CN114755280A - Ammonia gas sensor, method for measuring ammonia gas content in exhaust gas aftertreatment system and automobile exhaust gas aftertreatment system - Google Patents
Ammonia gas sensor, method for measuring ammonia gas content in exhaust gas aftertreatment system and automobile exhaust gas aftertreatment system Download PDFInfo
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- QGZKDVFQNNGYKY-UHFFFAOYSA-N Ammonia Chemical compound N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 title claims abstract description 291
- 238000000034 method Methods 0.000 title claims abstract description 21
- BASFCYQUMIYNBI-UHFFFAOYSA-N platinum Chemical compound [Pt] BASFCYQUMIYNBI-UHFFFAOYSA-N 0.000 claims abstract description 297
- 229910052697 platinum Inorganic materials 0.000 claims abstract description 149
- 239000007789 gas Substances 0.000 claims abstract description 85
- 239000002245 particle Substances 0.000 claims abstract description 63
- 238000001179 sorption measurement Methods 0.000 claims abstract description 48
- 239000007784 solid electrolyte Substances 0.000 claims abstract description 46
- 239000011159 matrix material Substances 0.000 claims abstract description 43
- 238000012360 testing method Methods 0.000 claims description 84
- 229910021529 ammonia Inorganic materials 0.000 claims description 61
- MWUXSHHQAYIFBG-UHFFFAOYSA-N Nitric oxide Chemical compound O=[N] MWUXSHHQAYIFBG-UHFFFAOYSA-N 0.000 claims description 42
- 238000003795 desorption Methods 0.000 claims description 32
- 238000010438 heat treatment Methods 0.000 claims description 28
- 239000000463 material Substances 0.000 claims description 16
- 238000010531 catalytic reduction reaction Methods 0.000 claims description 7
- 238000000746 purification Methods 0.000 claims description 7
- 229910001404 rare earth metal oxide Inorganic materials 0.000 claims description 6
- MCMNRKCIXSYSNV-UHFFFAOYSA-N ZrO2 Inorganic materials O=[Zr]=O MCMNRKCIXSYSNV-UHFFFAOYSA-N 0.000 claims description 5
- CMIHHWBVHJVIGI-UHFFFAOYSA-N gadolinium(III) oxide Inorganic materials [O-2].[O-2].[O-2].[Gd+3].[Gd+3] CMIHHWBVHJVIGI-UHFFFAOYSA-N 0.000 claims description 3
- MRELNEQAGSRDBK-UHFFFAOYSA-N lanthanum oxide Inorganic materials [O-2].[O-2].[O-2].[La+3].[La+3] MRELNEQAGSRDBK-UHFFFAOYSA-N 0.000 claims description 3
- KTUFCUMIWABKDW-UHFFFAOYSA-N oxo(oxolanthaniooxy)lanthanum Chemical compound O=[La]O[La]=O KTUFCUMIWABKDW-UHFFFAOYSA-N 0.000 claims description 3
- FKTOIHSPIPYAPE-UHFFFAOYSA-N samarium(III) oxide Inorganic materials [O-2].[O-2].[O-2].[Sm+3].[Sm+3] FKTOIHSPIPYAPE-UHFFFAOYSA-N 0.000 claims description 3
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N titanium dioxide Inorganic materials O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 claims description 3
- 239000001301 oxygen Substances 0.000 abstract description 37
- 229910052760 oxygen Inorganic materials 0.000 abstract description 37
- -1 oxygen ions Chemical class 0.000 abstract description 27
- 238000006243 chemical reaction Methods 0.000 abstract description 12
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 abstract description 9
- 230000000694 effects Effects 0.000 abstract description 8
- 125000004430 oxygen atom Chemical group O* 0.000 description 16
- MYMOFIZGZYHOMD-UHFFFAOYSA-N Dioxygen Chemical compound O=O MYMOFIZGZYHOMD-UHFFFAOYSA-N 0.000 description 4
- 229910001882 dioxygen Inorganic materials 0.000 description 4
- 230000009286 beneficial effect Effects 0.000 description 3
- 210000002858 crystal cell Anatomy 0.000 description 3
- XSQUKJJJFZCRTK-UHFFFAOYSA-N Urea Chemical compound NC(N)=O XSQUKJJJFZCRTK-UHFFFAOYSA-N 0.000 description 2
- 239000004202 carbamide Substances 0.000 description 2
- 230000008859 change Effects 0.000 description 2
- 238000000576 coating method Methods 0.000 description 2
- 238000001514 detection method Methods 0.000 description 2
- 238000010586 diagram Methods 0.000 description 2
- 238000007599 discharging Methods 0.000 description 2
- 238000002347 injection Methods 0.000 description 2
- 239000007924 injection Substances 0.000 description 2
- 230000004048 modification Effects 0.000 description 2
- 238000012986 modification Methods 0.000 description 2
- 230000008569 process Effects 0.000 description 2
- 230000009471 action Effects 0.000 description 1
- 229960001948 caffeine Drugs 0.000 description 1
- 210000004027 cell Anatomy 0.000 description 1
- 239000011248 coating agent Substances 0.000 description 1
- RKTYLMNFRDHKIL-UHFFFAOYSA-N copper;5,10,15,20-tetraphenylporphyrin-22,24-diide Chemical compound [Cu+2].C1=CC(C(=C2C=CC([N-]2)=C(C=2C=CC=CC=2)C=2C=CC(N=2)=C(C=2C=CC=CC=2)C2=CC=C3[N-]2)C=2C=CC=CC=2)=NC1=C3C1=CC=CC=C1 RKTYLMNFRDHKIL-UHFFFAOYSA-N 0.000 description 1
- 238000003912 environmental pollution Methods 0.000 description 1
- 230000002349 favourable effect Effects 0.000 description 1
- 150000002500 ions Chemical class 0.000 description 1
- 239000000376 reactant Substances 0.000 description 1
- 230000008439 repair process Effects 0.000 description 1
- 239000000243 solution Substances 0.000 description 1
- 235000019640 taste Nutrition 0.000 description 1
- RYYVLZVUVIJVGH-UHFFFAOYSA-N trimethylxanthine Natural products CN1C(=O)N(C)C(=O)C2=C1N=CN2C RYYVLZVUVIJVGH-UHFFFAOYSA-N 0.000 description 1
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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
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- F—MECHANICAL ENGINEERING; LIGHTING; HEATING; WEAPONS; BLASTING
