•1297283 發明說明： 【發明所屬之技術領域】 本發明係一種結合共沉法與酸處理以製造觸媒擔體之方 法’特別是指一種可以提升南溫處理後氧化銘的比表面積之方 法，化合物以共沈法獲得，經高溫處理而緻密化，藉由酸處理 之方式’大幅提升氧化銘之比表面積’以供做觸媒擔體。 【先前技術】 0 氧化鋁是一種常見的觸媒擔體，但它在經過10001以上 的高溫處理後，比表面積會大幅降至30m2 /g以下，此點對於 觸媒擔體而言，是一個極大的缺點，因為擔體的表面積越大， 代表所供反應物反應的區域越大，過小的表面積會導致觸 媒反應的活性急遽下降，例如汽機車觸媒轉化器的三向觸媒之 擔體，必須在高溫下進行煅燒以降低其熱膨脹係數及提升其機 械強度，但咼溫緞燒後擔體之比表面積卻急遽降低，必須再另 外/叉鑛層1%比表面積之物質才適合做為觸媒之擔體，但浸镀 • 層在經長時間的操作下極易脫落，導致觸媒活性降低，因此如 何能在固定的重量下，提高氧化銘（擔體）之高比表面積而不 再使用浸鍍層顯然有其必要性。 【發明内容】 本發明係一種結合共沉法與酸處理以製造觸媒擔體之方 法，其方法為： A、 利用共沈法以獲得鎂鋁複合氧化物； B、 將難複合氧化物進行冑溫處理，崎升溫方式加熱 1297283 至可令鎂鋁複合氧化物緻密化之溫度並停留一〜 間； 疋f c、將鎂域合氧化物置於酸㈣境巾進行酸處理，使其 充分與酸性溶液作用以除去鎂； 〃 D、獲得高比表面積之氧化鋁。 本發明具有下列功效： 1·本發明所製造出之氧化!g，在固定重量下，具有高比 籲面積，高比表面積的氧化紹將更適合作為觸媒擔體:、w 2. 本發明在處理的難中，施以不同之處理條件，例如酸 處理時間、酸處理溫度、酸處理均勻度等，可以獲得不同比表 面積之氧化銘，處理時之條件參數可視實際需求而變化。 效益 3. 本發赌使用之酸處理手段，其成本低廉，具有經濟 【實施方式】 本發明包括有下列步驟： 接」、_彻共沈法以獲得馳複合氧化物：該共沈法係為一 ^仔-種以上金屬元素複合氧化物之使用方法係將混合的 =鹽溶躲城_ ’在各齡均―齡後，制峨物再 經熱分解而製得微小粉體的方法。 B、將_複合氧化物進行高溫處理·其處理條件係以逐 =溫(例如每分鐘1(rc)的方式升溫至高溫狀態（例如 使顯複合氧化物緻槪，胁該高溫狀態下停留 一疋時間（例如1小時）。 1297283 c、將鎂鋁複合氧化物進行酸處理：其係將鎂鋁複合氧化 物置入酉夂性溶液（例如硝酸水溶液），工作溫度則介於室溫 與酸性溶液彿點之間（例如25。(：一1〇〇。(：），為求鎂銘複合氧化 物與酸性雜充分侧，可關祕以攪拌，酸處理之時間視 工作溫度而定，可介於〇·5小時至1〇〇小時之間。 D·獲得高比表面積之鎂鋁複合氧化物。 〜^上述各步驟中，有關B步驟中之逐漸升溫條件、高溫狀 ⑩態、高溫狀態下之停留時間，以及c步驛中有關酸處理之工作溫 度及酸處理之時間等，所列舉之參數僅為可行實施例之一，並 非本發明之唯一手段。 上述A步驟之共沈法，其可以是但不限於下列步驟： a·將硝酸鋁、硝酸鎂分別溶於蒸餾水中，其中藥品與蒸餾 水之比例分別為1克硝酸鋁/2毫升水、丨克硝酸鎂/2毫升水，此 —者為酸液。 b·用等體積之蒸餾水稀釋氨水（重量百分比為28)作為鹼 ❿ 液。 c·依照樣品之需要計算所需酸液量，並擾拌混合至一容器 t ° d·將鹼液倒入混合酸液中直至混合溶液邢值等於& 〇〇。 e·攪拌6小時，於攪拌過程中適時滴加鹼液至混合溶液 中使其值維持在8· 00±0· 〇2，在此過程中鋁及鎂會產生共 沈;殿形成懸淨膠液。 f·將步驟e ·之懸淨膠液過濾後再進行三次的水洗一過 1297283 濾’可得白色濾餅。 §·將濾餅於120°C烘乾12小時。 h·將步驟g.之樣品研磨成粉後擠壓成形。 依照上齡卩可製解莫耳數比之脑複合氧 化物。 為證實本發明上述實施例中之製造步驟碟實具有功效， 故進行不同處理條件的樣品實驗測試，其所產生之比表面積 φ (m /g)實驗結果如下表所示：BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a method for combining a coprecipitation method and an acid treatment to produce a catalyst carrier, particularly a method for improving the specific surface area of the oxidation after the treatment at the south temperature. The compound is obtained by a co-precipitation method and densified by high-temperature treatment, and the acid-treated method is used to greatly increase the specific surface area of the oxide to serve as a catalyst carrier. [Prior Art] 0 Alumina is a common catalyst carrier, but after a high temperature treatment of more than 10001, the specific surface area will drop to less than 30 m2 /g, which is a catalyst carrier. The great disadvantage is that the larger the surface area of the support, the larger the area representing the reaction of the reactants supplied, and the too small surface area causes the activity of the catalyst reaction to drop rapidly, for example, the three-way catalyst of the catalytic converter of a motor vehicle. The body must be calcined at a high temperature to reduce its thermal expansion coefficient and increase its mechanical strength. However, the specific surface area of the support after the satin burning is drastically reduced, and it is necessary to add another material of 1% specific surface area of the fork metal layer. It is a carrier for the catalyst, but the immersion plating layer is easily detached under a long period of operation, resulting in a decrease in the activity of the catalyst, so how to increase the high specific surface area of the oxidation (support) under a fixed weight. It is obviously necessary to stop using the immersion coating. SUMMARY OF THE INVENTION The present invention is a method for combining a coprecipitation method and an acid treatment to produce a catalyst carrier by: A. using a coprecipitation method to obtain a magnesium-aluminum composite oxide; B. performing