TWI460004B - Selective catalytic reduction plate catalyst and method of making the same - Google Patents
Selective catalytic reduction plate catalyst and method of making the same Download PDFInfo
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本發明係有關於一種板狀觸媒及其製造方法，特別是有關於利用選擇性觸媒還原反應(Selective Catalytic Reduction；SCR)之板狀觸媒與其製造方法。The present invention relates to a plate-like catalyst and a method for producing the same, and more particularly to a plate-like catalyst using a selective catalytic reduction (SCR) and a method for producing the same.
在一貫作業鋼廠或火力發電廠中，會產生大量氮氧化物，而氮氧化物為大氣中的主要污染源，會嚴重危害人體健康。為要清除氮氧化物，習知技術發展出利用氨作為主要還原劑的脫硝技術，亦稱為選擇性觸媒還原法。In the consistent operation of steel mills or thermal power plants, a large amount of nitrogen oxides are generated, and nitrogen oxides are the main source of pollution in the atmosphere, which will seriously endanger human health. In order to remove nitrogen oxides, conventional techniques have developed a denitration technique that utilizes ammonia as a primary reducing agent, also known as selective catalytic reduction.
習知之高溫選擇性觸媒還原反應觸媒主要有蜂巢狀與板狀兩種型式。蜂巢狀的觸媒的配置係利用含浸方式來進行，其係將釩酸銨等銨化合物溶於水中而配製成水溶液，以利於將其中之主成份均勻地含浸於擔體上。但因釩酸銨不易溶於水，故不易調配出最適宜的釩氧化物濃度，因而影響蜂巢狀的觸媒脫硝能力。另一方面，由於一貫作業之鋼廠所產生的廢氣夾帶有飛灰，為要避免飛灰中之重金屬或鹼金屬累積於SCR觸媒上，毒化SCR觸媒，而影響其脫硝效率，因而需採用廢氣容易流經且飛灰不易累積的板狀觸媒，且板狀觸媒之附著強度必須要能夠承受廢氣的衝擊。因此，習知配置蜂巢狀SCR觸媒所使用的含浸方式並不適用於製造板狀SCR觸媒。The conventional high temperature selective catalyst reduction reaction catalyst mainly has two types of honeycomb and plate. The configuration of the honeycomb-like catalyst is carried out by means of an impregnation method in which an ammonium compound such as ammonium vanadate is dissolved in water to prepare an aqueous solution to facilitate uniform impregnation of the main component therein onto the support. However, since ammonium vanadate is not easily soluble in water, it is difficult to formulate the optimum vanadium oxide concentration, thereby affecting the catalytic ability of the honeycomb to be denitrified. On the other hand, due to the fly ash contained in the exhaust gas produced by the steel mills that have been operating, in order to avoid accumulation of heavy metals or alkali metals in the fly ash on the SCR catalyst, the SCR catalyst is poisoned, which affects the denitration efficiency. It is necessary to use a plate-like catalyst in which the exhaust gas easily flows through and the fly ash does not easily accumulate, and the adhesion strength of the plate-like catalyst must be able to withstand the impact of the exhaust gas. Therefore, the impregnation method used in the conventional configuration of the honeycomb SCR catalyst is not suitable for the production of a plate-shaped SCR catalyst.
此外，由於習知之SCR觸媒係屬於高溫觸媒，其必須 在300~400℃的高溫下進行，方能達到高脫除率，故需對小於150℃之製程末端所產生的廢氣加熱，徒增能量的耗費，因而增加生產成本。另對於燃煤鍋爐而言，SCR反應器係置於除塵器和脫硫裝置之前，當於高溫下進行時，會縮短觸媒壽命，並增加脫硝反應器維護之成本。In addition, since the conventional SCR catalyst is a high temperature catalyst, it must It can be carried out at a high temperature of 300 to 400 ° C to achieve a high removal rate. Therefore, it is necessary to heat the exhaust gas generated at the end of the process of less than 150 ° C, thereby increasing the energy consumption and thus increasing the production cost. In the case of a coal-fired boiler, the SCR reactor is placed at a high temperature before the precipitator and the desulfurization unit, which shortens the life of the catalyst and increases the cost of maintenance of the denitration reactor.
因此，需發展出一種可於低溫(小於150℃)進行反應的SCR觸媒，以減少將置於製程末端之脫硝反應器的溫度提升至300至400℃所需耗費的燃料費用，並延長SCR觸媒的壽命。此外，為避免燒結工場中之脫硝反應器因飛灰而堵塞，亦需採用板狀SCR觸媒。Therefore, it is necessary to develop an SCR catalyst that can be reacted at a low temperature (less than 150 ° C) to reduce the cost of fuel required to raise the temperature of the denitration reactor placed at the end of the process to 300 to 400 ° C, and to extend The life of the SCR catalyst. In addition, in order to prevent the denitration reactor in the sintering plant from being clogged by fly ash, a plate-shaped SCR catalyst is also required.
針對進行脫硝反應的低溫SCR觸媒，習知技術以錳(Mn)系列低溫SCR觸媒為主，銅(Cu)系列低溫SCR觸媒為副。此外，亦有採用含浸鹼金屬的活性碳來進行氮氧化物的吸附作用。由於銅會促進燒結工場的戴奧辛再次生成，不利於戴奧辛的脫除，故不被應用於燒結工場中。以下說明錳系列低溫SCR觸媒的製作。For the low-temperature SCR catalyst for denitration reaction, the conventional technology mainly uses manganese (Mn) series low-temperature SCR catalyst, and copper (Cu) series low-temperature SCR catalyst is auxiliary. In addition, activated carbon impregnated with an alkali metal is also used for the adsorption of nitrogen oxides. Since copper will promote the re-generation of Dioxin in the sintering workshop, it is not suitable for the removal of Dioxin, so it is not used in the sintering workshop. The production of a manganese series low temperature SCR catalyst will be described below.
習知技術係使用含浸法或共同沉澱法來進行錳系列低溫SCR觸媒的配製，其所使用的錳原料為硝酸錳或醋酸錳。Conventional techniques use an impregnation method or a coprecipitation method to prepare a manganese series low temperature SCR catalyst, and the manganese raw material used is manganese nitrate or manganese acetate.