- F01—MACHINES OR ENGINES IN GENERAL; ENGINE PLANTS IN GENERAL; STEAM ENGINES
- F01N—GAS-FLOW SILENCERS OR EXHAUST APPARATUS FOR MACHINES OR ENGINES IN GENERAL; GAS-FLOW SILENCERS OR EXHAUST APPARATUS FOR INTERNAL COMBUSTION ENGINES
- F01N13/00—Exhaust or silencing apparatus characterised by constructional features ; Exhaust or silencing apparatus, or parts thereof, having pertinent characteristics not provided for in, or of interest apart from, groups F01N1/00 - F01N5/00, F01N9/00, F01N11/00
- F01N13/008—Mounting or arrangement of exhaust sensors in or on exhaust apparatus
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- F—MECHANICAL ENGINEERING; LIGHTING; HEATING; WEAPONS; BLASTING
- F01—MACHINES OR ENGINES IN GENERAL; ENGINE PLANTS IN GENERAL; STEAM ENGINES
- F01N—GAS-FLOW SILENCERS OR EXHAUST APPARATUS FOR MACHINES OR ENGINES IN GENERAL; GAS-FLOW SILENCERS OR EXHAUST APPARATUS FOR INTERNAL COMBUSTION ENGINES
- F01N13/00—Exhaust or silencing apparatus characterised by constructional features ; Exhaust or silencing apparatus, or parts thereof, having pertinent characteristics not provided for in, or of interest apart from, groups F01N1/00 - F01N5/00, F01N9/00, F01N11/00
- F01N13/009—Exhaust or silencing apparatus characterised by constructional features ; Exhaust or silencing apparatus, or parts thereof, having pertinent characteristics not provided for in, or of interest apart from, groups F01N1/00 - F01N5/00, F01N9/00, F01N11/00 having two or more separate purifying devices arranged in series
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Abstract
The disclosure relates to an ammonia gas sensor, a method for measuring the content of ammonia gas in an exhaust gas aftertreatment system and an automobile exhaust gas aftertreatment system. According to the ammonia gas sensor, the ammonia gas catching particles are arranged in the ammonia gas sensor, so that the ammonia gas to be adsorbed can be caught in the adsorption gaps, other gases do not have catching effects, and the accuracy of the ammonia gas sensor is improved; and in the ammonia gas sensor, the first platinum electrode and the second platinum electrode are respectively arranged on two sides of the solid electrolyte matrix, so that the mutual conversion between oxygen and oxygen ions and the movement conduction between the two platinum electrodes are realized to generate an electric signal to obtain the ammonia gas content, and important ammonia gas content information is provided for the accurate reaction of a tail gas aftertreatment system.
Description
Technical Field
The disclosure relates to the field of motor vehicle exhaust emission detection, in particular to an ammonia gas sensor, a method for measuring the content of ammonia gas in an exhaust gas aftertreatment system and an automobile exhaust gas aftertreatment system.
Background
By interpreting light-duty diesel vehicle (LDD) emissions regulations, an upgrade from 5(CN V) to 6b (CN VIb) NO can be foundXThe emission limit value is reduced by 82.1 percent and NOXEmissions exhibit a more stringent trend.
Currently, DPF devices (Diesel Particulate traps, Diesel Particulate filters), SDPF devices (DPF with SCR Function) and SCR devices (Selective Catalytic Reduction) are widely used in the industry in the main aftertreatment arrangement treatment mode of the emission route of light Diesel vehicles to the national vi emission regulations.
SCR or SDPF devices are used to purify Nitrogen Oxides (NO)X) In both of these purification devices, ammonia (NH)3) Is the necessary reactant, ammonia (NH)3) With Nitrogen Oxides (NO) in SCR or SDPFX) The reaction is shown in the following formulas (1) to (3):
2NH3+NO+NO2→2N2+3H2O (1)；
8NH3+6NO2→7N2+12H2O (2)；
4NH3+4NO+O2→4N2+6H2O (3)。
NH consumed by the reactions in the formulae (1) to (3)3The amount varies, but typically the urea injection system in the aftertreatment system will be properly over-injected (over-injected NH)3) NH caused thereby3The emissions are excessive, the gas tastes unpleasant and can cause pollution.
Disclosure of Invention
The invention aims to provide an ammonia gas sensor and an application method thereof, which are used for measuring the content of ammonia gas in a tail gas aftertreatment system.
In order to achieve the above object, the present disclosure provides an ammonia gas sensor comprising a gas test chamber, a solid electrolyte matrix, a first platinum electrode, a second platinum electrode, ammonia gas trapping particles, a first power supply, and an electrical signal measuring device;
the solid electrolyte matrix is provided with a test airflow inlet, and the gas test chamber extends towards the interior of the solid electrolyte matrix through the test airflow inlet;
the second platinum electrode is covered on the outer wall of the solid electrolyte matrix and extends along the flow direction of the test gas flow;
the first platinum electrode and the ammonia gas trapping particles are sequentially coated on the first inner wall of the gas testing chamber from inside to outside, and the pole pieces of the first platinum electrode and the second platinum electrode are oppositely arranged; an adsorption gap is formed between the first platinum electrode and the ammonia gas trapping particles;
the first power supply is connected between the first platinum electrode and the second platinum electrode, and the electric signal measuring device is arranged between the first platinum electrode and the second platinum electrode.
