TWI613150B - Method of manufacturing rice husk activated carbon and method of reactivating the same - Google Patents
Method of manufacturing rice husk activated carbon and method of reactivating the same Download PDFInfo
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Abstract
本發明係有關於一種製備稻殼活性碳的方法，係利用農業廢棄物之稻殼經pH值調整、活化、碳化與清洗後製成稻殼活性碳，利用製得的稻殼活性碳表面吸附廢水中的污染分子，以減低廢水中的污染物質，減輕廢水排放對環境的污染。本發明也進一步涉及將表面吸附廢水中的污染分子之稻殼活性碳進行再生活化的方法，使稻殼活性碳能重複再生使用，提高稻殼活性碳的利用率。 The invention relates to a method for preparing activated carbon of rice husk, which is prepared by using rice husk of agricultural waste by pH adjustment, activation, carbonization and washing to prepare rice husk activated carbon, and utilizing the obtained surface adsorption of rice hull activated carbon. Pollution molecules in wastewater to reduce pollutants in wastewater and reduce environmental pollution caused by wastewater discharge. The invention further relates to a method for regenerating and activating rice husk activated carbon of a contaminating molecule in a surface adsorption wastewater, so that the rice husk activated carbon can be repeatedly used for regeneration, thereby improving the utilization ratio of rice hull activated carbon.
Description
本發明係有關於一種製備稻殼活性碳及其再生活化方法。 The present invention relates to a method for preparing rice hull activated carbon and its regeneration activation.
台灣紡織產業在八、九零年代具有舉足輕重的地位，主要以生產耐隆絲、聚酯絲、人造纖維為主，在此期間染整、毛巾、織布等行業，在台灣各地蓬勃發展，具有完整的產業鏈。近年來，台灣紡織產業受到自由貿易衝擊，加上台灣又屬非天然纖維的生產國家，迫使台灣紡織產業開始轉型，而著重於紡織品的多樣化、特殊機能性、亮眼的外觀…等；其中，染整產業是紡織產業重要環節，因此，期望透過改善染整加工以提升紡織品的各項性能，便成為染整產業的使命，同時為了滿足流行多變的布料市場，成份複雜、特殊的染料不斷被開發出來利用在染色上，正因如此，整個染整產業製程走向複雜化，並且高度利用化學藥劑。 Taiwan's textile industry played a pivotal role in the 1980s and 1990s. It mainly produces Rylon, polyester yarn and man-made fiber. During this period, dyeing and finishing, towels, weaving and other industries flourished throughout Taiwan. Complete industrial chain. In recent years, Taiwan’s textile industry has been hit by free trade, and Taiwan’s non-natural fiber production countries have forced Taiwan’s textile industry to begin to transform, focusing on the diversification of textiles, special functions, and eye-catching appearances. The dyeing and finishing industry is an important part of the textile industry. Therefore, it is expected to improve the performance of textiles by improving dyeing and finishing to become the mission of the dyeing and finishing industry. At the same time, in order to meet the ever-changing fabric market, complex and special dyes are required. It has been continuously developed and used in dyeing, which is why the entire dyeing and finishing industry process is complicated and highly utilized chemical agents.
而由於染整流程環繞著水資源的消耗，包括退漿、精練、漂白、絲光、染色都需要水扮演質傳熱傳介質、洗滌流體等角色，根據民國81年經濟部水資局的統計資料，染整產業的用水量占整體紡織工業用水量的50%，所使用的水源以自來水(64%)及地下水(29%)為主，其餘為回收水(7%)，由此可以觀察出染整業對於水資源的倚賴；因此，染整產業產生大量的有機負荷高、色度深、溫度高、pH不穩定等特性複雜的廢水將無可避免，然而這些廢水必須予以妥善處理，否則將嚴重污染河川與土壤。 Because the dyeing and finishing process surrounds the consumption of water resources, including desizing, scouring, bleaching, mercerizing, and dyeing, water needs to play the role of heat transfer medium and washing fluid. According to the statistics of the Water Resources Bureau of the Ministry of Economic Affairs in 1981 The water consumption of the dyeing and finishing industry accounts for 50% of the total water consumption of the textile industry. The water source used is mainly tap water (64%) and groundwater (29%), and the rest is recycled water (7%), which can be observed. The dyeing and finishing industry relies on water resources; therefore, the dyeing and finishing industry produces a large number of wastewaters with complex organic loads, deep chroma, high temperature, and unstable pH, which are inevitable. However, these wastewaters must be properly disposed of. It will seriously pollute rivers and soil.
染整廠最常用的染料種類為酸性染料、反應性染料及分散性染料，其中，分散性染料的用量最多；因台灣多半生產非天然纖維，如聚酯纖維、聚醯胺纖維，此類人造纖維必須透過分散性染料疏水的特性，並添加助劑加以染色。染整助劑在染整工業中的應用是十分廣泛的，目前已進入到染整加工的各個角落，其主要用途有：潤滑、潤濕、滲透、促染、乳化、分散、助溶增溶、發泡、消泡、清洗、勻染、柔軟、固色、防水、防污、阻燃、抗靜電、防蛀、防霉等。酸性與反應性染料本身易溶於水，但兩者與纖維鍵結方式不同，酸性染料是將其官能基團與纖維之NH2以離子鍵結合；反應性染料則將官能基團與纖維之OH-、NH2 -及SH-等以共價鍵結合。 The most commonly used dyes in dyeing and finishing plants are acid dyes, reactive dyes and disperse dyes. Among them, disperse dyes are used most; because most of Taiwan produces non-natural fibers, such as polyester fibers and polyamide fibers, such artificial The fibers must pass through the hydrophobic nature of the disperse dye and be dyed with the addition of additives. The application of dyeing and finishing auxiliaries in the dyeing and finishing industry is very extensive. At present, it has entered various corners of dyeing and finishing. Its main purposes are: lubrication, wetting, penetration, dyeing, emulsification, dispersion, solubilization and solubilization. , foaming, defoaming, cleaning, leveling, soft, fixing, waterproof, anti-fouling, flame retardant, anti-static, anti-mite, anti-mildew, etc. The acidic and reactive dyes themselves are readily soluble in water, but the two are different from the way the fibers are bonded. The acid dyes bind their functional groups to the NH 2 of the fibers by ionic bonding; the reactive dyes bind the functional groups to the fibers. OH -, NH 2 - and SH - other covalently bound.
由於染整加工技術所使用的藥劑非常廣泛，比重、溶解性、生物可分解性、酸鹼值皆不盡相同，導致廢水特性不穩定。因此處理染整廢水時並不適合單獨採用一種處理技術，需設計多種處理單 元以搭配進行。常見的處理染整廢水的技術，包括生物污泥法、吸附法、化學氧化法、混凝沉澱法、加壓浮除法、光觸媒法等。 Because the dyeing and finishing technology uses a wide range of chemicals, the specific gravity, solubility, biodegradability, and pH value are all different, resulting in unstable wastewater characteristics. Therefore, it is not suitable to use a single treatment technology when dealing with dyeing and finishing wastewater. It is necessary to design a variety of treatment orders. Yuan is to match. Common techniques for treating dyeing and finishing wastewater include biological sludge method, adsorption method, chemical oxidation method, coagulation sedimentation method, pressure floating method, photocatalytic method, and the like.
活性污泥法所使用的設備主要包含四個基本單元，即曝氣槽、最終沉澱池、迴流污泥設備與排泥設備，其處理的基本原理是利用好氧性微生物去除廢水中的有機物質，即微生物以廢水中的有機物質為營養源，並藉由曝氣取得代謝所需的氧氣，而得以生長繁殖。 操作方式是將最初沉澱池處理後的有機廢水流入曝氣槽，使廢水與曝氣槽/生物反應槽內的好氧性微生物群之污泥充分混合接觸，曝氣槽的出流水再經最終沉澱池進行固液分離，沉澱分離後之污泥，大部分則連續回流至曝氣槽，以控制槽中的活性污泥濃度；另一部分污泥則成為廢氣污泥(waste sludge)排出，另行處理，液體部分則進入下一個處理單源或逕行放流。 The equipment used in the activated sludge process mainly consists of four basic units, namely aeration tank, final sedimentation tank, return sludge equipment and sludge discharge equipment. The basic principle of treatment is to use aerobic microorganisms to remove organic matter from wastewater. That is, the microorganisms grow and reproduce by taking the organic matter in the wastewater as a nutrient source and obtaining the oxygen required for metabolism by aeration. The operation mode is that the organic wastewater treated by the initial sedimentation tank flows into the aeration tank, and the wastewater is thoroughly mixed with the sludge of the aerobic microbial group in the aeration tank/biological reaction tank, and the outflow water of the aeration tank is finally passed. The sedimentation tank is subjected to solid-liquid separation, and the sludge after sedimentation and separation is continuously refluxed to the aeration tank to control the concentration of activated sludge in the tank; the other part of the sludge is discharged as waste sludge. After processing, the liquid portion enters the next processing single source or radial discharge.