習知技術係以醋酸錳與高錳酸鉀混合配製成無擔體之錳觸媒，因其具無晶體相(Amorphous)且高比表面積(50至150m2 /g)，故在空間流量為47000hr-1 且反應溫度為80℃時，其脫硝效率可達98%，而當反應溫度為100℃至150℃時，其脫硝效率可達100%。然而，當有二氧化硫和水的存在且反應溫度為80℃時，其脫硝效率會降至73%。The conventional technology is a manganese-free catalyst prepared by mixing manganese acetate with potassium permanganate. Because of its amorphous phase and high specific surface area (50 to 150 m 2 /g), the space flow is when 47000hr -1 and a reaction temperature of 80 ℃, denitration efficiency of 98%, and when the reaction temperature is 100 ℃ to 150 deg.] C, its denitration efficiency up to 100%. However, when sulfur dioxide and water are present and the reaction temperature is 80 ° C, the denitration efficiency is reduced to 73%.
又一習知技術係以氧化錳(MnOx )附著於不同擔體來進行SCR觸媒脫硝效率之測試，每種觸媒內之錳金屬化合物的重量百分比均為20%，其中以氧化錳附著於氧化鈦(TiO2 )與氧化鋁(γ-Al2 O3 )之兩種擔體較佳。然而，氧化錳係無晶體相，其脫硝效率優於呈晶體相(Crystalline)的脫硝效率。在空間流量為40000hr-1 ，且反應溫度為100℃至200℃之條件下，其脫硝效率係95%至100%。此外，若通入二氧化硫和水分子，對於附著於氧化鈦擔體之錳觸媒脫硝效率僅有些許之影響。Another conventional technique is to test the denitration efficiency of SCR catalyst by attaching manganese oxide (MnO x ) to different supports, and the weight percentage of manganese metal compounds in each catalyst is 20%, among which manganese oxide is used. Two kinds of supports attached to titanium oxide (TiO 2 ) and aluminum oxide (γ-Al 2 O 3 ) are preferred. However, the manganese oxide-based amorphous phase has a denitration efficiency superior to that of the crystalline phase (Crystalline). The denitration efficiency is 95% to 100% under the conditions of a space flow of 40,000 hr -1 and a reaction temperature of 100 ° C to 200 ° C. In addition, if sulfur dioxide and water molecules are introduced, there is only a slight influence on the denitration efficiency of the manganese catalyst attached to the titanium oxide support.
習知技術將鈰金屬加入錳系列低溫SCR觸媒係因：鈰金屬可藉由Ce+4 與Ce+3 之氧化還原反應來進行儲存與釋放氧氣，且鈰金屬可促進一氧化氮(NO)進行氧化反應以生成二氧化氮(NO2 )，而提升SCR觸媒之脫硝效率，其中錳金屬化合物/(錳金屬化合物和鈰金屬化合物)莫耳比值為0.4。在空間流量為42000hr-1 且反應溫度為150℃之條件下，其最佳脫硝效率為95%，而其主要生成產物為氮氣。習知技術係利用將氨(NH3 )吸附於SCR觸媒表面的路易士酸(Lewis Acid)上之過程中會與一氧化氮或亞硝酸(Nitrite)反應，來產生NH2 NO，再裂解為氮氣或水分子。The prior art adds a base metal to a manganese series low temperature SCR catalyst. The base metal can store and release oxygen by the oxidation reduction reaction of Ce +4 and Ce +3 , and the base metal can promote nitric oxide (NO). The oxidation reaction is carried out to form nitrogen dioxide (NO 2 ), which improves the denitration efficiency of the SCR catalyst, wherein the manganese metal compound/(manganese metal compound and base metal compound) has a molar ratio of 0.4. Under the condition of a space flow of 42000 hr -1 and a reaction temperature of 150 ° C, the optimum denitration efficiency is 95%, and the main product is nitrogen. The prior art utilizes the reaction of nitrogen monoxide or nitrite by reacting ammonia (NH 3 ) on Lewis acid on the surface of the SCR catalyst to produce NH 2 NO, which is then cleaved. It is a nitrogen or water molecule.
又一習知技術係將鈰金屬與錳金屬附著於氧化鈦擔體上，來進行SCR觸媒脫硝效率之測試，其中觸媒內錳金屬化合物之重量百分比為10%。在錳金屬化合物/(錳金屬化合物和鈰金屬化合物)莫耳比值係0.4，且反應溫度為120 ℃之條件下，當空間流量係由7000 hr-1 調高至42000hr-1 且脫硝效率由98%降約90%時，其仍具不錯之脫硝效率。此外，具有鈰金屬與氧化鈦擔體之錳系列低溫SCR觸媒對於二氧化硫與水分子具有不錯的抗阻性。Another conventional technique is to test the SCR catalyst denitration efficiency by attaching a base metal and a manganese metal to a titanium oxide support, wherein the weight percentage of the manganese metal compound in the catalyst is 10%. In the case of manganese metal compound / (manganese metal compound and base metal compound) molar ratio of 0.4, and the reaction temperature is 120 ° C, when the space flow rate is increased from 7000 hr -1 to 42000 hr -1 and the denitration efficiency is When 98% drops by about 90%, it still has good denitration efficiency. In addition, manganese series low temperature SCR catalysts with base metals and titanium oxide supports have good resistance to sulfur dioxide and water molecules.
習知技術係將鐵金屬加入具有氧化鈦擔體之錳系列低溫SCR觸媒，以在低溫下增加錳系列低溫SCR觸媒之觸媒脫硝效率，其中錳金屬化合物/鐵金屬化合物莫耳比值為1、反應溫度為120℃，且脫硝效率最佳。當空間流量為15000 hr-1 時，其脫硝效率可達100%。此外，加入鐵金屬可增加錳系列低溫SCR觸媒對於二氧化硫與水分子之抗阻性，其影響具有可逆性。The prior art adds iron metal to a manganese series low temperature SCR catalyst having a titanium oxide support to increase the catalytic denitration efficiency of the manganese series low temperature SCR catalyst at a low temperature, wherein the manganese metal compound/iron metal compound molar ratio 1. The reaction temperature is 120 ° C, and the denitration efficiency is the best. When the space flow is 15000 hr -1 , the denitration efficiency can reach 100%. In addition, the addition of iron metal can increase the resistance of manganese series low temperature SCR catalyst to sulfur dioxide and water molecules, and its effect is reversible.