Optionally, an ammonia gas trapping layer is arranged in the gas testing chamber, the first platinum electrode and the ammonia gas trapping layer are sequentially coated on the first inner wall from inside to outside, and the ammonia gas trapping layer contains the ammonia gas trapping particles;
Optionally, the thickness of the ammonia gas trapping layer is 1-10 μm;
optionally, the width of the ammonia gas trapping layer is 2-9 mm;
optionally, the length of the ammonia gas trapping layer is 2-9 mm.
Optionally said ammonia trapping particles comprise V2O5；
Optionally, the ammonia trapping particles further comprise WO3And TiO2One or two of them;
optionally, the V in the ammonia trapping particles2O5The amount of (B) is 60 to 90 wt%, preferably 80 to 90 wt%;
optionally, the particle size of the ammonia gas trapping particles is 1-10 μm, preferably 6-9 μm.
Alternatively, the ammonia gas sensor has an adsorption operation state and a desorption operation state which can be alternately set;
in the adsorption working state, the first platinum electrode is connected with the negative electrode of the first power supply, and the second platinum electrode is connected with the positive electrode of the first power supply;
in the desorption working state, the first platinum electrode is connected with the anode of the first power supply, and the second platinum electrode is connected with the cathode of the first power supply;
optionally, the ammonia gas sensor further comprises an electrode connection control device, and the electrode connection control device is used for enabling the ammonia gas sensor to be in the adsorption working state or the desorption working state alternately.
Optionally, the electrode connection control device is configured to sequentially enable the ammonia gas sensor to be in the adsorption working state and the desorption working state within a preset cycle period, where the preset cycle period includes a first time period and a second time period; wherein,
in the first time period, the ammonia gas sensor is in the adsorption working state;
and in the second time period, the ammonia gas sensor is in the desorption working state.
Optionally, the solid electrolyte matrix comprises ZrO2And a doping material; the doping material is selected from one or more of CaO, MgO and rare earth oxide, and the rare earth oxide is selected from Y2O3、La2O3、Gd2O3And Sm2O3One or more of the above;
optionally, in the solid electrolyte matrix, the ZrO2The particle size of the particles is 5-50 μm, preferably 10-20 μm;
optionally, in the solid electrolyte matrix, the particle size of the doping material is 5-50 μm, preferably 10-20 μm;
optionally, the doping material is selected from Y2O3And CaO;
optionally, the volume fraction of the doping material in the solid electrolyte matrix is 5-12%, more preferably 7.5-8.5%.
Optionally, the ammonia gas sensor further comprises a third platinum electrode and a heating element;
The third platinum electrode and the heating element are respectively embedded in the solid electrolyte matrix, and the third platinum electrode and the heating element are oppositely arranged at intervals;
optionally, the third platinum electrode and the heating element are disposed outside a second inner wall of the test chamber, and spaced apart from the second inner wall, and the second inner wall is disposed parallel to and spaced apart from the first inner wall;
optionally, a heating voltage device is arranged between the third platinum electrode and the heating element to control the heating temperature of the heating element.
A second aspect of the present disclosure provides a method for measuring the content of ammonia in an exhaust gas aftertreatment system, using the ammonia sensor according to the first aspect of the present disclosure, the method comprising the steps of:
-passing a test gas stream into the test chamber of the ammonia gas sensor through the test gas stream inlet;
-connecting the first platinum electrode to the negative pole of the first power source and the second platinum electrode to the positive pole of the first power source;
-measuring a first electrical signal value using said electrical signal measuring device, and determining the ammonia content of the test gas stream based on said first electrical signal value.
Optionally, the ammonia gas sensor is sequentially in an adsorption working state and a desorption working state in a preset cycle period, wherein the preset cycle period comprises a first time period and a second time period; wherein,
in the first time period, connecting the first platinum electrode with the cathode of the first power supply, and connecting the second platinum electrode with the anode of the first power supply, so that the ammonia gas sensor is in the adsorption working state;
in a second time period, connecting the first platinum electrode with the positive electrode of the first power supply, and connecting the second platinum electrode with the negative electrode of the first power supply, so that the ammonia gas sensor is in the desorption working state;
optionally, the durations of the first time period and the second time period are the same or different, preferably the same;
preferably, the duration of the first period and/or the second period is 0.5 to 3s, and more preferably 0.5 to 1.2 s.
Optionally, the method further comprises:
-passing a standard test gas stream of known ammonia content through the test gas stream inlet into the test chamber of the ammonia sensor;
-connecting the first platinum electrode to the negative pole of the first power source and the second platinum electrode to the positive pole of the first power source;
-measuring a standard electrical signal value using said electrical signal measuring device, determining the ammonia content in said test gas stream from said standard electrical signal value, the known ammonia content in said standard test gas stream, and said first electrical signal value.
A third aspect of the present disclosure provides an automobile exhaust gas after-treatment system, comprising a nitrogen oxide purification device and the ammonia gas sensor of the first aspect of the present disclosure;
optionally, the nitrogen oxide purification device comprises a diesel particulate trap and/or a selective catalytic reduction device, and the ammonia gas sensor is arranged at the downstream of the diesel particulate trap and the selective catalytic reduction device along the flow direction of the test gas.
Through the technical scheme, the ammonia gas trapping particles arranged in the ammonia gas sensor can trap and adsorb ammonia gas to be adsorbed in the adsorption gap, and have no trapping effect on other gases, so that the accuracy of the ammonia gas sensor is improved; and in the ammonia gas sensor, the first platinum electrode and the second platinum electrode are respectively arranged on two sides of the solid electrolyte matrix, so that the mutual conversion between oxygen and oxygen ions and the movement conduction between the two platinum electrodes are realized to generate an electric signal to obtain the ammonia gas content, and important ammonia gas content information is provided for the accurate reaction of the tail gas post-treatment system.
Additional features and advantages of the disclosure will be set forth in the detailed description which follows.
