectively arranged with reactor inlet and product exit on the inner cylinder；
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；
Central electrode, the central electrode are arranged in the inner cylinder；
Block media, the block media are circumferentially positioned on the inner sidewall of the inner cylinder or wrap up setting in described On the outer surface of heart electrode or the block media forms at least partly side wall of the inner cylinder and makes at least partly described resistance Dielectric ring is kept off around the central electrode；
Grounding electrode, the material for forming the grounding electrode is solid conductive material, and the grounding electrode is circumferentially positioned at On the lateral wall of the inner cylinder or the grounding electrode forms at least partly side wall of the inner cylinder, and the block media Setting position make the region of discharge between the central electrode and the grounding electrode by the block media interval；
Wherein, the distance between inner sidewall of the lateral wall of the central electrode and the grounding electrode is d1, Yi Jisuo State block media with a thickness of D1, and L1=d1-D1, L1With the length L of region of discharge2Between proportionate relationship are as follows: L1: L2=1: (0.5~6000).
In the present invention, in order to further increase the conversion ratio of hydrogen sulfide, under preferable case, in the low temperature plasma In reactor, L1: L2=1:(2~3000).
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.
Particularly, it was found by the inventors of the present invention that control L1: L2Proportionate relationship in aforementioned range of the invention, and L1With the thickness D of the block media1Proportionate relationship are as follows: (0.05~100): 1, particularly preferred L1: D1=(0.1~30): 1 When, when carrying out the decomposition of hydrogen sulfide using system of the invention, higher sulphur can be realized under relatively lower decomposition energy consumption Change hydrogen rates of decomposing and transforming.
In the reaction of low temperature plasma device, the preferably described central electrode is set to the central spindle position of inner cylinder, thus Be conducive to the Uniform Discharge of system of the invention.The central electrode for being set to central spindle position is connect with the plasma electrical source.
In the low-temperature plasma system of decomposing hydrogen sulfide of the invention, particularly, in the plasma reaction list In the reaction of low temperature plasma device of member, the design of collet core structure enables to heat-conducting medium to circulate in shell, is protecting Entire reaction member can be made to maintain in certain temperature range while demonstrate,proving strength of discharge, flow the sulphur generated in liquid form Reaction member out can effectively avoid hydrogen sulfide from decomposing the sulphur solidification generated, can make while reaching higher conversion ratio This decomposable process continue, stable realization long-term operation.
According to the first preferred embodiment, in the reaction of low temperature plasma device, the block media At least partly side wall for forming the inner cylinder makes at least partly described block media around the central electrode；And the ground connection Electrode is circumferentially positioned on the lateral wall of the inner cylinder.
In the first aforementioned preferred embodiment, the preferably described block media forms whole sides of the inner cylinder Wall.
According to second of preferred embodiment, in the reaction of low temperature plasma device, the block media Package is arranged on the outer surface of the central electrode, and the grounding electrode is circumferentially positioned on the inner sidewall of the inner cylinder. The block media of the invention can be fixed on the outer surface of the central electrode in a manner of any be capable of fixing, or Person, the block media can also be coated on the outer surface of the central electrode in the form of coating.
The aforementioned 2 kinds setting positions in relation to block media and grounding electrode are conducive to the high-power of reaction system of the invention Uniform Discharge.About between block media and grounding electrode fixed form or block media and grounding electrode with The fixed form of inner tube wall, the present invention do not require particularly, and those skilled in the art can be according to formation block media, inner cylinder Suitable fixed form is selected with the material of grounding electrode, there is no particular limitation to this by the present invention.
Preferably, in the reaction of low temperature plasma device, the material for forming the block media is electrically insulating material, The material for more preferably forming the block media is selected from least one of glass, ceramics, enamel, polytetrafluoroethylene (PTFE) and mica. The glass can be quartz glass or hard glass；The material for forming the block media can also have high-voltage electricity to be other Metal and nonmetallic composite of insulating Design etc..The ceramics can be aluminium oxide ceramics.
It preferably, further include ground line in the reaction of low temperature plasma device, the ground line is arranged in the outer cylinder Lateral wall on, and one end is electrically connected with the grounding electrode.
Preferably, in the reaction of low temperature plasma device, the top of the inner cylinder is arranged in the reactor inlet, The lower part and/or bottom of the inner cylinder is arranged in the product exit.
According to a kind of preferred embodiment, in the reaction of low temperature plasma device, the product exit packet Include product gas outlet and liquid product outlet, and the lower part of the inner cylinder and described is arranged in the product gas outlet The bottom of the inner cylinder is arranged in liquid product outlet.
In the reaction of low temperature plasma device, the ratio between aperture of the internal diameter of the inner cylinder and the product exit can be with For (0.1~100): 1.
In the reaction of low temperature plasma device, the aperture of the aperture of the reactor inlet and the product exit it Than that can be (0.1~120): 1.
In the reaction of low temperature plasma device, the ratio between the length of the inner cylinder and the internal diameter of the inner cylinder can Think (0.5~500): 1.
