1358318 九、發明說明： 【發明所屬之技術領域】 本發明係關於排氣處理用觸媒及排氣之處理方 法’再詳言之，係關於適合分解去除排氣中所含氧化 氮、戴奥辛類等有害物質之排氣處理用觸媒，及使用 該觸媒之排氣處理方法。 【先前技術】 &為分解去除排氣中所含氧化氮、戴奥辛類等有害 物質，已有許多觸媒及排氣處理方法提出。 例如，關於將排氣中所含氧化氮與氨同時進行接 觸反應以·性還原之觸媒，已知（a)含有硫與欽及 石夕或含有硫與鈦、肢石夕之含硫複合氧化物；⑼氧 化鈒；（C)含有擇自鎢、翻、鍚及射至少i種元素 之氧化物之氧化氮去除用觸媒（參照日本特公昭62、一 14339號公報）。 又，注目於觸媒之比表面積與固體酸量，提出特 定此等物性與觸媒組成之排氣處理㈣媒以有效去’ 除排氣中所含氧化氮、戴奥辛類等有害物質(參职曰 本專利第3457917號公報），其具體為將飢 '鶴、鉬 等之氧化物負載於鈦_石夕複合氧化物等載體上’且其 比表面積為1Gm2/g以上、固體酸量為G.36mm〇l/g 1358318 職處刻觸媒，就其性能而言尚未能 充刀滿足，故期望研發能夠以更良好效率去除排氣中 二化氮、戴奥辛類等有害物質之觸媒，二: U為具有更高去罐效率之排氣處理用觸媒。 【發明内容】 〔本發明所欲解決之問題〕 -产本發明之目的在於提供適合分解去除排氣中所 •.含氧化氮、戴奥辛類等有害物質之排氣處理用觸媒， 及使用該觸媒以良好效率處理排氣之方法。 - 〔解決問題之手段] \ 本發明者等為達成上述目的經一再悉心研究，乃 至獲知以下知識與見解。亦即得知，固體觸媒表面一 身又存在i、，’σ負子之布認斯特酸（Br〇nste(j acid)點與 接文電子對之路以士酸（Lewis acid)點，例如於進行 •去硝處理時布認斯特酸點與路以士酸點兩者均有助 於去硝觸媒活性，而布認斯特酸點與路以士酸點之存 在量比在特定範圍内時能夠獲得最高之去硝效率。 又於含有鈦系氧化物之排氣處理用觸媒，發現使 用具有酸強度pKag + 3.3之固體酸量為〇.3mmol/g 以上之鈦系氧化物’並將固體酸點區別為供給質子之 布認斯特酸點與接受電子對之路以士酸點，而使用布 说斯特酸（B)與路以士酸（l)之比率（b/l)為0/1〜1/1 (S) 1358318 範圍内之W氧化物’即能夠獲得有害物質之分解性 能優異之觸媒。 本發明係基於上述知識與見解所完成，其詳細如 下述。 ⑴-種排氣處判㈣，料含有鈦 他觸媒活性成分以分解去除排氣中有害物質之其 觸媒，其特徵為布認斯特酸（Br〇nstedacid 與路以士酸(Lewis ac：id)(L)之比 〜10/1之範圍内。 / )馮0/1 (2)Γ/ί⑴項記載之觸媒，其中之該比率為0/1〜 ⑶如上⑴項記載之觸媒，其中之鈦系氧化物為氧化 欽。 (4) 如上（1)項記載之觸媒，其中 •愛白鈕放机 中之鈦糸氧化物為鈦與 選自铭、夕、鉻、結、翻及鎮所構成 種元素之複合氧化物。 1 (5) 如上⑴項記载之觸媒’其中之鈦系 選自銘、石夕、鉻及錯所構成群中至小/為欽與 複合氧化物。 夕種几素之 (6) 如上（1)項記載之觸媒，其中 甲之欽糸氧化物 選自鋁、矽、及鍅所構成群中至少 物為鈦與 合氧化物。 夕 種元素之複 7 1358318 (7)=(二項記载之觸媒，其中之其他觸媒活性成分 為&自鈒、鎢及麵所構成群中至少 化合物。 種几素或其 ⑻如上⑴項記载之觸媒’其中之鈦系 含量為4〇〜％質量％’且其他觸媒活性成：: 6〇〜5質量%(但兩者合計為_質量%卜 ⑺如上⑴項記載之觸媒，其中之鈦系氧化物含量為 以觸媒全量為基準之75〜99 9質量％。 ⑽如上⑴項記載之觸媒，其中再含硫而組成。 (11)如上⑴項記載之觸媒，其中鈦系氧化物之(B/L) 比率為0/1〜1/1，pKag +3 3之固體酸量為 0.3mmol/g 以上。 (12)如上（11)項s己載之觸媒，其中pKa$ + 3 3之固體 酸量為 0.3 〜0.8mm〇l/g。 • (13)如上（10)項記載之觸媒，其中硫含量為觸媒總質 量之0.01〜3質量％。 (14)如上（1)項所記載之觸媒之一種製造方法，其特徵 為所使用鈦系複合氧化物係將含有選自鋁、矽、 鉻、鍅、鉬及鎢所構成群中至少1種元素之氨水 溶液加入於含有鈦化合物之酸性溶液中以生成 沈澱物時，經過由開始添加至完成添加全量為止 8 1358318 之時間為40分鐘以上之步驟所得鈦系複合氧化 物。 (15) 如上⑴項所記載之觸媒之一種製造方法，其特徵 為所使用鈦系複合氧化物係將含有鈦化合物之 酸性溶液加入於含有選自紹、石夕、鉻、錯、翻及 鎮所構成群中至少1種元素之氨水溶液中以生成 沈澱物時，經過由開始添加至完成添加全量為止 之時間4 40分鐘以上之步驟所得欽系複合氧化 物0 (16) 如上（1)項所記載之觸媒之一種製造方法，其特徵 為所使用鈦系複合氧化物係將氨水溶液加入於 含有選自鋁、矽、鉻、鍅、鉬及鎢所構成群中至 ;1種元素及鈦化合物之酸性溶液中以生成沈澱 物時，經過由開始添加至完成添加全量為止之時 間為40分鐘以上之步驟所得鈦系複合氧化物。 (17) 如上（1)項所記載之觸媒之一種製造方法，其特徵 為所使用鈦系複合氧化物係將含有選自鋁、矽、 鉻、鍅、鉬及鎢所構成群中至少i種元素及鈦化 合物之酸性溶液加入於氨水溶液中以生成沈澱 物時，經過由開始添加至完成添加全量為止之時 間為40分鐘以上之步驟所得鈦系複合氧化物。 9 1358318 排税之處理方法，其特徵 排氣與如上⑴〜⑽頂^ 3有害物質之 极雄 ’（3)項圮載之排氣處理用觸媒 接觸以分解去除該有害物質。 媒 〔發明效果〕 ^本發明之觸媒結果’能夠以良好效率分解去 '于、軋化氮、戴奥辛類等有害物質。 【實施方式】 於：發明，「有害物質」意指氧化氮及氯化戴奥 類二化戴奥辛類、聚氯化聯苯類、氯苯類、氣紛 排々〖本類等有機齒化物。有害物質為氧化氮時之 =處理為所謂去硝處理，係使用氨、尿素等還原劑 乳化亂還原分解。本發明之排氣處理用觸媒特別適 合使用於氧化氮之還原分解（去硝處理）。 依本發明之排氣處理用觸媒，係為含有鈦系氧化 物及其他觸媒活性成分以分解去除排氣中有害物質 之排氣處理用觸媒，其特徵為布認斯特酸 acid)(B)與路以士酸（Lewis acid)(L)之比率（b/l)為 〇/1〜10/1之範圍内。 該比率（B/L)為0/1〜ίο/：[，但以〇/1〜9/ι之範 圍較好，0.1/1〜8/1之範圍更好，〇 〜7"之範 圍最好。上述比率（B/L)如較〇/1小、或較大時， 觸媒之處理性能減低。 1358318 於本發明，「鈦系氧化物」意指氧化鈦及鈦與其 他金屬之複合氧化物。氧化鈦使用銳鈦礦（Anatase) 型鈦、金紅石（Rutile)型鈦或此等之混合物。複合氧 化物之代表例可舉鈦（Ti)與選自鋁（A1)、矽（Si)、鉻 (Cr)、锆（Zr)、鉬（Mo)及鎢（W)所構成群中至少i種 元素之複合氧化物。氧化鈦與鈦系複合氧化物可混合 使用。1358318 IX. Description of the Invention: [Technical Field] The present invention relates to a method for treating a catalyst and an exhaust gas for exhaust gas treatment, which is described in detail with respect to suitable decomposition and removal of nitrogen oxides and dioxin contained in exhaust gas. A catalyst for exhaust gas treatment such as a harmful substance, and an exhaust gas treatment method using the catalyst. [Prior Art] <After decomposing and removing harmful substances such as nitrogen oxides and dioxins in the exhaust gas, many catalysts and exhaust gas treatment methods have been proposed. For example, it is known that (a) contains sulfur and sulphur and titanium, and contains sulfur and titanium, and the sulfur-containing compound of the limbs is combined with the catalyst for simultaneously reducing the contact of nitrogen oxides contained in the exhaust gas with ammonia. Oxide; (9) Cerium oxide; (C) A catalyst for removing nitrogen oxides containing an oxide selected from the group consisting of tungsten, ruthenium, iridium, and at least one element (see Japanese Patent Publication No. Sho 62, No. 14339). In addition, attention is paid to the specific surface area of the catalyst and the amount of solid acid, and the exhaust treatment (four) medium of the specific physical properties and the catalyst composition is proposed to effectively remove the harmful substances such as nitrogen oxides and dioxins contained in the exhaust gas. Japanese Patent No. 3,457,917, specifically, an oxide such as a hungry crane or molybdenum is supported on a carrier such as a titanium-based composite oxide, and has a specific surface area of 1 Gm 2 /g or more and a solid acid amount of G. .36mm〇l/g 1358318 The catalyst is not satisfied with the performance of the catalyst, so it is expected to develop a catalyst that can remove harmful substances such as nitrogen dioxide and dioxin in the exhaust gas with better efficiency. Two: U is a catalyst for exhaust gas treatment with higher decanting efficiency. [Problem to be Solved by the Invention] - The object of the present invention is to provide a catalyst for exhaust gas treatment suitable for decomposing and removing harmful substances such as nitrogen oxides and dioxins in exhaust gas, and using the same A method in which the catalyst treats the exhaust gas with good efficiency. - [Means for Solving the Problem] \ The inventors have repeatedly studied carefully to achieve the above objectives, and have acquired the following knowledge and insights. That is to say, the surface of the solid catalyst has i, the 'σ 负 之 认 认 认 认 认 ( ( ( ( ( ( ( ( 认 认 认 认 认 认 认 认 认 认 认 认 认 认 认 认 认 认 认 认 认 认 认 认 认 认 认 认 固体For example, when performing denitrification treatment, both the Buster acid point and the road acid acid point contribute to the denitrification activity, and the ratio of the Buster acid point to the road acid point is The highest denitration efficiency is obtained in a specific range. In the exhaust gas treatment catalyst containing a titanium-based oxide, it was found that a titanium-based oxidation having a solid acid content of acid concentration pKag + 3.3 of 〇.3 mmol/g or more was used. The substance's distinction between the solid acid point and the donor acid point of the proton and the acceptor of the electron pair, and the ratio of the succinic acid (B) to the lysine (l) b/l) is a W oxide in the range of 0/1 to 1/1 (S) 1358318, which is capable of obtaining a catalyst having excellent decomposition