CN102485326A - Electrochemical catalyst converter - Google Patents
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- CN102485326A CN102485326A CN2010105756981A CN201010575698A CN102485326A CN 102485326 A CN102485326 A CN 102485326A CN 2010105756981 A CN2010105756981 A CN 2010105756981A CN 201010575698 A CN201010575698 A CN 201010575698A CN 102485326 A CN102485326 A CN 102485326A
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- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02A—TECHNOLOGIES FOR ADAPTATION TO CLIMATE CHANGE
- Y02A50/00—TECHNOLOGIES FOR ADAPTATION TO CLIMATE CHANGE in human health protection, e.g. against extreme weather
- Y02A50/20—Air quality improvement or preservation, e.g. vehicle emission control or emission reduction by using catalytic converters
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- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
- Y02E60/00—Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
- Y02E60/30—Hydrogen technology
- Y02E60/50—Fuel cells
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Abstract
The invention provides an electrochemical catalyst converter for removing oxynitrides (NOx), carbon monoxide (CO), hydrocarbons (HCs) and particulate materials (PM) from an exhaust gas. The electrochemical catalyst converter comprises: at least a cell modulate which comprises a cathode, an anode, a membrane electrode group and a heating unit, wherein the membrane electrode group is positioned between the cathode and the anode, the heating unit is embedded in the cell module, and the cathode comprises an oxidation catalyst; a reduction gas input unit connected with one side of the anode and a reduction gas output unit connected with the other side of the anode; a reduction gas cycle pump connected with the reduction gas input unit and the reduction output unit respectively; and an exhaust gas input unit connected with one side of the cathode and an exhaust gas output unit connected with the other side of the cathode, wherein the oxynitrides in the exhaust gas decompose to form nitrogen through electrochemical promotion, and carbon monoxide, the hydrocarbons and the particulate materials form carbon dioxide and water through catalyzing by the oxidation catalyst.
Description
Technical field
The present invention relates to a kind of electrochemical catalyst converter (or claiming the electrochemical catalysis converter); Especially refer to a kind of content that can effectively lower nitrogen oxides of exhaust gas, carbon monoxide, hydrocarbon and shot-like particle, so as to the electrochemical catalyst converter of control toxic emission.
Background technology
Pure and fresh and clean air is one of people's basic important document of living, and breathes clean free of contamination air and can guarantee human stable existence healthily.The brilliance of science and technology promotes, though drive rapid economic development, yet, come from the toxic emission of the vehicles and the various factory of standing in great numbers, really also cause air to be polluted, and very huge to human lives's air quality influence.Wherein, heavy industry factory and motor-driven are the main sources of numerous polluters.
With motor vehicles is example, improve though motor-driven discharge standard is disconnected because disconnected increasing, a discharging waste gas with air pollution problems inherent, still grow with each passing day.In general, the running of motor vehicle engine is that multi-form fuel is discharged heat energy via the cylinder internal combustion, and produces transmission power; Yet in combustion process; The waste gas that produces comprise usually nitrogen oxide (NOx), carbon monoxide (CO), hydrocarbon (hydrocarbons, HCs), (particulate matter PM) waits noxious pollutant to shot-like particle; These materials not only can form photochemical fog (photochemical smog); More can destroy the deterioration of ozone, aggravation greenhouse effects and cause acid rain etc., and then destroy ecological environment, be detrimental to health.
Wherein, carbon monoxide is from the imperfect combustion of engine, and what itself and ferroheme were combined into Carbon monoxide haemoglobin (COHb) can be combined into oxyhaemoglobin (HbO for ferroheme and oxygen
2) 300 times, so carbon monoxide is dense when too high in the air, with the function that influences the ferroheme delivering oxygen; Nitrogen oxide is then from the chemical combination of nitrogen and oxygen, mainly with nitric oxide (NO) or nitrogen dioxide (NO
2) form discharge; Form poisonous photochemical fog and after ultraviolet ray irradiation, react with hydrocarbon; Have special odor, stimulate eyes, injure plant; And atmospheric visibility is reduced, and nitrogen oxide and airborne water reaction formation nitric acid and nitrous acid, be composition for acid rain; Hydrocarbon can stimulate respiratory system when low concentration, if concentration improves, then can exert an influence to the running function of maincenter through system.
Therefore; No matter advanced countries such as China or European Union, Japan, the U.S.; All stipulated the waste gas emission standard (like U.S. rule BIN5 and Europe rule EURO 6) that benefit becomes strict; Stipulate standard to exhaust gas discharging such as nitrogen oxide, carbon monoxide, hydrocarbon and shot-like particles,, encourage the dealer to make, research and develop, introduce simultaneously and use the technological product of the anti-system of up-to-date pollution so as to control and minimizing discharge of harmful gases.