Under preferable case, in the reaction of low temperature plasma device, the product gas outlet is arranged in the electric discharge The lower section in region, and height H of the setting position of the product gas outlet relative to the inner cylinder bottom1With the region of discharge The length L in domain2Between 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, in the reaction of low temperature plasma device, the heat-conducting medium entrance and heat-conducting medium outlet It is separately positioned on the lower part and top of the outer cylinder.
In the present invention, in the reaction of low temperature plasma device, do not have to the internal diameter ratio between the inner barrel and outer barrel There is special restriction, is mainly used for that vulcanization hydroperoxide decomposition reaction occurs in the inner cylinder, and the outer cylinder is mainly used for mentioning for inner cylinder For required temperature, therefore, those skilled in the art can adjust according to the purposes and select between suitable inner barrel and outer barrel Internal diameter 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 When on the inner sidewall or lateral wall for be arranged in the inner cylinder, enable to carry out hydrogen sulfide using system provided by the invention When decomposition reaction, the conversion ratio of hydrogen sulfide improves more significantly.
The material for forming the central electrode is conductive material, it is preferable that the material for forming the central electrode is selected from stone At least one of Mo Guan, metal bar, metal tube and graphite rod.The metal bar, metal tube may include elemental metals stick, close Golden metal bar, elemental metals pipe, alloying metal pipe.The material of the formation central electrode of the invention has and can have to be other The rodlike and tubular material of electric conductivity.
The present invention can pass through the lateral wall of the inner cylinder in reaction of low temperature plasma device and the inside of the outer cylinder Region between wall introduces heat-conducting medium and the temperature for the reaction of low temperature plasma device for having jacket structured is made to maintain example Between 119~444.6 DEG C, region of discharge is flowed out in liquid form to guarantee that hydrogen sulfide decomposes the sulphur generated.
Can also be loaded in the reaction of low temperature plasma device of the invention can catalysed curing hydrogen resolve into elemental sulfur With the catalyst of hydrogen, the catalyst is preferably seated in the inner cylinder of the reaction of low temperature plasma device.The present invention is to institute The admission space and filling type for stating catalyst 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.
Condition of the reaction of low temperature plasma device provided by the invention to decomposition reaction involved in decomposing hydrogen sulfide It is not particularly limited, can be various items involved in the plasma decomposing hydrogen sulfide method in the art routinely used Part is decomposed, and lists to the embodiment of the present invention exemplary partial the condition of decomposing hydrogen sulfide, those skilled in the art It should not be construed as limiting the invention.
The reaction of low temperature plasma device provided by the invention is to the dense of the hydrogen sulfide in the gas at reactor inlet There is no particular limitation for degree, such as the concentration of hydrogen sulfide can be 0.01~100 volume % in gas.
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.
It can be anti-containing 1 or 2 or more low temperature plasma in the plasma reaction unit of the invention Answer device.
The preferred embodiment of present invention reaction of low temperature plasma device decomposing hydrogen sulfide above-mentioned presented below:
It is passed through nitrogen into the inner cylinder of reaction of low temperature plasma device from reactor inlet, to remove the sky in region of discharge Gas, and gas is drawn from product exit.Meanwhile introduce heat-conducting medium into outer cylinder from heat-conducting medium entrance, introducing it is thermally conductive Medium is exported from heat-conducting medium and is drawn.The temperature of heat-conducting medium remains the temperature of system response needs.Then enter from reactor Mouth is passed through the unstripped gas containing hydrogen sulfide into the inner cylinder of reaction of low temperature plasma device, steadily connects later to flow of feed gas high Voltage source makes to form plasma discharge field between central electrode and grounding electrode by adjusting voltage and frequency.Stink damp Body is ionized in region of discharge, is decomposed into hydrogen and elemental sulfur, and the elemental sulfur for generation of discharging slowly is flowed down along inner tube wall, and from Liquid product outlet outflow.Gas is mainly flowed out from product gas outlet after reaction.
Preferably, hydrogen sulfide cycling element is also contained in the low-temperature plasma system of decomposing hydrogen sulfide of the invention, it should Hydrogen sulfide cycling element is used to recycle the vulcanization by the gaseous substance containing hydrogen sulfide that obtains in the product separative unit Hydrogen, and resulting hydrogen sulfide is recycled to the gas supply-distribution unit or the plasma reaction unit.
Under preferable case, containing for absorbing the amine absorption tower of hydrogen sulfide and for making in the hydrogen sulfide cycling element Obtain the Analytic Tower of hydrogen sulfide parsing.
Preferably, in the low-temperature plasma system of decomposing hydrogen sulfide of the invention, contain in the product separative unit There is gas-liquid separator, and optionally contains particle clarifier and/or carrier-gas separator.
