TW202000995A - 電解釋氯用陽極 - Google Patents
電解釋氯用陽極 Download PDFInfo
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- TW202000995A TW202000995A TW108121396A TW108121396A TW202000995A TW 202000995 A TW202000995 A TW 202000995A TW 108121396 A TW108121396 A TW 108121396A TW 108121396 A TW108121396 A TW 108121396A TW 202000995 A TW202000995 A TW 202000995A
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- ruthenium
- iridium
- titanium
- tin
- electrode
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- 239000000460 chlorine Substances 0.000 title claims abstract description 25
- ZAMOUSCENKQFHK-UHFFFAOYSA-N Chlorine atom Chemical compound [Cl] ZAMOUSCENKQFHK-UHFFFAOYSA-N 0.000 title claims abstract description 22
- 229910052801 chlorine Inorganic materials 0.000 title claims abstract description 22
- 229910052741 iridium Inorganic materials 0.000 claims abstract description 64
- 229910052707 ruthenium Inorganic materials 0.000 claims abstract description 63
- 229910052718 tin Inorganic materials 0.000 claims abstract description 58
- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical compound [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 claims abstract description 54
- ATJFFYVFTNAWJD-UHFFFAOYSA-N Tin Chemical compound [Sn] ATJFFYVFTNAWJD-UHFFFAOYSA-N 0.000 claims abstract description 49
- 239000010936 titanium Substances 0.000 claims abstract description 48
- 229910052719 titanium Inorganic materials 0.000 claims abstract description 47
- GKOZUEZYRPOHIO-UHFFFAOYSA-N iridium atom Chemical compound [Ir] GKOZUEZYRPOHIO-UHFFFAOYSA-N 0.000 claims abstract description 44
- KJTLSVCANCCWHF-UHFFFAOYSA-N Ruthenium Chemical compound [Ru] KJTLSVCANCCWHF-UHFFFAOYSA-N 0.000 claims abstract description 43
- 229910052751 metal Inorganic materials 0.000 claims abstract description 40
- 239000002184 metal Substances 0.000 claims abstract description 40
- 238000000034 method Methods 0.000 claims abstract description 25
- 239000000758 substrate Substances 0.000 claims abstract description 17
- 238000004519 manufacturing process Methods 0.000 claims abstract description 11
- 230000008569 process Effects 0.000 claims abstract description 9
- QTBSBXVTEAMEQO-UHFFFAOYSA-N Acetic acid Chemical compound CC(O)=O QTBSBXVTEAMEQO-UHFFFAOYSA-N 0.000 claims description 65