properties of harmful substances. The present invention is based on the above knowledge and insights, and the details are as follows (1) - The type of exhaust gas is judged (4), which contains titanium active catalyst component to decompose and remove harmful substances in the exhaust gas. It is characterized by the ratio of Brünsted acid to Lewis ac: id (L) ~ 10/1. / ) von 0/1 (2) Γ / ί (1) In the catalyst, the ratio is 0/1 to (3) The catalyst described in the above item (1), wherein the titanium-based oxide is oxidized. (4) The catalyst described in the above item (1), wherein The titanium lanthanum oxide in the machine is a composite oxide of titanium and a compound selected from the group consisting of Ming, Xi, Chromium, Knot, Turn and Town. 1 (5) The catalyst described in (1) above From the group consisting of Ming, Shi Xi, Chromium and Wrong, it is composed of small to medium and complex oxides. (6) The catalyst described in (1) above, in which the At least the composition of the group consisting of aluminum, lanthanum, and cerium is titanium and comon. The complex of the element of the genus 7 1358318 (7) = (the catalyst described in the second item, wherein the other active ingredients of the catalyst are & At least a compound of the group consisting of ruthenium, tungsten, and noodles. The species or the (8) catalyst described in the above item (1) wherein the content of the titanium is 4〇% to 9% by mass and the other catalysts are: 6〇 ~5 The amount of the catalyst is as follows: (7) The catalyst described in the above item (1), wherein the titanium-based oxide content is 75 to 99% by mass based on the total amount of the catalyst. (10) The touch described in the above item (1) The medium is further composed of sulfur. (11) The catalyst described in the above item (1), wherein the ratio of the titanium-based oxide (B/L) is 0/1 to 1/1, and the solid acid amount of pKag + 3 3 is 0.3 mmol/g or more. (12) The catalyst of the above (11) item, wherein the solid acid amount of pKa$ + 3 3 is 0.3 to 0.8 mm 〇 l / g. (13) The catalyst according to the above (10), wherein the sulfur content is 0.01 to 3% by mass based on the total mass of the catalyst. (14) A method for producing a catalyst according to the above (1), characterized in that the titanium-based composite oxide used contains at least one selected from the group consisting of aluminum, ruthenium, chromium, ruthenium, molybdenum and tungsten. When the ammonia solution of the element is added to the acidic solution containing the titanium compound to form a precipitate, the titanium-based composite oxide obtained by the step of adding to the completion of the total addition of 8 1358318 for 40 minutes or more is obtained. (15) A method for producing a catalyst according to the above item (1), characterized in that the titanium-based composite oxide used is an acidic solution containing a titanium compound, which is selected from the group consisting of: Shao, Shi Xi, Chromium, Wrong, and When a precipitate is formed in the aqueous ammonia solution of at least one element in the group of the town, the compound compound 0 (16) obtained by the step from the start of the addition to the completion of the total addition of 4 40 minutes or more is as shown above (1) A method for producing a catalyst according to the invention, characterized in that the titanium-based composite oxide used is an aqueous ammonia solution added to a group selected from the group consisting of aluminum, lanthanum, chromium, lanthanum, molybdenum and tungsten; When a precipitate is formed in the acidic solution of the titanium compound, the titanium-based composite oxide obtained by the step of adding to the completion of the total addition for 40 minutes or more is obtained. (17) A method for producing a catalyst according to the above (1), characterized in that the titanium-based composite oxide used contains at least i selected from the group consisting of aluminum, ruthenium, chromium, ruthenium, molybdenum and tungsten. When the acidic solution of the element and the titanium compound is added to the aqueous ammonia solution to form a precipitate, the titanium-based composite oxide obtained by the step of adding the total amount until the completion of the addition is 40 minutes or more is obtained. 9 1358318 Tax treatment method, its characteristics Exhaust gas is contacted with the catalyst for exhaust gas treatment in the above (1) to (10) top 3 hazardous substances (3), to decompose and remove the harmful substances. Medium [Effect of the Invention] ^The catalyst result of the present invention can be decomposed with good efficiency to remove harmful substances such as nitrogen and dioxin. [Embodiment] In the invention, "hazardous substance" means organic nitrogen such as nitrogen oxides and chlorinated dioxins, dioxins, polychlorinated biphenyls, chlorobenzenes, gas, and sputum. When the harmful substance is nitrogen oxide, the treatment is called denitration treatment, and the reducing agent is emulsified and decomposed by using a reducing agent such as ammonia or urea. The catalyst for exhaust gas treatment of the present invention is particularly suitable for use in reduction decomposition (nitrification treatment) of nitrogen oxides. The catalyst for exhaust gas treatment according to the present invention is an exhaust gas treatment catalyst containing a titanium-based oxide and other catalytic active components to decompose and remove harmful substances in the exhaust gas, and is characterized by being an acid of the acid. (B) The ratio of the Lewis acid (L) (b/l) is in the range of 〇/1 to 10/1. The ratio (B/L) is 0/1~ίο/:[, but the range of 〇/1~9/ι is better, the range of 0.1/1~8/1 is better, and the range of 〇~7" it is good. When the above ratio (B/L) is smaller than 〇/1 or larger, the processing performance of the catalyst is lowered. 1358318 In the present invention, "titanium oxide" means a composite oxide of titanium oxide and titanium with other metals. The titanium oxide is an anatase type titanium, a rutile type titanium or a mixture of these. Representative examples of the composite oxide include titanium (Ti) and at least i selected from the group consisting of aluminum (A1), cerium (Si), chromium (Cr), zirconium (Zr), molybdenum (Mo), and tungsten (W). a composite oxide of various elements. Titanium oxide and a titanium-based composite oxide can be used in combination.