吸附法是利用吸附劑的吸附選擇性以吸附去除廢水中有機物的方法，對於染整廢水而言，不同的吸附劑對染料的吸附選擇性亦不同，其作用機制主要包括物理吸附、化學吸附和離子交換等作用。常用的吸附劑有碳質吸附劑(活性碳、煤焦碳、活化煤泥碳、乙炔黑焦化輪胎、煤渣)，無機吸附劑(高嶺土、黏土、漂土、矽膠、矽藻土、礬土、膨潤土、白土、矽酸鋁、矽酸鎂、麥飯石、蒙脫石、斜發沸石、氧化鎂)，有機吸附劑(鋸木屑、玉米棒、毛髮、離子交換纖維、纖維素吸附劑、水解木質素)及複合吸附劑。其中活性碳 一直是染整廢水的良好吸附劑，但只吸附廢水中的水溶性染料，不能吸附懸浮固體和不溶性染料，且價格昂貴，再生困難。 The adsorption method utilizes the adsorption selectivity of the adsorbent to adsorb and remove the organic matter in the wastewater. For the dyeing and finishing wastewater, different adsorbents have different adsorption selectivity to the dye, and the mechanism of action mainly includes physical adsorption, chemical adsorption and Ion exchange and other effects. Commonly used adsorbents are carbonaceous adsorbents (activated carbon, coal coke, activated slime carbon, acetylene black coking tires, cinder), inorganic adsorbents (kaolin, clay, puddle, tannin, diatomaceous earth, bauxite, Bentonite, clay, aluminum citrate, magnesium citrate, medical stone, montmorillonite, clinoptilolite, magnesium oxide), organic adsorbent (sawdust, corn cob, hair, ion exchange fiber, cellulose adsorbent, hydrolyzed wood) Quality) and composite adsorbents. Activated carbon It has always been a good adsorbent for dyeing and finishing wastewater, but it only adsorbs water-soluble dyes in wastewater, can not adsorb suspended solids and insoluble dyes, and is expensive and difficult to regenerate.
化學氧化法具有反應快速、不受污染物濃度限制之優點，成為近年來產業界常用之處理方法。此方法主要利用各種類型的氧化劑，將染整廢水中的污染物質氧化分解，最理想的狀態是將染料中的有機化合物全部分解為水與二氧化碳。有研究使用臭氧之氧化力進行殺菌、脫臭、脫色等處理，或使用氯氣之氧化力進行殺菌及染料去除，雖然具有效果但設備費用高，使氯氣氧化僅對單偶氮染料及蒽醌型染料陰離子有效，對直接性染料與水溶性較低的分散型染料之氧化效果不佳，故許多研究者針對氧化法加以改良，使其在染料廢水的處理上具有高效率的去除效果。較新技術如Fenton氧化法、電化學氧化法及光化學氧化法等，對於廢水色度之去除也有顯著之效果。 The chemical oxidation method has the advantages of rapid reaction and no restriction on the concentration of pollutants, and has become a commonly used treatment method in the industry in recent years. This method mainly utilizes various types of oxidants to oxidize and decompose pollutants in the dyeing and finishing wastewater. The most ideal state is to decompose all the organic compounds in the dye into water and carbon dioxide. Studies have used ozone oxidation to carry out sterilization, deodorization, decolorization, etc., or use oxidizing power of chlorine gas for sterilization and dye removal. Although effective, the equipment costs are high, so that chlorine gas is oxidized only to monoazo dyes and quinones. The dye anion is effective, and the oxidation effect of the direct dye and the water-soluble dispersion dye is not good. Therefore, many researchers have improved the oxidation method to have a highly efficient removal effect on the dye wastewater treatment. Newer technologies such as Fenton oxidation, electrochemical oxidation, and photochemical oxidation also have significant effects on the removal of chromaticity of wastewater.
光化學催化氧化是一種改良光化學氧化法之方法，以間接光解反應的UV/H2O2系統為例，H2O2受到紫外光解能夠而形成氫氧自由基(OH‧)，氫氧自由基是一種強氧化劑，其氧化力僅次於氟，可與有機物迅速起反應，分解後之產物易被微生物所消化分解。另外UV/H2O2處理染整廢水時，紫外光會被染整廢水中的色度所影響，水中色度值越高影響光穿透率越低，以致降低光分解之處理效率。 Photochemical catalytic oxidation is a method for improving photochemical oxidation. Taking the UV/H 2 O 2 system of indirect photolysis as an example, H 2 O 2 can be activated by ultraviolet photolysis to form hydroxyl radicals (OH‧). Hydroxyl radical is a strong oxidant, its oxidation power is second only to fluorine, and it can react rapidly with organic matter. The decomposed product is easily digested and decomposed by microorganisms. In addition, when UV/H 2 O 2 is used to treat the dyeing and finishing wastewater, the ultraviolet light is affected by the chromaticity in the dyeing and finishing wastewater. The higher the chromaticity value in the water, the lower the light transmittance, so that the treatment efficiency of photolysis is reduced.
混凝沉澱法主要藉加入化學混凝藥品(多元氯化鋁、硫酸鋁、氧化鐵及硫酸亞鐵)，使散佈在水溶液高穩定性的帶電粒子，最終凝結成 較大顆粒，以吸附或共沉方式可以去除廢水中的SS、膠質、油酯及色度。但此法僅能去除不可溶染料(分散性染料、硫化染料及水溶性染料中分子較大的部分直接染料等)。而高水溶性染料(酸性染料、金屬鉻合染料及直接染料的一部分等)與水之親和力大於與無機混凝劑之金屬間之作用，不容易形成膠體，因此去除效果有限。此外，混凝過程中產生大量污泥，而增加許多處理成本，為其存在最大的問題之一。 The coagulation and sedimentation method mainly uses chemical coagulation drugs (polyaluminum chloride, aluminum sulfate, iron oxide and ferrous sulfate) to disperse charged particles with high stability in aqueous solution, and finally condense into Larger particles can remove SS, colloid, oil ester and color in wastewater by adsorption or co-precipitation. However, this method can only remove insoluble dyes (dispersive dyes, sulfur dyes, and direct dyes with larger molecules in water-soluble dyes). The high water-soluble dye (acid dye, metal chrome dye, and a part of the direct dye) has a greater affinity with water than the metal of the inorganic coagulant, and it is not easy to form a colloid, so the removal effect is limited. In addition, a large amount of sludge is generated during the coagulation process, and many processing costs are added, which is one of the biggest problems.
加壓浮除法，係令沉降槽採槽體側邊中央進水，由切線方向流入進水整流箱，因進水整流箱具有整流功能，能將進流水均勻導入池中以利浮上或沉澱。將空氣以加壓方式溶入廢水中，促使廢水中污染物質絮凝成細小膠羽，使含有過飽和空氣之廢水經減壓流入浮除槽內，由於驟然減壓，過飽和空氣析出，形成多量的微細氣泡與廢水中的懸浮顆粒結合而共同上浮，進而達成浮上分離之目的，產生重力固液分離作用。上澄液由周邊出水渠之溢流堰板溢流，經出水渠集中後由出水管流出，而沉澱污泥則藉刮泥機刮泥鈑刮泥作用將其集中於池底污泥坑中，然後由排泥管排出，至於池面所產生之浮渣，則藉浮渣擋板及撇渣板之作用，將其刮到浮渣漏斗中，再由浮渣管排出。 The pressurized floating method is to make the water in the center of the side of the troughing tank of the settling tank flow into the inflow rectifier box from the tangential direction. Because the inlet water rectification tank has a rectifying function, the influent water can be uniformly introduced into the pool to facilitate floating or sedimentation. The air is dissolved into the waste water by pressure, and the pollutants in the waste water are flocculated into fine rubber feathers, so that the waste water containing supersaturated air flows into the floating tank through the decompression, and the supersaturated air is precipitated due to sudden decompression, forming a large amount of fine particles. The bubbles are combined with the suspended particles in the wastewater to float together, thereby achieving the purpose of floating separation, and generating gravity solid-liquid separation. The upper liquid overflows from the overflow raft of the surrounding water outlet, and is discharged from the outlet pipe after the discharge channel is concentrated. The sediment sludge is concentrated in the bottom sludge tank by scraping mud and scraping mud. Then, it is discharged by the drain pipe. As for the dross generated by the pool surface, it is scraped into the scum funnel by the action of the dross baffle and the slag plate, and then discharged by the scum pipe.
又，根據實際走訪染整廠，目前國內常見的染整廢水處理程序大致有兩個主要方式。其一採用化學混凝法加入破壞廢水中膠體顆粒的穩定性的混凝劑，再透過沉澱或浮除方式除去水中懸浮微粒(suspended sediment,SS)；其二採用生物活性污泥法，透過生物細 胞氧化分解其吸附凝聚的水中溶解染料，藉此去除廢水的真色色度(American Dye Manufactures Institute,MDMI)與化學需氧量(Chemical Oxygen Demand,COD)。而傳統活性污泥法並不利於生化性質不高的染整廢水，且其效率受限於不具彈性的活性污泥池容積，較不易配合水量與性質不穩定的染整廢水。若擴建活性污泥池容積則受限土地與設備成本的問題，因此必須另設處理單元改善染整廢水生化特性。 In addition, according to the actual visit to the dyeing and finishing plant, there are roughly two main ways in the domestic dyeing and finishing wastewater treatment procedures. The first one adopts chemical coagulation method to add a coagulant which destroys the stability of colloidal particles in the wastewater, and then removes suspended sediment (SS) by sedimentation or floating method; the second uses biological activated sludge method to pass through the organism. fine The oxidative decomposition of the lysed water dissolves the dye, thereby removing the true color chromaticity (American Dye Manufactures Institute, MDMI) and chemical oxygen demand (COD). The traditional activated sludge process is not conducive to the dyeing and finishing wastewater with low biochemical properties, and its efficiency is limited by the volume of the activated sludge tank which is not elastic, and it is difficult to mix the dyeing and finishing wastewater with unstable water quantity and nature. If the expansion of the activated sludge tank volume limits the cost of land and equipment, a separate treatment unit must be provided to improve the biochemical characteristics of the dyeing and finishing wastewater.
