CN109264671A - Plasma spray coating film cooperates with DBD catalytic methane dry reforming device and method - Google Patents
Plasma spray coating film cooperates with DBD catalytic methane dry reforming device and method Download PDFInfo
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- CN109264671A CN109264671A CN201810960123.8A CN201810960123A CN109264671A CN 109264671 A CN109264671 A CN 109264671A CN 201810960123 A CN201810960123 A CN 201810960123A CN 109264671 A CN109264671 A CN 109264671A
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- 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
- C01B3/32—Production of hydrogen or of gaseous mixtures containing a substantial proportion of hydrogen by reaction of gaseous or liquid organic compounds with gasifying agents, e.g. water, carbon dioxide, air
- C01B3/34—Production of hydrogen or of gaseous mixtures containing a substantial proportion of hydrogen by reaction of gaseous or liquid organic compounds with gasifying agents, e.g. water, carbon dioxide, air by reaction of hydrocarbons with gasifying agents
- C01B3/342—Production of hydrogen or of gaseous mixtures containing a substantial proportion of hydrogen by reaction of gaseous or liquid organic compounds with gasifying agents, e.g. water, carbon dioxide, air by reaction of hydrocarbons with gasifying agents with the aid of electrical means, electromagnetic or mechanical vibrations, or particle radiations
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- C01B2203/00—Integrated processes for the production of hydrogen or synthesis gas
- C01B2203/02—Processes for making hydrogen or synthesis gas
- C01B2203/0205—Processes for making hydrogen or synthesis gas containing a reforming step
- C01B2203/0227—Processes for making hydrogen or synthesis gas containing a reforming step containing a catalytic reforming step
- C01B2203/0238—Processes for making hydrogen or synthesis gas containing a reforming step containing a catalytic reforming step the reforming step being a carbon dioxide reforming step
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- C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
- C01B2203/00—Integrated processes for the production of hydrogen or synthesis gas
- C01B2203/10—Catalysts for performing the hydrogen forming reactions
- C01B2203/1041—Composition of the catalyst
- C01B2203/1047—Group VIII metal catalysts
- C01B2203/1064—Platinum group metal catalysts
- C01B2203/107—Platinum catalysts
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- C01B2203/00—Integrated processes for the production of hydrogen or synthesis gas
- C01B2203/12—Feeding the process for making hydrogen or synthesis gas
- C01B2203/1205—Composition of the feed
- C01B2203/1211—Organic compounds or organic mixtures used in the process for making hydrogen or synthesis gas
- C01B2203/1235—Hydrocarbons
- C01B2203/1241—Natural gas or methane
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- Y02P20/00—Technologies relating to chemical industry
- Y02P20/50—Improvements relating to the production of bulk chemicals
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Abstract
The invention discloses a kind of plasma spray coating films to cooperate with DBD catalytic methane dry weight engagement positions, comprising: pulse generating unit is made of triggering box and the pulse power connecting with triggering box；DBD reactor is made of electrode stem, DBD quartz ampoule, copper mesh and polytetrafluoroethylene (PTFE) firmware, with the TiO of plasma spray coating source spraying on electrode stem2Film；Gas generation apparatus is made of two gas cylinders, two mass flow control meters, standing current equalizer and gas circuit A.The present invention also provides a kind of ionomer spray films to cooperate with DBD catalytic methane dry weight adjusting method.Beneficial effects of the present invention: realizing photocatalysis film preparation using atmospheric pressure plasma spraying source and binding medium barrier discharge (DBD) plasma carries out plasma-photocatalysis and cooperates with reforming methane, improves gas conversions, synthesis gas yield and energy utilization efficiency.
Description
Technical field
The present invention relates to greenhouse gases transformation technology fields, cooperate in particular to a kind of plasma spray coating film
DBD catalytic methane dry reforming device and method.
Background technique
What high-grade energy was produced in greenhouse gases conversion is the research hotspot that current clean energy resource utilizes field, wherein methane
Dry reforming technology can be simultaneously by two kinds of greenhouse gases (CH4And CO2) resource utilization, and become research heat both domestic and external
Point.At present in industrial application based on traditional thermocatalytic reforming method, J.H.Park etc. uses bimetallic catalyst Co Zn/
ZrO2Dry weight is carried out to methane to realize effective conversion (Park J H, Yeo S, Kang the T J, et of greenhouse gases
al.Effect of Zn promoter on catalytic activity and stability of Co/
ZrO2catalyst for dry reforming of CH4[J].Journal of CO2Utilization,2018,23:10-
19.).Application publication number is the patent of CN 107073427A, propose it is a kind of for gas renormalizing and prepare synthesis gas or
The shell-tube type reactor and its application method of hydrogen, wherein the reactor includes Hydrogen Separation film, core reaction device and is used for
The heat exchanger of heating, while catalyst filling can effectively improve operating efficiency in the reactor enclosure body, obtain high-purity
Hydrogen and collection carbon dioxide.Although current conventional high-temperature high-pressure catalytic reforming technique technique can be realized higher transformation efficiency
And selectivity, but this method still has the problems such as process is complicated, equipment cost is high, catalyst easy in inactivation, and low-temperature plasma
Body is a kind of effective means that can be activated in a mild condition using the high activity particle gas molecule stable to chemical property,
Feasible way is provided to solve the above problems.A.Ozkan et al. realizes greenhouse gas under temperate condition using DBD plasma
The effective activation and synthesis gas of body are produced, and the synthesis gas produced can be used as F- T synthesis and prepare the raw material of other industrial chemicals
(Ozkan A,Dufour T,Arnoult G,et al.CO2-CH4,conversion and syngas formation at
atmospheric pressure using a multi-electrode dielectric barrier discharge[J]
.Journal of CO2Utilization,2015,9:74-81.).However due in DBD system electron density it is lower,
The yield of gas conversions and synthesis gas is not high, and in order to further increase its changing effect, many scholars introduce catalyst
This purpose is realized to DBD reforming system.D.Mei et al. has carried out DBD plasma and Ni/ γ-Al2O3Catalyst collaboration
Methane dry reforming reaction under effect, successfully by CH4And CO2Conversion ratio be respectively increased 2% (Mei D, Ashford B,
He Y,et al.Plasma-catalytic reforming of biogas over supported Ni catalysts
in a dielectric barrier discharge reactor:Effect of catalyst supports[J]
.Plasma Processes&Polymers,2016,14.).It is that a kind of promoted turns that DBD plasma is combined with catalyst
Change the effective ways of performance, but current research mostly uses the filling of spherical or strip catalyst, therefore catalyst occupies electric discharge
Space causes gas residence time to reduce, and has seriously affected treatment effeciency and changing effect.