上述鈦系複合氧化物中，以鈦（Ti)與選自鋁 (A1)、矽（Si)、鉻（Cr)及鍅（Zr)所構成群中至少1種元 素之複合氧化物，尤其與選自紹 所構成群中至…元素之複合氧 複合氧化物為Ti - Si複合氧化物等二元系複合氧化 物，或Ti- Si- Zr複合氧化物等三元系複合氧化物 均可又’才复合氧化物」即指其χ射線繞射圖式不 表現歸類為氧化鈦以外物質之明顯固有峰值，而就氧 化鈦而言不表現歸類為銳鈦礦型氧化鈦之固有峰 值，或即使表現亦表現較銳鈦礦型氧化鈦之繞射峰值 更寬大之繞射峰值。 又關於钥及鎢存在於觸媒中之形態，如其總量鱼 鈦共同構成鈦系複合氧化物而存在於觸媒中、或其碑、 量與鈦系複合氧化物以外之形態存在於觸或= =分與欽共同構成鈦系複合氧化“ _#錢、 以其以外之形態存在於觸媒中均可。 1358318 關於本發明之排氣處理用觸媒組成，其代表例示 如下述： (1) Ti - Si複合氧化物+ (V、W及/或Mo) (2) Ti - A1複合氧化物+ (V、W及/或Mo) (3) Ti - Zr複合氧化物+ (V、W及/或Mo) (4) Ti - W複合氧化物+ (V、W及/或Mo) (5) Ti - Si - Zr複合氧化物+ (V、W及/或Mo) (6) Ti - Si - Mo複合氧化物+ (V及/或W) (7) Ti - Si - Mo複合氧化物+ (V、W及/或Mo) (8) Ti - Si - W複合氧化物+ (V及/或Mo) (9) Ti - Si - W複合氧化物+ (V、W及/或Mo) (10)氧化鈦+ (V、W及/或Mo) 布認斯特（Bronsted acid)酸量（B)與路以士 (Lewis acid)酸量（L)可依使用吡啶當作探針（pr〇be) 之紅外線分光法（FT - IR)精確測定。吡啶具有來自吡 啶環面内振動之1700〜1400-1範圍紅外線吸收光譜 帶’但因吡啶是否為氫鍵結（PyH)、配位鍵結（PyL) 或質子和（PyB)而其吸收光譜帶顯著不同。其中， PyL(1450—1附近）與PyB(l54〇-i附近）之吸收光譜帶 分別為來自吡啶吸著於路以士酸點與布認斯特酸點 之19b振動方式，故求得以PyL峰面積除PyB峰面 積之峰面積比（B/L)，即能決定布認斯特酸量對路以 士酸量之比例。 12 1358318 於本發明，「布認斯特酸量（B)」與「路以士酸量 (L)」分別意指依使用吡啶當作探針之下述紅外線分 光（FT - IR)分析法所測定來自布認斯特酸點之峰面 積與來自路以士酸點之峰面積。 < FT-IR分析法> FT - IR裝置使用尼科來公司製之 ΡΚ〇ΤΈ(3Ε4όΟ，安裝在原器（in situ)擴散反射型槽進 行測定。將試料粉碎成100網目以下後取0.02g，不 •用KBr等稀釋直接以粉末狀態裝載於擴散反射型槽 之試料臺上，在以40mL/min流速通入含5容量％氧 • 氣（〇2)之氦氣下加熱至400°C，並於400°C保持60分 鐘。其次在通入氦氣下冷卻至15〇°C，於150°C注入 * 吡啶10 // L使試料吸收吡啶。隨後於150°C通入氦氣 120分鐘以除去物理性吸著於試料之吡啶，冷卻至室 溫，於4cm— 1分解能測定FT - IR光譜。布認斯特酸 φ 量（B)由其測得FT - IR光譜之1515〜1565—1範圍進 行積分而求取，路以士酸量（L)則由其測得FT - IR光 譜之1425〜1465_ 1範圍進行積分而求取。 至於布認斯特酸量（B)與路以士酸量（L)之比率 (B/L)則可由上述FT - IR分析法所求得之布認斯特 酸量（B)與路以士酸量（L)容易求得。 本發明之排氣處理用觸媒之組成並無特別限 制，只要上述比率（B/L)在0/1〜10/1之範圍内即 13 1358318 可。其中以含有鈦系氧化物與選自釩（v)、鎢（w)及鉬 (Mo)中至少i種元素之觸媒較好。 上述比率（B/L)為0/1〜1/1時，於本發明所使用 之「鈇系氧化物」，其pKa$ + 3.3之固體酸量為 〇.3mmol/g以上，並以〇 3〜〇 8mm〇1/g之範圍較 好，0.35 〜〇.7mmol/g 之範圍更好，〇.4 〜〇.6mm〇1/g 之範圍最好〇如pKaS + 3.3之固體酸量較 CK3mmol/g少時’減少有害物質吸著於觸媒表面，結 馨果減低觸媒之有害物質分解性能。又，上述固體酸量 可視為鈦系氧化物表面上之布認斯特酸與路以士酸 . 之合計酸量。 泰 - 本發明之「PKa $+3.3之固體酸量」依下述方 B 法測定。 <固體酸量之測定方法> 使用對二甲基胺基偶氮苯當作pKa== +3.3之指 # 示劑，依正丁基胺滴定法求得❶用精密天平秤取以 120 C乾燥3小時以上之粉體試料〇 2g放入試管中再 加入笨約20mL »對此加入將上述指示劑溶解於苯之 /谷液數滴，栓·緊振盡混合時呈現指示劑酸性顏色之紅 色。對此以微滴管加入〇.13min〇l/mL正丁基胺之苯 溶液，當試料變成指示劑鹼性顏色之黃色時當作滴定 終點，由滴定量與試料質量，依下式計算固體酸量 (mmol/g)。 固體酸1 =(正丁基胺溶液濃度（mmol/mL)x滴定量 (mL)) / (試料質量（g)) 於上述固體酸量，本發明所使用之「鈦系氧化 物」’其布認斯特酸量（B)與路以士酸量（L)之比率 (B/L)為0/：^；^，並以〇…之範圍較好， 〇·1/1〜0.8/1之範圍更好。±述比率（B/L)超過… 時，使用此種鈦系氧化物所製得之排氣處理用觸媒， 其有害物質分解性能變低，故不宜。 齡本發明之pKag + 3.3之固體酸量為0.3mm〇1/g 以上，且布認斯特酸量（B)與路以士酸量（L)之比率 ；(B/L)為0/1〜之範圍内之鈦系氧化物，能夠以各 • 種方法調製，玆以鈦與選白鋁、矽、及锆中至少了種 .元素之鈦系複合氧化物當作鈦系氧化物之例，說明其 调製方法如下述。 起始原料並無特別限制，可使用一般使用於調製 I 含鈦複合氧化物之化合物。 欽源可由如四氯化鈦、硫酸鈦等無機鈦化合物及 草酸欽、四異丙基欽酸醋專有機欽化合物中適當選擇 使用。 鋁源可由如硝酸鋁、硫酸鋁等無機鋁化合物及醋 酸鋁等有機鋁化合物中適當選擇使用β 石夕源可由如膠態石夕、水玻璃、微粒石夕、四氯化石夕、 矽凝膠體等無機矽化合物及四乙基矽酸酯等有機石夕 ④ 15 1358318 化合物中適當選擇使用。 錯源可由如氣化锆、硫酸錯等無機錯化合物及草 酸鍅等有機鉛化合物中適當選擇使用。 本發明之鈦系複合氧化物之製法如下：例如製造 鈦-矽複合氧化物時，先將膠態矽等矽化合物分散於 氨水溶液中以調製溶液（A);其次在溶液（A)攪拌下， 滴加硫酸鈦等鈦化合物溶液於其中，且開始滴加至混 合液pH呈現8為止之時間需要40分鐘以上，並以 • 4〇〜1440分鐘較好、60〜1080分鐘更好、90〜720 分鐘最好；最後將所得漿體過濾並乾燥，再以300〜 ， 600°C燒成即可製得。又，如製造鈦-矽-鋁複合氧 • 化物時，在上述溶液（A)中除滴加鈦化合物外亦滴加 * 銘化合物溶液，此時開始滴加至混合液pH呈現8為 止之時間需要40分鐘以上，並以40〜1440分鐘較 好、60〜1080分鐘更好、90〜720分鐘最好，最後將 所得漿體過濾並乾燥，再以300〜600°C燒成即可製 •得° 即使將氨水溶液滴加於欽化合物與石夕化合物之 混合溶液中或將鈦化合物溶液滴加於氨水溶液時，如 在開始滴加至混合液pH呈現8為止之時間以少於40 分鐘之條件進行滴加，則不能獲得目標之具酸性性質 之鈦系氧化物，而有不能獲得充分之排氣處理性能之 慮。 (§) 16 1358318 鈦系複合氧化物中之鈦含量，為鈦與其他元素、 如選自鋁、矽、鉻、鍅、翻及鎢中至少α種元素之合 計質量之40〜95質量％較好，並以5〇〜95質量％更 好，60〜95質量％最好。至於其他元素含量，】二元 系複合氧化物或三元系複合氧化物而不同，前者之其 他元素含量為鈦與其他元素合計質量之5〜6〇質量％ 較好，並以5〜50質量％更好，5〜4〇質量％最好； 而後者之其他元素含量為鈦與其他元素合計質量之^ 〜60質量％較好，並以5〜5〇質量％更好，5〜4〇質 量％最好。（但，鈦系複合氧化物與其他觸媒活性成分 之合計為100質量％。） 本發明之排氣處理用觸媒中之鈦系氧化物含 量，以觸媒總質量為基準之75〜99.9質量％較好，並 以80〜99.5質量％更好，85〜99質量％最好。鈦系氧 化物含量超過99.9質量％時，選自釩、鎢及鉬中至少 1種7L素之含量過少而使觸媒性能減低，又如鈦系氧 化物含量較小於75質量％時，鈒等元素之含量變多， 但不忐獲得與其相稱之觸媒性能之提升，反而提高觸 媒成本而不宜。 關於鈦系氧化物形狀並無特別限制，可直接使用 以上述調製方法所製得鈦系氧化物，或適當成形為片 狀、波浪片狀、網狀、蜂巢狀、圓柱狀、球狀、圓筒 狀、丸狀等使用《一般而言，先考慮觸媒成品形狀再 ⑧ 17 1358318 決疋欽系氧化物形狀。 本發明之布認斯特酸量（B)與路以士酸量（L)之比 率（B/L)為ι/：^^之排氣處理用觸媒，以使用如 上述調製之鈦系複合氧化物，再加入選自釩、鑛及钥 中至> 1種το素而製得。關於此方法可使用沈殿法（共 沈法）、水解法、溶膠凝膠（s〇1 gel)法、沈積法、混練 法等具體而g，將鈦系氧化物粉末與通常進行此種 成形時所使用有機或無機成形辅劑同時加入含有 瞻釩、鎢及/或鉬之起始原料水溶液中後，一面混合、 ，練，一面加熱蒸發水分，形成可擠壓之糊狀，以擠 -壓成形機形成蜂巢狀等後乾燥，再於空氣中以高溫 :(200〜600°c較好）進行燒成之方法等。又，另外亦可 •採用先將鈦系氧化物粉末形成球狀、圓柱丸狀、蜂巢 格子狀等並燒成後，再浸入含有釩、鎢及/或鉬之起 始原料水溶液中之方法。另外亦可採用將鈦系氧化物 Φ粉末與釩、鎢及/或鉬之氧化物粉末直接混練之方 法。又’於調製鈦系氧化物之步驟，將含有鈒、鎢及 /或銦之化合物水溶液加入含鈦溶液或漿體中之方 法，或於調製鈦系氧化物之步驟，以過濾等將水分由 及體去除而得之濾餅加入含有飢、鶴及/或銷之化合 物水溶液後混合、乾燥、燒成之方法等亦可採用。 飢源如氧化釩以外，可適當選擇使用氫氧化物、 敍鹽、草酸鹽、鹵化物、硫酸鹽等釩化合物。 18 1358318 鎢源可適當選擇使用氧化鎢、對鎢酸銨、間鎢酸 銨、鎢酸等。 鉬源如鉬之氧化物、氫氧化物、銨鹽、齒化物等， 只要能夠以燒成形成鉬酸化物者均可，具體可適當選 擇使用對鉬酸銨、鉬酸等。 本發明之排氣處理用觸媒中之釩、鎢及/或鉬含 量，以觸媒總質量為基準之01〜25質量％較好，並 以0.5〜20質量％更好，1〜Μ質量％最好。 • 本發明之排氣處理用觸媒以含有硫（S)較好。至 於添加硫之方法可適當選擇使用：將觸媒浸潰於硫酸 水溶液或硫酸鹽等之水溶液之方法，或將含有二氧化 • 硫（S〇2)等氣體與觸媒接觸之方法等。 ' 硫源可適當選擇使用硫酸、硫酸銨、硫酸氫銨、 一氧化硫氣等。 本發明之排氣處理用觸媒如含有硫時，其含量為 φ觸媒總質量之0·01〜3質量％較好，並以— s質量 %更好’ 0,5〜3質量％最好。 有關本發明之排氣處理用觸媒僅以上述鈦系氧 =物與釩、鎢及/或鉬（以下將此等總稱為觸媒成分） 當作觸媒構成材料使用，再將此觸媒成分以一定形狀 成形而成之成形型觸媒為較適合形態；但將觸媒成分 $持於具所希望形狀之任意不活性載體而成之載持 型觸媒，或將上述成形型觸媒與載持型觸媒適當組合 1358318 而成之觸媒亦可。 本發明之排氣處理用觸媒之形狀並無特別限 制，可由此種觸媒一般所使用形狀，如蜂巢狀、球狀、 片狀、網狀、圓柱狀、圓筒狀、浪板（corrUgated sheet) 狀、管狀、環狀等適當選擇決定。 本發明之排氣處理用觸媒之微細孔容積通常為 0.2 〜0.8cm3/g，並以 0.25 〜〇.7cm3/g 較好，0.25 〜 〇-6cm3/g 更好。 又’本發明之排氣處理用觸媒之BET比表面積 並無特別限制’但以30〜250m2/g較好，40〜 250m2/g 更好，45〜250m2/g 最好。 如上述’將含有氧化氮、戴奥辛類等有害物質之 排氣與本發明之排氣處理用觸媒接觸時，能夠分解有 害物質而處理排氣。接觸條件並無特別限制，可在此 種處理一般所使用條件下實施。排氣之空間速度通常 為 100〜I00,000hr-MSTP)，而以 2〇〇〜5〇〇〇〇hr_ ^stp)較好，200〜29 〇〇〇hr-1(STp)更好。至於處理 又被處理排氣溫度通常為1〇〇〜5〇〇。〇，而以2〇〇 〜500°c較好，250〜500ec更好。 (實施例） 以下列舉表現本發明之有利實施形態之實施 例’更具體說明本發明。 (實施例1) 20 1358318 < Ti - Si複合氧化物（a) > 於25質量％氨水137L中加入司諾帝克_ 2〇(曰 產化學股份有限公司製、含Si〇2約20質量％)i〇kg 並攪拌混合後，在攪拌下以120分鐘以上時間滴加硫 酸鈦之硫酸溶液（以T i〇2計算為7〇g/L、硫酸濃度 287g/L)257L於其中（pH8)。所得凝膠經放置2〇小時 後過濾、水洗，接著在12(rc乾燥2〇小時。將此以In the titanium-based composite oxide, a composite oxide of at least one element selected from the group consisting of titanium (Ti) and aluminum (A1), cerium (Si), chromium (Cr), and cerium (Zr) is particularly The composite oxygen composite oxide selected from the group consisting of the elements of the group is a binary composite oxide such as a Ti-Si composite oxide, or a ternary composite oxide such as a Ti-Si-Zr composite oxide. 'Compound oxides' means that the χ-ray diffraction pattern does not exhibit a distinct intrinsic peak of a substance classified as titanium oxide, and does not exhibit an intrinsic peak classified as anatase-type titanium oxide in terms of titanium oxide. Or even the performance shows a larger diffraction peak than the diffraction peak of anatase titanium oxide. Further, regarding the form in which the molybdenum and the tungsten are present in the catalyst, if the total amount of the fish and titanium together constitutes the titanium-based composite oxide, it exists in the catalyst, or the form of the monument or the amount of the titanium-based composite oxide exists in the contact or = = The sub-combination of the titanium-based composite oxidation " _# money, and other forms may exist in the catalyst. 1358318 The composition of the catalyst for exhaust gas treatment of the present invention is exemplified as follows: (1) Ti - Si composite oxide + (V, W and / or Mo) (2) Ti - A1 composite oxide + (V, W and / or Mo) (3) Ti - Zr composite oxide + (V, W And/or Mo) (4) Ti - W composite oxide + (V, W and / or Mo) (5) Ti - Si - Zr composite oxide + (V, W and / or Mo) (6) Ti - Si - Mo composite oxide + (V and / or W) (7) Ti - Si - Mo composite oxide + (V, W and / or Mo) (8) Ti - Si - W composite oxide + (V and / or Mo) (9) Ti - Si - W composite oxide + (V, W and / or Mo) (10) titanium oxide + (V, W and / or Mo) Bronsted acid acid (B) and Lewis acid acidity (L) can be accurately determined by infrared spectroscopy (FT-IR) using pyridine as a probe (pr〇be). Pyridine has an infrared absorption spectrum band from 1700 to 1400-1 in the in-plane vibration of the pyridine ring. But whether the pyridine is a hydrogen bond (PyH), a coordination bond (PyL) or a proton and (PyB), its absorption band Significantly different, in which the absorption bands of PyL (near 1450-1) and PyB (near l54〇-i) are respectively 19b vibration modes in which pyridine is adsorbed on the road to the acid point and the Buchen acid point. It is determined that the PyL peak area is divided by the peak area ratio (B/L) of the PyB peak area, that is, the ratio of the amount of Bucson acid to the amount of the acid of the channel is determined. 