現今雖然有各種廢水處理技術能處理染整廢水，例如電漿前處理、超過濾膜、生物可分解染料技術，但是在台灣染整業尚未轉型完整的情況下，染整業者需負荷國際高攀的油價、土地成本及原物料上漲與自由貿易下的削價競爭等因素，大部分業者無法再同時負荷高價位的廢水整治設備更新。依據最新民國99年環保署修訂放流水排放標準，目前仍有多數染整廠無法達到排放標準，導致染整業者傾向採用自然水體稀釋排放等遊走法律邊緣方式處理。對台灣的環境與經濟造成極大的窘境，因此針對台灣染整業現狀以環境工程角度分析，急需符合染者業者當前符合處理成本且簡易可行的廢水整治技術。 Although various wastewater treatment technologies can deal with dyeing and finishing wastewater, such as plasma pretreatment, ultrafiltration membrane, and biodegradable dye technology, in the case that the dyeing and finishing industry in Taiwan has not yet been transformed, the dyeing and finishing industry needs to load the international high climb. Oil prices, land costs and rising raw materials and competition for price cuts under free trade, most of the industry can no longer load high-priced wastewater remediation equipment. According to the latest revised effluent discharge standards of the Environmental Protection Agency in the Republic of China in 1999, there are still many dyeing and finishing plants that are unable to meet the discharge standards, resulting in the dyeing and finishing industry tending to use natural water dilution and other legal methods. It has caused great dilemma to Taiwan's environment and economy. Therefore, in view of the environmental engineering perspective of the status of Taiwan's dyeing and finishing industry, it is urgent to meet the current wastewater treatment technology that meets the processing cost and is simple and feasible.
本發明人即是鑑於上述之情形，同時利用活性碳一直是良好污染物吸附劑的既有知識，研發出一種符合處理成本且簡易可行的 廢水整治技術，提供一種製備稻殼活性碳的方法，而此即為本發明之主要目的。 The present inventors have developed a method that is consistent with the processing cost and is simple and feasible in view of the above situation, while utilizing the existing knowledge that activated carbon has always been a good pollutant adsorbent. The wastewater remediation technology provides a method for preparing rice husk activated carbon, which is the main purpose of the present invention.
而本發明的另一個主要目的，係提供一種製備稻殼活性碳的再生活化方法，主要係透過再生活化的技術，去除稻殼活性碳表面的污染附著物，使稻殼活性碳能再生以達重複使用之目的。 Another main object of the present invention is to provide a method for regenerating and activating activated carbon of rice hulls, which mainly removes contaminated attachments on the surface of activated carbon of rice husks through regeneration and activation technology, and enables regeneration of rice hull activated carbon. For the purpose of reuse.
上述本發明之主要目的，是由以下之具體技術手段所達成：一種製備稻殼活性碳的方法，其包括以下步驟：步驟一：前處理，將稻殼浸泡於0.09~0.1N的氫氧化鈉水溶液2小時進行鹼洗，之後除去氫氧化鈉水溶液，接著以清水浸洗後將稻殼置入乾燥烘箱內以去除水分；步驟二：活化，將經前處理後的稻殼及0.87~1.07M的氫氧化鉀水溶液置於密閉容器中，令密閉容器在76.5~93.5℃下浸泡3小時，之後將稻殼置入乾燥烘箱內以去除水分；步驟三：碳化，將經活化後的稻殼於720~880℃下悶燒4小時；以及步驟四：後處理，在76.5~93.5℃的恆溫水浴槽中將冷卻後的碳化稻殼浸泡於去離子水中。 The above main object of the present invention is achieved by the following specific technical means: a method for preparing rice husk activated carbon, comprising the following steps: Step 1: Pretreatment, immersing rice husk in 0.09~0.1N sodium hydroxide The aqueous solution is subjected to alkali washing for 2 hours, and then the aqueous sodium hydroxide solution is removed, and then the rice husk is placed in a drying oven to remove water after being immersed in water; Step 2: activation, pre-treated rice husk and 0.87-1.07M The potassium hydroxide aqueous solution is placed in a closed container, and the closed container is immersed at 76.5~93.5 ° C for 3 hours, and then the rice husk is placed in a drying oven to remove water; Step 3: carbonization, the activated rice husk is Squeeze for 4 hours at 720~880°C; and Step 4: Post-treatment, soak the cooled carbonized rice husk in deionized water in a constant temperature water bath at 76.5~93.5 °C.
如上所述之製備稻殼活性碳的方法，其中，在步驟一中，最佳係以0.1N氫氧化鈉水溶液浸泡稻殼。 The method for preparing rice husk activated carbon as described above, wherein, in the first step, the rice hull is soaked in a 0.1 N aqueous sodium hydroxide solution.
如上所述之製備稻殼活性碳的方法，其中，在步驟二中，最 佳係以1M氫氧化鉀水溶液於密閉容器中浸泡稻殼。 a method for preparing rice husk activated carbon as described above, wherein, in step two, the most The best is to soak the rice husk in a closed container with a 1 M aqueous solution of potassium hydroxide.
如上所述之製備稻殼活性碳的方法，其中，在步驟二中，最佳係以85℃於密閉容器中浸泡稻殼。 The method for preparing rice husk activated carbon as described above, wherein, in the second step, the rice hull is soaked in a closed container at 85 ° C.
如上所述之製備稻殼活性碳的方法，其中，在步驟三中，最佳係以800℃下悶燒活化後的稻殼。 The method for preparing rice husk activated carbon as described above, wherein, in the third step, the husk after activation is smoldered at 800 ° C.
如上所述之製備稻殼活性碳的方法，其中，在步驟四中，所述恆溫水浴槽最佳溫度為85℃。 The method for preparing rice husk activated carbon as described above, wherein, in the fourth step, the optimum temperature of the constant temperature water bath is 85 °C.
上述本發明之另一主要目的，是由以下之具體技術手段所達成：一種製備稻殼活性碳的再生活化方法，其包括下列步驟：步驟一：將吸附飽和的稻殼活性碳置於濃度為0.75~1.25mM EDTA-Fe水溶液及濃度為5~6%雙氧水中浸泡，同時輔以UV光源照射3小時；步驟二：將經步驟一之稻殼活性碳以去離子水清洗，即可得再生活化之稻殼活性碳。 Another main object of the present invention is achieved by the following specific technical means: a regeneration activation method for preparing rice husk activated carbon, which comprises the following steps: Step 1: concentrating the saturated rice husk activated carbon at a concentration It is immersed in a 0.75~1.25mM EDTA-Fe aqueous solution and a concentration of 5~6% in hydrogen peroxide, and is irradiated with UV light source for 3 hours. Step 2: After step one, the rice husk activated carbon is washed with deionized water. Regenerated and activated rice hull activated carbon.
如上所述之製備稻殼活性碳的再生活化方法，其中，在步驟一中，所述EDTA-Fe水溶液的濃度以1mM最佳。 A method for regenerating and activating rice husk activated carbon as described above, wherein, in the first step, the concentration of the aqueous EDTA-Fe solution is preferably 1 mM.
如上所述之製備稻殼活性碳的再生活化方法，其中，在步驟一中，所述雙氧水濃度以5.55%最佳。 The method for regenerating activated rice straw activated carbon as described above, wherein in the first step, the hydrogen peroxide concentration is optimal at 5.55%.
本發明之優點：本發明主要是採用農業廢棄物之稻殼作為活性碳的材料，除成本低廉外，其主要由纖維、半纖維與矽組成，故材料組成中的無機成分頗高，較能承受以氧化劑破壞吸附質時受到破壞，可達到重複使用目的；另外，稻殼經過簡易的前置作業與熱處理，便能使稻殼材料達到多孔洞、高比表面積，而能有效幫助提升污染分子的吸附量，達到良好的廢水處理效果。 The invention has the advantages that the invention mainly adopts the rice husk of agricultural waste as the material of activated carbon, and is mainly composed of fiber, semi-fiber and strontium, in addition to low cost, so the inorganic component in the material composition is quite high, and is relatively high in energy. It can be destroyed by destroying the adsorbate with oxidant, which can achieve the purpose of repeated use. In addition, the simple operation of the rice husk and heat treatment can make the rice husk material reach porous hole and high specific surface area, which can effectively improve the pollution molecules. The amount of adsorption reaches a good wastewater treatment effect.
第一圖：本發明之製備稻殼活性碳的方法的流程圖 First Figure: Flowchart of the method for preparing rice husk activated carbon of the present invention
第二圖：本發明製備稻殼活性碳的再生活化方法的流程圖 Second Figure: Flowchart of the regeneration activation method for preparing rice husk activated carbon by the present invention
第三圖：酸鹼前處理與碳化溫度之效應圖 Figure 3: Effect diagram of acid-base pretreatment and carbonization temperature
第四圖：添加活化劑與後處理之效應圖 Figure 4: Effect diagram of adding activator and post-treatment
第五圖：稻殼活性碳K-1之氮氣吸脫附曲線圖 Figure 5: Nitrogen absorption and desorption curve of rice husk activated carbon K-1
第六圖：碳化時間效應圖 Figure 6: Carbonization time effect diagram
第七圖：稻殼活性碳K-1對RB-5等溫吸附曲線圖 Figure 7: Isotherm adsorption curve of rice hull activated carbon K-1 on RB-5
第八圖：市售活性碳對RB-5等溫吸附曲線圖 Figure 8: Isothermal adsorption curve of commercially available activated carbon to RB-5
第九圖：稻殼活性碳K-1孔徑分布圖 Ninth map: pore size distribution map of rice husk activated carbon K-1
第十圖：稻殼活性碳K-1對RB-5吸附動力曲線圖 Figure 10: Adsorption dynamics curve of rice husk activated carbon K-1 on RB-5
第十一圖：市售活性碳對RB-5吸附動力曲線圖 Figure 11: Commercially available activated carbon versus RB-5 adsorption dynamics
第十二圖：稻殼活性碳K-1對AR-114吸附動力曲線圖 Twelfth map: Adsorption dynamics curve of rice husk activated carbon K-1 on AR-114
第十三圖：影響氧化再生活性碳之因子曲線圖 Figure 13: Curve of factors affecting oxidative regeneration of activated carbon
第十四圖：再生氧化劑量變化之影響曲線圖 Figure 14: Effect of the change in the amount of regenerated oxidant
第十五圖：再生EDTA-Fe量變化之影響曲線圖 Figure 15: Effect diagram of the change in the amount of EDTA-Fe
第十六圖：累積流量與出流濃度圖 Figure 16: Cumulative flow and outflow concentration map
第十七圖：稻殼活性碳吸附水中甲醛效應圖 Figure 17: The effect of formaldehyde on the adsorption of rice husk activated carbon
第十八圖：稻殼活性碳吸附水中乙醇效應圖 Figure 18: Effect of rice hull activated carbon adsorption on ethanol
第十九圖：稻殼活性碳吸附水中甲醇效應圖 Figure 19: Effect of rice husk activated carbon adsorption on methanol
為令本發明所運用之技術內容、發明目的及其達成之功效有更完整且清楚的揭露，茲於下詳細說明之，並請一併參閱所揭之圖式及圖號：需要說明的是，在本說明書中，使用“~”表示的數值範圍是指包含“~”前後所記載的數值作為下限值和上限值的範圍。 For a more complete and clear disclosure of the technical content, the purpose of the invention and the effects thereof achieved by the present invention, the following is a detailed description, and the drawings and drawings are also referred to. In the present specification, the numerical range expressed by "~" means a range including the numerical values described before and after "~" as the lower limit value and the upper limit value.