On the other hand, in recent years in waste gas pollution control and treatment field Photocatalitic Technique of Semiconductor due to have low energy consumption, it is pollution-free,
Mechanism is simple, mild condition, it is at low cost many advantages, such as and the extensive concern by researchers at home and abroad.However tradition is partly led
The problems such as that there are spectral response ranges is narrow for body catalyst, electrons and holes are easily compound, carrier utilization efficiency is low.On solving
Problem is stated, is urged by the way that the noble metal granule of nano-scale to be supported on semiconductor catalyst to the surface plasma light realized
Change technology causes the highest attention of people in the recent period.It is numerous studies have shown that plasma technique not only can effectively substitute tradition
Driving source of the ultraviolet source as semiconductor light-catalyst, while being capable of providing a large amount of high energy electron and stronger electromagnetic field ring
Border can effectively overcome many weakness of conventional ultra-violet photocatalysis；It introduces in plasma exhaust-gas treatment system and partly leads simultaneously
Body photocatalytic system can greatly improve the conversion of goal response object, while can also efficiently use the light radiation in plasma production
Energy efficiency is promoted, the mutual supplement with each other's advantages both realized.
Application publication number is the patent of 106607015 A of CN, has applied for a kind of nanometer titanium dioxide for preparing double particle diameter distributions
The method of titanium photochemical catalyst, this method include that organic titanate is dissolved in alcoholic solution, while stirring be added dropwise polyacrylic acid and
The aqueous solution of polyvinylpyrrolidone obtains transparent TiO 2 sol；Further add commodity nano titanium dioxide powder
It is stirred by ultrasonic to obtain translucent TiO 2 sol；Finally to the translucent colloidal tio 2 be spray-dried from
And the nano titanium dioxide photocatalyst of double particle diameter distributions is made.The active catalyst can stablize placement 6 months or more, and can be
Efficient degradation is carried out to organic matter under sunlight, the results showed that compared with existing goods titanium deoxide catalyst, degradation efficiency is mentioned
Gao Liao.But the disadvantages of traditional method for preparing catalyst is there are high operation requirements, controllability is poor, later period coating is inconvenient.
Application publication number provides a kind of vacuum plasma coating apparatus for the patent of 106637120 A of CN, comprising vacuum chamber and with
Its radio-frequency power supply being connected, vacuum chamber up/down end are respectively equipped with target/for holding the anode of sample, Anodic and rotation
Mechanism connection.Plasma needle one end is injected in vacuum chamber by movable sealing structure from vacuum chamber upper end, and the other end and control pass
Defeated system is connected, to realize parametric control and intelligent automatic plated film, but structure is complicated and there is load for radio-frequency power supply
With problem, while vacuum environment requires to further improve production cost.
From the point of view of to sum up, on the one hand traditional methane dry reforming needs technically based on thermocatalytic to entire reaction cavity
It is heated, exists simultaneously the disadvantages of energy consumption is high, temperature is high, the device is complicated.And using plasma technology carries out weight to methane
It is whole that equipment cost, process simplification, such as DBD plasma can be effectively reduced.DBD corona treatment methane is deposited at present
In the disadvantage that conversion performance is poor, can be effectively improved by combined catalyst；However it DBD reactor filler particles or spherical urges
When agent, effective discharge volume can be reduced and reduce gas residence time, cause improvement unobvious.On the other hand, at present
Through the TiO that can prepare high activity and high stability2Powder photocatalyst, however there are high operation requirements, controllability is poor, the later period
Coating procedure it is cumbersome and inconvenient.
Summary of the invention
To solve the above problems, the purpose of the present invention is to provide a kind of plasma spray coating film collaboration DBD to be catalyzed first
Alkane dry reforming device and method realizes that plasma-photocatalysis synergy carries out methane reforming, improves gas conversions, closes
At gas yield and energy utilization efficiency.
