201021912 ratio is between 0.1 and 1. Preferential oxidation of CO in hydrogen stream over these catalysts is carried out in a fixed bed reactor to remove CO. The 02/C0 molar ratio is between 0.5 and 5. This invention can be applied in removing CO in firel cell gas to prevent from poisoning of the electrode of fuel cell. 四、 指定代表圖： 無指定代表圖 五、 本案若有化學式時，請揭示最能顯示發明特徵的化學式·· w%Au/CuOx/Ti〇2(Cu/Ti=x/100-x)為本發明製備之觸媒， w為觸媒(w%Au/ CuOx /Ti02)中之金佔全部觸媒重量之百分 率’（Cu/Ti=x/100-x)為觸媒中銅與鈦的原子比。 CO + 1/2 〇2 C〇2 H2 + 1/2 〇2 ^ C〇2 以上為此項發明的化學反應式，第一個反應式為主產物反應式， 第一個反應式為副產物反應式。 ⑩六、發明說明： 【發明所屬之技術領域】 本發明揭示一種製備承載於氧化銅及二氧化鈦之金觸媒方 及一種在奈米金承載於氧化銅及二氧化鈦之觸媒催化下，在 富含氫氣環境下，一氧化碳與氧氣反應以去除一氧化碳之方法； 其中氧化銅及二氧化鈦係依不同元素比例混合，氧化銅/二氧化鈇 ，子比為αΐ與1之間，承載之金顆粒直徑為1與6奈米之間。 ，，明以含有金/脉銅—二氧化賴絲—祕碳、氧氣及氫氣 =在下’氧氣/一氧化碳莫耳比為0.5與5之間，使用連續式填充 應:器，用於選擇性氧化一氧化碳，以去除一氧化碳，此項發 月可應用於去除燃料電池的燃料中的一氧化碳，以避免一氧化碳 201021912 毒化燃料電池的電極 【先前技術】 目前新能_開發以及有__儲存 Ϊ料電化學能高效率的轉化為電能，並能方便的儲存妒’ 度分類為’綠龍料電峨作溫度_= 參 常見。但由於這些燃料電池中的電極非常容易被一 t t:PAFCsx能容忍2% 一氧化碳的存在，聰i是 :士存在小ppm的一氧化碳，故如何獲得乾淨的氫氣來源，就 成為燃料電池的研究中最重要的課題。 ' ，料電池中所使㈣氫氣，可贱種方絲獲得，其中甲烧 組反應（steamref_e〇是目前最經濟的氫氣來源， ϋ點疋需要-連串純化航的步驟，另外也有採用其他碳化 巧裂解，或者是使用不會產生COx副產物的氨氣裂解反應生 成虱氣。在重組反應中，甲烷及水氣的重組必定會生成副產物一 氧化碳，而一氧化碳是降低電極效能的主因，故必須經過一連串 移除二氧化碳的反應，才可將氫氣導入PEM中；在一連串的反應 中，首先利用高溫的水氣與一氧化碳氧化反應（watergasshift reactors, WGSs)操作在35〇〜55(rc，常使用氧化鐵/氧化鉻的混和 觸媒，可將一氧化碳濃度降到3% ;接下來經過低溫的WGS反應， 使用氧化銅/氧化鋅/氧化鋁作為觸媒將一氧化碳濃度再降到 〇.5% ’其溫度為200〜300°C ;最後進入選擇性氧化反應(preferential oxidation reactor, PR0X)將一氧化碳減至幾個ppm。 選擇性一氧化碳氧化反應是目前最能有效移除一氧化碳方法 之一，早期常用於此類反應的觸媒，通常都同時具有高度的一氧 化碳氧化能力及氫氣的氧化能力，最被廣泛使用的莫過於是白金 觸媒；但是白金觸媒的反應活性雖好，卻也使得氫氣的氧化量也 跟著增加，所以隨著溫度的升高一氧化碳轉化率就會下降，選擇 201021912 ❹ 率也隨之降低。另外在Oh及Sinketvitch等人的論文中提到[J. Catal. 第142卷（1993)第245頁起]，應用Ru、Rh、Pd等金屬觸媒應用 在這個反應上，其一氧化碳轉化率如同白金觸媒一般，隨著溫度 升高而遞減。一氧化碳轉化率遞減的情況在各種觸媒中，分別為 Ru/A1203 > Rh/Al203> Pt/Al203> Pd/Al203 (同樣在0.5%的金屬含量 下）°Matralis等人的文獻中[Catal. Today 第75卷(2002)第157至 167 頁]比較5 wt.% Pt/ r -Al2〇3、2.9 wt. % Au/a-Fe203 及Cu0-Ce02三 種不同觸媒，在反應溫度25-250 °C間PROX反應的情況，發現金 觸媒適合在100°c以下進行反應’銅觸媒則適合1〇〇〜2〇〇°c，白金 觸媒則是在200°C有100°/。的一氧化碳轉化率，並且發現反應氣體中 二氧化碳的存在會降低一氧化碳的轉化率，尤其是金觸媒更為明 顯。相較於白金觸媒’金觸媒不但能在低於1〇〇t^具有很高的活 性’疋其他貴金屬觸媒所不能比擬的’並且金的原料也比白金便 宜且價格穩定許多’其操作溫度也較適合低溫麵料電池，不用 另行加溫。然而，文獻中指出這些觸並沒有很高的活性和選擇 的靡Γϊίίί」?關金觸媒專利大部分都在一氧化碳氧化上 氣環境下進行選擇性—氧化碳氧化反應’並 下進ίϊϊ 化鈦齡性氧化物作為_，在100°c以 觸顧專_於表—。由已公開 大多-氧化碳氧化反應之觸媒， (2_/02)揭示—種氫氣上操;=了 33_ 氧化觸獻料妓，觸縣擇性 Rh或Pt-Rh合金，能在2〇π〜抑。广戰在氧化物擔體如氧化銘上之Pt、 除，但在較高溫的_下：下^氫重組氣中之C0選擇性移 境下反應。日本專利JP2004、284920 201021912 (2004/10/14)揭示一種選擇性氧化反應裝置及使用該裝置移除一氧 化碳的方法，使用一種含二觸媒段之選擇性氧化反應器將含氫重 組氣體中之CO移除，所用之觸媒為負載在金屬氧化物擔體如氧化 銘或氧化矽上之Pt及Ru觸媒。美國專利US 6787118 (2004/09/07)揭 示一種自氫氣流中選擇性移除一氧化碳的方法，使用之觸媒為負 載在以共沉澱法製得之含鈽及其他金屬如錯、鐵、錳、銅等混合 氧化物上之Pt、Pd及Au觸媒。美國專利US6780386(2004/08/24)揭 示一種一氧化碳氧化觸媒及製造含氫氣體的方法，以負載在氧化 鈦及氧化铭上之Ru為觸媒，將富氫氣體中之c〇濃度由〇.6〇/。降至約 10PPm。日本專利JP2004-223415 (2004/08/12)揭示選擇性氧化一氧 化碳之觸媒及燃料系統中降低一氧化碳濃度之方法，實施例中以 負載在氧化鋁上之RU為觸媒，於149〜2〇5。(：下能將富氫氣體中之 匚〇濃度由6000卩卩111降至10??1]1以下。美國專利仍6673742 (2004/01/06)與US6409939(2002/01/25)揭示製造一種優先氧化觸媒 及製造富氫燃料氣流的方法，製得之05〜3%Ru/Al2〇3觸媒在 70〜130°C溫度下能選擇性氧化富氳進料中之一氧化碳(〇47%)，出 料氣中之CO濃度可降至5〇 ppm。美國專利US6559〇94(2〇〇3/05/06) 揭示一用於選擇性氧化一氧化碳之催化材料的製備方法，典型使 用的觸媒為5%Pt-0.3%Fe/Al2〇3。美國專利US6531106(2003/03/11) ❿ j示一種選擇性移除一氧化碳的方法，將pt、Pd、Ru、Rh或Ir等 貴金屬負載在結晶矽酸鹽上為觸媒，於實施例中處理含〇 6% C〇、 24% C〇2、20% HzO、0.6% 〇2、54.8% H2之氣體，不同溫度下多 數能將00濃度降至5(^!11以下。曰本專利邛2〇〇3_1〇47〇3 (2003/04/09)揭示降低一氧化碳的方法及燃料電池系統，實施例中 製備Ru-Pt/Al2〇3觸媒，能將含氫重組氣體中之c〇濃度由6〇〇〇ppm 降至4ppm。美國專利US6287529(2001/09/ll)與US5874041 (1999/02/23)揭示選擇性催化氧化一氧化碳的裝置和方法，該裝置 為多階段式co氧化反應器’以負載在人12〇3解石上之贼仙為觸 媒’能將富氫氣流中之CO降至4〇 ppm以下。曰本專利 JP2000-169107 ¢2000/06/20)揭示降低一氧化碳製造含氫氣體的方 201021912 法，實施例中製備負載在氧化鈦及氧化鋁擔體上之含鹼金屬或鹼 土金屬之Ru觸媒’於60〜16〇。〇範圍能將含氫氣體中之c〇濃度由 0.6%降至50ppm以下。歐洲專利EP〇955351 (1999/11/10)與日本專 利JP11310402 (1999/09/11)揭示一氧化碳濃度降低裝置及一氧化 峡選擇性氧化觸媒的製造方法，該觸媒為以不同比例負載在人12〇3 上之Pt和Ru ’ Pt和Ru的比例會改變選擇性氧化反應的溫度。美國 專利US5258340 (1993/11/02)揭示一種用於低溫轉化一氧化破之 混合過渡金屬氧化物觸媒的製造方法，以順序沉澱法(sequential precipitation method)製得内層含氧化鈷，外層含其他金屬如鐵、 • 鎳、銅、鋅、鉬、鎢或錫之氧化物的層狀金屬氧化物，此層狀金 屬氧化物也可擔載在二氧化矽擔體上，最後將貴金屬如金、鉑、 把、铑或其混合物負載至層狀金屬氧化物上，所得觸媒用於低溫 氧化CO，實施例1-10中顯示T50 (C0轉化率達50%所需之溫度)隨觸 媒組成而異，介於46~240°C之間。日本專利JP05201702 (1993/08/10) 揭示選擇性移除一氧化碳之方法及裝置，以Ru/Al2〇3及]^八12〇3 為觸媒’於120°C以下能將含氫氣體中之CO濃度降至0.01%以下。 美國目前有關選擇性一氧化碳氧化之應用專利列於表二。 表一國内相關專利檢索 公告號 公告日 專利名稱 1 200410754 2004/07/01 奈米金觸媒及其製備方法 2 00222233 1994/04/11 一氧化碳氧化之金觸媒的製備方法 表二國外相關專利檢索201021912 ratio is between 0.1 and 1. Preferential oxidation of CO in hydrogen stream over these catalysts is carried out in a fixed bed reactor to remove CO. The 02/C0 molar ratio is between 0.5 and 5. This invention can be applied in removing CO In firel cell gas to prevent from poisoning of the electrode of fuel cell. IV. Designated representative figure: No designation is shown in Figure 5. If there is a chemical formula in this case, please disclose the chemical formula that best shows the characteristics of the invention·· w%Au/CuOx/ Ti〇2 (Cu/Ti=x/100-x) is the catalyst prepared by the present invention, and w is the percentage of gold in the catalyst (w%Au/CuOx/Ti02) to the total weight of the catalyst' (Cu/Ti =x/100-x) is the atomic ratio of copper to titanium in the catalyst. CO + 1/2 〇2 C〇2 H2 + 1/2 〇2 ^ C〇2 The above is the chemical reaction formula of the invention, the first reaction formula is the main product reaction formula, and the first reaction formula is a by-product Reaction formula. 