In oxygen-enriched combusting (lean burn) the toxic emission control technology commonly used, not having any single device or converter can transform nitrogen oxide (NOx), carbon monoxide (CO), hydrocarbon (HCs) and shot-like particle simultaneously.Catalyst converter with the oxygen-enriched combusting motor vehicle exhaust system; It only carries out catalysis to carbon monoxide and hydrocarbon mostly, and the catalytic smoke filter then captures and the oxidation shot-like particle, and for nitrogen oxide; Then must rely on other auxiliary device or system, it is transformed.For example: the blast pipe of diesel vehicle is except that the oxidation catalyst converter being installed in order to catalysis carbon monoxide and the OXIDATION OF HYDROCARBONS now; Majority gas recirculation system (the exhaust gas recirculation that must arrange in pairs or groups separately again; The discharging of control nitrogen oxide such as EGR); Then (selective catalytic reduction, SCR) system comes nitrogen oxides reduction to new person to install SCR additional.
Selective catalytic reduction system operating is to utilize ammonia (NH
3) or urea (urea, CO (NH
2)
2) aqueous solution is as reactant, aqueous solution of urea injects blast pipe through nozzle can form ammonia with the water reaction, then reacts with nitrogen oxide again, makes it change nitrogen (N into
2) and water (H
2O).Yet the ammonia of tool toxicity is difficult for leaking outside except that storage the risk, can cause secondary pollution when it reacts incomplete; Moreover, this selective catalytic reduction system operating bulky, and most must collocation sophisticated sensor assist control.
In addition, " the Electrochemical catalytic reduction cell for the reduction of NOx in an O of No. the 5401372nd, United States Patent (USP)
2-containing exhaust emission " disclose a kind of device of independent removal nitrogen oxide, be to utilize the electrochemical catalysis reduction reaction, cooperate vanadic anhydride (vanadium pentaoxide, V
2O
5) the auxiliary conversion of nitrogen oxides of catalyst is nitrogen; This device must additional power source supply, one of cause in this device electrochemical cell to operate, so not only expend the energy and can't reach the target of removing pernicious gas in the waste gas simultaneously.
In addition; " the electrochemical catalyst converter of control toxic emission and generating " that No. the 201010232080.5th, one Chinese patent application; It is another origination techniques of the inventor of this case; It discloses a kind of converter that waste gas is electric energy that transforms, and the harmful substance that not only can transform in the waste gas is pollution-free material, and reaches the purpose that generating utilizes; Yet; This device must extra fuel supply, cause the solid-oxide fuel cell running in this device, so not only consume fuel and palpus fuel up treatment system when being used in motor vehicles; Increase fixing and running cost, and can reduce the useful life of device because of fuel causes carbon distribution.
Summary of the invention
Therefore, the object of the present invention is to provide a kind of electrochemical catalyst converter,, remove nitrogen oxides from exhaust gas, hydrocarbon, carbon monoxide and shot-like particle simultaneously, and avoid the consumption of power supply and fuel in order to discharge of harmful gases in the control waste gas.
In order to realize aforementioned purpose, electrochemical catalyst converter of the present invention comprises: at least one battery module, a reducing gases input block, a reducing gases output unit, a reducing gases circulating pump, a waste gas input block and a waste gas output unit.This battery module comprises a negative pole part, an anode portion, a mea and a heating unit of layered arrangement, and this mea is between this negative pole part and this anode portion, and this negative pole part comprises oxidation catalyst, and this heating unit is embedded in this battery module; This reducing gases input block and this reducing gases output unit are connected to this anode portion both sides, the input and the output of one reducing gases with as this battery module running the time, and carry out the closed circulation of reducing gases through the reducing gases circulating pump; This waste gas input block and this waste gas output unit are connected to this negative pole part both sides, the input and the output of a waste gas of handling as this battery module desire.
Wherein, this this mea to one operating temperature of heating unit heating causes this reducing gases to produce electromotive force (electromotive force) in this mea; This nitrogen oxides from exhaust gas then promotes to be decomposed to form nitrogen in this mea by the electrochemistry of this electromotive force; Carbon monoxide in this waste gas, hydrocarbon and shot-like particle are then borrowed this oxidation catalyst catalysis and are formed carbon dioxide and water, so as to purifying this waste gas.