- 238000000576 coating method Methods 0.000 claims description 46
- 239000011248 coating agent Substances 0.000 claims description 42
- 238000010438 heat treatment Methods 0.000 claims description 31
- 239000003054 catalyst Substances 0.000 claims description 30
- LCIMJULVQOQTEZ-UHFFFAOYSA-N 2-hydroxyacetyl chloride Chemical compound OCC(Cl)=O LCIMJULVQOQTEZ-UHFFFAOYSA-N 0.000 claims description 14
- 238000005868 electrolysis reaction Methods 0.000 claims description 9
- 238000005979 thermal decomposition reaction Methods 0.000 claims description 9
- 229910000510 noble metal Inorganic materials 0.000 claims description 8
- HGCLZPAIXMKYJQ-UHFFFAOYSA-N 2-hydroxyacetyl chloride titanium Chemical compound [Ti].OCC(Cl)=O HGCLZPAIXMKYJQ-UHFFFAOYSA-N 0.000 claims description 7
- VEXZGXHMUGYJMC-UHFFFAOYSA-M Chloride anion Chemical compound [Cl-] VEXZGXHMUGYJMC-UHFFFAOYSA-M 0.000 claims description 3
- 239000003513 alkali Substances 0.000 claims description 2
- 150000001875 compounds Chemical class 0.000 claims description 2
- 239000003014 ion exchange membrane Substances 0.000 claims description 2
- 210000005069 ears Anatomy 0.000 claims 1
- 239000012528 membrane Substances 0.000 claims 1
- 230000003197 catalytic effect Effects 0.000 abstract 1
- 239000000243 solution Substances 0.000 description 40
- 239000000203 mixture Substances 0.000 description 22
- 239000010970 precious metal Substances 0.000 description 17
- 238000011068 loading method Methods 0.000 description 10
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 9
- 230000008859 change Effects 0.000 description 9
- 239000008367 deionised water Substances 0.000 description 9
- 229910021641 deionized water Inorganic materials 0.000 description 9
- 238000001035 drying Methods 0.000 description 9
- 239000007788 liquid Substances 0.000 description 9
- 238000005406 washing Methods 0.000 description 9
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 9
- 229910052760 oxygen Inorganic materials 0.000 description 8
- DDQFDVNEPSUPFB-UHFFFAOYSA-N OCC(=O)Cl.[Ir] Chemical compound OCC(=O)Cl.[Ir] DDQFDVNEPSUPFB-UHFFFAOYSA-N 0.000 description 7
- OLNBBXZKZZUJQH-UHFFFAOYSA-N OCC(=O)Cl.[Ru] Chemical compound OCC(=O)Cl.[Ru] OLNBBXZKZZUJQH-UHFFFAOYSA-N 0.000 description 7
- 238000006243 chemical reaction Methods 0.000 description 7
