經濟部中央標準局員工消費合作社印製 A7 B7 五、發明説明（1 ) 發明背暑 1.發明領城 · 本發明係有關一種電化學電池及一種將本質上無水之鹵 化氫轉化成本質上乾燥之鹵氣之方法。本發明方法可用Μ 將無水鹵化氫，特別是氯化氫，溴化氫及碘化氫轉化成鹵 氣如氯，氟，溴或碘。特別是於本發明中，該電化學電池 具有可增加電池中反應物與產物之擴散電阻之質量流場。 2 .相關抟蓊夕敘沭 氯化氫（HC1)或鹽酸為許多使用氯之製造製程中之反應 副產物，例如，氯係用以製造聚氛乙烯，異氰酸酯及氯化 烴類/氟化烴類，而氯化氫為這些製程之副產物。由於供 過於求，所產生之氯化氫或酸經常無法銷售或使用，甚至 在謹慎纯化後。長距離之裝載並不經濟，環境上亦不允許 使酸或氯離子排至廢水中。使氯回收並回饋至製造製程為 處理此HC 1副產物之最理想途徑。 已發展有數種商業製程將HC1轉化成可用之氯氣，例如 參見F.R. Hinz之”循環氯之HC卜電解技術”，拜耳AG,電 化學加工會議，Innovation & Progress, Glasgow, S c o 11 a n d , U K，4 / 2 Η / 2 3 , 1 9 9 3 。 目前出現熱催化之氧化製程將無水HC1及含水HC1轉化 成氯。已知如"SheH-Chlor” ，”Ke 卜 Chlor” 及"MT-Chlor”製程之商業製程係Μ迪肯（Deacon)反應為主。在 1870年發展之原始迪肯反應係使用含氯化銅鹽之流體化床 作為觸媒。此迪肯反應一般表示如下： -4- 本紙張尺度適用中國國家標準（CNS ) Α4規格（210Χ297公釐） (請先閱讀背面之注意事項再填寫本頁) .裝·A7 B7 printed by the Staff Consumer Cooperative of the Central Bureau of Standards of the Ministry of Economic Affairs V. Description of the invention (1) Invention summer 1. The invention leads the invention. This invention relates to an electrochemical cell and a method for converting essentially anhydrous hydrogen halide into qualitatively dry The method of halogen gas. The method of the present invention can use M to convert anhydrous hydrogen halide, especially hydrogen chloride, hydrogen bromide and hydrogen iodide, into halogen gas such as chlorine, fluorine, bromine or iodine. Especially in the present invention, the electrochemical cell has a mass flow field that can increase the diffusion resistance of reactants and products in the cell. 2. Related 把 擊 湊 歊 湭 hydrochloride (HC1) or hydrochloric acid are reaction by-products in many manufacturing processes that use chlorine, for example, chlorine is used to produce polyvinyl chloride, isocyanate and chlorinated hydrocarbons / fluorinated hydrocarbons Hydrogen chloride is a by-product of these processes. Due to oversupply, the generated hydrogen chloride or acid often cannot be sold or used, even after careful purification. Long-distance loading is not economical and environmentally does not allow acid or chloride ions to be discharged into the wastewater. Recovering and returning chlorine to the manufacturing process is the most ideal way to deal with this HC 1 by-product. Several commercial processes have been developed to convert HC1 into usable chlorine gas. For example, see FR Hinz, "Circulating Chlorine HC Bu Electrolysis Technology", Bayer AG, Electrochemical Processing Conference, Innovation & Progress, Glasgow, S co 11 and, UK , 4/2 Η / 2 3, 1 9 9 3. A thermally catalyzed oxidation process currently occurs to convert anhydrous HC1 and aqueous HC1 into chlorine. It is known that commercial processes such as "SheH-Chlor", "Ke Bu Chlor" and "MT-Chlor" processes are mainly based on Deacon reaction. The original Deakin reaction developed in 1870 used a fluidized bed containing copper chloride as a catalyst. This Deacon reaction is generally expressed as follows: -4- This paper scale is applicable to the Chinese National Standard (CNS) Α4 specification (210Χ297 mm) (please read the precautions on the back before filling this page).
,1T 五、發明説明（2 ) 觸媒 A7 B7 經濟部中央標準局員工消費合作社印裝 4HC1 + 〇2 其中可使用下 而定。 觸媒 Cu C u，稀土，驗 N〇2, NOHSO^. C Γ m 0 η 對迪肯反應之 Μ外*又使用其 及氧化鉻，以改 苛化學反應條件 這些熱氧化製程 純度因此較複雜 其需要昂貴之構 催化氧化製程係 目前出現一種 水HC1轉化成氯 程。在U h d e製程 饋至電化學電池 中導致電化學反 氫氣。聚合物隔 需使所產生之稀 -» 2Cl2 + 2H2〇 列觸媒，端視使用程式（1) 反應或製程 迪肯 She 1 1 -Ch 1 or Ke1-Chlor MT-Ch 1 or 商業改良除了或取代迪肯反 他觸媒如稀土化合物，各種 良轉化率，降低输入之能量 產生對製程設備之腐蝕效果 由於需要分離不同之反應成 。其亦包含會製造高度腐蝕 造材料K用於此反應糸統。 在250T：或更高之高溫下搡 電化學製程，藉電流直接通 氣。目前之電化學商業製程 中，約22¾之HC1水溶液在 之兩個隔室，於該處曝露於 應且降低HC1濃度至17¾ ， 板分開此兩個隔室。此製程 (17!〇HCl再循環並再生22¾ (1) 之反應或製程 應中所 型式之 ，及減 。然而 份K達 性之中 再者， 作。 過溶液 已知如 6 5°至 電池之 而產生 在電解 之HC 1 用之銅 氧化氮 少由嚴 ，通常 到產物 間物， 這些熱 而使含 ϋ h d e 製 8 0°C 下 直流電 氯氣及 步驟中 溶液供 (請先閱讀背面之注意事項再4.寫本頁) -裝_ 訂 5 本紙張尺度適用中國國家標準（CNS ) A4規格（210X 297公釐） 經濟部中央標準局員工消費合作社印裝 A7 B7 五、發明説明（3 ) 饋入電化學電池中。Uhde製程之總反應Μ下列程式表示： 電解 2HC1 (含水）-^ Η2 (濕）+ CU (濕）（2) 由程式（2)明顯看出，由（Ihde製程製得之氯氣為溼的， 一般含有約1¾至2¾之水。此溼氯氣接著需再加工而製得乾 煉之可用氣體。若水中HC1濃度變得太低，則可能自 Uhde製程中存在之水產生氧。Uhde製程因水存在而可能之 副反應K下式程式表示·· 2H20 -> 〇2 + 4H * + 4e - (3)· 再者，llhde製程中存在之水限制了電池可進行至低於 500 amps/ft2時之電流密度，係由於此副反應之故。此副 反應導致電效率降低及電池元件之腐蝕。 處理含水HC1之其他電化學製程述於Balko之美國專利 第4,31 1,568號。Balko使用具有固賭聚合物電解質隔膜 之電解電池。在水溶液中圼氫雛子及氛離子態之氯化氫係 導入電解電池中，此固體聚合物電解質隔膜結合至陰極’ Μ自陰極表面傳送至隔膜。於Balko中，控制及使氧逸出 之副反應減至最小為重要之考慮。氧逸出降低電池效率並 引致電池元件之快速腐蝕。Balko所用之陰極孔徑及電極 厚度之設計及構造使氯離子之输送達最大，此引致有效之 氯逸出同時使氧逸出達最小，此係由於氯雜子在接近陰極 表面會消耗之條件下，氧逸出傾向於增加之故。在Balko 中，雖然氧逸出可減至最小，但並未消除，由Balko之圖 3至5可看出，總電流密度增加時，氧逸出率增加，其可 -6 本紙張尺度適用中國國家標準（CNS ) A4規格（210X297公釐） (請先閲讀背面之注意事項再填寫本頁) 訂 經濟部中央標準局員工消費合作社印製 A7 _ B7 五·、發明説明（4 ) 由產生之氛中發現到氧濃度增加而得証。Balko可在較高 之電流密度下操作，但受氧逸出之有害影響所限制。若 B a I k 〇電池在高電流密度下操作，則陰極將損害。 發明概沭 本發明藉由提供一種電化學電池而用Μ自本質上無水之 鹵化氫直接製得本質上乾燥之鹵氣而可解決習知技藝之問 題。此電池及方法可使製造製程副產物之無水鹵化氫直接 加工，而不需先溶解鹵化氫於水中，當進行時，此直接製 造本質上乾燥之鹵氣（例如氯氣）之製程比需自氯氣分離水 之習知製程更節省資本。此製造本質上乾燥之鹵氣之直接 製程亦比習知氯化氫之電化學轉換需要更低之成本。此儍 點可直接降低習知技藝之於含水電化學製程中產生之氯之 每磅粉末之成本。此直接製造本質上乾燥之鹵氣之製程亦 提供一種與習知技藝之電化學或催化糸統所製得者比較， 可Μ更少加工步驟製造更乾燥氯氣之製程，因此可簡化加 工條件及降低資金成本。 特別是，本發明之電化學電池包括氣體擴散層，此層厚 度可·增加，其將增加電池之反應物及產物之擴散電阻。 為了達到前述解決法且依據本文所包含且較廣之本發明 目的，係提供一種由反應物製造產物之電化學電池，包括 電極，配置於與電極之一側接觸之隔膜；將電流導向電極 之電流匯流排，其中該電流匯流排係置於電極之另一側； 及配置於電極與電流匯流排間之流場，供增加電池之反應 物及產物之擴散電阻。 ~ 7 - 本紙張尺度適用中國國家標準（CNS ) Α4規格（210Χ 297公釐） (請先閱讀背面之注意事項再填寫本頁) .人-裝· ,1Τ 經濟部中央標準局員工消費合作社印製 A7 B7 __ ____—- 五、發明説明（5 ) 再依據本發明之目的，係提供一種自本質上無水之齒化 氫直接製造本質上乾燥之鹵氣之電池，該電化學謹池包Μ 使本質上無水之鹵化氫之分子氧化以製造本質上乾燥之處 氣及質子之裝置；於其内输送質子之陽離子输送裝置’其 中該氧化裝置係置於與該陽離子输送裝置之一側接觸；$ 原所输送之質子之装置，其中遨原裝置係置於與該曝離子 输送装置之一側接觸，及置於該選原装置及锺流匯流排之 間Μ增加電池之反應物與產物之擴散電阻之裝置。 圖式之簡要說明 圖1為本發明第一及第二具體例之自無水鹵化氫製造_ 氣之電化學電池之剖面分解圖。 圖1Α為圖1所示之陰極及陽極質量流場之上視剖面圖° 圖2為本發明第三具體例之自含水鹵化氫製造例如商氣 之電化學電池之透視圖。 較住亘鵲例之紡沭 現參考附圖所說明之本較佳具體例作更詳细敘述° 依據本發明之第一及第二具體例，係提供一種自無水之 鹵化氫直接製造本質上乾燥之鹵氣之雷化學電池。此種® 池一般示如圖1之10;本發明之電池係以本發明之較佳具 體例加以說明，其係自無水氯化氫直接製造本質上乾燥之 氯氣。此電池又可用κ自個別無水鹵化氬，如溴化氫’氣 化氫及碘化氫製得其他鹵氣體，如溴、氟及碘。”直接”一 詞意指此電化學電池可除去自所製得之鹵氣移除水之需求 或在電化學處理前將本質上無水之鹵化氫轉化成含水鹵人 本紙張尺度適用中國國家標準（CNS ) Α4規格（210 X 297公釐）. (請先閱讀背面之注意事項真填寫本貰) -装. 訂 經濟部中央標準局員工消費合作社印製. A7 B7 五、發明説明（6 ) 氫之需求。第一具體例中，於此電池中產生氯氣及氫。於 第二具體例中，藉此電池產生水及氯氣，將於下文更詳细 說明。 第一及第二具體例之電人電池包括電極。或者，第一及 第二具體例之電化學電池可敘述為包括使本質上無水之鹵 化氫之分子氧化而製得本質上乾燥之鹵氣及質子之裝置， 此氧化裝置為電極，或更詳而言之，為圖1所示之陰極 12。在陰極側，電化學電池1〇具有陰極側入口14及陰極側 出口 16。由於於此較佳具體例中，無水HC1係經過該入載 送，且氯氣係經由出口載送，因此入口及出口可K全氟聚 合物親裡，如E.I du Pont de Nemours及達拉威威靈頓公 司（後文中表示為”杜邦·’）銷售之TEFLON® PFA (後文中 表示為” TEFLON*® PFA”）。 第一及第二具體例之電化學電池亦包括输送質子於其内 之陽離子输送裝置*其中氧化裝置之一側係置於與陽離子 输送裝置之一側接觸。較好，陽離子输送裝置為圖1所示 之陽離子输送隔膜18。更詳而言之，隔膜18可為由氟-或 全氟聚合物，較好為兩種或多種氟-或全氟單體（其至少 —種具有側鏈磺酸基）之共聚物所製得之而售陽雜子隔膜 。由於羧酸基當被質子化時易降低隔膜之導電性，因此其 存在為不期望者。各種適宜樹脂材質為可商業購得者或可 依據等利文獻製得，其包含具有一 CF2CFRS〇3Fm -〇CF2CF2CF2S〇3H型側鏈之氟化聚合物（其中R為F, Cl ,CF2C1或（：1至（：1。全氟烷基）。此隔膜樹脂可為例如四氟 -9 - 本紙張尺度適用中國國家標準（CNS ) A4说格（210X 297公釐） ----.---.—{—裝— (請先聞讀背面之注意事項再填寫本頁) 訂 經濟部中央標準局員工消費合作社印褽 A7 B7 五、發明説明（7 ) 乙烯與 CF2= CFOCF2CF(CF3)OCF2CF2S〇3H 之共聚物。有時 候此等樹脂可呈具有側链- s〇2f基態而非- s〇3h基。此氟 化磺醢基可藉氫氧化鉀水解成- S〇3K基，接著與酸交換成 -s〇3h基。由聚四氟乙烯及含磺酸基側鐽之聚氟化磺醯乙 烯醚之水合共聚物製得之適宜陽離子隔膜係由E. I. Du Pont de Nemours及達拉威威靈頓公司（下文中表不為” 杜邦” ）M商標"NAFIONM下文中表示為HAFI0N® )提供 。特定言之，含側鏈磺酸基之NAFI0N®隔膜包含NAFI0N® 117, NAFI0N® 324 及 HAFION®» 417。第一種 NAFI0N® 為 未支撐者且具有1100克之當量重量，當量重量定義為中和 1升之1M氫氧化納溶液所需之樹脂量。其他兩種NAF Ι0Ν®» 均係支撐於氟碳織物上者，NAF ION® 417之當量重量亦為 11 0 0克；N A F I 0 N 3 2 4具有兩層结構，一具有11 0 0克當 霣重量之125微米厚之隔膜及具有1 500克當量重量之25微 米厚之隔膜。其亦MHAFION® 117F级提供，其係具有可 轉化成磺酸基之側鏈-S〇2F基之先質隔膜。 雖然本發明使用固體聚合物電質隔膜，但使用非聚合物 之其他陽離子輸送隔膜亦在本發明範圍内。例如可使用導 質子之陶磁如/3 -氧化鋁。/3 -氧化鋁為具有一般結構為 Na2〇xAl2〇3(其中X自5(/3”-氧化鋁）至11( /3-氧化鋁 )之範圍）之非化學計量结晶化合物類。此材質及數種可 用於本發明之固體電解質敘述於A.J. Appleby及F.R. Foulkes，Van Nostrand Reinhold，之燃料電池手冊，妞 約，1989年，第308-312頁。其他可用之固體態質子導體 -10- 本紙張尺度適用中國國家標準（CNS ) A4規格（210X297公釐） (請先閱讀背面之注意事項再填寫本頁) 丨裝. 