TWI385848B - Reduction method for zno of zinc air fuel cell - Google Patents
Reduction method for zno of zinc air fuel cell Download PDFInfo
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- TWI385848B TWI385848B TW098141835A TW98141835A TWI385848B TW I385848 B TWI385848 B TW I385848B TW 098141835 A TW098141835 A TW 098141835A TW 98141835 A TW98141835 A TW 98141835A TW I385848 B TWI385848 B TW I385848B
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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
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- Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
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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
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Description
本發明係關於一種氧化鋅的還原方法,特別是關於一種鋅空氣燃料電池之氧化鋅的還原方法。The present invention relates to a method for reducing zinc oxide, and more particularly to a method for reducing zinc oxide in a zinc air fuel cell.
金屬燃料電池是以空氣中的氧氣作為電池中的氧化物,並且使用金屬物質作為負極,這樣的結構在各種電池中是屬於具有高能量密度、長期保存性及低成本特性的高性能電池,因此金屬燃料電池之研究及發展已受到各界之重視。其中又以鋅空氣燃料電池最具有代表性。A metal fuel cell uses oxygen in the air as an oxide in a battery and uses a metal substance as a negative electrode. Such a structure is a high-performance battery having high energy density, long-term storage, and low cost characteristics in various batteries. The research and development of metal fuel cells has received attention from all walks of life. Among them, zinc air fuel cells are the most representative.
請參照第1圖所示,其係為鋅空氣燃料電池之結構示意圖,通常鋅空氣燃料電池之主要結構係包含有:一空氣極板91作為陰極、一鋅極板92作為陽極及一電解液93。電解液93係介於該空氣極板91及鋅極板92之間,以於空氣極板91及鋅極板92之間傳導離子。Please refer to FIG. 1 , which is a schematic diagram of the structure of a zinc air fuel cell. Generally, the main structure of the zinc air fuel cell includes an air plate 91 as a cathode, a zinc plate 92 as an anode and an electrolyte. 93. The electrolyte 93 is interposed between the air plate 91 and the zinc plate 92 to conduct ions between the air plate 91 and the zinc plate 92.
該空氣極板91所進行之陰極反應如式(1)所示:The cathode reaction performed by the air plate 91 is as shown in the formula (1):
該鋅極板92所進行之陽極反應如式(2)所示:The anode reaction performed by the zinc plate 92 is as shown in the formula (2):
Zn (s )+2OH - →ZnO +H 2 O +2e - E 0 =1.25V……..(2) Zn ( s )+2 OH - → ZnO + H 2 O +2 e - E 0 =1.25V........(2)
其淨反應如式(3)所示:The net response is shown in equation (3):
鋅空氣燃料電池實際之開路電壓為1.35~1.45伏特(Volt)之間,而一般實際操作之電壓為0.9~1.2伏特之間。The actual open circuit voltage of the zinc air fuel cell is between 1.35 and 1.45 volts (Volt), while the voltage of the actual operation is between 0.9 and 1.2 volts.