The present invention provides a kind of plasma spray coating films to cooperate with DBD catalytic methane dry weight engagement positions, comprising:
Pulse generating unit is made of triggering box and the pulse power connecting with the triggering box, the pulse electricity
Source is equipped with the low pressure connecting line of high-pressure connection line and ground connection；
DBD reactor is made of electrode stem, DBD quartz ampoule, copper mesh and polytetrafluoroethylene (PTFE) firmware, in the electrode stem
It sets in the DBD quartz ampoule and is placed on insulating support, the electrode stem is connected to the high-pressure connection line, the electrode stem
The upper TiO with the spraying of plasma spray coating source2Film, DBD quartz ampoule both ends are fixed with the polytetrafluoroethylene (PTFE) firmware
Sealing, the copper mesh are wrapped in outside the DBD quartz ampoule and are grounded；
Gas generation apparatus is made of, institute two gas cylinders, two mass flow control meters, standing current equalizer and gas circuit A
It states two gas cylinders and is respectively connected to described two mass flow control meters, the tow channel gas of described two mass flow control meter outputs
Body is connected to the standing current equalizer and is mixed, and the mixed gas for standing current equalizer output is connected to institute by the gas circuit A
State DBD quartz ampoule.
As further improvement of the invention, the high-field electrode in the plasma spray coating source is connected to the high pressure connection
Line, the low-field electrode in the plasma spray coating source are connected to the low pressure connecting line, and described two gas cylinders are respectively connected to described
The gas all the way of two mass flow control meters, a mass flow control meter output is connected to by gas circuit B as excited gas
The access of gas all the way of the plasma spray coating source gas entrance, the control meter output of another mass flow is equipped with predecessor
TEOS+HAuCl4Air-blowing bottle after be connected to the plasma spray coating source gas entrance as carrier gas；
Plasma spray coating source electric discharge generates atmospheric pressure plasma, and by predecessor TEOS+HAuCl4It is sprayed on
TiO is formed on the electrode stem2Film.
Improved as of the invention further, the plasma spray coating source be DBD plasma, jet plasma,
Slide one of arc plasma or Helicon wave plasma.
Improved as of the invention further, the pulse power be high voltage nanosecond pulse power supply or microsecond pulse power supply or
High frequency and high voltage power supply, the voltage magnitude of the pulse power are 13kV, and frequency is 3~10kHz.
It is respectively methane and carbon dioxide in described two gas cylinders as further improvement of the invention, two-way gas
Flow velocity is 20~50sccm.
Improved as of the invention further, the pulse power be high voltage nanosecond pulse power supply or microsecond pulse power supply or
High frequency and high voltage power supply, the voltage magnitude of the pulse power are 5~10kV, and frequency is 1~10kHz；
It is argon gas, nitrogen or helium in described two gas cylinders, the flow of excited gas is 1~5slm, the flow of carrier gas
For 20~100sccm.
As further improvement of the invention, the electrode stem is made of stainless steel, diameter 17.6mm, and length is
200mm；
The DBD quartz pipe outside diameter is 25.1mm, internal diameter 22.1mm, length 200mm；
The copper mesh length is 100mm.
The present invention also provides a kind of plasma spray coating films to cooperate with DBD catalytic methane dry weight adjusting method, including following
Step:
Step 1, the electrode stem of DBD reactor is placed on insulating support；
Step 2, building plasma spray coating source makes electrode stem described in its face, and the plasma spray coating source is swashed
It encourages, react predecessor and generates the intermediate product of the group containing Ti, and spray on the electrode stem, form TiO2Film；
Step 3, the cooling electrode stem, and overturn；
Step 4, DBD reactor is assembled:
The electrode stem is placed in DBD quartz ampoule, and solid with polytetrafluoroethylene (PTFE) firmware at DBD quartz ampoule both ends
Fixed sealing, copper mesh is wrapped in outside the DBD quartz ampoule, then the electrode stem is placed on the insulating support；
Step 5, the gas circuit of the DBD reactor work is connected:
Two gas cylinders are respectively connected to two mass flow control meters, the two-way gas of two mass flow control meter output
It is connected in the DBD quartz ampoule after standing current equalizer mixing by the gas circuit A, while checking the air-tightness of gas circuit；
Step 6, the circuit of the DBD reactor work is connected:
The electrode stem is connect, the copper mesh ground connection with the high-pressure connection line, while high-voltage probe, current line are set
Circle and digital oscilloscope monitor the voltage current waveform of the pulse power in real time, and will triggering box and pulse power company
It connects, the low pressure connecting line ground connection；
Step 7, trigger signal is arranged in adjusting gas flow, and triggering generates atmospheric dielectric barrier discharge plasma:
The flow of described two mass flow control meter control output gas is adjusted, two-way gas is in the standing current equalizer
Enter in the DBD quartz ampoule after mixing a period of time, power supply trigger signal is set, triggering electric discharge obtains stable atmospheric pressure and is situated between
Matter barrier discharge plasma；
Step 8, temperature is monitored using thermal infrared imager, after temperature reaches and stablizes, passes through gas chromatograph pair
The product of DBD reactor carries out on-line checking, can analyze product distribution.
As further improvement of the invention, two-way gas methane and carbon dioxide flow velocity is adjusted to 20~50sccm respectively,
Mixed gas 20min；
The voltage that the pulse power is arranged is 13kV, and rising edge is 150~500ns, and failing edge is 100~500ns, arteries and veins
Width is 0~500ns.