請參看第一圖，係揭示本發明之製備稻殼活性碳的方法的流程圖。 Referring to the first figure, a flow chart of a method for preparing rice husk activated carbon of the present invention is disclosed.
本發明製備稻殼活性碳的方法的處理步驟為：步驟一：前處理，將稻殼浸泡於0.09~0.1N的氫氧化鈉水溶液2小時進行鹼洗，之後除去氫氧化鈉水溶液，接著以清水浸洗 後將稻殼置入乾燥烘箱內以去除水分；步驟二：活化，將經前處理後的稻殼及0.87~1.07M的氫氧化鉀水溶液置於密閉容器中，令密閉容器在76.5~93.5℃下浸泡3小時，之後將稻殼置入乾燥烘箱內以去除水分；步驟三：碳化，將經活化後的稻殼於720~880℃下悶燒4小時；以及步驟四：後處理，在76.5~93.5℃的恆溫水浴槽中將冷卻後的碳化稻殼浸泡於去離子水中。 The method for preparing the rice husk activated carbon of the present invention comprises the following steps: Step 1: Pretreatment, immersing the rice husk in a sodium hydroxide aqueous solution of 0.09-0.1 N for 2 hours for alkali washing, then removing the aqueous sodium hydroxide solution, followed by clear water. Dipping After the rice husk is placed in a drying oven to remove water; Step 2: activation, the pretreated rice husk and 0.87~1.07M potassium hydroxide aqueous solution are placed in a closed container, so that the closed container is at 76.5~93.5 °C Soak for 3 hours, then put the rice husk into the drying oven to remove water; Step 3: Carbonize, smolder the activated rice husk at 720~880 °C for 4 hours; and Step 4: Post-treatment, at 76.5 The cooled carbonized rice husk was immersed in deionized water in a constant temperature water bath of ~93.5 °C.
<配製目標污染物> <Preparation of target pollutants>
首先，配製AR-114、RB-5及DB-EX-SF溶液為目標污染物，做為模擬實廠染整廢水之目標污染物。 First, the AR-114, RB-5 and DB-EX-SF solutions were prepared as target pollutants, which were used as the target pollutants for the simulated dyeing and finishing wastewater.
<<配製2000mg/L目標污染物儲備液>> <<Preparation of 2000mg/L target pollutant stock solution>>
秤量Acid Red-114(以下簡稱AR-114)、Reactive Black-5(以下簡稱RB-5)及Disperse Black-EX-SF(以下簡稱DB-EX-SF)各2g溶於1000mL去離子水中，即成為200mg/L目標污染物儲備液，用於活性碳吸附之飽和處理。 2g of Acid Red-114 (hereinafter referred to as AR-114), Reactive Black-5 (hereinafter referred to as RB-5) and Disperse Black-EX-SF (hereinafter referred to as DB-EX-SF) are dissolved in 1000mL of deionized water, ie It becomes a 200mg/L target pollutant stock solution for saturation treatment of activated carbon adsorption.
<<配製500mg/L目標污染物儲備液>> <<Preparation of 500mg/L target pollutant stock solution>>
秤量AR-114、RB-5及DB-EX-SF各0.5g溶於1000mL去離子水中，即成為500mg/L目標污染物儲備液，用於等溫吸附實驗與低濃度污染水配製。 Weigh 0.5g of AR-114, RB-5 and DB-EX-SF in 1000mL deionized water to become 500mg/L target pollutant stock solution for isothermal adsorption experiment and low concentration polluted water.
<<配製125mg/L目標污染物儲備液>> <<Preparation of 125mg/L target pollutant stock solution>>
將AR-114、RB-5及DB-EX-SF之500mg/L儲備液，各取25mL以去離子水定量至100mL，即為125mg/L目標污染物儲備液，用於動力吸附實驗與校正標準品的配製。 500mg/L stock solution of AR-114, RB-5 and DB-EX-SF, each taking 25mL to deionized water to 100mL, which is 125mg/L target pollutant stock solution for dynamic adsorption experiment and correction Preparation of standard products.
<<配製內標準液>> <<Preparation of standard solution>>
選擇的內標準品為Disperse Red，配製1,00mg/L之內標準液。秤取0.01g之Disperse Red，以去離子水定量至100mL，即成為100mg/L之內標準液。 The internal standard selected was Disperse Red, and a standard solution of 1,00 mg/L was prepared. Weigh 0.01 g of Disperse Red and quantify it to 100 mL with deionized water to become a standard solution of 100 mg/L.
<不同酸鹼進行稻殼前處理與碳化溫度之試驗> <Experiment of rice husk pretreatment and carbonization temperature with different acid and alkali>
為了測試染料分子的吸附行為，是否傾向於酸性或鹼性含氧官能基，因此在稻殼前處理階段，使用不同酸鹼處理，同時以不同的碳化溫度，觀察稻殼活性碳對染料吸附能力之影響。在此使用的酸鹼溶液主要有氫氧化鈉、硫酸、硝酸，分別配製成0.1N 1500ml的水溶液，詳細試驗步驟如下：1、以2L燒杯盛裝120g乾淨稻殼，並依表1的試驗設計來選用浸泡溶液；2、浸泡全程2小時均使用玻璃棒攪拌，完畢後使用粗孔徑篩網將液體去除；3、再浸濕的稻殼裝置在白鐵圓桶，並置入高溫爐進行4小時的碳化；4、最後以去離子水浸洗3次做為後處理。 In order to test the adsorption behavior of dye molecules, whether acidic or basic oxygen-containing functional groups are preferred, so in the pre-treatment stage of rice husk, different acid-base treatments are used, and at different carbonization temperatures, the adsorption capacity of rice-shell activated carbon for dyes is observed. The impact. The acid-base solution used here mainly consists of sodium hydroxide, sulfuric acid and nitric acid, and is prepared into 0.1N 1500ml aqueous solution respectively. The detailed test procedure is as follows: 1. 120g clean rice husk is packed in 2L beaker, and according to the test design of Table 1. The soaking solution is selected; 2. The glass rod is stirred for 2 hours in the whole process of immersion, and the liquid is removed by using a coarse-diameter screen after completion; 3. The re-wet rice husk is placed in a white iron drum and placed in a high temperature furnace for 4 hours. Carbonization; 4, finally dipped in deionized water 3 times for post-treatment.
將依上述步驟所取得的6種不同稻殼活性碳分別對初始濃度125mg/L的AR-114與RB-5進行批次吸附試驗，批次吸附試驗的步驟如下： The six different rice husk activated carbons obtained in the above steps were subjected to batch adsorption test on AR-114 and RB-5 with an initial concentration of 125 mg/L, respectively. The steps of the batch adsorption test are as follows:
1、添加稻殼活性碳：將50ml錐形瓶放置在精密天秤後歸零，並加入需要量稻殼活性碳。 1. Add rice husk activated carbon: Place the 50ml Erlenmeyer flask on the precision scale and return to zero, and add the required amount of rice husk activated carbon.
2、添加染料水溶液：一律添加20ml的染料水溶液，並視試驗選擇不同初始濃度。 2. Adding dye aqueous solution: 20 ml of dye aqueous solution is added uniformly, and different initial concentrations are selected according to the test.
3、添加磷酸緩衝液：加入1ml的1.36M磷酸緩衝溶液，確保其在中性pH下發生吸附反應。 3. Add phosphate buffer: Add 1 ml of 1.36 M phosphate buffer solution to ensure adsorption reaction at neutral pH.
實驗結果如第三圖(請一併參看表2)，空白組之RB-5的去除率，可能來自檢量線在稀釋時產生的誤差，因為理論上不該會有RB-5在水中自解。而空白組之AR-114有約六成的去除率，原因推測來自AR-114具有一解離度(pka=7.4)，而在實驗設計上為了使pH控制在中性範圍，添加了緩衝強度足夠的緩衝溶液(pH=7.1)。 當溶液其溶質pka剛好為溶液pH時，該溶質會有50%是解離態、50%為非解離態。這說明了很可能是溶液pH造成之影響。 The experimental results are shown in the third figure (please refer to Table 2). The removal rate of RB-5 in the blank group may come from the error caused by the calibration line during dilution, because theoretically there should be no RB-5 in the water. solution. The AR-114 of the blank group has a removal rate of about 60%. The reason is that the AR-114 has a dissociation degree (pka=7.4). In the experimental design, in order to control the pH in the neutral range, the buffer strength is sufficient. Buffer solution (pH = 7.1). When the solution solute pka is just the solution pH, the solute will be 50% dissociated and 50% non-dissociated. This shows that it is likely to be the effect of the pH of the solution.