- 238000005516 engineering process Methods 0.000 description 7
- 239000010410 layer Substances 0.000 description 7
- KFZMGEQAYNKOFK-UHFFFAOYSA-N Isopropanol Chemical compound CC(C)O KFZMGEQAYNKOFK-UHFFFAOYSA-N 0.000 description 6
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 6
- 239000012267 brine Substances 0.000 description 6
- 230000000694 effects Effects 0.000 description 6
- 239000001301 oxygen Substances 0.000 description 6
- HPALAKNZSZLMCH-UHFFFAOYSA-M sodium;chloride;hydrate Chemical compound O.[Na+].[Cl-] HPALAKNZSZLMCH-UHFFFAOYSA-M 0.000 description 6
- 229910006404 SnO 2 Inorganic materials 0.000 description 5
- 230000000052 comparative effect Effects 0.000 description 5
- 238000009472 formulation Methods 0.000 description 5
- 239000000463 material Substances 0.000 description 5
- 150000002739 metals Chemical class 0.000 description 5
- FAPWRFPIFSIZLT-UHFFFAOYSA-M Sodium chloride Chemical compound [Na+].[Cl-] FAPWRFPIFSIZLT-UHFFFAOYSA-M 0.000 description 4
- 229910052715 tantalum Inorganic materials 0.000 description 4
- GUVRBAGPIYLISA-UHFFFAOYSA-N tantalum atom Chemical compound [Ta] GUVRBAGPIYLISA-UHFFFAOYSA-N 0.000 description 4
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 3
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 3
- 229910010413 TiO 2 Inorganic materials 0.000 description 3
- 239000007864 aqueous solution Substances 0.000 description 3
- 230000008901 benefit Effects 0.000 description 3
- 238000002149 energy-dispersive X-ray emission spectroscopy Methods 0.000 description 3
- 230000006872 improvement Effects 0.000 description 3
- 238000002360 preparation method Methods 0.000 description 3
- KPZGRMZPZLOPBS-UHFFFAOYSA-N 1,3-dichloro-2,2-bis(chloromethyl)propane Chemical compound ClCC(CCl)(CCl)CCl KPZGRMZPZLOPBS-UHFFFAOYSA-N 0.000 description 2
- TZGPACAKMCUCKX-UHFFFAOYSA-N 2-hydroxyacetamide Chemical compound NC(=O)CO TZGPACAKMCUCKX-UHFFFAOYSA-N 0.000 description 2
- LGRFSURHDFAFJT-UHFFFAOYSA-N Phthalic anhydride Natural products C1=CC=C2C(=O)OC(=O)C2=C1 LGRFSURHDFAFJT-UHFFFAOYSA-N 0.000 description 2
- 229910001069 Ti alloy Inorganic materials 0.000 description 2
- 229910021627 Tin(IV) chloride Inorganic materials 0.000 description 2
- 238000004458 analytical method Methods 0.000 description 2