The further improved technical scheme according to the present invention, said mea comprises a dielectric substrate, a cathode layer and an anode layer; Said dielectric substrate is between said cathode layer and said anode layer, and said cathode layer then is connected said negative pole part and said anode portion respectively with said anode layer; Said negative pole part also includes the layer of oxidation catalyst that a negative electrode road and is formed by oxidation catalyst; Said anode portion comprises an anode road; Said heating unit places said anode flow channel; Wherein said waste gas input block is communicated with said negative electrode road, causes said waste gas to carry out oxidation reaction at said negative pole part, and arrives said cathode layer and carry out decomposition reaction; Said reducing gases input block is communicated with said anode road, causes said reducing gases can arrive said anode layer and produces electromotive force.
The further improved technical scheme according to the present invention; Said negative pole part, said mea, said heating unit and said anode portion are layered arrangement, cause said negative electrode road, said layer of oxidation catalyst, said cathode layer, said dielectric substrate, said anode layer, said heating unit and said anode road range upon range of in regular turn each other.
The further improved technical scheme according to the present invention; Said anode portion, said heating unit, said mea and said negative pole part pile up in regular turn and are overmolding to a tubular structure; Cause said anode road to be positioned at the center of said tubular structure, said heating unit, said anode layer, said dielectric substrate, said cathode layer, said layer of oxidation catalyst and said negative electrode road are range upon range of around said anode road in regular turn.
The further improved technical scheme according to the present invention, said operating temperature is 350～700 ℃.
The further improved technical scheme according to the present invention, said heating unit is a heating.
The further improved technical scheme according to the present invention, the material of said oxidation catalyst is selected from the group that is made up of metal, alloy, fluorite structure metal oxide, perovskite structure metal oxide and combination thereof.
The further improved technical scheme according to the present invention, said oxidation catalyst is overlying on said cathode flow channels with the particulate pattern.
The further improved technical scheme according to the present invention, said oxidation catalyst is overlying on said cathode layer with the particulate pattern.
The further improved technical scheme according to the present invention, the material of said dielectric substrate is selected from the group that is made up of fluorite structure metal oxide, perovskite structure metal oxide and combination thereof.
The further improved technical scheme according to the present invention, the material of said anode layer are selected from by nickel and fluorite structure and belong to the group that oxide genus pottery, perovskite structure metal oxide, fluorite structure metal oxide, the perovskite structure metal oxide that adds metal, the fluorite structure metal oxide that adds metal and combination thereof are formed.
The further improved technical scheme according to the present invention, the material of said cathode layer are selected from the group that is made up of perovskite structure metal oxide, fluorite structure metal oxide, the perovskite structure metal oxide that adds metal, the fluorite structure metal oxide that adds metal and combination thereof.
The further improved technical scheme according to the present invention, said waste gas input block comprise an air and add the unit to add air to waste gas.
The further improved technical scheme according to the present invention, said reducing gases is selected from the group that is made up of the gaseous mixture of the gaseous mixture of hydrogen, carbon monoxide and carbon dioxide, carbon monoxide and hydrogen, natural gas and combination thereof.
The further improved technical scheme according to the present invention, said reducing gases circulating pump comprise the temperature of a heat exchanger with the adjustment reducing gases.
Can know by above-mentioned explanation, promote decomposition reaction and catalytic oxidation, can effectively remove the harmful components in the waste gas through electrochemistry.With respect to prior art, the present invention possesses better exhaust-gas treatment mechanism, is about to needed NOx restoring system of prior art and oxidation catalyst converter and integrates, and possess better exhaust-gas treatment efficient.Moreover compared to the structure of waste gas conversion and generating, the present invention simplifies Circuits System, and then reaches low-cost, easy to manufacture advantage.And the present invention more repeats to use reducing gases through this reducing gases circulating pump, must the fuel up treatment system not produce this reducing gases, and is minimized fixing and running cost, and can select not anode-side reducing gases that can carbon distribution for use and the useful life of promoting device.
Relevant detailed technology content of the present invention and preferred embodiment, conjunction with figs. explanation as after.
Description of drawings
Fig. 1 is the system schematic of one embodiment of the invention;
Fig. 2 is the configuration diagram of the present invention one battery module embodiment;
Fig. 3 is the system schematic of another embodiment of the present invention; And
Fig. 4 is the configuration diagram of another battery module of the present invention embodiment.
