CN105606656A - Anti-silicon poisoning anti-sulfur-poisoning hot wire methane sensor - Google Patents
Anti-silicon poisoning anti-sulfur-poisoning hot wire methane sensor Download PDFInfo
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- CN105606656A CN105606656A CN201510750344.9A CN201510750344A CN105606656A CN 105606656 A CN105606656 A CN 105606656A CN 201510750344 A CN201510750344 A CN 201510750344A CN 105606656 A CN105606656 A CN 105606656A
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Abstract
The invention discloses an anti-silicon poisoning anti-sulfur-poisoning hot wire methane sensor. The anti-silicon poisoning anti-sulfur-poisoning hot wire methane sensor comprises a catalytic element and a reference element which are arranged in a hot wire structure; the catalytic element comprises an active carbon particle carrier, and a SnO2 gas sensitive layer, a Pt/Pd catalyst, and an Al2O3/SiO2 separation layer loaded on the active carbon particle carrier; the reference element comprises aluminum oxide small balls, and a conductive carbon black-doped SnO2-C/TiO2-C gas sensitive layer, an Au/CuO catalyst, and an Al2O3/SiO2 separation layer loaded on the aluminum oxide small balls. With considering of preparation cost and ensuring of service life, the hot wire structure is adopted, and the problems of the SnO2 element on improving of methane detection sensitivity, linear output, selectivity, poisoning resistance, and stability are solved.
Description
Technical field
The present invention relates to a kind of making of hot wire type methane transducer of anti-silicon sulfur poisoning-resistant, forBe the detection of the industry spot methane gas of siliceous sulfur-bearing, belong to the SnO of doping2Bulk resistorThe one of control type semiconductor gas sensor.
Background technology
Metal-oxide semiconductor (MOS) gas sensor (MetalOxideSemiconductorgasSensor, MOS) detection principle be: under certain condition (temperature), tested gas arrivesReach semiconductor surface, with the oxygen that is adsorbed on semiconductor surface, in the process of generation chemical reaction, accompanyShift with electric charge, cause the variation of semiconductor resistor, real by the variation of measurement semiconductor resistorThe now detection to gas.
Methane is stable especially tetrahedral structure, and hydrocarbon bond energy is 412.5kJ/mol, destroysHydrocarbon key needs very macro-energy, and under normal circumstances, methane gas is difficult for occurring other except burningChemical reaction. SnO2Being a kind of N-type semiconductor of wide gap, is easily to outside donates electronsMaterial, adsorb oxygen is at SnO2Material surface is oxidized to O2(ad)，O-(ad)，O2-(ad)Three kinds of ADSORPTION STATE, this process has been adsorbed the electronics in skin-material conduction band, and carrier concentration is becomeLittle, depletion layer increases, and electric conductivity declines, and the resistance value of sensing element is larger; When material exposesIn methane time, methane, by the adsorb oxygen reaction in material surface, reduces surperficial oxygen concentration,The electronics being adsorbed is released back again in conduction band and makes conduction band increase. When high temperature, methane also can enterOne step and SnO2The Lattice Oxygen of material internal reacts, and generates CO2And steam, andIntermediate CHn or CHnO, the new Surface Oxygen room forming becomes alms giver and loses electronics,Surface potential barrier reduces, and confesses electronics by conduction band, makes material electric conductivity further increase, sensingThe resistance value of element significantly reduces, and the variable quantity of resistance is directly related with the concentration of methane.
The methane transducer of a function admirable should have following characteristic feature:
1. pair methane is highly sensitive, and rapidly, recovery time is short in response;
2. with the linear output relation of methane concentration;
3. pair monitoring of environmental common gas is without response, or sensitivity is low as far as possible, as CO;
4. pair monitoring of environmental common interference gas, cross sensitivity is low and stable, as ethanol;
5. anti-silicon sulfur poisoning-resistant, as HMDS and H2S；
6. long-term behaviour is stable;
Although existing SnO at present2The methane transducer of heater-type structure, but in industrial environmentWhile detecting methane, there are 4 obvious defects:
1. output signal is non-linear;
2. gas-selectively is poor, and reducibility gas nearly all has gas-sensitive property, makes the detection of methaneEasily be disturbed;
3. poor stability, is subject to ambient temperature and humidity impact, and long-term work exists asking of signal driftTopic;
4. nonreactive silicon sulfur poisoning-resistant characteristic.
Summary of the invention
The object of the present invention is to provide a kind of hot wire type methane transducer of anti-silicon sulfur poisoning-resistant,To solve existing the problems referred to above in prior art.
