201215869 六、發明說明： 【發明所屬之技術領域】 本發明是有關於一種戴奥辛類測試樣品之製造方法， 特別是有關於一種利用含氯之金屬高溫製程產生的飛灰製 造戴奧辛類測試樣品之方法。 【先前技術】201215869 VI. Description of the Invention: [Technical Field] The present invention relates to a method for manufacturing a dioxin test sample, and more particularly to a method for manufacturing a dioxin test sample using fly ash produced by a high temperature process of a chlorine-containing metal . [Prior Art]
根據我國現行中小型廢棄物焚化爐戴奥辛管制及排放 標準第二條規定’戴奥辛類（dioxins)係指兩個氧原子連結 一對本％類化合物之多氣二聯苯戴奥辛（p〇lyChl〇rinated dibenzo-pflrfl-dioxins ; PCDDs ;以下簡稱戴奥辛）及多氯二 聯本咬喃（polychlorinated dibenzo-furans ; PCDFs ;以下簡 稱咬喃），為約210種不同化合物之總稱，在其他情況中， 有時亦包含共平面多氣聯苯（C〇planar biphenyls ; C〇-PCBs)。戴奥辛/呋喃之來源可包括火山爆 發、工業製程(例如煉鋼業製程）的副產物、人類活動(例如 廢棄物燃燒、汽機車排放之廢氣)等。近數十年來，由於戴 的毒性極強’不易分解…旦進人线體内，具 有致痤瘡性、致癌性及致略 、 涊為極母·的物質，而有「 不 “ I 疋、、，己之毒」之稱。 用活性二附= 含脫，除了可利 式，將戴奥辛/呋喃裂解二$之外，亦可採取觸酶催化方 脫除。為了評估觸酶對於戴^1化碳、水與鹽酸氣體而加以 要先建立觸酶活性的晋制=興辛/呋喃的脫除能力，一般需 '、'技術，藉此找出脫除能力較佳的 3 201215869 觸媒，以於製程現場進行後續戴奥辛脫除能力的測試。 一般而言，評估觸媒之戴奥辛脫除能力的方法可概分 為兩類。一種常用的方式係以戴奥辛前驅物作為典型反應 物（model compounds)，例如氣苯（chlorobenzenes)或氯紛 (chlorophenols)，以避免戴奥辛的接觸。在反應前與反應後 收集典型反應物的樣品，利用氣相層析儀（gas chromatography ; GC)分析其間濃度的變化，以計算出典型 反應物對戴奥辛的脫除能力。 另一種方式則以戴奥辛為反應物，其係購入市售戴奥 辛標準品（溶於正葵烷），再加以稀釋處理。其反應過程的 取樣、淨化與定量等步驟，可依照美國環境保護局 (environmental protection agency ; EPA)制定的 EPA 23A方法 進行。戴奥辛/呋喃(PCDDs/PCDFs)的濃度可利用高解析度 氣相層析（high resolution gas chromatography ; HRMS)儀與 高解析度質譜儀(high resolution mass spectrometer ; HRMS) 量測’計算反應前與反應後戴奥辛毒性當量（toxicity equivalency quantity ; TEQ)的變化，以計算出戴奥辛的脫 除能力。 惟上述方法仍存在以下問題。一方面，以戴奥辛前驅 物作為替代反應物時，所使用的前驅物濃度（百分比)往往 遠大於製程現場廢氣中所含的戴奥辛濃度（奈克；ng)，使 得測試的反應條件與製程現場有相當大的差異，故由此所 測得的結果只能作戴奥辛脫除能力的比較參考。 另一方面，市售戴奥辛標準品較為昂貴，且其組成大 多侷限於含4個、6個、或8個氯數目的戴奥辛/呋喃 201215869 (PCDDs/PCDFs) ’無法涵括4個氣至8個氣數目的所有戴奥 辛/吱喃（PCDDs/PCDFs)。由於以市售戴奥辛標準品作為反 應物的組成與製程現場排放廢氣中的戴奥辛組成仍有相當 大的差距，故所測得之結果仍無法真正反應出製程現場應 呈現的結果。 & 有鑑於此，亟需提供一種戴奥辛類測試樣品之製造方 法’以克服習知戴奥辛類測試樣品無法真正反應出製程現 場應呈現的結果以及市售戴奥辛標準品較為昂貴等問題。 【發明内容】 因此，本發明之一態樣是在提供一種戴奥辛類測試樣 品之製造方法，此方法係利用含氯之金屬進行高溫製程伴 隨產生的飛灰，從中萃取出組成與製程現場廢氣相似之戴 奥辛類測試樣品，以作為測試戴奥辛脫除能力的反應物， 並降低購買戴奥辛標準品之成本。 “ ，根據本發明之上述態樣，提出一種戴奥辛類測試樣品 • 之製造方法。在一實施例中，此方法可以先進行萃取步驟， 二利用第一有機溶劑萃取飛灰以獲得粗萃溶液，並使此粗 萃溶液經減壓濃縮為粗萃物，其中飛灰可由含氣之金屬進 =向溫製程伴隨產生。接著，進行淨化步驟，以從前述粗 萃物獲得戴奥辛類化合物。在一例示中，此淨化步驟可包 括進行酸洗淨化步驟、管柱淨化步驟以及濃縮步驟。前述 之酸洗淨化步驟可利用第二有機溶劑溶解前述粗萃物而形 成粗萃溶液’並利用酸性溶液淨化此粗萃溶液至少一次。 月IJ述之管柱淨化步驟則使經酸洗之粗萃溶液通過淨化管桂 201215869 淨化’並利用第三有機溶劑流洗此淨化管柱至少一次，以 獲得流洗液。至於前述之濃縮步驟係去除前述第二有機溶 劑以及第三有機溶劑’獲得戴奥辛類化合物。之後，進行 一配製步驟，以將前述戴奥辛類化合物溶解於第四有機溶 劑中，而形成淨化液。然後，進行裂解步驟，其係於例如 500 C至550 C之溫度、淨化液之供應流速為每小時2微升 (pL/hr)至8 HL/hr、且載氣之流量為每分鐘〇 5升^址⑻至 1 L/min下，裂解淨化液中例如85百分比至99百分比之第 四有機溶劑，而獲得戴奥辛類測試樣品。所得之戴奥辛類 測試樣品之煙道氣流的濃度例如可為標準狀態下每立方公 尺 0.1 奈克-毒性當量(ng-TEQ/Nm3)至 48.5 ng-TEQ/Nm3， 且此戴奥辛類測試樣品之回收率例如可為9〇百分比至11 〇 百分比。 依據本發明一實施例，上述之金屬可包括但不限於 鐵、鋅、銅或錯。 依據本發明一實施例，上述之高溫製程可包括但不限 於燒結製程、冶金製程或熔煉製程。 依據本發明一實施例，在上述萃取步驟之前’可選擇 性利用靜電集塵器（electrostatic precipitat〇r ; Ep)捕捉前述 之飛灰。 依據本發明一實施例，上述之第二有機溶劑例如可為 碳數介於1至10之脂肪烴。 依據本發明一實施例，上述之淨化管柱例如可為酸性 石夕膠管柱及/或酸性氧化鋁管柱。在另一例示中，上述之淨 化管柱例如可為活性碳/矽藻土管柱。 201215869 依據本發明一實施例，上述之濃縮步驟可利用例如一 惰性氣體吹除上述之第二有機溶劑以及第三有機溶劑。 應用本發明之戴奥辛類測試樣品之製造方法，其係利 用含氯之金屬進行高溫製程伴隨產生的飛灰，從中萃取出 組成與製程現場廢氣相似之戴奥辛類測試樣品❶因此，所 得之戴奥辛類測試樣品可作為測試戴奧辛脫除能力的反應 物，更可降低購買戴奥辛標準品之成本。 【實施方式】 承則所述，本發明提供一種戴奥辛類測試樣品之製造 方法，其係利用含氯之金屬進行高溫製程伴隨產生的飛 灰’從中萃取出組成與製程現場廢氣相似之戴奥辛類測試 樣品。 本發明此處所稱之「戴奥辛類測試樣品」，係指例如多 氣二聯苯戴奥辛（PCDDs)以及多氣二聯苯呋喃（PCDFs) 等。此戴奥辛類測試樣品係利用含氯之金屬進行高溫製 程，例如含氣之鐵、鋅、銅或鉛等含氯之金屬，於例如電 弧爐、感應爐、坩鍋爐、反射爐或燒結爐等進行例如燒結 製程、冶金製程或熔煉製程等高溫製程時，伴隨所產生的 飛灰，從中萃取而得。所得之戴奥辛類測試樣品的戴奥辛 以及咳喃之組成與製程現場廢氣十分相似。 在本發明一實施例中，上述含氯之金屬進行高溫製程 伴隨產生的飛灰，可進一步從尹萃取出組成與製程現場廢 氣相似之戴奥辛類測試樣品。請參閱第1圖，其係繪示根 據本發明一實施例的戴奥辛類測試樣品之製造方法〗〇的 IS1 7 201215869 部分流程圖。首先，如步驟11之所示，可先進行萃取步驟， 以利用第一有機溶劑’例如甲苯，利用例如索氏萃取步驟 (Soxhlet extraction process)，萃取前述之飛灰約24小時， 以獲得粗萃溶液，並使此粗萃溶液經第一減壓濃縮步驟去 除第一有機溶劑，而形成粗萃物。 前述之第一減壓濃縮步驟可利用一惰性氣體，例如氮 氣’吹除第一有機溶劑。此外，在萃取步驟之前，可選擇 性利用靜電集塵器（electrostatic precipitator ; EP)捕捉前述 之飛灰。 接著，如步驟13之所示，進行淨化步驟，以從前述粗 萃物獲得戴奥辛類化合物。