The hydrogen sulfide cycling element of the invention can be attached in the product separative unit, also, preferable case Under, the connection type of the product separative unit and the hydrogen sulfide cycling element includes: the gas in the product separative unit Liquid/gas separator is connect by pipeline with the plasma reaction unit, so that the gas phase from the plasma reaction unit Product and liquid phase sulphur simple substance are able to enter separation in the gas-liquid separator and are appointed with obtaining the first gaseous material and liquid sulfur respectively First gaseous material is introduced in particle clarifier and obtains residual solid sulphur and the second gaseous state with further separation by selection of land Substance, the liquid sulfur and the residual solid sulphur can be drawn by pipeline low temperature of decomposing hydrogen sulfide of the invention etc. from Daughter system.Further, the hydrogen sulfide cycling element is connect by pipeline with the product separative unit, so that described the Two gaseous materials can be entered in the amine absorption tower in the hydrogen sulfide cycling element by pipeline, vulcanisation to obtain respectively Hydrogen and sulfide hydrogen liquid, the vulcanisation hydrogen optionally pass through pipeline enter in carrier-gas separator separate wherein may Existing carrier gas, to obtain hydrogeneous crude product, the hydrogeneous crude product, which can according to need, further to be purified；The sulfur-bearing Change hydrogen liquid and be introduced in Analytic Tower by pipeline and parses hydrogen sulfide gas to be used for the gas supply-distribution unit or described Plasma reaction unit.
Preferably, in the gas supply-distribution unit of the invention containing hydrogen sulfide containing gas and carrier gas can be adjusted The equipment of volume ratio can obtain suitable gaseous species by the gas supply-distribution unit and hydrogen sulfide contains that is, described The unstripped gas of amount is to enter in the plasma reaction unit.For example, described state can be containing mixing in gas supply-distribution unit Device, so that the gas containing hydrogen sulfide is re-used as unstripped gas and enters in the plasma reaction unit after mixing with carrier gas.
As previously mentioned, the second aspect of the present invention provides a kind of method of decomposing hydrogen sulfide, this method is before this invention It states and implements in low-temperature plasma system described in first aspect, this method comprises:
Entered in plasma reaction unit from unstripped gas of the gas supply-distribution unit containing hydrogen sulfide by pipeline；
By in the plasma reaction unit reaction of low temperature plasma device and plasma electrical source generate etc. In the presence of ionic discharge field, the unstripped gas is entered by reactor inlet carries out sulphur in the inner cylinder of reaction of low temperature plasma device Change hydroperoxide decomposition reaction, it is anti-that the gaseous substance obtained after reaction and liquid phase sulphur simple substance by product exit draw the low temperature plasma Answer device；
Gaseous substance and liquid phase sulphur simple substance from the reaction of low temperature plasma device enter in product separative unit and divide From to obtain elemental sulfur, hydrogen and hydrogen sulfide containing tail gas respectively；
Optionally the hydrogen sulfide containing tail gas obtained in the product separative unit is introduced in hydrogen sulfide cycling element It is separated to obtain the hydrogen sulfide for being recycled to the gas supply-distribution unit or the plasma reaction unit.
Preferably, in the method for the invention, gaseous substance and liquid phase sulphur from the reaction of low temperature plasma device Simple substance enters separation in the gas-liquid separator of product separative unit and optionally will with obtaining the first gaseous material and liquid sulfur respectively First gaseous material is introduced in the particle clarifier optionally contained in the product separative unit to be obtained with further separation Obtain residual solid sulphur and the second gaseous material.Further, second gaseous material enters in the hydrogen sulfide cycling element Amine absorption tower in, to obtain vulcanisation hydrogen and sulfide hydrogen liquid respectively, the optionally described vulcanisation hydrogen into Enter and separate wherein carrier gas that may be present in the carrier-gas separator optionally contained in the product separative unit, to obtain hydrogeneous Crude product.It is parsed in the Analytic Tower that the aforementioned sulfide hydrogen liquid that the present invention obtains is introduced in the hydrogen sulfide cycling element Hydrogen sulfide gas, and the gas supply-distribution unit or the plasma reaction are recycled back to by the hydrogen sulfide that parsing obtains In unit.
In the present invention, it is preferred to contain hydrogen sulfide and carrier gas in the unstripped gas, it is not special to the type of the carrier gas Restriction, can be for hydrogen, nitrogen, argon gas, helium, carbon dioxide, carbon monoxide, air, gaseous hydrocarbons etc..Institute of the invention The source for stating the hydrogen sulfide gas in unstripped gas can be pure hydrogen sulfide, or what is obtained in industrial production contains sulphur Change the industrial waste gas of hydrogen and other gases, also, when containing carrier gas in the unstripped gas, preferably for example, by valve and stream The equipment such as meter control volume content of the carrier gas in unstripped gas.
Hydrogeneous crude product of the invention, which can according to need, further to be purified.The present invention is to further purifying hydrogeneous thick production There is no particular limitation for the method for object, such as hydrogeneous crude product can be introduced in the alkaline solution containing sodium hydroxide.
The liquid sulfur and the residual solid sulphur obtained in method of the invention is for recycling.
A kind of knot of preferred embodiment of reaction of low temperature plasma device of the invention is provided below in conjunction with Fig. 1 Structure, specifically:
The reactor has coaxial collet core structure, and the reactor includes:
Inner cylinder 1 is respectively arranged with reactor inlet 11 and product exit on the inner cylinder 1；
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；
Central electrode 3, the central electrode 3 are arranged in the inner cylinder 1；
Grounding electrode 4, the material for forming the grounding electrode 4 is solid conductive material, and the grounding electrode 4 is arranged in institute On the lateral wall for stating inner cylinder 1；
Wherein, at least partly tube structure of the inner cylinder 1 is formed by block media, so that at least partly block media ring It is around the distance between the lateral wall of the central electrode 3 and the central electrode 3 and the inner sidewall of the grounding electrode D1, the block media 6 with a thickness of D1, and L1=d1-D1, L1With the length L of region of discharge2Between proportionate relationship are as follows: L1: L2=1:(0.5~6000).