習知技術係因活性碳具高比表面積與化學穩定性，而將活性碳加入擔體中。在配製具有活性碳與陶瓷之錳系列低溫SCR觸媒時，先將PF樹酯作為活性碳來源，並將活性碳附著於陶瓷上，再進行含浸與超音波震盪步驟，以將錳與其他金屬化合物均勻附著於活性碳和陶瓷上，其中錳金屬含量係8重量百分比，反應溫度係100℃。當空間流量係10600 hr-1 ，具有活性碳與陶瓷之錳系列低溫SCR觸媒脫硝效率為約30%。然而，在加入鈰金屬後，其脫硝效率可提升至78%；當溫度調整至150℃至250℃，其脫硝效率可大於90%；當加入鐵金屬後，亦可提高對二氧化硫毒化之抗阻性。Conventional techniques incorporate activated carbon into a support due to the high specific surface area and chemical stability of the activated carbon. In the preparation of manganese series low temperature SCR catalysts with activated carbon and ceramics, PF resin is used as the active carbon source, and activated carbon is attached to the ceramic, followed by impregnation and ultrasonic oscillation steps to transfer manganese and other metals. The compound was uniformly attached to activated carbon and ceramics, wherein the manganese metal content was 8 weight percent and the reaction temperature was 100 °C. When the spatial flow rate is 10600 hr -1 , the denitration efficiency of the activated carbon and ceramic manganese series low temperature SCR catalyst is about 30%. However, after the addition of base metal, the denitration efficiency can be increased to 78%; when the temperature is adjusted to 150 ° C to 250 ° C, the denitration efficiency can be greater than 90%; when iron metal is added, the poisoning of sulfur dioxide can also be increased. Resistance.
又一習知技術係利用活性碳纖維作為活性碳來源。首先，預先烘乾活性碳纖維，再進行含浸步驟，以將活性碳纖維含浸於硝酸錳或硝酸鈰水溶液中，其係以1公克(g)的活性碳纖維含浸於20毫升(ml)的水溶液中。相較於硝酸錳水溶液或硝酸錳與硝酸鈰的水溶液，含浸於硝酸鈰水溶液具有較佳的脫硝效率，在反應溫度介於120℃至250℃之條件下，當空間流量為20000 hr-1 時，其脫硝效率保持於85%。Yet another conventional technique utilizes activated carbon fibers as a source of activated carbon. First, the activated carbon fibers are preliminarily dried, and then subjected to an impregnation step to impregnate the activated carbon fibers in an aqueous solution of manganese nitrate or lanthanum nitrate, which is impregnated with an aqueous solution of 20 milliliters (ml) of activated carbon fibers of 1 gram (g). Compared with the aqueous solution of manganese nitrate or the aqueous solution of manganese nitrate and lanthanum nitrate, the aqueous solution of cerium nitrate has better denitration efficiency, and the reaction flow temperature is between 120 ° C and 250 ° C when the space flow is 20000 hr -1 . At the time, the denitration efficiency was maintained at 85%.
以下說明含浸鹼金屬的活性碳的製作。The production of activated carbon impregnated with an alkali metal will be described below.
習知技術係利用活性碳作為還原劑、觸媒或觸媒擔體。在探討原殘存在活性碳表面或於活性碳加入不同無機物質之功效時，習知技術發現鉀(K)金屬具有作為觸媒之潛力。在以活性碳進行吸附一氧化氮作用時，由所得的結果可知：鉀金屬具催化功能，並且活性碳之BET比表面積係與脫除一氧化氮之活性相關。意即，當活性碳含浸於氫氧化鉀(KOH)時，可提升氮氧化物的吸附能力。Conventional techniques utilize activated carbon as a reducing agent, catalyst or catalyst support. In discussing the effect of the presence of activated carbon on the surface of activated carbon or the addition of different inorganic substances to activated carbon, conventional techniques have found that potassium (K) metal has potential as a catalyst. When adsorbing nitric oxide by activated carbon, it is known from the results that potassium metal has a catalytic function, and the BET specific surface area of activated carbon is related to the activity of removing nitric oxide. That is, when the activated carbon is impregnated with potassium hydroxide (KOH), the adsorption capacity of the nitrogen oxides can be enhanced.
又一習知技術係將活性碳進行氫氧化鈉(NaOH)、碳酸鈉(NaCO3 )與氫氧化鉀等鹼金屬水溶液之含浸步驟後，再進行吸附一氧化氮作用，其中以氫氧化鉀的效果最佳。在無通入氧氣且反應溫度為160度時，含浸氫氧化鉀之活性碳的吸附能力為5.87毫莫耳氮氧化物/公克碳化合物(mol NOx /g-AC)，而含浸氫氧化鈉或碳酸鈉之活性碳的吸附能力分別為2.07與2.70mol NOx /g-AC。在通入氧氣後，由於氧氣會先吸附至活性碳上，使得活性碳表面的一氧化氮氧化變成二氧化氮，而二氧化氮易被活性碳吸附，故可提升氮氧化物的吸附能力至6.16mol NOx /g-AC。此外，活性碳之 孔徑大小與一氧化氮之吸附能力有關，其最佳的孔徑為1.1毫米。習知之低溫SCR觸媒均以含浸法或共同沉澱法來進行配製，其須於水溶液中進行，故步驟繁瑣，並需較多單元設備方可進行配製，且易受二氧化硫與水分子之毒化，因而增加低溫SCR觸媒之製程的困難度與成本。Another conventional technique is to carry out an impregnation step of an activated carbon with an alkali metal aqueous solution such as sodium hydroxide (NaOH), sodium carbonate (NaCO 3 ) and potassium hydroxide, followed by adsorption of nitric oxide, wherein potassium hydroxide is used. The best results. In the absence of oxygen fed and the reaction temperature is 160 degrees, the adsorption capacity of the activated carbon impregnated with potassium hydroxide oxynitride 5.87 mmol / g carbon compound (mol NO x / g-AC ), and sodium hydroxide impregnated adsorption capacity of activated carbon or sodium carbonate and 2.07 respectively 2.70mol NO x / g-AC. After the oxygen is introduced, the oxygen is first adsorbed onto the activated carbon, so that the nitric oxide on the surface of the activated carbon is oxidized to become nitrogen dioxide, and the nitrogen dioxide is easily adsorbed by the activated carbon, so that the adsorption capacity of the nitrogen oxide can be improved to 6.16mol NO x / g-AC. In addition, the pore size of the activated carbon is related to the adsorption capacity of nitric oxide, and the optimum pore diameter is 1.1 mm. The conventional low temperature SCR catalysts are prepared by impregnation method or coprecipitation method, which must be carried out in an aqueous solution, so the steps are cumbersome, and more unit equipment is required for preparation, and is susceptible to poisoning by sulfur dioxide and water molecules. Therefore, the difficulty and cost of the process of the low temperature SCR catalyst are increased.