在一例示中，此淨化步驟可參 考Ψ華民國環境保護署環境檢驗所（National Institute ofAccording to the current regulations of China's current small and medium-sized waste incinerators, Dioxin's control and emission standards, 'dioxins' refers to two oxygen atoms that link a pair of this type of compound to the poly-type diphenyl dioxin (p〇lyChl〇rinated dibenzo). -pflrfl-dioxins; PCDDs; hereinafter referred to as "Dioxin" and polychlorinated dibenzo-furans (PCDFs; hereinafter referred to as "biting"), which is a general term for about 210 different compounds. In other cases, sometimes Contains coplanar polybiphenyls (C〇planar biphenyls; C〇-PCBs). Sources of dioxin/furan may include volcanic eruptions, by-products of industrial processes (such as steelmaking processes), human activities (such as waste burning, exhaust emissions from steam locomotives), and the like. In recent decades, due to the extremely toxic nature of Dai, it is not easy to decompose... When it enters the human body, it has substances that cause acne, carcinogenicity, and ignorance, and it is a very important mother, and there is "not" I 疋, The name of the poison. With the active two attached = containing, in addition to the profitable, the dioxin / furan cleavage two dollars, can also be removed by catalytic enzymes. In order to evaluate the ability of the catalase to remove the carbon dioxide, water and hydrochloric acid gas to establish the catalytic activity of the enzyme = Xingxin / furan, it is generally necessary to ',' the technology to find out the removal ability. The preferred 3 201215869 catalyst is used to test the subsequent dioxin removal capability at the process site. In general, the methods for assessing the dioxin removal ability of a catalyst can be broadly classified into two categories. One common approach is to use dioxin precursors as typical model compounds, such as chlorobenzenes or chlorophenols, to avoid contact with dioxin. Samples of typical reactants were collected before and after the reaction, and the change in concentration between them was analyzed by gas chromatography (GC) to calculate the ability of the typical reactants to remove dioxin. In another way, dioxin is used as a reactant, which is purchased from a commercially available dioxin standard (dissolved in n-tanol) and then diluted. The steps of sampling, purification and quantification of the reaction process can be carried out in accordance with the EPA 23A method established by the Environmental Protection Agency (EPA). The concentration of dioxin/furan (PCDDs/PCDFs) can be measured by high resolution gas chromatography (HRMS) and high resolution mass spectrometer (HRMS). The change in toxicity equivalency quantity (TEQ) was calculated to calculate the ability to remove dioxin. However, the above methods still have the following problems. On the one hand, when the dioxin precursor is used as a substitute reactant, the concentration (percentage) of the precursor used is often much larger than the concentration of dioxin contained in the process gas at the process site (Nike; ng), so that the reaction conditions and process conditions of the test are Considerable differences, so the results measured can only be used as a reference for the ability to remove dioxin. On the other hand, commercially available dioxin standards are more expensive, and their composition is mostly limited to dioxin/furan 201215869 (PCDDs/PCDFs) with 4, 6 or 8 chlorine numbers. 