10 VI. Description of the Invention: [Technical Field] The present invention discloses a gold catalyst carrier prepared by carrying copper oxide and titanium dioxide and a catalyst catalyzed by nano-catalyst supported on copper oxide and titanium dioxide. In a hydrogen atmosphere, carbon monoxide reacts with oxygen to remove carbon monoxide; wherein copper oxide and titanium dioxide are mixed according to different element ratios, copper oxide/cerium oxide, and the subratio is between αΐ and 1, and the diameter of the gold particles carried is 1 and Between 6 nanometers. , with gold/pulse copper-diazonium-secreting carbon, oxygen and hydrogen=between the oxygen/carbon monoxide molar ratio between 0.5 and 5, using a continuous filling device for selective oxidation Carbon monoxide to remove carbon monoxide, this month can be applied to remove carbon monoxide in the fuel cell fuel to avoid carbon monoxide 201021912 poisoning fuel cell electrode [prior art] current new energy _ development and __ storage material electrochemical energy Highly efficient conversion to electrical energy, and easy to store 妒 'degree classification as 'green dragon electricity 峨 温度 temperature _ = common. However, since the electrodes in these fuel cells are very easy to be tolerated by 2% carbon monoxide in a tt:PAFCsx, Congyi is: there is a small ppm of carbon monoxide, so how to obtain a clean source of hydrogen becomes the most research in fuel cells. Important topic. ', the battery in the battery (4) hydrogen, can be obtained from the square wire, in which the combustion group (steamref_e〇 is currently the most economical source of hydrogen, the need for a series of purification steps, in addition to other carbonization The cleavage is carried out by using ammonia cracking reaction which does not produce COx by-products. In the recombination reaction, the recombination of methane and water vapor must produce carbon monoxide as a by-product, and carbon monoxide is the main cause of reducing the efficiency of the electrode. After a series of reactions to remove carbon dioxide, hydrogen can be introduced into the PEM; in a series of reactions, first use high temperature water vapor and carbon monoxide oxidation reaction (watersshift reactors, WGSs) operating at 35 〇 55 (rc, often used oxidation A mixed catalyst of iron/chromium oxide can reduce the concentration of carbon monoxide to 3%; then, after a low temperature WGS reaction, the concentration of carbon monoxide is reduced to 〇.5% using copper oxide/zinc oxide/alumina as a catalyst. The temperature is 200~300 °C; finally, the selective oxidation reactor (PR0X) is used to reduce carbon monoxide to a few ppm. Oxidation of carbon oxide is one of the most effective methods for removing carbon monoxide. The catalysts commonly used in such reactions in the early stage usually have high carbon monoxide oxidation capacity and hydrogen oxidation capacity. The most widely used one is platinum. Catalyst; however, the reactivity of the platinum catalyst is good, but it also increases the amount of hydrogen oxidation. Therefore, as the temperature increases, the carbon monoxide conversion rate will decrease, and the selectivity of 201021912 will also decrease. Also in Oh And in the paper by Sinketvitch et al. [J. Catal. Vol. 142 (1993), p. 245], the application of Ru, Rh, Pd and other metal catalysts in this reaction, the carbon monoxide conversion rate is like platinum catalyst. Generally, it decreases with increasing temperature. The decrease in carbon monoxide conversion rate is Ru/A1203 >Rh/Al203>Pt/Al203> Pd/Al203 (also at 0.5% metal content) in various catalysts. °Matralis et al. [Catal. Today Vol. 75 (2002) pp. 157-167] compares 5 wt.% Pt/r-Al2〇3, 2.9 wt.% Au/a-Fe203 and Cu0-Ce02 Different catalysts, in response The degree of PROX reaction between 25-250 °C, found that the gold catalyst is suitable for reaction below 100 °c 'copper catalyst is suitable for 1 〇〇 ~ 2 〇〇 ° c, platinum catalyst is at 200 ° C The carbon monoxide conversion rate of 100 ° /., and found that the presence of carbon dioxide in the reaction gas will reduce the conversion rate of carbon monoxide, especially the gold catalyst is more obvious. Compared with the platinum catalyst, the gold catalyst can not only be highly active at less than 1〇〇t^, but also cannot be compared with other precious metal catalysts. And the raw materials of gold are also cheaper than platinum and the price is much more stable. The operating temperature is also suitable for low temperature fabric batteries without additional heating. However, it is pointed out in the literature that these touches do not have high activity and selectivity. Most of the patents for Guanjin catalysts are selective oxidation-oxidation of carbon monoxide in a carbon monoxide oxidation atmosphere. Age-oriented oxides are used as _, at 100 °c to patronize the __ table. From the catalyst that has been disclosed to most of the oxidation of carbon oxides, (2_/02) reveals that hydrogen is operated on the gas; = 33_ oxidized touch 妓, touched the selective Rh or Pt-Rh alloy, can be in 2〇π ~ Suppress. The GW is on the oxide support such as Pt, except for oxidation, but it is reacted under C0 selective migration in the higher temperature _ lower: lower hydrogen recombination gas. Japanese Patent JP2004, 284920 201021912 (2004/10/14) discloses a selective oxidation reaction device and a method for removing carbon monoxide using the same, wherein a hydrogen-containing recombination gas is used in a selective oxidation reactor containing a two-catalyst segment The CO is removed, and the catalyst used is Pt and Ru catalyst supported on a metal oxide support such as oxidized or ruthenium oxide. U.S. Patent No. 6,787,118 (2004/09/07) discloses a method for the selective removal of carbon monoxide from a hydrogen stream using a catalyst supported by a coprecipitation method comprising ruthenium and other metals such as iron, manganese, Pt, Pd and Au catalysts on mixed oxides such as copper. US Patent No. 6,780,386 (2004/08/24) discloses a carbon monoxide oxidation catalyst and a method for producing a hydrogen-containing gas, wherein Ru is supported on titanium oxide and oxidized, and the concentration of c〇 in the hydrogen-rich gas is determined by 〇 .6〇/. Dropped to about 10PPm. Japanese Patent No. 2004-223415 (2004/08/12) discloses a method for reducing the concentration of carbon monoxide in a catalyst for selectively oxidizing carbon monoxide and a fuel system. In the embodiment, RU supported on alumina is used as a catalyst, at 149~2〇 5. (: The concentration of ruthenium in hydrogen-rich gas can be reduced from 6000卩卩111 to below 10??1]1. U.S. Patent No. 6,667,742 (2004/01/06) and US6409939 (2002/01/25) disclose manufacturing. A method for preferentially oxidizing a catalyst and producing a hydrogen-rich fuel gas stream, wherein the 05~3% Ru/Al2〇3 catalyst can selectively oxidize one of the carbon oxides in the cerium-rich feed at a temperature of 70 to 130 ° C (〇47 %), the CO concentration in the feed gas can be reduced to 5 〇 ppm. US Patent No. 6,559 〇 94 (2〇〇3/05/06) discloses a preparation method for a catalytic material for selective oxidation of carbon monoxide, typically used. The catalyst is 5% Pt-0.3% Fe/Al2〇3. U.S. Patent No. 6,531,106 (2003/03/11) shows a method for selectively removing carbon monoxide, which is loaded with precious metals such as pt, Pd, Ru, Rh or Ir. In the embodiment, the catalyst is treated with 〇6% C〇, 24% C〇2, 20% HzO, 0.6% 〇2, 54.8% H2, and most of them can be 00 at different temperatures. The concentration is reduced to 5 (^! 11 or less. 曰 Patent 邛 2〇〇3_1〇47〇3 (2003/04/09) discloses a method for reducing carbon monoxide and a fuel cell system, and in the examples, Ru-Pt/Al2〇3 is prepared. Catalyst, can The concentration of c〇 in the hydrogen-containing reformed gas is reduced from 6 〇〇〇 ppm to 4 ppm. U.S. Patent Nos. 6,287,529 (2001/09/11) and 5,874,041 (1999/02/23) disclose apparatus and methods for selectively catalyzing the oxidation of carbon monoxide, The device is a multi-stage co-oxidation reactor, which can reduce the CO in the hydrogen-rich stream to less than 4 〇ppm by using the thief-loaded catalyst on the human 12〇3 calculus. This patent JP2000-169107 ¢2000 /06/20) discloses a method for reducing the production of hydrogen-containing gas by carbon monoxide 201021912. In the examples, a Ru catalyst containing an alkali metal or an alkaline earth metal supported on a titanium oxide and an alumina support is prepared at 60 to 16 Torr. The range can reduce the concentration of c〇 in the hydrogen-containing gas from 0.6% to less than 50 ppm. European Patent No. 955351 (1999/11/10) and Japanese Patent JP11310402 (1999/09/11) disclose a carbon monoxide concentration reducing device and oxidation. A method for producing a gorge selective oxidation catalyst which has a ratio of Pt and Ru 'Pt and Ru supported on human 12〇3 in different proportions to change the temperature of the selective oxidation reaction. US Pat. No. 5,258,340 (1993/11) /02) reveals a mixture for low temperature conversion and oxidation In the method for producing a transition metal oxide catalyst, a layer containing cobalt oxide is formed by a sequential precipitation method, and an outer layer contains a layer of an oxide of another metal such as iron, nickel, copper, zinc, molybdenum, tungsten or tin. a metal oxide, the layered metal oxide may also be supported on a cerium oxide support, and finally a noble metal such as gold, platinum, rhodium, ruthenium or a mixture thereof is supported on the layered metal oxide, and the resulting catalyst is used. Oxidizing CO at low temperatures, T50 (temperature required for C0 conversion of 50%) is shown in Examples 1-10, depending on the composition of the catalyst, between 46 and 240 °C. Japanese Patent JP05201702 (1993/08/10) discloses a method and a device for selectively removing carbon monoxide, which can be used in a hydrogen-containing gas at a temperature below 120 ° C using Ru/Al 2 〇 3 and ] 8 〇 8 〇 3 as a catalyst. The CO concentration falls below 0.01%. The current US patent applications for selective carbon monoxide oxidation are listed in Table 2. Table 1 Domestic related patent search announcement number Announcement date Patent name 1 200410754 2004/07/01 Nano gold catalyst and preparation method 2 00222233 1994/04/11 Preparation method of gold catalyst for carbon monoxide oxidation Table 2 Foreign related Patent search