因此，須提供一種利用SCR反應板狀觸媒與其製造方法，以改善習知SCR觸媒的缺點。Therefore, it is necessary to provide an SCR reaction plate-like catalyst and a manufacturing method thereof to improve the disadvantages of the conventional SCR catalyst.
因此，本發明之一態樣係在提供一種SCR板狀觸媒組成物與其製造方法，以改善習知於水溶液中配置SCR觸媒之繁瑣液態方法的缺點。Accordingly, one aspect of the present invention is to provide an SCR plate-like catalyst composition and a method of manufacturing the same to improve the conventional liquid handling method of arranging an SCR catalyst in an aqueous solution.
本發明之另一態樣係在提供一種SCR板狀觸媒組成物，以使用低溫觸媒進行SCR脫硝反應，來減少能源與觸媒成本。Another aspect of the present invention provides an SCR plate-like catalyst composition for use in a SCR denitration reaction using a low temperature catalyst to reduce energy and catalyst costs.
根據本發明之上述目的，提出一種SCR板狀觸媒組成物，此SCR板狀觸媒組成物包含由鋁金屬化合物、鋯金屬化合物、鈦金屬化合物和矽金屬化合物所組成的擔體、錳金屬化合物、由鐵金屬化合物和鈰金屬化合物所組成的促進劑、碳化合物、無機纖維、以及黏土。According to the above object of the present invention, an SCR plate-like catalyst composition comprising a support composed of an aluminum metal compound, a zirconium metal compound, a titanium metal compound and a base metal compound, and a manganese metal is proposed. A compound, an accelerator composed of an iron metal compound and a base metal compound, a carbon compound, an inorganic fiber, and a clay.
依照本發明一實施例，上述之鋁金屬化合物包括三氧化二鋁；鋯金屬化合物包括氧化鋯氧化物、硝酸鋯或上述之任意組合；鈦金屬化合物包括二氧化鈦氧化物、偏鈦酸或上述之任意組合；而矽金屬化合物包括氧化矽氧化物。According to an embodiment of the invention, the aluminum metal compound comprises aluminum oxide; the zirconium metal compound comprises zirconium oxide oxide, zirconium nitrate or any combination thereof; the titanium metal compound comprises titanium dioxide oxide, metatitanic acid or any of the above Combination; and the base metal compound includes cerium oxide oxide.
依照本發明一實施例，上述之錳金屬化合物包括醋酸錳、硝酸錳或上述之任意組合；鐵金屬化合物包括硝酸鐵、氯化亞鐵或上述之任意組合；鈰金屬化合物包括硝酸鈰。According to an embodiment of the invention, the manganese metal compound comprises manganese acetate, manganese nitrate or any combination thereof; the iron metal compound comprises iron nitrate, ferrous chloride or any combination thereof; and the base metal compound comprises barium nitrate.
依照本發明一實施例，上述之碳化合物包括活性碳、褐煤或上述之任意組合；無機纖維包含鋁與矽氧化物；黏土包含鋁與矽氧化物。According to an embodiment of the invention, the carbon compound comprises activated carbon, lignite or any combination thereof; the inorganic fiber comprises aluminum and cerium oxide; and the clay comprises aluminum and cerium oxide.
依照本發明一實施例，上述之鋁金屬化合物的含量係介於5重量百分比(wt%)至30wt%之間，較佳是介於7wt%至10wt%之間；鋯金屬化合物的含量係介於5wt%至25wt%之間，較佳是介於6wt%至10wt%之間；鈦金屬化合物的含量係介於20wt%至47wt%之間，較佳是介於20wt%至33wt%之間；矽金屬化合物的含量係介於5wt%至25wt%之間，較佳是介於8wt%至12wt%之間；錳金屬化合物的含量係介於20wt%至45wt%之間，較佳是介於21wt%至26wt%之間；鐵金屬化合物的含量係介於5wt%至20wt%之間，較佳是介於9wt%至13wt%之間；鈰金屬化合物的含量係介於5wt%至20wt%之間，較佳是介於5wt%至8wt%之間；碳化合物可例如介於2wt%至10wt%之間，較佳是介於3wt%至6wt%之間；無機纖維的含量係介於5wt%至15wt%之間，較佳是介於6wt%至9wt%之間；而黏土的含量係介於1wt%至6wt%之間，較佳是介於2wt%至4wt%之間。According to an embodiment of the invention, the content of the aluminum metal compound is between 5 wt% and 30 wt%, preferably between 7 wt% and 10 wt%; and the content of the zirconium metal compound is Between 5 wt% and 25 wt%, preferably between 6 wt% and 10 wt%; the content of the titanium metal compound is between 20 wt% and 47 wt%, preferably between 20 wt% and 33 wt% The content of the ruthenium metal compound is between 5 wt% and 25 wt%, preferably between 8 wt% and 12 wt%; the content of the manganese metal compound is between 20 wt% and 45 wt%, preferably Between 21 wt% and 26 wt%; the content of the iron metal compound is between 5 wt% and 20 wt%, preferably between 9 wt% and 13 wt%; the content of the rhodium metal compound is between 5 wt% and 20 wt%. Between %, preferably between 5 wt% and 8 wt%; the carbon compound may be, for example, between 2 wt% and 10 wt%, preferably between 3 wt% and 6 wt%; Between 5 wt% and 15 wt%, preferably between 6 wt% and 9 wt%; and the clay content is between 1 wt% and 6 wt%, preferably between 2 wt% and 4 wt%.