As further improvement of the invention, step 2 is specifically included:
Step 201, building plasma spray coating source makes electrode stem described in its face；
Step 202, the gas circuit of the plasma spray coating source work is connected:
Two gas cylinders are respectively connected to two mass flow control meters, the gas all the way of a mass flow control meter output
By being used as excited gas to be connected to the plasma spray coating source gas entrance, another quality after the gas circuit B of rubber hard tube
The access of gas all the way of flow control meter output is mounted with predecessor TEOS+HAuCl4Air-blowing bottle after be connected to institute again as carrier gas
Plasma spray coating source gas entrance is stated, while checking the air-tightness of gas circuit；
Step 203, the circuit of the plasma spray coating source work is connected:
The high-pressure connection line of the high-field electrode in the plasma spray coating source and the pulse power is connected, low-field electrode and institute
The low pressure connecting line connect and ground of the pulse power is stated, while high-voltage probe, current coil and digital oscilloscope are set and supervised in real time
The voltage current waveform of the pulse power is controlled, and triggering box is connect with the pulse power；
Step 204, adjusting gas flow and trigger signal is set, triggering generates atmospheric pressure plasma spraying source and simultaneously formed
TiO2Film:
The flow of described two mass flow control meter control output gas is adjusted, excited gas excites plasma all the way
Predecessor is taken out of and is passed into the plasma spray coating source again by body, another way carrier gas, and power supply trigger signal, triggering electric discharge is arranged
Atmosphere pressure plasma jet flow is obtained, meanwhile, predecessor is reacted by atmosphere pressure plasma jet flow and generates group containing Ti
Intermediate product, and spray on the electrode stem, form TiO2Film.
The invention has the benefit that
The present invention combines two kinds of plasma techniques, using atmospheric pressure plasma spraying technology by surface plasma
Body semiconductor light-catalyst is introduced into electrode structure in the form of plated film, utilizes surface plasma Photocatalytic enhancement technology and Jie
Matter barrier discharge plasma technique has complementary advantages, and this method utilizes plasma-photocatalysis synergistic effect, to promote first
Transformation efficiency, target product selectivity and the Technical Economy of alkane reforming reaction, can effectively be extended to industrialized production
In.
Compared to the reaction unit of other catalyst fillings, the present invention can obtain bigger discharge volume and more stop
The time is stayed, to make gas sufficiently participate in reacting, to obtain higher gas conversions, synthesis gas yield and energy utilization effect
Rate.
Detailed description of the invention
Fig. 1 is that atmospheric pressure plasma spraying source of the invention sprays TiO2Film apparatus schematic diagram；
Fig. 2 is atmospheric dielectric barrier discharge plasma methane reformer schematic diagram of the invention；
Fig. 3 is that a kind of process of the method for jet plasma deposition film concerted catalysis methane dry reforming of the invention is shown
It is intended to.
In figure, 1, triggering box；2, the pulse power；3, high-pressure connection line；4, plasma spray coating source；5, gas circuit B；6, quality
Flow control meter；7, gas cylinder；8, air valve；9, electrode stem；10, insulating support；11, low pressure connecting line；12, air-blowing bottle；13, it stands
Current equalizer；14, DBD reactor；15 ground；16, DBD quartz ampoule；17, copper mesh；18, polytetrafluoroethylene (PTFE) firmware；20, gas circuit A.
Specific embodiment
The present invention is described in further detail below by specific embodiment and in conjunction with attached drawing.
A kind of plasma spray coating film of embodiment 1, the embodiment of the present invention cooperates with DBD catalytic methane dry weight engagement positions,
Make predecessor TEOS+HAuCl first with atmosphere pressure plasma jet flow4Group containing Ti is reacted and generates, and on electrode stem
Form one layer of TiO2Film；It will assemble after electrode stem cooling with DBD reactor other assemblies, put using atmosphere medium blocking again
Electro-plasma cooperates with reforming methane/carbon dioxide with photochemical catalyst.
For the structure convenient for simplifying whole device, spray to form TiO in atmosphere pressure plasma jet flow2When film and atmosphere
When dielectric barrier discharge plasma being pressed to carry out methane reforming, it is all made of identical pulse generating unit and gas generation apparatus.
Difference is, sprays to form TiO in atmosphere pressure plasma jet flow2When film, plasma spray coating source 4 and pulse generation are filled
It sets and is connected with gas generation apparatus, when atmospheric dielectric barrier discharge plasma carries out methane reforming, by DBD reactor 14
Connect with pulse generating unit and gas generation apparatus, meanwhile, two kinds reaction when gas generation apparatus be slightly different, below in detail
It states.
As shown in Figure 1, atmospheric pressure plasma spraying source sprays TiO2The connection structure of film apparatus is as follows:
Pulse generating unit is made of triggering box 1 and the pulse power 2 connecting with triggering box 1, and the pulse power 2 is equipped with
High-pressure connection line 3 and low pressure connecting line 11, low pressure connecting line 11 are grounded.Wherein, the pulse power 2 be high voltage nanosecond pulse power supply or
Microsecond pulse power supply or high frequency and high voltage power supply, it is preferred to use high-voltage pulse power source.
Gas generation apparatus counts 6 by two gas cylinders, 7, two mass flow controls, predecessor TEOS+HAuCl is housed4Drum
Gas cylinder 12 and gas circuit B 5 are formed.Wherein, air-blowing bottle 12 is the explosion-proof type glass air-blowing bottle that capacity is 500mL, wherein being equipped with
TEOS+HAuCl4.It is provided with valve 8 on two gas cylinders 7, convenient for opening and closing the conveying of gas.
