CN110231427A - A kind of chromatography detection sensor of doped zirconia solid fuel cell - Google Patents
A kind of chromatography detection sensor of doped zirconia solid fuel cell Download PDFInfo
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- CN110231427A CN110231427A CN201910459901.XA CN201910459901A CN110231427A CN 110231427 A CN110231427 A CN 110231427A CN 201910459901 A CN201910459901 A CN 201910459901A CN 110231427 A CN110231427 A CN 110231427A
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- G—PHYSICS
- G01—MEASURING; TESTING
- G01N—INVESTIGATING OR ANALYSING MATERIALS BY DETERMINING THEIR CHEMICAL OR PHYSICAL PROPERTIES
- G01N27/00—Investigating or analysing materials by the use of electric, electrochemical, or magnetic means
- G01N27/26—Investigating or analysing materials by the use of electric, electrochemical, or magnetic means by investigating electrochemical variables; by using electrolysis or electrophoresis
- G01N27/403—Cells and electrode assemblies
- G01N27/406—Cells and probes with solid electrolytes
- G01N27/407—Cells and probes with solid electrolytes for investigating or analysing gases
- G01N27/409—Oxygen concentration cells
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- G—PHYSICS
- G01—MEASURING; TESTING
- G01N—INVESTIGATING OR ANALYSING MATERIALS BY DETERMINING THEIR CHEMICAL OR PHYSICAL PROPERTIES
- G01N30/00—Investigating or analysing materials by separation into components using adsorption, absorption or similar phenomena or using ion-exchange, e.g. chromatography or field flow fractionation
- G01N30/02—Column chromatography
- G01N30/62—Detectors specially adapted therefor
- G01N30/64—Electrical detectors
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Abstract
The invention belongs to chromatography detection sensor field more particularly to a kind of chromatography detection sensor of doped zirconia solid fuel cell and its quantitative analysis methods, mainly for detection of the trace dissolved gas in analysis transformer oil.Implementation column of the present invention provides a kind of chromatography detection sensor of doped zirconia solid fuel cell, including structure and preparation method, air-sensitive response mechanism and quantitative approach, sensor uses tubular structure, solid electrolyte uses a kind of doped zirconia powder, particle diameters are 0.7 μm, be yttrium oxide that molar ratio is 8% and 3% scandia stabilized Zirconium oxide powder.Quantitative approach uses N-S model, compared with conventional sensors and its quantitative approach ratio, simplifies the Hardware Design and testing process while promoting detection system stability, accuracy and sensitivity and reduces system cost.
Description
Technical field
The invention belongs to chromatography detection sensor field more particularly to a kind of chromatographies of doped zirconia solid fuel cell
Detection sensor and preparation method, mainly for detection of the trace dissolved gas in transformer oil.
Background technique
Power transformer is mostly oil immersed type at present, and in transformer station high-voltage side bus, transformer oil can be by electric field and temperature etc.
It influences, produces the gases such as low molecular hydrocarbon, the operation of transformer can be determined by corresponding gas content in real-time detection analysis oil
State prevents incipient fault, prevents failure further expansion.Therefore become in chromatography detection technique can not for detection sensor
Or scarce component part.The type of gas sensor has much at present, but all there is different degrees of limitation, such as heat-conducted biography
Sensor, sensitivity is low, and because it uses helium to lead to higher cost as carrier gas；Semi-conductor type gas sensor, although can be right
Multiple gases are detected, but it generally has biggish volume, is also easy to produce gas diffusion, and electromagnetic eddy phenomenon is caused to generate,
And then generate error.And feulcell prototype detector has also taken into account the stabilization of detector while then maintain higher sensitivity
Property.
But inventors have found that although conventional fuel cell gas sensitive detector high sensitivity, generally first carries out known concentration
The detection of gas, then the gas of unknown concentration is detected, system complex, each component gas in oil when being unable to satisfy transformer fault
Independent detection, and then influence fault type analysis.
Summary of the invention
In order to solve existing fuel cell gas sensitive detector system complex, can not ask what each component gas individually detected
Topic, the application propose a kind of chromatography detection sensor of novel doped zirconia solid fuel cell, by choosing solid electrolytic
Matter, and the total electromotive force generated when solid electrolyte work is measured, solve the problems, such as this.
Concrete scheme provided by the present application is as follows:
A kind of chromatography detection sensor of doped zirconia solid fuel cell, heating furnace and sensor main body, feature
It is that the sensor main body includes pedestal and cylindrical body shell, is buckled in main body cover on pedestal.
Further, the pedestal includes Base body and ceramic conduit, and ceramic conduit runs through Base body.