Another preferred embodiment of reaction of low temperature plasma device of the invention is provided below in conjunction with Fig. 2 Structure, specifically:
The reactor has coaxial collet core structure, and the reactor includes:
Inner cylinder 1 is respectively arranged with reactor inlet 11 and product exit on the inner cylinder 1；
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；
Central electrode 3, the central electrode 3 are arranged in the inner cylinder 1；
Grounding electrode 4, the material for forming the grounding electrode 4 is solid conductive material, and the grounding electrode 4 is around setting On the inner sidewall of the inner cylinder 1；
Block media 6, the block media 6 is arranged on at least partly outer surface of the central electrode 3, so that at least It partially protrudes into and is enclosed with the block media 6 on the outer surface of the central electrode 3 in the inner cylinder 1；
Wherein, the distance between inner sidewall of the lateral wall of the central electrode 3 and the grounding electrode is d1, the resistance Keep off medium 6 with a thickness of D1, and L1=d1-D1, L1With the length L of region of discharge2Between proportionate relationship are as follows: L1: L2=1: (0.5~6000).
In fig. 1 and 2, reaction of low temperature plasma device preferably of the invention also has the feature that
It is preferred that the reactor further includes ground line 5, the outer wall of the outer cylinder 2, and one end and institute is arranged in the ground line 5 State the connection of grounding electrode 4.
It is preferred that the top of the inner cylinder 1 is arranged in the reactor inlet 11, the product exit is arranged in the inner cylinder 1 Lower part and/or bottom.
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.
Preferably, the lower section of the region of discharge, and the product gas outlet is arranged in the product gas outlet 12 Height H of the 12 setting position relative to 1 bottom of inner cylinder1With 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)。
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.
The a kind of preferred specific real of the low-temperature plasma system of decomposing hydrogen sulfide of the invention is provided below in conjunction with Fig. 3 The process of mode is applied, specifically:
Contain the gas supply-distribution unit for passing sequentially through pipeline connection in the low-temperature plasma system of the decomposing hydrogen sulfide A, plasma reaction unit B, product separative unit and hydrogen sulfide cycling element C contain in the plasma reaction unit Reaction of low temperature plasma device B1 and plasma electrical source (not shown).Under preferable case, the reaction of low temperature plasma device B1 has structure shown in fig. 1 or fig. 2.Also, it is preferred that containing multiple in the plasma reaction unit B, such as 4 low temperature Plasma reactor B1.
Preferably, mixer A1 is contained in the gas supply-distribution unit A, the mixer A1 for that will contain sulphur on demand Change hydrogen and such as carrier gas is mixed to form unstripped gas, and obtained unstripped gas is introduced in plasma reaction unit B Reaction of low temperature plasma device B1 in carry out vulcanization hydroperoxide decomposition reaction, the product after reaction enters product separative unit and vulcanization In hydrogen cycling element C, for example, the product after reaction is introduced into gas-liquid separator C1 and carries out gas-liquid separation, obtained after gas-liquid separation Liquid sulfur enter in sulphur memory C6, the first gaseous material obtained after gas-liquid separation enter in particle clarifier C2 into Row further separation, the solid sulfur that further separation obtains can also enter in sulphur memory C6.By the particle clarifier The second gaseous material obtained in C2 enters in amine absorption tower C3 to obtain vulcanisation hydrogen and sulfide hydrogen liquid respectively (amine liquid), the preferably described vulcanisation hydrogen, which enters in carrier-gas separator C5, separates wherein carrier gas that may be present, to obtain Hydrogeneous crude product containing a large amount of hydrogen.It is preferred that aforementioned amine liquid is introduced to and parses hydrogen sulfide gas in Analytic Tower C4 and (referred to as solve Inhale hydrogen sulfide), the hydrogen sulfide gas for parsing acquisition is recycled back in the gas supply-distribution unit A1 by pipeline.
The low-temperature plasma system of decomposing hydrogen sulfide provided by the invention has the advantages that following specific:
(1) due to the decomposition using reaction of low temperature plasma device progress hydrogen sulfide, and the reactor uses conductive solids Material is as grounding electrode, and compared with liquid grounding electrode, the micro discharge electric current that such grounding electrode electric discharge generates is bigger, more has Conducive to the electric discharge decomposition reaction of hydrogen sulfide molecule, therefore it can be used for big flow, the hydrogen sulfide treatment process of high concentration.
(2) due to the decomposition using reaction of low temperature plasma device progress hydrogen sulfide, and on the outside of the reactor grounding electrode Be arranged it is jacket structured, can by control collet in heat-conducting medium temperature come to reactor carry out temperature control, hydrogen sulfide can be made to put The sulphur that electrolysis generates smoothly flows out region of discharge, avoids sulphur frozen plug reactor, makes continual and steady progress of discharging.