The high-field electrode in plasma spray coating source 4 is connected to high-pressure connection line 3, and the low-field electrode in plasma spray coating source 4 connects
To low pressure connecting line 11, two gas cylinders 7 are respectively connected to two mass flow control meters 6,6 output of mass flow control meter
Gas all the way 4 gas access of plasma spray coating source is connected to as excited gas by gas circuit B 5, another mass flow control
The access of gas all the way of 6 output of system meter is equipped with predecessor TEOS+HAuCl4Air-blowing bottle 12 after be connected to plasma as carrier gas
4 gas access of spraying source.
Electric discharge generate atmosphere pressure plasma jet flow when: the voltage magnitude of the pulse power 2 be 5~10kV, frequency be 1~
10kHz.It can be argon gas, nitrogen or helium, the two-way gas exported after 6 speed regulation of mass flow control meter in two gas cylinders 7
In, the flow of excited gas is 1~5slm, and the flow of carrier gas is 20~100sccm.
According to the trigger signal of the pulse power 2, the electric discharge of plasma spray coating source 4 generates atmospheric pressure plasma, by big
Atmospheric pressure plasma jet stream makes predecessor TEOS+HAuCl4The intermediate product of the group containing Ti is reacted and generated, and is sprayed on electrode
TiO is formed on bar 92Film.
As shown in Fig. 2, the connection structure of atmospheric dielectric barrier discharge plasma methane reformer is as follows:
Pulse generating unit is for example aforementioned.
DBD reactor 14 is made of electrode stem 9, DBD quartz ampoule 16, copper mesh 17 and polytetrafluoroethylene (PTFE) firmware 18, electrode stem 9
It being built in DBD quartz ampoule 16 and is placed on insulating support 10, electrode stem 9 is connected to high-pressure connection line 3, and 16 liang of DBD quartz ampoule
End 18 fixing seal of polytetrafluoroethylene (PTFE) firmware, copper mesh 17 is wrapped in outside DBD quartz ampoule 16 and ground connection 15, the positive equity of electrode stem 9
Ionomer spray source 4 makes the TiO sprayed thereon with plasma spray coating source 42Film.Specifically, electrode stem 9 is anti-as DBD
The high-field electrode for answering device 14, is made of stainless steel, diameter 17.6mm, length 200mm.16 outer diameter of DBD quartz ampoule is
25.1mm, internal diameter 22.1mm, length 200mm.17 length of copper mesh is 100mm.Electrode stem 9, DBD quartz ampoule 16, copper mesh 17
DBD reactor 14 is formed with polytetrafluoroethylene (PTFE) firmware 18 4, when discharge excitation, electrode stem 9 connects high pressure, and copper mesh 17 is grounded.
Gas generation apparatus is slightly different, gentle by two gas cylinders 7, two mass flow control meters 6, standing current equalizers 13
Road A 20 is formed, and two gas cylinders 7 are respectively connected to two mass flow control meters 6, and two mass flow controls count the two of 6 outputs
Road gas is connected to standing current equalizer 13 and is mixed, and stands the mixed gas that current equalizer 13 exports and is connected to DBD by gas circuit A 20
Quartz ampoule 16.Air-blowing bottle 12 is eliminated, increases and stands current equalizer 13.
Plasma spray coating source 4 can be the plasma of DBD or jet stream or sliding arc or spiral waveshape.
When electric discharge generates atmospheric dielectric barrier discharge plasma: the voltage magnitude of the pulse power 2 is 13kV, frequency
For 3~10kHz.It is respectively methane and carbon dioxide in two gas cylinders 7, two-way gas is adjusted by mass flow control meter 6
Control, two-way gas are passed into DBD reactor after mixing through standing current equalizer 13 and are excited.The stream of two-way gas
Speed is 20~50sccm.
According to the trigger signal of the pulse power 2, atmospheric dielectric barrier discharge plasma and as photochemical catalyst
TiO2Catalysis reaction occurs for film, realizes methane dry reforming.
Dielectric barrier discharge plasma of the invention uses single tube mode (i.e. an electrode stem 9), and simple operations can also
To increase volume of plasma and gas residence time using multitube parallel or series connection, changing effect and efficiency are further increased.
Plasma spray coating film collaboration DBD catalysis process of the invention is not limited only to carry out methane reforming, can also use
In terms of the pollution administrations such as desulphurization denitration gas.
Embodiment 2, as shown in figure 3, a kind of jet plasma deposition film concerted catalysis methane dry reforming of the present invention
Method, comprising the following steps:
Step 1, the electrode stem 9 of DBD reactor 14 is placed on insulating support 10.
Step 2, building plasma spray coating source 4 makes its face electrode stem 9, and plasma spray coating source 4 is motivated, is made
Predecessor reacts and generates the intermediate product of the group containing Ti, and sprays on electrode stem 9, forms TiO2Film.In the step, etc.
Ionomer spray source 4 can be the plasma of DBD or jet stream or sliding arc or spiral waveshape.It specifically includes:
Step 201, building plasma spray coating source 4 makes its face electrode stem 9.
Step 202, two gas cylinders 7 gas circuit that connection plasma spray coating source 4 works: are respectively connected to two mass flows
Control meter 6, a mass flow control are used as excited gas after counting the gas circuit B 5 that the gas all the way that 6 export passes through rubber hard tube
Body is connected to 4 gas access of plasma spray coating source, before the access of gas all the way of 6 output of another mass flow control meter is mounted with
Drive object TEOS+HAuCl4Air-blowing bottle 12 after be connected to 4 gas access of plasma spray coating source again as carrier gas, while checking gas circuit
Air-tightness.