Preferably, there are gas ports in Base body.
Further, the main body cover is made of solid electrolyte, and it is anode electrode that shell wall region is surveyed in main body cover,
It is cathode electrode on the outside of shell wall, respectively has a conducting wire to lead to sensor external on anode and cathode electrode.
It preferably, further include thermocouple in the inside heating furnace cavity.
Preferably, the connection type of the heating furnace and main body cover is that main body cover protrudes into heating far from pedestal one end
In furnace and integrated with heating furnace cast.
The application provides the preparation method of the chromatography detection sensor of the doped zirconia solid fuel cell simultaneously,
It is characterized in that plaster mold is made with spare by drawing first, is that 8% yttrium oxide and 4% scandium oxide are mixed into surely by molar ratio
Fixed Zirconium oxide powder.
Further, the Arabic gum that siccative specific gravity is 3% to 5% is sufficiently mixed with distilled water for adhesive and at it
Middle addition Zirconium oxide powder is sufficiently mixed.
Further, mixed material is operated after 400 meshes are fully ground sieving by vacuum defoamation, is obtained thin
Change zirconium oxide, and is put into ready plaster mold in advance.
Preferably, after the vacuumizing and defoaming refers to the n-butanol defoaming agent of 0.05~0.1wt% of addition, in vacuum degree-
Deaeration processing is carried out under the conditions of 0.10Mpa.
Further, remaining adhesive is rushed in plaster mold by heating, drying and is rejected.Then zirconium oxide will be filled
Plaster mold ties burning at 1200 DEG C to 1300 DEG C, ties at 1400 DEG C to 1700 DEG C again after progress repaired biscuit and is fired into matrix.
Further, hydrofluoric acid and distilled water are mixed into 5% to 10% hydrofluoric acid solution, then the matrix that will be prepared
It is placed in one, takes out matrix after impregnating 3 hours and dries washing.Platinum electrode is equably smeared repeatedly on obtained matrix
It is dried after slurry, the matrix after drying carries out high temperature knot at 1100 DEG C to 1500 DEG C and burns to obtain electrode.
Technical solution provided by the present application compared with the existing technology its generate have the beneficial effect that:
By proposing new measurement method, the function of individually detecting to gas component not of the same race is realized, while meeting
Accuracy and sensitivity etc. realize summarized chromatogram device hardware configuration under the premise of requiring, and reduce the effect of cost.
The additional aspect and advantage of the application will be set forth in part in the description, and will partially become from the following description
It obtains obviously, or recognized by the practice of the application.
Detailed description of the invention
Fig. 1 is inventive sensor structural schematic diagram；
Fig. 2 is inventive sensor gypsum mold schematic diagram；
Fig. 3 is inventive sensor combustible gas detection schematic diagram；
Fig. 4 is that inventive sensor detects Gases Dissolved in Transformer Oil structural block diagram；
Fig. 5 is inventive sensor H2 concentration Testing value and standard value comparison diagram；
Fig. 6 is inventive sensor CH4 concentration Testing value and standard value comparison diagram；
Fig. 7 is inventive sensor C2H4 concentration Testing value and standard value comparison diagram；
Fig. 8 is inventive sensor C2H6 concentration Testing value and standard value comparison diagram；
Fig. 9 is inventive sensor C2H2 concentration Testing value and standard value comparison diagram.
Specific embodiment
Embodiments herein is described below in detail, examples of the embodiments are shown in the accompanying drawings, wherein from beginning to end
Same or similar label indicates same or similar element or element with the same or similar functions.Below with reference to attached
The embodiment of figure description is exemplary, it is intended to for explaining the application, and should not be understood as the limitation to the application.
Embodiment one
A kind of chromatography detection sensor of novel doped zirconia solid fuel cell, by heating furnace 5 and sensor main body
It constitutes, it is characterised in that there are thermocouple 6 in 5 internal cavities of heating furnace, the sensor main body includes pedestal and theme
Shell, the main body cover are cylindrical in shape, be buckled on pedestal between main body cover and the two can integration cast；The pedestal includes
Base body and ceramic conduit 4, there are gas ports in Base body, Base body for ceramic conduit 4；The main body cover by
Solid electrolyte 3 is made, and protrudes into heating furnace far from pedestal one end and fixes with heating furnace 5, integrated can cast between the two
At surveying shell wall region in main body cover is anode electrode 3, is cathode electrode 2 on the outside of shell wall, respectively has one on anode and cathode electrode
Root conducting wire leads to other devices of sensor external as shown in Figure 4.