如前述,經完全放電後之鋅空氣燃料電池內之鋅將形成氧化鋅沈澱。目前通常係收集鋅空氣燃料電池內之氧化鋅,並以固態碳(C)來將氧化鋅還原為鋅,還原獲得之鋅便可做進一步之應用。於1200K之溫度下,以固態碳還原氧化鋅的還原反應如式(4)所示:As described above, the zinc in the zinc air fuel cell after complete discharge will form a zinc oxide precipitate. At present, zinc oxide in a zinc air fuel cell is usually collected, and zinc oxide is reduced to zinc by solid carbon (C), and the zinc obtained by reduction can be further applied. The reduction reaction of zinc oxide by solid carbon at a temperature of 1200 K is as shown in formula (4):
ZnO(s) +C(s) →Zn(g) +CO(g) ,△H1200K =367.4kJ/mol........(4)ZnO (s) + C (s) → Zn (g) + CO (g) , △ H 1200K = 367.4kJ / mol........(4)
然而,以固態碳作為還原劑還原氧化鋅之吸熱量△H1200K 較高,因此需要提供較多之能量方可產生反應,造成進行還原反應之熱耗能增加;再且,以該固態碳作為還原劑,相較於其他液態及氣態之還原劑,該固態碳與該氧化鋅之接觸及混合均勻度較低,造成容易有固態碳未完全反應之缺點;再且,由於進行上述還原反應之溫度需達1200K以上,目前係以各種燃料或燃氣加熱至該1200K之高溫,造成熱源成本相對提高許多;再且,目前並未建立將鋅空氣燃料電池內的氧化鋅循環回收再利用於鋅空氣燃料電池之方法,因此,有必要對鋅空氣燃料電池之氧化鋅的還原方法進行進一步之規劃。However, the heat absorption of zinc oxide by using solid carbon as a reducing agent is higher than ΔH 1200K , so it is necessary to provide more energy to generate a reaction, resulting in an increase in heat energy consumption for the reduction reaction; further, using the solid carbon as the reducing agent Compared with other liquid and gaseous reducing agents, the reducing agent has a low degree of contact and mixing uniformity with the zinc oxide, which causes a defect that the solid carbon is not completely reacted; further, due to the above reduction reaction The temperature needs to be more than 1200K. At present, it is heated to the high temperature of 1200K by various fuels or gas, which causes the heat source cost to be relatively improved. Moreover, the zinc oxide in the zinc air fuel cell is not recycled and reused in zinc. The method of air fuel cell, therefore, it is necessary to further plan the reduction method of zinc oxide of zinc air fuel cell.
本發明目的乃改良上述缺點,以提供一種鋅空氣燃料電池之氧化鋅的還原方法,以將氧化鋅還原獲得之鋅應用於鋅空氣燃料電池之製造為目的。SUMMARY OF THE INVENTION The object of the present invention is to improve the above disadvantages to provide a method for reducing zinc oxide in a zinc air fuel cell, in order to apply zinc obtained by zinc oxide reduction to the manufacture of a zinc air fuel cell.
本發明次一目的係提供一種鋅空氣燃料電池之氧化鋅的還原方法,以降低還原反應所需之熱耗能。A second object of the present invention is to provide a method for reducing zinc oxide in a zinc air fuel cell to reduce the heat energy required for the reduction reaction.
本發明再一目的係提供一種鋅空氣燃料電池之氧化鋅的還原方法,以降低整體製程之熱源成本。Still another object of the present invention is to provide a method for reducing zinc oxide in a zinc air fuel cell to reduce the heat source cost of the overall process.
根據本發明的鋅空氣燃料電池之氧化鋅的還原方法,係包含:一回收步驟,係由放電後之鋅空氣燃料電池中回收氧化鋅;一還原步驟,將回收之氧化鋅設置於一太陽能反應裝置內,並以一氧化碳作為還原劑將該氧化鋅還原為氣態鋅;一冷卻步驟,以將該氣態鋅冷卻形成固態鋅;及一電極製作步驟,將該固態鋅用以製作鋅空氣燃料電池中的鋅電極。The method for reducing zinc oxide of a zinc air fuel cell according to the present invention comprises: a recovery step of recovering zinc oxide from a zinc air fuel cell after discharge; and a reducing step of setting the recovered zinc oxide to a solar energy reaction In the apparatus, the zinc oxide is reduced to gaseous zinc by using carbon monoxide as a reducing agent; a cooling step is performed to cool the gaseous zinc to form solid zinc; and an electrode forming step is used to prepare the zinc air fuel cell. Zinc electrode.