根據本發明之上述目的，另提出一種SCR板狀觸媒組成物之製造方法。首先，進行球磨步驟經一段球磨時間，藉以使用球磨機來混合並研磨鋁金屬化合物、鋯金屬化合物、鈦金屬化合物與矽金屬化合物，以形成第一擔體。然 後，於第一乾燥溫度下進行第一乾燥步驟經第一乾燥時間，用以乾燥第一擔體，以形成第二擔體。接著，於空氣氣氛中，並於第一煅燒溫度下進行第一煅燒步驟，以煅燒第二擔體，而形成第三擔體。接著，進行第一捏拌步驟，藉以使用捏合機來混合且捏拌第三擔體、錳金屬化合物、鐵金屬化合物、鈰金屬化合物、碳化合物與軟水，而形成第一糰料。然後，進行第二捏拌步驟，藉以使用捏合機來混合且捏拌無機纖維、黏土與第一糰料，而形成第二糰料。接著，進行輥軋步驟，藉以使用金屬輥輪來將第二糰料輥軋於網狀金屬上，以形成第一基材。然後，進行成型步驟，藉以使用壓力壓塑第一基材，以形成第二基材。接著，於第二乾燥溫度下進行第二乾燥步驟，用以乾燥第二基材，以形成第三基材。然後，於一氣氛中，並於第二煅燒溫度下進行第二煅燒步驟，用以煅燒第三基材，而形成選擇性的觸媒還原反應板狀觸媒。According to the above object of the present invention, a method of producing an SCR plate-like catalyst composition is also proposed. First, the ball milling step is performed for a first time by a ball milling time to mix and grind the aluminum metal compound, the zirconium metal compound, the titanium metal compound and the base metal compound using a ball mill. Of course Thereafter, the first drying step is performed at the first drying temperature for a first drying time to dry the first support to form a second support. Next, a first calcination step is performed in an air atmosphere at a first calcination temperature to calcine the second support to form a third support. Next, a first kneading step is carried out, whereby a third support, a manganese metal compound, an iron metal compound, a base metal compound, a carbon compound and soft water are mixed and kneaded using a kneader to form a first mass. Then, a second kneading step is carried out whereby a kneader is used to mix and knead the inorganic fibers, the clay and the first mass to form a second mass. Next, a rolling step is performed whereby a second roll is rolled onto the mesh metal using a metal roll to form a first substrate. Then, a molding step is performed whereby the first substrate is compression molded using pressure to form a second substrate. Next, a second drying step is performed at a second drying temperature to dry the second substrate to form a third substrate. Then, a second calcination step is carried out in an atmosphere at a second calcination temperature for calcining the third substrate to form a selective catalyst reduction reaction plate-like catalyst.
依照本發明一實施例，上述之球磨步驟係使用一球磨機；進行第一捏拌步驟係使用一捏合機；第二捏拌步驟係使用捏合機；壓力成型步驟係使用一模具。According to an embodiment of the invention, the ball milling step uses a ball mill; the first kneading step uses a kneader; the second kneading step uses a kneader; and the pressure forming step uses a mold.
依照本發明一實施例，上述之球磨機之轉速係實質介於每分鐘40轉(rpm)至80rpm之間，球磨時間係實質介於12小時至24小時之間。In accordance with an embodiment of the invention, the rotational speed of the ball mill described above is substantially between 40 revolutions per minute (rpm) and 80 rpm, and the ball milling time is substantially between 12 hours and 24 hours.
依照本發明一實施例，上述之捏合機之轉速係實質介於每分鐘400rpm至800rpm之間，第一捏拌時間係實質介於1小時至4小時之間；第二捏拌時間係實質介於1小時至4小時之間。According to an embodiment of the invention, the rotation speed of the kneader is substantially between 400 rpm and 800 rpm, and the first kneading time is substantially between 1 hour and 4 hours; the second kneading time is substantially Between 1 hour and 4 hours.
依照本發明一實施例，上述之捏合機之轉速係實質介於每分鐘500rpm至600rpm之間，第一捏拌時間係實質介於2小時至3小時之間；第二捏拌時間係實質介於2小時至3小時之間。According to an embodiment of the present invention, the rotation speed of the kneading machine is substantially between 500 rpm and 600 rpm, and the first kneading time is substantially between 2 hours and 3 hours; the second kneading time is substantially It is between 2 hours and 3 hours.
依照本發明一實施例，上述之第一乾燥溫度實質係150℃，且第一乾燥時間實質係1小時；第一煅燒溫度實質介於400℃至500℃，且第一煅燒時間實質係3小時；第一煅燒溫度實質介於400℃至450℃；第二乾燥溫度實質係150℃，且第二乾燥時間實質係1小時；第二煅燒步驟之氣氛為氮氣氛，第二煅燒溫度實質介於300℃至500℃，且第二煅燒時間實質係3小時。According to an embodiment of the invention, the first drying temperature is substantially 150 ° C, and the first drying time is substantially 1 hour; the first calcination temperature is substantially between 400 ° C and 500 ° C, and the first calcination time is substantially 3 hours. The first calcination temperature is substantially between 400 ° C and 450 ° C; the second drying temperature is substantially 150 ° C, and the second drying time is substantially 1 hour; the atmosphere of the second calcination step is a nitrogen atmosphere, and the second calcination temperature is substantially 300 ° C to 500 ° C, and the second calcination time is substantially 3 hours.
依照本發明一實施例，上述之第二基材為Z型。According to an embodiment of the invention, the second substrate is a Z-shape.
依照本發明一實施例，上述第二煅燒步驟之氣氛為空氣氣氛中進行；第二煅燒溫度實質介於300℃至350℃。According to an embodiment of the invention, the atmosphere of the second calcination step is carried out in an air atmosphere; and the second calcination temperature is substantially between 300 ° C and 350 ° C.
由上述之實施例可知，應用本發明之SCR板狀觸媒及其製造方法，可有效克服習知於水溶液中配製SCR觸媒之步驟繁瑣配製方式的缺點，並於低溫下仍具備良好的脫硝效率，以降低製造成本與能源消耗。It can be seen from the above embodiments that the SCR plate-like catalyst of the present invention and the manufacturing method thereof can effectively overcome the shortcomings of the conventionally complicated preparation method for preparing the SCR catalyst in an aqueous solution, and have good desorption at low temperatures. Nitrogen efficiency to reduce manufacturing costs and energy consumption.