When working sensor, heating furnace 5 heats temperature in internal cavities, and by the feedback of thermocouple 6, temperature is controlled
At 600 DEG C to 1000 DEG C, while ceramic conduit 4 is passed through under test gas into sensor main body.Since outside is deposited in the shell wall
In oxygen concentration difference, under conditions of high temperature and noble metal are urged, outside can generate oxygen concentration difference electromotive force in the shell wall；At the same time,
When there are electrochemical reaction as shown in Figure 3, generation electrochemistry electricity when fuel gas, can also occur at anode 3 under test gas
Kinetic potential.Oxygen concentration difference electromotive force is transmitted to by the electrochemical emf and oxygen concentration difference electromotive force by the conducting wire of cathode and anode
Outside sensor, and using this total electromotive force as the basis of detection under test gas ingredient.
In the present embodiment, main body cover is cylindrical shape.In other embodiments, main body cover be can be other shapes
Shape, than following small big truncated cone-shaped.
In order to more accurately detect each component under test gas, the operating temperature of chromatography detection sensor is preferably 700 DEG C.
Embodiment two
A kind of chromatography detection sensor preparation method of novel doped zirconia solid fuel cell, including solid electrolyte
Preparation and electrode preparation
It is that 8% yttrium oxide and 4% scandium oxide are mixed by molar ratio firstly, plaster mold is made with spare by drawing
Stable Zirconium oxide powder.The Arabic gum that siccative specific gravity is 3% to 5% is sufficiently mixed with distilled water for adhesive and at it
Middle addition Zirconium oxide powder is sufficiently mixed.Mixed material is grasped after 400 meshes are fully ground sieving by vacuum defoamation
Make, obtains refinement zirconium oxide, and be put into ready plaster mold in advance.Remaining adhesive is rushed by heating, drying
It is rejected in plaster mold.Then the plaster mold for filling zirconium oxide is tied at 1200 DEG C to 1300 DEG C burning, existed again after carrying out repaired biscuit
Knot is fired into matrix at 1400 DEG C to 1700 DEG C.
Hydrofluoric acid and distilled water are mixed into 5% to 10% hydrofluoric acid solution, then the matrix prepared is placed in one,
Matrix is taken out after impregnating 3 hours and dries washing.It is laggard equably to smear platinum electrode slurry repeatedly on obtained matrix
Row drying, the matrix after drying carry out high temperature knot at 1100 DEG C to 1500 DEG C and burn to obtain electrode.
In order to preferably purify to zirconium oxide, in above-mentioned steps, vacuumizing and defoaming refers to 0.05~0.1wt% of addition
N-butanol defoaming agent after, under the conditions of vacuum degree -0.10Mpa carry out deaeration processing.
Embodiment three
The present invention is based on oxygen concentration cell models and Nernst equation to construct quantitative math-model (the N-S mould of sensor
Type), detailed process is as follows: according to Nernst equation, can there is following statement
In formula, R, T, n and F respectively represent calibrating gas constant, the operating temperature of detector, the receiving and losing electrons number on electrode
And Faraday constant, P0For reference side partial pressure of oxygen, PXIt is partial pressure of oxygen in tested gas, it is assumed that corresponding oxygen concentration is Cx, enable a
=RT/nF, according to above formula
Assuming that the flow of detection system is L, standard atmospheric pressure P, then when available dt in the time interval of very little
Amount of oxygen (mol) in the interior carrier gas to flow away are as follows:
If t1At the beginning of appearance, t2It is obtained for the end time using integral transformation:
Assuming that Δ t=t2-t1, then Q is the oxygen amount of flowing away in the Δ t time in formula, if Δ Q is that fuel gas disappears in the Δ t time
The amount of oxygen of consumption can release following result:
E (t) is the output voltage signal of sensor in formula, it is contemplated that sample variance value, above-mentioned integrated value can use number
Trapezoidal method or runge kutta method in value integral are calculated.
It is assumed that the stoichiometric ratio that combustible W is reacted with oxygen is N, quantitative pipe volume is V, is enabled:
Then flammable gas concentration are as follows:
In the description of this specification, reference term " one embodiment ", " some embodiments ", " example ", " specifically show
The description of example " or " some examples " etc. means specific features, structure, material or spy described in conjunction with this embodiment or example
Point is contained at least one embodiment or example of the application.In the present specification, schematic expression of the above terms are not
It must be directed to identical embodiment or example.Moreover, particular features, structures, materials, or characteristics described can be in office
It can be combined in any suitable manner in one or more embodiment or examples.In addition, without conflicting with each other, the skill of this field
Art personnel can tie the feature of different embodiments or examples described in this specification and different embodiments or examples
It closes and combines.