- JHIWVOJDXOSYLW-UHFFFAOYSA-N butyl 2,2-difluorocyclopropane-1-carboxylate Chemical compound CCCCOC(=O)C1CC1(F)F JHIWVOJDXOSYLW-UHFFFAOYSA-N 0.000 description 2
- 239000007789 gas Substances 0.000 description 2
- 230000003647 oxidation Effects 0.000 description 2
- 238000007254 oxidation reaction Methods 0.000 description 2
- BASFCYQUMIYNBI-UHFFFAOYSA-N platinum Chemical compound [Pt] BASFCYQUMIYNBI-UHFFFAOYSA-N 0.000 description 2
- 239000000047 product Substances 0.000 description 2
- WOCIAKWEIIZHES-UHFFFAOYSA-N ruthenium(iv) oxide Chemical compound O=[Ru]=O WOCIAKWEIIZHES-UHFFFAOYSA-N 0.000 description 2
- 239000011780 sodium chloride Substances 0.000 description 2
- 239000000126 substance Substances 0.000 description 2
- -1 tantalum Chemical class 0.000 description 2
- HPGGPRDJHPYFRM-UHFFFAOYSA-J tin(iv) chloride Chemical compound Cl[Sn](Cl)(Cl)Cl HPGGPRDJHPYFRM-UHFFFAOYSA-J 0.000 description 2
- GIMXAEZBXRIECN-UHFFFAOYSA-J 2-hydroxyacetate;titanium(4+) Chemical compound [Ti+4].OCC([O-])=O.OCC([O-])=O.OCC([O-])=O.OCC([O-])=O GIMXAEZBXRIECN-UHFFFAOYSA-J 0.000 description 1
- 238000010521 absorption reaction Methods 0.000 description 1
- 230000001133 acceleration Effects 0.000 description 1
- 125000000218 acetic acid group Chemical group C(C)(=O)* 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 238000001354 calcination Methods 0.000 description 1
- 230000002860 competitive effect Effects 0.000 description 1
- 238000001514 detection method Methods 0.000 description 1
- 238000006056 electrooxidation reaction Methods 0.000 description 1
- 238000005265 energy consumption Methods 0.000 description 1
- 238000007689 inspection Methods 0.000 description 1
- 239000011159 matrix material Substances 0.000 description 1
- 238000004452 microanalysis Methods 0.000 description 1
- 229910003455 mixed metal oxide Inorganic materials 0.000 description 1
- 238000010943 off-gassing Methods 0.000 description 1
- 239000003973 paint Substances 0.000 description 1
- 230000036961 partial effect Effects 0.000 description 1
- 229910052697 platinum Inorganic materials 0.000 description 1
- 238000005070 sampling Methods 0.000 description 1
- 238000000550 scanning electron microscopy energy dispersive X-ray spectroscopy Methods 0.000 description 1
- 235000011121 sodium hydroxide Nutrition 0.000 description 1
- 239000013589 supplement Substances 0.000 description 1