Drawings
The accompanying drawings, which are included to provide a further understanding of the disclosure and are incorporated in and constitute a part of this specification, illustrate embodiments of the disclosure and together with the description serve to explain the disclosure without limiting the disclosure. In the drawings:
FIG. 1 is a schematic structural diagram of an ammonia gas sensor provided in an embodiment of the present disclosure;
fig. 2 is a schematic diagram of the working principle of the ammonia gas sensor provided by the embodiment of the disclosure.
Description of the reference numerals
1-gas test chamber, 2-solid electrolyte matrix, 3-first platinum electrode, 4-second platinum electrode, 5-ammonia trapping particles, 6-test gas flow inlet, 7-first power supply, 8-electric signal measuring device, 9-third platinum electrode, 10-heating element, 11-heating voltage device, 12-negative electrode area, 13-positive electrode area, 14-solid electrolyte, 15-oxygen, 16-electron, 17-platinum electrode
Detailed Description
The following detailed description of specific embodiments of the present disclosure is provided in connection with the accompanying drawings. It should be understood that the detailed description and specific examples, while indicating the present disclosure, are given by way of illustration and explanation only, not limitation.
In the present disclosure, unless otherwise specified, the terms "first", "second", "third", and the like are used only for distinguishing different members and do not have actual meanings such as the order of connection before and after the present disclosure. In the present disclosure, the terms of orientation such as "upper" and "lower" are used for upper and lower in the normal use state of the device, and "inner" and "outer" are used for the outline of the device, for example, "the inner side of the first pole piece and the second pole piece" refers to the region sandwiched between the two pole pieces, i.e. the side of the first pole piece close to the second pole piece, and the side of the second pole piece close to the first pole piece.
As shown in fig. 1, the present disclosure provides, in a first aspect, an ammonia gas sensor including a gas testing chamber 1, a solid electrolyte matrix 2, a first platinum electrode 3, a second platinum electrode 4, ammonia trapping particles 5, a first power supply 7, and an electric signal measuring device 8;
the solid electrolyte matrix 2 is provided with a test gas flow inlet 6, and the gas test chamber 1 extends towards the inside of the solid electrolyte matrix 2 through the test gas flow inlet 6;
the second platinum electrode 4 is covered on the outer wall of the solid electrolyte matrix 2 and extends along the flow direction of the test gas flow;
the first platinum electrode 3 and the ammonia capture particles 5 are sequentially coated on the first inner wall of the gas testing chamber 1 from inside to outside, and the pole pieces of the first platinum electrode 3 and the second platinum electrode 4 are oppositely arranged; an adsorption gap is formed between the first platinum electrode 3 and the ammonia trapping particles 5;
The first power supply 7 is connected between the first platinum electrode 3 and the second platinum electrode 4, and the electric signal measuring device 8 is disposed between the first platinum electrode 3 and the second platinum electrode 4.
According to the ammonia gas sensor, the ammonia gas catching particles are arranged in the ammonia gas sensor, so that the ammonia gas to be adsorbed can be caught in the adsorption gaps, and other gases do not have catching effects, and the accuracy of the ammonia gas sensor is improved; and in the ammonia gas sensor, the first platinum electrode and the second platinum electrode are respectively arranged on two sides of the solid electrolyte matrix, so that the mutual conversion between oxygen and oxygen ions and the movement conduction between the two platinum electrodes are realized to generate an electric signal to obtain the ammonia gas content, and important ammonia gas content information is provided for the accurate reaction of the tail gas post-treatment system.
The term "ammonia trapping particles" in the present disclosure means having a trapping effect on ammonia gas and on other gases such as N2、O2And the like, and the ammonia gas trapping particles can resolve oxygen atoms for combining with electrons to form oxygen ions after adsorbing ammonia gas.
Specifically, the operation principle of the ammonia gas sensor will be described by taking the ammonia gas sensor shown in fig. 1 of the present disclosure as an example:
the test airflow enters the gas test chamber, ammonia in the test airflow is captured by the ammonia capture particles and stored in the adsorption gap, the ammonia capture particles capturing the ammonia are split into one oxygen atom, and one oxygen atom obtains two electrons at the first platinum electrode and is converted into one oxygen ion O 2-And oxygen ions move to the second platinum electrode through the solid electrolyte matrix under the action of the positive electrode of the first power supply to generate electric signal change, and then the amount of adsorbed ammonia gas and the ammonia gas content in the test airflow are obtained according to the electric signal change value.
In one embodiment, the first platinum electrode and the second platinum electrode of the ammonia gas sensor are coated on the solid electrolyte matrix in the form of coatings, and gaps are formed among platinum particles in the platinum electrodes, and the gaps of the platinum electrodes allow electrons and oxygen ions to flow through.
In one embodiment, the thickness of the first platinum electrode may be 1 to 11 μm, preferably 9.5 to 10.5 μm; the thickness of the second platinum electrode may be 1 to 11 μm, preferably 9.5 to 10.5 μm.
In one embodiment, the thickness of the solid electrolyte matrix between the second platinum electrode and the first platinum electrode may be 0.3 to 3mm, preferably 0.3 to 1 mm.
In one embodiment, the ammonia trapping particles 5 in the ammonia gas sensor are coated on the first platinum electrode 3 in the form of a coating. In this embodiment, an ammonia gas trapping layer is disposed in the test chamber 1, the first platinum electrode 3 and the ammonia gas trapping layer sequentially cover the first inner wall from inside to outside, and the ammonia gas trapping layer includes ammonia gas trapping particles 5. In this embodiment, the first platinum electrode is coated on the first inner wall, and then the ammonia gas trapping layer is coated on the first platinum electrode, which is beneficial for ammonia gas trapping particles to trap ammonia gas, and can also facilitate oxygen atoms separated from the ammonia gas trapping particles after trapping ammonia gas to obtain electrons easily on the first platinum electrode to form oxygen ions, and is beneficial for the oxygen ions to be transferred from the first platinum electrode to the second platinum electrode in the solid electrolyte matrix.