本發明之選擇性觸媒還原反應的板狀觸媒組成物包含由鋁金屬化合物、鋯金屬化合物、鈦金屬化合物和矽金屬化合物所組成的擔體、錳金屬化合物、由鐵金屬化合物和鈰金屬化合物所組成的促進劑、碳化合物、無機纖維，以及黏土。The plate-like catalyst composition of the selective catalyst reduction reaction of the present invention comprises a support composed of an aluminum metal compound, a zirconium metal compound, a titanium metal compound and a base metal compound, a manganese metal compound, an iron metal compound and a base metal. An accelerator composed of a compound, a carbon compound, an inorganic fiber, and a clay.
本發明之鋁金屬化合物可例如：介於5重量百分比(wt%)至30wt%之間，較佳是介於7wt%至10wt%之間；鋯金屬化合物可例如：介於5wt%至25wt%之間，較佳是介於6wt%至10wt%之間；鈦金屬化合物可例如：介於20wt%至47wt%之間，較佳是介於20wt%至33wt%之間；矽金屬化合物可例如：介於5wt%至25wt%之間，較佳是介於8wt%至12wt%之間；錳金屬化合物可例如：介於20wt%至45wt%之間，較佳是介於21wt%至26wt%之間；鐵金屬化合物可例如：介於5wt%至20wt%之間，較佳是介於9wt%至13wt%之間；鈰金屬化合物可例如：介於5wt%至20wt%之間，較佳是介於5wt%至8wt%之間；碳化合物可例如：介於2wt%至10wt%之間，較佳是介於3wt%至6wt%之間；無機纖維可例如：介於5wt%至15wt%之間，較佳是介於6wt%至9wt%之間；而黏土可例如：介於1wt%至6wt%之間，較佳是介於2wt%至4wt%之間。The aluminum metal compound of the present invention may, for example, be between 5 weight percent (wt%) and 30 wt%, preferably between 7 wt% and 10 wt%; the zirconium metal compound may, for example, be between 5 wt% and 25 wt% Preferably, between 6 wt% and 10 wt%; the titanium metal compound may, for example, be between 20 wt% and 47 wt%, preferably between 20 wt% and 33 wt%; the base metal compound may for example : between 5 wt% and 25 wt%, preferably between 8 wt% and 12 wt%; the manganese metal compound may, for example, be between 20 wt% and 45 wt%, preferably between 21 wt% and 26 wt% The iron metal compound may, for example, be between 5 wt% and 20 wt%, preferably between 9 wt% and 13 wt%; the rhodium metal compound may, for example, be between 5 wt% and 20 wt%, preferably It is between 5 wt% and 8 wt%; the carbon compound can be, for example, between 2 wt% and 10 wt%, preferably between 3 wt% and 6 wt%; the inorganic fibers can be, for example, between 5 wt% and 15 wt%. Between %, preferably between 6 wt% and 9 wt%; and the clay may, for example, be between 1 wt% and 6 wt%, preferably between 2 wt% and 4 wt%.
在本實施例中，鋁金屬化合物可為例如：三氧化二鋁；鋯金屬化合物可為例如：氧化鋯氧化物、硝酸鋯或其上述材料之任意組合；鈦金屬化合物可為：例如二氧化鈦氧化物、偏鈦酸或其上述之任意組合；矽金屬化合物可為：例如氧化矽氧化物。錳金屬化合物可為例如：醋酸錳、硝酸錳或其上述之任意組合；鐵金屬化合物可為例如：硝酸鐵、氯化亞鐵或其上述之任意組合；鈰金屬化合物可為例如：硝酸鈰。碳化合物可為例如：活性碳、褐煤或其上述之任意組合；無機纖維可為例如：鋁與矽氧化物；黏土可為例如：鋁與矽氧化物。In this embodiment, the aluminum metal compound may be, for example, aluminum oxide; the zirconium metal compound may be, for example, zirconia oxide, zirconium nitrate or any combination thereof; the titanium metal compound may be, for example, titanium oxide oxide. And a metatitanic acid or any combination thereof; the ruthenium metal compound may be, for example, ruthenium oxide oxide. The manganese metal compound may be, for example, manganese acetate, manganese nitrate or any combination thereof; the iron metal compound may be, for example, iron nitrate, ferrous chloride or any combination thereof; the base metal compound may be, for example, cerium nitrate. The carbon compound may be, for example, activated carbon, lignite or any combination thereof; the inorganic fibers may be, for example, aluminum and cerium oxide; the clay may be, for example, aluminum and cerium oxide.
請參照第1圖，其繪示本發明之選擇性觸媒還原反應的板狀觸媒組成物之製造方法的流程示意圖。首先，進行球磨步驟112，其係藉由球磨機，以每分鐘40rpm至80rpm之間轉速進行12小時至24小時，來混合並研磨鋁金屬化合物、鋯金屬化合物、鈦金屬化合物與矽金屬化合物，以形成第一擔體，所得之第一擔體之粒徑係實質介於12網目至40網目。然後，進行第一乾燥步驟113，其係於150℃下進行1小時，以乾燥第一擔體，而形成第二擔體。接著，在空氣氣氛下，進行第一煅燒步驟114，其係於400℃至500℃下進行3小時，較佳係介於400℃至450℃之間，煅燒第二擔體，而形成第三擔體。Referring to Fig. 1, there is shown a schematic flow chart of a method for producing a plate-like catalyst composition for selective catalyst reduction reaction of the present invention. First, a ball milling step 112 is performed by mixing and grinding an aluminum metal compound, a zirconium metal compound, a titanium metal compound and a base metal compound by a ball mill at a rotation speed of 40 rpm to 80 rpm per minute for 12 hours to 24 hours. The first support is formed, and the obtained first support has a particle size substantially ranging from 12 mesh to 40 mesh. Then, a first drying step 113 was carried out, which was carried out at 150 ° C for 1 hour to dry the first support to form a second support. Next, in a air atmosphere, a first calcination step 114 is performed, which is carried out at 400 ° C to 500 ° C for 3 hours, preferably between 400 ° C and 450 ° C, to calcine the second support to form a third Support.