No. Patent No. Date Title 1 JP2004- 338981 2004/12/02 Hydrogen purifying apparatus, its operation method, and manufacturing method of carbon monoxide selective oxidation catalyst 2 JP2004- 284920 2004/10/14 Selective oxidation reaction device, and method for removing carbon monoxide using the same 201021912No. Patent No. Date Title 1 JP2004- 338981 2004/12/02 Hydrogen purifying apparatus, its operation method, and manufacturing method of carbon monoxide selective oxidation catalyst 2 JP2004- 284920 2004/10/14 Selective oxidation reaction device, and method for Removing carbon monoxide using the same 201021912
3 US6787118 2004/09/07 Selective removal of carbon monoxide 4 JP2004- 223415 2004/08/12 Catalyst for selective oxidation of carbon monoxide, method for decreasing carbon monoxide concentration, and fuel cell system 5 US6780386 2004/08/24 Carbon monoxide oxidation catalyst, and method for production of hydrogen-containing gas 6 US6673742 2004/01/06 Method for producing a preferential oxidation catalyst 7 US6559094 2003/05/06 Method for preparation of catalytic material for selective oxidation and catalyst members thereof 8 JP2003- 104703 2003/04/09 Method for lowering carbon monoxide concentration and fuel cell system 9 US6531106 2003/03/11 Selective removing method of carbon monoxide 10 US6409939 2002/01/25 Method for producing a hydrogen-rich fuel stream 11 US6287529 2001/09/11 Method for selective catalytic oxidation of carbon monoxide 12 JP2000- 169107 2000/06/20 Production of hydrogen-containing gas reduced in carbon monoxide 13 US6168772 2001/01/02 Process for the selective oxidation of carbon monoxide in reformed gases 14 EP0955351 1999/11/10 Carbon monoxide concentration reducing apparatus and method, and production method for carbon monoxide-selective oxidation catalyst 15 US5271916 1993/12/21 Device for staged carbon monoxide oxidation 16 US5258340 1993/11/02 Mixed transition metal oxide catalysts for conversion of carbon monoxide and method for producing the catalysts 17 JP05201702 1993/08/10 Method and apparatus for selectively removing carbon monoxide 【發明内容】 本發明揭示一種製備承載於氧化銅及二氧化鈦之金觸媒方 及一種在奈米金承載於氧化銅及二氧化鈦之觸媒催化下，在 富含氫氣環境下，一氧化碳與氧氣反應以去除一氧化碳之方法； 其中氧化銅及二氧化鈦係依不同元素比例混合，氧化銅/二氧化鈦 201021912 原子比為H與1之間，承載之金顆粒：|[徑為丨與6奈米之間。 本發明以^金/氧灿—三氧饿觸在—氧傾、氧氣及氫氣 存在下，氧氣/-氧化碳莫耳比為05與5之間，使用連續式填充 床反應器’，於選#性氧化一氧化碳，以去除一氧化碳，此項發 明可應麟去除轉電池的燃料中的—氧化碳，以避免一氧化碳 毒化燃料電池的電極。 【實施方式】 f施方式1 : 浸法製備銅·鈦之複合性金屬氧化物，作為負載金的 擔體’/、中氧化銅及二氧化鈦係依不同元素比例混合，稱取適量 蒸二中:f其猶銅水溶液慢慢滴入適 宜的-祕財並雛，在线t斑㈣燒4小時，即生 銅一二氧化鈦粉末，並取出研磨。 f施例1 : L 含製作織比為1/99的氧化物擔體，稱取硝酸銅 0.18克，將其以4.6毫升蒸館水溶解； 參 2.稱取2.82克三氧化鈦’將步驟一之水溶液慢慢獻其中 观職4 树， 膂施例2 ： 1· = J含浸法製作銅/鈦比為2/98的氧化物擔體，酸 0.35克，將其以4.5毫升蒸館水溶解； 織銅 2.稱取5.65克二氧化鈦，將步驟一之水溶液慢慢滴入其 ^ ’在空氣中35(TC烺燒4小時，即生成氧化銅—二氧H 末，並取出研磨。 匕鈦粉 营施例3 ： 1·以初濕含浸法製作銅/鈦比為4.7/95.3的氧化物細，稱取俩 201021912 銅0.78克，將其以4.2毫升蒸館水溶解； 2·稱取5.22克二氧化鈦，將步驟一之水溶液慢慢滴入其中並 拌’在空氣中350 C煅燒4小時，即生成氧化銅—二氧化鈦粉 末，並取出研磨。 管施例4 ： 1·以初濕含浸法製作銅/鈦比為10/90的氧化物擔體，稱取硝酸銅 3.02克’將其以2.4毫升蒸餾水溶解； 2.稱取2.98克二氧化鈦’將步驟一之水溶液慢慢滴入其中並 拌’在空氣中350°C烺燒4小時，即生成氧化銅—二氧化鈦粉 末，並取出研磨。 響 f施方式2 · 1. 稱取適當比例的氧化銅一二氧化鈦粉末198克放入2〇〇毫升蒸 餾水中，以磁石攪拌之，並加熱至65°c，並維持之； ’、 2. 稱取四氣金酸0.035克，將其溶解於4〇毫升蒸餾水，其中金佔 0.02 克； 、幻口 3. 以0.1M氨水將步驟2之溶液酸鹼值控制在7±〇 2，再將四氣金 酸溶液以每分鐘10毫升的速率滴入此溶液中，並同時控制鹼 在7±0.2，溫度維持65°C ; Φ 4·滴定完成後以磁石擾拌混合兩小時，維持酸驗值在7±〇·2，溫声 65°C，使其反應完全； 又 5. 將得到的沈澱物過濾，並以65°C之蒸餾水水洗多次，直到完全 除去氯離子’再於80°C烘乾16小時； 6. 將烘乾後的觸媒在180。(：於空氣中燒4小時，即生成ι% Au/CuOx—Ti02適當比例的氧化銅一二氧化鈦粉末； 7. 將觸媒〇.1〇克的1机％人\1/€11〇/11〇2’適當銅/鈦莫耳數比的粉 末置於直立式填充床反應器内，進行在富氫環境下選擇性氧化 一氧化碳的反應，以固定床反應器進行實驗，管内外直徑為12 公分及0.6公分，長度57公分，中間有0.7公分之融溶石英砂， 201021912 以擔載反應之觸媒，但可以透氣，另外在反應管内有一内外直 徑為0·6公分及〇.4公分之底部密封玻璃管，是為了放置測量觸 媒表面溫度的熱電偶溫度計； 8. 在一氧化碳、氧氣及氫氣存在下，氧氣/一氧化礙體積比為2， 以質量流率控制器控制總流量為每分鐘50毫升，在室溫下通入 反應器中，反應氣體產物以氣象層析儀（中國層析型號9800) 分析之’使用3.5公尺Molecular sieve 5Α不銹鋼管柱； 9. 反應器溫度由圓筒狀電偶加熱爐控制，其加熱爐外層長度約η 公分’直徑11公分，内部鋪有4公分玻璃纖維之保溫設備’反 應器溫度以每分鐘2度由攝氏25度升高，並分別在60、80、 100、120度平衡1〇分鐘，再利用氣相層析儀偵測其出口濃度 (ppm) ° 實施例5 ： 1. 稱取CuOx—Ti〇2粉末(銅/鈦莫耳數比為1/99) 0.98克放入200 毫升蒸餾水中，以磁石攪拌之，並加熱至65它，並維持之； 2. 稱取四氯金酸0.035克’將其溶解於40毫升蒸餾水，其中金佔 0.02 克； ' 3. 以0.1M氨水將步驟2之溶液酸驗值控制在7±〇.2，再將四氣金 酸溶液以母分鐘10毫升的速率滴入此溶液中，並同時控制驗值 在7±0.2，溫度維持65°C ; 4. 滴定完成後以磁石攪拌混合兩小時，維持酸鹼值在7±〇2，溫度 65°C，使其反應完全； 5. 將得到的沈澱物過濾，並以65。〇之蒸顧水水洗多次，直到完全 除去氯離子，再於80。(：烘乾16小時； 6. 將烘乾後的觸媒在i80°C於空氣中燒4小時，即生成p/0 Au/CuOx—Ti〇2粉末，銅/鈦莫耳數比為1/99 ; 7. 將觸媒0.10克的1 wt% Au/Cu〇x/Ti〇2 ’銅/鈦莫耳數比為1/99 的粉末置於直立式填充床反應器内，進行在富氫環境下選擇性 201021912 氧化一氧化碳的反應，以固定床反應器進行實驗，管内外直徑 為1·2公分及〇.6公分，長度57公分，中間有〇 7公分之融熔 石英砂，以擔載反應之觸媒，但可以透氣，另外在反應管内有 一内外直徑為0.6公分及〇.4公分之底部密封玻璃管，是^放 置測量觸媒表面溫度的熱電偶溫度計；' 8. 在一氧化碳、氧氣及氫氣存在下，氧氣/一氧化碳體積比為2， 以質量流率控制器控制總流量為每分鐘5〇毫升，在室溫;通入 反應器中，反應氣體產物以氣象層析儀（中國層析型f98〇〇) 分析之，使用3.5公尺Molecular sieve 5A不錄鋼管柱； 9. 反應器溫度由圓筒狀電偶加熱爐控制，其加熱爐外層長度約17 參 公分，直徑11公分，内部鋪有4公分玻璃纖維之保溫設備，反 應器溫度以每分鐘2度由攝氏25度升高，並分別在6〇、8〇、 100、120度平衡10分鐘，再利用氣相層析儀偵測其出口 (ppm)。