從溫度與酸鹼數據觀察較能顯著比較之RB-5的去除率，發 現碳化溫度為500℃與800℃時，無論是氫氧化鈉或硝酸，800℃的效率比500℃還要有效。這代表了稻殼在800℃進行碳化會比在500℃進行碳化所產生之稻殼活性碳具有較佳RB-5的去除率，這是因為在800℃下產生的鹼性官能基較多，染料可能較傾向吸附於吸附質表面的鹼性含氧官能基。 From the temperature and acid-base data observation, the removal rate of RB-5 can be significantly compared. When the carbonization temperature is 500 ° C and 800 ° C, whether it is sodium hydroxide or nitric acid, the efficiency of 800 ° C is more effective than 500 ° C. This represents that the carbonization of rice husk at 800 ° C has a better removal rate of RB-5 than the rice husk activated carbon produced by carbonization at 500 ° C, because more basic functional groups are produced at 800 ° C. The dye may be more prone to adsorb to the basic oxygen-containing functional groups on the surface of the adsorbate.
<添加活化劑與後處理之試驗> <Addition of activator and post-treatment test>
為了使稻殼碳之比表面積增加，加入氫氧化鉀做為活化劑，並嘗試用鹽酸或去離子水去除碳化時留在孔隙內部的鉀鹽。詳細步驟如下：1、以2L燒杯盛裝120g乾淨稻殼，浸泡至0.1N 1500ml的NaOH水溶液2小時，其全程用玻璃棒攪拌；2、將浸濕稻殼用粗篩網去除液體，再以清水浸洗3次後置入乾燥烘箱內持續8小時以去除水分； 3、取105g之前處理後稻殼，置入1L能密閉的血清瓶，加入0.965L之0.97M KOH，並置入85℃之恆溫水浴槽3小時，之後置入乾燥烘箱內持續8小時以去除水分；4、取添加活化劑過後的稻殼10g，以坩鍋承載並用光面朝內的鋁箔進行包附並戳上小孔。將該坩鍋置入白鐵圓桶，再放入高溫爐內進行4小時的碳化；5、從高溫爐取出後，在85℃的恆溫水浴槽中分別浸泡於去離子水和0.1N HCl進行後處理。其中，以去離子水進行後處理之稻殼活性碳記為K-1，以HCl進行後處理之稻殼活性碳記為K-2。 In order to increase the specific surface area of the rice hull carbon, potassium hydroxide was added as an activator, and an attempt was made to remove the potassium salt remaining inside the pores during carbonization with hydrochloric acid or deionized water. The detailed steps are as follows: 1. Fill 120g of clean rice husk in a 2L beaker, soak in 0.1N 1500ml NaOH aqueous solution for 2 hours, and stir it with glass rod throughout the whole process; 2. Remove the liquid from the wet rice husk with coarse sieve, then use water Dipping 3 times and placing in a drying oven for 8 hours to remove moisture; 3. Take 105g of the previously treated rice husk, place 1L of the sealed serum bottle, add 0.965L of 0.97M KOH, and place it in a constant temperature water bath at 85 °C for 3 hours, then put it into a drying oven for 8 hours to remove Moisture; 4, take 10g of rice husk after the addition of activator, carry it in a crucible and wrap it with a light-faced aluminum foil and poke a small hole. The crucible is placed in a white iron drum and placed in a high temperature furnace for carbonization for 4 hours. 5. After being taken out from the high temperature furnace, it is immersed in deionized water and 0.1 N HCl in a constant temperature water bath at 85 ° C. deal with. Among them, the rice husk activated carbon which was post-treated with deionized water was recorded as K-1, and the rice husk activated carbon which was post-treated with HCl was recorded as K-2.
將兩種不同後處理之稻殼碳進行各種染料的吸附實驗與比表面積的分析，觀察其影響結果(請一並參看表3)。 Two different post-treatment rice husk carbons were subjected to adsorption experiments and specific surface area analysis of various dyes to observe the effect (see Table 3).
從第四圖可以發現，有添加活化劑所製成的稻殼活性碳對RB-5去除率明顯的從11%增加至99.4%，RB-5去除效率的明顯增加，可以歸因於稻殼活性碳比表面積的大幅增加。未添加活化劑的稻殼活性碳的表面積為227.52m2/g，添加活化劑後，稻殼活性碳的表面積上升為1124m2/g。添加活化劑稻殼K-1比表積大幅上升之外，觀察第五圖，其氮氣吸脫附曲線近似Tpye I型的吸附曲線，意謂著稻殼活性碳具有許多的微孔。但從脫附曲線可以發現出現了凝滯現象，該現象是具有中孔的特徵。因此推斷該稻殼活性碳存在中孔與許多細小微孔。另外無添加活化劑之稻殼活性碳 S-2與稻殼活性碳K-1比較，發現稻殼活性碳K-1對AR-114與DB-EX-SF似乎沒有顯著的影響，這暗示稻殼活性碳K-1對RB-5可能存在針對性。 From the fourth figure, it can be found that the removal rate of RB-5 from the rice husk activated carbon prepared by adding activator increased from 11% to 99.4%, and the RB-5 removal efficiency increased significantly, which can be attributed to rice husk. The specific surface area of activated carbon is greatly increased. The surface area of rice husk activated carbon to which no activator was added was 227.52 m 2 /g, and the surface area of rice husk activated carbon was increased to 1124 m 2 /g after the addition of the activator. In addition to the fact that the activator rice husk K-1 has a large increase in the surface area, the fifth graph is observed, and the nitrogen adsorption-desorption curve approximates the adsorption curve of the Tpye type I, meaning that the rice husk activated carbon has many micropores. However, it can be seen from the desorption curve that stagnation occurs, which is characterized by mesopores. Therefore, it is inferred that the rice husk activated carbon has mesopores and many fine micropores. In addition, rice straw activated carbon S-2 without added activator was compared with rice husk activated carbon K-1, and it was found that rice husk activated carbon K-1 did not seem to have a significant effect on AR-114 and DB-EX-SF, suggesting that rice Shell activated carbon K-1 may be targeted to RB-5.
觀察分別以鹽酸與去離子水做後處理的兩種稻殼碳對三種染料的吸附量，RB-5、AR-114差異不大，並無特殊針對性。唯DB-EX-SF在以鹽酸後處理時略增了3.3%。 The adsorption capacity of the three kinds of dyes by the two kinds of rice husk carbon treated with hydrochloric acid and deionized water were observed. The difference between RB-5 and AR-114 was not significant and there was no specificity. Only DB-EX-SF increased slightly by 3.3% after treatment with hydrochloric acid.
<碳化時間對染料去除率之試驗> <Test of carbonization time on dye removal rate>
此試驗係欲得知較合適的碳化時間，因此重複上述<添加活化劑與後處理>之試驗步驟一至三，並改變步驟四的碳化時間，分別為2、3、4hr，且在步驟五時延遲了後處理，在此試驗中使用稻殼活性碳K-2。又，因稻殼活性碳K-2對AR-114與DB-EX-SF似乎沒有顯著的影響，因此在本試驗中將RB-5做為指標污染物，且只對RB-5進行批次吸附試驗，RB-5初始濃度為125mg/L，批次吸附試驗步驟同於<不同酸鹼進行稻殼前處理與碳化溫度之試驗>中所述之批次吸附試驗。從第六圖可以發現，隨著碳化的時間的增加，對RB-5之去除率同時增加(請一併參看表4)。 This test is to know the appropriate carbonization time, so repeat the above test steps 1 to 3 of adding activator and post-treatment, and change the carbonization time of step 4, respectively, 2, 3, 4 hr, and at step 5 Post-treatment was delayed and rice hull activated carbon K-2 was used in this test. Moreover, since rice husk activated carbon K-2 does not seem to have a significant effect on AR-114 and DB-EX-SF, RB-5 was used as an indicator pollutant in this test, and only batches were applied to RB-5. In the adsorption test, the initial concentration of RB-5 was 125 mg/L, and the batch adsorption test procedure was the same as the batch adsorption test described in <Test of rice husk pretreatment and carbonization temperature with different acid and alkali>. From the sixth graph, it can be found that as the carbonization time increases, the removal rate of RB-5 increases at the same time (please refer to Table 4 together).
表4 碳化時間對染料去除率之影響
<自製稻殼活性碳與市售活性碳之等溫吸附與吸附動力試驗> <Isothermal adsorption and adsorption kinetics test of homemade rice husk activated carbon and commercially available activated carbon>
為了比較自製稻殼活性碳K-1與市售活性碳間對RB-5吸附量與吸附行為之差異，觀察劑量比在遞增的情形下，於24小時後吸附量的變化。採用初始濃度為500mg/L 20ml之RB-5進行批次吸附試驗(步驟同於<不同酸鹼進行稻殼前處理與碳化溫度之試驗>中所述之批次吸附試驗)，其劑量配置如表5所示。 In order to compare the difference between the adsorption amount and the adsorption behavior of RB-5 between the self-made rice husk activated carbon K-1 and the commercially available activated carbon, the change of the adsorption amount after 24 hours was observed under the increasing dose ratio. The batch adsorption test was carried out using RB-5 with an initial concentration of 500 mg/L 20 ml (the same as the batch adsorption test described in <Test of rice husk pretreatment and carbonization temperature with different acid and alkali>), and the dosage configuration is as follows. Table 5 shows.