為讓本發明之上述及其他目的、特徵及優點能更明顯易懂,下文特舉本發明之較佳實施例,並配合所附圖式,作詳細說明如下:The above and other objects, features and advantages of the present invention will become more <RTIgt;
本發明所提供之鋅空氣燃料電池之氧化鋅的還原方法,係將回收的氧化鋅還原成固態鋅,再將該固態鋅用於製作鋅空氣燃料電池之鋅電極,以使鋅空氣燃料電池之氧化鋅可重複循環利用於鋅空氣燃料電池中。The method for reducing zinc oxide in a zinc air fuel cell provided by the present invention reduces the recovered zinc oxide to solid zinc, and then uses the solid zinc to prepare a zinc electrode of a zinc air fuel cell, so that the zinc air fuel cell Zinc oxide can be recycled in a zinc air fuel cell.
請參照第2圖所示,本發明之鋅空氣燃料電池之氧化鋅的還原方法係包含一回收步驟S1、一還原步驟S2、一冷卻步驟S3及一電極製作步驟S4。Referring to FIG. 2, the zinc oxide reduction method of the zinc-air fuel cell of the present invention comprises a recovery step S1, a reduction step S2, a cooling step S3, and an electrode preparation step S4.
請參照第2圖所示,本發明之回收步驟S1係由放電後之鋅空氣燃料電池中回收氧化鋅。更詳言之,由於鋅空氣燃料電池於放電過程中,鋅電極將進行化學反應而形成氧化鋅(ZnO)並沈積於電極中,其所進行之化學反應式如式(2)至(4)所示。因此,本實施例該氧化鋅之來源較佳於鋅空氣燃料電池完全放電後,由該鋅空氣燃料電池內回收氧化鋅,以降低製作成本。Referring to Fig. 2, the recovery step S1 of the present invention recovers zinc oxide from the discharged zinc air fuel cell. More specifically, since the zinc air fuel cell is in a discharge process, the zinc electrode will chemically react to form zinc oxide (ZnO) and deposit it in the electrode, and the chemical reaction formula is as shown in the formulas (2) to (4). Shown. Therefore, in the present embodiment, the source of the zinc oxide is preferably such that after the zinc air fuel cell is completely discharged, the zinc oxide is recovered from the zinc air fuel cell to reduce the manufacturing cost.
請參照第2及3圖所示,本發明之還原步驟S2係將該回收之氧化鋅設置於一太陽能反應裝置1內,並以一氧化碳作為還原劑將該氧化鋅還原為氣態鋅。更詳言之,本實施例回收之氧化鋅係設置於該太陽能反應裝置1內,並將一氧化碳通入該太陽能反應裝置1內,以透過該太陽能反應裝置1提供太陽能作為反應能量,使該一氧化碳將該氧化鋅還原為氣態鋅。Referring to FIGS. 2 and 3, the reducing step S2 of the present invention comprises disposing the recovered zinc oxide in a solar energy reactor 1 and reducing the zinc oxide to gaseous zinc using carbon monoxide as a reducing agent. More specifically, the zinc oxide recovered in the present embodiment is disposed in the solar energy reaction device 1 and passes carbon monoxide into the solar energy reaction device 1 to provide solar energy as reaction energy through the solar energy reaction device 1 to make the carbon monoxide. The zinc oxide is reduced to gaseous zinc.
其中,請參照4圖所示,該太陽能反應裝置1係設有一反應腔室11、一進料口12、一出料口13、一光輸入口14及一氧化鋅流體化床15。該反應腔室11係設置於該太陽能反應裝置1內;該進料口12及出料口13分別連通該反應腔室11;該光輸入口14開設於該太陽能反應裝置1,以供太陽能輸入該太陽能反應裝置1對該反應腔體11進行加熱;前述該回收之氧化鋅便以流體化床之形式設置為該氧化鋅流體化床15,該氧化鋅流體化床15係設置於該反應腔室11內。其中,太陽能較佳係透過一聚光鏡16聚光後經過該光輸入口14輸入,而供應反應所需熱量。For example, as shown in FIG. 4, the solar energy reaction device 1 is provided with a reaction chamber 11, a feed port 12, a discharge port 13, a light input port 14, and a zinc oxide fluidized bed 15. The reaction chamber 11 is disposed in the solar energy reaction device 1; the feed port 12 and the discharge port 13 respectively communicate with the reaction chamber 11; the light input port 14 is opened in the solar energy reaction device 1 for solar energy input The solar energy reaction device 1 heats the reaction chamber 11; the recovered zinc oxide is disposed in the form of a fluidized bed as the zinc oxide fluidized bed 15, and the zinc oxide fluidized bed 15 is disposed in the reaction chamber. Inside the chamber 11. Preferably, the solar energy is concentrated by a concentrating mirror 16 and then input through the light input port 14 to supply heat required for the reaction.