'Cannot cover 4 gas to 8 The number of gas is all dioxin / 吱 ( (PCDDs / PCDFs). Since the composition of the commercially available dioxin standard as a reactant is still quite different from the composition of the dioxin in the process exhaust gas, the measured results still cannot truly reflect the results that should be presented at the process site. & In view of this, there is a need to provide a method of manufacturing dioxin test samples to overcome the problem that conventional dioxin test samples do not truly reflect the results of the process and the relatively expensive commercially available dioxin standards. SUMMARY OF THE INVENTION Accordingly, one aspect of the present invention provides a method for producing a dioxin-like test sample which utilizes a chlorine-containing metal for the fly ash accompanying the high-temperature process, and the composition extracted therefrom is similar to the process gas at the process. The dioxin test sample serves as a reagent for testing the dioxin removal ability and reduces the cost of purchasing the dioxin standard. According to the above aspect of the present invention, a manufacturing method of a dioxin test sample is proposed. In an embodiment, the method may first perform an extraction step, and second, extract the fly ash with a first organic solvent to obtain a crude extract solution. And the crude extract solution is concentrated under reduced pressure into a crude extract, wherein the fly ash can be produced by the gas-containing metal into the warm process. Next, a purification step is performed to obtain the dioxin compound from the crude extract. In an illustration, the purifying step may include performing a pickling purifying step, a column purifying step, and a concentration step. The pickling and purifying step may dissolve the foregoing crude extract with a second organic solvent to form a crude extract solution and utilize acidity. The solution is purified by the solution at least once. The column purification step of the month IJ is performed by purifying the acid-washed crude extract solution through the purification tube 201215869 and purging the purification column at least once with a third organic solvent to obtain Flow washing liquid. As described above, the concentration step removes the aforementioned second organic solvent and the third organic solvent to obtain a dioxin compound. Performing a preparation step of dissolving the aforementioned dioxin compound in the fourth organic solvent to form a purification liquid. Then, performing a cleavage step at a temperature of, for example, 500 C to 550 C, and a supply flow rate of the purification liquid is hourly. 2 μL (pL/hr) to 8 HL/hr, and the flow rate of the carrier gas is 升5 liters per minute (8) to 1 L/min, and the fourth organic solvent is, for example, 85 to 99% in the clarification purification solution. The dioxin test sample is obtained, and the concentration of the flue gas stream of the obtained dioxin test sample can be, for example, 0.1 ng-toxic equivalent (m-TEQ/Nm3) to 48.5 ng-TEQ/Nm3 per cubic meter in a standard state. And the recovery rate of the dioxin-like test sample may be, for example, from 9 〇 to 11 〇. According to an embodiment of the invention, the metal may include, but is not limited to, iron, zinc, copper or er. According to an embodiment of the invention The high temperature process described above may include, but is not limited to, a sintering process, a metallurgical process, or a smelting process. According to an embodiment of the invention, an electrostatic precipit may be selectively utilized prior to the above extraction step. In accordance with an embodiment of the present invention, the second organic solvent may be, for example, an aliphatic hydrocarbon having a carbon number of from 1 to 10. According to an embodiment of the present invention, the above-described purification tube The column may be, for example, an acid stone tube column and/or an acid alumina column. In another example, the above-described purification column may be, for example, an activated carbon/diatomite column. 