(3) due to the decomposition using reaction of low temperature plasma device progress hydrogen sulfide, and the reactor passes through control L1With L2 Proportionate relationship are as follows: L1: L2=1:(0.5~6000) (d1 is the lateral wall of the central electrode and the inside of the grounding electrode The distance between wall, D1For the thickness of the block media, and L1=d1-D1)；It is preferred that L1: L2=1:(2~3000) when, cooperation The structure of reactor enables to the conversion ratio of hydrogen sulfide to significantly improve and decomposes energy consumption reduction.
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 0.2L, and the reaction of remaining embodiment and comparative example fills The volume for setting inner cylinder can be calculated according to corresponding data to be obtained.
Embodiment 1
Hydrogen sulfide is carried out using the low-temperature plasma system of the decomposing hydrogen sulfide with flow chart shown in Fig. 3 to decompose instead It answers, and the reaction of low temperature plasma device in the present embodiment has structure shown in FIG. 1.
The process flow of the present embodiment is as shown in previous embodiment, also, the knot of reaction of low temperature plasma device Structure parameter is as follows:
Reaction of low temperature plasma device includes:
Inner cylinder, is respectively arranged with reactor inlet, product gas outlet and liquid product outlet on the inner cylinder, it is described in Whole tube structures of cylinder are formed by block media, and the material for forming the block media is hard glass；
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；
The axial centerline of the inner cylinder is arranged in central electrode, the central electrode, forms the central electrode Material is stainless steel metal stick；
Grounding electrode, the grounding electrode are wrapped on the lateral wall of the inner cylinder, form the material of the grounding electrode For stainless steel metal foil, and the lower edge of the central electrode in the present embodiment is lower than the lower edge of the grounding electrode；
The L of the present embodiment1With the length L of region of discharge2Between proportionate relationship are as follows: L1: L2=1:1600；
L1With the thickness D of block media1Ratio be 8:1；
Height H of the setting position of product gas outlet relative to the inner cylinder bottom1With the length L of the region of discharge2 Between proportionate relationship are as follows: H1: L2=1:40；
The operating procedure of the low-temperature plasma system of decomposing hydrogen sulfide:
Nitrogen is introduced from gas supply-distribution unit into the reaction of low temperature plasma device of plasma reaction unit, nitrogen Gas is from the inner cylinder that reactor inlet enters reaction of low temperature plasma device, to remove the air in region of discharge, and gas It is drawn from product gas outlet and liquid product outlet.Meanwhile it is (specific to introduce heat-conducting medium into outer cylinder from heat-conducting medium entrance For dimethicone), the heat-conducting medium of introducing is exported from heat-conducting medium draws, and the temperature of heat-conducting medium remains 145 DEG C.
Then hydrogen sulfide gas and Ar carrier gas are passed sequentially through into air distribution system and mixer mixes, obtain unstripped gas, it is former Expect H in gas2S volume fraction is 35%, and unstripped gas is from the inner cylinder that reactor inlet enters reaction of low temperature plasma device, control Feed gas flow rates make gas region of discharge mean residence time be 8.2s.After unstripped gas is passed through reactor 30min, connects and hand over High voltage power supply is flowed, makes to form plasma discharge field between central electrode and grounding electrode by adjusting voltage and frequency.Wherein Discharging condition are as follows: voltage 18.0kV, frequency 3.8kHz, electric current 0.94A.In region of discharge electricity occurs for hydrogen sulfide gas From, be decomposed into hydrogen and elemental sulfur, the elemental sulfur for generation of discharging slowly is flowed down along inner tube wall, and from liquid product outlet flow out. Gas is mainly flowed out from product gas outlet after reaction.
The gaseous product and product liquid of above-mentioned acquisition, which enter, carries out gas-liquid in the gas-liquid separator of product separative unit Separation, to obtain the first gaseous material and liquid sulfur respectively, first gaseous material enters in particle clarifier with further Separation obtains residual solid sulphur and the second gaseous material, the liquid sulfur and the residual solid sulphur enter sulphur memory In.Further, second gaseous material enters in the amine absorption tower in the hydrogen sulfide cycling element, to obtain respectively Vulcanisation hydrogen and sulfide hydrogen liquid, the vulcanisation hydrogen, which enters, separates carrier gas in carrier-gas separator, to obtain Hydrogeneous crude product, the sulfide hydrogen liquid, which enters, parses hydrogen sulfide gas in Analytic Tower, and the hydrogen sulfide that parsing is obtained Gas is recycled back to gas supply-distribution unit.The hydrogeneous crude product is introduced in the solution containing sodium hydroxide and is further purified To obtain hydrogen.
As a result: the vulcanization hydroperoxide decomposition reaction of the present embodiment measures H after persistently carrying out 20min2S conversion ratio is 76.5%；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 13.5eV/H2S molecule (1 molecule H of every decomposition2The energy that S needs is 13.5eV).
Comparative example 1
This comparative example carries out hydrogen sulfide decomposition using the low-temperature plasma system of decomposing hydrogen sulfide similar to Example 1 Reaction, except that:
The grounding electrode of reaction of low temperature plasma device in this comparative example is liquid grounding electrode, and is molten condition Molar ratio is the LiCl and AlCl of 1:13, which is also heat-conducting medium, and keeping temperature is 145 DEG C, and is placed on In reactor outer cylinder.