本實施例之一氧化碳較佳係於973~1373K溫度環境下以式(5)之反應製得,亦可混以金屬觸媒有助於反應進行:In the present embodiment, the carbon oxide is preferably obtained by the reaction of the formula (5) under a temperature of 973 to 1373 K, or may be mixed with a metal catalyst to facilitate the reaction:
C(s) +H2 O(g) =CO(g) +H2(g) ........(5)C (s) +H 2 O (g) =CO (g) +H 2(g) ........(5)
如此,所產生的氫氣與一氧化碳可經由觸媒塗佈多孔性不銹鋼薄膜(catalyst-coated porous stainless steel membrane)進行分離。分離後之氫氣,可進一步作為氫燃料電池之燃料,或者作為作為燃氣供應後續其他製程所需之熱源。而所獲得之一氧化碳則導入該太陽能反應裝置1中,以使一氧化碳將回收之氧化鋅氧化為氣態鋅。Thus, the generated hydrogen and carbon monoxide can be separated via a catalyst-coated porous stainless steel membrane. The separated hydrogen can be further used as a fuel for a hydrogen fuel cell or as a heat source for other processes subsequent to the gas supply. The obtained carbon monoxide is introduced into the solar reactor 1 so that carbon monoxide oxidizes the recovered zinc oxide into gaseous zinc.
請再參照第3及4圖所示,承上述,該回收之氧化鋅係以該氧化鋅流體化床15之形式設置於該太陽能反應裝置1內,該一氧化碳係由該進料口12通入該反應腔室11,並流經該氧化鋅流體化床15,與氧化鋅均勻混合接觸,以於1200~1600K之溫度環境下將氧化鋅還原成氣態鋅,反應如式(6)所示:Referring to FIGS. 3 and 4, the recovered zinc oxide is disposed in the solar energy reactor 1 in the form of the zinc oxide fluidized bed 15, and the carbon monoxide is introduced into the feed port 12. The reaction chamber 11 flows through the zinc oxide fluidized bed 15 and is uniformly mixed with zinc oxide to reduce zinc oxide to gaseous zinc at a temperature of 1200 to 1600 K. The reaction is as shown in the formula (6):
ZnO(s) +CO(g) =Zn(g) +CO2(g) △H1200K =185.6kJ/mol.....(6)ZnO (s) +CO (g) =Zn (g) +CO 2(g) △H 1200K =185.6kJ/mol.....(6)
反應所產生之產物氣態鋅Zn(g) 及二氧化碳CO2 便可由該出料口13輸出。The product gaseous zinc Zn (g) and carbon dioxide CO 2 produced by the reaction can be output from the discharge port 13.
如此,由於本發明係透過該太陽能反應裝置1供應太陽能作為反應能量,因此可大幅降低因高溫而造成之熱源成本;再且,將欲還原之氧化鋅以該氧化鋅流體化床15之形式設置於該太陽能反應裝置1內,可增加一氧化碳之氣體擴散速率,因此由該出料口13輸出之氣體中僅有少量未反應之一氧化碳;再且,以一氧化碳進行反應所需之吸熱量△H1200K 較低,亦可降低進行反應所需之熱耗能;再且,以該氣態之一氧化碳作為還原劑,可增加該一氧化碳與該氧化鋅之混合效率,進而增進反應率。Thus, since the present invention supplies solar energy as reaction energy through the solar energy reaction device 1, the heat source cost due to high temperature can be greatly reduced; and further, the zinc oxide to be reduced is set in the form of the zinc oxide fluidized bed 15. In the solar energy reaction device 1, the gas diffusion rate of carbon monoxide can be increased, so that only a small amount of unreacted carbon monoxide is emitted from the gas output from the discharge port 13; and the heat absorption required for the reaction with carbon monoxide is ΔH 1200K. Lower, it can also reduce the heat energy required to carry out the reaction; further, using the gaseous carbon monoxide as a reducing agent can increase the mixing efficiency of the carbon monoxide and the zinc oxide, thereby increasing the reaction rate.