The specific embodiment
The present invention proposes a kind of electrochemical catalyst converter, in order to reduce the discharging of nitrogen oxides of exhaust gas (NOx), carbon monoxide (CO), hydrocarbon (HCs) and shot-like particle (PM).What must explain is that electrochemical catalyst converter of the present invention is applicable to any exhaust gas discharging device, for example: the exhaust emission device of factory chimney, generator, various vehicles, the vehicles, boats and ships etc. etc. do not have special qualification at this.And the present invention says it " waste gas ", and then general reference is desired the gas of purified treatment, and it can comprise above-mentioned four harmful components, or only comprises one of which or its two; So the present invention says that it " waste gas " must not be made up of above-mentioned four harmful components.Relevant detailed description of the present invention and technology contents, existing conjunction with figs. is explained as follows:
See also Fig. 1 to shown in Figure 2; It is the configuration diagram of a system schematic of the present invention and a battery module embodiment, and is as shown in the figure: electrochemical catalyst converter 1 of the present invention comprises a battery module 10, a heating unit 20, a waste gas input block 30, a waste gas output unit 40, a reducing gases input block 50, a reducing gases output unit 60 and a reducing gases circulating pump 90; This heating unit 20 makes it to reach its operating temperature in order to heat this battery module 10; This waste gas input block 30 is connected battery module 10 respectively with this waste gas output unit 40; Input and output as these battery module 10 purifying exhaust airs; Wherein waste gas input block 30 can be from an exhaust gas source 70 input waste gas; This exhaust gas source 70 for example boiler, chimney, generator, car engine etc. produces the source exhaust gas person, and wherein this waste gas input block 30 can comprise an air and add unit 80 to add air to waste gas, and this air adds unit 80 and can be an air pump; This reducing gases input block 50 is connected battery module 10 respectively with this reducing gases output unit 60; As reducing gases input and output that these battery module 10 runnings are provided; And connect reducing gases circulating pump (Circulating Pump) 90 respectively; Wherein this reducing gases input block 50 can comprise a reducing gases storage cylinder, and storage reducing gases is delivered to reducing gases input 50 in it.Wherein, this reducing gases circulating pump 90 can comprise a heat exchanger (heat exchanger) (not shown), with the temperature of adjustment reducing gases.
Wherein, the stacked structure of this battery module 10 can be a solid-oxide fuel cell (solid oxide fuel cell, stacked structure SOFC) comprises (tubular) of tubulose and (planar) on plane, but do not exceed with it.This battery module 10 can thin again portion be distinguished, and comprises: and a negative pole part 11 (cathode compartment), an anode portion 12 (anode compartment) and a mea 13 (membrane-electrode assembly, MEA).This negative pole part 11, anode portion 12 and mea 13 be layered arrangement each other, and this mea 13 is between negative pole part 11 and anode portion 12.
Further, this mea 13 comprises: a cathode layer 131 (cathode layer), an anode layer 132 (anode layer) and a dielectric substrate 133 (electrolyte layer); This dielectric substrate 133 is between cathode layer 131 and anode layer 132.The place that this mea 13 produces electromotive force and decompose nitrogen oxides for the present invention, wherein dielectric substrate 133 lays respectively at the gas of cathode layer 131 and anode layer 132 in order to obstruct.
In an above-mentioned embodiment, this dielectric substrate 133 can be a solid electrolyte, and this solid electrolyte belongs to the non-porous film structure, can intercept both sides gas and conducting ion with the film mode; The group that the optional free fluorite structure metal oxide of its material (fluorite metal oxides), perovskite structure metal oxide (perovskite metal oxides) and combination thereof are formed; For example: yttria-stabilized zirconia (the yttria-stabilized zirconia of fluorite structure; YSZ), gadolinium oxide doped cerium oxide (the gadolinia-doped ceria of stabilized zirconia, fluorite structure; GDC), the strontium of doped cerium oxide, perovskite structure and magnesium doped lanthanum gallate (strontium/magnesium-doped lanthanum gallate, LSGM), doped lanthanum gallate.
Waste gas input block 30 of the present invention and waste gas output unit 40 are the two ends that are connected in negative pole part 11, and wherein negative pole part 11 can comprise again: the layer of oxidation catalyst 112 (oxidation catalyst layer) that a cathode flow channels 111 (cathode channel) and is formed by oxidation catalyst.Wherein, Those oxidation catalysts can the particulate pattern be overlying on the surface of cathode flow channels 111; Or can be the porous layer (porous layer) that is connected between this cathode layer 131 and the cathode flow channels 111 and form this layer of oxidation catalyst 112, it is in order to the oxidation reaction of catalytic gas; These cathode flow channels 111 both sides then connect this waste gas input block 30 and this waste gas output unit 40 respectively.
