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.
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 methods of plasma decomposing hydrogen sulfide, this method comprises: hindering in medium
It keeps off under discharging condition, the unstripped gas containing hydrogen sulfide is introduced in the plasma system containing plasma reactor and is carried out
Vulcanize hydroperoxide decomposition reaction, according to logistics direction, gas supply-distribution unit, plasma is successively contained in the plasma system
Reaction member and product separative unit, and contain plasma electrical source and the plasma in the plasma reaction unit
Reactor, the dielectric barrier discharge condition include: that discharge voltage is 5~30kV, and discharge frequency is 200~30000Hz;And
It is 0~800 DEG C that the condition of the vulcanization hydroperoxide decomposition reaction, which includes: reaction temperature, and reaction pressure is -0.06MPa to 0.6MPa, instead
Answering residence time of the object in the plasma reactor is 1 × 10-5~120s.
In more preferred situation, the dielectric barrier discharge condition includes: that discharge voltage is 5~20kV, and discharge frequency is
500~15000Hz.
Under preferable case, discharge current is 0.1~100A, preferably 0.5~10A.
Preferably, it is described vulcanization hydroperoxide decomposition reaction condition include: reaction temperature be 40~500 DEG C, reaction pressure be-
0.06MPa to 0.3MPa, residence time of the reactant in the plasma reactor are 2 × 10-5~60s.
Compared with the existing technology, the method for decomposing hydrogen sulfide provided by the invention can significantly improve the conversion ratio of hydrogen sulfide
And it reduces and decomposes energy consumption.
Under preferable case, the vulcanization hydroperoxide decomposition reaction carries out in the presence of carrier gas, the carrier gas be selected from nitrogen, hydrogen,
At least one of helium, argon gas, vapor, carbon monoxide, carbon dioxide, methane, ethane and propane;It is highly preferred that described
Carrier gas is selected from least one of hydrogen, argon gas, helium and nitrogen.
In the present invention, the unstripped gas does not include aforementioned carrier gas of the invention, and the unstripped gas is pure hydrogen sulfide
Gas or the industrial waste gas etc. containing hydrogen sulfide and other gases to be obtained in industrial production, although in the unstripped gas
May containing the gas of carrier gas identical type defined with the present invention, still, the carrier gas that the present invention defines be actively added with
The gas mixed with the unstripped gas, also, method of the invention can control on demand the load volume of addition.
Under preferable case, the content of the hydrogen sulfide gas in the unstripped gas makes the reaction of the plasma reactor
The content of the hydrogen sulfide gas of device inlet is 0.1~100 volume %;More preferably 10~50 volume %.
There is no particular limitation for the structure of preceding method plasma reactor of the invention, can be using in the art
Conventional generates the plasma reactor of electric field by dielectric barrier discharge to carry out preceding method of the invention.However, this
Invention is decomposed inventors have found that being carried out hydrogen sulfide of the invention using the plasma reactor for having the following structure feature
When reaction, the conversion ratio of hydrogen sulfide can be further improved.
The plasma reactor 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, formed the grounding electrode material be solid conductive material, and the grounding electrode formed it is each
At least partly side wall or the grounding electrode of the reaction tube are circumferentially positioned at respectively on the side wall of each reaction tube;
Block media, at least partly side wall that the block media forms each reaction tube make at least partly described
Block media is around the central high pressure electrode;Or the block media is circumferentially positioned at the inner sidewall of each reaction tube
On;Or the block media is arranged on at least partly outer surface of the central high pressure electrode, so that being extending at least partially into
The block media is enclosed on the outer surface of central high pressure electrode in the inner cylinder;
In each reaction tube, the setting position of the block media makes the central high pressure electrode and described connects
Region of discharge between ground electrode is by the block media interval;
And the unstripped gas containing hydrogen sulfide enters in the plasma reactor from the reactor inlet.
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, in order to further increase the conversion ratio of hydrogen sulfide, under preferable case, in the plasma reaction
In device, in each reaction tube, between the lateral wall of the central high pressure electrode and the inner sidewall of the grounding electrode
Distance is d1 and the block media with a thickness of D1, L1=d1-D1, L1With the length L of region of discharge2Between ratio close
System are as follows: L1: L2=1:(0.5~6000), more preferable L1: L2=1:(2~3000).
Particularly, it was found by the inventors of the present invention that in each reaction tube, L is controlled1: L2Proportionate relationship of the invention
In aforementioned range, and control L1With the thickness D of the block media1Proportionate relationship are as follows: L1: D1=(0.05~100): 1;
More preferable L1: D1=(0.1~30):, can be relatively lower when carrying out the decomposition of hydrogen sulfide using system of the invention when 1
It decomposes and realizes higher hydrogen sulfide rates of decomposing and transforming under energy consumption.