In a preferred embodiment, the thickness of the ammonia gas trapping layer may be 1 to 10 μm; the width of the ammonia gas trapping layer can be 2-9 mm; the length of the ammonia gas trapping layer can be 2-9 mm. The length direction of the ammonia gas trapping layer is the same as that of the first platinum electrode, and the ammonia gas trapping layer and the first platinum electrode are both the direction in which the testing chamber extends towards the inside of the solid electrolyte matrix and also the flowing direction of the testing airflow.
In one embodiment, the ammonia trapping particles 5 comprise V2O5(ii) a In a preferred embodiment, the ammonia trapping particles further comprise WO3And TiO2One or two of them, for improving the effect of trapping ammonia gas.
In the present embodiment, ammonia gas is trappedTrapping V in particles2O5The amount of (b) may be 60 to 90% by weight, preferably 80 to 90% by weight; the ammonia gas trapping particles may have a particle diameter of 1 to 10 μm, preferably 6 to 9 μm.
In one embodiment, the solid electrolyte matrix 2 comprises ZrO2And a doping material; the doping material is selected from one or more of CaO, MgO and rare earth oxide, and the rare earth oxide is selected from Y2O3、La2O3、Gd2O3And Sm2O3One or more of them.
In a preferred embodiment, ZrO in the solid electrolyte matrix 22The particle diameter of the particles is 5 to 50 μm, preferably 10 to 20 μm.
In a preferred embodiment, the particle size of the doping material in the solid electrolyte matrix 2 is 5 to 50 μm, preferably 10 to 20 μm.
In a preferred embodiment, the doping material is selected from Y2O3And CaO.
In a further preferred embodiment, the volume fraction of the doping material in the solid electrolyte matrix 2 is 5 to 12%, further preferably 7.5 to 8.5%.
The preferred embodiment can improve the ion conduction performance of the solid electrolyte matrix in the ammonia gas sensor, and the added doping material can improve the concentration of oxygen ion vacancies and can ensure ZrO2At low temperature, the crystal cell exists in a tetragonal or cubic form, and larger gaps exist in the crystal cell, so that oxygen ions are unobstructed in the gaps, and the conductivity/oxygen ion flow rate of the crystal cell is improved.
Further, the principle of converting oxygen into oxygen ions using a solid electrolyte matrix and conducting through the solid electrolyte matrix is shown in fig. 2. When a voltage (for example, 1V) is applied to the solid electrolyte 14 in two stages, the negative electrode region 12 communicates with the negative electrode of the power supply, and the positive electrode region 13 communicates with the positive electrode of the power supply. Wherein the power supply supplies electrons 16 to a platinum electrode 17 in the cathode region, O of the cathode region 12 215 obtaining electrons to form oxygen ions O2-The reaction process is shown in the following formula (4); oxygen ion passing throughOxygen vacancies in the solid electrolyte 14 migrate to the platinum electrode 17 in the positive electrode region 13 on the low oxygen concentration side, the positive electrode region is connected to the positive electrode of the power source, and oxygen ions lose electrons to form O2The form is released and the reaction process is described in the following formula (5);
O2+4e-→2O2-formula (4);
2O2--4e-→O2formula (5).
In one embodiment, the present disclosure provides an ammonia gas sensor having an adsorption operating state and a desorption operating state that are alternately settable, wherein "adsorption" and "desorption" are both with respect to adsorption and desorption of ammonia gas by ammonia gas trapping particles;
in the adsorption working state, the first platinum electrode 3 is connected with the negative electrode of the first power supply 7, and the second platinum electrode 4 is connected with the positive electrode of the first power supply 7;
in the desorption operation state, the first platinum electrode 3 is connected to the positive electrode of the first power supply 7, and the second platinum electrode 4 is connected to the negative electrode of the first power supply 7.
Specifically, the principle of the adsorption working state and the desorption working state in which the ammonia gas sensor can be alternately arranged is as follows:
when the ammonia gas sensor is in an adsorption working state, the first platinum electrode is connected with the negative electrode of the first power supply, so that ammonia gas trapping particles can trap and adsorb ammonia gas, and oxygen atoms split by the ammonia gas trapping particles obtain electrons at the first platinum electrode to form oxygen ions; and the second platinum electrode is connected to the positive electrode of the first power supply, so that oxygen ions formed at the first platinum electrode move to the second platinum electrode through the solid electrolyte matrix. Specifically, the ammonia gas is used for catching particles as V 2O5The description is given for the sake of example: in the adsorption operating state V2O5Capture and adsorb ammonia gas V in the adsorption gap2O5Splitting itself into one O to become V2O4The "O" gets electrons to form O2-And moving to the second platinum electrode, removing electrons at the second platinum electrode and removing electrons with O2The form escapes. In one embodiment, a V2O5The molecule can adsorb an ammonia molecule and can be automatically splitOne oxygen atom being followed by one V2O4Molecule, and one oxygen atom combines two electrons to form one oxygen ion.