- 239000002344 surface layer Substances 0.000 description 1
- 238000004876 x-ray fluorescence Methods 0.000 description 1
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- C25B11/073—Electrodes formed of electrocatalysts on a substrate or carrier characterised by the electrocatalyst material
- C25B11/091—Electrodes formed of electrocatalysts on a substrate or carrier characterised by the electrocatalyst material consisting of at least one catalytic element and at least one catalytic compound; consisting of two or more catalytic elements or catalytic compounds
- C25B11/097—Electrodes formed of electrocatalysts on a substrate or carrier characterised by the electrocatalyst material consisting of at least one catalytic element and at least one catalytic compound; consisting of two or more catalytic elements or catalytic compounds comprising two or more noble metals or noble metal alloys
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Abstract
本發明係關於電極製造方法,此電極可用做製氯電解池中之陽極。所得電極包括觸媒層,含錫、釕、銥和鉭之氧化物,施加於閥金屬之基材上。
Description
本發明係關於電極製造方法,此電極可用做製氯電解池中之陽極。所得電極包括觸媒層,含錫、釕、銥和鉭之氧化物,施加於閥金屬之基材上。
本發明領域係關於碱氯鹽水電解製法中所用電極的觸媒塗料之製法,該塗料係施加於導電性基材上,通常為鈦、鈦合金或其他閥金屬。
碱氯鹽水,例如氯化鈉鹽水,電解以生產氯和苛性蘇打之方法,通常於陽極進行,陽極基材為鈦或其他閥金屬,以二氧化釕(RuO2)表面層活化,具有降低陽極釋氯反應之過電壓。
例如EP 0153586記載,在基於RuO2與SnO2之配方,添加某量之第二種貴金屬,選自銥和鉑,可達成部份改進氯過電壓,因而改善製程電壓和整體能量消耗;然而,如US 4513102所述,此配方以及含錫之其他配方,同時也會產生問題,即降低釋氧競爭反應之過電壓,以及陽極反應生產的氯帶來過量氧。
又如WO 2016083319所載,在金屬基材上,應用基於RuO2和SnO2之配方,添加少量IrO2,可得進一步少許改進效益。同樣配方可得最佳電池電位值,和適量氧。然而,此項最後所述配方及上述其他配方,對工廠故障時不免發生的電流逆流,無法賦予電極以最佳電阻。
US 2013/186750 A1記載釋氯電極,由金屬基材構成,交替塗二層不同組成物,即一層包括銥、釕和例如鉭之閥金屬的氧化物,另一層包括銥、釕和錫的氧化物。
在Chellamall等人撰寫〈使用塗在鈦陽極上的RuO2-IrO2-SnO2-TiO2之酞酐陽極煅燒〉(發表於《阿拉伯化學會刊》(2012)第9卷補遺2(2016年11月),第S1690-S1699頁)一文中,載明酞酐之電化學氧 化用的陽極,由鈦基材構成,塗以熱分解法製成的RuO2、IrO2、SnO2和TiO2之混合金屬氧化物。
此外,習知技術之塗料,例如JPS6338592所載配方,基於錫和貴金屬之氧化物,一般製法是從四價錫母質,尤其是四氯化錫(SnCl4)開始,在水溶液中混合相對應貴金屬母質。然而,所得母質之極大揮發性,使其在工業製法應用不便。
所以,顯然在碱氯鹽水電解製程中,為在電解池中釋出氣態生成物,電極亟需有新的觸媒塗料,其特徵為,在通常操作條件下,相較於習知技術之配方,有更高之觸媒活性和更高電阻。
本發明諸項要旨,列於所附申請專利範圍。
本發明包含把基於RuO2、IrO2、SnO2和TiO2之配方,施加於金屬基材;所得配方在電流逆流情況下,導致明顯改善電極之電阻,而且可提高反應生產Cl2/O2之選擇性,有利於前者。
在一要旨中,本發明係關於電解製程中之釋氣電極,包括閥金屬基材,和觸媒塗料,含5-40%錫、3.6-15%銥、18-40%釕和30-70%鈦,呈金屬或其氧化物之形式,就元素之莫耳%而言,該觸媒塗料係由含銥、釕、錫和鈦之羥基乙醯氯錯合物之乙酸溶液熱分解而得。
本發明人等觀察到,在含釕和銥的氧化物之觸媒層內,有錫和鈦呈金屬或其氧化物之形式存在(開始由含有此等成份的羥基乙醯氯錯合物之乙酸溶液,按上述濃度應用),在電流逆流情形下,可明顯增加最後電極之電阻,大於單獨鈦存在所得。