201215869 According to an embodiment of the invention, the above The concentration step may blow off the second organic solvent and the third organic solvent by using, for example, an inert gas. The manufacturing method of the dioxin test sample of the present invention is a fly ash which is accompanied by a high-temperature process using a chlorine-containing metal. The dioxin-like test sample, which is similar in composition to the process gas, is extracted therefrom. Therefore, the obtained dioxin test sample can be used as a reactant for testing the dioxin-removing ability, and the cost of purchasing the dioxin standard can be reduced. [Embodiment] As stated in the specification, the present invention provides a method for manufacturing a dioxin-like test sample, which utilizes a chlorine-containing metal for high-temperature process accompanying fly ash to extract a dioxin-like test having a composition similar to that of a process site exhaust gas. sample. The "Dioxin test sample" referred to herein means, for example, polydiphenyldioxin (PCDDs) and polydiphenylfuran (PCDFs). The dioxin test sample is subjected to a high temperature process using a chlorine-containing metal, such as a chlorine-containing metal such as a gas-containing iron, zinc, copper or lead, for example, in an electric arc furnace, an induction furnace, a helium boiler, a reverberatory furnace, or a sintering furnace. For example, in a high-temperature process such as a sintering process, a metallurgical process, or a smelting process, the resulting fly ash is extracted therefrom. The composition of the dioxin test sample obtained by the dioxin test sample and the cough is very similar to that of the process. In one embodiment of the present invention, the chlorine-containing metal is subjected to a fly ash which is accompanied by a high-temperature process, and a dioxin-like test sample having a composition similar to that of the process site waste gas can be further extracted from Yin. Referring to Fig. 1, there is shown a flow chart of an IS1 7 201215869 portion of a method for producing a dioxin test sample according to an embodiment of the present invention. First, as shown in step 11, an extraction step may be first performed to extract the fly ash for about 24 hours using a first organic solvent such as toluene, for example, by a Soxhlet extraction process, to obtain a crude extract. The solution is passed, and the crude extract solution is subjected to a first vacuum concentration step to remove the first organic solvent to form a crude extract. The aforementioned first vacuum concentration step may blow off the first organic solvent using an inert gas such as nitrogen. In addition, the aforementioned fly ash can be selectively captured using an electrostatic precipitator (EP) prior to the extraction step. Next, as shown in step 13, a purification step is carried out to obtain a dioxin compound from the foregoing crude extract. In an example, this purification step can be referred to the Environmental Institute of the Environmental Protection Agency of the Republic of China (National Institute of Environmental Protection Institute).
Environmental Analysis ;NIEA)公告第 NIEAA808.73B 號的 「排放管道中戴奥辛及呋喃檢測方法」，或者參酌歐、美、 曰等其他國家或世界衛生組織(world health organization ; WHO)頒布的相關方法進行。 簡言之，此淨化步驟可包括進行酸洗淨化步驟、管柱 淨化步驟以及第二減歷濃縮步驟。前述之酸洗淨化步驟可 利用第二有機溶劑溶解前述粗萃物，而形成粗萃溶液，並 利用酸性溶液，例如濃硫酸，淨化此粗萃溶液至少一次。 在一例示中，第二有機溶劑例如可為碳數介於1至1〇之脂 肪烴。在另一例示中，第二有機溶劑例如可為正己烷。 前述之管柱淨化步驟則使經酸洗之粗萃溶液通過淨化 管柱淨化，並利用第三有機溶劑流洗此淨化管柱至少一 ""人，以獲得流洗液。在一例示中，前述之淨化管柱例如可 為酸性矽膠管柱及/或酸性氧化鋁管柱。在此例示中，第三 8 201215869 有機溶劑可包含但不限於正己烷、二氯曱烷、正己烷/二氣 曱烷之混合液或上述之任意組合。此例示在進行管柱淨化 步驟之前，更可包括進行管柱預洗步驟，以利用第二有機 溶劑，例如正己炫，預洗此淨化管柱。 在另一例示中，前述之淨化管柱例如可為活性碳/矽藻 土管柱。在此例示中，第三有機溶劑可包含但不限於甲醇、 曱苯、二氯曱烷、二氯曱烷/曱醇/甲苯之混合液、環己烷/ 二氣甲烧之混合液、正己烧或上述之任意組合。此例示在 進行管柱淨化步驟之前，亦可包括進行管柱預洗步驟，以 利用第五有機溶劑，例如包含但不限於曱醇、曱苯、二氣 甲烷/甲醇/甲苯之混合液、環己烷/二氯甲烷之混合液、正 己烷或上述之任意組合，預洗此淨化管柱。 然後，進行第二減壓濃縮步驟，其係利用一惰性氣體， 例如氮氣，去除前述第二有機溶劑以及第三有機溶劑，獲 得戴奥辛類化合物。