When the sensor is in the adsorption working state for a period of time, the ammonia gas sensor can be switched to the desorption working state. In a desorption working state, the second platinum electrode is connected with the anode of the first power supply, the oxygen source around the second platinum electrode is tail gas, and oxygen obtains electrons at the second platinum electrode to form oxygen ions; the first platinum electrode is connected with the anode of the first power supply, oxygen ions at the second platinum electrode move to the first platinum electrode through the solid electrolyte matrix, and after the ammonia gas trapping particles of the first platinum electrode pass through the adsorption working state, one oxygen atom is lost, and one part of the oxygen ions moving to the first platinum electrode are used for repairing the ammonia gas trapping particles (adding one oxygen atom) and are used for the next adsorption working state; a part of the oxygen ions lose electrons at the first platinum electrode and escape as oxygen gas, and the oxygen gas reacts with the ammonia gas in the adsorption gap according to the following formula (6): 4NH 3+3O2→2N2+6H2O formula (6); ammonia trapping particles for N2And H2O has no trapping property and basically has no adsorption effect, and N2And H2O escapes from the adsorption gap to achieve the effect of ammonia desorption. Specifically, the ammonia gas is used for capturing particles as V2O5The description is given for the sake of example: after the adsorption working state, the ammonia gas catches the particle and becomes V2O4，V2O4Still has the capacity of adsorbing and capturing ammonia gas, and V2O4Is difficult to continue to self-disassemble to form V2O3When the ammonia gas sensor is in a desorption working state, oxygen ions move to the first platinum electrode and lose electrons to become oxygen atoms, a part of the oxygen atoms overflow the first platinum electrode in the form of oxygen gas, and the oxygen gas and the ammonia gas in the adsorption gap react in the formula (4) to generate N2And H2O; another part of the oxygen atoms with V2O4Contacting, V2O4Repaired to V2O5. Therein, theIn the process, V2O4And V2O5For N generated by reaction2、H2O has substantially no adsorption effect, N2And H2O escapes from the adsorption gap, which is beneficial to adsorbing ammonia gas in the next adsorption working state.
In one embodiment, the ammonia gas sensor further comprises an electrode connection control device for alternately putting the ammonia gas sensor in an adsorption operation state or a desorption operation state. In one embodiment, the sensor may be disposed inside the nox sensor or outside the nox sensor; and the electrode connection control device is a conventional control device in the field and can be purchased by conventional means.
In a preferred embodiment, the electrode connection control device is used for enabling the ammonia gas sensor to be in an adsorption working state and a desorption working state in sequence in a preset cycle period, and the preset cycle period comprises a first time period and a second time period; wherein,
in a first time period, the ammonia gas sensor is in an adsorption working state;
and in the second time period, the ammonia gas sensor is in a desorption working state.
The electrode connection control device is arranged, so that the switching of two working states of the nitrogen oxide sensor is facilitated, and the working efficiency of the sensor is improved.
In a preferred embodiment, the first power voltage in the ammonia gas sensor may be 0.1 to 0.9V, preferably 0.4 to 0.5V. In one embodiment, the voltage of the first power supply is 0.45V. By adopting the voltage range provided by the preferred implementation, when the ammonia gas sensor is in an adsorption working state, enough electrons can be provided for oxygen atoms separated from ammonia gas trapping particles, and the ammonia gas trapping particles are favorably converted into oxygen ions; and when the desorption working state is realized, oxygen can be converted into enough oxygen ions, the ammonia desorption and ammonia capture particle repair of the first platinum electrode are facilitated, and the detection accuracy of the ammonia sensor is improved
As shown in fig. 1, in one embodiment, the ammonia gas sensor further comprises a third platinum electrode 9 and a heating element 10;
the third platinum electrode 9 and the heating element 10 are respectively embedded in the solid electrolyte matrix 5, and the third platinum electrode 9 and the heating element 10 are oppositely arranged at intervals; optionally, the third platinum electrode 9 and the heating element 10 are disposed outside the second inner wall of the testing chamber 1, and have a space with the second inner wall, and the second inner wall is disposed in parallel with the first inner wall at a space; optionally, a heating voltage device 11 is arranged between the third platinum electrode 9 and the heating element 10 for controlling the heating temperature of the heating element 10.
By adopting the embodiment, the temperature of the ammonia gas sensor covered on the solid electrolyte matrix and the first platinum electrode and the second platinum electrode is stable, the oxygen concentration potential most conforms to the Nernst equation, the error generated by the test condition is reduced, and the accuracy of the ammonia gas sensor is improved.
In a preferred embodiment, the heating temperature of the heating element 10 in the ammonia gas sensor is kept between 600 ℃ and 700 ℃, which is favorable for V2O4Repaired to V2O5And simultaneously, the reaction of nitrogen oxide in the test gas flow at the first platinum electrode can be avoided.
In one embodiment, the gas testing chamber of the ammonia gas sensor further comprises at least one test gas flow outlet, and the test gas flow outlet may be arranged on a side wall of the testing chamber, the side wall not being in contact with the solid electrolyte matrix. The test gas outlet is used for discharging the test gas, especially discharging N generated in desorption working state 2And H2And O, the test air flow in the test chamber is kept pure, and the test error is reduced.
In one embodiment, the electrical signal measuring device 8 comprises a current measuring device or a voltage measuring device, which is conventional in the art.
A second aspect of the present disclosure provides a method for measuring the content of ammonia in an exhaust gas aftertreatment system, using the ammonia sensor of the first aspect of the present disclosure, the method comprising the steps of:
-passing a test gas flow into the test chamber 1 of the ammonia sensor through the test gas flow inlet 6;
connecting the first platinum electrode 3 to the negative pole of the first power source 7 and the second platinum electrode 4 to the positive pole of the first power source 7;
-measuring a first electrical signal value by means of the electrical signal measuring device 8, and determining the ammonia content of the test gas stream on the basis of the first electrical signal value.
The method for measuring the content of the ammonia gas in the tail gas aftertreatment system is simple, convenient and high in accuracy.
In one embodiment, the method of measuring the ammonia content in an exhaust aftertreatment system further comprises:
-passing a standard test gas stream of known ammonia content through the test gas stream inlet 6 into the test chamber 1 of the ammonia sensor;
connecting the first platinum electrode 3 to the negative pole of the first power source 7 and the second platinum electrode 4 to the positive pole of the first power source 7;
-measuring a standard electrical signal value by means of the electrical signal measuring device 8, and determining the ammonia content in the test gas stream on the basis of the standard electrical signal value, the known ammonia content in the standard test gas stream and the first electrical signal value.
In this embodiment, do not need the ammonia sensor to adsorb the ammonia in the test air current is whole just can obtain comparatively accurate testing result, reduces and detects requirement and the degree of difficulty, makes to detect easily to realize.