Step 203, the circuit that connection plasma spray coating source 4 works: by the high-field electrode and arteries and veins in plasma spray coating source 4
The high-pressure connection line 3 for rushing power supply 2 connects, and 11 connect and ground of low pressure connecting line of low-field electrode and the pulse power 2 is arranged simultaneously
The voltage current waveform of high-voltage probe, current coil and the digital oscilloscope real time monitoring pulse power 2, and will triggering box 1 and arteries and veins
Rush the connection of power supply 2.
Step 204, adjusting gas flow and trigger signal is set, triggering generates atmospheric pressure plasma spraying source and simultaneously formed
TiO2Film: adjusting the flow of two 6 control output gas of mass flow control meter, and a mass flow controls 6 output of meter
Excited gas excites plasma all the way, and predecessor is taken in the carrier gas all the way of 6 output of another mass flow control meter out of to be led to again
Entering to plasma spray coating source 4, power supply trigger signal is set, triggering electric discharge obtains atmosphere pressure plasma jet flow, meanwhile, pass through
Atmosphere pressure plasma jet flow reacts predecessor and generates the intermediate product of the group containing Ti, and sprays on electrode stem 9, is formed
TiO2Film.
Step 3, cooling electrode stem 9, and overturn.
Step 4, it assembles DBD reactor 14: electrode stem 9 being placed in DBD quartz ampoule 16, and at 16 liang of DBD quartz ampoule
End 18 fixing seal of polytetrafluoroethylene (PTFE) firmware, copper mesh 17 is wrapped in outside DBD quartz ampoule 16, then electrode stem 9 is placed on absolutely
On edge bracket 10.
Step 5, two gas cylinders 7 gas circuit that connection DBD reactor 14 works: are respectively connected to two mass flow control meters
6, the two-way gas of two 6 outputs of mass flow control meter is connected to DBD by gas circuit A 20 after standing current equalizer 13 and mixing
In quartz ampoule 16, while checking the air-tightness of gas circuit.Two-way gas methane and carbon dioxide flow velocity is adjusted to 20~50sccm respectively,
Mixed gas 20min, to ensure not having air residual in reactor and gas circuit.
Step 6, the circuit that connection DBD reactor 14 works: electrode stem 9 is connect with high-pressure connection line 3, copper mesh 17 is grounded
15, while the voltage current waveform of high-voltage probe, current coil and the digital oscilloscope real time monitoring pulse power 2 is set, and will
Triggering box 1 is connect with the pulse power 2, and low pressure connecting line 11 is grounded.
Step 7, trigger signal is arranged in adjusting gas flow, and triggering generates atmospheric dielectric barrier discharge plasma: adjusting
The flow of two 6 control output gas of mass flow control meter is saved, two-way gas enters DBD quartz after 1 mixing a period of time
In pipe 16, power supply trigger signal is set, triggering electric discharge obtains stable atmospheric dielectric barrier discharge plasma.Pulse is set
The voltage of power supply 2 is 13kV, and rising edge is 150~500ns, and failing edge is 100~500ns, and pulsewidth is 0~500ns, is put
Electricity, to obtain stable plasma.
Step 8, temperature is monitored using thermal infrared imager, after temperature reaches and stablizes, passes through gas chromatograph pair
The product of DBD reactor 14 carries out on-line checking, can analyze product distribution.
Plasma spray coating film of the invention cooperates with DBD catalytic methane dry weight adjusting method, utilizes atmospheric pressure plasma
Photocatalysis film preparation is realized in spraying source and binding medium barrier discharge (DBD) plasma carries out plasma-photocatalysis association
Same reforming methane is divided into two parts, and first part is that atmosphere pressure plasma jet flow realizes photocatalysis film build method, i.e., above-mentioned
Step 1-2 utilizes plasma chemical vapor chemical deposition (PECVD) catalyst precursors (TEOS+HAuCl4), thus in electrode stem
It is upper to form one layer of TiO with photocatalytic activity2Film, second part are that atmospheric pressure plasma cooperative photocatalysis agent carries out
Methane dry reforming, i.e. above-mentioned steps 3-8 are coated with the electrode stem of photochemical catalyst as in DBD plasma producing apparatus
High-field electrode realizes the processing to greenhouse gases and obtains synthesis gas.By atmospheric pressure plasma spraying technology and dielectric impedance
The method that discharge plasma combines realizes that Plasma catalyst synergistic effect carries out methane reforming.Pass through the expensive gold of nanometer
Coupling between the charge density wave and incident electromagnetic wave of the free electron on metal particles surface is generated propagates along metal surface
Surface plasma wave, energy is transferred in plasma (metal surface free electron) from photon, can effectively be widened
The spectral response range of semiconductor catalyst, while improving the utilization rate of visible light wave range.Meanwhile in noble metal and semiconductor industry
Schottky barrier can be generated on face, can effectively be captured the light induced electron of photoionization generation, effectively be prevented light induced electron and hole
It is compound.Simultaneously because coupling generate light induced electron have very high energy, when being moved to interface can directly into
Enter semiconductor conduction band, further promotes its redox property.Therefore, the plasma-photocatalysis Synergistic method can obtain
Preferable methane conversion performance.