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 reactor of the invention.It is set to each central spindle position
The central high pressure electrode in each reaction tube set can be connect with power supply respectively;It is set to each of each central spindle position
Central high pressure electrode in reaction tube can also be connected in parallel in the inner cylinder of the reaction member, then each by what is be connected in parallel
A central high pressure electrode is connect with power supply.
According to the first preferred embodiment, in the reaction of low temperature plasma device, the block media
At least partly side wall for forming each reaction tube makes at least partly described block media around the central high pressure electrode.
It is highly preferred that the side wall of each reaction tube is all formed by the block media.
According to another preferred embodiment, in the reaction of low temperature plasma device, each described anti-
Ying Guanzhong, the block media is arranged on at least partly outer surface of the central high pressure electrode, so that being extending at least partially into
Be enclosed with the block media on the outer surface of central high pressure electrode in the inner cylinder and the grounding electrode formed it is each
At least partly side wall of the reaction tube.
In plasma system of the invention, particularly, in the plasma reactor, collet core structure is set
Meter, enables to heat-conducting medium to circulate in shell, entire reactor can be made to maintain one while guaranteeing strength of discharge
Determine in temperature range, makes the sulphur generated outflow reactor in liquid form, hydrogen sulfide can effectively be avoided to decompose the sulphur generated
Sulphur solidification can be such that this decomposable process continues, stable realization long-term operation while reaching higher conversion ratio.
The aforementioned setting position in relation to block media and grounding electrode is conducive to the high-power equal of reaction system of the invention
Even electric discharge.About between block media and grounding electrode fixed form or block media and grounding electrode with it is interior
The fixed form of barrel, the present invention do not require particularly, those skilled in the art can according to formed block media, inner cylinder and
The material of grounding electrode selects suitable fixed form, and there is no particular limitation to this by the present invention.
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, in the plasma reactor, the material for forming the block media is electrically insulating material, more excellent
Form slection is selected from least one of glass, ceramics, enamel, polytetrafluoroethylene (PTFE) and mica at the material of the block media.It is described
Glass can be quartz glass or hard glass.The material for forming the block media can also have high voltage electrical isolation to be other
Metal and nonmetallic composite of design etc..The ceramics can be aluminium oxide ceramics.
It preferably, further include ground line in the plasma reactor, the outer of the outer cylinder is arranged in described be grounded
On side wall, and one end is electrically connected with the grounding electrode on the side wall of each reaction tube.
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.
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 of the invention and the ratio between the aperture of the product exit can be (0.1~120):
1。
Ratio between the length of the reaction tube of the invention and the internal diameter of the reaction tube can be (0.5~500):
1。
Under preferable case, in the plasma reactor, the product gas outlet setting is in all electric discharges
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 plasma reactor, the heat-conducting medium entrance and heat-conducting medium outlet difference
The lower part and top of the outer cylinder are set.
In the present invention, it is mainly used for that vulcanization hydroperoxide decomposition reaction occurs in the inner cylinder, and the outer cylinder is mainly used for tieing up
The required temperature of plasma reactor is held, therefore, those skilled in the art can adjust according to the purposes and select suitably
Size ratio between inner barrel and outer barrel.
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
On the side wall that the inner cylinder is set or when forming at least partly side wall of each reaction tube, enable to using this
When the plasma system that invention provides 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
Expect in the mechanical impurity selected from graphite rod, graphite-pipe, graphite powder, metal bar, metal tube, metal powder and conductive powder body at least
It is a kind of.The metal bar, metal tube may include elemental metals stick, alloying metal stick, elemental metals pipe, alloying metal pipe.This
The material of the formation central high pressure electrode of invention, which has, to be the rodlike and tubular material of other conductive energy.
The present invention can by the inner sidewall of the lateral wall of the inner cylinder in plasma reactor and the outer cylinder it
Between region introduce heat-conducting medium and make the temperature for the plasma reactor for having jacket structured maintain such as 119~
Between 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 plasma reactor of the invention can catalysed curing hydrogen resolve into elemental sulfur and hydrogen
The catalyst of gas, the catalyst are preferably seated in the inner cylinder of the plasma reactor.The present invention is to the catalyst
Admission space and filling type do not require particularly, about the type of catalyst, for example, can for CN102408095A,
In catalyst disclosed in CN101590410A and CN103495427A any one or it is a variety of.
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 containing 1 or 2 or more plasma reactor in the plasma reaction unit of the invention.