12 1358318 In the present invention, "the amount of the acid (B)" and "Royceic acid amount (L)" mean the peak area from the Buickest acid point determined by the following infrared spectroscopy (FT-IR) analysis using pyridine as a probe. The area of the peak from the road to the acid point. < FT-IR analysis method> The FT-IR apparatus was measured by using Nikon Co., Ltd. (3Ε4όΟ, mounted in an in situ diffuse reflection type groove). The sample was pulverized to 100 mesh or less and taken 0.02. g, not • diluted with KBr and directly loaded on the sample stage of the diffuse reflection type groove in a powder state, and heated to 400° under a helium gas containing 5 vol% of oxygen and gas (〇2) at a flow rate of 40 mL/min. C, and kept at 400 ° C for 60 minutes. Secondly, it was cooled to 15 ° C under helium gas injection, and * pyridine 10 / L was injected at 150 ° C to allow the sample to absorb pyridine. Then helium gas was introduced at 150 ° C. The FT-IR spectrum was measured by decomposing at 4 cm-1 for 120 minutes to remove the pyridine which was physically adsorbed to the sample, and cooled to room temperature. The amount of Buchner's acid φ (B) was determined by the FT-IR spectrum of 1515~ The range of 1565-1 is obtained by integrating, and the amount of Lushi acid (L) is obtained by integrating the range of 1425~1465_1 of the FT-IR spectrum. As for the amount of Bupper acid (B) and The ratio of the amount of Lewis acid (L) (B/L) can be determined by the above FT-IR analysis method (B) and the amount of acid (L) The composition of the catalyst for exhaust gas treatment of the present invention is not particularly limited as long as the above ratio (B/L) is in the range of 0/1 to 10/1, that is, 13 1358318. Preferably, the material is at least one element selected from the group consisting of vanadium (v), tungsten (w) and molybdenum (Mo). When the ratio (B/L) is 0/1 to 1/1, the present invention The "lanthanide oxide" used has a solid acid amount of pKa$ + 3.3 of 〇.3 mmol/g or more, and preferably ranges from 〇3 to 〇8 mm〇1/g, and 0.35 to 〇.7 mmol/g. The range is better, the range of 〇.4 〇.6mm〇1/g is best. For example, when the amount of solid acid of pKaS + 3.3 is less than CK3mmol/g, the harmful substances are absorbed on the surface of the catalyst, and the fruit is reduced. The decomposition property of the harmful substance of the medium. Further, the amount of the solid acid mentioned above can be regarded as the total amount of acid of the Buchneric acid and the lysine acid on the surface of the titanium-based oxide. Thai - "PKa $+3.3 solid of the present invention" The amount of acid is determined by the following method B. <Method for measuring the amount of solid acid> Using p-dimethylamino azobenzene as the indicator of pKa== +3.3, titrating with n-butylamine Law to obtain precision The flat scale is taken at 120 C for more than 3 hours. The powder sample is placed in a test tube and added to the test tube. Then add about 20 mL. » Add the above indicator to the benzene/cold solution, and mix the plug and the shaker. Presenting the red color of the indicator acid color. Add benzene solution of 〇.13min〇l/mL n-butylamine to the micropipette, and use the titration end point when the sample becomes the yellow color of the indicator alkaline color. For the sample quality, the amount of solid acid (mmol/g) was calculated according to the following formula. Solid acid 1 = (n-butylamine solution concentration (mmol/mL) x titration (mL)) / (sample mass (g)) The amount of the above solid acid, the "titanium oxide" used in the present invention The ratio of the amount of Bucson acid (B) to the amount of the acid (L) of the road (B/L) is 0/:^;^, and the range of 〇... is better, 〇·1/1~0.8/ The range of 1 is better. When the ratio (B/L) exceeds the temperature, the catalyst for exhaust gas treatment obtained by using such a titanium-based oxide has a low decomposition property of harmful substances, which is not preferable. The amount of solid acid of pKag + 3.3 of the present invention is 0.3 mm 〇 1 /g or more, and the ratio of the amount of Buchskin acid (B) to the amount of lysine (L); (B/L) is 0/ The titanium-based oxide in the range of 1 to 1 can be prepared by various methods, and titanium and the selected white aluminum, tantalum, and zirconium are used as the titanium-based oxide. For example, the modulation method is as follows. The starting material is not particularly limited, and a compound generally used for preparing a titanium-containing composite oxide can be used. Qinyuan can be suitably selected from inorganic titanium compounds such as titanium tetrachloride and titanium sulfate, and oxalic acid and tetraisopropyl acid vinegar. The aluminum source can be appropriately selected from inorganic aluminum compounds such as aluminum nitrate, aluminum sulfate, and the like, and the organic aluminum compound such as aluminum acetate can be used, such as colloidal stone, water glass, micronized stone, tetrachloride, sputum gel An organic sulfonium compound such as a compound or an organic phosphatase such as tetraethyl phthalate is suitably used. The source of the error may be appropriately selected from organic lead compounds such as zirconium oxide, sulfuric acid, and the like, and an organic lead compound such as bismuth oxalate. The titanium-based composite oxide of the present invention is produced by, for example, preparing a titanium-ruthenium composite oxide by dispersing a ruthenium compound such as colloidal ruthenium in an aqueous ammonia solution to prepare a solution (A); secondly, stirring the solution (A) The titanium compound solution such as titanium sulfate is added dropwise thereto, and the time until the pH of the mixture is 8 is started to be 40 minutes or more, and it is preferably 4 to 1440 minutes, preferably 60 to 1080 minutes, and 90 to 90 minutes. The best is 720 minutes; finally, the obtained slurry is filtered and dried, and then fired at 300 to 600 ° C to obtain. Further, when a titanium-bismuth-aluminum composite oxygen compound is produced, a solution of the * compound is added dropwise to the solution (A) in addition to the titanium compound, and the time is started until the pH of the mixture is 8 It takes 40 minutes or more, and is preferably 40 to 1440 minutes, more preferably 60 to 1080 minutes, and most preferably 90 to 720 minutes. Finally, the obtained slurry is filtered and dried, and then fired at 300 to 600 ° C. °° Even if an aqueous ammonia solution is added dropwise to a mixed solution of a compound of a compound and a compound of a compound, or a solution of a titanium compound is added dropwise to an aqueous ammonia solution, as in the case of starting to drip until the pH of the mixture is 8, it takes less than 40 minutes. When the conditions are dripped, the target titanium-based oxide having an acidic property cannot be obtained, and sufficient exhaust gas treatment performance cannot be obtained. (§) 16 1358318 The titanium content in the titanium-based composite oxide is 40 to 95% by mass of the total mass of titanium and other elements such as at least α elements selected from the group consisting of aluminum, lanthanum, chromium, lanthanum, and tungsten. Good, and better with 5〇~95% by mass, 60~95% by mass. As for the content of other elements, the binary compound oxide or the ternary composite oxide is different, and the other element content of the former is 5 to 