To achieve these goals, technical scheme of the present invention is as follows:
A hot wire type methane transducer for anti-silicon sulfur poisoning-resistant, it comprises is arranged to hot wire type knotThe catalysis element of structure and reference element, described catalysis element comprise activated carbon granule carrier andImmobilized SnO on described activated carbon granule carrier2Gas sensing layer, Pt/Pd catalyst andAl2O3/SiO2Separating layer, described reference element comprises alumina globule and at described aluminium oxideThe immobilized SnO that mixes conductive black on bead2-C/TiO2-C gas sensing layer, Au/CuO catalysisAgent, Al2O3/SiO2Separating layer.
As preferred version, the preparation method of described catalysis element is:
Activated carbon granule is dispersed in water under ultrasonic condition, forms that active carbon is water base is suspendedLiquid;
To in the water base suspension of described active carbon according to the atomicity ratio of C and Sn be 4.0～4.5:1 adds Pd, Pt and Fe2O3The SnO of codope2Powder, after ultrasonic dispersion, then addsEnter Al2O3/SiO2Colloidal sol, has children outside the state plan after dispersion again, and centrifugation goes out solid product, washesWash dry after, for subsequent use, the ratio of wherein controlling the atomicity of Sn, Al, Si is (10～11):(0.9～1.0)：(0.2～0.3)；
Described solid product and water, according to the weight ratio of 2～5:1, are mixed with to viscosity and areThe slurries of 50～500cps;
By described slurry or be coated on platinum wire coil body coil, at 500 DEG C, burnKnot, obtains catalysis element; Or
Activated carbon granule is dispersed in water under ultrasonic condition, forms that active carbon is water base is suspendedLiquid;
To in the water base suspension of described active carbon according to the atomicity ratio of C and Sn be 4.0～4.5:1 adds Pd, Pt and Fe2O3The SnO of codope2Powder, after ultrasonic dispersion, centrifugalIsolate solid product, after washing is dry, for subsequent use;
Described solid product and water, according to the weight ratio of 2～5:1, are mixed with to viscosity and areThe slurries of 50～500cps;
By described slurry or be coated on platinum wire coil body coil, after resistance sintering, dippingOr coating one deck aluminium ion solution and Ludox, again carry out resistance sintering, obtain catalysis element.
As preferred version, the particle diameter of described activated carbon granule is that 5～90 μ m, iodine number are900～1100, specific area 900～1200m2/ g, ash content 4～5wt%, molasses value maximum is180～250。
As preferred version, the preparation of the described SnO2 air-sensitive particle doped with Pt/Pd particleMethod is: in SnO2 colloidal sol or the water base suspension of SnO2 air-sensitive particle, drip containing noble metalInorganic chloric acid, obtain the SnO2 air-sensitive particle doped with Pt/Pd particle.
As preferred version, doped with the SnO of Pt/Pd particle2In air-sensitive particle, Sn, Pd,The ratio of the atomicity of Pt is (10～11): (1.8～1.9): (0.9～1.0).
As preferred version, the described inorganic chloric acid containing noble metal is the mixed of chloroplatinic acid and the acid of chlorine palladiumCompound, the preparation method of described chlorine palladium acid is: in hydrochloric acid, add palladium bichloride, the acid of chlorine palladium.
As preferred version, the preparation method of described SnO2 colloidal sol is: at aqueous citric acid solutionIn add SnCl4·5H2After O, regulating pH is 3, produces Sn (OH)4Precipitation, described in inciting somebody to actionSn(OH)4Precipitate and separate out, is dissolved in acetic acid after chlorion is removed in washing, obtains SnO2Colloidal sol;
The preparation method of the water base suspension of described SnO2 air-sensitive particle is: under vigorous stirring,The ammoniacal liquor of 1mol/L is dropwise added to the SnCl of 0.25mol/L4In solution, until solutionPH value is 7, obtains suspension, and centrifugal by carrying out after described suspension stirring, washing is removedAfter chlorion, obtain SnO2The water base suspension of air-sensitive particle.
As preferred version, the choice criteria of the presoma of the described aluminium ion aqueous solution is: aluminium fromSub-aqueous solution decomposes, can form continuous, ventilative aluminium oxide separating layer, described aluminium fromThe presoma of the sub-aqueous solution is selected from nano aluminium oxide aqueous dispersions, hydrazine aluminum sulfate, 18 water sulphurAcid aluminium, nine water aluminum nitrates, aluminium secondary butylate, basic aluminium acetate, Carbon Dioxide aluminium, acetylacetone,2,4-pentanedioneAt least one in aluminium;
The solid content of described Ludox is that 15%, pH is 11, and viscosity is 5cps, SiO2ParticleParticle diameter be 4nm.