補充說明的是，在前述萃取步驟以及 淨化步驟中，並未添加13c12-同位素標誌内標準品。 之後，如步驟15之所示，進行配製步驟，以將前述戴 奥辛類化合物溶解於第四有機溶劑中，而形成淨化液。在 一例示中，前述之第四有機溶劑例如可為正己烧。 隨後，如步驟17之所示，進行裂解步驟，其係於例如 500°C至550°C之溫度、淨化液之供應流速為每小時約2微 升（pL/hr)至約8 pL/hr、且載氣(例如空氣）之流量為每分鐘 約0.5升(L/min)至約1 L/min下，利用例如戴奥辛類流連續 產生設備，裂解淨化液中例如85百分比至99百分比之第 四有機溶劑，而獲得戴奥辛類測試樣品。所得之戴奥辛類 測試樣品之煙道氣流的濃度例如可為標準狀態下每立方公js] 201215869 尺約Ο.1奈克 '毒性當量（ng-TEQ/Nm3)至約48.5 ng-TEQ/Nm3 ’且此戴奥辛類測試樣品之回收率例如可為約 90百分比至約11〇百分比。在另一例式中’前述戴奥辛類 測試樣品之煙道氣流的濃度例如可為約11〇 ng-TEQ/Nm3 至約13.0 ng-TEQ/Nm3。在進行裂解步驟之前，可另進行定 量步驟’利用例如高解析度質譜儀(HRMS)’測定多氣二聯 苯戴奥辛(PCDDs)以及多氯二聯苯呋喃(PCDFs)的含量。在 一例示中’前述之多氯二聯苯戴奥辛(PCDDs)例如可包含 15至20種PCDDs異構物’而多氯二聯笨呋喃 包含四至八氣異構物。 請參閱第2圖’其係繪示根據本發明一實施例之戴奥 辛類流連續產生設備的示意圖。此戴奥辛類流連續產生設 備100的規模例如可為實驗室級或工業級。在一實施例 中，首先，可利用例如高精密注射筒式幫浦，由注入口 1〇1 連續注入含有預定含量之戴奥辛類化合物之淨化液。此淨 化液可與進流載氣（例如空氣）在石英爐管110内進行混 合。在一例示中，石英爐管110例如可為石英爐管，其腔 體内可填充玻璃珠混合床(glass bead mixer)l 11。進流空氣 可由空氣筒103提供，並利用氣體流量控制計(mass flow controller)105控制空氣筒103提供的進流空氣之流速。進 流空氣與淨化液混合之前，進流空氣更可藉由例如預熱區 (pre-heated area)107預熱後，再與淨化液於石英爐管11〇 的玻璃珠混合設備（glass bead mixer)lll内進行混合。在一 例示中，淨化液之第四有機溶劑的供應流速例如可為7.5 pg/Nm3 (1 μΐ/hr)至 75 pg/Nm3 (10 μΐ/hr)之間，進流空氣的 流量例如可為0· 1 L/min至3 L/min。在另一例示中，淨化^ 1 201215869 液之第四有機溶劑的供應流速例如可為30 pg/Nm3 (4 μΐ/hr) 至60 pg/Nm3 (8 μΐ/hr)之間’進流空氣的流量例如可為〇 5 L/min 至 2 L/min。 此淨化液與進流空氣進入石英爐管11〇後，可利用溫 度控制器120控制石英爐管no的溫度約5501至550°C， 以裂解淨化液中例如85百分比至99百分比之第四有機溶 劑，而獲得戴奥辛類測試樣品。裂解過程中可藉由例如三 向閥104的切換，於預設間隔時間收集石英爐管11〇出口 的戴奥辛類化合物，並利用例如氣相層析儀/火焰離子化偵 測器（gas Chromat〇graphy/flame ionizati〇n detect〇r ; GC/HD)130即時偵測第四有機溶劑的濃度。之後，第四有 機溶劑被裂解的戴奥辛類化合物可藉由管路131、管路 133、管路135及管路137，經過吸收管柱丨4ia、吸收管柱 142a以及空置官柱143a。另-種方式，第四有機溶劑被裂 解的戴奥辛類化合物亦可藉由管路132、管路134、管路 136及管路138，經過經過吸收管柱141b、吸收管柱14孔 以及空置管柱143b的吸收。在一例示中，吸收管柱Mia、 吸收管柱142a、吸收管柱141b以及吸收管柱142b可包括 甲苯溶液，以吸附殘餘的第四有機溶劑。在另一例式中， 吸收管柱池以及吸㈣柱⑷b可另添加擬似標準品 (surrogate standard)，例如根據美國 ePA m23 方 擬似標準品，藉以監測其採樣效率。 斤揭不的 之後，藉由例如三向閥106的切換，前述被 奥辛類化合物可通過卿管柱161吸附殘餘的水分解然後 收集於冷凝箱1川中並利用真空幫浦18G抽真 獲得戴奥辛類測試樣品。 1 201215869 值得一提的是，上述產生的戴奥辛類測試樣品量相當 穩定，其中此戴奥辛類測試樣品之煙道氣流的濃度可維持 在例如 0.1 ng-TEQ/Nm3 至 48.5 ng-TEQ/Nm3，且此戴奥辛 類測試樣品之回收率例如可為90百分比至110百分比。上 述之ng為奈克（10·9公克），TEQ為毒性當量（toxic# equivalency quantity)，而Nm3為標準狀態（凱式溫度二七三 度(273K)及一大氣壓）下每立方公尺體積。此處所稱之「毒 性當量」，係指根據 2,3,7,8-四氣戴奥辛 (2,3,7,846以(^1〇01^16(1(1比6112〇-卩-(1丨(^丨11)以及下式（1)，計算 戴奥辛濃度之毒性當量： TEQ = Σ {^DDi x ^L)+ ([PCDF, x TEF]n)} (I) 其中/為戴奥辛各含氯之異構物的實際濃度，而w為 含氣之異構物總數’而泣尸為毒性當量因子（toxieity equivalency factor)。至於毒性當量因子可參酌歐、美、曰 等其他國家或世界衛生組織（world health organization ; WHO)頒布的戴奥辛國際毒性當量因子值，此處不另贅古。Environmental Analysis; NIEA) Announcement No. NIEAA 808.73B “Daisin and Furan Detection Methods in Emission Pipelines”, or in other countries such as Europe, the United States, and China, or related methods promulgated by the World Health Organization (WHO). Briefly, the purging step can include performing a pickling purification step, a column purification step, and a second subtraction enrichment step. The aforementioned pickling and purifying step may dissolve the crude extract by using a second organic solvent to form a crude extract solution, and purify the crude extract solution at least once with an acidic solution such as concentrated sulfuric acid. In one example, the second organic solvent may be, for example, an aliphatic hydrocarbon having a carbon number of from 1 to 1 Torr. In another illustration, the second organic solvent can be, for example, n-hexane. In the foregoing column purification step, the acid-washed crude extract solution is purified through a purification column, and the purification column is washed with a third organic solvent to at least one "" person to obtain a flow washing liquid. In one example, the aforementioned purification column may be, for example, an acid tantalum tube column and/or an acidic alumina column. In this illustration, the third 8 201215869 organic solvent may include, but is not limited to, a mixture of n-hexane, dichlorodecane, n-hexane/dioxane