In one embodiment, the electrical signal measuring device 8 is a current measuring device, and the standard electrical signal value and the first electrical signal value measured by the electrical signal measuring device 8 are changes in the current value. In a specific embodiment, taking an example that one ammonia gas trapping particle adsorbs one ammonia gas and one oxygen atom is split, one oxygen atom obtains two electrons to form oxygen ions, and if the electric signal measuring device 8 measures the current value, n is known1The number of oxygen atoms is (n) when an electron flows1(n) ammonia gas captured by ammonia gas capturing particles1And/2) the number of the cells.
In a preferred embodiment, the method of measuring the ammonia content in an exhaust gas aftertreatment system further comprises:
enabling the ammonia gas sensor to be in an adsorption working state and a desorption working state in sequence in a preset cycle period, wherein the preset cycle period comprises a first time period and a second time period; wherein,
In a first period, connecting the first platinum electrode 3 with the cathode of a first power supply 7, and connecting the second platinum electrode 4 with the anode of the first power supply 7, so that the ammonia gas sensor is in an adsorption working state;
in the second period, the first platinum electrode 3 is connected to the positive electrode of the first power supply 7, and the second platinum electrode 4 is connected to the negative electrode of the first power supply 7, so that the ammonia gas sensor is in the desorption operation state. In this embodiment, the ammonia sensor is alternately in two working states in each preset cycle period, so that not only can the ammonia capture particles be repaired and the ammonia adsorbed in the adsorption gap be cleaned, but also the airflow in the tail gas aftertreatment system can be continuously and automatically detected.
In a preferred embodiment, the first and second periods of time are of the same or different duration, preferably of the same duration. In a preferred embodiment, the duration of the first period and/or the second period is 0.5 to 3s, more preferably 0.5 to 1.2 s.
The detailed structure and principle of the ammonia sensor used in the method for measuring the content of ammonia in the exhaust gas aftertreatment system provided by the present disclosure have been described in detail in the foregoing, and are not repeated herein.
In one embodiment, the ammonia gas content in the exhaust gas after-treatment system is measured by using the ammonia gas sensor shown in fig. 1, and the method comprises the following steps:
let the known ammonia content w0The standard test airflow is introduced into a test chamber 1 of the ammonia gas sensor; connecting the first platinum electrode 3 with the cathode of a first power supply 7, connecting the second platinum electrode 4 with the anode of the first power supply 7, and adding 0.45V voltage to the first power supply; measuring the standard electrical signal value E by the electrical signal measuring device 80；
-the duration of the first time segment and the second time segment of the preset cycle period of the preset ammonia gas sensing are both 1 s; by passing a test gas stream through a test gas stream inlet 6 into an ammonia gas sensorIn the test chamber 1, in a first time period of a preset cycle period, an electrode connection control device of the ammonia gas sensor enables a first platinum electrode 3 to be connected with a negative electrode of a first power supply 7, a second platinum electrode 4 to be connected with a positive electrode of the first power supply 7, so that the ammonia gas sensor is in an adsorption working state, and in the process, a first electric signal value E is measured by an electric signal measuring device 81(ii) a In a second time period of the preset cycle period, the electrode connection control device of the ammonia gas sensor connects the first platinum electrode 3 with the positive electrode of the first power supply 7, and connects the second platinum electrode 4 with the negative electrode of the first power supply 7, so that the ammonia gas sensor is in a desorption working state;
-determining the ammonia content w in the test gas stream from the standard electrical signal value, the known ammonia content in the standard test gas stream and the first electrical signal value1For example, the calculation formula may be: w is a1＝w0.E1/E0The calculation formula is used only for illustration, and a more accurate calculation formula can be obtained according to the actual test airflow, which is not limited by the present disclosure.
A third aspect of the present disclosure provides an automotive exhaust aftertreatment system comprising a nitrogen oxide purification device and the ammonia sensor of the first aspect of the present disclosure;
optionally, the nitrogen oxide purification device comprises a diesel particulate trap and/or a selective catalytic reduction device, and the ammonia gas sensor is arranged downstream of the diesel particulate trap and the selective catalytic reduction device in the flow direction of the test gas.
Wherein, along the test gas flow direction, the upper reaches of nitrogen oxide purifier all are provided with urea injection apparatus.
The automobile exhaust aftertreatment system provided by the disclosure can effectively purify nitrogen oxides, reduce the emission of excessive ammonia gas and reduce environmental pollution.
The preferred embodiments of the present disclosure are described in detail with reference to the accompanying drawings, however, the present disclosure is not limited to the specific details of the above embodiments, and various simple modifications may be made to the technical solution of the present disclosure within the technical idea of the present disclosure, and these simple modifications all belong to the protection scope of the present disclosure.
It should be noted that the various features described in the above embodiments may be combined in any suitable manner without departing from the scope of the invention. In order to avoid unnecessary repetition, various possible combinations will not be separately described in this disclosure.
In addition, any combination of various embodiments of the present disclosure may be made, and the same should be considered as the disclosure of the present disclosure, as long as it does not depart from the spirit of the present disclosure.
Claims (11)
1. An ammonia gas sensor is characterized by comprising a gas testing chamber (1), a solid electrolyte matrix (2), a first platinum electrode (3), a second platinum electrode (4), ammonia gas capturing particles (5), a first power supply (7) and an electric signal measuring device (8);
a test gas flow inlet (6) is formed in the solid electrolyte matrix (2), and the gas test chamber (1) extends towards the interior of the solid electrolyte matrix (2) through the test gas flow inlet (6);
the second platinum electrode (4) is covered on the outer wall of the solid electrolyte matrix (2) and extends along the flow direction of the test gas flow;
the first platinum electrode (3) and the ammonia gas trapping particles (5) are sequentially coated on the first inner wall of the gas testing chamber (1) from inside to outside, and pole pieces of the first platinum electrode (3) and the second platinum electrode (4) are oppositely arranged; an adsorption gap is formed between the first platinum electrode (3) and the ammonia trapping particles (5);
The first power supply (7) is connected between the first platinum electrode (3) and the second platinum electrode (4), and the electric signal measuring device (8) is arranged between the first platinum electrode (3) and the second platinum electrode (4).