These anode portion 12 two ends connect reducing gases input block 50 and reducing gases output unit 60 respectively, and it is made up of an anode flow channel 121 (anode channel); In present embodiment, this heating unit 20 places between this anode flow channel 121 and this mea 13; These anode flow channel 121 both sides connect this reducing gases input block 50 and this reducing gases output unit 60 respectively, and connect reducing gases circulating pump 90 respectively, to carry out the closed circulation of reducing gases.
Whereby, desire to carry out the cathode flow channels 111 that waste gas that decontamination handles can be delivered to negative pole part 11 from waste gas input block 30.Further, nitrogen oxides from exhaust gas can be delivered to cathode layer 131 generation decomposition reactions and generate nitrogen; Carbon monoxide in the waste gas, hydrocarbon and shot-like particle then can borrow layer of oxidation catalyst 112 to be oxidized to carbon dioxide and water; At last, have neither part nor lot in the waste gas and the reacted gas of reaction, can be delivered to waste gas output unit 40 via cathode flow channels 111 again and discharge.And aspect anode portion 12, reducing gases can be delivered to the anode flow channel 121 of anode portion 12 by reducing gases circulating pump 90 autoreduction gas input blocks 50, and the reducing gases that is positioned at anode flow channel 121 is delivered to anode layer 132 again and produces electromotive force; Reducing gases can be delivered to this reducing gases circulating pump 90 through reducing gases output unit 60 again and carry out closed circulation.
The present invention is the cartalytic decomposition effect that promotes cathode layer 131 through the electromotive force that mea 13 is produced, and through the oxidation catalyst oxidizes in the negative pole part 11, in battery module 10, removes the harmful components in the waste gas simultaneously.Below will be directed against the electrochemical action and the catalytic reaction of anode layer 132 and cathode layer 131 respectively, and the reaction principle of above-mentioned pernicious gas details respectively.
At first, be used in reducing gases of the present invention and can be hydrogen (H
2), the gaseous mixture (manufactured gas, synthetic gas) of gaseous mixture, carbon monoxide and the hydrogen of carbon monoxide and carbon dioxide or natural gas etc.But those reducing gases autoreduction gas input blocks 50 are conveyed into anode portion 12.The reducing gases that gets into anode layer 132 can produce electromotive force (Δ E) in mea 13, this electromotive force be for open-circuit voltage (open-circuit voltage, OCV), its generation is according to following principle:
ΔE(OCV)＝[(RT)/(4F)]·ln[(P
O2|Cathode)/(P
O2|Anode)] (1)
Wherein, R is gas constant (gas constant), and T is an absolute temperature, and F is Faraday constant (Faradic constant), P
O2Be partial pressure of oxygen.The corresponding different oxygen partial pressure value of the different types of reducing gases of anode (Anode) side, and can produce different electromotive force; The also corresponding different oxygen partial pressure value of the oxygen concentration that negative electrode (Cathode) side is different; Also can produce different electromotive force; Be that the high more then electromotive force of oxygen content in the cathode side waste gas is big more, thereby nitrogen oxide of the present invention is big more through the ability that electrochemistry promotes to be decomposed to form nitrogen.And this reducing gases circulating pump 90 carries out circulating of reducing gases; Can promote effective entering of reducing gases and be uniformly distributed in anode layer 132; So that the electromotive force quilt is effective and evenly generation, thereby nitrogen oxide promotes the effectively generation and the evenly distribution of ability quilt of decomposition through electrochemistry.
Then 131 reactions are innocuous gas with cathode layer at negative pole part 11 from the harmful components in the waste gas.Wherein, harmful nitrogen oxide is mainly nitric oxide (NO) and nitrogen dioxide (NO
2), decomposition reaction can take place and produce nitrogen and oxygen in nitric oxide in cathode layer 131, and its reaction equation is following formula (2).
2NO→N
2+O
2 (2)
Decomposition reaction can take place and produce nitric oxide in nitrogen dioxide in cathode layer 131, and its reaction equation is following formula (3).
2NO
2→2NO+O
2 (3)
Decomposition reaction can take place and produce nitrogen and oxygen in cathode layer 131 in its nitric oxide again.
Mea 13 of the present invention is through heating unit 20 heat energy to be provided, to produce electromotive force; Consider the temperature control accuracy of system architecture of the present invention and heating unit 20, heating unit 20 of the present invention can be a heating (electrical heating element); In an above-mentioned embodiment, this heating unit 20 can porous type (porous) hollow electrothermal tube mode chimeric (embedded) between the anode portion 12 and this mea 13 of this battery module 10, with to mea 13 heating, but do not exceed with it; In above-mentioned another embodiment, this heating unit 20 can heat the operating temperature interval of 13 to 350～700 ℃ of mea, causes the generation electromotive force; Consider the improvement and the lower conversion of nitrogen oxides demand of dielectric substrate 133 materials, above-mentioned operating temperature can moderately reduce.