The foregoing is only a preferred embodiment of the present invention, is not intended to restrict the invention, for the skill of this field
For art personnel, the invention may be variously modified and varied.All within the spirits and principles of the present invention, made any to repair
Change, equivalent replacement, improvement etc., should all be included in the protection scope of the present invention.
Claims (10)
1. a kind of plasma spray coating film cooperates with DBD catalytic methane dry weight engagement positions characterized by comprising
Pulse generating unit is made of, the arteries and veins triggering box (1) and the pulse power (2) connecting with triggering box (1)
Rush the low pressure connecting line (11) of power supply (2) equipped with high-pressure connection line (3) and ground connection；
DBD reactor (14), by electrode stem (9), DBD quartz ampoule (16), copper mesh (17) and polytetrafluoroethylene (PTFE) firmware (18) group
At the electrode stem (9) is built in the DBD quartz ampoule (16) and is placed on insulating support (10), the electrode stem (9)
It is connected to the high-pressure connection line (3), with the TiO of plasma spray coating source (4) spraying on the electrode stem (9)2Film, it is described
DBD quartz ampoule (16) both ends are wrapped in the DBD stone with polytetrafluoroethylene (PTFE) firmware (18) fixing seal, the copper mesh (17)
English pipe (16) outside and ground connection (15)；
Gas generation apparatus by two gas cylinders (7), two mass flow control meters (6), stands current equalizer (13) and gas circuit A
(20) it forms, described two gas cylinders (7) are respectively connected to described two mass flow control meters (6), described two mass flows
The two-way gas of control meter (6) output is connected to the standing current equalizer (13) and is mixed, standing current equalizer (13) output
Mixed gas the DBD quartz ampoule (16) is connected to by the gas circuit A (20).
2. plasma spray coating film according to claim 1 cooperates with DBD catalytic methane dry weight engagement positions, feature exists
In the high-field electrode of the plasma spray coating source (4) is connected to the high-pressure connection line (3), the plasma spray coating source (4)
Low-field electrode be connected to the low pressure connecting line (11), described two gas cylinders (7) are respectively connected to described two mass flow controls
System meter (6), the gas all the way of mass flow control meter (6) output are connected to by gas circuit B (5) as excited gas described etc.
The access of gas all the way of ionomer spray source (4) gas access, another mass flow control meter (6) output is equipped with predecessor
TEOS+HAuCl4Air-blowing bottle (12) be connected to plasma spray coating source (4) gas access as carrier gas afterwards；
The plasma spray coating source (4) electric discharge generates atmospheric pressure plasma, and by predecessor TEOS+HAuCl4It is sprayed on institute
It states and forms TiO on electrode stem (9)2Film.
3. plasma spray coating film according to claim 2 cooperates with DBD catalytic methane dry weight engagement positions, feature exists
In, the plasma spray coating source (4) be DBD plasma, jet plasma, sliding arc plasma or helicon etc. from
One of daughter.
4. plasma spray coating film according to claim 1 cooperates with DBD catalytic methane dry weight engagement positions, feature exists
In the pulse power (2) is high voltage nanosecond pulse power supply or microsecond pulse power supply or high frequency and high voltage power supply, the pulse
The voltage magnitude of power supply (2) is 13kV, and frequency is 3~10kHz；
It is respectively methane and carbon dioxide in described two gas cylinders (7), the flow velocity of two-way gas is 20~50sccm.
5. plasma spray coating film according to claim 2 cooperates with DBD catalytic methane dry weight engagement positions, feature exists
In the pulse power (2) is high voltage nanosecond pulse power supply or microsecond pulse power supply or high frequency and high voltage power supply, the pulse
The voltage magnitude of power supply (2) is 5~10kV, and frequency is 1~10kHz.
6. plasma spray coating film according to claim 2 cooperates with DBD catalytic methane dry weight engagement positions, feature exists
In interior described two gas cylinders (7) are argon gas, nitrogen or helium, and the flow of excited gas is 1~5slm, and the flow of carrier gas is
20~100sccm.
7. plasma spray coating film according to claim 1 cooperates with DBD catalytic methane dry weight engagement positions, feature exists
In the electrode stem (9) is made of stainless steel, diameter 17.6mm, length 200mm；
DBD quartz ampoule (16) outer diameter is 25.1mm, internal diameter 22.1mm, length 200mm；
Copper mesh (17) length is 100mm.
8. a kind of plasma spray coating film cooperates with DBD catalytic methane dry weight adjusting method, which comprises the following steps:
Step 1, the electrode stem (9) of DBD reactor (14) is placed on insulating support (10)；
Step 2, building plasma spray coating source (4) makes electrode stem described in its face (9), by the plasma spray coating source (4)
It is motivated, react predecessor and generates the intermediate product of the group containing Ti, and sprayed on the electrode stem (9), formed
TiO2Film；
Step 3, the cooling electrode stem (9), and overturn；
Step 4, DBD reactor (14) are assembled:
The electrode stem (9) is placed in DBD quartz ampoule (16), and in DBD quartz ampoule (16) both ends polytetrafluoroethyl-ne
Copper mesh (17) is wrapped in the DBD quartz ampoule (16) outside by alkene firmware (18) fixing seal, then the electrode stem (9) are placed
On the insulating support (10)；
Step 5, the gas circuit of DBD reactor (14) work is connected:
Two gas cylinders (7) are respectively connected to two mass flow control meters (6), described two mass flow control meter (6) outputs
Two-way gas to be connected to the DBD quartz ampoule (16) by the gas circuit A (20) after standing current equalizer (13) mixing interior, together
When check gas circuit air-tightness；
Step 6, the circuit of DBD reactor (14) work is connected:
The electrode stem (9) is connect with the high-pressure connection line (3), the copper mesh (17) is grounded (15), while high pressure is arranged
Probe, current coil and digital oscilloscope monitor the voltage current waveform of the pulse power (2) in real time, and will trigger box (1)
It is connect with the pulse power (2), low pressure connecting line (11) ground connection；
Step 7, trigger signal is arranged in adjusting gas flow, and triggering generates atmospheric dielectric barrier discharge plasma:
The flow of described two mass flow control meter (6) control output gas is adjusted, two-way gas is in the standing current equalizer
(13) enter in the DBD quartz ampoule (16) after mixing a period of time, power supply trigger signal is set, triggering electric discharge obtains stable
Atmospheric dielectric barrier discharge plasma；
Step 8, temperature is monitored using thermal infrared imager, it is anti-to DBD by gas chromatograph after temperature reaches and stablizes
It answers the product of device (14) to carry out on-line checking, product distribution can be analyzed.