or any combination of the above. This example may include performing a column pre-washing step to pre-wash the purification column with a second organic solvent, such as hexamethylene, prior to performing the column purification step. In another illustration, the aforementioned purification column can be, for example, an activated carbon/diatomite column. In this illustration, the third organic solvent may include, but is not limited to, a mixture of methanol, toluene, dichlorosilane, dichloromethane, methanol/toluene, cyclohexane/dioxane, and Burn or any combination of the above. This example may also include performing a column pre-washing step to perform a column pre-washing step to utilize a fifth organic solvent such as, but not limited to, a mixture of decyl alcohol, terpene, di-methane/methanol/toluene, and a ring. The purification column is pre-washed with a mixture of hexane/dichloromethane, n-hexane or any combination of the above. Then, a second vacuum concentration step is carried out which removes the aforementioned second organic solvent and the third organic solvent using an inert gas such as nitrogen to obtain a dioxin compound. It is additionally noted that the 13c12-isotopically labeled internal standard was not added in the aforementioned extraction step and purification step. Thereafter, as shown in step 15, a preparation step is carried out to dissolve the aforementioned dioxin compound in the fourth organic solvent to form a purification liquid. In one example, the fourth organic solvent may be, for example, hexanone. Subsequently, as shown in step 17, a cracking step is carried out at a temperature of, for example, 500 ° C to 550 ° C, and the supply flow rate of the cleaning liquid is about 2 μL (pL/hr) to about 8 pL/hr per hour. And the flow rate of the carrier gas (for example, air) is about 0.5 liters (L/min) to about 1 L/min per minute, using, for example, a continuous generation device of a dioxin-like stream, for example, 85 to 99 percent of the lysate Four organic solvents were obtained, and a dioxin test sample was obtained. The concentration of the flue gas stream of the obtained dioxin test sample can be, for example, Js per unit of the standard state, 201215869 ft. 奈.1 Nike 'toxic equivalent (ng-TEQ/Nm3) to about 48.5 ng-TEQ/Nm3 ' And the recovery rate of the dioxin test sample can be, for example, from about 90% to about 11%. In another embodiment, the concentration of the flue gas stream of the aforementioned dioxin test sample may be, for example, from about 11 ng-TEQ/Nm3 to about 13.0 ng-TEQ/Nm3. Prior to the cleavage step, a further quantitation step can be performed to determine the levels of poly-diphenyldiazine (PCDDs) and polychlorinated diphenyl furans (PCDFs) using, for example, a high resolution mass spectrometer (HRMS). In one example, the aforementioned polychlorinated diphenyl dioxin (PCDDs) may, for example, comprise from 15 to 20 PCDDs isomers and the polychlorinated dipyridamole comprises four to eight gas isomers. Referring to Fig. 2, there is shown a schematic diagram of a dioxin-like flow continuous generating apparatus according to an embodiment of the present invention. The size of this dioxin-like stream continuous generating apparatus 100 can be, for example, laboratory or industrial. In one embodiment, first, a cleaning liquid containing a predetermined amount of a dioxin compound can be continuously injected from the injection port 1〇1 using, for example, a high-precision syringe pump. This cleaning fluid can be mixed with the inbound carrier gas (e.g., air) in the quartz furnace tube 110. In one example, the quartz furnace tube 110 can be, for example, a quartz furnace tube, and the chamber can be filled with a glass bead mixer l 11 . The inflowing air may be