而自製稻殼活性碳K-1與市售活性碳之吸附速率的比較，必須要觀察時間遞增下對RB-5吸附量之變化。採用初始濃度為125mg/L 20m之RB-5進行批次吸附試驗(步驟同於<不同酸鹼進行稻殼前處理與碳化溫度之試驗>中所述之批次吸附試驗)，其設計如表6所示。 The comparison of the adsorption rate of homemade rice husk activated carbon K-1 with commercially available activated carbon must observe the change of RB-5 adsorption amount under increasing time. The batch adsorption test was carried out using RB-5 with an initial concentration of 125 mg/L 20 m (the same as the batch adsorption test described in <Test of rice husk pretreatment and carbonization temperature with different acid and alkali>), and its design is as follows. 6 is shown.
表6 採用初始濃度為125mg/L 20m之RB-5進行批次吸附試驗的時間遞增配置
稻殼活性碳K-1同時進行對AR-114的等溫吸附試驗，將表7所示的克數稻殼活性碳K-1置入50ml錐形瓶，加入20ml之500mg/L AR-114，最後加入1ml磷酸緩衝液，吸附時間為24小時。 Rice hull activated carbon K-1 was simultaneously subjected to isothermal adsorption test on AR-114. The grams of rice husk activated carbon K-1 shown in Table 7 were placed in a 50 ml Erlenmeyer flask, and 20 ml of 500 mg/L AR-114 was added. Finally, 1 ml of phosphate buffer was added, and the adsorption time was 24 hours.
從第七、八圖(請同時參看表8、表9)可知，在劑量比較低的前三點數據(20、50、100)，由於單位吸附劑被分配到的染料較低，無論稻殼活性碳K-1或市售活性碳幾乎是將染料溶液吸附至澄清，因此在低劑量比之前三點數據會呈線性關係，但之後隨著劑量比的增加，吸附量增加的情形趨於平緩。差異較為明顯的地方在於，稻殼活性碳K-1至劑量比為2000mg/g仍然有上升之趨勢，而市售活性碳在劑量比500至2000mg/g時就出現平緩的趨勢，另外市售活性碳比表面積為1085m2/g。將兩等溫吸附實驗數據代入模式的回歸可以得到如表10的數據，從RSS觀察，自製稻殼活性碳K-1與市售活性碳在這三種模式回歸中，皆以Langmuir isotherm有最小RSS值，意謂最符合。尤其可以注意自製稻殼活性碳K-1在Langmuir isotherm回歸中，有著更小的RSS值，從第 七圖也能觀察到實驗數據點與Langmuir Curve相當接近。這揭示了自製稻殼活性碳K-1對RB-5的吸附行為為單層吸附。從第九圖自製稻殼活性碳K-1孔徑分布圖觀察，雖然無法得知微孔數量，但明顯的存在許多2.4~2.9nm的中孔。回顧RB-5的結構，可以發現其可能發生最大的尺寸為29.9Å，因此假設當自製稻殼活性碳K-1對RB-5進行吸附反應時，這些中孔可以順暢的容納接近1~2個RB-5分子，恰巧維持在單層吸附。 From the seventh and eighth figures (please also refer to Table 8, Table 9), the first three points of the relatively low dose (20, 50, 100), because the unit of adsorbent is assigned a lower dye, regardless of the rice husk Activated carbon K-1 or commercially available activated carbon almost adsorbs the dye solution to clarification, so there is a linear relationship between the three points before the low dose ratio, but then as the dose ratio increases, the increase in the adsorption amount tends to be gentle. . The obvious difference is that the rice husk activated carbon K-1 to dose ratio of 2000mg/g still has an increasing trend, while the commercially available activated carbon has a gentle trend at a dose ratio of 500 to 2000mg/g, and is also commercially available. The activated carbon specific surface area was 1085 m 2 /g. Substituting the two isothermal adsorption experimental data into the regression of the model can obtain the data as shown in Table 10. From the observation of RSS, the self-made rice husk activated carbon K-1 and the commercially available activated carbon in these three modes of regression, all have the minimum RSS with Langmuir isotherm The value means the best match. In particular, it can be noted that the self-made rice hull activated carbon K-1 has a smaller RSS value in the Langmuir isotherm regression. From the seventh figure, it can be observed that the experimental data points are quite close to the Langmuir Curve. This reveals that the adsorption behavior of self-made rice husk activated carbon K-1 on RB-5 is monolayer adsorption. From the ninth figure, the pore size distribution map of the rice husk activated carbon K-1 was observed. Although the number of micropores could not be known, there were many mesopores of 2.4 to 2.9 nm. Looking back at the structure of RB-5, it can be found that the largest size is 29.9 Å, so it is assumed that when the self-made rice hull activated carbon K-1 adsorbs RB-5, these mesopores can be smoothly accommodated close to 1~2. One RB-5 molecule, which happens to be maintained in a single layer of adsorption.
表10 稻殼活性碳K-1與市售活性碳對RB-5等溫吸附模式回歸數據
從第十、十一圖可以觀察到稻殼活性碳K-1與市售活性碳對RB-5吸附動力的數據點相當接近，在十分鐘內去除率達一半，在五十分鐘以後將染料水溶液吸附至澄清。但從動力模式的回歸可以得到表11。從RSS值的觀察，可以發現無論稻殼活性碳K-1或市售活性碳，皆較為符合假二階模式。比較其中的k值，可以發現稻殼活性碳K-1對RB-5的吸附速率略快速於市售活性碳。若稻殼活性碳具有快速的吸附能力，同時意謂較能進行後續的吸附管柱貫穿曲線試驗。 It can be observed from the tenth and eleventh figures that the rice husk activated carbon K-1 and the commercially available activated carbon are quite close to the data point of RB-5 adsorption kinetics, and the removal rate is half in ten minutes, and the dye is taken after fifty minutes. The aqueous solution is adsorbed to clarification. But from the regression of the dynamic model, we can get Table 11. From the observation of RSS values, it can be found that both rice straw activated carbon K-1 and commercially available activated carbon are more consistent with the pseudo second-order mode. Comparing the k values, it can be found that the adsorption rate of RB-5 by rice husk activated carbon K-1 is slightly faster than that of commercially available activated carbon. If the rice husk activated carbon has a rapid adsorption capacity, it also means that the subsequent adsorption column penetration curve test can be carried out.
另外Intra-particle diffusion模式貌似不適用於稻殼活性碳K-1或市售活性碳對RB-5吸附速率情形。這或許能說明兩種活性碳皆存在尺寸大於2.9nm的過渡孔。 In addition, the Intra-particle diffusion mode appears to be unsuitable for the case of ABA-5 adsorption rate of rice husk activated carbon K-1 or commercially available activated carbon. This may indicate that both activated carbons have transition pores larger than 2.9 nm in size.
從第十二圖得知，稻殼活性碳K-1對AR-114的吸附現象，吸附量幾乎與劑量比形成線性關係。將吸附量對劑量比進行等溫 吸附模式的回歸，參數如表7。回歸結果可以發現，實驗數據最適於Freundlich isotherm，其n=1.05說明完全接近線性的吸附關係。 From the twelfth figure, it is known that the adsorption of rice husk activated carbon K-1 on AR-114 has a linear relationship with the dose ratio. Isotope is dosed to the dose ratio The regression of the adsorption mode, the parameters are shown in Table 7. The regression results show that the experimental data is most suitable for Freundlich isotherm, and its n=1.05 indicates a nearly linear adsorption relationship.
請參看第二圖所示，為揭示本發明製備稻殼活性碳的再生活化方法的流程圖。 Please refer to the second figure for the purpose of revealing a flow chart of the regeneration activation method for preparing rice husk activated carbon of the present invention.
本發明製備稻殼活性碳的再生活化方法的處理步驟為：步驟一：將吸附飽和的稻殼活性碳置於濃度為0.75~1.25mM EDTA-Fe水溶液及濃度為5~6%雙氧水中浸泡，同時輔以UV光源照射3小時；步驟二：將經步驟一之稻殼活性碳以去離子水清洗，即可得再生活化之稻殼活性碳。 The treatment step of the regeneration activation method for preparing rice husk activated carbon of the invention is as follows: Step 1: immersing the saturated rice husk activated carbon in an aqueous solution of EDTA-Fe with a concentration of 0.75 to 1.25 mM and soaking in a concentration of 5 to 6% hydrogen peroxide. At the same time, it is irradiated with UV light source for 3 hours; Step 2: The stepped rice husk activated carbon is washed with deionized water to obtain regenerated activated rice hull activated carbon.
<配製催化劑> <Preparation of catalyst>
<<配製EDTA溶液>> <<Preparation of EDTA solution>>
取1.264g之EDTA溶於20mL之緩衝液(buffer)，濃度為216mM。 1.264 g of EDTA was dissolved in 20 mL of a buffer at a concentration of 216 mM.
<<配製Fe2+溶液>> <<Preparation of Fe 2+ solution>>
取1.2g之FeSO4．7H2O溶於20mL之去離子水，濃度為216mM。 Take 1.2g of FeSO 4 . 7H 2 O was dissolved in 20 mL of deionized water at a concentration of 216 mM.
<<配製EDTA-Fe溶液>> <<Preparation of EDTA-Fe solution>>
將EDTA溶液與Fe2+溶液以1：1的量混合，即為EDTA-Fe溶液108mM。 The EDTA solution was mixed with the Fe 2+ solution in an amount of 1:1, which was 108 mM of the EDTA-Fe solution.