接著，進行第一捏拌步驟115，藉以使用捏合機來混合且捏拌第三擔體、錳金屬化合物、鐵金屬化合物、鈰金屬化合物、碳化合物與軟水，捏合機係以每分鐘400rpm至800rpm間之轉速進行1小時至4小時，較佳是以每分鐘500rpm至600rpm之轉速進行2小時至3小時，而形成第一糰料。然後，進行第二捏拌步驟116，藉以使用捏合機來混合且捏拌無機纖維、黏土與第一糰料以形成第二糰料，捏合機係以每分鐘400rpm至800rpm間之轉速進行1小時至4小時，較佳是每分鐘500rpm至600rpm之轉速進行2小時至3小時。然後，將無機纖維撕裂成絲，並與黏***同混紡於第二糰料中，以增強第二糰料隨後輥軋於不鏽鋼網上之強度。Next, a first kneading step 115 is performed, whereby a kneader is used to mix and knead the third support, the manganese metal compound, the iron metal compound, the base metal compound, the carbon compound and the soft water, and the kneading machine is 400 rpm to 800 rpm per minute. The number of revolutions is from 1 hour to 4 hours, preferably from 500 rpm to 600 rpm per minute for 2 hours to 3 hours to form a first mass. Then, a second kneading step 116 is performed, whereby a kneader is used to mix and knead the inorganic fibers, the clay and the first bolus to form a second bolus, and the kneading machine is operated at a rotation speed of 400 rpm to 800 rpm per minute for 1 hour. The rotation speed is from 2 hours to 3 hours, preferably from 500 rpm to 600 rpm, to 4 hours. The inorganic fibers are then torn into filaments and co-blended with the clay in a second mass to enhance the strength of the second mass which is subsequently rolled onto the stainless steel mesh.
接著，進行輥軋步驟117，藉以使用金屬輥輪來將第二糰料輥軋於網狀金屬上，以形成第一基材。然後，進行 成型步驟118，以利用壓力塑造第一基材，來形成第二基材，其中第二基材之外型係例如Z型。然後，進行第二乾燥步驟119，以於150℃下進行1小時，來乾燥第二基材，而形成第三基材。接著，在一氣氛(例如：空氣氣氛；較佳係氮氣氛)中，於300℃至500℃的溫度(較佳係介於300℃至350℃)下進行第二煅燒步驟120經3小時，，以煅燒第二基材，而形成選擇性的觸媒還原反應板狀觸媒。Next, a rolling step 117 is performed whereby a second roll is rolled onto the mesh metal using a metal roll to form a first substrate. Then, proceed Forming step 118 to shape the first substrate with pressure to form a second substrate, wherein the second substrate is of a Z-type. Then, a second drying step 119 is performed to dry the second substrate at 150 ° C for 1 hour to form a third substrate. Next, the second calcination step 120 is carried out for 3 hours in an atmosphere (for example, an air atmosphere; preferably a nitrogen atmosphere) at a temperature of 300 ° C to 500 ° C (preferably, 300 ° C to 350 ° C). To calcine the second substrate to form a selective catalyst reduction reaction plate-like catalyst.
以下比較低溫SCR板狀觸媒與習知高溫SCR觸媒之物性，以及SCR觸媒之脫硝效率。The following compares the physical properties of the low temperature SCR plate-like catalyst with the conventional high temperature SCR catalyst and the denitration efficiency of the SCR catalyst.
請參照第2圖，其繪示本發明實施例之低溫SCR板狀觸媒與習知高溫SCR觸媒之物性比對表，其係利用比表面積分析儀(BET)，來針對所得之低溫SCR板狀觸媒進行物性之分析。如第2圖所示，本發明之實施例之低溫SCR板狀觸媒的比表面積為80平方公尺/公克(m2 /g)，孔徑體積為0.19立方公分/公克(cm3 /g)，孔徑大小為8.75奈米(nm)。相對地，習知高溫SCR觸媒比表面積為50至65 m2 /g，孔徑體積為0.15至0.21 cm3 /g，孔徑大小為8.98至11.88奈米。本發明之實施例之低溫SCR板狀觸媒的比表面積係高於習知高溫SCR觸媒，可增加脫硝作用面積，有助於加速脫硝反應之進行，而本發明之實施例之低溫SCR板狀觸媒的孔徑體積與孔徑大小與習知高溫SCR觸媒物性相似。Please refer to FIG. 2 , which illustrates a physical property comparison table of a low temperature SCR plate catalyst and a conventional high temperature SCR catalyst according to an embodiment of the present invention, which uses a specific surface area analyzer (BET) to obtain a low temperature SCR obtained. The plate-like catalyst was analyzed for physical properties. As shown in Fig. 2, the low-temperature SCR plate-like catalyst of the embodiment of the present invention has a specific surface area of 80 m 2 /g (m 2 /g) and a pore volume of 0.19 cm 3 /cm (cm 3 /g). The pore size is 8.75 nanometers (nm). In contrast, conventional high temperature SCR catalysts have a specific surface area of 50 to 65 m 2 /g, a pore volume of 0.15 to 0.21 cm 3 /g, and a pore size of 8.98 to 11.88 nm. The low-temperature SCR plate-like catalyst of the embodiment of the present invention has a higher specific surface area than the conventional high-temperature SCR catalyst, which can increase the denitration area and help accelerate the denitration reaction, and the low temperature of the embodiment of the present invention The pore volume and pore size of the SCR plate-like catalyst are similar to those of conventional high temperature SCR catalysts.
請參照第3圖，其繪示發明實施例之低溫SCR板狀觸媒與習知高溫SCR觸媒之脫硝效率比對表，其係利用氮氧化物反應前後的濃度變化，來獲得觸媒之脫硝效率。此測試法是先將本發明之選擇性的觸媒還原反應板狀觸媒，由
板狀刮下並篩選出粒徑12至16網目的顆粒狀觸媒，再與0.4公分之玻璃球混合均勻後裝載於長50公分、直徑1.5公分之石英玻璃反應管內。然後，由此石英玻璃反應管的入口處，將氮氧化物、氨氣與空氣混合物通入至石英玻璃反應管，並由此石英玻璃反應管出口處，以化學激光分析儀(Chemiluminescence)分析反應後之氮氧化物濃度，並與反應前之氮氧化物濃度比對，其脫硝效率計算公式如下：
由第3圖可知，本發明實施例之低溫SCR板狀觸媒的反應溫度為150℃，脫硝效率為80%至86%之間。相對地，習知高溫SCR觸媒的反應溫度為300℃，脫硝效率為80%至90%。本發明之實施例之低溫SCR板狀觸媒於低溫(150℃)脫硝效率即可達80%至86%之間，其脫硝效率與習知的高溫SCR觸媒於高溫300℃脫硝效率相當，故可減少將置於製程末端之脫硝反應器的溫度提升至300至400℃所需耗費的燃料費用。As can be seen from Fig. 3, the reaction temperature of the low-temperature SCR plate-like catalyst of the embodiment of the present invention is 150 ° C, and the denitration efficiency is between 80% and 86%. In contrast, the conventional high temperature SCR catalyst has a reaction temperature of 300 ° C and a denitration efficiency of 80% to 90%. The low temperature SCR plate-like catalyst of the embodiment of the invention can be denitrated at a low temperature (150 ° C) efficiency of between 80% and 86%, and the denitration efficiency and the conventional high temperature SCR catalyst are denitrated at a high temperature of 300 ° C. The efficiency is equivalent, so the cost of fuel required to raise the temperature of the denitration reactor placed at the end of the process to 300 to 400 °C can be reduced.