訂 經濟部中央標準局員工消費合作社印製 A7 B7 五、發明説明（8 ) ，特別是緦及鋇之鈽酸鹽如鈽酸鑌酸緦 (SrCe〇.B5Yb〇.〇5〇3-a )及紳酸敎酸銀 (83〇6〇.0}'1〇1〇.〇1〇3-«)述於』6>/1)151<1,〇3 1*1>及]?6111^1<之最 終報導D0E/MC/242 1 8 -2957 ，其係為1 990年12月美國伊利 諾州芝加哥之氣體技術協會之摩根市能源技術中心之化石 能源局之能源部份所作之準備。 第一及第二具體例之電化學電池亦包括電極，或陽極 20;或者，第一及第二具體例之電化學電池可敘述為包括 邐原所榆送之質子之装置，其中該堪原裝置係置於與陽離 子輸送裝置之另一側接觸。此邐原裝置包括陽極20，其中 陽極20係置於與隔膜18之另一側（與陰極接觸側相反之一 側）接觸，如圖1所說明。陽極20具有陽極側入口 24及陽 極側出口 2 6，如圖1所示。由於於此較佳具髏例中，係處 理無水HC1 ，且由於某些氯化物通過隔瞑且因此HC1存在 於電池之陽極側，因此該陽極人口及出口可以TELF0N® PFA襯裡。 如熟悉本技藝已知者，若電極置於隔膜相反面’則陽離 子電荷（HC1反應中之質子）經由隔膜自陰極输送至陽極’ 而各電極進行半電池反應。於第一及第二具體例中’無水 氯化氫分子係經由陰極側入口 14输送至陰極表面’無水氯 化氫之分子經氧化產生本質上乾燦之氯氣及質子° 本質 上乾燥之氯氣經由陰極側出口 16排出，如圖1所不°質子 (1T)經隔膜输送並在陽極運原，此將更詳述如1" ° 陰極及陽極可包括多孔之氣體擴散電棰’此種電極提高 -11- 本紙張尺度適用中國國家標準（CNS〉A4規格（210X297公釐） (請先閲讀背面之注意事項再4.寫本頁) —裝. 訂, 1T V. Description of the invention (2) Catalyst A7 B7 Printed and printed by 4HC1 + 〇2 of the employee consumer cooperative of the Central Bureau of Standards of the Ministry of Economic Affairs, which can be used depending on the use. The catalyst Cu Cu, rare earth, NO2, NOHSO ^. C Γ m 0 η is also used for the Deakin reaction * and its chromium oxide to improve the chemical reaction conditions. These thermal oxidation process purity is more complicated Its need for an expensive catalytic oxidation process is the conversion of water HC1 to chlorine. Feeding into the electrochemical cell in the U h d e process leads to electrochemical dehydrogenation. The polymer needs to make the produced dilute-»2Cl2 + 2H2〇 series catalyst, depending on the use of the program (1) reaction or process Deakin She 1 1 -Ch 1 or Ke1-Chlor MT-Ch 1 or commercial improvement except or Replacing Deakin anti-catalysts such as rare earth compounds, various good conversion rates, reducing the energy input to produce corrosion effects on process equipment due to the need to separate different reaction components. It also contains the highly corrosive material K used for this reaction system. The electrochemical process is carried out at a temperature of 250T: or higher, and the current is directly ventilated. In the current electrochemical commercial process, about 22¾ of the HC1 aqueous solution is in the two compartments, where it is exposed to and reduces the HC1 concentration to 17¾, the plate separates the two compartments. This process (17! 〇HCl recycle and regenerate 22¾ (1) The reaction or process should be of the type and reduced. However, it is the best in the performance of K. The solution is known as 65 ° to the battery The resulting copper oxynitride used in electrolysis of HC 1 is less stringent, usually to the product intermediary. These heats make it contain DC current chlorine gas and solution in the step at 80 ° C made by ϋ hde (please read the notes on the back first Matter 4. Write this page again)-Installation _ Order 5 This paper standard is applicable to the Chinese National Standard (CNS) A4 specification (210X 297 mm) A7 B7 printed and printed by the Staff Consumer Cooperative of the Central Bureau of Standards of the Ministry of Economy V. Description of invention (3) It is fed into the electrochemical cell. The total reaction of the Uhde process is expressed by the following formula: Electrolysis 2HC1 (aqueous)-^ Η2 (wet) + CU (wet) (2) Obviously seen from the formula (2), obtained by the (Ihde process The chlorine gas is wet and generally contains about 1¾ to 2¾ of water. This wet chlorine gas needs to be reprocessed to make a dry usable gas. If the HC1 concentration in the water becomes too low, it may be generated from the water present in the Uhde process Oxygen. Possible side reaction of Uhde process due to the presence of water K The formula expression ·· 2H20-> 〇2 + 4H * + 4e-(3) · In addition, the water present in the llhde process limits the current density that the battery can carry to below 500 amps / ft2, due to this Because of side reactions. This side reaction leads to a reduction in electrical efficiency and corrosion of battery components. Other electrochemical processes for the treatment of water-containing HC1 are described in US Patent No. 4,31 1,568 to Balko. Balko uses electrolysis with solid polymer electrolyte separators Batteries. In aqueous solution, hydrogen larvae and atmospheric ionic hydrogen chloride are introduced into an electrolytic cell. This solid polymer electrolyte separator is coupled to the cathode. M is transferred from the cathode surface to the separator. In Balko, it controls and allows oxygen to escape. Minimizing the reaction is an important consideration. Oxygen escape reduces battery efficiency and causes rapid corrosion of battery components. The design and construction of the cathode aperture and electrode thickness used by Balko maximizes the transport of chloride ions, which results in effective chlorine escape At the same time, the oxygen escape is minimized. This is due to the fact that chlorine escapes tend to increase under the conditions that the chlorine impurities will be consumed near the cathode surface. In Balko, although oxygen escape It can be reduced to the minimum, but it has not been eliminated. As can be seen from Figures 3 to 5 of Balko, when the total current density increases, the oxygen escape rate increases. 210X297mm) (Please read the precautions on the back before filling in this page) Printed by the Ministry of Economic Affairs Central Standards Bureau Employee Consumer Cooperative A7 _ B7 V. Description of invention (4) From the increase in oxygen concentration found in the resulting atmosphere Certified. Balko can operate at a higher current density, but is limited by the harmful effects of oxygen evolution. If the B a I k 〇 battery is operated at a high current density, the cathode will be damaged. SUMMARY OF THE INVENTION The present invention can solve the problems of the conventional art by providing an electrochemical cell to directly produce an essentially dry halogen gas from hydrogen halide which is essentially anhydrous. This battery and method can directly process the anhydrous hydrogen halide as a by-product of the manufacturing process without first dissolving the hydrogen halide in water. When proceeding, the process of directly manufacturing an essentially dry halogen gas (such as chlorine gas) requires less than that from chlorine gas. The conventional process of separating water saves more capital. This direct process for producing essentially dry halogen gas also requires lower cost than the conventional electrochemical conversion of hydrogen chloride. This stupidity can directly reduce the cost per pound of chlorine generated in the aqueous electrochemical process by conventional techniques. This process for directly producing essentially dry halogen gas also provides a process that can produce a drier chlorine gas in fewer processing steps than those made by conventional techniques of electrochemical or catalytic systems, thus simplifying processing conditions and Reduce capital costs. In particular, the electrochemical cell of the present invention includes a gas diffusion layer whose thickness can be increased, which will increase the diffusion resistance of the reactants and products of the cell. In order to achieve the foregoing solution and in accordance with the broader and broader object of the invention contained herein, an electrochemical cell is provided that produces products from reactants, including an electrode, and a separator disposed