<<配製1.37M之磷酸鹽緩衝液(buffer)>> <<Preparation of 1.37M phosphate buffer (buffer)>>
為了維持穩定之中性pH值。取59.64g之Na2HPO4及114g之NaH2PO4溶解在1公升的去離子水中，並以NaOH調整pH值至7。 In order to maintain a stable neutral pH. 59.64 g of Na 2 HPO 4 and 114 g of NaH 2 PO 4 were dissolved in 1 liter of deionized water and the pH was adjusted to 7 with NaOH.
<確定氧化再生條件因子> <determination of oxidation regeneration condition factor>
在本試驗中，主要係測試雙氧水在EDTA-Fe、UV light搭配組合下，飽和之稻殼活性碳K-2之再生效率，其試驗操作步驟如下：1、將稻殼活性碳K-2置入錐形瓶，加入20ml之2000mg/L RB-5，再加入1ml磷酸緩衝液，並置入迴轉式振盪培養箱24小時；2、以篩網(0.053mm)過濾樣本，再以500ml去離子水沖洗，並用500ml錐形瓶承接流洗液；3、待稻殼活性碳K-2在瓶內沉澱後，抽取大部分上層液再轉移置底層稻殼活性碳K-2至標有20ml刻度之50ml錐型瓶，待稻殼活性碳K-2在瓶內沉澱後，抽取20ml刻度以上液體；4、加入1ml磷酸鹽緩衝液、EDTA-Fe(催化劑)、雙氧水(氧化劑)，其添加劑量如表12所示，添加完畢後放入UV Box內並開啟紫外光照射；5、經氧化3小時後，重複上述步驟二與三(改刻度15ml)，將再生之稻殼活性碳K-2採取，待稻殼活性碳K-2沉澱在瓶內後，抽取15ml刻度以上液體，再加入1ml磷酸鹽緩衝液與5ml之500mg/L RB-5進行吸附反應； 6、吸附反應4小時後分析殘餘濃度。 In this test, the regeneration efficiency of saturated rice hull activated carbon K-2 under the combination of EDTA-Fe and UV light was tested. The test procedure was as follows: 1. The rice hull activated carbon K-2 was set. Into the Erlenmeyer flask, add 20ml of 2000mg/L RB-5, add 1ml phosphate buffer, and put into the rotary shaker incubator for 24 hours; 2. Filter the sample with sieve (0.053mm), then deionize with 500ml Rinse with water and use a 500ml conical flask to carry the flow washing liquid; 3. After the rice husk activated carbon K-2 is precipitated in the bottle, extract most of the upper liquid and transfer the bottom rice hull activated carbon K-2 to the mark with 20ml mark. 50ml conical flask, after the rice hull activated carbon K-2 is precipitated in the bottle, extract 20ml of the above liquid; 4, add 1ml phosphate buffer, EDTA-Fe (catalyst), hydrogen peroxide (oxidant), the amount of additive As shown in Table 12, after the addition, put it into the UV Box and turn on the ultraviolet light; 5. After oxidizing for 3 hours, repeat the above steps 2 and 3 (change the scale 15ml) to regenerate the rice hull activated carbon K-2. Take, after the rice hull activated carbon K-2 is precipitated in the bottle, extract 15ml above the liquid, then add 1ml phosphate The adsorption reaction was carried out with 5 ml of 500 mg/L RB-5; 6. The residual concentration was analyzed after 4 hours of adsorption reaction.
從第十三圖(請同時參看表13)可以知道，單純使用雙氧水氧化之再生去除率達41.5%，配合EDTA-Fe時增加了12.9%，配合UV光時增加了17.2%。當雙氧水同時配合兩者時，再生後對RB-5之去出率增加了32.7%。其增加的去除率幾乎等於雙氧水分別配合EDTA-Fe與UV光的去除率總和(30.1%)。此說明了EDTA-Fe與UV光兩者是獨立的正相關。 From the thirteenth chart (please also refer to Table 13), it can be known that the regeneration removal rate of the hydrogen peroxide alone is 41.5%, the increase of 12.9% with EDTA-Fe, and the increase of 17.2% with UV light. When hydrogen peroxide was combined at the same time, the rate of RB-5 removal after regeneration increased by 32.7%. The increased removal rate is almost equal to the sum of the removal rates of EDTA-Fe and UV light (30.1%). This illustrates that EDTA-Fe and UV light are independent positive correlations.
<確立最佳再生條件劑量> <establish the optimal regeneration condition dose>
以化學再生活性碳是一種氧化還原反應，同樣劑量通常是關 鍵的因素。本試驗將透過再生活性碳對RB-5之去除率，來找尋最佳的氧化劑、催化劑用量。試驗的步驟細節與<確定氧化再生條件因子>所述相同，唯添加劑量做為變數。找尋最佳氧化劑用量的試驗中，首先添加固定濃度的EDTA-Fe，接續分別添加不同濃度的H2O2，最後瓶內的各物質濃度應同於表9。找尋最佳氧化劑用量的試驗中，首先添加固定濃度的H2O2，接續分別添加不同濃度的EDTA-Fe，最後瓶內的各物質濃度應同於表14。 Regeneration of activated carbon by chemical is a redox reaction, and the same dose is usually a key factor. This test will find the best oxidant and catalyst dosage by regenerating activated carbon to the removal rate of RB-5. The details of the steps of the test are the same as those described in <Determining the Oxidation Regeneration Condition Factor>, and only the amount of the additive is used as a variable. In the test for the optimum amount of oxidant, first add a fixed concentration of EDTA-Fe, and then add different concentrations of H 2 O 2 respectively . Finally, the concentration of each substance in the bottle should be the same as in Table 9. In the test for the optimum amount of oxidant, first add a fixed concentration of H 2 O 2 , and then add different concentrations of EDTA-Fe, respectively. Finally, the concentration of each substance in the bottle should be the same as in Table 14.
以下試驗中的各樣本再生後的去除率，是先被計算過的。為了達到去除率的校正，各再生樣本的去除率與同時間進行的稻殼活性碳K-2殘餘濃度做修正。 The removal rate after regeneration of each sample in the following test was first calculated. In order to achieve the correction of the removal rate, the removal rate of each regenerated sample was corrected with the residual concentration of rice husk activated carbon K-2 performed at the same time.
其算式為
CF表示為新鮮活性碳組在吸附時間4小時的殘餘濃度，此次實驗為9.599mg/L。 C F is the residual concentration of the fresh activated carbon group at the adsorption time of 4 hours, and the experiment was 9.599 mg/L.
Ci表示為染料的初始濃度，為125mg/L。 Ci is expressed as the initial concentration of the dye and is 125 mg/L.
從第十四圖，可以觀察到隨著氧化劑(雙氧水)濃度上升，再生後對RB-5去除率也增加，並有趨於平緩的趨勢。雙氧水濃度為5.55%時，有最高的再生後吸附去除率88%。另外注意到，氧化劑量為0%再生時，仍有50%的去除率，能夠確定的是，這些去除率確實來自於吸附作用。在無氧化劑的情況下，這些再生主要來自UV光的照射。表15為雙氧水最佳再生條件劑量表。 From the fourteenth graph, it can be observed that as the concentration of the oxidant (hydrogen peroxide) increases, the removal rate of RB-5 increases after regeneration, and tends to be gentle. When the hydrogen peroxide concentration is 5.55%, the highest post-regeneration adsorption removal rate is 88%. It is also noted that when the amount of oxidant is 0%, there is still a 50% removal rate, and it can be confirmed that these removal rates are indeed derived from adsorption. In the absence of an oxidant, these regenerations are primarily from the illumination of UV light. Table 15 shows the optimal regeneration condition dosage form for hydrogen peroxide.
而在催化劑(EDTA-Fe)最佳用量時的現象，並不是隨著EDTA-Fe的劑量上升也有同樣的去除率上升情形，如第十五圖所示，EDTA-Fe濃度到從0.5mM至1mM時，再生後的吸附去除率有隨濃度顯著的上升，但是接著增加EDTA-Fe濃度至2mM、4mM時，再生後的吸附去除率反而有些微的下降。從試驗結果評估，EDTA-Fe只需要維持在約1mM的濃度即滿足最佳條件。表16為EDTA-Fe最佳再生條件劑量表。 However, in the optimum amount of catalyst (EDTA-Fe), the same removal rate does not increase with the dose increase of EDTA-Fe. As shown in Fig. 15, the concentration of EDTA-Fe is from 0.5 mM to At 1 mM, the adsorption removal rate after regeneration significantly increased with concentration, but when the concentration of EDTA-Fe was increased to 2 mM and 4 mM, the adsorption removal rate after regeneration was slightly decreased. From the test results, it was evaluated that EDTA-Fe only needs to be maintained at a concentration of about 1 mM, which satisfies the optimum conditions. Table 16 shows the EDTA-Fe optimal regeneration condition dosage form.
<吸附管柱的貫穿曲線試驗> <Permeability test of adsorption column>
首先將能通過0.053mm篩網的稻殼活性碳K-1填充於一長約為6cm、內徑為0.8cm的細管柱內，有效體積約2.8ml，總填充量為0.2g，並在管柱的兩端塞入玻璃纖維棉，吸附管柱的兩端銜接塑膠管，並用一蠕動泵將染整廠廢水進流入吸附管柱下端，吸附管柱上端則為廢水出流端。為了避免管柱阻塞而影響流量，採用的染整廢水事先透過孔徑為0.45μm的濾紙過濾，最後將流量設定約為0.15ml/min，其水力停留時間約為18.7min。 First, the rice husk activated carbon K-1 which can pass through a 0.053 mm sieve is filled in a thin column of about 6 cm in length and 0.8 cm in inner diameter, and the effective volume is about 2.8 ml, and the total filling amount is 0.2 g. The two ends of the column are inserted with glass fiber cotton, the two ends of the adsorption tube are connected with the plastic tube, and a peristaltic pump is used to feed the wastewater of the dyeing and finishing plant into the lower end of the adsorption tube column, and the upper end of the adsorption tube column is the waste water outlet end. In order to avoid the pipe blockage and affect the flow rate, the dyeing and finishing wastewater used was previously filtered through a filter paper with a pore size of 0.45 μm. Finally, the flow rate was set to about 0.15 ml/min, and the hydraulic retention time was about 18.7 min.