反應結果如下： 溫度(度C) 60 80 100 120 出口 一氧化碳濃度(ppm) 4.3 2.8 3.1 3.7 f施例6 :3 US6787118 2004/09/07 Selective removal of carbon monoxide 4 JP2004- 223415 2004/08/12 Catalyst for selective oxidation of carbon monoxide, method for decreasing carbon monoxide concentration, and fuel cell system 5 US6780386 2004/08/24 Carbon monoxide oxidation Catalyst, and method for production of hydrogen-containing gas 6 US6673742 2004/01/06 Method for producing a preferential oxidation catalyst 7 US6559094 2003/05/06 Method for preparation of catalytic material for selective oxidation and catalyst members thereof 8 JP2003- 104703 2003 /04/09 Method for lowering carbon monoxide concentration and fuel cell system 9 US6531106 2003/03/11 Selective removing method of carbon monoxide 10 US6409939 2002/01/25 Method for producing a hydrogen-rich fuel stream 11 US6287529 2001/09/11 Method for selective catalytic oxidation of carbon monoxide 12 JP2000- 169107 2000/06/20 Production of hydrogen-containing gas reduced in carbon monoxide 13 US6168772 2001/01/02 Process for the select Ie oxidation of carbon monoxide in reformed gases 14 EP0955351 1999/11/10 Carbon monoxide concentration reducing apparatus and method, and production method for carbon monoxide-selective oxidation catalyst 15 US5271916 1993/12/21 Device for staged carbon monoxide oxidation 16 US5258340 1993/ 11/02 Mixed transition metal oxide catalysts for conversion of carbon monoxide and method for producing the catalysts 17 JP05201702 1993/08/10 Method and apparatus for selectively removing carbon monoxide. SUMMARY OF THE INVENTION The present invention discloses preparation of copper oxide and titanium dioxide. Gold catalyst and a method for removing carbon monoxide by reacting carbon monoxide with oxygen in a hydrogen-rich environment under the catalysis of nano-gold supported by copper oxide and titanium dioxide; wherein copper oxide and titanium dioxide are mixed according to different element ratios , copper oxide / titanium dioxide 201021912 atomic ratio between H and 1, bearing gold particles: | [path between 丨 and 6 nm. The invention adopts a continuous packed bed reactor in the presence of ^ gold/oxycan-trioxane in the presence of oxygen, oxygen and hydrogen, and an oxygen/carbon oxide molar ratio of between 05 and 5. #性氧化氧化碳的碳碳的碳碳, the invention can remove the carbon-carbon in the fuel of the battery to avoid the carbon monoxide poisoning the electrode of the fuel cell. [Embodiment] f application method 1: a copper-titanium composite metal oxide is prepared by a dip method, and the gold-supported support '/, medium copper oxide, and titanium dioxide are mixed according to different element ratios, and an appropriate amount of steam is added: f Its aqueous solution of copper is slowly dripped into the appropriate - secret money and chicks, on-line t-spot (four) burned for 4 hours, that is, raw copper-titanium dioxide powder, and taken out and ground. f Example 1: L contains an oxide support having a weave ratio of 1/99, weigh 0.18 g of copper nitrate, and dissolve it in 4.6 ml of steamed water; cf. 2. Weigh 2.82 g of titanium dioxide. One of the aqueous solutions is slowly dedicated to the 4 trees, 膂Example 2: 1· = J is impregnated to make a copper/titanium oxide ratio of 2/98, 0.35 g of acid, and 4.5 ml of steamed water Dissolve; woven copper 2. Weigh 5.65 g of titanium dioxide, and slowly add the aqueous solution of step one to it in the air. (In the air, simmer for 4 hours to form copper oxide - dioxin H, and take out the grinding. 匕Titanium Powder Camp Example 3: 1·Prepare the oxide with a copper/titanium ratio of 4.7/95.3 by incipient wetness method, and weigh 0.78 g of 201021912 copper, and dissolve it in 4.2 ml steaming water; 2·Weigh 5.22 g of titanium dioxide, the aqueous solution of step one is slowly dropped into it and mixed and calcined in air at 350 C for 4 hours to form copper oxide-titanium dioxide powder, and taken out and ground. Tube Example 4: 1·Incipient wetness impregnation method An oxide support having a copper/titanium ratio of 10/90 was prepared, and 3.02 g of copper nitrate was weighed and dissolved in 2.4 ml of distilled water; 2. Weighed 2.98 Titanium Dioxide 'The aqueous solution of Step 1 is slowly dropped into it and mixed with 'steaming at 350 ° C for 4 hours in the air to form copper oxide - titanium dioxide powder, and taken out and ground. 响 f施式2 · 1. Weigh the appropriate proportion 198 g of copper oxide-titania powder was placed in 2 ml of distilled water, stirred with a magnet, heated to 65 ° C, and maintained; ', 2. Weighed 0.035 g of four gas gold acid, dissolved in 4 〇 ml of distilled water, of which gold accounts for 0.02 g; 幻口 3. Control the pH value of the solution of step 2 to 7±〇2 with 0.1M ammonia water, and then drop the four gas gold acid solution at a rate of 10 ml per minute. Into this solution, and at the same time control the alkali at 7 ± 0.2, the temperature is maintained at 65 ° C; Φ 4 · After the completion of the titration, the magnetic stirrer is mixed for two hours, maintaining the acid test value at 7 ± 〇 · 2, warm sound 65 ° C , the reaction is completed; 5. The precipitate obtained is filtered and washed with distilled water at 65 ° C for several times until the chloride ion is completely removed and then dried at 80 ° C for 16 hours; The catalyst is at 180. (: burned in air for 4 hours, ie, the appropriate proportion of oxygen is generated by 1% Au/CuOx-Ti02 Copper-titanium dioxide powder; 7. 