6 〇 mass% of the total mass of titanium and other elements, and is preferably 5 to 50 mass. % is better, 5~4〇% by mass is the best; and the other elements of the latter are the total mass of titanium and other elements ^~60% by mass, and preferably 5~5〇% by mass, 5~4〇 The best quality is %. (The total amount of the titanium-based composite oxide and the other catalyst active component is 100% by mass.) The content of the titanium-based oxide in the catalyst for exhaust gas treatment of the present invention is 75 to 99.9 based on the total mass of the catalyst. The mass% is better, and more preferably 80 to 99.5% by mass, and most preferably 85 to 99% by mass. When the content of the titanium-based oxide exceeds 99.9% by mass, the content of at least one of 7L of vanadium, tungsten, and molybdenum is too small to reduce the catalyst performance, and when the content of the titanium-based oxide is less than 75% by mass, 鈒The content of other elements increases, but it does not increase the performance of the catalyst, which is commensurate with it, but it is not suitable to increase the cost of the catalyst. The shape of the titanium-based oxide is not particularly limited, and a titanium-based oxide obtained by the above-described preparation method may be used as it is, or may be suitably formed into a sheet shape, a wave sheet shape, a mesh shape, a honeycomb shape, a column shape, a spherical shape, or a circle shape. Use in the form of a cylinder, a pellet, etc. "In general, consider the shape of the finished catalyst first and then determine the shape of the oxide." In the present invention, the ratio of the amount of the bismuth acid (B) to the amount of the lysine (L) (B/L) is ι/:^^, and the catalyst for exhaust treatment is used, and the titanium system prepared as described above is used. The composite oxide is obtained by further adding a compound selected from vanadium, ore and key to > In this method, a method such as a shoal method (co-precipitation method), a hydrolysis method, a sol gel method, a deposition method, a kneading method, or the like can be used, and when a titanium-based oxide powder is usually formed, After the organic or inorganic forming auxiliary agent is added to the aqueous solution containing the starting material of vanadium, tungsten and/or molybdenum, the mixture is mixed, and then heated to evaporate water to form a squeezable paste to be squeezed-pressed. The molding machine is formed by forming a honeycomb or the like, drying it, and then baking it in the air at a high temperature: (200 to 600 ° C is preferable). Further, a method in which the titanium-based oxide powder is first formed into a spherical shape, a cylindrical pellet shape, a honeycomb lattice shape, or the like, and then immersed in an aqueous starting material solution containing vanadium, tungsten, and/or molybdenum may be used. Alternatively, a method in which a titanium-based oxide Φ powder is directly mixed with an oxide powder of vanadium, tungsten, and/or molybdenum may be employed. Further, in the step of preparing a titanium-based oxide, a method of adding an aqueous solution of a compound containing cerium, tungsten and/or indium to a titanium-containing solution or a slurry, or a step of preparing a titanium-based oxide, The filter cake obtained by removing the body may be added to an aqueous solution containing a compound of hunger, crane and/or pin, followed by mixing, drying, and baking. As the source of hunger, such as vanadium oxide, a vanadium compound such as a hydroxide, a salt, an oxalate, a halide or a sulfate may be appropriately selected. 18 1358318 Tungsten source can be appropriately selected from tungsten oxide, ammonium tungstate, ammonium tungstate, tungstic acid, and the like. The molybdenum source such as an oxide of molybdenum, a hydroxide, an ammonium salt, a dentate or the like may be used as long as it can form a molybdate by firing, and specifically, ammonium molybdate, molybdic acid or the like can be suitably used. The content of vanadium, tungsten and/or molybdenum in the catalyst for exhaust gas treatment of the present invention is preferably from 01 to 25% by mass based on the total mass of the catalyst, and more preferably from 0.5 to 20% by mass, more preferably 1 to Μ. %the best. • The catalyst for exhaust gas treatment of the present invention preferably contains sulfur (S). As for the method of adding sulfur, a method of immersing the catalyst in an aqueous solution of a sulfuric acid aqueous solution or a sulfate or the like, or a method of contacting a gas such as sulfur dioxide (S〇2) with a catalyst may be appropriately selected. 'Sulphur source can be selected as appropriate using sulfuric acid, ammonium sulfate, ammonium hydrogen sulfate, sulfur monoxide gas, and the like. When the catalyst for exhaust gas treatment of the present invention contains sulfur, the content thereof is preferably 0. 01 to 3 mass% of the total mass of the φ catalyst, and more preferably - s mass% '0, 5 to 3 mass%. it is good. The catalyst for exhaust gas treatment according to the present invention is used as a catalyst constituent material only by using the above-mentioned titanium-based oxygen-containing material and vanadium, tungsten, and/or molybdenum (hereinafter collectively referred to as a catalyst component), and then using the catalyst. A molding type catalyst in which a component is formed into a shape is a suitable form; but a catalyst component is held in a carrier-type catalyst having any inactive carrier having a desired shape, or the molding catalyst is formed. A suitable combination of 1358318 with a carrier-type catalyst can also be used. The shape of the catalyst for exhaust gas treatment of the present invention is not particularly limited, and may be generally used in the shape of such a catalyst, such as a honeycomb, a spherical shape, a sheet shape, a mesh shape, a cylindrical shape, a cylindrical shape, or a corrugated sheet. ) Appropriate selection of shapes, tubes, rings, etc. The micropore volume of the catalyst for exhaust gas treatment of the present invention is usually 0.2 to 0.8 cm 3 /g, preferably 0.25 to 7.7 cm 3 /g, more preferably 0.25 to -6 cm 3 /g. Further, the BET specific surface area of the catalyst for exhaust gas treatment of the present invention is not particularly limited, but is preferably 30 to 250 m 2 /g, more preferably 40 to 250 m 2 /g, and most preferably 45 to 250 m 2 /g. When the exhaust gas containing a harmful substance such as nitrogen oxide or dioxin is brought into contact with the catalyst for exhaust gas treatment of the present invention, the exhaust gas can be decomposed and treated. The contact conditions are not particularly limited and can be carried out under the conditions generally used for such treatment. The space velocity of the exhaust gas is usually 100 to I00,000 hr-MSTP), and preferably 2 〇〇 to 5 hr hr_^stp), and 200 to 29 〇〇〇 hr-1 (STp) is more preferable. As for the treatment, the exhaust gas temperature is usually 1 〇〇 to 5 〇〇. Oh, and better with 2〇〇 ~500°c, 250~500ec is better. (Examples) Hereinafter, the present invention will be more specifically described by way of Examples exemplifying advantageous embodiments of the present invention. (Example 1) 20 1358318 < Ti - Si composite oxide (a) > In the case of 25% by mass of ammonia water 137L, Snydick _ 2 〇 (manufactured by Suga Chemical Co., Ltd., containing Si 〇 2 about 20) After the mass%) i〇kg was stirred and mixed, a sulfuric acid solution of titanium sulfate (7 〇g/L calculated as T i 〇 2 and a sulfuric acid concentration of 287 g/L) 257 L was added thereto with stirring for 120 minutes or more. pH8). The resulting gel was allowed to stand for 2 hours, filtered, washed with water, and then dried at 12 (rc for 2 hours).