on one side of the electrode; directing current to the electrode Current bus bar, where the current bus bar is placed on the other side of the electrode; and the flow field between the electrode and the current bus bar is used to increase the diffusion resistance of the reactants and products of the battery. ~ 7-This paper scale is applicable to the Chinese National Standard (CNS) Α4 specification (210Χ 297 mm) (please read the precautions on the back before filling out this page). People-equipment Manufacture A7 B7 __ ____—- V. Description of the invention (5) According to the purpose of the present invention, it is to provide a battery that directly manufactures essentially dry halogen gas from intrinsically anhydrous hydrogenated hydrogen. The electrochemical cell contains M A device that oxidizes essentially anhydrous hydrogen halide molecules to produce gas and protons that are essentially dry; a cation delivery device that transports protons therein, where the oxidation device is placed in contact with one side of the cation delivery device; $ The original proton device, where the original device is placed in contact with one side of the ion-exposed delivery device, and placed between the original device and the bus bar to increase the reactants and products of the battery Diffusion resistance device. BRIEF DESCRIPTION OF THE DRAWINGS FIG. 1 is an exploded cross-sectional view of an electrochemical cell manufactured from anhydrous hydrogen halide gas in the first and second specific examples of the present invention. FIG. 1A is a top cross-sectional view of the mass flow field of the cathode and anode shown in FIG. 1 FIG. 2 is a perspective view of an electrochemical cell for manufacturing, for example, commercial gas from aqueous hydrogen halide according to a third embodiment of the present invention. The spinning example of the current example is described in more detail with reference to the preferred specific example described in the accompanying drawings. According to the first and second specific examples of the present invention, it provides a direct production of anhydrous hydrogen halide. Dry halogen gas Lei chemical battery. Such a ® cell is generally shown in Figure 1-10; the battery of the present invention is described in the preferred embodiment of the present invention, which directly produces essentially dry chlorine gas from anhydrous hydrogen chloride. This battery can also use κ to produce other halogen gases, such as bromine, fluorine and iodine, from individual anhydrous argon halide, such as hydrogen bromide, hydrogenated hydrogen and hydrogen iodide. The term "direct" means that this electrochemical cell can remove the need to remove water from the prepared halogen gas or convert the essentially anhydrous hydrogen halide into water-containing halogen before electrochemical treatment. (CNS) Α4 specification (210 X 297 mm). (Please read the notes on the back to fill in this book)-Packed. Printed by the Staff Consumer Cooperative of the Central Bureau of Standards of the Ministry of Economy. A7 B7 5. Description of the invention (6) The demand for hydrogen. In the first specific example, chlorine gas and hydrogen are generated in this battery. In the second specific example, the battery generates water and chlorine gas, which will be described in more detail below. The electric battery of the first and second specific examples includes electrodes. Alternatively, the electrochemical cells of the first and second specific examples can be described as including a device that oxidizes molecules of substantially anhydrous hydrogen halide to produce substantially dry halogen gas and protons. The oxidizing device is an electrode, or more specifically In short, it is the cathode 12 shown in FIG. 1. On the cathode side, the electrochemical cell 10 has a cathode-side inlet 14 and a cathode-side outlet 16. Since in this preferred example, anhydrous HC1 is carried through the inlet and the chlorine gas is carried through the outlet, the inlet and outlet can be perfluoropolymer, such as EI du Pont de Nemours and Dalawivi TEFLON® PFA (hereinafter referred to as “TEFLON * ® PFA”) sold by Lington Company (hereinafter referred to as “Dupont”). The electrochemical cells of the first and second specific examples also include the transport of protons therein Cation transport device * wherein one side of the oxidation device is placed in contact with one side of the cation transport device. Preferably, the cation transport device is the cation transport diaphragm 18 shown in FIG. 1. More specifically, the diaphragm 18 can be made of Fluorine- or perfluorinated polymer, preferably a copolymer of two or more fluorine- or perfluorinated monomers (at least one of which has pendant sulfonic acid groups), which is sold as a heteropoly membrane. The acid group tends to reduce the conductivity of the separator when it is protonated, so its presence is undesirable. Various suitable resin materials are commercially available or can be prepared according to other literature, which includes a CF2CFRS〇3Fm -〇 CF2CF2CF2S〇3H side chain fluorine Polymer (where R is F, Cl, CF2C1 or (: 1 to (: 1. Perfluoroalkyl). This separator resin can be, for example, tetrafluoro-9-This paper scale is applicable to China National Standard (CNS) A4 (210X 297 mm) ----.---.— {— 装 — (Please read the precautions on the back and then fill out this page) Order the A7 B7 printed by the Consumer Cooperative of the Central Standards Bureau of the Ministry of Economy V. Inventions Explanation (7) Copolymer of ethylene and CF2 = CFOCF2CF (CF3) OCF2CF2S〇3H. Sometimes these resins may have side chains-s〇2f group state instead of-s〇3h group. This fluorinated sulfonyl group can be borrowed Potassium hydroxide is hydrolyzed to -S〇3K group, and then exchanged with acid to -S〇3h group. It is suitable to be prepared from hydrated copolymer of polytetrafluoroethylene and polyfluorinated sulfonyl vinyl ether containing sulfonic acid side pendant. The cationic membrane is provided by EI Du Pont de Nemours and Dallas Wellington (hereinafter referred to as "DuPont") M trademark " NAFIONM hereinafter referred to as HAFI0N®.> Specifically, it contains side chain sulfonic acid The NAFI0N® based diaphragm includes NAFI0N® 117, NAFI0N® 324 and HAFION® »417. The first NAFI0N® is unsupported and has 1100 The equivalent weight is defined as the amount of resin needed to neutralize 1 liter of 1M sodium hydroxide solution. The other two NAF Ι0Ν® »are supported on fluorocarbon fabrics, and the equivalent weight of NAF ION® 417 is also 1 100 g; NAFI 0 N 3 2 4 has a two-layer structure, a 125-micron-thick diaphragm with a weight of 1 100-gram equivalent and a 25-micron-thick diaphragm with an equivalent weight of 1,500 grams. It is also available in MHAFION® 117F grade, which is a precursor membrane with a side chain-S〇2F group that can be converted into a sulfonic acid group. Although the invention uses solid polymer membranes, it is within the scope of the invention to use other cation transport membranes other than polymers. For example, proton conductive ceramics such as / 3-alumina can be used. / 3-Alumina is a non-stoichiometric crystalline compound with a general structure of Na2〇xAl2〇3 (where X ranges from 5 (/ 3 ”-alumina) to 11 (/ 3-alumina)). This material And several kinds of solid electrolytes that can be used in the present invention are described in AJ Appleby and FR Foulkes, Van Nostrand Reinhold, Fuel Cell Handbook, Niuyue, 1989, pages 308-312. Other available solid state proton conductors -10- The paper standard is in accordance with the Chinese National Standard (CNS) A4 (210X297mm) (please read the notes on the back before filling in this page) 丨 installed. Order A7 B7 printed by the employee consumer cooperative of the Central Standards Bureau of the Ministry of Economy V. Description of invention ( 8), especially plutonium salts of barium and barium such as plutonium acid acid salt (SrCe〇.B5Yb〇.