9. plasma spray coating film according to claim 8 cooperates with DBD catalytic methane dry weight adjusting method, feature exists
In two-way gas methane and carbon dioxide flow velocity is adjusted to 20~50sccm respectively, mixes gas 20min；
The voltage that the pulse power (2) is arranged is 13kV, and rising edge is 150~500ns, and failing edge is 100~500ns, arteries and veins
Width is 0~500ns.
10. plasma spray coating film according to claim 8 cooperates with DBD catalytic methane dry weight adjusting method, feature exists
In step 2 specifically includes:
Step 201, building plasma spray coating source (4) makes electrode stem described in its face (9)；
Step 202, the gas circuit of plasma spray coating source (4) work is connected:
Two gas cylinders (7) are respectively connected to two mass flow control meters (6), a mass flow control counts the one of (6) output
Road gas is connected to plasma spray coating source (4) gas as excited gas afterwards by the gas circuit B (5) of rubber hard tube and enters
Mouthful, the access of gas all the way of another mass flow control meter (6) output is mounted with predecessor TEOS+HAuCl4Air-blowing bottle
(12) it is connected to plasma spray coating source (4) gas access again as carrier gas afterwards, while checks the air-tightness of gas circuit；
Step 203, the circuit of plasma spray coating source (4) work is connected:
The high-field electrode of the plasma spray coating source (4) is connect with the high-pressure connection line (3) of the pulse power (2), low tension
Low pressure connecting line (11) connect and ground of pole and the pulse power (2), while high-voltage probe, current coil and number are set
Oscillograph monitors the voltage current waveform of the pulse power (2) in real time, and triggering box (1) is connected with the pulse power (2)
It connects；
Step 204, adjusting gas flow and trigger signal is set, triggering generates atmospheric pressure plasma spraying source and simultaneously forms TiO2
Film:
The flow of described two mass flow control meter (6) control output gas is adjusted, excited gas excites plasma all the way,
Predecessor is taken out of and is passed into the plasma spray coating source (4) again by another way carrier gas, and power supply trigger signal, triggering electric discharge is arranged
Atmospheric pressure plasma is obtained, meanwhile, predecessor is reacted by atmosphere pressure plasma jet flow and is generated in group containing Ti
Between product, and spray on the electrode stem (9), form TiO2Film.
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| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201810960123.8A CN109264671A (en) | 2018-08-22 | 2018-08-22 | Plasma spray coating film cooperates with DBD catalytic methane dry reforming device and method |
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| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201810960123.8A CN109264671A (en) | 2018-08-22 | 2018-08-22 | Plasma spray coating film cooperates with DBD catalytic methane dry reforming device and method |
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Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN110394127A (en) * | 2019-07-30 | 2019-11-01 | 徐州工程学院 | A kind of plasma couples the fluidized bed methane dry reforming reaction unit and method of ultraviolet light in situ |
| CN112710697A (en) * | 2020-12-23 | 2021-04-27 | 武汉理工大学 | High-controllable high-stability automatic sample introduction type photo-thermal catalytic reactor and testing method |
| CN114130327A (en) * | 2021-11-10 | 2022-03-04 | 中国人民解放军空军工程大学 | Gas reforming device based on nanosecond pulse rapid ionization wave |
-
2018
- 2018-08-22 CN CN201810960123.8A patent/CN109264671A/en active Pending
Cited By (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN110394127A (en) * | 2019-07-30 | 2019-11-01 | 徐州工程学院 | A kind of plasma couples the fluidized bed methane dry reforming reaction unit and method of ultraviolet light in situ |
| CN110394127B (en) * | 2019-07-30 | 2023-08-22 | 徐州工程学院 | Fluidized bed methane dry reforming reaction device and method with plasma in-situ coupled ultraviolet light |
| CN112710697A (en) * | 2020-12-23 | 2021-04-27 | 武汉理工大学 | High-controllable high-stability automatic sample introduction type photo-thermal catalytic reactor and testing method |
| CN114130327A (en) * | 2021-11-10 | 2022-03-04 | 中国人民解放军空军工程大学 | Gas reforming device based on nanosecond pulse rapid ionization wave |
| CN114130327B (en) * | 2021-11-10 | 2023-10-03 | 中国人民解放军空军工程大学 | Gas reforming device based on nanosecond pulse rapid ionization wave |
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Application publication date: 20190125 |