As preferred version, the preparation method of described reference element is:
After platinum wire coil body coil is flooded or apply containing the aluminum ions aqueous solution, switch onSintering, obtains alumina globule;
Surface at described alumina globule is repeatedly flooded/is applied and mixes conductive black and metal is urgedThe water-based slurry of the TiO2-C/SnO2-C air-sensitive particle of agent, carries out resistance sintering, formsSnO2-C/TiO2-C gas sensing layer;
Using described TiO2-C/SnO2The water-based slurry of-C air-sensitive particle carries out alumina globuleWhen sintering, between different sensitive layers, dipping/coating one deck is molten containing the aluminum ions aqueous solution and siliconThe mixture of glue, resistance sintering, forms Al2O3/SiO2Separating layer.
As preferred version, describedly comprise nano aluminium oxide aqueous dispersion containing the aluminum ions aqueous solutionLiquid, hydrazine aluminum sulfate, 18 water aluminum sulfate, nine water aluminum nitrates, aluminium secondary butylate, alkali formula acetic acidAt least one in aluminium, Carbon Dioxide aluminium, aluminium acetylacetonate.
As preferred version, described SnO2-C/TiO2The preparation method of-C air-sensitive particle is: willConductive black is dispersed in isopropyl alcohol under ultrasonic condition, then adds isopropyl alcohol tin/isopropyl alcoholTitanium, after mixing, adds water to make tin oxide/titanium oxide hydrolysate at 0 DEG C, obtains SnO2-C/TiO2-CMixture, by described SnO2-C/TiO2-C mixture at room temperature stirs 24 hours, obtainsPowder be filtered washing, finally, room temperature vacuum drying 24 hours, obtain SnO2-C/TiO2-CAir-sensitive particle.
As preferred version, described SnO2-C and TiO2In the preparation method of-C air-sensitive particle,Press element atomic ratio Sn:C=0.9～1.0:1.4～1.6, Ti:C=0.9～1.0:2.4～2.6。
As preferred version, the particle diameter of described conductive black is 5～60 nanometers, iodine number 200～400, specific area 200～400m2/g, ash content < 1wt%.
As preferred version, SnO2-C and TiO2In-C composite air-sensitive particle, by element atomRatio Sn:Ti=0.9～1.0:7.0～8.0.
As preferred version, described metallic catalyst mixes TiO2-C/SnO2-C air-sensitive particleMethod is: by SnO2-C、TiO2-C mixes air-sensitive particle and is distributed to gold chloride HAuCl4Water-solubleIn liquid, after 1 hour, the pH value to 10 of regulation system, stirs 1h, clean after chlorion,Dry.
As preferred version, mix the TiO of simple substance gold2-C/SnO2In-C air-sensitive particle, by unitElement atomic ratio Ti:Au=0.9～1.0:0.03～0.04.
As preferred version, described in mix the TiO of simple substance gold2-C/SnO2In-C air-sensitive particle, go backDoped with cupric oxide, the method for mixing of described cupric oxide is:
To the TiO that mixes simple substance gold2-C/SnO2In-C air-sensitive particle, add nano cupric oxideGrain.
As preferred version, the preparation method of described nano cupric oxide particle is: by Cu (OAc)2Be dissolved in isopropyl alcohol, be made into the solution of 0.05mol/L, stir lower warming-in-water to 83 DEG C,Solution becomes blue muddy gradually, reacts and adds 20mL water after 1 hour, and blueness is suspended thing and turnsChange into black precipitate CuO, then stir after 1 hour, cooling centrifuge washing, naturally dry under room temperatureDry, after grinding, obtain black nano CuO particle, wherein, by element atomic ratio Ti:Cu=0.9～1.0：0.10～0.15。
For above problem, this patent is from material, and component structure and manufacturing process three aspects: have doneTechnological innovation and improvement:
1. for ensureing that element has enough sensitivity and linear output, this patent has been taked three kinds of processingMethod:
1) adopt hot wire type bulk resistor control structure, by SnO2Powder is supported on activated carbon granuleAbove, make the porous spherical structure of Surface Contact area maximum, make surface reaction extend to three-dimensionalSpace, causes resistance variations to maximize;
2) by operating sensor at " heat " state, make methane and SnO2The Lattice Oxygen of material internal is sent outRaw reaction, the interference that further improves reaction rate and reduction humidity;
3) in operation element, doped precious metal Pd and Pt strengthen the sensitivity to methane, SnO2The O of adsorption2-(ad) depart from gradually with temperature rise, temperature is higher than after 170 DEG C, absorptionAmount significantly reduces. By the palladium bichloride (PdCl that adulterates in material2), utilize Pd2+" storing spot "Effect, constantly to SnO2Surface provides O2-(ad), improve element sensitivity. And doping PtPromote the decomposition of oxygen, increase O2-(ad) concentration, accelerates reaction rate.