1% of the catalyst of the catalyst 〇.1 \g/1/11〇/11〇2' suitable copper/titanium molar ratio powder is placed in the vertical packed bed reactor The reaction of selectively oxidizing carbon monoxide in a hydrogen-rich environment was carried out in a fixed bed reactor. The inner and outer diameters of the tube were 12 cm and 0.6 cm, the length was 57 cm, and the dissolved quartz sand was 0.7 cm in the middle, 201021912 to carry The catalyst of the reaction, but it can be ventilated. In addition, there is a bottom sealing glass tube with an inner and outer diameter of 0.6 cm and 44 cm in the reaction tube for placing a thermocouple thermometer for measuring the surface temperature of the catalyst; 8. in carbon monoxide, In the presence of oxygen and hydrogen, the oxygen/oxidation volume ratio is 2, the mass flow rate controller controls the total flow rate to 50 ml per minute, and is introduced into the reactor at room temperature, and the reaction gas product is a meteorological chromatograph ( China Chromatography Model 9800) Analytical 'Using a 3.5 m Molecular sieve 5Α stainless steel column; 9. The reactor temperature is controlled by a cylindrical galvanic furnace, the outer length of the furnace is about η cm' diameter 11 cm, internal The 4 cm glass fiber insulation equipment 'reactor temperature is increased by 25 degrees Celsius at 2 degrees per minute, and is balanced at 60, 80, 100, 120 degrees for 1 minute, respectively, and then detected by gas chromatography. Effluent concentration (ppm) ° Example 5: 1. Weigh CuOx-Ti〇2 powder (copper/titanium molar ratio of 1/99) 0.98 g into 200 ml of distilled water, stir with magnet and heat to 65 it, and maintain it; 2. Weigh 0.035 grams of tetrachloroauric acid' to dissolve it in 40 ml of distilled water, of which gold accounted for 0.02 grams; ' 3. Control the acidity of the solution of step 2 with 0.1M ammonia water at 7 ±〇.2, then the tetragastric acid solution was added to the solution at a rate of 10 ml of the mother minute, and the control value was 7±0.2 at the same time, and the temperature was maintained at 65 °C. 4. After the titration was completed, the magnet was stirred and mixed. For two hours, the pH was maintained at 7 ± 〇 2 and the temperature was 65 ° C to complete the reaction; 5. The resulting precipitate was filtered and taken at 65. Wash the water and wash it several times until the chloride ion is completely removed and then at 80. (: drying for 16 hours; 6. The dried catalyst is fired in air at i80 ° C for 4 hours to form p / 0 Au / CuOx - Ti 〇 2 powder, copper / titanium molar ratio of 1 /99 ; 7. A catalyst of 0.10 g of 1 wt% Au/Cu〇x/Ti〇2 'copper/titanium molar ratio of 1/99 is placed in a vertical packed bed reactor. Selective 201021912 oxidation of carbon monoxide in a hydrogen environment, the experiment was carried out in a fixed-bed reactor. The inner and outer diameters of the tube were 1·2 cm and 〇6 cm, the length was 57 cm, and the fused silica sand was 〇7 cm in the middle. The catalyst for carrying the reaction, but it can be ventilated. In addition, there is a bottom sealing glass tube with an inner and outer diameter of 0.6 cm and 〇4 cm in the reaction tube, which is a thermocouple thermometer for measuring the surface temperature of the catalyst; ' 8. in carbon monoxide, In the presence of oxygen and hydrogen, the oxygen/carbon monoxide volume ratio is 2, and the mass flow rate controller controls the total flow rate to 5 〇ml per minute at room temperature; into the reactor, the reaction gas product is a meteorological chromatograph (China) Chromatography type f98〇〇) analysis, using 3.5 m Molecular sieve 5A does not record steel pipe column; The temperature of the furnace is controlled by a cylindrical electric heating furnace. The outer layer of the heating furnace is about 17 cm in length and 11 cm in diameter. The inside is covered with 4 cm glass fiber insulation equipment. The reactor temperature is 2 degrees Celsius from 25 degrees Celsius. High, and balanced at 6〇, 8〇, 100, 120 degrees for 10 minutes, respectively, and then use gas chromatograph to detect its outlet (ppm). The reaction results are as follows: Temperature (degree C) 60 80 100 120 Export carbon monoxide concentration (ppm) 4.3 2.8 3.1 3.7 f Example 6:
1. 稱取CuOx—Τι〇2粉末(銅/鈦莫耳數比為2/98) 〇 98克放入· 毫升蒸德水中’以磁石之，並加熱至机，並維持之； 2. 稱取四氣金酸0.035克，將其溶解於4〇毫升蒸餾水，其中金佔 0.02 克； 3.以0.1Μ氨水將步称2之職酸驗健制在7±〇 2，再將四 酸溶液以每分鐘Κ)毫升_率•聽射， 在7±0.2，溫度轉65。(：； 4·滴定完成後以磁石勝混合兩小時，維持紐值在7±Q 65°C，使其反應完全； 5.將得到齡織/猶、’紅65ΐ之細水水洗乡:欠，直到完全 201021912 除去氣離子，再於8〇°C烘乾16小時； 6. 將烘乾後的觸媒在18〇t：於空氣中燒4小時，即生成1% Au/CuOx—Ti02粉末，銅/鈦莫耳數比為2/98 ; ° 7. 將觸媒0.10克的1机％ Au/CuOx/Ti〇2，銅/鈦莫耳數比為2/98 的粉末置於直立式填充床反應器内，進行在富氫環境下選擇性 氧化一氧化碳的反應，以固定床反應器進行實驗，管内外直徑 為1.2公分及0.6公分，長度57公分，中間有0.7公分之融熔 石英砂，以擔載反應之觸媒，但可以透氣，另外在反應管内有 一内外直徑為0.6公分及0.4公分之底部密封玻璃管，是為了放 置測量觸媒表面溫度的熱電偶溫度計； μ 8. 在一氧化碳、乳氣及虱氣存在下，氧氣/一氧化碳體積比為2， 以質量流率控制器控制總流量為每分鐘5〇毫升，在室溫下通入 反應器中，反應氣體產物以氣象層析儀（中國層析型號9800) 分析之’使用3.5公尺Molecular sieve 5Α不錄鋼管柱； 9. 反應器bn·度由圓筒狀電偶加熱爐控制’其加熱爐外居β麼的I? 公分，直徑11公分’内部鋪有4公分玻璃纖^之保溫設備，反 應器溫度以每分鐘2度由攝氏25度升高，並分別在6〇、go、 100、120度平衡10分鐘，再利用氣相層析儀偵測其出口濃度 (ppm)。反應結果如下： 溫度(度C) 60 80 100 120 出口 一氧化碳濃度(ppm) 4.1 3.2 3.6 4.2 實施例1: 1. 稱取CuOx—Ti〇2粉末(銅/鈦莫耳數比為4 7/95 3) 〇 98克放入 200毫升蒸餾水中，以磁石攪拌之，並加熱至65t：，並維持之； 2. 稱取四氯金酸0.035克，將其溶解於4〇毫升蒸餾水，其中金佔 12 201021912 0.02 克； 3. 以0.1M ^丨水將步驟2之溶液酸鹼值控制在7±〇 2，再將四氯金 酸溶液以每分鐘10毫升的速率滴入此溶液中，並同時控制鹼值 在7±0.2 ’溫度維持65°C ; 4. 滴定完成後以磁石攪拌混合兩小時，維持酸鹼值在7±〇 2 ,溫产 65°C，使其反應完全； 又 5. 將得到的沈澱物過濾，並以65。〇之蒸餾水水洗多次，直到完全 除去氯離子，再於8(TC烘乾16小時； 6. 將烘乾後的觸媒在18〇。〇於空氣中燒4小時，即生成 φ Au/Cu〇x—Ti〇2粉末’銅/鈦莫耳數比為4.7/95.3 ; 7. 將觸媒0.10克的1 wt.