〇5〇3-a) and silver acid acid acid (83〇6〇.0) '1〇1 〇.〇1〇3- «) described in" 6 > / 1) 151 < 1, 〇3 1 * 1 > and]? 6111 ^ 1 < The final report D0E / MC / 242 1 8-2957, which is 1 December 990 Preparations made by the Energy Section of the Fossil Energy Bureau of the Morgan City Energy Technology Center, Gas Technology Association, Chicago, Illinois, USA. First and second specific The electrochemical cell of the example also includes an electrode, or anode 20; or, the electrochemical cells of the first and second specific examples can be described as a device that includes protons sent from Yuyuan, where the original device is placed in contact with cations The other side of the delivery device is in contact. The original device includes an anode 20, where the anode 20 is placed in contact with the other side of the diaphragm 18 (the side opposite to the cathode contact side), as illustrated in Figure 1. The anode 20 has The anode-side inlet 24 and anode-side outlet 26 are shown in Figure 1. Since in this preferred example, the anhydrous HC1 is treated, and because some chloride passes through the barrier, HC1 is present on the anode side of the battery Therefore, the anode population and outlet can be lined with TELFON® PFA. As is known to those skilled in the art, if the electrode is placed on the opposite side of the separator, the cation charge (protons in the HC1 reaction) is transported from the cathode to the anode through the separator and each electrode Carry out a half-cell reaction. In the first and second specific examples, 'anhydrous hydrogen chloride molecules are transported to the surface of the cathode through the cathode-side inlet 14'. Anhydrous hydrogen chloride molecules are oxidized to produce essentially dry chlorine Gas and proton ° Essentially dry chlorine gas is discharged through the cathode side outlet 16, as shown in FIG. 1 ° Proton (1T) is transported through the diaphragm and transported at the anode, which will be described in more detail as 1 " ° cathode and anode may include porous The gas diffusion electrode 'this electrode is improved -11- This paper scale is applicable to Chinese national standard (CNS> A4 specification (210X297 mm) (please read the precautions on the back before 4. write this page)-install.
五、發明説明（9 ) 經濟部中央標準局員工消費合作杜印製 高比表面積之儍點，如热悉本技藝者已知者。此陰極及陽 極包括鄰置於陽離子输送隔膜表面（意指在其上或其下） 之電化學活性材質，可直接於該隔膜上塗上一薄膜之該電 化學活性材質。或者，該雷化學活性材質可熱壓至隔膜上 ，如 A.J. Appleby及 E.B. Yeager 於能源，第 11卷，第 137頁（1986年）中所示者；或者，該電化學活性材質可澱 積至隔膜中，如FedkU之美國專利第4,959, 1 32所示。此 電化學活性材質可包括任何種類之觸媒或金鼷材質或金羼 氧化物，只要材質可支持電荷轉移即可。較好，此電化學 活性材質可包括觸媒材質如鉑，釕，餓，铼，铑，銥，鈀 ，金，鈦或锆及其氧化物，合金或混合物。然而，通常陽 極不使用這些材質之氧化物。其他適用於本發明之觸媒材 質可包含（但不限於）呈單體及聚合物態之過渡金鼷大循環 及過渡金屬氧化物，包含鈣鈦礦及燎綠石。 於熱壓電極中，電化學活性材質可包括在載體物料上之 觸媒材質，此載體物料可包括碳粒及聚四氟乙烯粒，其係 由E.I. Du Pont de Nemours及達拉威威靈頓公司以商標 ” TEFLON” （下文表示為TEFLON®)銷售。此電化學活性材 質可藉TEFLON®黏結至碳紙或石墨布之載體結構上並熱壓 至陽離子輸送隔膜，TEFLON®之疏水性質不會使水膜在陰 極上形成*電極中之水障壁曆將阻礙HC1擴散至反應位置 。此電極較好熱壓至隔膜中Μ在觸媒與隔膜閭具有良好接 觸。 電化學活性物料之負載可依據應用至隔膜之方法而改變 (請先閲讀背面之注意事項再4.寫本頁) .Λ.,裝. 訂 本紙張尺度適用中國國家標準（CNS ) Α4規格（210Χ297公釐） 經濟部中央標準局員工消費合作社印製 A7 B7 五、發明説明（10 ) ;熱壓之氣體擴散電極通常具有〇.〇1至0.50毫克/公分2 之負載。Μ其他可利用之澱積方法使低負載為可能，如自 油墨使其Κ薄膜分佈至隔膜上，如Wilson及Gattesfeld 於”聚合物電解質燃料電池之超低Pt負載之高性能催化隔 膜”，洛安莫國家賁驗室，電化學協會期刊，第139卷， 第2期，L-28-30, 1992年所述*其中油墨含有溶解之 NAFI0N®離聚物Μ增強觸媒離聚物之表面接觸並作為對 NAFI0N®隔膜片之粘结劑。Κ此糸統，可達低如每平方公 分0.017毫克之活性物料。 如上所述，本發明之電極包括觸媒層。此外，此電極包 括置於與面遠離隔膜之層之一側上之觸媒層接觸之氣體擴 散層，此氣體擴散層通常由碳紙製得，申請人發現藉增加 (或相反地減少）氣體擴散層之厚度，可增加（或相反地減 少）電池中反應物與產物之擴散電阻，且提供限制電池之 電流密度之自動調節機制。此在陽極為特別重要者，於該 處所有水可通過該擴散層，本發明之自動調節擴散層在需 藉控制隔膜中水之量而保護隔膜方面為重要者。此方法中 ，可控制或調節限制電流密度。又擴散電阻可藉調整擴散 層之親水性而調整。此擴散電阻可藉改變擴散餍之孔隙度 而調整。又擴散電阻可藉調整流場之親水性而調整，或者 流槽道可面向遠離陰極及陽極而分別達到相同结果，該流 槽道可為差別間隔。 第一及第二具體例之電化學電池又包括置於與陰極接觸 之陰極流場28及置於與陽極接觸之陽離流場30。此流場為 -13- 本紙張尺度適用中國國家操準（CNS ) A4規格（210X297公釐） (請先閲锖背面之注意事項再填寫本頁) .丄-裝. -9 經濟部中央標準局員工消費合作社印製 A7 B7__ 11 " _ . 丨丨 1"" ~ 五、發明説明（11 ) 専電性且同時可作為質量及電流流場。第一及第一具體例 之陰極流場之目的為使反應物如無水HC1達到陰極’且自 陰極得到產物如本質上乾燥之氛氣。陽極流埸之目的為使 陽極電解物如第一具體例中之水或第二具體例中之氧氣到 達陽極並自陽極得到產物如第一具體例中之氫氣或第二具 體例中之水氣（h2〇 U))更詳而言之，質量流場可包含數個 陰極流槽道29及數個場極流槽道31，如圖1A所示（其為僅 顯示圖1之流場之上視剖面圖）。流槽道29及31將無水 H C 1導向陰極且於第一具體例中添加水至陽極或於第二具 體例中添加含氧氣體（可含有水蒸氣供淫化作用）至陽極 ，水蒸氣為必要者Κ保持隔膜含水。然而，由於此具體例 中所添加之氧（〇2)之電化學反應可產生水，因此於此具體 例中水為非必要，將討論於後文。此陰極及陽極質量流場 可包括紋道孔狀石墨紙*此流場亦可由圼發泡狀，布狀或 蓆狀之多孔碳製得。 第一及第二具體例之電化學電池亦可包括陰極質量流歧 管32及陽極質量流歧管34，如圖1所示，此種歧管之目的 為使陰極電解物流向陰極及自陰極流出產物，及使陽極電 解物流向陽極及自陽極流出產物。此外，此歧管分別在陰 極質量流場周圍形成框架及陰極，及在陽極質量流場周圍 形成框架及陽極。此種歧管較好由耐腐蝕物料如杜邦以商 標TEFLON® PFA銷售之全氟聚合物製得。墊片36及38亦可 在涸別陰極及陽極質量流場周圍形成框架。這些墊Η較好 亦由耐腐蝕物料製得，如聚四氟乙烯，由杜邦以商標 -14- 本紙張尺度適用中國國家標準（CNS ) Α4規格（210Χ297公釐） (請先閱讀背面之注意事項再填寫本頁) -裝· 訂 經濟部中央標準局員工消費合作社印製 A7 B7 五、發明説明（12 ) TEFLON® PTFE 銷售。 於含水或無水情況中*本發明之雷化學電池又包括置於 與流場接觸之電流分佈器，陰極電流分佈器40係置成與陰 極流場28接觸，及陽極電流分佈器42係置成與陽極流場 30接觸。陰極電流分佈器藉導電作用使電流分佈至陰極並 使電流自陰極流出；陽極電流分佈器藉導電作用使電流分 佈至陽極並使電流流向陽極。此陰極及陽極電流分佈器較 好各包括非孔狀層。此陰極電流分佈器提供陰極電流匯流 排與無水鹵化氫如氯化氫及鹵氣如氯之間之障壁。該陽極 電流分佈器提供陽極電流匯流排與添加至陽極入口之水及 自陽極出口流出之氫氣（H2U))(第一具體例）或添加至 陽極入口之氧氣（02(g))及自陽極流出之水蒸氣 (H2〇(g))(第二具體例）之間之障壁。本發明之電流分佈 器可由各種材質製得，且用於陰極電流分佈器之材質不需 與陽極電流分佈器所用之材質相同。於一例中，陰極電流 分佈器係由鍍鉑之鉅製得，且陽極電流分佈器係由鎳基合 金如 UNS 10665(由國際海尼斯（Haynes) M HASTELLOY® B-2銷售）製得。 第一及第二具體例之電化學電池亦包括陰極電流匯流排 46及陽極電流匯流排48，如圖1所示。電流匯流排使電流 導向電壓電源（未圖示）並自其流出；特定言之，陰極電流 匯流排46連接至電壓電源之正端，陽極電流匯流排48連接 至電壓電源之負端，因而當電壓供應至電池時，電流流經 所有電池元件至電流匯流排46之右側（如圖1所示），包含 -15- 本紙張尺度適用中國國家標準（CNS ) A4規格（210X297公後） {請先閱讀背面之注意事項再4.寫本頁) •裝. 訂 經濟部中央標準局員工消費合作社印製 A7 B7 五、發明説明（u) 電流匯流排48，並由匯流排48回到電壓電源。此電流匯流 排係由導電材質如銅所製得。 於第一及第二具體例中，電化學電池又包括置於與陰極 電流分佈器40接觸之導電结構支架44。在陰極側上之支架 較好由UNS 31603(316L不銹鋼）製成。較好呈〇 -環且由杜 邦Μ商標KALREZ®銷售之全氟彈性體製得之墊圈係置於陰 極側上之結構支架44與陰極電流分佈器40之間。陽極電流 分佈器可作為陽極側上之耐腐蝕结構墊座。 當使用一對Κ上之陰極陽極對時，在製造時如热悉本技 藝者知悉者，Μ雙極排列較佳。本發明之電化學電池可用 於雙極姐套。為了產生此種隻極組套，電流分佈器40及 42及置於其間之所有元件（如圖1所示）係沿著電池長度重 複且電流匯流排置於姐套之外側。 又依據本發明之第一及第二具體例，係提供一種由本質 上無水之鹵化氫直接製造本質之乾燥之鹵氣之方法。該無 水鹵化氫可包括氯化氫，溴化氫，氟化氫或碘化氫。然而 ，如上所述，當用於本發明時，氟化氫特別具腐蝕性；當 電化學電池在高溫（即對溴約601C及更高及對碘為約190Ό 及更高）操作時，可完成溴氣及碘氣之製造。在碘之情況 中，需使用NAFI0N*®M外之材質製得隔膜。 第一具體例之電化學電池操作（其中藉電池製得氫及氯 氣）現將敘述為本發明方法之較佳具體例，其中無水鹵化 氫為氯化氫。於操作中，電流藉導電作用分佈至陰極，且 電流流向陰極電流匯流排46並自其流出至陰極電流分佈器 本紙張尺度適用中國國家標準（CNS〉A4規格（210X297公釐） (請先閱讀背面之注意事項再4.寫本頁) Λ-裝. 訂 五、發明説明（14) 40，本質上 經陰極質量 分子在由電 生本質上乾 程式表示： 2HC 1 (g) 氯氣（Ch 子（H + )經由 A7 B7 無水之氯化氫氣之分子饋至陰極側入口 14並流 流場28中之流槽道29並输送至陰極12之表面。 壓電源產生之電位之下在陰極氧化而在陰極產 燥之氯氣（CU(g))及質子（H + )，此反應Μ下式 電能 -^ 2Η* + Cl2 (g) + 2e_ (g))經由陰極側出口 16流出，如 隔膜（作為電解質）输送，输送之 原，第一具體例之此反應K下式程式表示： 電能 ——i Ha (g) (5) (4) 圖1所示。質 質子在陽極選 請 先 閱 讀 背 之 注 意 事 項 再 裝 經濟部中央標準局員工消費合作社印製 2H" + 2e 水經由陽 至陽極Μ水 。第一具體 側出口 26放 TEFLON*® 影 電流分佈器 依第二具 佳具體例敘 上無水之氯 28之紋道输 氣或富含氧 入口 24及經 亟側人口 24及經由陽極流場30中 合該隔膜且因而增加質子經由隔 例中，在電極與隔膜之界面放出 出_，如圖1所示。氫經由水吹泡 響。電流藉導電作用分佈至陽極 42流至陽極電流匯流排48。 體例之電化學電池之操作將以本 述，其中無水鹵化氫為氯化氫。 化氫分子饋至陰極側入口 1 4並經 送至陰極12表面 > 含氧氣體如氧 之空氣（即含大於21莫耳％氧之氮 由陽極質量流場30中形成之紋道 之紋道而输送 膜輸送之效率 之氫經由陽極 且未受電極中 且電流自陽極 發明方法之較 操作中，本質 陰極質量流場 (〇2(g))，空 )經由陽極側 導入。雖然使 訂 -17- 本紙張尺度適用中國國家標準（CNS ) A4規格（210X297公釐） A7 B7 經濟部中央標準局員工消費合作社印製 五、發明説明（l5 ) 用空氣較便宜，但當使用富含氧之空氣或氧時可增強電池 性能；此陽極饋入氣體可溼化Μ助於控制隔膜之溼度。電 流藉導電作用分佈至陰極且電流自陰極鼋流分佈器40流至 陰極電流匯流排46。氯化氫（HC丨（g))分子在由電壓電源產 生之電位下氧化而在陰棰產生本質上乾燥之氯氣及質子 (IT ) Μ上述程式（4 )表示。