Control gaseous mixture flow velocity make gas region of discharge mean residence time be 18.5s.
Remaining is in the same manner as in Example 1.
As a result: the vulcanization hydroperoxide decomposition reaction of this comparative example measures H after persistently carrying out 20min2S conversion ratio is 14.9%, 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 117eV/H2S molecule.
Comparative example 2
This comparative example carries out hydrogen sulfide decomposition using the low-temperature plasma system of decomposing hydrogen sulfide similar with comparative example 1 Reaction, except that:
L in reaction of low temperature plasma device in this comparative example1: L2=1:6500；
Control gaseous mixture flow velocity make gas region of discharge mean residence time be 18.5s.
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 4.3%, is continued H after electric discharge 1.5h2S conversion ratio is reduced to 1.3%.
The decomposition energy consumption of this comparative example is 134eV/H2S molecule.
Embodiment 2
Hydrogen sulfide is carried out using the low-temperature plasma system of the decomposing hydrogen sulfide with flow chart shown in Fig. 3 to decompose instead It answers, and the reaction of low temperature plasma device in the present embodiment has structure shown in Fig. 2.
The process flow of the present embodiment is as shown in previous embodiment, also, the knot of reaction of low temperature plasma device Structure parameter is as follows:
Reaction of low temperature plasma device includes:
Inner cylinder is respectively arranged with reactor inlet, product gas outlet and liquid product outlet on the inner cylinder；
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；
The axial centerline of the inner cylinder is arranged in central electrode, the central electrode, forms the central electrode Material is stainless steel metal stick；
Grounding electrode, the grounding electrode are arranged on the inner sidewall of the inner cylinder, form the material of the grounding electrode For stainless steel metal foil, and the lower edge of the central electrode in the present embodiment is lower than the lower edge of the grounding electrode；
The appearance for the part that the central electrode stretches in the inner cylinder is arranged in block media, the block media On face, and the upper edge of block media is higher than the upper edge of grounding electrode, and the material for forming the block media is hard glass；
L1: L2=1:2800；
L1With the thickness D of block media1Ratio be 10:1；
H1With the length L of the region of discharge2Between proportionate relationship are as follows: H1: L2=1:350；
The operating procedure of the low-temperature plasma system of decomposing hydrogen sulfide is same as Example 1.
As a result: the vulcanization hydroperoxide decomposition reaction of the present embodiment measures H after persistently carrying out 20min2S conversion ratio is 73.1%；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 13.7eV/H2S molecule.
Comparative example 3
This comparative example carries out hydrogen sulfide decomposition using the low-temperature plasma system of decomposing hydrogen sulfide similar to Example 2 Reaction, except that:
The grounding electrode of reaction of low temperature plasma device in this comparative example is liquid grounding electrode, and is molten condition Molar ratio is the LiCl and AlCl of 1:13, which is also heat-conducting medium, and keeping temperature is 145 DEG C, and is placed on In reactor outer cylinder.
Control gaseous mixture flow velocity make gas region of discharge mean residence time be 19.8s.
Remaining is in the same manner as in Example 2.
And this comparative example carries out vulcanization hydroperoxide decomposition reaction using operating method same as Example 2.
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 5.7%.
The decomposition energy consumption of this comparative example is 115eV/H2S molecule.
Comparative example 4
This comparative example carries out hydrogen sulfide decomposition using the low-temperature plasma device of decomposing hydrogen sulfide similar with comparative example 3 Reaction, except that:
L in reaction of low temperature plasma device in this comparative example1: L2=1:6500；
Control gaseous mixture flow velocity make gas region of discharge mean residence time be 19.8s.
Remaining is identical with comparative example 3.
As a result: the vulcanization hydroperoxide decomposition reaction of this comparative example measures H after persistently carrying out 20min2S conversion ratio is 4.5%, is continued H after electric discharge 1.5h2S conversion ratio is reduced to 1.4%.
The decomposition energy consumption of this comparative example is 132eV/H2S molecule.
Embodiment 3
The present embodiment carries out hydrogen sulfide decomposition using the low-temperature plasma system of decomposing hydrogen sulfide similar to Example 1 Reaction, the difference is that in the present embodiment:
Whole side walls of inner cylinder are formed by grounding electrode, and the material for forming the grounding electrode is stainless steel metal foil；
Block media is circumferentially positioned on the inner sidewall of inner cylinder；
L1: L2=1:200；
L1With the thickness D of block media1Ratio be 18:1；
H1With the length L of the region of discharge2Between proportionate relationship are as follows: H1: L2=1:130；
H is passed through into the inner cylinder of plasma reactor from reactor inlet in the present embodiment2S/Ar gaseous mixture, wherein H2S Volume fraction is 35%, control gaseous mixture flow velocity make gas region of discharge mean residence time be 10.2s.H2S/Ar mixing After gas is passed through reactor 30min, connect ac high voltage source, by adjust voltage and frequency make central electrode and grounding electrode it Between formed plasma discharge field.Wherein discharging condition are as follows: voltage 21.3kV, frequency 7.0kHz, electric current 1.01A.
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 77.2%；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 14.1eV/H2S molecule.