2. The ammonia gas sensor according to claim 1, wherein an ammonia gas trapping layer is arranged in the gas testing chamber (1), the first platinum electrode (3) and the ammonia gas trapping layer are sequentially coated on the first inner wall from inside to outside, and the ammonia gas trapping layer comprises the ammonia gas trapping particles (5);
optionally, the thickness of the ammonia gas trapping layer is 1-10 μm;
optionally, the width of the ammonia gas trapping layer is 2-9 mm;
optionally, the length of the ammonia gas trapping layer is 2-9 mm.
3. An ammonia gas sensor according to claim 1, wherein the ammonia gas trapping particles (5) comprise V2O5；
Optionally, the ammonia trapping particles further comprise WO3And TiO2One or two of them;
optionally, the V in the ammonia trapping particles2O5The amount of (B) is 60 to 90 wt%, preferably 80 to 90 wt%;
optionally, the particle size of the ammonia gas trapping particles is 1-10 μm, preferably 6-9 μm.
4. The ammonia gas sensor according to claim 1, wherein the ammonia gas sensor has an adsorption operation state and a desorption operation state which are alternately set;
In the adsorption working state, the first platinum electrode (3) is connected with the negative electrode of the first power supply (7), and the second platinum electrode (4) is connected with the positive electrode of the first power supply (7);
in the desorption working state, the first platinum electrode (3) is connected with the positive electrode of the first power supply (7), and the second platinum electrode (4) is connected with the negative electrode of the first power supply (7);
optionally, the ammonia gas sensor further comprises an electrode connection control device for alternately bringing the ammonia gas sensor into the adsorption operation state or the desorption operation state.
5. The ammonia gas sensor of claim 4, wherein the electrode connection control device is configured to sequentially place the ammonia gas sensor in the adsorption operating state and the desorption operating state within a preset cycle period, wherein the preset cycle period comprises a first time period and a second time period; wherein,
in the first time period, the ammonia gas sensor is in the adsorption working state;
and in the second time period, the ammonia gas sensor is in the desorption working state.
6. An ammonia gas sensor according to any one of claims 1-5, characterized in that the solid electrolyte matrix (2) comprises ZrO 2And a doping material; the doping material is selected from one or more of CaO, MgO and rare earth oxide, and the rare earth oxide is selected from Y2O3、La2O3、Gd2O3And Sm2O3One or more of the above;
optionally, in the solid electrolyte matrix (2), the ZrO2The particle size of the particles is 5-50 μm, preferably 10-20 μm;
optionally, in the solid electrolyte matrix (2), the particle size of the doping material is 5-50 μm, preferably 10-20 μm;
optionally, the doping material is selected from Y2O3And CaO;
optionally, the volume fraction of the doping material in the solid electrolyte matrix (2) is 5-12%, and more preferably 7.5-8.5%.
7. An ammonia gas sensor according to claim 1, further comprising a third platinum electrode (9) and a heating element (10);
the third platinum electrode (9) and the heating element (10) are respectively embedded in the solid electrolyte matrix (5), and the third platinum electrode (9) and the heating element (10) are oppositely arranged at intervals;
optionally, the third platinum electrode (9) and the heating element (10) are arranged outside and spaced from a second inner wall of the gas testing chamber (1), the second inner wall being arranged parallel to and spaced from the first inner wall;
Optionally, a heating voltage device (11) is arranged between the third platinum electrode (9) and the heating element (10) for controlling the heating temperature of the heating element (10).
8. A method for measuring the content of ammonia in an exhaust gas aftertreatment system, which is characterized in that the ammonia sensor of any one of claims 1 to 7 is adopted, and the method comprises the following steps:
-passing a test gas flow through the test gas flow inlet (6) into the gas test chamber (1) of the ammonia gas sensor;
-connecting the first platinum electrode (3) to the negative pole of the first power source (7) and the second platinum electrode (4) to the positive pole of the first power source (7);
-measuring a first electrical signal value using said electrical signal measuring device (8), determining the ammonia content of the test gas stream from said first electrical signal value.
9. The method of claim 8, further comprising: enabling the ammonia gas sensor to be in an adsorption working state and a desorption working state in sequence in a preset cycle period, wherein the preset cycle period comprises a first time period and a second time period; wherein,
connecting the first platinum electrode (3) with the negative electrode of the first power supply (7) and connecting the second platinum electrode (4) with the positive electrode of the first power supply (7) in the first time period so as to enable the ammonia gas sensor to be in the adsorption working state;
Connecting the first platinum electrode (3) with the positive electrode of the first power supply (7) and connecting the second platinum electrode (4) with the negative electrode of the first power supply (7) in a second time period so as to enable the ammonia gas sensor to be in the desorption working state;
optionally, the durations of the first time period and the second time period are the same or different, preferably the same;
preferably, the duration of the first period and/or the second period is 0.5-3 s, and more preferably 0.5-1.2 s.
10. The method of claim 8, further comprising:
-passing a standard test gas stream of known ammonia content through the test gas stream inlet (6) into the gas test chamber (1) of the ammonia sensor;
-connecting the first platinum electrode (3) to the negative pole of the first power source (7) and the second platinum electrode (4) to the positive pole of the first power source (7);
-measuring a standard electrical signal value using said electrical signal measuring device (8), determining the ammonia content in said test gas stream from said standard electrical signal value, the known ammonia content in said standard test gas stream and said first electrical signal value.
11. An automobile exhaust gas after-treatment system, which is characterized by comprising a nitrogen oxide purification device and an ammonia gas sensor according to any one of claims 1 to 7;
Optionally, the nitrogen oxide purification device comprises a diesel particulate trap and/or a selective catalytic reduction device, and the ammonia gas sensor is arranged downstream of the diesel particulate trap and the selective catalytic reduction device in the flow direction of the test gas.
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