氯氣（C U )經由陰極側出口 16流出，如圖1所示。質子（Η + )經由隔膜（作為電解質 )輸送，電流藉導電作用分佈至陽極且電流自陽極電流分 佈器42流至陽極電流匯流排48。氧及所输送之質子在陽極 堪原成水，其Μ下式程式表示： 1/2 02(g) + 2e~ + 2H* -> H20 (g) (6) 程式（6)中形成之水與任何氮及未反應之氧經陽極側出 口 26流出，如圖1所示。水亦有助於維持隔膜之水合作用 ，將於下文中說明。 第二具體例中，陽極反應為形成水，此陽極反應之優點 為如第一具體例中之更有利於H2在陽極上之熱力學生成， 此係由於此具體例中之總反應（Μ下列程式表示）： 電能 2HC1 (g) + 1/2 〇2 (g) -；~~^ H20 (g) + Cl2 (g) (7) 比第一具體例中總反應（以下列程式表示）之自由能改變具 有更小之自由能改變之故： 電能 2HCl(g) -> H2 (g) + CU (g) (8) 因此，於第二具體例中減小输入電池所需之電壓或能量 (請先聞讀背面之注意事項再填寫本頁) > —^1 Λ—裝. 訂 本紙張尺度適用中國國家標準（CNS ) A4規格（210X297公釐） 物公〇7 經濟部中央標準局員工消費合作社印製 A7 B7五、發明説明（16 ) 之量。 於無水情況中，第一及第二具體例之隔膜均需經水合K 具有有效率之質子输送，因此，於第一及第二具體例中， 隔膜之陽極則需维持水合Μ增加經由隔膜输送質子之效率 。第一具體例中，具有產生氫之陽極，而隔膜之水合作用 可藉使液態水與陽極接觸而達成，液態水通過氣體擴散電 極並與隔膜接觸。第二具體例中，具有產生水之陽極，而 隔膜水合作用可藉上式（6)表示之生成之水及藉導於溼化 之氧饋入或空氣饋入氣流中之水而完成。此可維持隔膜高 導電度。 無水之情況下，第一或第二具體例中，電化學電池可在 廣範圍溫度内操作，溫度愈高，電池電壓愈小。然而，由 於使用作為電池元件之材質之性質因此需限制溫度。例如 ，當電池在高於120¾操作時，NAFION®隔膜之性質會改 變。聚合物電解質隔膜之性質使其難以在高於150¾ 之溫 度下操作電池。當隔膜係由其他材質如陶磁材質例如/3-氧化鋁製得時，可能可使電池在高於2 0 0 °C之溫度下操作 。亦需注意在第一或第二具體例中電化學電池搡作並未限 制在大氣壓下操作。電池可在差壓梯度下進行，其會改變 水或電池中其他元件（包含隔膜）之输送特性。 圖2說明本發明第三具體例，任何可能之處，對應於圖 1具體例之元件之元件將Μ與圖1相同之參考數表示，但 將加Μ加撇符號（’）表示。第三具體例之電化學電池通常 示如圖2之10'。第三具體例之電化學電池將以較佳具體 -19- (請先閱讀背面之注意事項再填寫本頁) ----Λ·裝- 訂 本紙張尺度適用中國國家標準（CNS ) Α4規格（210Χ297公釐） A7 一 _ _B7 五、發明説明（π ) 例敘述，其中鹵氣如氯係藉鹵化氩如鹽酸之水溶液電解而 產生者。然而亦可使用此電池於其他用途，例如用於 chlor-鐮糸統（含食鹽液及鹽酸）。或者，此電池可使用作 為燃料電池。 第三具體例之電化學電池包括電極，或更詳言之為包括 陰極12’ 。第Ξ具體例之電化學電池亦包括置於與電極一 側接觸之隔膜。隔膜18'示於圖2 ，其一側與陰極12，之 —側接觸；不似第一具體例之隔膜，此隔膜不需為陽離子 输送隔膜；此第三具體例之電化學電池亦包括電極，或更 詳言之包括陽極20’ ，其中陽極20，置於與隔膜之另一側 (與陰極接觸之側相反之一側）接觸，如圖2所說明。電池 中反應物與產物之擴散電阻相對於前兩個具體例會如上述 般增加。 第三具體例之電化學電池又包括與電極接觸之質量流場 *此質量流場可為與陰極接觸之陰極質量流場28’ ，或與 陽極接觸之陽極質量流場30’ 。第三具髏例中陰極流場之 目的為使陰極電解物如含水H C 1流向陰極及自陰極得到產 物如溼氯氣。陽極流埸之目的係使陽極電解物流向陽極並 (請先閲讀背面之注意事項再填寫本頁) Λ-裝. 經濟部中央標準局員工消費合作社印裝 氣中 氫 j極 物If向 具 產Itfcl# 到 ί 物 得道解 其紋電 自或極 更 示 顯 未 道陽 榷將 流及 含極 包陰 場向 流導 量 1 質HC ，水 之含 言將 定而 特— 流流排 電電流 之極匯 極陰流 電。電 向上。 導側 2 流一圖 電另於 將之示 括極， 包電48 亦於排 池置流 電排匯 學流流 化匯電 電流極 之電陽 例中及 體其， ί 6 具，4 三排排 第流流 匯匯 本紙張尺度適用中國國家標準（CNS ) Α4規格（210Χ297公釐） 經濟部中央標準局員工消費合作社印製 A7 __ B7_____ 五、發明説明（18 ) 使電流自電壓電源（未顯示）導出；特定言之，陰極電流匯 流排46’連接至電壓電源之正端·，及陽極電流匯流排48’ 連接至電壓電源之負端，因此當電壓供應至電池時，電流 經由所有元件自電壓電源流至電流匯流排之右側（如圖2 所示）包含電流匯流排48’ ，電流自其回至電壓電源。如 前兩個具體例，第三具髏例之電流匯流排係由導電材質如 銅製得。 第三具體例之電化學電池又包括置於電極一側上之電流 分佈器。陰極電流分佈器40·置於陰極12’之一側上，及 陽極電流分佈器42’置於陽極20’之一側上。如前兩個具 體例，此陰極電流分佈器藉導電作用使電流分佈至陰極且 使電流自陰極流出。陽極電流分佈器藉導電作用使電流分 佈至陽極並使電流流向陽極，此陰極及陽極電流分佈器較 好各包括非孔狀曆。再者，如前兩個具體例*此陰極電流 分佈器提供陰極電流匯流排與反應物如含水氛化氫及產物 如溼氯氣之間之障壁；陽極電流分佈器提供陽極電流匯流 排與陽極電解物之間之障壁。 如热悉本技藝已知者》若電極置於隔膜之相反面上，陽 離子電荷（M HC1反應中之質子敘述）經由隔膜自陰極输送 至陽極，而各電極進行半電池反應。第三具體例中，Μ箭 頭14'(表示陰極側入口）導入之鹽酸在陰極12’電解而 產生氯氣[其Μ箭頭16’（表示陰極側出口）流出]及氫離子 (Η”。此Η +離子與某些水及某些鹽酸一起输送通過隔膜 18’到達陽極20'氫離子經由陽極側出口 24·在陽極放電 -21- 本紙張尺度適用中國國家標準（CNS ) Α4規格（210X297公釐） (請先閱讀背面之注意事項再4-寫本頁) .Λ— 裝. 訂 A7 B7 五、發明説明（19 ) 热悉本技藝者將可了解其他優.點及改質’因此本發明並 未限制於所述之詳细說明，代表性裝置及說明性實例’據 此，在不違離由附屬申請專利範圍所界定之本發明範圍及 其同等語之精神或範圍下，可自此種詳细說明作變更。 (請先閱讀背面之注意Ϋ-項再填寫本頁) 丨裝. -'° 經濟部中央標準局員工消費合作社印製 本紙張尺度適用中國國家標準（CNS)A4規格（210x297公釐）V. Description of the invention (9) Employee consumption cooperation of the Central Bureau of Standards of the Ministry of Economic Affairs to produce dumb points of high specific surface area, as known by those skilled in the art. The cathode and anode include an electrochemically active material adjacent to the surface of the cation transport membrane (meaning above or below it), which can be coated directly with a thin film of the electrochemically active material. Alternatively, the Thunder chemically active material can be hot pressed onto the diaphragm, as shown by AJ Appleby and EB Yeager in Energy, Volume 11, page 137 (1986); or, the electrochemically active material can be deposited to In the diaphragm, as shown in US Patent No. 4,959,132 of FedkU. The electrochemically active material may include any kind of catalyst or gold or gold material or gold oxide, as long as the material can support charge transfer. Preferably, the electrochemically active material may include a catalyst material such as platinum, ruthenium, zinc, rhenium, rhodium, iridium, palladium, gold, titanium or zirconium and their oxides, alloys or mixtures. However, usually the anode does not use oxides of these materials. Other catalyst materials suitable for use in the present invention may include (but are not limited to) the transition cycle metal oxide and transition metal oxides in the monomeric and polymer states, including perovskite and pyrophyllite. In the hot-pressed electrode, the electrochemically active material may include a catalyst material on a carrier material, and the carrier material may include carbon particles and polytetrafluoroethylene particles, which are produced by EI Du Pont de Nemours and Dara Wellington The company sells it under the trademark "TEFLON" (hereinafter referred to as TEFLON®). This electrochemically active material can be bonded to the carrier structure of carbon paper or graphite cloth by TEFLON® and hot pressed to the cation transport membrane. The hydrophobic nature of TEFLON® will not cause the water film to form on the cathode * The water barrier in the electrode will be Prevent HC1 from diffusing to the reaction site. This electrode is preferably hot pressed into the diaphragm. M has good contact between the catalyst and the diaphragm. The load of the electrochemically active material can be changed according to the method applied to the diaphragm (please read the precautions on the back and then 4. write this page). Λ., Installed. The size of this paper is applicable to China National Standard (CNS) Α4 specifications ( 210Χ297 mm) A7 B7 printed by the employee consumer cooperative of the Central Bureau of Standards of the Ministry of Economic Affairs 5. Description of the invention (10); hot-pressed gas diffusion electrodes usually have a load of 0.01 to 0.50 mg / cm2. Μ Other available deposition methods make low loading possible, such as distributing the K film from the ink to the separator, such as Wilson and Gattesfeld's "High-Performance Catalytic Separator with Ultra-Low Pt Load for Polymer Electrolyte Fuel Cells", Luo An Mo National Laboratory, Journal of the Electrochemical Society, Volume 139, No. 2, L-28-30, described in 1992 * where the ink contains dissolved NAFION® ionomer Μ enhanced catalyst ionomer surface Contact and act as an adhesive for NAFION® diaphragms. ΚThis system can reach as low as 0.017 mg of active material per square centimeter. As described above, the electrode of the present invention includes the catalyst layer. In addition, this electrode includes a gas diffusion layer placed in contact with the catalyst layer on the side of the layer facing away from the diaphragm, this gas diffusion layer is usually made of carbon paper, the applicant found that by increasing (or conversely reducing) the gas The thickness of the diffusion layer can increase (or conversely reduce) the diffusion resistance of reactants and products in the battery, and provides an automatic adjustment mechanism that limits the current density of the battery. This is particularly important at the anode, where all water can pass through the diffusion layer. The automatic adjustment of the diffusion layer of the present invention is important in that the membrane needs to be protected by controlling the amount of water in the membrane. In this method, the current density can be controlled or adjusted. The diffusion resistance can be adjusted by adjusting the hydrophilicity of the diffusion layer. This diffusion resistance can be adjusted by changing the porosity of the diffusion barrier. Furthermore, the diffusion resistance can be adjusted by adjusting the hydrophilicity of the flow field, or the flow channel can face away from the cathode and the anode to achieve the same result, respectively, and the flow channels can be at different intervals. The electrochemical cells of the first and second specific examples further include a cathode flow field 28 placed in contact with the cathode and a cationic flow field 30 placed in contact with the anode. This flow field is -13- This paper scale is applicable to China National Standards (CNS) A4 (210X297mm) (please read the notes on the back before filling in this page). 