5〇〇°C燒成5小時，再用鎚磨機粉碎、分級機分級， 得平均粒徑12 // m粉體。 上得粉體之X射線繞射圖示如圖i。由於未表現 Si〇2之明顯固有峰值而表現2(9 = 253。之寬廣繞射 峰值，故確認上得粉體為鈦與矽之複合氧化物（Ti_ Si複合氧化物）（a)。 <蜂巢狀觸媒>The mixture was fired at 5 ° C for 5 hours, and then pulverized by a hammer mill and classified by a classifier to obtain an average particle diameter of 12 // m powder. The X-ray diffraction diagram of the powder obtained is shown in Figure i. Since the broad intrinsic peak of 2 (9 = 253) is exhibited without exhibiting the apparent intrinsic peak of Si〇2, it is confirmed that the obtained powder is a composite oxide of titanium and tantalum (Ti_Si composite oxide) (a). ; Honeycomb Catalyst >
將間叙酸銨Hg、對鎢酸銨19kg、草酸2 〇kg 及一乙醇胺1.2kg與水81^混合溶解調製得均勻溶 液。將上述調製之Ti_ Si複合氧化物（a)i8 Gkg投入 捏揉機後，將上得均勻溶液與有機黏合劑(澱粉叫) 等成㈣劑-起加入並。再一面加入適量水一面 用摻合機混合’並以連續式捏揉機充分混練後，擠壓 成形為外形8Gmm四方、網眼4 G_、厚2 〇腿、 長500咖之蜂巢狀。此成形物在_乾燥後，以· 。(：燒成5小時得觸媒⑴。此觸媒組成為mi: (§> 21 1358318 W= 78.3 : 8.7 : 5 : W〇3之比例）。 、 IR刀析法所得觸媒（1)之記錄紙示如圖 2,而依此記錄求得之比率（B/L)則示於表^ (實施例2) 於貝施例1除以對錮酸銨2 〇kg代替對鶴酸銨 1.9kg外’其他依與實施例i相同方法得觸媒⑺。此 觸媒(2)之組成為 Ti : Si : v : M〇= % 3 : 8 7 : 5 : 8(換 算為T i〇2 . Si〇2 · V2〇5 : M〇〇3之比例）。以FT - IR 分析法所求得觸媒（2)之比率（B/L)示於表工。 (實施例3) < Ti _ Si - Mo複合氧化物（b) >A homogeneous solution was prepared by mixing and dissolving ammonium sulphate Hg, ammonium tungstate ammonium 19 kg, oxalic acid 2 〇 kg, and monoethanolamine 1.2 kg with water 81. After the above-prepared Ti_Si composite oxide (a) i8 Gkg is put into a kneading machine, a uniform solution is added to the organic binder (starch) to form a (four) agent. Further, while adding an appropriate amount of water, it was mixed with a blender' and thoroughly kneaded by a continuous kneading machine, and then extruded into a honeycomb shape of a shape of 8 Gmm square, a mesh of 4 G_, a thickness of 2 legs, and a length of 500 coffee. This formed product is dried after _. (: Catalyst (1) after firing for 5 hours. The composition of this catalyst is mi: (§> 21 1358318 W= 78.3 : 8.7 : 5 : ratio of W〇3), and the catalyst obtained by IR knife analysis (1) The recording paper is shown in Fig. 2, and the ratio (B/L) obtained according to the record is shown in Table ^ (Example 2). In Example 1, the sample is divided by the ammonium citrate 2 〇kg instead of the ammonium hexanoate. The catalyst (7) was obtained in the same manner as in Example i except for 1.9 kg. The composition of the catalyst (2) was Ti: Si : v : M〇 = % 3 : 8 7 : 5 : 8 (converted to T i〇) 2. Si〇2 · V2〇5 : ratio of M〇〇3. The ratio (B/L) of the catalyst (2) obtained by FT-IR analysis is shown in the table. (Example 3) < Ti _ Si - Mo composite oxide (b) >
8(換算為 丁 i〇2 : Si〇2 : V2O5 : 於石夕溶膠（司諾帝克-30、日產化學股份有限公 司製、換算為Si〇2含約30質量％)3.3kg、工業用氨 水（含25質量％氨）1034及水58L之混合溶液中， 加入鉬酸3.4kg並攪拌使鉬酸完全溶解得均勻溶液。 此均勻溶液在攪拌下以120分鐘以上時間滴加硫酸 鈦之硫酸溶液（以T i〇2計算為7〇g/ L、硫酸滚度 287g/L)228L使生成沈殿（pH8)。所得共沈漿體經放 置約40小時後過滤、用水充分洗清，接著在1〇〇。匸 乾燥1小時。再將此在空氣環境下以500°C燒成5小 時。用趟磨機粉碎、分級機分級，得平均粒徑12 β m 粉體。 22 1358318 上知粕體之x射線繞射圖示如圖1。由於未表現 Sl〇2與Moos之明顯固有峰值而表現20=253。之寬 廣繞射峰值’故確認上得粉體為鈦與矽與鉬之複合氧 化物（Ti- Si- Mo複合氧化物）(b)。 <蜂巢狀觸媒> 將間釩酸銨1.8kg、草酸167kg及一乙醇胺〇.4kg 與水8L混合溶解調製得均勻溶液。將上述調製之 Ti Sl _ Mo複合氧化物（b)18 6kg投入捏揉機後，將 上得3鈒溶液與有機黏合劑（澱粉〗等成形輔劑 人起加入並攪拌。再一面加入適量水一面用摻合機混 ；合，亚以連續式捏揉機充分混練後，擠壓成形為外形 8〇inm 四方、網眼 4.0mm、厚 1.0mm、長 500mm 之 蜂巢狀。此成形物在6(TC乾燥後，以450°C燒成5小 時得觸媒（3)。此觸媒組成為Ή : Si : Mo : V = 74.3 : 4·7 · 14 : 7(換算為τ i〇2 : Si〇2 : Mo〇3 : V2〇5之比 _例）。以FT _ IR分析法求得觸媒（3)之比率（B/L)示於 表1 〇 (實施例4) 將間釩酸銨1.8kg、硫酸銨i.7kg、草酸167kg 及一乙醇胺〇.4kg與水8L·混合溶解調製得均勻溶 液。將市售粉體Ti〇2(DT-51(商品名稱）、米列尼亞 △司製）6.2kg投入捏揉機後，將上得含鈒溶液與有機 黏合劑（澱粉1.5kg)等成形辅劑一起加入並攪拌。再 23 ^58318 及乙醇胺1.2kg與水8L混合溶解調製得 液。將上述調mSi複合氧化物(d〉i8.〇kg投入 揉機後’將上得含鈒與鶴溶液與有機黏合劑（殿粉 •5kg)等成形輔劑—起加人並㈣。再—面加入適量 水一面用摻合機m以連續式捏揉機充分混練 後’擠壓成形為外形80mm四方、網眼4 〇mm、厚 ).0mm、長500mm之蜂巢狀。此成形物在6〇£>c乾燥 後，以45(TC燒成5小時得觸媒（5卜此觸媒組成為 Ή : Sl ·’ V ·· 78.3 : 8.7 ·· 5 ·· 8(換算為 T i〇2 : Si〇2 : V2〇5: W〇3之比例)。以FT_IR分析法所得觸媒⑼ 之記錄紙示如圖4，而依此記錄求得之比率（B/L)則 不於表1。 (比較例2) 一將市售粉體V2〇5 1,4kg與市售粉狀銳鈦礦型 氧化鈦（DT- 51(商品名稱）、米列尼亞公司製）18 6kg 投入捏搮機後，再一面與有機黏合劑（澱粉i 5k幻等 成形輔劑一起加入適量水一面用摻合機混合，並以連 續式捏揉機充分混練後，擠壓成形為外形8〇mm四 方、網眼4.0mm、厚l.〇mm、長5〇〇mm之蜂巢狀。 此成形物在60Ϊ乾燥後，以5〇(TC燒成5小時得觸媒 (6)。此觸媒組成為V=95: 5(換算為T i〇2: V205 之比例）。 又’上述粉狀銳鈦礦型氧化鈦之X射線繞射圖示 1358318 ？1〇2計算含36質量％)78L代替硫酸鈦之硫 文冷液288L外，其他依與實施例3相同方法得丁卜 Γ二、。複合氧化物(f)。就所得Ti-si~M〇複合氧 化物⑴之PKu+3.3之固體酸量示於表2，又以 FT: IR分析法求得之比率(b/l)亦示於表2。 <蜂巢狀觸媒> 將間鈒酸錄l.29kg、草酸167kg及一乙醇胺 〇.4kg與水8L混合溶解調製得均勻溶液。將上述調 製之粉體Ti-Si_Mo複合氧化物（fm〇kg投入捏 揉機後’將上得含叙溶液與有機黏合劑（澱粉工御） 等成形輔劑一起加入並授摔。再一面加入適量水一面 用摻合機混合，並以連續式捏揉機充分混練後，擠壓 成形為外形80mm四方、網眼4.0mm、厚i 0mm、 長5〇〇mmt蜂巢狀。此成形物在6〇t乾燥後，以45〇 °C燒成5小時得觸媒(3)。此觸媒組成為Ti:si :M〇 ·· V= 76.4 : 4.8 : 14.2 : 5(換算為 T i〇2 : Si〇2 : M〇〇3 : V2O5之比例）。 (實施例9) < T i〇2粉體（g)> 於25質量％氨水160L中，在攪拌下以12〇分鐘 以上時間滴加硫酸鈦之硫酸溶液（以T i〇2計算為 7〇g/L、硫酸濃度287g/L)3〇〇L(pH8)。所得凝膠經 放置20小時後過濾、水洗，接著在12〇t：乾燥如小 29 1358318 時。將此以520°C燒成3小時，再用鎚磨機粉碎、分 級機分級，得平均粒徑12# m T i02粉體（g)。 此T i〇2粉體之pKaS +3.3之固體酸量示於表 2,又以FT - IR分析法求得之比率（B/L)亦示於表2。 <蜂巢狀觸媒> 於實施例8,除使用上述丁 i〇2粉體（g)以代替 Ti - Si - Mo複合氧化物⑴外，其他依與實施例8相 同方法得觸媒（10)。此觸媒（10)之組成為Ti: V=95 : 鲁5(換算為T i〇2 : V2〇5之比例）。 (比較例3) ； 於比較例1除將氨水量變更為69kg，並以四氣 .化鈦（以丁幻2計算含36質量％)88L代替硫酸鈦之硫 ‘酸溶液257L外，其他依與比較例！相同方法得丁卜 &複合氧化物（+就所得Ti_s@合氧化物㈨之 之固體酸量示於表2，又以n分析 •法所得記錄紙示*圖7，而依此記錄求得之比 則示於表2。 丁 ν ’ ν <蜂巢狀觸媒> 將間釩酸銨1.3kg、對鎢酸銨19kg v 叹权丄.Mg、草酸2.0 ㈣i.2kg與水8L混合溶解調製得均 液。將上述調製之Ti_ Si複 捏赶地仏攸 设0氣化物⑻I8.〇kg投 =機後，將上得含飢及鶴溶液與有機黏合二 .g)#成形辅劑-起加入並攪拌。再一面加上適 30 1358318 水一面用摻合機混合，並以連續式捏揉機充分混練 後，擠壓成形為外形80mm四方、網眼4.〇mm、厚 1.0mm、長500mm之蜂巢狀。此成形物在6〇ΐ乾燥 後，以450°C燒成5小時得觸媒（11)。此觸媒組成為8 (converted to Dingi〇2: Si〇2: V2O5: 3.3kg for industrial use in Shishi Sol (Sinotek-30, manufactured by Nissan Chemical Co., Ltd., converted to Si〇2) In a mixed solution of ammonia water (containing 25 mass% ammonia) 1034 and water 58 L, 3.4 kg of molybdic acid was added and stirred to completely dissolve the molybdic acid to obtain a homogeneous solution. The homogeneous solution was added dropwise with stirring for more than 120 minutes. The solution (calculated as 7 μg / L in Ti 2 2 and 287 g / L in sulfuric acid) was used to form a shoal (pH 8). The resulting co-precipitated slurry was allowed to stand for about 40 hours, filtered, washed thoroughly with water, and then 1 〇〇 dry for 1 hour, and then fired at 500 ° C for 5 hours in an air atmosphere, pulverized by a honing machine, and classified by a classifier to obtain an average particle diameter of 12 β m. 22 1358318 The x-ray diffraction diagram of the body is shown in Fig. 1. Since the apparent intrinsic peak of Sl2 and Moos is not expressed, the broad diffraction peak is expressed as 20=253. Therefore, it is confirmed that the powder is a composite of titanium and tantalum and molybdenum. Oxide (Ti-Si-Mo composite oxide) (b) <Honeycomb catalyst> 1.8 