另觀察到,由含有羥基乙醯氯錯合物的母質所得本配方,可得電池電位最佳值。
在一具體例,本發明係關於一種電極,具有觸媒塗料,包括混合物,含6-30%錫、3.7-12%銥、20-30%釕和50-70%鈦,呈金屬或其氧化物形式。
本發明人觀察到,具有相同觸媒塗料之電極,含實質量之閥金屬,可得適當濃度之氧,改進Cl2/O2生產反應之選擇性,有利於前者。
在又一具體例中,本發明係關於一種電極,其觸媒塗料包括 混合物,含8-18%錫、4-10%銥、18-36%釕和45-65%鈦,呈金屬或其氧化物形式。
此最後所述具體例之優點是,增加電極之使用壽命,又能保持氯和氧釋出反應之最佳選擇性。
在又一要旨中,本發明係關於電解製程中釋氣電極,包括閥金屬基材,具有觸媒塗料,包括混合物,含錫、銥、釕和鈦,呈金屬或其氧化物形式,其中Ru:Ir莫耳比介於1.5和8之間,Ti:Sn莫耳比介於1和6之間,而閥金屬量對貴金屬量之莫耳比,介於1.2和5之間,其中該觸媒塗料係由含前述金屬的羥基乙醯氯錯合物之乙酸溶液熱分解層所構成。
本發明人等觀察到,施加類似觸媒塗料,具有貴金屬量對閥金屬量在該比率範圍之電極,對電流逆流時之電阻而言,可得高效益,又能維持釋氯之良好觸媒活性,以及Cl2/O2生產反應有利於前者之良好選擇性。
在又一具體例中,觸媒塗料具有貴金屬比載(specific loading),以銥和釕合計表示為6至12g/m2,而較佳閥金屬基材為鈦或鈦合金。
本發明又一要旨係關於一種電極,包括閥金屬基材和觸媒塗料,其中該觸媒塗料係由含銥、釕、錫和鈦之羥基乙醯氯錯合物之乙酸溶液熱分解而得,該溶液含5-40%錫、3.6-15%銥、18-40%釕和30-70%鈦,以元素之莫耳%計。
本發明又一要旨係關於供電解池內釋出氣態生成物,例如碱性鹽水電解池中釋氯之電極製造方法,包括如下步驟:(a)在閥金屬基材施加含銥、釕、錫和鈦之羥基乙醯氯錯合物之乙酸溶液,隨即在50-60℃乾燥,並在450-600℃熱分解5至30分鐘,直到貴金屬比載以銥和釕合計為0.4-1g/m2;(b)重複步驟(a),直到觸媒塗料獲得貴金屬比載為6-12g/m2;(c)在450-600℃熱處理,為時50至120分鐘。
按照上述製法之一具體例,該乙酸溶液含5-40%錫、3.6-15%銥、18-40%釕和30-70%鈦,以6-30%錫、3.7-12%銥、20-30%釕和50-70%鈦為佳,而以8-18%錫、4-10%銥、18-36%釕和45-65%鈦更佳,均以元素 之莫耳%計。
在本發明又一具體例中,係關於電解製程中釋氣電極之生產方法,包括如下步驟:(a)在閥金屬基材施加含銥、釕、錫和鈦之羥基乙醯氯錯合物之乙酸溶液,含5-40%錫、3.6-15%銥、18-40%釕和30-70%鈦,就元素之莫耳%計;隨即在50-60℃乾燥,並在450-600℃熱分解5至30分鐘,直到貴金屬比載以銥和釕合計為0.4-1g/m2;(b)重複(a)步驟,直到觸媒塗料獲得貴金屬比載為6至12g/m2;(c)最後在450-600℃熱處理,為時50至200分鐘。
該乙酸溶液含6-30%錫、3.7-12%銥、20-30%釕和50-70%鈦,更好是8-18%錫、4-10%銥、18-36%釕和45-65%鈦,均以元素之莫耳%計。
包括錫之羥基乙醯氯錯合物連同銥、釕和鈦之羥基乙醯氯錯合物的母質,使用時,藉提供具有良好控制化學組成份之陽極觸媒塗料,可克服習知技術之限制。習知技術之主要關鍵,在於四氯化物之揮發性,於澱積觸媒層所必要之各種熱處理中,會造成該四氯化物無法控制的損失。
在一具體例中,步驟(a)和(c)之熱分解溫度,介於480和550℃。
本發明又一要旨係關於碱氯溶液之電解池,包括陽極室和陰極室,其中陽極室裝設電極,呈上述形式之一,做為釋氯陽極。
本發明又一要旨係關於一種工業電解槽,從碱氯溶液生產氯和碱,甚至不用保護極化設備,包括電解池模組配置,具有陽極室和陰極室,以離子交換膜或隔膜隔開,其中陽極包括電極,呈上述形式之一,做為陽極。
茲以如下實施例和附圖,詳述本發明。
第1圖為實施例1所述電極截面之掃描電子微觀影像;第2圖為實施例2所述電極截面之掃描電子微觀影像。
以下實施例用來證明本發明特殊具體例,其可行性已在所請求數值範圍內獲得充分證明。精於技術之專家均知,下列實施例所載組成份和技術,代表本發明人在實施中發現發明操作良好之組成份和技術;然而技術專家亦知,鑑於本案所說明,對所述各種具體例可以有各種變化,仍然可得一致或相似結果,依舊在本發明範圍內。
實施例1
取一片鈦網,尺寸為10公分×10公分,在60℃脫離子水內洗三次,每次換液體。洗後,在350℃熱處理2小時。網再在20% HCl溶液內處理,煮沸30分鐘。
製成乙酸溶液100ml,含錫之羥基乙醯氯錯合物,連同釕之羥基乙醯氯錯合物,銥之羥基乙醯氯錯合物和鈦之羥基乙醯氯錯合物,具有莫耳組成份等於20% Ru、7% Ir、17% Sn和56% Ti。
溶液刷塗在鈦網片上,塗14次。每次塗後,在50-60℃進行乾燥約10分鐘,接著500℃熱處理10分鐘。網片每次經空氣冷卻後,再施以下一次塗佈。
重複此程序,直到貴金屬總載量,以Ir和Ru合計就金屬言,等於8g/m2。然後,在500℃進行最後熱處理100分鐘。
所得電極標記為樣本1號。
實施例2
取一片鈦網,尺寸為10公分×10公分,在60℃脫離子水內洗三次,每次換液體。洗後,在350℃熱處理2小時。網再在20% HCl溶液內處理,煮沸30分鐘。