因此，由上述本發明較佳實施例可知，應用本發明之優點為：步驟簡單、比表面積高而具較多反應面積、並可於低溫150℃作用，不必加熱至高溫300℃方可作用，因而降低成本。Therefore, it can be seen from the above preferred embodiments of the present invention that the advantages of the application of the present invention are: simple steps, high specific surface area, more reaction area, and can be operated at a low temperature of 150 ° C, without being heated to a high temperature of 300 ° C, Thus reducing costs.
雖然本發明已以實施方式揭露如上，然其並非用以限定本發明，在本發明所屬技術領域中任何具有通常知識者，在不脫離本發明之精神和範圍內，當可作各種之更動 與潤飾，因此本發明之保護範圍當視後附之申請專利範圍所界定者為準。The present invention has been disclosed in the above embodiments, and is not intended to limit the present invention. Any one of ordinary skill in the art to which the present invention pertains can make various changes without departing from the spirit and scope of the invention. And the scope of the present invention is defined by the scope of the appended claims.
112‧‧‧球磨步驟112‧‧‧Ball grinding steps
113‧‧‧第一乾燥步驟113‧‧‧First drying step
114‧‧‧第一煅燒步驟114‧‧‧First calcination step
115‧‧‧第一捏拌步驟115‧‧‧First kneading step
116‧‧‧第二捏拌步驟116‧‧‧Second kneading step
117‧‧‧輥軋步驟117‧‧‧Rolling step
118‧‧‧成型步驟118‧‧‧Molding steps
119‧‧‧第二乾燥步驟119‧‧‧Second drying step
120‧‧‧第二煅燒步驟120‧‧‧second calcination step
為讓本發明之上述和其他目的、特徵、優點與實施例能更明顯易懂，所附圖式之說明如下： 第1圖係繪示根據本發明一實施例之選擇性的觸媒還原反應板狀觸媒之製造方法的流程圖。The above and other objects, features, advantages and embodiments of the present invention will become more apparent and understood. 1 is a flow chart showing a method of manufacturing a selective catalyst reduction reaction plate-like catalyst according to an embodiment of the present invention.
第2圖係繪示根據本發明一實施例與習知高溫SCR觸媒之物性比對表。2 is a table showing the physical properties of a conventional high temperature SCR catalyst according to an embodiment of the present invention.
第3圖係繪示根據本發明一實施例與習知高溫SCR觸媒之脫硝效率比對表。Figure 3 is a graph showing the denitration efficiency comparison table of a conventional high temperature SCR catalyst according to an embodiment of the present invention.
112‧‧‧球磨步驟112‧‧‧Ball grinding steps
113‧‧‧第一乾燥步驟113‧‧‧First drying step
114‧‧‧第一煅燒步驟114‧‧‧First calcination step
115‧‧‧第一捏拌步驟115‧‧‧First kneading step
116‧‧‧第二捏拌步驟116‧‧‧Second kneading step
117‧‧‧輥軋步驟117‧‧‧Rolling step
118‧‧‧成型步驟118‧‧‧Molding steps
119‧‧‧第二乾燥步驟119‧‧‧Second drying step
120‧‧‧第二煅燒步驟120‧‧‧second calcination step
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| TWI615198B (en) * | 2015-12-16 | 2018-02-21 | 國立交通大學 | Method of preparing selective catalytic reduction composite catalyst |
| TWI789962B (en) * | 2021-05-05 | 2023-01-11 | 傑智環境科技股份有限公司 | Green house gas purification system |
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| JPH03154637A (en) * | 1989-11-10 | 1991-07-02 | Babcock Hitachi Kk | Flat catalyst |
| CN101011659A (en) * | 2007-02-07 | 2007-08-08 | 南开大学 | Catalyst for SCR denitration in boiler low-temperature fume and preparation method thereof |
| CN102389807A (en) * | 2011-09-09 | 2012-03-28 | 杭州凯大催化金属材料有限公司 | Multi-metal supported catalyst, and preparation and application thereof |
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| CZ343796A3 (en) * | 1994-05-30 | 1997-04-16 | Siemens Ag | Catalyst for reducing amount of nitrogen oxides in flowing media and process for preparing thereof |
| US8148295B2 (en) * | 2009-02-16 | 2012-04-03 | Millennium Inorganic Chemicals, Inc. | Catalyst promoters in vanadium-free mobile catalyst |
| CN102166514B (en) * | 2010-02-26 | 2013-07-03 | 中国大唐集团科技工程有限公司 | Preparation method of structured flue gas denitration catalyst, prepared catalyst and application of catalyst |
| CN102527373A (en) * | 2010-12-29 | 2012-07-04 | 中国科学院广州能源研究所 | Selective catalytic reduction (SCR) denitration catalyst with TiO2 as carrier |
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| JPH03154637A (en) * | 1989-11-10 | 1991-07-02 | Babcock Hitachi Kk | Flat catalyst |
| CN101011659A (en) * | 2007-02-07 | 2007-08-08 | 南开大学 | Catalyst for SCR denitration in boiler low-temperature fume and preparation method thereof |
| CN102389807A (en) * | 2011-09-09 | 2012-03-28 | 杭州凯大催化金属材料有限公司 | Multi-metal supported catalyst, and preparation and application thereof |
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| TWI615198B (en) * | 2015-12-16 | 2018-02-21 | 國立交通大學 | Method of preparing selective catalytic reduction composite catalyst |
| TWI789962B (en) * | 2021-05-05 | 2023-01-11 | 傑智環境科技股份有限公司 | Green house gas purification system |
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