〇/0 Au/CuOx/Ti02，銅/鈦莫耳數屮盔 4.7/95.3的粉末置於直立式填絲反應_，進A富氫環境下 選擇性氧化一氧化碳的反應，以固定床反應器進行實驗，管内 外直徑為1.2公分及〇.6公分，長度57公分，中間有〇 7公分 之融熔石英砂，以擔載反應之觸媒，但可以透氣，另外在反應 管内有一内外直徑為0.6公分及〇.4公分之底部密封玻璃管，是 為了放置測量觸媒表面溫度的熱電偶溫度計； 8. 在一氧化碳、氧氣及氫氣存在下，氧氣/一氧化碳體積比為2， 以質量流率控制器控制總流量為每分鐘5〇毫升，在室溫下通入 © 反應器中，反應氣體產物以氣象層析儀（中國層析型號9800) 分析之，使用3.5公尺Molecular sieve 5A不錢鋼管柱； 9. 反應器溫度由圓筒狀電偶加熱爐控制，其加熱爐外層長度約 公分，直徑11公分，内部鋪有4公分玻璃纖維之保溫設備，反 應器溫度以每分鐘2度由攝氏25度升高，並分別在6〇、80、 100、120度平衡10分鐘，再利用氣相層析儀偵測其出口濃度 (ppm)。反應結果如下： 溫度(度C) 60 80 100 120 出口 一氧化碳淡度(ppm) 3.9 2.4 3.0 3.8 13 201021912 實施例8 ： 1·稱取CuOx〜Ti〇2粉末(銅/鈦莫耳數比為10/90) 0.98克放入200 毫升蒸，水中，以磁石攪拌之，並加熱至65乞，並雄持之； 2. 稱取四氯金酸0.035克’將其溶解於4〇毫升蒸餾水’其中金佔 0.02 克； 3. 以0.1M氨水將步驟2之溶液酸鹼值控制在7±0.2，再將四氣金 酸溶液以每分鐘1〇毫升的速率滴入此溶液中，並同時控制驗值 在7±0.2，溫度維持65°C ; 4. 滴定完成後以磁石攪拌混合兩小時，維持酸驗值在7±〇 2，溫度 φ 65°C，使其反應完全； 5. 將得到的沈殿物過濾，並以65。〇之蒸餾水水洗多次，直到完全 除去氯離子’再於80。(：烘乾16小時； 6. 將烘乾後的觸媒在180〇c於空氣中燒4小時，即生成1% Au/CuOx-~Ti〇2粉末，銅/鈦莫耳數比為ι〇/9〇 ; 7. 賴媒0.10克的1 wt.% Au/Cu〇x/Ti〇2，銅/鈦莫耳數比為1〇/9〇 的粉末置於直立式填充床反應器内，進行在富氫環境下選擇性 氧化一氧化碳的反應’以固定床反應器進行實驗，管内外直徑 為i.2公分及0·6公分，長度57公分，中間有0.7公分之融熔 石英砂’以擔載反應之觸媒’但可以透氣，另外在反應管内有 一内外直徑為0.6公分及0.4公分之底部密封玻璃管，是為了放 置測量觸媒表面溫度的熱電偶溫度計； 〃 8. 在一氧化碳、氧氣及氫氣存在下，氧氣/一氧化碳體積比為2， 以質量流率控制器控制總流量為每分鐘5〇毫升，在室溫下通入 ^應器中，反應氣體產物以氣象層析儀（中國層析型號98〇〇) 分析之，使用3.5公尺Molecular sieve 5Α不銹鋼管柱； 9. 反應器溫度由圓筒狀電偶加熱爐控制，其加熱爐外層長度約口 公分’直徑11公分’内部鋪有4公分玻璃纖維之保溫設備，反 應器溫度以每分鐘2度由攝氏25度升高，並分別在6〇、8〇、 100、120度平衡10分鐘’再利用氣相層析儀偵測其出口濃度 201021912 (ppm)。反應結果如下： 溫度(度C) 60 80 100 120 出口 一氧化礙濃度(ppm) 4.1 2.2 3.1 4.0 上述實施方式之反應結果如下；其中一氧化碳轉化率及選擇率定 義如下： 一氧化碳轉化率=(進口 一氧化碳濃度一出口 一氧化碳濃度）+進 口一氧化碳濃度；一氧化碳選擇率=一氧化碳氧化消耗氧氣量+( — 氧化碳消耗氧氣量+氫氣氧化消耗氧氣量）由這些結果證實本發 ® 明之觸媒能有效去除氣體中之一氧化碳。1. Weigh CuOx-Τι〇2 powder (copper/titanium molar ratio is 2/98) 〇98g into ·ml of steamed water 'to the magnet, and heat to the machine, and maintain it; Take 0.035 grams of four gas gold acid, dissolve it in 4 ml of distilled water, of which gold accounts for 0.02 g; 3. Use 0.1 Μ ammonia water to step 2 the acid test at 7 ± 〇 2, then the tetraacid solution In milliliters per minute 率 rate • listening, at 7 ± 0.2, the temperature is turned 65. (:; 4) After the completion of the titration, the magnet is mixed for two hours, and the value of the value is maintained at 7±Q 65 °C to make the reaction complete; 5. The water will be washed from the water of the age of woven/Jewish and red 65: Until the complete removal of the gas ions in 201021912, and then drying at 8 ° ° C for 16 hours; 6. After drying the catalyst at 18 °t: in the air for 4 hours, the formation of 1% Au / CuOx - Ti02 powder , copper / titanium molar ratio of 2 / 98; ° 7. 0.10 grams of catalyst 1% of Au / CuOx / Ti 〇 2, copper / titanium molar ratio of 2 / 98 powder placed in vertical In the packed bed reactor, the selective oxidation of carbon monoxide in a hydrogen-rich environment was carried out, and the experiment was carried out in a fixed bed reactor. The inner and outer diameters of the tube were 1.2 cm and 0.6 cm, the length was 57 cm, and the melted quartz sand was 0.7 cm in the middle. To support the catalyst of the reaction, but it can be ventilated. In addition, there is a bottom sealing glass tube with an inner and outer diameter of 0.6 cm and 0.4 cm in the reaction tube for placing a thermocouple thermometer for measuring the surface temperature of the catalyst; μ 8. in carbon monoxide In the presence of milk and helium, the oxygen/carbon monoxide volume ratio is 2, with mass flow rate controller The total flow rate was 5 〇ml per minute, and it was introduced into the reactor at room temperature. The reaction gas product was analyzed by a gas chromatograph (Chinese tomograph model 9800) using a 3.5 m Molecular sieve 5 Α unrecorded steel pipe column; 9. The bn degree of the reactor is controlled by a cylindrical electric heating furnace. The I? centimeters of the outside of the heating furnace, the diameter of 11 cm is internally insulated with 4 cm glass fiber, and the reactor temperature is per The 2 degree is increased by 25 degrees Celsius and equilibrated at 6 〇, go, 100, and 120 degrees for 10 minutes, respectively, and the outlet concentration (ppm) is detected by gas chromatography. The reaction results are as follows: Temperature (degree C 60 80 100 120 Export carbon monoxide concentration (ppm) 4.1 3.2 3.6 4.2 Example 1: 1. Weigh CuOx-Ti〇2 powder (copper/titanium molar ratio is 4 7/95 3) 〇98g into 200 In milliliters of distilled water, stir with a magnet and heat to 65t: and maintain it; 2. Weigh 0.035g of tetrachloroauric acid and dissolve it in 4ml of distilled water, of which gold accounts for 12 201021912 0.02 grams; 0.1M ^ hydrophobic water to control the pH value of the solution in step 2 to 7 ± 〇 2, and then the tetrachloroauric acid solution in 1 per minute Drop the solution at a rate of 0 ml, and control the base value to maintain 65 °C at 7±0.2 ′. 4. After the titration is completed, stir the magnet for two hours to maintain the pH value of 7±〇2. 65 ° C, the reaction is complete; and 5. The resulting precipitate is filtered and washed with 65 ° distilled water for several times until the chloride ion is completely removed, and then dried at 8 (TC for 16 hours; 6. will be baked After the dry catalyst is at 18 〇. When the crucible is burned in air for 4 hours, the φ Au/Cu〇x-Ti〇2 powder is formed. The copper/titanium molar ratio is 4.7/95.3. 