kg of ammonium metavanadate and 167 kg of oxalic acid Ethanolamine 〇.4kg is mixed with 8L of water to prepare a homogeneous solution. After the above-mentioned Ti Sl _ Mo composite oxide (b) 18 6kg is put into a kneading machine, the 3 鈒 solution and the organic binder (starch) are formed. The auxiliary agent is added and stirred. After adding an appropriate amount of water, it is mixed with a blending machine; the mixture is fully mixed with a continuous kneading machine, and then extruded into a shape of 8 〇inm square, mesh 4.0 mm, thickness 1.0 mm. The shape of the honeycomb is 500 mm long. The formed product is obtained by firing the catalyst at a temperature of 450 ° C for 5 hours after TC drying. The composition of the catalyst is Ή : Si : Mo : V = 74.3 : 4·7 · 14 : 7 (converted to τ i〇2 : Si〇2 : Mo〇3 : V2〇5 ratio _ example). The ratio of the catalyst (3) (B/L) is obtained by FT_IR analysis. In Table 1 〇 (Example 4) 1.8 kg of ammonium metavanadate, i. 7 kg of ammonium sulfate, 167 kg of oxalic acid, and 4 kg of monoethanolamine and 8 L of water were mixed to prepare a homogeneous solution. Commercially available powder Ti〇2 (DT-51 (trade name), Millenia △ system) 6.2kg was put into the kneading machine, and the yttrium-containing solution was added and stirred together with a molding aid such as an organic binder (starch 1.5kg). Then, 23 ^ 58318 and 1.2 kg of ethanolamine and 8 L of water were mixed to dissolve the solution. After the above mSi composite oxide (d>i8.〇kg was put into the machine), the solution containing the strontium and the crane and the organic binder (the temple powder) • 5kg) and other forming aids - add people and (4). Then, add a proper amount of water to the surface and mix it with a blending machine m in a continuous kneading machine, and then "extruded into a shape of 80 mm square, mesh 4 mm, thick". 0 mm, 500 mm long honeycomb. After the molded product was dried at 6 &>c, it was obtained by baking at 45 (TC for 5 hours) (5 此: The composition of the catalyst was Sl: Sl · ' V ·· 78.3 : 8.7 ············ Converted to T i〇2 : Si〇2 : V2〇5: ratio of W〇3). The recording paper of the catalyst (9) obtained by the FT_IR analysis method is shown in Fig. 4, and the ratio obtained according to this record (B/L) ) (Table 2) (Comparative Example 2) A commercially available powder V2〇5 1,4 kg and a commercially available powdered anatase type titanium oxide (DT-51 (trade name), manufactured by Millenia Co., Ltd.) 18 6kg is put into the kneading machine, and then mixed with an organic binder (starch i 5k phantom forming auxiliary agent) with a proper amount of water, mixed with a blender, and fully kneaded by a continuous kneading machine, and then extruded into a shape. 8〇mm square, mesh 4.0mm, thickness l.〇mm, length 5〇〇mm honeycomb. This molded product is dried at 60Ϊ, 5〇 (TC is fired for 5 hours to get the catalyst (6). The catalyst composition is V=95: 5 (converted to the ratio of T i〇2: V205). Also, the above-mentioned powdery anatase type titanium oxide X-ray diffraction diagram 1358318 ?1〇2 is calculated to contain 36% by mass. ) 78L instead of sulphuric acid cold 288L, other In the same manner as in Example 3, the composite oxide (f) was obtained. The solid acid amount of PKu+3.3 of the obtained Ti-si~M〇 composite oxide (1) is shown in Table 2, and analyzed by FT: IR. The ratio (b/l) obtained by the method is also shown in Table 2. <Honeycomb Catalyst> A mixture of 1.29 kg of citric acid, 167 kg of oxalic acid, and 4 kg of monoethanolamine and 8 L of water were dissolved to prepare a homogeneous solution. The above-prepared powder Ti-Si_Mo composite oxide (fm〇kg is put into a kneading machine), and the forming auxiliary solution is added together with a forming auxiliary agent such as an organic binder (starch), and then added. Appropriate amount of water is mixed with a blender and thoroughly kneaded by a continuous kneading machine, and then extruded into a shape of 80 mm square, 4.0 mm in mesh, 0 mm in thickness, and 5 mm in length. The formed product is 6 inches. After drying, the catalyst (3) is obtained by firing at 45 ° C for 5 hours. The composition of the catalyst is Ti:si : M〇·· V = 76.4 : 4.8 : 14.2 : 5 (converted to T i〇2 : Si〇2 : M〇〇3 : ratio of V2O5) (Example 9) <T i〇2 powder (g)> In a volume of 160% by mass of ammonia water 160L, it was dripped for 12 minutes or more. Titanium sulfate Sulfuric acid solution (7 〇g/L calculated as Ti 2 , 287 g/L sulfuric acid) 3 〇〇 L (pH 8). The obtained gel was allowed to stand for 20 hours, filtered, washed with water, then dried at 12 〇t: Such as small 29 1358318. This was fired at 520 ° C for 3 hours, and then pulverized by a hammer mill and classified by a classifier to obtain an average particle diameter of 12 # m T i02 powder (g). The solid acid amount of pKaS + 3.3 of this Ti 2 powder was shown in Table 2, and the ratio (B/L) obtained by FT-IR analysis is also shown in Table 2. <Hive-like catalyst> In Example 8, a catalyst was obtained in the same manner as in Example 8 except that the above-mentioned di-i 2 powder (g) was used instead of the Ti-Si-Mo composite oxide (1). 10). The composition of this catalyst (10) is Ti: V=95: Lu 5 (converted to the ratio of T i〇2 : V2〇5). (Comparative Example 3); In Comparative Example 1, except that the amount of ammonia was changed to 69 kg, and the sulphuric acid solution of 257 liters of titanium sulphate was replaced by tetrahydrogenated titanium (36% by mass calculated by Ding Xing 2) 88 L. And comparison examples! In the same way, the amount of solid acid of Dingbu & composite oxide (+ obtained Ti_s@ combined oxide (9) is shown in Table 2, and the recording paper obtained by n analysis and method is shown in Fig. 7, and the record is obtained according to this record. The ratio is shown in Table 2. Ding ν ' ν < Honeycomb Catalyst > 1.3 kg of ammonium metavanadate, 19 kg of ammonium tungstate, sputum, Mg, oxalic acid 2.0 (four) i. 2 kg and water 8L mixed The prepared liquid is prepared. The above-prepared Ti_Si is kneaded and set to 0 gas (8) I8. 〇kg cast = machine, and then the hunger and the crane solution and the organic bonding II.g) #forming auxiliary agent- Add and stir. On the other hand, the water was mixed with a blender at a temperature of 30 1358318, and thoroughly kneaded by a continuous kneading machine, and then extruded into a honeycomb shape of a shape of 80 mm square, a mesh of 4. mm, a thickness of 1.0 mm, and a length of 500 mm. This molded product was dried at 6 Torr and fired at 450 ° C for 5 hours to obtain a catalyst (11). The composition of this catalyst is