製成乙酸溶液100ml,含錫之羥基乙醯氯錯合物,連同釕之羥基乙醯氯錯合物,銥之羥基乙醯氯錯合物和鈦之羥基乙醯氯錯合物,具有莫耳組成份等於30% Ru、4% Ir、15% Sn和51% Ti。
溶液刷塗在鈦網片上,塗14次。每次塗後,在50-60℃進行乾燥約10分鐘,接著500℃熱處理10分鐘。網片每次經空氣冷卻後,再施以下一次塗佈。
重複此程序,直到貴金屬總載量,以Ir和Ru合計就金屬言,等於8g/m2。然後,在500℃進行最後熱處理100分鐘。
所得電極標記為樣本2號。
實施例3
取一片鈦網,尺寸為10公分×10公分,在60℃脫離子水內洗三次,每次換液體。洗後,在350℃熱處理2小時。網再在20% HCl溶液內處理,煮沸30分鐘。
製成乙酸溶液100ml,含錫之羥基乙醯氯錯合物,連同釕之羥基乙醯氯錯合物,銥之羥基乙醯氯錯合物和鈦之羥基乙醯氯錯合物,具有莫耳組成份等於23% Ru、12% Ir、19% Sn和46% Ti。
溶液刷塗在鈦網片上,塗14次。每次塗後,在50-60℃進行乾燥約10分鐘,接著500℃熱處理10分鐘。網片每次經空氣冷卻後,再施以下一次塗佈。
重複此程序,直到貴金屬總載量,以Ir和Ru合計就金屬言,等於8g/m2。然後,在500℃進行最後熱處理100分鐘。
所得電極標記為樣本3號。
實施例4
取一片鈦網,尺寸為10公分×10公分,在60℃脫離子水內洗三次,每次換液體。洗後,在350℃熱處理2小時。網再在20% HCl溶液內處理,煮沸30分鐘。
製成乙酸溶液100ml,含錫之羥基乙醯氯錯合物,連同釕之羥基乙醯氯錯合物,銥之羥基乙醯氯錯合物和鈦之羥基乙醯氯錯合物,具有莫耳組成份等於20% Ru、10% Ir、16% Sn和54% Ti。
溶液刷塗在鈦網片上,塗14次。每次塗後,在50-60℃進行乾燥約10分鐘,接著500℃熱處理10分鐘。網片每次經空氣冷卻後,再施以下一次塗佈。
重複此程序,直到貴金屬總載量,以Ir和Ru合計就金屬言,等於12g/m2。然後,在500℃進行最後熱處理100分鐘。
所得電極標記為樣本4號。
實施例5
取一片鈦網,尺寸為10公分×10公分,在60℃脫離子水內洗三次,每次換液體。洗後,在350℃熱處理2小時。網再在20% HCl溶 液內處理,煮沸30分鐘。
製成乙酸溶液100ml,含錫之羥基乙醯氯錯合物,連同釕之羥基乙醯氯錯合物,銥之羥基乙醯氯錯合物和鈦之羥基乙醯氯錯合物,具有莫耳組成份等於21% Ru、7% Ir、32% Sn和40% Ti。
溶液刷塗在鈦網片上,塗14次。每次塗後,在50-60℃進行乾燥約10分鐘,接著500℃熱處理10分鐘。網片每次經空氣冷卻後,再施以下一次塗佈。
重複此程序,直到貴金屬總載量,以Ir和Ru合計就金屬言,等於9g/m2。然後,在500℃進行最後熱處理100分鐘。
所得電極標記為樣本5號。
實施例6
取一片鈦網,尺寸為10公分×10公分,在60℃脫離子水內洗三次,每次換液體。洗後,在350℃熱處理2小時。網再在20% HCl溶液內處理,煮沸30分鐘。
製成乙酸溶液100ml,含錫之羥基乙醯氯錯合物,連同釕之羥基乙醯氯錯合物,銥之羥基乙醯氯錯合物和鈦之羥基乙醯氯錯合物,具有莫耳組成份等於21% Ru、9% Ir、29% Sn和41% Ti。
溶液刷塗在鈦網片上,塗14次。每次塗後,在50-60℃進行乾燥約10分鐘,接著500℃熱處理10分鐘。網片每次經空氣冷卻後,再施以下一次塗佈。
重複此程序,直到貴金屬總載量,以Ir和Ru合計就金屬言,等於9g/m2。然後,在500℃進行最後熱處理100分鐘。
所得電極標記為樣本6號。
比較例1
取一片鈦網,尺寸為10公分×10公分,在60℃脫離子水內洗三次,每次換液體。洗後,在350℃熱處理2小時。網再在20% HCl溶液內處理,煮沸30分鐘。
製成醇水溶液100ml,在異丙醇溶液內含RuCl3.3H2O、H2IrCl6.6H2O、TiCl3,莫耳組成份等於27% Ru、12% Ir、61% Ti。
溶液刷塗於鈦網片,塗14次。每次塗後,在50-60℃進行 乾燥10分鐘,接著在500℃熱處理10分鐘。網片每次經空氣冷卻後,再施以下一次塗佈。
重複此程序,直到貴金屬總載量,以Ir和Ru合計就金屬言,等於13g/m2。然後,在500℃進行最後熱處理100分鐘。
所得電極標記為樣本1C號。
比較例2
取一片鈦網,尺寸為10公分×10公分,在60℃脫離子水內洗三次,每次換液體。洗後,在350℃熱處理2小時。網再在20% HCl溶液內處理,煮沸30分鐘。
製成醇水溶液100ml,在異丙醇溶液內含RuCl3.3H2O、H2IrCl6.6H2O、TiCl3、SnCl4,莫耳組成份等於20% Ru、7% Ir、17% Sn、56% Ti。
溶液刷塗於鈦網片,塗14次。每次塗後,在50-60℃進行乾燥10分鐘,接著在500℃熱處理10分鐘。網片每次經空氣冷卻後,再施以下一次塗佈。
重複此程序,直到貴金屬總載量,以Ir和Ru合計就金屬言,等於8g/m2。然後,在500℃進行最後熱處理100分鐘。
所得電極標記為樣本2C號。
比較例3
取一片鈦網,尺寸為10公分×10公分,在60℃脫離子水內洗三次,每次換液體。洗後,在350℃熱處理2小時。網再在20% HCl溶液內處理,煮沸30分鐘。
製成乙酸溶液100ml,含錫之羥基乙醯氯錯合物,連同釕之羥基乙醯氯錯合物和銥之羥基乙醯氯錯合物,莫耳組成份等於35% Ru、6% Ir、59% Ti。