For the reaction aspect of removing carbon monoxide (CO), hydrocarbon (HCs) and shot-like particle in the waste gas, it can form innocuous gas through these layer of oxidation catalyst 112 catalysis, and wherein the carbon monoxide in the waste gas is oxidable is carbon dioxide; Hydrocarbon and shot-like particle (carbon containing (C) material) are oxidable to be carbon dioxide and water, and its reaction equation is respectively as shown in the formula (4), (5) and (6):
2CO+O
2→2CO
2 (4)
HCs+O
2→H
2O+CO
2 (5)
C+O
2→CO
2 (6)
In an above-mentioned embodiment, the material of oxidation catalyst is selected from by metal, alloy, fluorite structure metal oxide, perovskite structure metal oxide and other group that forms for the oxide of catalyst carrier such as aluminium oxide.
Please consult shown in Figure 3ly again, it is the system schematic of another embodiment of electrochemical catalyst converter of the present invention.Present embodiment and previous embodiment difference are that in the present embodiment, this electrochemical catalyst converter 2 comprises a plurality of battery modules 10 and a plurality of heating unit 20, and each battery module 10 piles up setting mutually; The quantity of those heating units 20 can equate with the quantity of battery module 10 or not wait, but each battery module 10 can receive those heating unit 20 heating and operate.Pattern can be in charge of, be shunted to this waste gas input block 30 and this reducing gases input block 50, with waste gas or each battery module 10 of reducing gases input; Relatively, waste gas and reducing gases that each battery module 10 last desires are discharged again being in charge of or shunt pattern and compile, and are concentrated to this waste gas output unit 40 and this reducing gases output unit 60.Whereby, the waste gas that gets into electrochemical catalyst converter 2 can be converted into pollution-free gas via the more battery module 10 of number, can relatively promote the efficient of exhaust-gas treatment.
Electrochemical catalyst converter 1,2 of the present invention also can be connected or reverse parallel connection uses, to increase the efficient that exhaust-gas treatment or heat energy use.The stacked structure that reverse parallel connection is based on this battery module 10 is the stacked structure of the solid-oxide fuel cell (planar SOFC) on a plane; The example that is stacked as with two battery modules 10; It is that each layer of one of which battery module 10 complied with reversed arrangement shown in Figure 2; And the anode layer 132 of the anode layer 132 that makes this battery module 10 and another battery module 10 and connect same heating unit 20; And a heating unit 20 provides this two battery modules, 10 heating thus, thereby can reduce the quantity of heating unit 20, and increases the efficient that heat energy uses.
Please consult shown in Figure 4ly again, it is the configuration diagram of another battery module of electrochemical catalyst converter of the present invention 10 embodiment, only because of its operation principle be same as above-mentioned, so below only be directed against the different place of structure and explain.Compared to the foregoing description, in the present embodiment, the layer stack of battery module 10 becomes the stacked structure of a tubulose solid-oxide fuel cell (tubular SOFC); As shown in the figure: this battery module 10 from the tubular structure center outward the stratiform direction comprise in regular turn: an anode road 121, a heating unit 20, a mea 13 and a negative pole part 11; Wherein, mea 13 from-inner-to-outers comprise again: an anode layer 132, a dielectric substrate 133 and a cathode layer 131; These negative pole part 11 from-inner-to-outers comprise again: a layer of oxidation catalyst 112 and a negative electrode road 111.This heating unit 20 is embedded in this anode road 121 with porous type hollow electrothermal tube mode and connects airtight in anode layer 132, in order to heat this battery module 10, makes it to reach operating temperature.In one embodiment, the group that optional free metal of the material of this layer of oxidation catalyst 112 and fluorite structure metal oxide are formed, for example: silver, palladium, platinum and gadolinium oxide doped cerium oxide etc.And comprise at electrochemical catalyst converter 2 of the present invention in the battery module 10 of a plurality of tubular structures as shown in Figure 4; Therefore its all negative electrode roads 111 are to join, and can not must adopt to be in charge of, shunt pattern and export waste gas to this waste gas output unit 40 from these waste gas input block 30 input waste gas to battery modules 10 or from battery module 10.