請參照第2及3圖所示,本發明之冷卻步驟S3係將該氣態鋅進行冷卻形成固態鋅。更詳言之,本實施例中,由式(6)反應還原獲得之氣態鋅由該出料口13排出後便通入一冷卻器2中,以進行冷卻成顆粒狀之固態鋅,便可進行進一步之應用。此外,由該進料口13導出之二氧化碳經冷卻後便可進一步與氧化鈣(CaO)反應形成碳酸鈣,反應如式(7)所示:Referring to Figures 2 and 3, the cooling step S3 of the present invention cools the gaseous zinc to form solid zinc. More specifically, in the present embodiment, the gaseous zinc obtained by the reaction of the formula (6) is discharged from the discharge port 13 and then introduced into a cooler 2 to be cooled into a granular solid zinc. Further application. In addition, the carbon dioxide derived from the feed port 13 can be further cooled to react with calcium oxide (CaO) to form calcium carbonate, and the reaction is as shown in the formula (7):
CaO(s) +CO2(g) →CaCO3(s) ...............(7)CaO (s) +CO 2(g) →CaCO 3(s) ...............(7)
而該二氧化碳及氣態鋅因冷卻而放出的熱便可作為熱源對其他製程進行預熱。The heat released by the carbon dioxide and gaseous zinc due to cooling can be used as a heat source to preheat other processes.
其中,由於該固態鋅之顆粒大小較不均勻,因此如第3圖所示,該固態鋅較佳係再進行一篩選程序,以獲得顆粒較小且分佈均勻之固態鋅,較適合應用於鋅空氣燃料電池中鋅電極之製作。本實施例之篩選程序係將該冷卻後之固態鋅導入一氣旋機3中,透過該氣旋機3將顆粒較大之固態鋅由底部導出,而顆粒較小之固態鋅由頂部導出;由頂部導出之固態鋅進一步再導入一集塵器4中,以獲得最佳粒徑的鋅粉之固態鋅之微細顆粒,再以該篩選後之固態鋅做為材料進行該電極製作步驟S4。Wherein, since the particle size of the solid zinc is relatively uneven, as shown in FIG. 3, the solid zinc is preferably subjected to a screening process to obtain a solid zinc having a small particle size and uniform distribution, which is suitable for application to zinc. Production of zinc electrodes in air fuel cells. The screening process of this embodiment introduces the cooled solid zinc into a cyclone 3, through which the larger solid zinc is derived from the bottom, and the smaller solid zinc is derived from the top; The derived solid zinc is further introduced into a dust collector 4 to obtain fine particles of solid zinc of the zinc powder of the optimum particle size, and the electrode preparation step S4 is performed using the sieved solid zinc as a material.
請參照第2圖所示,本發明之電極製作步驟S4係將該固態鋅用以製作鋅空氣燃料電池中的鋅電極。更詳言之,本實施例係將該冷卻步驟S3所獲得之固態鋅透過粉末冶金或鑄造等加工方式製作為預定形狀之鋅電極,例如,該固態鋅若為粉末狀則可以粉末冶金之方式經燒結製為鋅電極,再進一步設置於鋅空氣燃料電池進行應用。如此,本發明便可由鋅空氣燃料電池中回收氧化鋅,再利用於鋅空氣燃料電池中作為鋅電極使用,以建立完整的鋅空氣燃料電池之氧化鋅的還原方法。Referring to FIG. 2, in the electrode fabrication step S4 of the present invention, the solid zinc is used to fabricate a zinc electrode in a zinc air fuel cell. More specifically, in this embodiment, the solid zinc obtained by the cooling step S3 is processed into a zinc electrode of a predetermined shape by a method such as powder metallurgy or casting. For example, if the solid zinc is in a powder form, it can be powder metallurgy. It is sintered to form a zinc electrode, and is further disposed on a zinc air fuel cell for application. Thus, the present invention can recover zinc oxide from a zinc air fuel cell and reuse it in a zinc air fuel cell as a zinc electrode to establish a complete zinc oxide fuel cell zinc oxide reduction method.