The preferred embodiment of present invention plasma reactor decomposing hydrogen sulfide above-mentioned presented below:
It is passed through nitrogen into the inner cylinder of plasma reactor from reactor inlet, to remove the air in region of discharge,
And gas is drawn from product exit.Meanwhile heat-conducting medium, the heat-conducting medium of introducing are introduced into outer cylinder from heat-conducting medium entrance
It exports and draws from heat-conducting medium.The temperature of heat-conducting medium remains the temperature of system response needs.Then from reactor inlet to
The unstripped gas containing hydrogen sulfide is passed through in the inner cylinder of plasma reactor, unstripped gas is full of in each reaction tube, to unstripped gas
Levelling surely after connect high voltage power supply, by adjust voltage and frequency make to be formed between central high pressure electrode and grounding electrode etc. from
Daughter electric discharge field.Hydrogen sulfide gas is ionized in region of discharge, is decomposed into hydrogen and elemental sulfur, the elemental sulfur edge for generation of discharging
Inner tube wall slowly flows down, and flows out from product exit.
Preferably, according to logistics direction, gas supply-distribution unit, plasma is successively contained in the plasma system
Reaction member and product separative unit, and contain plasma electrical source and the plasma in the plasma reaction unit
Reactor.
Under preferable case, hydrogen sulfide cycling element is also contained in the 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.
It is highly preferred that in the hydrogen sulfide cycling element containing for absorb hydrogen sulfide amine absorption tower and be used for so that
The Analytic Tower of hydrogen sulfide parsing.
Preferably, containing for will be from the gaseous substance of the plasma reaction unit in the product separative unit
The gas-liquid separator of gas-liquid separation is carried out with liquid phase substance, and optionally contains particle clarifier and/or carrier-gas separator;It is described
Particle clarifier is for carrying out further separation for the first gaseous material that be obtained by the gas-liquid separator separates to obtain the
Two gaseous materials and residual sulfur solid and the carrier-gas separator are used for first gaseous material or second gaseous state
The carrier gas optionally contained in substance is separated with hydrogen.
Under preferable case, distribution equipment and mixer are contained in the gas supply-distribution unit, the distribution equipment is used for will
The unstripped gas is dispensed on demand with carrier gas and the mixer is for will be from the unstripped gas and load of the distribution equipment
Gas is mixed to obtain the reactant in the plasma reactor for entering the plasma reaction unit.
Particularly, the hydrogen sulfide cycling element of the invention can be attached in the product separative unit, also, excellent
In the case of choosing, the connection type of the product separative unit and the hydrogen sulfide cycling element includes: the product separative unit
In gas-liquid separator connect with the plasma reaction unit by pipeline so that from the plasma reaction unit
Gas-phase product and liquid phase sulphur simple substance be able to enter in the gas-liquid separator separation to obtain the first gaseous material and liquid respectively
First gaseous material is optionally introduced in particle clarifier and obtains residual solid sulphur and the with further separation by body sulphur
Two gaseous materials, the liquid sulfur and the residual solid sulphur can draw plasma system of the invention by pipeline.
Further, the hydrogen sulfide cycling element is connect by pipeline with the product separative unit, so that the second gaseous state object
Matter can by pipeline enter the hydrogen sulfide cycling element in amine absorption tower in, with obtain respectively vulcanisation hydrogen and
Sulfide hydrogen liquid, the vulcanisation hydrogen, which optionally passes through pipeline and enters in carrier-gas separator, separates wherein load that may be present
Gas, to obtain hydrogeneous crude product, the hydrogeneous crude product, which can according to need, further to be purified;The sulfide hydrogen liquid
It is introduced in Analytic Tower by pipeline and parses hydrogen sulfide gas to be recycled to the gas supply-distribution unit or the plasma
Reaction member.
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 can be recovered.
A kind of structure of preferred embodiment of plasma reactor of the invention is provided below in conjunction with Fig. 1,
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, also, contains in the inner cylinder 1
There are at least two reaction tubes 14 being set side by side, the top and bottom of each reaction tube 14, which respectively correspond, to be communicated, so that by
The raw material that the reactor inlet 11 enters can have respectively entered in each reaction tube 14, and make each described anti-
The product that should be generated in pipe 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 formed respectively
At least partly side wall or the grounding electrode 4 of a reaction tube 14 are circumferentially positioned at each reaction tube 14 respectively
On side wall;
Block media, at least partly side wall that the block media forms each reaction tube 14 make at least partly institute
Block media is stated around the central high pressure electrode 3;Or the block media is circumferentially positioned at each reaction tube 14
On inner sidewall;
In each reaction tube 14, the setting position of the block media makes the central high pressure electrode and described
Region of discharge between grounding electrode is by the block media interval.