2. for common reducibility gas carbon monoxide and ethanol in industrial environment, at SnO2TableFace and negative oxygen ion generation redox reaction, the electronics of releasing negative oxygen ion constraint, causes materialThe electricity of material is led increase, embodies gas sensitive effect. This patent is at reference element SnO2/TiO2SemiconductorIn carrier, doping has the gold of higher sensitivity to carbon monoxide, and ethanol is had to higher sensitivityCupric oxide, offset the response of catalysis element to carbon monoxide and ethanol. Mix appropriate simultaneouslyConductive black, the electric conductivity of raising reference element Semiconductor gas sensors layer;
3. for sulfur-bearing common in industrial environment and organosilicon gas, as SO2，H2S，HMDSDeng, easily making that noble metal catalyst is poisoning, inactivation, this patent has been taked two kinds of solutions:
1) catalysis element has taked activated carbon granule to support SnO2The structure of powder, at three-dimensional spaceBetween introduced activated carbon adsorption layer, absorption sulfur-bearing toxic gas is inhaled by controlling active carbon simultaneouslyThe aperture in attached hole, is blocked in SnO by silicone macromolecules such as HMDS2Outside sensitive layer, playThe effect that anti-silicon is poisoning;
2) noble metal catalyst supports in SnO2Surface, utilizes SnO2Change the electricity of Pt, PdMinor structure, improves the sensitivity to methane, has strengthened anti-poisoning performance;
4. for SnO2Surperficial control type oxide gas-sensing material, while placement for a long time, withSensitive material surface adsorbed oxygen number change, the long-time stability meeting variation of element sensitivity,This patent is at SnO2Particle surface is introduced the ventilative Al of one deck2O3/SiO2Separating layer, by SnO2Surface adsorbed oxygen and air oxygen molecule are separated, and have improved stability.
In sum, the present invention is considering cost of manufacture and is ensureing, under the condition in life-span, to adopt heatLinear structure, emphasis concentrates to have solved how to improve SnO2Element to methane detect sensitivity,The problem of linear output, selective, anti-poisoning and stability.
Brief description of the drawings
Fig. 1 is SnO2Hot wire type methane transducer catalysis element mode of appearance and microstructure,Fig. 1 a is the SEM figure of its mode of appearance, the SEM figure that Fig. 1 b is its microstructure;
Fig. 2 is SnO2The white element mode of appearance of hot wire type methane transducer and microstructure, figure2a is the SEM figure of its mode of appearance, the SEM figure that Fig. 2 b is its microstructure.
Detailed description of the invention
A hot wire type methane transducer for anti-silicon sulfur poisoning-resistant, it comprises is arranged to hot wire type knotThe catalysis element of structure and reference element, described catalysis element comprise activated carbon granule carrier andImmobilized SnO on described activated carbon granule carrier2Gas sensing layer, Pt/Pd catalyst andAl2O3/SiO2Separating layer, described reference element comprises alumina globule and at described aluminium oxideThe immobilized SnO that mixes conductive black on bead2-C/TiO2-C gas sensing layer, Au/CuO catalysisAgent, Al2O3/SiO2Separating layer.
As preferred version, the preparation method of described catalysis element is:
Activated carbon granule is dispersed in water under ultrasonic condition, forms that active carbon is water base is suspendedLiquid;
To in the water base suspension of described active carbon according to the atomicity ratio of C and Sn be 4.0～4.5:1 adds Pd, Pt and Fe2O3The SnO of codope2Powder, after ultrasonic dispersion, then addsEnter Al2O3/SiO2Colloidal sol, has children outside the state plan after dispersion again, and centrifugation goes out solid product, washesWash dry after, for subsequent use, the ratio of wherein controlling the atomicity of Sn, Al, Si is (10～11):(0.9～1.0)：(0.2～0.3)；
Described solid product and water, according to the weight ratio of 2～5:1, are mixed with to viscosity and areThe slurries of 50～500cps;
By described slurry or be coated on platinum wire coil body coil, at 500 DEG C, burnKnot, obtains catalysis element; Or
Activated carbon granule is dispersed in water under ultrasonic condition, forms that active carbon is water base is suspendedLiquid;
To in the water base suspension of described active carbon according to the atomicity ratio of C and Sn be 4.0～4.5:1 adds Pd, Pt and Fe2The SnO of O3 codope2Powder, after ultrasonic dispersion, fromThe heart is isolated solid product, after washing is dry, for subsequent use;
Described solid product and water, according to the weight ratio of 2～5:1, are mixed with to viscosity and areThe slurries of 50～500cps;
By described slurry or be coated on platinum wire coil body coil, after resistance sintering, dippingOr coating one deck aluminium ion solution and Ludox, again carry out resistance sintering, obtain catalysis element,Its surface topography and microstructure are as shown in Figure 1.