Although embodiments herein has been shown and described above, it is to be understood that above-described embodiment is example
Property, it should not be understood as the limitation to the application, those skilled in the art within the scope of application can be to above-mentioned
Embodiment is changed, modifies, replacement and variant.
Claims (7)
1. a kind of chromatography detection sensor of novel doped zirconia solid fuel cell, including heating furnace (5) and sensor master
Body, it is characterised in that the sensor main body includes pedestal and cylindrical body shell, and main body cover, the pedestal are buckled on pedestal
Including Base body and ceramic conduit (4), there are gas ports in Base body, Base body for ceramic conduit (4)；The master
Body case is made of solid electrolyte (1), and shell wall region is anode electrode (3) on the inside of main body cover, is cathode electricity on the outside of shell wall
Pole (2) respectively has a conducting wire to lead to sensor external on anode and cathode electrode.
2. chromatography detection sensor as described in claim 1, it is characterised in that further include heat in the inside heating furnace cavity
Galvanic couple (6).
3. chromatography detection sensor as described in claim 1, it is characterised in that the connection of heating furnace (5) and main body cover
Mode are as follows: shell is protruded into heating furnace far from pedestal one end and integrated with heating furnace cast.
4. a kind of chromatography detection sensor preparation method of novel doped zirconia solid fuel cell, which is characterized in that including
Following steps:
The first step is made plaster mold by drawing with spare, is that 8% yttrium oxide and 4% scandium oxide are mixed into surely by molar ratio
Fixed Zirconium oxide powder；By siccative specific gravity be 3% to 5% Arabic gum and distilled water be sufficiently mixed as adhesive and wherein
Zirconium oxide powder is added to be sufficiently mixed.
Second step, mixed material pass through 400 meshes, are operated after being fully ground sieving by vacuum defoamation, obtain refinement oxygen
Change zirconium, and is put into ready plaster mold in advance.Remaining adhesive is rushed in plaster mold by heating, drying and is rejected.
Then the plaster mold for filling zirconium oxide is tied at 1200 DEG C to 1300 DEG C burning, carried out after repaired biscuit again at 1400 DEG C to 1700 DEG C
Knot is fired into matrix.
Hydrofluoric acid and distilled water are mixed into 5% to 10% hydrofluoric acid solution, then the matrix prepared are placed in it by third step
In, matrix is taken out after impregnating 3 hours and dries washing.After equably smearing platinum electrode slurry repeatedly on obtained matrix
It is dried, the matrix after drying carries out high temperature knot at 1100 DEG C to 1500 DEG C and burns to obtain electrode.
5. preparation method as claimed in claim 4, it is characterised in that the vacuumizing and defoaming refers to 0.05~0.1wt% of addition
N-butanol defoaming agent after, under the conditions of vacuum degree -0.10Mpa carry out deaeration processing.
6. a kind of gasometry method of the chromatography detection sensor of new fuel cell, it is characterised in that the component of under test gas
Concentration is measured by following formula:
Wherein the unit of C is μ L/L；N is the stoichiometric ratio that combustible gas is reacted with oxygen；P0For reference side partial pressure of oxygen；V0
For quantitative pipe volume；P is atmospheric pressure；t1For peak time started, t2For the peak end time；R is calibrating gas constant, and T is the biography
Temperature when sense device working, n are the receiving and losing electrons number on the electrode, and F is Faraday constant；The i.e. described sensor of E (t) it is defeated
Voltage signal out.
7. gasometry method as claimed in claim 6, it is characterised in that described with reference to survey voltage P0Volume can be used when calculating
Concentration replaces, and specific value is 209600 μ L/L.
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| CN201910459901.XA CN110231427A (en) | 2019-05-30 | 2019-05-30 | A kind of chromatography detection sensor of doped zirconia solid fuel cell |
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| CN201910459901.XA CN110231427A (en) | 2019-05-30 | 2019-05-30 | A kind of chromatography detection sensor of doped zirconia solid fuel cell |
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Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN114509472A (en) * | 2022-04-19 | 2022-05-17 | 佛山速敏智能仪器科技有限公司 | Gas detection system, detection method and gas detection device in transformer oil |
| CN114894943A (en) * | 2022-03-21 | 2022-08-12 | 南京智鹤电子科技有限公司 | Transformer oil gas online monitoring method |
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Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN114894943A (en) * | 2022-03-21 | 2022-08-12 | 南京智鹤电子科技有限公司 | Transformer oil gas online monitoring method |
| CN114509472A (en) * | 2022-04-19 | 2022-05-17 | 佛山速敏智能仪器科技有限公司 | Gas detection system, detection method and gas detection device in transformer oil |
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