Ti : Si : V : W= 78·3 : 8.7 : 5 : 8(換算為 τ i〇2 : Si〇2 : V2〇5 : W〇3之比例）。 (比較例4) < T i〇2粉體（i)> 於實施例9之調製τ i〇2粉體（g)時，所得凝膠過 濾後不水洗，直接在120°C乾燥20小時。將此以52〇 °C燒成3小時，再用鎚磨機粉碎、分級機分級，得平 均粒徑12 a m T i〇2粉體⑴。 此Ti〇2粉體⑴之？1^+3.3之固體酸量示於 表2,又以FT - IR分析法求得之比率（b/l)亦示於表 2 〇 接著於實施例9,使用Ti〇2粉體⑴以代替Ti〇2 粉體（g)外’其他依與實施例9相同方法調製蜂巢狀 觸媒製得觸媒（12)。此觸媒組成為Ti: v:s=85: 5 : 10(換算為T i〇2 : V2〇5 : S之比例）。 (實施例10) -〜〜。平父例3〜4所得觸媒（7)〜 ⑽’以下錢件騎活性評輯 氯曱笨分解試驗）。 31 1358318 於實施例1 ’除以90分鐘時間滴加硫酸鈦之硫 酸溶液外，其他依與實施例1相同方法得Ti _ Si複 合氧化物⑴及觸媒（13)。以FT - IR分析法求得觸媒 (1S)之比率（B/L)示於表3’而Ti-Si複合氧化物⑴ 之pKaS + 3.3之固體酸量示於表4,以FT_ IR分析 法求得之比率（B/ L)亦示於表4。 (實施例12) 於實施例1，除以60分鐘時間滴加硫酸鈦之硫 • 酸溶液外，其他依與實施例1相同方法得Ti _ Si複 合氧化物（k)及觸媒（14)。以FT - IR分析法求得觸媒 (1句之比率（B/L)示於表3，而Ti - Si複合氧化物以) 之pKa $ + 3.3之固體酸置不於表4，以ft - ir八析 • 法求得之比率（B/ L)亦示於表4。 (實施例13) 於實施例1，除將25質量％氨水137乙與司諾帝 φ克—20 10kS之混合溶液在攪拌下以120分鐘時間滴 加於硫酸欽之硫酸溶液257L中外，其他依與實施例 1相同方法得Ti- Si複合氧化物⑴及觸媒（15)。以 FT- IR分析法求得觸媒（15)之比率（B/L)示於表3， 而Ti - Si複合氧化物（1)之pKag +3.3之固體酸量示 於表4,以FT - IR分析法求得之比率（B/L)亦示於表 4 〇 (實施例I4) 33 使用實施例1、、12、13及比較例1所得觸媒 (1)、（13)、（14)、（15)及（5)，以與實施例5相同條件 進行活性評估試驗。結果如表3所示。 (實施例I5) 使用實施例6、11、12、13及比較例3所得觸媒 (7)、（13)、U4)、（15)及（11)，以與實施例1〇相同條 件進行活性評估試驗。結果如表3所示。Ti : Si : V : W = 78·3 : 8.7 : 5 : 8 (converted to τ i〇2 : Si〇2 : V2〇5 : ratio of W〇3). (Comparative Example 4) <T i〇2 Powder (i)> When the τ i〇2 powder (g) was prepared in Example 9, the obtained gel was filtered without filtration, and dried at 120 ° C directly. hour. This was fired at 52 ° C for 3 hours, and then pulverized by a hammer mill and classified by a classifier to obtain an average particle diameter of 12 a m T i〇2 powder (1). What is this Ti〇2 powder (1)? The solid acid amount of 1^+3.3 is shown in Table 2, and the ratio (b/l) obtained by FT-IR analysis is also shown in Table 2, followed by Example 9, using Ti〇2 powder (1) instead. The Ti(2) powder (g) was used to prepare a catalyst (12) by modulating a honeycomb catalyst in the same manner as in Example 9. The composition of this catalyst is Ti: v:s=85: 5 : 10 (converted to T i〇2 : V2〇5 : S ratio). (Example 10) -~~. Ping father example 3~4 obtained catalyst (7) ~ (10)' below the money ride riding activity evaluation Chloroquinone decomposition test). 31 1358318 Ti-Si composite oxide (1) and catalyst (13) were obtained in the same manner as in Example 1 except that the sulfuric acid solution of titanium sulfate was added dropwise over 90 minutes. The ratio of catalyst (1S) obtained by FT-IR analysis (B/L) is shown in Table 3' and the solid acid amount of pKaS + 3.3 of Ti-Si composite oxide (1) is shown in Table 4, analyzed by FT_IR. The ratio (B/L) obtained by law is also shown in Table 4. (Example 12) In the same manner as in Example 1, except that the sulfuric acid solution of titanium sulfate was added dropwise over 60 minutes, the Ti_Si composite oxide (k) and the catalyst (14) were obtained in the same manner as in Example 1. . The catalyst was obtained by FT-IR analysis (the ratio of one sentence (B/L) is shown in Table 3, and the solid acid of pKa $ + 3.3 of Ti-Si composite oxide) was not shown in Table 4, with ft - ir eight analysis • The ratio obtained by law (B/L) is also shown in Table 4. (Example 13) In Example 1, except that a mixed solution of 25% by mass of ammonia water 137B and Snordi φ gram - 20 10 kS was added dropwise to 257 L of sulfuric acid sulphuric acid solution under stirring for 120 minutes. The Ti-Si composite oxide (1) and the catalyst (15) were obtained in the same manner as in Example 1. The ratio of the catalyst (15) determined by FT-IR analysis (B/L) is shown in Table 3, and the solid acid amount of pKag + 3.3 of the Ti-Si composite oxide (1) is shown in Table 4, with FT. - The ratio (B/L) obtained by the IR analysis is also shown in Table 4 (Example I4). 33 The catalysts (1), (13), (1), (1), (13) obtained in Examples 1, 12, 13 and Comparative Example 1 were used. 14), (15) and (5), the activity evaluation test was carried out under the same conditions as in Example 5. The results are shown in Table 3. (Example I5) Using the catalysts (7), (13), U4), (15) and (11) obtained in Examples 6, 11, 12, 13 and Comparative Example 3, the same conditions as in Example 1 were carried out. Activity assessment test. The results are shown in Table 3.
34 ⑶ 8318 【圖式簡單說明】 圖1為實施例1所得Ti — Si複合氧化物之X射 線繞射圖。 圖2為實施例1所得觸媒（1)之吡啶吸著FT_ IR 光譜圖。 圖3為比較例1所得Ti - Si複合氧化物之x射 線繞射圖。 圖4為比較例1所得觸媒（5)之吡啶吸著FT - IR φ 光譜圖。 圖5為比較例2所使用銳鈦礦型氧化鈦粉體之X 射線繞射圖。 * 圖6為實施例6所得Ti - Si複合氧化物（e)之吡 * 啶吸著FT - IR光譜圖。 圖7為比較例3所得Ti - Si複合氧化物（h)之吡 啶吸著FT - IR光譜圖。34 (3) 8318 BRIEF DESCRIPTION OF THE DRAWINGS Fig. 1 is a X-ray diffraction diagram of a Ti-Si composite oxide obtained in Example 1. 2 is a pyridine sorption FT_IR spectrum of the catalyst (1) obtained in Example 1. Fig. 3 is a x-ray diffraction diagram of a Ti-Si composite oxide obtained in Comparative Example 1. 4 is a pyridine sorption FT-IR φ spectrum of the catalyst (5) obtained in Comparative Example 1. Fig. 5 is an X-ray diffraction diagram of an anatase type titanium oxide powder used in Comparative Example 2. * Fig. 6 is a FT-IR spectrum of the pyridyl sorption of the Ti-Si composite oxide (e) obtained in Example 6. Fig. 7 is a chart showing the pyridine adsorption FT-IR spectrum of the Ti-Si composite oxide (h) obtained in Comparative Example 3.
35 氣甲苯 分解率 (%) VO CO 〇\ 寸 〇\ CN 00 ΟΝ IS. 寸 00 52.8 去硝率（％> 400°C 94.1 00 CO ON tN 〇\ ON ο Os rH v〇 00 80.9 30(1 °C CO (N ON CO CN Ον τ-ί • CO ΟΝ cs . 00 00 〇\ rH 00 ON ON VO 200°C 00 ON 〇s Ο 00 m 寸 00 CO tN v〇 v〇 55.1 複合氧化物 比率 (B/L) 0.1/1 0.1/1 0.7/1 0/1 0.3/1 1.3/ 1 固體酸量 (mmol/g) in 寸 ο 0.45 Ο LO ο CN CO o -r-( <N 〇 0.47 複合氧錄 編號 QJ S s λ 觸媒組成 \ + .Λ > Η \ ο + .Λ > Η V/ Ti-Si-Mo > H \ + .上 > H \·. > H 觸媒編號 IN >*—«% 00 ΟΝ y—s o V—✓ s rH N·»·^ ·Ν. CN r-H 實施例6 實施例7 實施例8 實施例9 比較例3 比較例4 135831835 gas toluene decomposition rate (%) VO CO 〇 \ inch 〇 \ CN 00 ΟΝ IS. inch 00 52.8 denitration rate (% > 400 ° C 94.1 00 CO ON tN 〇 \ ON ο Os rH v〇00 80.9 30 ( 1 °C CO (N ON CO CN Ον τ-ί • CO ΟΝ cs . 00 00 〇\ rH 00 ON ON VO 200°C 00 ON 〇s Ο 00 m 00 00 CO tN v〇v〇55.1 Composite oxide ratio (B/L) 0.1/1 0.1/1 0.7/1 0/1 0.3/1 1.3/ 1 Solid acid amount (mmol/g) in inch ο 0.45 Ο LO ο CN CO o -r-( <N 〇0.47 Complex Oxygen Recording Number QJ S s λ Catalyst Composition \ + .Λ > Η \ ο + .Λ > Η V/ Ti-Si-Mo > H \ + .上上 >gt H \·. > H Touch Media number IN >*—«% 00 ΟΝ y—so V—✓ s rH N·»·^·Ν. CN rH Example 6 Example 7 Example 8 Example 9 Comparative Example 3 Comparative Example 4 1358318