As preferred version, the particle diameter of described activated carbon granule is that 5～90 μ m, iodine number are900～1100, specific area 900～1200m2/ g, ash content 4～5wt%, molasses value maximum is180～250。
As preferred version, the described SnO doped with Pt/Pd particle2The preparation side of air-sensitive particleMethod is: to SnO2Colloidal sol or SnO2In the water base suspension of air-sensitive particle, drip the nothing containing noble metalMachine chloric acid, obtains the SnO2 air-sensitive particle doped with Pt/Pd particle.
As preferred version, doped with the SnO of Pt/Pd particle2In air-sensitive particle, Sn, Pd,The ratio of the atomicity of Pt is (10～11): (1.8～1.9): (0.9～1.0).
As preferred version, the described inorganic chloric acid containing noble metal is the mixed of chloroplatinic acid and the acid of chlorine palladiumCompound, the preparation method of described chlorine palladium acid is: in hydrochloric acid, add palladium bichloride, the acid of chlorine palladium.
As preferred version, described SnO2The preparation method of colloidal sol is: at aqueous citric acid solutionIn add SnCl4·5H2After O, regulating pH is 3, produces Sn (OH)4Precipitation, described in inciting somebody to actionSn(OH)4Precipitate and separate out, is dissolved in acetic acid after chlorion is removed in washing, obtains SnO2Colloidal sol;
Described SnO2The preparation method of the water base suspension of air-sensitive particle is: under vigorous stirring,The ammoniacal liquor of 1mol/L is dropwise added to the SnCl of 0.25mol/L4In solution, until solutionPH value is 7, obtains suspension, and centrifugal by carrying out after described suspension stirring, washing is removedAfter chlorion, obtain SnO2The water base suspension of air-sensitive particle.
As preferred version, the choice criteria of the presoma of the described aluminium ion aqueous solution is: aluminium fromSub-aqueous solution decomposes, can form continuous, ventilative aluminium oxide separating layer, described aluminium fromThe presoma of the sub-aqueous solution is selected from nano aluminium oxide aqueous dispersions, hydrazine aluminum sulfate, 18 water sulphurAcid aluminium, nine water aluminum nitrates, aluminium secondary butylate, basic aluminium acetate, Carbon Dioxide aluminium, acetylacetone,2,4-pentanedioneAt least one in aluminium;
The solid content of described Ludox is that 15%, pH is 11, and viscosity is 5cps, SiO2ParticleParticle diameter be 4nm.
As preferred version, the preparation method of described reference element is:
After platinum wire coil body coil is flooded or apply containing the aluminum ions aqueous solution, switch onSintering, obtains alumina globule;
Surface at described alumina globule is repeatedly flooded/is applied and mixes conductive black and metal is urgedThe TiO of agent2-C/SnO2The water-based slurry of-C air-sensitive particle, carries out resistance sintering, formsSnO2-C/TiO2-C gas sensing layer;
Using described TiO2-C/SnO2The water-based slurry of-C air-sensitive particle carries out alumina globuleWhen sintering, between different sensitive layers, dipping/coating one deck is molten containing the aluminum ions aqueous solution and siliconThe mixture of glue, resistance sintering, forms Al2O3/SiO2Separating layer. Its surface topography and micro-Structure as shown in Figure 2.
As preferred version, describedly comprise nano aluminium oxide aqueous dispersion containing the aluminum ions aqueous solutionLiquid, hydrazine aluminum sulfate, 18 water aluminum sulfate, nine water aluminum nitrates, aluminium secondary butylate, alkali formula acetic acidAt least one in aluminium, Carbon Dioxide aluminium, aluminium acetylacetonate.
As preferred version, described SnO2-C/TiO2The preparation method of-C air-sensitive particle is: willConductive black is dispersed in isopropyl alcohol under ultrasonic condition, then adds isopropyl alcohol tin/isopropyl alcoholTitanium, after mixing, adds water to make tin oxide/titanium oxide hydrolysate at 0 DEG C, obtains SnO2-C/TiO2-CMixture, by described SnO2-C/TiO2-C mixture at room temperature stirs 24 hours, obtainsPowder be filtered washing, finally, room temperature vacuum drying 24 hours, obtain SnO2-C/TiO2-CAir-sensitive particle.