本發明係提供一種鋅空氣燃料電池之氧化鋅的還原方法,以將氧化鋅還原成固態鋅,用以製造鋅電極,使得氧化鋅可重複循環回收應用於鋅空氣燃料電池中。The invention provides a method for reducing zinc oxide of a zinc air fuel cell to reduce zinc oxide into solid zinc for manufacturing a zinc electrode, so that the zinc oxide can be recycled in a zinc air fuel cell.
本發明係提供一種鋅空氣燃料電池之氧化鋅的還原方法,以一氧化碳還原該氧化鋅,以降低熱吸收量。The invention provides a method for reducing zinc oxide of a zinc air fuel cell, which reduces the zinc oxide with carbon monoxide to reduce the amount of heat absorption.
本發明係提供一種鋅空氣燃料電池之氧化鋅的還原方法,利用太陽能提供反應所需之熱耗能,以降低整體製程之熱源成本。The invention provides a method for reducing zinc oxide of a zinc air fuel cell, which uses solar energy to provide heat energy required for the reaction, so as to reduce the heat source cost of the overall process.
本發明係提供一種鋅空氣燃料電池之氧化鋅的還原方法,利用將氧化鋅以流體化床方式設置於該太陽能反應裝置中,以提升一氧化碳之擴散效率及整體反應率。The invention provides a method for reducing zinc oxide in a zinc air fuel cell, which is arranged in a fluidized bed manner in the solar energy reaction device to enhance the diffusion efficiency of carbon monoxide and the overall reaction rate.
雖然本發明已利用上述較佳實施例揭示,然其並非用以限定本發明,任何熟習此技藝者在不脫離本發明之精神和範圍之內,相對上述實施例進行各種更動與修改仍屬本發明所保護之技術範疇,因此本發明之保護範圍當視後附之申請專利範圍所界定者為準。While the invention has been described in connection with the preferred embodiments described above, it is not intended to limit the scope of the invention. The technical scope of the invention is protected, and therefore the scope of the invention is defined by the scope of the appended claims.
1...太陽能反應裝置1. . . Solar reactor
11...反應腔室11. . . Reaction chamber
12...進料口12. . . Inlet
13...出料口13. . . Outlet
14...光輸入口14. . . Optical input
15...氧化鋅流體化床15. . . Zinc oxide fluidized bed
16...聚光鏡16. . . Condenser
2...冷卻器2. . . Cooler
3...氣旋機3. . . Cyclone
4...集塵器4. . . Dust collector
91...空氣極板91. . . Air plate
92...鋅極板92. . . Zinc plate
93...電解液93. . . Electrolyte
第1圖:習用鋅空氣燃料電池之示意圖。Figure 1: Schematic diagram of a conventional zinc air fuel cell.
第2圖:本發明之鋅空氣燃料電池之氧化鋅的還原方法的流程圖。Fig. 2 is a flow chart showing a method for reducing zinc oxide in the zinc air fuel cell of the present invention.
第3圖:本發明之鋅空氣燃料電池之氧化鋅的還原方法的製程示意圖。Fig. 3 is a schematic view showing the process of the method for reducing zinc oxide in the zinc-air fuel cell of the present invention.
第4圖:本發明之太陽能反應裝置的示意圖。Figure 4: Schematic diagram of the solar energy reactor of the present invention.
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