The present invention promotes decomposition reaction and catalytic oxidation through electrochemistry, can effectively remove the harmful components in the waste gas.On the practice, the oxygen content in the waste gas is high more, can relatively promote the operational paradigm of electrochemical catalyst converter 1,2, and therefore, the present invention is fit to be applied to the exhaust-gas treatment of oxygen enrichment combustion engine especially, for example is installed on the gas extraction system of diesel vehicle; In addition; No matter again the present invention can handle the NOx of high concentration; Therefore the diesel vehicle gas recirculation system (EGR) of need not arranging in pairs or groups is again controlled the discharging of nitrogen oxide, can fully improve the oxygen content and the temperature of engine, so the NOx of institute's generation engine middle and high concentration can be removed easily; And the generation concentration of shot-like particle can so that no longer need smoke filter by abundant reduction in the engine, institute generate micro-shot-like particle can use the oxidation catalyst treatment it.That is the present invention integrates needed NOx restoring system of prior art and oxidation catalyst converter, and possesses better exhaust-gas treatment mechanism and treatment effeciency than prior art; Simultaneously, the oxygen content of engine and the raising of temperature can be promoted its efficiency of combustion, and the fuel that can generate shot-like particle when comprising original employing EGR is burnt in engine, thereby can be significantly fuel-efficient.
Moreover; Structure compared to waste gas conversion and generating; The present invention simplifies Circuits System; The current collection device that no longer needs anode and cathode side, but and thereby the material of its layer of oxidation catalyst 112 no longer needs collected current and can select for use all to commonly use in the oxidation catalyst of catalysis carbon monoxide, hydrocarbon and shot-like particle, and then reach low-cost, high efficiency and advantage easy to manufacture.And the present invention more repeats to use reducing gases through the notion of this reducing gases circulation, does not need the outside reducing gases of extra interpolation can supply inner long-term utilization.
In addition; Electrochemical catalyst converter of the present invention can be at 450 to 600 degrees centigrade temperature operation; Can quickly heat up to operating temperature through heating unit 20 equally with preceding waste gas conversion and the structure of generating electricity; Thereafter then can by the decomposition of waste gas and oxidation institute liberated heat be kept or part is kept its operating temperature, notice that the nitric oxide decomposition of cathode side and the oxidation of carbon monoxide, hydrocarbon and shot-like particle are exothermic reaction; Reducing gases circulating pump 90 of the present invention passes through heat exchanger with the temperature of adjustment reducing gases and then the temperature of adjustment electrochemical catalyst converter; Therefore by the function of the adjustment temperature of heating unit and reducing gases circulation, the waste gas that the present invention can handle any temperature is with the operation change that adapts to engine and the variation of external environment condition.
The above is merely the preferred embodiments of the present invention, and the scope of patent protection of non-desire limitation patent of the present invention so the equivalence of using specification of the present invention and accompanying drawing content to do such as changes and modifies, all in like manner is contained in rights protection scope of the present invention.
Claims (15)
1. electrochemical catalyst converter, in order to the control toxic emission, said electrochemical catalyst converter comprises:
At least one battery module (10); Said battery module (10) comprises a negative pole part (11), an anode portion (12), a mea (13) and a heating unit (20); Said mea (13) is positioned between said negative pole part (11) and the said anode portion (12); Said heating unit (20) is embedded in said battery module (10), and said negative pole part (11) comprises an oxidation catalyst;
An one reducing gases input block (50) and a reducing gases output unit (60) are connected to said anode portion (12) both sides, an input and an output of a reducing gases when operating as said battery module (10) respectively;
One reducing gases circulating pump (90) is connected to said reducing gases input block (50) and said reducing gases output unit (60), to carry out the closed circulation of reducing gases; And
An one waste gas input block (30) and a waste gas output unit (40) are connected to said negative pole part (11) both sides, with an input and an output of the waste gas handled as said battery module (10) desire respectively;
Wherein, said heating unit (20) heats said mea (13) to an operating temperature, causes said reducing gases to produce electromotive force in said mea (13); Said nitrogen oxides from exhaust gas is then carried out decomposition reaction and is formed nitrogen in said mea (13); Carbon monoxide in the said waste gas, hydrocarbon and shot-like particle then form carbon dioxide and water through said oxidation catalyst catalysis, so as to purifying said waste gas.
2. electrochemical catalyst converter according to claim 1 is characterized in that, said mea (13) comprises a dielectric substrate (133), a cathode layer (131) and an anode layer (132); Said dielectric substrate (133) is positioned between said cathode layer (131) and the said anode layer (132), and said cathode layer (131) then is connected said negative pole part (11) and said anode portion (12) respectively with said anode layer (132); Said negative pole part (11) also includes the layer of oxidation catalyst (112) that a negative electrode road and is formed by oxidation catalyst; Said anode portion (12) comprises an anode road; Said heating unit (20) places said anode flow channel (121); Wherein said waste gas input block (30) is communicated with said negative electrode road, causes said waste gas to carry out oxidation reaction in said negative pole part (11), and arrives said cathode layer (131) and carry out decomposition reaction; Said reducing gases input block (50) is communicated with said anode road, causes said reducing gases can arrive said anode layer (132) and produces electromotive force.