As preferred version, described SnO2-C and TiO2In the preparation method of-C air-sensitive particle,Press element atomic ratio Sn:C=0.9～1.0:1.4～1.6, Ti:C=0.9～1.0:2.4～2.6。
As preferred version, the particle diameter of described conductive black is 5～60 nanometers, iodine number 200～400, specific area 200～400m2/ g, ash content < 1wt%.
As preferred version, SnO2-C and TiO2In-C composite air-sensitive particle, by element atomRatio Sn:Ti=0.9～1.0:7.0～8.0.
As preferred version, described metallic catalyst mixes TiO2-C/SnO2-C air-sensitive particleMethod is: by SnO2-C、TiO2-C mixes air-sensitive particle and is distributed to gold chloride HAuCl4Water-solubleIn liquid, after 1 hour, the pH value to 10 of regulation system, stirs 1h, clean after chlorion,Dry.
As preferred version, mix the TiO of simple substance gold2-C/SnO2In-C air-sensitive particle, by unitElement atomic ratio Ti:Au=0.9～1.0:0.03～0.04.
As preferred version, described in mix the TiO of simple substance gold2-C/SnO2In-C air-sensitive particle, go backDoped with cupric oxide, the method for mixing of described cupric oxide is:
To the TiO that mixes simple substance gold2-C/SnO2In-C air-sensitive particle, add nano cupric oxideGrain.
As preferred version, the preparation method of described nano cupric oxide particle is: by Cu (OAc)2Be dissolved in isopropyl alcohol, be made into the solution of 0.05mol/L, stir lower warming-in-water to 83 DEG C,Solution becomes blue muddy gradually, reacts and adds 20mL water after 1 hour, and blueness is suspended thing and turnsChange into black precipitate CuO, then stir after 1 hour, cooling centrifuge washing, naturally dry under room temperatureDry, after grinding, obtain black nano CuO particle, wherein, by element atomic ratio Ti:Cu=0.9～1.0：0.10～0.15。
For above problem, this patent is from material, and component structure and manufacturing process three aspects: have doneTechnological innovation and improvement:
1. for ensureing that element has enough sensitivity and linear output, this patent has been taked three kinds of processingMethod:
1) adopt hot wire type bulk resistor control structure, by SnO2Powder is supported on activated carbon granuleAbove, make the porous spherical structure of Surface Contact area maximum, make surface reaction extend to three-dimensionalSpace, causes resistance variations to maximize;
2) by operating sensor at " heat " state, make methane and SnO2The Lattice Oxygen of material internal is sent outRaw reaction, the interference that further improves reaction rate and reduction humidity;
3) in operation element, doped precious metal Pd and Pt strengthen the sensitivity to methane, SnO2The O of adsorption2-(ad) depart from gradually with temperature rise, temperature is higher than after 170 DEG C, absorptionAmount significantly reduces. By the palladium bichloride that adulterates in material (PdCl2), utilize Pd2+" storing spot "Effect, constantly to SnO2Surface provides O2-(ad), improve element sensitivity. And doping PtPromote the decomposition of oxygen, increase O2-(ad) concentration, accelerates reaction rate.
2. for common reducibility gas carbon monoxide and ethanol in industrial environment, at SnO2TableFace and negative oxygen ion generation redox reaction, the electronics of releasing negative oxygen ion constraint, causes materialThe electricity of material is led increase, embodies gas sensitive effect. This patent is at reference element SnO2/TiO2SemiconductorIn carrier, doping has the gold of higher sensitivity to carbon monoxide, and ethanol is had to higher sensitivityCupric oxide, offset the response of catalysis element to carbon monoxide and ethanol. Mix appropriate simultaneouslyConductive black, the electric conductivity of raising reference element Semiconductor gas sensors layer;
3. for sulfur-bearing common in industrial environment and organosilicon gas, as SO2，H2S，HMDSDeng, easily making that noble metal catalyst is poisoning, inactivation, this patent has been taked two kinds of solutions:
1) catalysis element has taked activated carbon granule to support SnO2The structure of powder, at three-dimensional spaceBetween introduced activated carbon adsorption layer, absorption sulfur-bearing toxic gas is inhaled by controlling active carbon simultaneouslyThe aperture in attached hole, is blocked in SnO by silicone macromolecules such as HMDS2Outside sensitive layer, playThe effect that anti-silicon is poisoning;
2) noble metal catalyst supports in SnO2Surface, utilizes SnO2Change the electricity of Pt, PdMinor structure, improves the sensitivity to methane, has strengthened anti-poisoning performance;
4. for SnO2Surperficial control type oxide gas-sensing material, while placement for a long time, withSensitive material surface adsorbed oxygen number change, the long-time stability meeting variation of element sensitivity,This patent is at SnO2Particle surface is introduced the ventilative Al of one deck2O3/SiO2Separating layer, by SnO2Surface adsorbed oxygen and air oxygen molecule are separated, and have improved stability.