Embodiment 4
The present embodiment carries out hydrogen sulfide decomposition using the low-temperature plasma system of decomposing hydrogen sulfide similar to Example 1 Reaction, except that:
Whole side walls of inner cylinder are formed by grounding electrode, and the material for forming the grounding electrode is copper foil；
Block media is circumferentially positioned on the inner sidewall of inner cylinder；
L1: L2=1:1000；
L1With the thickness D of block media1Ratio be 0.5:1；
H1With the length L of the region of discharge2Between proportionate relationship are as follows: H1: L2=1:150；
H is passed through into the inner cylinder of plasma reactor from reactor inlet in the present embodiment2S/Ar gaseous mixture, wherein H2S Volume fraction is 35%, control gaseous mixture flow velocity make gas region of discharge mean residence time be 9.6s.H2S/Ar mixing After gas is passed through reactor 30min, connect ac high voltage source, by adjust voltage and frequency make central electrode and grounding electrode it Between formed plasma discharge field.Wherein discharging condition are as follows: voltage 14.7kV, frequency 1.3kHz, electric current 1.17A.
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 76.8%；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 14.5eV/H2S molecule.
Embodiment 5
The present embodiment carries out hydrogen sulfide decomposition using the low-temperature plasma system of decomposing hydrogen sulfide similar to Example 1 Reaction, the difference is that in the present embodiment:
L1With the thickness D of block media1Ratio be 35:1.
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 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 23.5eV/H2S molecule.
Embodiment 6
The present embodiment carries out hydrogen sulfide decomposition using the low-temperature plasma system of decomposing hydrogen sulfide similar to Example 2 Reaction, except that:
L1With the length L of region of discharge2Between proportionate relationship are as follows: L1: L2=1:3500.
Remaining is in the same manner as in Example 2.
And the present embodiment carries out vulcanization hydroperoxide decomposition reaction using operating method same as Example 2.
As a result: the vulcanization hydroperoxide decomposition reaction of the present embodiment measures H after persistently carrying out 20min2S conversion ratio is 71.6%；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 24.5eV/H2S molecule.
Sulphur is carried out using the low-temperature plasma device of decomposing hydrogen sulfide provided by the invention it can be seen from the above results Change the conversion ratio and decomposition sulphur provided by the invention that can improve hydrogen sulfide when the decomposition of hydrogen compared with the existing technology significantly The low-temperature plasma device for changing hydrogen can keep to long period high hydrogen sulfide conversion ratio 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 (15)

1. a kind of low-temperature plasma system of decomposing hydrogen sulfide, match in the system containing the gas supply-for passing sequentially through pipeline connection Gas unit, plasma reaction unit and product separative unit contain low temperature plasma in the plasma reaction unit Reactor and plasma electrical source, the reactor include:
Inner cylinder (1) is respectively arranged with reactor inlet (11) and product exit on the inner cylinder (1)；
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)；
Central electrode (3), the central electrode (3) are arranged in the inner cylinder (1)；
Block media (6), the block media (6) are circumferentially positioned on the inner sidewall of the inner cylinder (1) or wrap up setting and exist On the outer surface of the central electrode (3) or at least partly side wall of the block media (6) the formation inner cylinder (1) makes At least partly described block media (6) is obtained around the central electrode (3)；
Grounding electrode (4), the material for forming the grounding electrode (4) is solid conductive material, and the grounding electrode (4) surround and sets It sets on the lateral wall of the inner cylinder (1) or the grounding electrode (4) forms at least partly side wall of the inner cylinder (1), and The setting position of the block media makes the region of discharge between the central electrode (3) and the grounding electrode (4) by institute State block media interval；
Wherein, the distance between the lateral wall of the central electrode (3) and the inner sidewall of the grounding electrode (4) they are d1, and The block media (6) with a thickness of D1, and L1=d1-D1, L1With the length L of region of discharge2Between proportionate relationship are as follows: L1: L2=1:(0.5~6000).
2. the low-temperature plasma system of decomposing hydrogen sulfide according to claim 1, wherein in the low temperature plasma In reactor, L1: L2=1:(2~3000).
3. the low-temperature plasma system of decomposing hydrogen sulfide according to claim 1, wherein in the low temperature plasma In reactor, L1With the thickness D of the block media (6)1Proportionate relationship are as follows: L1: D1=(0.05~100): 1, preferably L1: D1 =(0.1~30): 1.
4. the low-temperature plasma system of decomposing hydrogen sulfide described in any one of -3 according to claim 1, wherein described In reaction of low temperature plasma device, at least partly side wall that the block media (6) forms the inner cylinder (1) makes at least partly The block media (6) is around the central electrode (3)；And the grounding electrode (4) is circumferentially positioned at the outer of the inner cylinder (1) On side wall；Preferably,
The block media (6) forms whole side walls of the inner cylinder (1).
5. the low-temperature plasma system of decomposing hydrogen sulfide described in any one of -3 according to claim 1, wherein described In reaction of low temperature plasma device, block media (6) package is arranged on the outer surface of the central electrode (3), and institute Grounding electrode (4) is stated to be circumferentially positioned on the inner sidewall of the inner cylinder (1).