3. electrochemical catalyst converter according to claim 2; It is characterized in that; Said negative pole part (11), said mea (13), said heating unit (20) and said anode portion (12) are layered arrangement, cause said negative electrode road, said layer of oxidation catalyst (112), said cathode layer (131), said dielectric substrate (133), said anode layer (132), said heating unit (20) and said anode road range upon range of in regular turn each other.
4. electrochemical catalyst converter according to claim 2; It is characterized in that; Said anode portion (12), said heating unit (20), said mea (13) and said negative pole part (11) pile up in regular turn and are overmolding to a tubular structure; Cause said anode road to be positioned at the center of said tubular structure, said heating unit (20), said anode layer (132), said dielectric substrate (133), said cathode layer (131), said layer of oxidation catalyst (112) and said negative electrode road are range upon range of around said anode road in regular turn.
5. electrochemical catalyst converter according to claim 2 is characterized in that, said operating temperature is 350～700 ℃.
6. electrochemical catalyst converter according to claim 2 is characterized in that, said heating unit (20) is a heating.
7. electrochemical catalyst converter according to claim 2 is characterized in that, the material of said oxidation catalyst is selected from the group that is made up of metal, alloy, fluorite structure metal oxide, perovskite structure metal oxide and combination thereof.
8. electrochemical catalyst converter according to claim 2 is characterized in that, said oxidation catalyst is overlying on said cathode flow channels (111) with the particulate pattern.
9. electrochemical catalyst converter according to claim 2 is characterized in that, said oxidation catalyst is overlying on said cathode layer (131) with the particulate pattern.
10. electrochemical catalyst converter according to claim 2 is characterized in that, the material of said dielectric substrate (133) is selected from the group that is made up of fluorite structure metal oxide, perovskite structure metal oxide and combination thereof.
11. electrochemical catalyst converter according to claim 2; It is characterized in that the material of said anode layer (132) is selected from by nickel and fluorite structure and belongs to the group that oxide genus pottery, perovskite structure metal oxide, fluorite structure metal oxide, the perovskite structure metal oxide that adds metal, the fluorite structure metal oxide that adds metal and combination thereof are formed.
12. electrochemical catalyst converter according to claim 2; It is characterized in that the material of said cathode layer (131) is selected from the group that is made up of perovskite structure metal oxide, fluorite structure metal oxide, the perovskite structure metal oxide that adds metal, the fluorite structure metal oxide that adds metal and combination thereof.
13. electrochemical catalyst converter according to claim 1 is characterized in that, said waste gas input block (30) comprises an air and adds unit (80) to add air to waste gas.
14. electrochemical catalyst converter according to claim 1 is characterized in that said reducing gases is selected from the group that is made up of the gaseous mixture of the gaseous mixture of hydrogen, carbon monoxide and carbon dioxide, carbon monoxide and hydrogen, natural gas and combination thereof.
15. electrochemical catalyst converter according to claim 1 is characterized in that, said reducing gases circulating pump (90) comprises the temperature of a heat exchanger with the adjustment reducing gases.
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| CN2010105756981A CN102485326A (en) | 2010-12-06 | 2010-12-06 | Electrochemical catalyst converter |
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| CN2010105756981A CN102485326A (en) | 2010-12-06 | 2010-12-06 | Electrochemical catalyst converter |
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| TWI474859B (en) * | 2012-09-24 | 2015-03-01 | Ta Jen Huang | An electro-catalytic honeycomb for controlling exhaust emissions |
| CN109772165A (en) * | 2018-12-14 | 2019-05-21 | 深圳大学 | A kind of tail gas clean-up reactor and preparation method thereof reacts pile with tail gas clean-up |
| CN110152438A (en) * | 2019-02-21 | 2019-08-23 | 邬佩希 | A kind of integrated conduct method of industrial waste gas and old and useless battery |
| CN110180385A (en) * | 2019-06-19 | 2019-08-30 | 沈阳理工大学 | Porous ceramics catalytic oxidizer and its preparation method, multipurpose high-efficiency air cleaning unit |
| CN112601599A (en) * | 2018-08-22 | 2021-04-02 | 约翰逊Ip控股有限公司 | Exhaust energy recovery converter |
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Application publication date: 20120606 |