provided by the air cylinder 103 and the flow rate of the inflowing air provided by the air cylinder 103 is controlled by a mass flow controller 105. Before the influent air is mixed with the purification liquid, the inflow air can be preheated by, for example, a pre-heated area 107, and then mixed with the purification liquid in the quartz furnace tube 11 glass bead mixer (glass bead mixer) ) lll mix. In an example, the supply flow rate of the fourth organic solvent of the cleaning liquid may be, for example, between 7.5 pg/Nm 3 (1 μΐ/hr) and 75 pg/Nm 3 (10 μΐ/hr), and the flow rate of the inflowing air may be, for example, 0·1 L/min to 3 L/min. In another example, the supply flow rate of the fourth organic solvent of the purified liquid may be, for example, between 30 pg/Nm 3 (4 μΐ/hr) and 60 pg/Nm 3 (8 μΐ/hr). The flow rate can be, for example, 〇5 L/min to 2 L/min. After the purified liquid and the inflowing air enter the quartz furnace tube 11 , the temperature of the quartz furnace tube no can be controlled by the temperature controller 120 to be about 5501 to 550 ° C to lyse the fourth organic organic compound, for example, 85 to 99 percent. The solvent was used to obtain the dioxin test sample. During the cracking process, the dioxin compound of the outlet of the quartz furnace tube 11 can be collected at a preset interval by, for example, switching of the three-way valve 104, and using, for example, a gas chromatograph/flame ionization detector (gas Chromat〇) GRAPHICS/flame ionizati〇n detect〇r ; GC/HD) 130 instantly detects the concentration of the fourth organic solvent. Thereafter, the dioxin-like compound which is cleaved by the fourth organic solvent can pass through the absorption tube column 4ia, the absorption tube column 142a, and the vacant column 143a through the line 131, the line 133, the line 135, and the line 137. Alternatively, the dioxin-like compound from which the fourth organic solvent is cleaved may also pass through the absorption tube column 141b, the absorption tube column 14 hole, and the vacant tube through the line 132, the line 134, the line 136, and the line 138. Absorption of column 143b. In an illustration, the absorption column Mia, the absorption column 142a, the absorption column 141b, and the absorption column 142b may include a toluene solution to adsorb the residual fourth organic solvent. In another example, the absorption column cell and the suction (four) column (4)b may be additionally supplemented with a surrogate standard, for example, according to the US ePA m23 square standard, to monitor the sampling efficiency. After the knuckle is uncovered, the above-mentioned oxin-like compound can be decomposed by the residual water by the column 161 by the switching of the three-way valve 106, and then collected in the condensing tank 1 and used the vacuum pump 18G to obtain the dioxin. Class test samples. 1 201215869 It is worth mentioning that the amount of the dioxin test sample produced above is quite stable, wherein the concentration of the flue gas stream of the dioxin test sample can be maintained, for example, from 0.1 ng-TEQ/Nm3 to 48.5 ng-TEQ/Nm3, and The recovery rate of this dioxin test sample can be, for example, from 90% to 110%. The above ng is Nike (10·9 g), TEQ is toxic# equivalency quantity, and Nm3 is the standard state (Kelvin temperature 273 (273K) and one atmosphere) per cubic meter volume . The term "toxic equivalent" as used herein refers to Dioxin according to 2,3,7,8-four gas (2,3,7,846 to (^1〇01^16(1(1 to 6112〇-卩-(1丨) (^丨11) and the following formula (1), calculate the toxic equivalent of dioxin concentration: TEQ = Σ {^DDi x ^L)+ ([PCDF, x TEF]n)} (I) where / is dioxin The actual concentration of the isomer, and w is the total number of gas-containing isomers' and the toxieity equivalency factor. As for the toxicity equivalent factor, it can be considered in other countries such as Europe, America, and China, or the World Health Organization. The value of the dioxin international toxicity equivalent factor issued by the (world health organization; WHO) is not uncommon here.