6. the low-temperature plasma system of decomposing hydrogen sulfide according to claim 1, wherein in the low temperature plasma In reactor, the material for forming the block media is electrically insulating material；Preferably,
The material for forming the block media is selected from least one of glass, ceramics, enamel, polytetrafluoroethylene (PTFE) and mica.
7. the low-temperature plasma system of decomposing hydrogen sulfide described in any one of -5 according to claim 1, wherein described low It further include ground line (5) in isothermal plasma reactor, the ground line is arranged on the lateral wall of the outer cylinder (2), and one End is electrically connected with the grounding electrode (4).
8. the low-temperature plasma system of decomposing hydrogen sulfide described in any one of -5 according to claim 1, wherein described In reaction of low temperature plasma device, the reactor inlet (11) is arranged on the top of the inner cylinder (1), and the product exit is set It sets in the lower part and/or bottom of the inner cylinder (1).
9. the low-temperature plasma system of decomposing hydrogen sulfide according to claim 8, wherein in the low temperature plasma In reactor, the product exit includes product gas outlet (12) and liquid product outlet (13), and the reactor inlet (11) setting is arranged on the top of the inner cylinder (1), the product gas outlet (12) in the lower part of the inner cylinder (1), and Bottom of liquid product outlet (13) setting in the inner cylinder (1).
10. the low-temperature plasma system of decomposing hydrogen sulfide according to claim 9, wherein in the low-temperature plasma In reactor according, the lower section of the region of discharge, and the product gas outlet is arranged in the product gas outlet (12) (12) height H of the setting position relative to the inner cylinder (1) bottom1With 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)。
11. the low-temperature plasma system of decomposing hydrogen sulfide described in any one of -5 according to claim 1, wherein in institute It states in reaction of low temperature plasma device, the heat-conducting medium entrance (21) and heat-conducting medium outlet (22) are separately positioned on institute State the lower part and top of outer cylinder (2).
12. the low-temperature plasma system of decomposing hydrogen sulfide described in any one of -5 according to claim 1, wherein in institute It states in reaction of low temperature plasma device, the material for forming the grounding electrode (4) is selected from graphite-pipe, metal tube, metal foil or gold Belong to net；Preferably,
The material for forming the central electrode (3) is selected from least one of graphite-pipe, metal bar, metal tube and graphite rod.
13. the low-temperature plasma system of decomposing hydrogen sulfide according to claim 1, wherein also contain sulphur in the system Change hydrogen cycling element, which is used to recycle the gas containing hydrogen sulfide by obtaining in the product separative unit Hydrogen sulfide in phase substance, and resulting hydrogen sulfide is recycled to the gas supply-distribution unit or the plasma reaction list Member；Preferably,
Containing the amine absorption tower for absorbing hydrogen sulfide and for so that hydrogen sulfide parsed in the hydrogen sulfide cycling element Analytic Tower.
14. the low-temperature plasma system of decomposing hydrogen sulfide according to claim 1, wherein the product separative unit In contain gas-liquid separator, and optionally contain particle clarifier and/or carrier-gas separator.
15. a kind of method of decomposing hydrogen sulfide, decomposing hydrogen sulfide of this method described in any one of claim 1-14 Implement in low-temperature plasma system, this method comprises:
Entered in plasma reaction unit from unstripped gas of the gas supply-distribution unit containing hydrogen sulfide by pipeline；
In the plasma by reaction of low temperature plasma device and plasma electrical source generation in the plasma reaction unit It discharges in the presence of field, the unstripped gas is entered by reactor inlet carries out hydrogen sulfide in the inner cylinder of reaction of low temperature plasma device Decomposition reaction, the gaseous substance obtained after reaction and liquid phase sulphur simple substance draw the reaction of low temperature plasma by product exit Device；
Gaseous substance and liquid phase sulphur simple substance from the reaction of low temperature plasma device enter in product separative unit separate with Elemental sulfur, hydrogen and hydrogen sulfide containing tail gas are obtained respectively；
Optionally the hydrogen sulfide containing tail gas obtained in the product separative unit is introduced in hydrogen sulfide cycling element and is carried out Separation is to obtain the hydrogen sulfide for being recycled to the gas supply-distribution unit or the plasma reaction unit.
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CN103204466A (en) * 2013-04-24 2013-07-17 滨州学院 Device and method for preparing hydrogen through temperature controlled continuous decomposition of hydrogen sulfide
WO2016074111A1 (en) * 2014-11-15 2016-05-19 李建庆 Temperature-controlled apparatus for hydrogen production by continuous decomposition of hydrogen sulfide
CN107001033A (en) * 2014-09-30 2017-08-01 普拉斯科转换技术有限公司 A kind of nonequilibrium plasma system and method for refining synthesis gas

Patent Citations (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN102577629A (en) * 2009-09-15 2012-07-11 三菱电机株式会社 Plasma generation device
CN103204466A (en) * 2013-04-24 2013-07-17 滨州学院 Device and method for preparing hydrogen through temperature controlled continuous decomposition of hydrogen sulfide
CN107001033A (en) * 2014-09-30 2017-08-01 普拉斯科转换技术有限公司 A kind of nonequilibrium plasma system and method for refining synthesis gas
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