The knot of another preferred embodiment of plasma reactor 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, also, contains in the inner cylinder 1
There are at least two reaction tubes 14 being set side by side, the top and bottom of each reaction tube 14, which respectively correspond, to be communicated, so that by
The raw material that the reactor inlet 11 enters can have respectively entered in each reaction tube 14, and make each described anti-
The product that should be generated in pipe 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 formed respectively
At least partly side wall of a reaction tube 14;
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;
In each reaction tube 14, the setting position of the block media makes the central high pressure electrode and described
Region of discharge between grounding electrode is by the block media interval.
In fig. 1 and 2, plasma reactor preferably of the invention also has the feature that
Preferably, in each reaction tube 14, lateral wall and the grounding electrode of the central high pressure electrode 3
The distance between inner sidewall is d1 and the block media 6 with a thickness of D1, L1=d1-D1, L1With the length L of region of discharge2
Between proportionate relationship be L1: L2=1:(0.5~6000), more preferable L1: L2=1:(2~3000).
Under preferable case, in each reaction tube 14, 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 outer cylinder 2 is arranged in the ground line 5
On lateral wall, and one end is electrically connected with the grounding electrode 4 on the side wall of 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.It is highly preferred that the product exit includes product gas outlet 12 and liquid product outlet 13, and
The lower part of the inner cylinder 1 is arranged in the product gas outlet 12 and the liquid product outlet 13 is arranged in the inner cylinder 1
Bottom.
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.
A kind of process of preferred embodiment of plasma system of the invention is provided below in conjunction with Fig. 3, is had
Body:
Contain the gas supply-distribution unit A, plasma reaction list for passing sequentially through pipeline connection in the plasma system
First B, product separative unit and hydrogen sulfide cycling element C contain plasma reactor B1 in the plasma reaction unit
With plasma electrical source (not shown).Under preferable case, the plasma reactor B1 has structure shown in fig. 1 or fig. 2.
Also, it is preferred that containing multiple plasma reactor B1 in the plasma reaction unit B.
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
Plasma reactor B1 in carry out vulcanization hydroperoxide decomposition reaction, the product after reaction enters product separative unit and hydrogen sulfide follows
In ring 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 enters in sulphur memory C6, the first gaseous material obtained after gas-liquid separation enter in particle clarifier C2 carry out into
The separation of one step, the solid sulfur that further separation obtains can also enter in sulphur memory C6.By in the particle clarifier C2
The second gaseous material obtained enters in amine absorption tower C3 to obtain vulcanisation hydrogen and sulfide hydrogen liquid (amine respectively
Liquid), the preferably described vulcanisation hydrogen, which enters in carrier-gas separator C5, separates wherein carrier gas that may be present, to be contained
The hydrogeneous crude product of a large amount of hydrogen.It is preferred that aforementioned amine liquid, which is introduced in Analytic Tower C4, parses hydrogen sulfide gas (referred to as desorption sulphur
Change hydrogen), the hydrogen sulfide gas for parsing acquisition is recycled back in the gas supply-distribution unit A1 by pipeline.
The method of plasma decomposing hydrogen sulfide provided by the invention has the advantages that following specific:
(1) present invention provides specific discharging condition and specific vulcanization hydroperoxide decomposition reaction condition enables to hydrogen sulfide
Conversion ratio significantly improves;
(2) under preferable case, since using plasma reactor carries out the decomposition of hydrogen sulfide, and the reactor uses gold
Category, alloy or other conductive solids materials are as grounding electrode, and compared with liquid grounding electrode, such grounding electrode cooperates this hair
The micro discharge electric current that electric discharge generates when bright specified conditions and structure of reactor is bigger, is more advantageous to the electric discharge point of hydrogen sulfide molecule
Solution reaction.
(3) under preferable case, since using plasma reactor carries out the decomposition of hydrogen sulfide, and reactor ground connection is electric
Setting is jacket structured on the outside of pole, can carry out temperature control to reactor by heat-conducting medium temperature in control collet, can make sulphur
Change hydrogen electric discharge decomposes the sulphur generated and smoothly flows out region of discharge, avoids sulphur frozen plug reactor, makes to discharge continually and steadily
It carries out.
(4) under preferable case, since using plasma reactor carries out the decomposition of hydrogen sulfide, and the reactor is preferably controlled
L processed1With L2Between proportionate relationship are as follows: L1: L2=1:(0.5~6000), more preferable L1: L2=1:(2~3000), complex reaction
The structure of device and specific discharging condition and decomposition condition, enable to the conversion ratio of hydrogen sulfide to significantly improve and decompose energy consumption
It 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, the volume of the reaction unit inner cylinder of remaining embodiment
It can be calculated and be obtained according to corresponding data.