本試驗每30min從出流端採樣並進行分析，且以連續流的方式進行8小時的試驗。本試驗的目標污染物非單一染料，而是實際染整廢水，因此分析方法採用化學需氧量。 The test was sampled and analyzed from the outflow end every 30 minutes, and the test was carried out in a continuous flow for 8 hours. The target pollutant in this test is not a single dye, but the actual dyeing and finishing wastewater, so the analytical method uses chemical oxygen demand.
<<化學需氧量分析方法>> <<Chemical oxygen demand analysis method>>
是利用強氧化劑重鉻酸鉀來氧化水樣中的有機物。具有氧化力之Cr+6會被還原為Cr+3，水溶液的顏色也會從橘紅色逐漸轉為藍綠色，並利用Cr+6、Cr+3在吸收波長600nm、440nm顯著差異的吸光能力，透過分光光度儀取得吸光度與濃度之線性關係並繪製檢量線，進而得知該水樣之化學需氧量。分析前需事先配製重鉻酸鉀混合液，其詳細步驟如下： It is the use of strong oxidizing agent potassium dichromate to oxidize organic matter in water samples. The oxidizing power of Cr +6 will be reduced to Cr +3 , and the color of the aqueous solution will gradually change from orange to blue-green, and the absorption ability of Cr +6 and Cr +3 at the absorption wavelengths of 600 nm and 440 nm will be significantly different. The linear relationship between the absorbance and the concentration is obtained by a spectrophotometer and a calibration curve is drawn to know the chemical oxygen demand of the water sample. Before the analysis, the potassium dichromate mixture should be prepared in advance. The detailed steps are as follows:
1、重鉻酸鉀溶液配製 1. Preparation of potassium dichromate solution
量取3.0644g重鉻酸鉀置入250mL定量瓶中溶於75mL ddH2O後，加入137.5mL濃硫酸使上述溶液完全溶解後，再以ddH2O定量至250mL使其完全溶解，再裝瓶並置於陰暗處保存，暫置於陰暗處。 After taking 3.0644g of potassium dichromate into a 250mL quantitative bottle and dissolving it in 75mL of ddH 2 O, add 137.5mL of concentrated sulfuric acid to completely dissolve the above solution, then quantify it to 250mL with ddH 2 O to completely dissolve it, and then bottle it. Store in a dark place and temporarily in a dark place.
2、硫酸-硫酸銀溶液配製 2. Preparation of sulfuric acid-silver sulfate solution
量取3.75g硫酸銀放入250mL定量瓶中，添加濃硫酸定量至250mL後，以磁石攪拌或靜置1至2天使硫酸銀完全溶解，暫置於陰暗處。 Measure 3.75g of silver sulfate into a 250mL quantitative bottle, add concentrated sulfuric acid to 250mL, stir it with magnet or let stand 1 to 2 angelic silver sulfate completely dissolved, temporarily placed in the dark.
3、重鉻酸鉀混合液配製 3. Preparation of potassium dichromate mixture
量取3g硫酸汞放入500ml血清瓶中，並將上述重鉻酸鉀溶液(a)與硫酸銀溶液(b)依序倒入該血清瓶，以磁石攪拌使混和液均勻，再置於陰暗處保存。 3 g of mercury sulphate was placed in a 500 ml serum bottle, and the above potassium dichromate solution (a) and silver sulphate solution (b) were sequentially poured into the serum bottle, and the mixture was uniformly stirred by a magnet, and then placed in a dark state. Save it.
當重鉻酸鉀混合液配製完成後方能進行分析，其詳細分析方法與步驟如下：1、用1500mg/L COD標準液分別稀釋成150、300、600、900、1200、1500mg/L的COD溶液；2、量取4ml高範圍重鉻酸鉀混合液沿管壁添加至消化管，再各別加入上述COD標準液2ml，另以ddH2O代替COD標準溶液作為Blank； 3、將樣本及空白組置入COD加熱爐內進行消化，消化時溫度設定為150℃，消化時間設定為120分鐘； 4、使用DR-890檢測儀選擇Prgm 17，首先置入Blank消化管，再按下zero。再依序置入各不同濃度的COD標準夜消化管，按下Ready測定COD值(似吸光度)作校正曲線。 The analysis can be carried out after the preparation of potassium dichromate mixture is completed. The detailed analysis methods and steps are as follows: 1. Diluted into 150, 300, 600, 900, 1200, 1500 mg/L COD solution with 1500 mg/L COD standard solution. 2, measure 4ml high range potassium dichromate mixture is added to the digestive tract along the tube wall, then add 2ml of the above COD standard solution, and replace DDH 2 O with COD standard solution as Blank; 3. Sample and blank The group was placed in a COD heating furnace for digestion. The temperature was set to 150 ° C during digestion, and the digestion time was set to 120 minutes. 4. Use the DR-890 detector to select Prgm 17, first place the Blank digestive tube, and then press zero. The COD standard night digestive tubes of different concentrations were placed in sequence, and the COD value (like absorbance) was measured by Ready as a calibration curve.
試驗結果如第十六圖所示，虛線所標示的為進流染整廢水之濃度，約為1359mg/L，橫軸之累積流量為累積時間(min)×流量(ml/min)。從出流濃度可以發現，前3小時的出流濃度有逐漸上升的趨勢，而後維持在約1020mg/L。其中，稻殼活性碳累積吸附量的計算為：進流濃度與各點出流濃度差之平均乘上累積流量再除吸附劑重量。由此得知在8小時內，稻殼活性碳所吸附的總量約為494mg/g。表17為吸附管住的貫穿試驗數據。 The test results are shown in Fig. 16. The dotted line indicates the concentration of the influent dyeing and finishing wastewater, which is about 1359 mg/L, and the cumulative flow rate on the horizontal axis is the cumulative time (min) × flow rate (ml/min). From the outflow concentration, it was found that the outflow concentration in the first 3 hours gradually increased, and then maintained at about 1020 mg/L. Among them, the cumulative adsorption amount of rice straw activated carbon is calculated as: the average of the difference between the influent concentration and the outflow concentration at each point multiplied by the cumulative flow rate and then the adsorbent weight. It was thus found that the total amount of rice husk activated carbon adsorbed in about 8 hours was about 494 mg/g. Table 17 shows the penetration test data for the adsorption tube.
從試驗結果可以發現其吸附管柱的水力停留時間為18.7min顯得過於短暫，使得初始出流濃度即有貫穿的情形。若要使貫穿點明顯則需增加吸附管柱有效體積。平均出流濃度為1004.7mg/L，可以發現在此吸附管柱操作條件下，去除約26.1%的廢水濃度。 From the test results, it can be found that the hydraulic retention time of the adsorption column is 18.7 min, which is too short, so that the initial outflow concentration is penetrated. To make the penetration point obvious, increase the effective volume of the adsorption column. The average outflow concentration was 1004.7 mg/L, and it was found that about 26.1% of the wastewater concentration was removed under the operating conditions of the adsorption column.
此外，本發明之稻殼活性碳可用於吸附水中的甲醛、乙醇及甲醇；如第十七圖所示，為將本發明之稻殼活性碳製成不同粗細，且在水中加入不同份量倍數之稻殼活性碳，結果顯示，本發明之稻殼活性碳能吸附水中14%的甲醛；第十八圖所示，同樣將本發明之稻殼活性碳製成不同粗細，且在水中加入不同份量倍數之稻殼活性碳，結果顯示，本發明之稻殼活性碳能吸附水中30%的乙醇；第十九圖所示，同樣將本發明之稻殼活性碳製成不同粗細， 且在水中加入不同份量倍數之稻殼活性碳，結果顯示，本發明之稻殼活性碳能吸附水中14%的甲醇。 In addition, the rice husk activated carbon of the present invention can be used for adsorbing formaldehyde, ethanol and methanol in water; as shown in FIG. 17 , in order to make the rice husk activated carbon of the present invention into different thicknesses, and adding different amounts of multiples in water. Rice husk activated carbon, the results show that the rice husk activated carbon of the present invention can adsorb 14% of formaldehyde in water; as shown in FIG. 18, the rice husk activated carbon of the present invention is also made into different thicknesses, and different amounts are added in water. a multiple of rice hull activated carbon, the results show that the rice husk activated carbon of the present invention can adsorb 30% of ethanol in water; as shown in FIG. 19, the rice husk activated carbon of the present invention is also made into different thicknesses. Moreover, different ratios of rice husk activated carbon were added to the water, and the results showed that the rice husk activated carbon of the present invention can adsorb 14% of methanol in water.
以上所舉者僅係本發明之部份實施例，並非用以限制本發明，致依本發明之創意精神及特徵，稍加變化修飾而成者，亦應包括在本專利範圍之內。 The above is only a part of the embodiments of the present invention, and is not intended to limit the present invention. It is intended to be included in the scope of the present invention.
綜上所述，本發明實施例確能達到所預期之使用功效，又其所揭露之具體技術手段，不僅未曾見諸於同類產品中，亦未曾公開於申請前，誠已完全符合專利法之規定與要求，爰依法提出發明專利之申請，懇請惠予審查，並賜准專利，則實感德便。 In summary, the embodiments of the present invention can achieve the expected use efficiency, and the specific technical means disclosed therein have not been seen in similar products, nor have they been disclosed before the application, and have completely complied with the patent law. The regulations and requirements, the application for invention patents in accordance with the law, and the application for review, and the grant of patents, are truly sensible.
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