a difficult composite oxide胄When treatment, the temperature is heated to 1,929,283 to the temperature at which the magnesium-aluminum composite oxide is densified and stays one to two; 疋fc, the magnesium domain oxide is placed in the acid (four) environment for acid treatment, making it fully acidic The solution acts to remove magnesium; 〃 D, to obtain a high specific surface area of alumina. The invention has the following effects: 1. The oxidized g produced by the invention has a high specific area under a fixed weight, and the high specific surface area of the oxide is more suitable as a catalyst carrier: w 2. The invention In the difficulty of the treatment, different treatment conditions, such as acid treatment time, acid treatment temperature, acid treatment uniformity, etc., can be obtained, and the oxidation parameters of different specific surface areas can be obtained, and the condition parameters at the time of treatment can be changed according to actual needs. Benefits 3. The acid treatment method used in this bet is low in cost and economical. [Embodiment] The present invention includes the following steps: 接, _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ The method of using the above-mentioned metal element composite oxide is a method in which the mixed salt is dissolved in the salt _ 'after all ages, and the sputum is thermally decomposed to obtain a fine powder. B. The _composite oxide is subjected to high temperature treatment, and the treatment conditions are such that the temperature is raised to a high temperature state by, for example, 1 (rc) per minute (for example, the composite oxide is caused to cause enthalpy, and the temperature is maintained at a high temperature. Time (for example, 1 hour) 1297283 c. Acid treatment of magnesium-aluminum composite oxide: the magnesium-aluminum composite oxide is placed in an inert solution (for example, an aqueous solution of nitric acid), and the working temperature is between room temperature and an acidic solution. Between the points (for example, 25 ((: 1). (:), for the magnesium-based composite oxide and acid miscellaneous side, can be secreted to stir, the acid treatment time depends on the working temperature, can be between 〇····························································································· The residence time, and the working temperature of the acid treatment and the time of the acid treatment in the step c, etc., are listed as one of the possible embodiments, and are not the only means of the invention. The above-mentioned A-step co-precipitation method can Yes but not limited to Column steps: a· Dissolve aluminum nitrate and magnesium nitrate in distilled water respectively, wherein the ratio of the medicine to the distilled water is 1 gram of aluminum nitrate/2 ml of water, gram of magnesium nitrate/2 ml of water, respectively, which is an acid solution. b. Dilute ammonia water (28% by weight) with an equal volume of distilled water as the alkali mash. c· Calculate the required amount of acid according to the needs of the sample, and mix and mix to a container t ° d · Pour the lye into the mixture In the acid solution until the mixed solution is equal to & 〇〇 e. Stir for 6 hours, while adding the alkali solution to the mixed solution during the stirring process to maintain the value at 8·00±0· 〇2, in the process The aluminum and magnesium will form a co-precipitation; the temple will form a suspending glue. f· Filter the eluent of step e · and then wash it three times and then pass the 1297728 filter to obtain a white cake. §·Filter cake Drying at 120 ° C for 12 hours h. The sample of step g. is ground into a powder and then extruded. The brain composite oxide can be prepared according to the age of the cockroach. To confirm the above embodiment of the present invention The manufacturing steps of the dish are effective, so the sample test of different processing conditions is performed. The results generated by surface area ratio φ (m / g) as shown below:
其中該樣本甲係置入90°C的硝酸溶液中攪拌〇 5 樣本乙則置人7(rc _酸溶液中· 2小時；樣本丙=置 '1297283 入口25°C的猶溶液帽拌8小時；樣本丁為未施以酸處理之 樣品；戊則為未添加鎂且未施以酸處理之樣品。 由上表中所列出經酸處理後之樣本甲、乙、丙及未經酸處 理之樣本丁的比表面積之比較，可明顯的看出經過酸處理的樣 本甲、乙、丙，其微孔表面積較未經過酸處理之樣本丁，大幅 提升了 1.6-20.8倍，且外部（Externamt表面積也增加^ 3.3-5.4 因此經過酸處理後的樣本甲、乙、丙的總比表面 積，均遠大於未紐處理樣本了_比表面積，亦遠大於未添 加錤及未經__樣核，此點證實了製備時添加駭高溫 處理後進打酸處理，有助於提昇高溫處理後氧她之比表面 積。 取第二組不同之樣本，使其鋁/鎂=1〇，結果如下表： ------ 樣本 甲二 乙二 丙二 丁二 戊二 鋁/鎂 銘/鎮=10 ^/rn^io 鋁/鎂=10 紹/鎖=10 氧化鋁 煅燒溫度 1200°C 1200°C 1200°C 1200°C 1200°C 酸處理 有 __有 古 lSL — 無 Μ 酸處理溫度 90 °C 70 °C 25 °C 一 酸處理時間 〇·5小時 2小時 8小時 微孔比表面積 1.96 4.34 0.93 0.21 0.47 外部比表面積 30.66 48.17 26.49 5.84 4.11 總比表面積 (B.E.T.) 32.62 52.51 --- 27.42 6.05 4.58 '1297283 由上表中所列出經酸處理後之樣本甲二、乙二、丙二及未 經酸處理之樣本丁二的比表面積之比較，可_的看出無論在 90C、70°C《 25°C的酸處理環境下，樣本甲二、乙二與丙 二，其微孔比表面積、外部比表面積與總比表面積 ，均遠大於 未經酸處理樣本丁二，亦遠大於未添加鎂且未經酸處理之樣品 戊，The sample is placed in a nitric acid solution at 90 ° C and stirred. 5 sample B is placed in human 7 (rc _ acid solution for 2 hours; sample C = set '1297283) at 25 ° C inlet solution for 8 hours. The sample is a sample that has not been subjected to acid treatment; the sample is a sample that is not added with magnesium and is not subjected to acid treatment. The acid-treated samples listed in the above table are treated with A, B, C and unacid. Comparing the specific surface area of the sample, it can be clearly seen that the acid-treated samples A, B, and C have a micropore surface area that is 1.6-20.8 times higher than that of the untreated sample, and the external (Externamt The surface area also increases ^ 3.3-5.4 Therefore, the total specific surface area of the samples treated with acid, A, B, and C is much larger than that of the untreated sample, which is much larger than the unfilled and un-nucleated nucleus. This point confirms that the addition of strontium to the acid treatment after the preparation of high temperature treatment helps to increase the specific surface area of oxygen after high temperature treatment. Take a second set of different samples to make aluminum/magnesium = 1 〇, the results are as follows: ----- Sample methyldiethylenedipropane dipentaluminum/magnesium Ming / town = 10 ^ / rn ^ io aluminum / magnesium = 10 Shao / lock = 10 alumina calcination temperature 1200 ° C 1200 ° C 1200 ° C 1200 ° C 1200 ° C acid treatment _ _ ancient lSL - no Μ Acid treatment temperature 90 °C 70 °C 25 °C One acid treatment time 〇·5 hours 2 hours 8 hours Micropore specific surface area 1.96 4.34 0.93 0.21 0.47 External specific surface area 30.66 48.17 26.49 5.84 4.11 Total specific surface area (BET) 32.62 52.51 - -- 27.42 6.05 4.58 '1297283 The comparison of the specific surface areas of the acid-treated samples of the second, second, and second, and unacidified samples, as listed in the above table, can be seen in 90C, 70 ° C "25 ° C acid treatment environment, the sample of two, two and two, the microporous specific surface area, external specific surface area and total specific surface area, are much larger than the untreated sample D, It is also much larger than the sample without added magnesium and not treated with acid.
【圖式簡單說明】 無 【主要元件符號說明】[Simple description of the diagram] None [Main component symbol description]