In sum, this patent is being considered cost of manufacture and is ensureing, under the condition in life-span, to adopt heatLinear structure, emphasis concentrates to have solved how to improve SnO2Element to methane detect sensitivity,The problem of linear output, selective, anti-poisoning and stability.
In sum, be only preferred embodiment of the present invention, be not used for limiting the present inventionThe scope of implementing, all according to shape, structure, feature and essence described in the claims in the present invention scopeThe equalization that god does changes and modifies, and all should be included within the scope of claim of the present invention.
Claims (10)
1. a hot wire type methane transducer for anti-silicon sulfur poisoning-resistant, is characterized in that, comprises catalysis element and the reference element of being arranged to hot wire type structure, and described catalysis element comprises activated carbon granule carrier and immobilized SnO on described activated carbon granule carrier2Gas sensing layer, Pt/Pd catalyst and Al2O3/SiO2Separating layer, described reference element comprises alumina globule and the immobilized SnO that mixes conductive black on described alumina globule2-C/TiO2-C gas sensing layer, Au/CuO catalyst, Al2O3/SiO2Separating layer.
2. hot wire type methane transducer as claimed in claim 1, is characterized in that, the preparation method of described catalysis element is:
Activated carbon granule is dispersed in water under ultrasonic condition, forms the water base suspension of active carbon;
In the water base suspension of described active carbon, be that 4.0～4.5:1 adds Pd, Pt and Fe according to the atomicity ratio of C and Sn2O3The SnO of codope2Powder, after ultrasonic dispersion, then adds Al2O3/SiO2Colloidal sol, has children outside the state plan after dispersion again, and centrifugation goes out solid product, after washing is dry, for subsequent use, and the ratio of wherein controlling the atomicity of Sn, Al, Si is (10～11): (0.9～1.0): (0.2～0.3);
Described solid product and water, according to the weight ratio of 2～5:1, are mixed with to the slurries that viscosity is 50～500cps;
By described slurry or be coated on platinum wire coil body coil, at 500 DEG C, carry out sintering, obtain catalysis element; Or
Activated carbon granule is dispersed in water under ultrasonic condition, forms the water base suspension of active carbon;
In the water base suspension of described active carbon, be that 4.0～4.5:1 adds Pd, Pt and Fe according to the atomicity ratio of C and Sn2O3The SnO of codope2Powder, after ultrasonic dispersion, centrifugation goes out solid product, after washing is dry, for subsequent use;
Described solid product and water, according to the weight ratio of 2～5:1, are mixed with to the slurries that viscosity is 50～500cps;
By described slurry or be coated on platinum wire coil body coil, after resistance sintering, dipping or coating one deck aluminium ion solution and Ludox, carry out resistance sintering again, obtains catalysis element.
3. hot wire type methane transducer as claimed in claim 1, is characterized in that, the particle diameter of described activated carbon granule is that 5～90 μ m, iodine number are 900～1100, specific area 900～1200m2/ g, ash content 4～5wt%, molasses value maximum is 180～250, the described SnO doped with Pt/Pd particle2The preparation method of air-sensitive particle is: to SnO2Colloidal sol or SnO2In the water base suspension of air-sensitive particle, drip the inorganic chloric acid containing noble metal, obtain the SnO doped with Pt/Pd particle2Air-sensitive particle, doped with the SnO of Pt/Pd particle2In air-sensitive particle, the ratio of the atomicity of Sn, Pd, Pt is (10～11): (1.8～1.9): (0.9～1.0).
4. hot wire type methane transducer as claimed in claim 3, is characterized in that, the described inorganic chloric acid containing noble metal is the mixture of chloroplatinic acid and the acid of chlorine palladium, and the preparation method of described chlorine palladium acid is: in hydrochloric acid, add palladium bichloride, the acid of chlorine palladium, described SnO2The preparation method of colloidal sol is: in aqueous citric acid solution, add SnCl4·5H2After O, regulating pH is 3, produces Sn (OH)4Precipitation, by described Sn (OH)4Precipitate and separate out, is dissolved in acetic acid after chlorion is removed in washing, obtains SnO2Colloidal sol;
Described SnO2The preparation method of the water base suspension of air-sensitive particle is: under vigorous stirring, the ammoniacal liquor of 1mol/L is dropwise added to the SnCl of 0.25mol/L4In solution, until pH is 7, obtain suspension, centrifugal by carrying out after described suspension stirring, washing is removed after chlorion, obtains SnO2The water base suspension of air-sensitive particle.