丄-装. -9 Central Standard of the Ministry of Economic Affairs A7 B7__ 11 " _. 丨 丨 1 " " ~ 5. Invention description (11) It is electrical and can also be used as a quality and current flow field. The purpose of the cathode flow field of the first and first specific examples is to allow a reactant such as anhydrous HC1 to reach the cathode 'and obtain a product such as an essentially dry atmosphere from the cathode. The purpose of the anode flow field is to make the anode electrolyte such as water in the first specific example or oxygen in the second specific example reach the anode and obtain a product such as hydrogen in the first specific example or water vapor in the second specific example from the anode (H2〇U)) In more detail, the mass flow field may include a number of cathode flow channels 29 and a number of field flow channels 31, as shown in FIG. 1A (which shows only the flow field of FIG. 1 Top view). The flow channels 29 and 31 guide the anhydrous HC 1 to the cathode and add water to the anode in the first specific example or oxygen-containing gas (which may contain water vapor for obscene action) to the anode in the second specific example. The water vapor is If necessary, K keeps the membrane hydrated. However, since the electrochemical reaction of the added oxygen (〇2) in this specific example can produce water, water is not necessary in this specific example and will be discussed later. The cathode and anode mass flow fields may include textured pore graphite paper. * This flow field may also be made of porous carbon in the form of foam, cloth or mat. The electrochemical cells of the first and second specific examples may also include a cathode mass flow manifold 32 and an anode mass flow manifold 34, as shown in FIG. 1, the purpose of such a manifold is to flow the cathode electrolysis to the cathode and from the cathode The product flows out, and the anode electrolytic stream flows to and from the anode. In addition, this manifold forms a frame and a cathode around the cathode mass flow field, and a frame and an anode around the anode mass flow field, respectively. Such manifolds are preferably made of corrosion-resistant materials such as perfluoropolymer sold by DuPont under the trademark TEFLON® PFA. Gaskets 36 and 38 can also form a frame around the mass flow field of the cathode and anode. These pads are preferably made of corrosion-resistant materials, such as polytetrafluoroethylene, which is trademarked by DuPont -14- This paper scale is applicable to the Chinese National Standard (CNS) Α4 specification (210Χ297 mm) (please read the notes on the back first Please fill in this page for details)-Binding · Order A7 B7 printed by the Employee Consumer Cooperative of the Central Bureau of Standards of the Ministry of Economic Affairs 5. Invention Instructions (12) TEFLON® PTFE sales. In the case of water or no water * The Lei chemical battery of the present invention further includes a current distributor placed in contact with the flow field, the cathode current distributor 40 is placed in contact with the cathode flow field 28, and the anode current distributor 42 is placed in Contact with anode flow field 30. The cathode current distributor distributes the current to the cathode and causes the current to flow out from the cathode by the conduction effect; the anode current distributor distributes the current to the anode and conducts the current to the anode by the conduction effect. The cathode and anode current distributors preferably each include a non-porous layer. This cathode current distributor provides a barrier between the cathode current bus and anhydrous hydrogen halide such as hydrogen chloride and halogen gas such as chlorine. The anode current distributor provides anode current bus and water added to the anode inlet and hydrogen gas (H2U) flowing from the anode outlet (first specific example) or oxygen gas added to the anode inlet (02 (g)) and from the anode The barrier between the outgoing water vapor (H2〇 (g)) (the second specific example). The current distributor of the present invention can be made of various materials, and the material used for the cathode current distributor need not be the same as the material used for the anode current distributor. In one example, the cathode current distributor is made from a platinum-plated giant, and the anode current distributor is made from a nickel-based alloy such as UNS 10665 (sold by Haynes M HASTELLOY® B-2). The electrochemical cells of the first and second specific examples also include a cathode current bus 46 and an anode current bus 48, as shown in FIG. The current bus directs the current to and from the voltage power supply (not shown); in particular, the cathode current bus 46 is connected to the positive terminal of the voltage power supply, and the anode current bus 48 is connected to the negative terminal of the voltage power supply. When the voltage is supplied to the battery, the current flows through all battery elements to the right of the current bus 46 (as shown in Figure 1), including -15- This paper size is applicable to the Chinese National Standard (CNS) A4 specification (210X297) (Please Read the precautions on the back first and then 4. Write this page) • Install. Order A7 B7 printed by the Staff Consumer Cooperative of the Central Bureau of Standards of the Ministry of Economic Affairs 5. Invention Instructions (u) The current bus 48, and return it to the voltage power supply from the bus 48 . The current bus is made of conductive material such as copper. In the first and second specific examples, the electrochemical cell further includes a conductive structure holder 44 placed in contact with the cathode current distributor 40. The support on the cathode side is preferably made of UNS 31603 (316L stainless steel). A perfluoroelastomer gasket, which is preferably O-ring and sold by DuPont M brand KALREZ®, is placed between the structural support 44 on the cathode side and the cathode current distributor 40. The anode current distributor can be used as a corrosion-resistant structural pedestal on the anode side. When a pair of cathode and anode pairs on K is used, the M bipolar arrangement is preferred if it is known to those skilled in the art during manufacturing. The electrochemical cell of the present invention can be used for bipolar sister sets. In order to produce such a pole-only set, the current distributors 40 and 42 and all the components placed between them (as shown in FIG. 1) are repeated along the length of the battery and the current busbar is placed outside the sister set. According to the first and second specific examples of the present invention, there is provided a method for directly producing essentially dry