7. The catalyst is 0.10 g of 1 wt.〇/0 Au/ CuOx/Ti02, copper/titanium Moir Helmet 4.7/95.3 powder is placed in the vertical wire filling reaction _, selective oxidation of carbon monoxide in a hydrogen-rich environment, experiment in a fixed bed reactor, inside and outside diameter of the tube It is 1.2 cm and 〇6 cm, with a length of 57 cm, and a zirconia quartz sand of 公7 cm in the middle to support the catalyst of the reaction, but it can be ventilated, and there is an inner and outer diameter of 0.6 cm and 〇4 in the reaction tube. The glass tube is sealed at the bottom of the centimeter to place a thermocouple thermometer for measuring the surface temperature of the catalyst. 8. In the presence of carbon monoxide, oxygen and hydrogen, the oxygen/carbon monoxide volume ratio is 2, and the mass flow rate controller controls the total flow rate per 5 〇 ml per minute, passed into the reactor at room temperature, and the reaction gas product was analyzed by a meteorological chromatograph (Chinese tomograph model 9800) using a 3.5 m Molecular sieve 5A steel column; 9. Reactor The temperature is controlled by a cylindrical electric heating furnace, and the heating furnace The outer layer is about cm cm in length and 11 cm in diameter. The inside is covered with 4 cm glass fiber insulation equipment. The reactor temperature is raised by 25 degrees Celsius at 2 degrees per minute and balanced at 6 〇, 80, 100, 120 degrees for 10 minutes. Then, the outlet concentration (ppm) was detected by a gas chromatograph. The reaction results are as follows: Temperature (degree C) 60 80 100 120 Outlet carbon monoxide lightness (ppm) 3.9 2.4 3.0 3.8 13 201021912 Example 8: 1· Weigh CuOx~Ti〇2 powder (copper/titanium molar ratio is 10 /90) Put 0.98 g into 200 ml of steamed water, stir with a magnet, and heat to 65 乞, and hold it; 2. Weigh 0.035 g of tetrachloroauric acid and dissolve it in 4 ml of distilled water. Gold accounted for 0.02 grams; 3. Control the pH value of the solution of step 2 to 7±0.2 with 0.1M ammonia water, and then add the four gas gold acid solution to the solution at a rate of 1〇ml per minute, and simultaneously control the test. The value is 7±0.2, and the temperature is maintained at 65°C. 4. After the titration is completed, stir the magnet for two hours, maintain the acid value at 7±〇2, and the temperature is φ65°C to make the reaction complete; 5. The obtained The sediment is filtered and taken at 65. Wash the distilled water several times until the chloride ion is completely removed and then at 80. (: drying for 16 hours; 6. The dried catalyst is fired in air at 180 °c for 4 hours to produce 1% Au/CuOx-~Ti〇2 powder, and the copper/titanium molar ratio is ι 〇/9〇; 7. Resin 0.10g of 1 wt.% Au/Cu〇x/Ti〇2, copper/titanium molar ratio of 1〇/9〇 powder placed in a vertical packed bed reactor The reaction of selectively oxidizing carbon monoxide in a hydrogen-rich environment was carried out in a fixed bed reactor. The inner and outer diameters of the tube were i.2 cm and 0.6 cm, the length was 57 cm, and the melted quartz sand was 0.7 cm in the middle. The catalyst for carrying the reaction 'but can be ventilated, and the bottom of the reaction tube has a bottom sealing glass tube with an inner and outer diameter of 0.6 cm and 0.4 cm for placing a thermocouple thermometer for measuring the surface temperature of the catalyst; 〃 8. in carbon monoxide, In the presence of oxygen and hydrogen, the volume ratio of oxygen to carbon monoxide is 2, and the total flow rate is controlled by a mass flow rate controller of 5 〇ml per minute, and it is passed into the reactor at room temperature, and the reaction gas product is a meteorological chromatograph ( Chinese tomograph model 98〇〇) analysis, using a 3.5 m Molecular sieve 5Α stainless steel column; The temperature of the reactor is controlled by a cylindrical electric heating furnace. The outer length of the heating furnace is about 2 cm in diameter and 11 cm in diameter. The inside of the furnace is covered with 4 cm glass fiber insulation equipment. The reactor temperature is 2 degrees Celsius and 25 degrees Celsius. High, and balanced at 6〇, 8〇, 100, 120 degrees for 10 minutes respectively> Reuse the gas chromatograph to detect its outlet concentration 201021912 (ppm). The reaction results are as follows: Temperature (degree C) 60 80 100 120 Export Oxidation concentration (ppm) 4.1 2.2 3.1 4.0 The reaction results of the above embodiments are as follows; wherein carbon monoxide conversion rate and selectivity are defined as follows: carbon monoxide conversion rate = (incoming carbon monoxide concentration - outlet carbon monoxide concentration) + inlet carbon monoxide concentration; carbon monoxide selectivity = The amount of oxygen consumed by oxidation of carbon monoxide + (- the amount of oxygen consumed by carbon oxides + the amount of oxygen consumed by hydrogen oxidation) These results confirm that the catalyst of the present invention can effectively remove one of the carbon oxides in the gas.
15 201021912 【圖式簡單說明】 無圖式簡單說明 【主要元件符號說明】 無主要元件符號說明15 201021912 [Simple description of the diagram] Simple description without diagram [Description of main component symbols] No main component symbol description