5. hot wire type methane transducer as claimed in claim 4, it is characterized in that, the choice criteria of the presoma of the described aluminium ion aqueous solution is: aluminium ion aqueous solution decomposes, can form continuous, ventilative aluminium oxide separating layer, the presoma of the described aluminium ion aqueous solution is selected from least one in nano aluminium oxide aqueous dispersions, hydrazine aluminum sulfate, 18 water aluminum sulfate, nine water aluminum nitrates, aluminium secondary butylate, basic aluminium acetate, Carbon Dioxide aluminium, aluminium acetylacetonate;
The solid content of described Ludox is that 15%, pH is 11, and viscosity is 5cps, SiO2The particle diameter of particle is 4nm.
6. hot wire type methane transducer as claimed in claim 1, is characterized in that, the preparation method of described reference element is:
After platinum wire coil body coil is flooded or applying containing the aluminum ions aqueous solution, resistance sintering, obtains alumina globule;
The TiO that mixes conductive black and metallic catalyst is repeatedly flooded/applies on surface at described alumina globule2-C/SnO2The water-based slurry of-C air-sensitive particle, carries out resistance sintering, forms SnO2-C/TiO2-C gas sensing layer;
Using described TiO2-C/SnO2When the water-based slurry of-C air-sensitive particle carries out sintering to alumina globule, between different sensitive layers, dipping/coating one deck is containing the mixture of the aluminum ions aqueous solution and Ludox, and resistance sintering, forms Al2O3/SiO2Separating layer.
7. hot wire type methane transducer as claimed in claim 6, it is characterized in that, describedly comprise at least one in nano aluminium oxide aqueous dispersions, hydrazine aluminum sulfate, 18 water aluminum sulfate, nine water aluminum nitrates, aluminium secondary butylate, basic aluminium acetate, Carbon Dioxide aluminium, aluminium acetylacetonate containing the aluminum ions aqueous solution;
Described SnO2-C/TiO2The preparation method of-C air-sensitive particle is: conductive black is dispersed in isopropyl alcohol under ultrasonic condition, then adds isopropyl alcohol tin/isopropyl titanate, after mixing, add water to make tin oxide/titanium oxide hydrolysate at 0 DEG C, obtain SnO2-C/TiO2-C mixture, by described SnO2-C/TiO2-C mixture at room temperature stirs 24 hours, and the powder of acquisition is filtered washing, finally, room temperature vacuum drying 24 hours, obtains SnO2-C/TiO2-C air-sensitive particle;
Described SnO2-C and TiO2In the preparation method of-C air-sensitive particle, by element atomic ratio Sn:C=0.9～1.0:1.4～1.6, Ti:C=0.9～1.0:2.4～2.6.
8. hot wire type methane transducer as claimed in claim 7, is characterized in that, the particle diameter of described conductive black is 5～60 nanometers, iodine number 200～400, specific area 200～400m2/ g, ash content < 1wt%;
SnO2-C and TiO2In-C composite air-sensitive particle, by element atomic ratio Sn:Ti=0.9～1.0:7.0～8.0.
9. hot wire type methane transducer as claimed in claim 8, is characterized in that, described metallic catalyst mixes TiO2-C/SnO2The method of-C air-sensitive particle is: by SnO2-C、TiO2-C mixes air-sensitive particle and is distributed to gold chloride HAuCl4In the aqueous solution, after 1 hour, the pH value to 10 of regulation system, stirs 1h, cleans after chlorion, dry;
Mix the TiO of simple substance gold2-C/SnO2In-C air-sensitive particle, by element atomic ratio Ti:Au=0.9～1.0:0.03～0.04.
The described TiO that mixes simple substance gold2-C/SnO2In-C air-sensitive particle, also doped with cupric oxide, the method for mixing of described cupric oxide is: to the TiO that mixes simple substance gold2-C/SnO2In-C air-sensitive particle, add nano cupric oxide particle.
10. hot wire type methane transducer as claimed in claim 9, is characterized in that, the preparation method of described nano cupric oxide particle is: by Cu (OAc)2Be dissolved in isopropyl alcohol, be made into the solution of 0.05mol/L, stir lower warming-in-water to 83 DEG C, solution becomes blue muddy gradually, react and add 20mL water after 1 hour, blueness is suspended thing and changes into black precipitate CuO, then stirs after 1 hour cooling centrifuge washing, natural drying under room temperature, after grinding, obtain black nano CuO particle, wherein, by element atomic ratio Ti:Cu=0.9～1.0:0.10～0.15.
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