halogen gas from essentially anhydrous hydrogen halide. The anhydrous hydrogen halide may include hydrogen chloride, hydrogen bromide, hydrogen fluoride or hydrogen iodide. However, as described above, when used in the present invention, hydrogen fluoride is particularly corrosive; when the electrochemical cell is operated at high temperatures (ie, about 601C and higher for bromine and about 190Ό and higher for iodine), bromine can be completed Manufacture of gas and iodine. In the case of iodine, a membrane other than NAFION * ®M is required. The first specific example of the operation of an electrochemical cell (where hydrogen and chlorine are produced from the cell) will now be described as a preferred specific example of the method of the present invention, in which the anhydrous hydrogen halide is hydrogen chloride. During operation, the current is distributed to the cathode by conduction, and the current flows to the cathode current bus 46 and flows out from it to the cathode current distributor. The paper size is applicable to the Chinese national standard (CNS> A4 specification (210X297 mm) (please read Note on the back 4. Write this page) Λ-installation. Order V. Description of the invention (14) 40. Essentially, the cathode mass molecule is expressed by the essentially dry process of the electric generation: 2HC 1 (g) Chlorine (Ch (H +) A7 B7 Anhydrous hydrogen chloride molecules are fed to the cathode side inlet 14 and flow channel 29 in the cocurrent flow field 28 and transported to the surface of the cathode 12. The potential generated by the voltage source is below the cathode oxidation The cathode produces dry chlorine gas (CU (g)) and protons (H +). This reaction Μ following formula-^ 2Η * + Cl2 (g) + 2e_ (g)) flows out through the cathode side outlet 16, such as a diaphragm (as a Electrolyte) transport, the origin of the transport, the first specific example of this reaction K is expressed by the following formula: Electrical energy-i Ha (g) (5) (4) shown in Figure 1. Protons are selected at the anode, please read the back Matters needing attention Reprinted by the Employee Consumer Cooperative of the Central Bureau of Standards of the Ministry of Economic Affairs 2H " + 2e water passes from the anode to the anode M water. The first specific side outlet 26 releases the TEFLON * ® shadow current distributor according to the second specific example. The anhydrous chlorine 28 is used for gas transmission or oxygen-rich inlet 24 In the emergency side population 24 and through the anode flow field 30, the diaphragm is closed and thus protons are added. In the partition, the interface between the electrode and the diaphragm emits _, as shown in FIG. 1. Hydrogen is bubbled through water. The current is borrowed The conductive effect is distributed to the anode 42 and flows to the anode current bus 48. The operation of the electrochemical cell in the system will be described here, in which the anhydrous hydrogen halide is hydrogen chloride. The hydrogen chloride molecules are fed to the cathode side inlet 14 and sent to the surface of the cathode 12 > Oxygen-containing gas such as oxygen air (ie, nitrogen containing more than 21 mol% oxygen is transported by the grooves of the grooves formed in the anode mass flow field 30 and transported by the membrane. In the comparison operation of the current self-anode invention method, the intrinsic cathode mass flow field (〇2 (g)), empty) is introduced through the anode side. Although the order -17- this paper scale is applicable to the Chinese National Standard (CNS) A4 specification (210X297 Mm) A7 B7 Printed by the Employee Consumer Cooperative of the Central Bureau of Standards of the Ministry of Economic Affairs 5. Description of invention (l5) The use of air is cheaper, but when using oxygen-enriched air or oxygen, the battery performance can be enhanced; this anode feed gas can be humidified to help control The humidity of the diaphragm. The current is distributed to the cathode by electrical conduction and the current flows from the cathode flow distributor 40 to the cathode current busbar 46. Hydrogen chloride (HC 丨 (g)) molecules are oxidized at the potential generated by the voltage power supply and become cloudy Produce essentially dry chlorine and protons (IT) Μ The above formula (4) is expressed. Chlorine gas (CU) flows out through the cathode-side outlet 16, as shown in FIG. Protons (H +) are transported through the membrane (as an electrolyte), current is distributed to the anode by conduction and current flows from the anode current distributor 42 to the anode current bus 48. Oxygen and the protons transported in the anode can be formed into water, and its formula is expressed as: 1/2 02 (g) + 2e ~ + 2H *-> H20 (g) (6) Formula (6) Water and any nitrogen and unreacted oxygen flow out through the anode-side outlet 26, as shown in FIG. Water also helps maintain the hydration of the diaphragm, which will be explained below. In the second specific example, the anode reaction is to form water. The advantage of this anode reaction is that it is more conducive to the thermodynamic generation of H2 on the anode as in the first specific example. This is due to the total reaction in this specific example (Μ following formula Representation): Electric energy 2HC1 (g) + 1/2 〇2 (g)-; ~~ ^ H20 (g) + Cl2 (g) (7) Freer than the total reaction in the first specific example (represented by the following formula) Can change the reason for the smaller free energy change: Electric energy 2HCl (g)-> H2 (g) + CU (g) (8) Therefore, in the second specific example, reduce the voltage or energy required to input the battery (Please read the precautions on the back first and then fill out this page) > — ^ 1 Λ—Package. The size of the paper is applicable to the Chinese National Standard (CNS) A4 specification (210X297 mm). Public Corporation 07 Central Bureau of Economic Affairs A7 B7 printed by employee consumer cooperatives. The amount of invention description (16). In the absence of water, the diaphragms of the first and second specific examples need to be transported by hydrated K to have efficient protons. Therefore, in the first and second specific examples, the anode of the diaphragm needs to maintain hydration and increase the transport through the diaphragm. Proton efficiency. In the first specific example, there is an anode that generates hydrogen, and the hydration of the diaphragm can be achieved by bringing liquid water into contact with the anode. The liquid water passes through the gas diffusion electrode and comes into contact with the diaphragm. In the second specific example, there is an anode that generates water, and the diaphragm hydration can be accomplished by the generated water represented by the above formula (6) and the water fed into the airflow by humidified oxygen feed or air feed. This maintains the high conductivity of the diaphragm. In the absence of water, in the first or second specific example, the electrochemical cell can be operated over a wide range of temperatures. The higher the temperature, the lower the battery voltage. However, due to the nature of the material used as the battery element, the temperature needs to be limited. For example, when the battery is operated above 120¾, the properties of the NAFION® separator will change. The nature of the polymer electrolyte separator makes it difficult to operate the battery