溶液刷塗於鈦網片,塗14次。每次塗後,在50-60℃進行乾燥10分鐘,接著在500℃熱處理10分鐘。網片每次經空氣冷卻後,再施以下一次塗佈。
重複此程序,直到貴金屬總載量,以Ir和Ru合計就金屬言,等於8g/m2。然後,在500℃進行最後熱處理100分鐘。
所得電極標記為樣本3C號。
樣本鑑定
四氯化錫的高揮發性,及其在熱處理中相關失控的損失,已分別由實施例1電極(樣本1)和比較例2電極(樣本2C)二個樣本的SEM EDX分析確認加以證明。
分析是使用掃描電極顯微鏡(市售FEI製造SEM/FEG檢驗F 50,具備EDAX微分析系統),裝備Everhart-Thomley檢測系統,用於反向散射模式;作業距離設定10mm,加速電壓在20kV,放大範圍介於10000X和100000X之間。
第1圖和第2圖分別表示實施例1和比較例2製成電極的觸媒塗料之斷面影像,和使用ZAF校正法確定之相對應組成份形態(ZAF指取樣矩陣效應之校正;Z指原子序數效應,A指X射線吸收效應,F指X射線螢光效應)。
由攸關實施例1電極(樣本1)之第1圖可見,錫呈現遍佈在觸媒塗料斷面。此外,EDX分析檢測到金屬組成份,可與樣本1之初始乙酸溶液,含錫、釕、銥、鉭之羥基乙醯氯錯合物之莫耳組成份等於20% Ru、7% Ir、17% Sn和56% Ti相當。
由攸關實施例2電極(樣本2C)之第2圖可見,在觸媒塗料全斷面只有微少錫存在。由EDX分析檢測金屬組成份,與樣本2C之初始醇水溶液,含錫、釕、銥、鉭之莫耳組成份等於20% Ru、7% Ir、17% Sn和56% Ti相較之下,可證明大部份錫損失。
釋氯測試
各實施例之諸樣本檢驗為實驗電池之釋氯陽極,供應氯化鈉鹽水,濃度為200g/l,密切控制pH在數值3。
表1顯示在電流密度3kA/m2測量之氯過電壓,所製成氯之含氧容量%,以及藉貴金屬損失表示的對逆流之電阻。
前述無意限制本發明,可按照各種具體例使用,不違標的,其範圍依附帶申請專利範圍明確界定。
在本案說明專利申請專利範圍中,「包括」和「包含」無意排除其他元件、組件或製法步驟存在。
本說明中所論及文件、作用、材料、裝置、論文等,單純為提供本發明之脈絡。並非擬議或表示此等論述部份或全部,係本案各項申請專利範圍優先權日之前,在本發明相關領域內之習知技術或一般常識。
Claims (13)
- 一種在電解製程中釋氣用電極,包括閥金屬基材,和觸媒塗料,含5-40%錫、3.6-15%銥、18-40%釕和30-70%鈦,呈金屬或其氧化物形式,按元素之莫耳%計,該觸媒塗料是由含銥、釕、錫和鈦的羥基乙醯氯錯合物之乙酸溶液,經熱分解而得者。
- 如申請專利範圍第1項之電極,其中該觸媒塗料含6-30%錫、3.7-12%銥、20-30%釕和50-70%鈦,呈金屬或其氧化物形式,按元素之莫耳%計者。
- 如前述申請專利範圍之電極,其中該觸媒塗料含8-18%錫、4-10%銥、18-36%釕和45-65%鈦,呈金屬或其氧化物形式,按元素之莫耳%計者。
- 如前述申請專利範圍任一項之電極,其中該觸媒塗料具有貴金屬比載,以銥和釕合計,介於8和12g/m 2間者。
- 如前述申請專利範圍任一項之電極,其中該觸媒塗料係由含5-40%錫、3.6-15%銥、18-40%釕和30-70%鈦(按元素之莫耳%計)的銥、釕、錫和鈦的羥基乙醯氯錯合物之乙酸溶液,經熱分解而得者。
- 一種如前述申請專利範圍所界定電極之製造方法,包括如下步驟:(a)對閥金屬基材施加含銥、釕、錫和鈦的羥基乙醯氯錯合物之乙酸溶液,隨即在50-60℃乾燥,並在450-600℃熱分解5至30分鐘,直到貴金屬比載,以銥和釕合計,介於0.4至1g/m 2間;(b)重複步驟(a),直到觸媒塗料獲得貴金屬比載6至12g/m 2為止;(c)在450-600℃熱處理,為時50至200分鐘者。
- 如申請專利範圍第6項之方法,其中該乙酸溶液含5-40%錫、3.6-15%銥、18-40%釕和30-70%鈦,以6-30%錫、3.7-12%銥、20-30%釕和50-70%鈦為佳,而以8-18%錫、4-10%銥、18-36%釕和45-65%鈦尤佳,均按元素之莫耳%計者。
- 一種在電解製程中釋氣用電極之製造方法,包括如下步驟:(a)對閥金屬基材施加含銥、釕、錫和鈦的羥基乙醯氯錯合物之乙酸溶液,含5-40%錫、3.6-15%銥、18-40%釕和30-70%鈦,按元素之莫耳%計,隨後在50-60℃乾燥,並在450-600℃熱分解,為時5至30分鐘,直到貴金屬比載,以銥和釕合計表示,在0.4至1g/m 2;(b)重複(a)步驟,直到觸媒塗料獲得貴金屬比載為6至12g/m 2; (c)在450-600℃熱處理,為時50至200分鐘者。
- 如申請專利範圍第8項之方法,其中該乙酸溶液含6-30%錫、3.7-12%銥、20-30%釕和50-70%鈦,以8-18%錫、4-10%銥、18-36%釕和45-65%鈦為佳,均按元素之莫耳%計者。
- 如申請專利範圍第6-8項任一項之方法,其中在(a)和(c)之該熱分解溫度,介於480和550℃之間者。
- 一種碱性氯化物溶液之電解用電池,包括陽極室和陰極室,其中陽極室裝設有申請專利範圍第1-5項任一項之電極者。
- 如申請專利範圍第11項之電解用電池,其中該陽極室和該陰極室,係利用隔膜或離子交換膜隔開者。
- 一種由碱氯溶液製造氯和碱用之電解槽,包括申請專利範圍第12項電池之模組配置者。
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