at temperatures above 150¾. When the separator is made of other materials such as ceramic materials such as / 3-alumina, the battery may be operated at a temperature higher than 200 ° C. It should also be noted that in the first or second specific example, the operation of the electrochemical cell is not limited to operation at atmospheric pressure. The battery can be operated under a differential pressure gradient, which changes the transport characteristics of water or other components in the battery (including the diaphragm). FIG. 2 illustrates a third specific example of the present invention. Wherever possible, the element corresponding to the specific example of FIG. 1 is indicated by the same reference number as M in FIG. 1, but indicated by adding M and the apostrophe ('). The electrochemical cell of the third specific example is generally shown as 10 'in Fig. 2. The third specific example of the electrochemical battery will be better -19- (please read the precautions on the back before filling in this page) ---- Λ · installation- The size of the paper is applicable to China National Standard (CNS) Α4 specifications (210Χ297mm) A7 I _ _B7 V. Description of the invention (π) Example, in which halogen gas such as chlorine is produced by electrolysis of an aqueous solution of halogenated argon such as hydrochloric acid. However, the battery can also be used for other purposes, such as the chlor-simit system (containing saline and hydrochloric acid). Alternatively, this battery can be used as a fuel cell. The electrochemical cell of the third specific example includes an electrode, or more specifically, a cathode 12 '. The electrochemical cell of the third embodiment also includes a separator placed in contact with the electrode side. Separator 18 'is shown in FIG. 2, one side of which is in contact with cathode 12, one side; unlike the separator of the first specific example, this separator need not be a cation transport separator; the electrochemical cell of this third specific example also includes electrodes Or, more specifically, the anode 20 ', where the anode 20 is placed in contact with the other side of the separator (the side opposite to the side in contact with the cathode), as illustrated in FIG. The diffusion resistance of reactants and products in the battery will increase as described above with respect to the first two specific examples. The electrochemical cell of the third specific example further includes a mass flow field in contact with the electrode * This mass flow field may be a cathode mass flow field 28 'in contact with the cathode, or an anode mass flow field 30' in contact with the anode. The purpose of the cathode flow field in the third skeleton is to flow the cathode electrolyte such as aqueous HCl to the cathode and obtain products such as wet chlorine gas from the cathode. The purpose of the anode flow field is to make the anode electrolysis flow to the anode (please read the precautions on the back and then fill out this page) Λ-installation. The Ministry of Economic Affairs Central Standards Bureau employee consumer cooperatives printed hydrogen in the gas. Itfcl # to ί things get a solution to their grains. The self-or extremely shows that there is no way to talk about the current and the flow of the cathode field containing the cathode. The quality of the flow is 1 quality HC. The content of the water will be specific-current discharge The pole of the current is extremely negative. Power up. Leading side 2 currents and pictures are shown in brackets, including electricity 48 is also included in the row of the pool and the current is collected in the case of the galvanic current and the current electrode of the fluidized sink, ί 6 tools, 4 three The paper standard of the row-to-stream confluence is applicable to the Chinese National Standard (CNS) Α4 specification (210Χ297 mm). The A7 __ B7_____ printed by the Employee Consumer Cooperative of the Central Bureau of Standards of the Ministry of Economic Affairs 5. Description of the invention (18) The current self-voltage power supply ( Not shown) derived; in particular, the cathode current bus 46 'is connected to the positive terminal of the voltage supply, and the anode current bus 48' is connected to the negative terminal of the voltage supply, so when the voltage is supplied to the battery, the current flows through all The component flows from the voltage source to the right side of the current bus (as shown in Figure 2) containing the current bus 48 ', from which the current returns to the voltage source. As in the previous two specific examples, the current busbar of the third skeleton is made of conductive material such as copper. The electrochemical cell of the third specific example further includes a current distributor placed on one side of the electrode. Cathode current distributor 40 is placed on one side of cathode 12 ', and anode current distributor 42' is placed on one side of anode 20 '. As in the previous two specific examples, this cathode current distributor distributes the current to the cathode and conducts the current out of the cathode by conducting electricity. The anode current distributor distributes the current to the anode and conducts the current to the anode by conduction. The cathode and anode current distributor preferably each include a non-porous calendar. Furthermore, as in the previous two specific examples *, this cathode current distributor provides a barrier between the cathode current bus and reactants such as aqueous hydrogen hydride and products such as wet chlorine; the anode current distributor provides anode current bus and anode electrolysis The barrier between objects. As is known in the art, if the electrodes are placed on the opposite side of the diaphragm, the cation charge (described by the proton in the M HC1 reaction) is transferred from the cathode to the anode through the diaphragm, and each electrode undergoes a half-cell reaction. In the third specific example, hydrochloric acid introduced into the M arrow 14 '(representing the cathode side inlet) is electrolyzed at the cathode 12' to produce chlorine gas [the M arrow 16 '(representing the cathode side outlet) flows out] and hydrogen ions (Η ". + Ions are transported together with some water and some hydrochloric acid through the diaphragm 18 'to the anode 20' hydrogen ions through the anode side outlet 24 · discharge at the anode -21- This paper scale is applicable to China National Standard (CNS) Α4 specification (210X297 mm ) (Please read the precautions on the back and then 4-write this page). Λ— Binding. Order A7 B7 5. Description of the invention (19) Those who are familiar with this skill will be able to understand other advantages, points and modifications. Therefore, this invention It is not limited to the detailed descriptions described, representative devices and illustrative examples' accordingly, without departing from the spirit or scope of the scope of the invention defined by the scope of the accompanying patent application and its equivalents The detailed descriptions are subject to change. (Please read the note Ϋ- item on the back before filling in this page) 丨 installed.-'° The paper size printed by the Employee Consumer Cooperative of the Central Standards Bureau of the Ministry of Economic Affairs is applicable to the Chinese National Standard (CNS) A4 specifications (210x297mm)