由於所得之戴奥辛類測試樣品的組成與製程現場廢氣 相似，可作為測試觸酶對於戴奥辛脫除能力的反應物，更 可降低購貝戴奥辛標準品之成本。上述觸酶例如可為商品 化觸酶或其他觸媒，其材料可包括但不限於釩_鎢/二氧化鈦 (v-w/Ti〇2)、釩-钥/二氧化鈦(V-Mo/Ti〇2)、五氧化二銳/氧 化鎢（V2〇5/W〇3)、鈦/釩(Ti/V)、五氧化二釩-氧化鎢/二氧化 鈦(V2〇5_W〇3/Ti〇2)、鉑/三氧化二鋁(pt/Ti〇2)、五氧化二飢 /二氧化鈦MCVTiO2)、三氧化二鐵/二氧化鈦的办/了叫） 或上述之任意組合。觸媒在特定的溫度與氧氣供應下，可 使戴奥辛產生斷鍵反應而分解，產生無害的c〇2、Η2〇易U 12 201215869 HC卜 以下利用實施例以說明本發明之應用，然其並非用以 限定本發明’本發明技術領域中具有通常知識者，在不脫 離本發明之精神和範圍内，當叮作各種之更動與潤飾。 實施例一：製備戴奥辛類測試樣品 在此實施例中，首先，可選擇性利用靜電集塵器捕捉 含氣之金屬進行高溫製程，例如含氯之鐵、鋅、鋼或錯等 鲁 含氣之金屬’於例如電弧爐、感應爐、坩鍋爐、反射爐或 燒結爐等進行例如燒結製程、冶金製程或炫煉製程等高溫 製程時，伴隨所產生的飛灰。 接著，進行萃取步驟，取例如約50公克之飛灰置於圓 筒濾紙，移入習知之索氏萃取裝置之中段後，利用例如甲 苯’萃取前述之飛灰約24小時’以獲得粗萃溶液，並使此 粗萃溶液利用惰性氣體，例如氮氣，進行第一減壓濃縮步 驟’以去除甲苯至近乾，而形成粗萃物。 φ 之後’進行淨化步驟，以從前述粗萃物獲得戴奥辛類 化合物。在一例示中，此淨化步驟可參考中華民國環境保 護署環境檢驗所（National Institute of EnvironmentalSince the composition of the obtained dioxin test sample is similar to that of the process site exhaust gas, it can be used as a reaction to test the contact enzyme's ability to remove the dioxin, and the cost of purchasing the beta dioxin standard can be reduced. The above-mentioned contact enzyme may be, for example, a commercially available contact enzyme or other catalyst, and the materials thereof may include, but are not limited to, vanadium-tungsten/titanium dioxide (vw/Ti〇2), vanadium-key/titanium dioxide (V-Mo/Ti〇2), Bismuth oxide/tungsten oxide (V2〇5/W〇3), titanium/vanadium (Ti/V), vanadium pentoxide-tungsten oxide/titanium dioxide (V2〇5_W〇3/Ti〇2), platinum/three Aluminium oxide (pt/Ti〇2), pentoxide/titanium dioxide MCVTiO2), iron oxide/titanium dioxide, or any combination thereof. At a specific temperature and oxygen supply, the catalyst can decompose the dioxin by breaking the bond reaction, resulting in harmless c〇2, Η2〇U 12 201215869 HC. The following examples are used to illustrate the application of the present invention, but it is not In order to define the invention, it is to be understood that various modifications and changes may be made without departing from the spirit and scope of the invention. Example 1: Preparation of Diaoxin Test Samples In this embodiment, first, an electrostatic precipitator can be selectively used to capture gas-containing metals for high-temperature processes, such as chlorine-containing iron, zinc, steel, or the like. The metal' is accompanied by a fly ash generated in a high-temperature process such as an electric arc furnace, an induction furnace, a helium boiler, a reverberatory furnace, or a sintering furnace, for example, a sintering process, a metallurgical process, or a smelting process. Next, an extraction step is performed, for example, about 50 grams of fly ash is placed on a cylindrical filter paper, and after being transferred into a middle section of a conventional Soxhlet extraction apparatus, the fly ash is extracted by, for example, toluene for about 24 hours to obtain a crude extract solution. The crude extract solution is subjected to a first vacuum concentration step using an inert gas such as nitrogen to remove toluene to near dryness to form a crude extract. After φ, a purification step is carried out to obtain a dioxin compound from the aforementioned crude extract. In an example, the purification step can be referred to the Environmental Institute of the Republic of China Environmental Protection Agency (National Institute of Environmental
Analysis ; NIEA)公告第NIEAA808.73B號的「排放管道中 戴奧辛及呋喃檢測方法」進行。 簡言之，此淨化步驟可包括進行酸洗淨化步驟、管柱 淨化步驟以及第二減壓濃縮步驟。前述之酸洗淨化步驟可 利用碳數介於1至1〇之脂肪烴或正己烷溶解前述粗萃物， 而形成粗萃溶液，並利用酸性溶液，例如濃硫酸，淨化此 13 201215869 粗萃溶液至少一次。 前述之管柱淨化步驟則使經酸洗之粗萃溶液通過例如 酸性矽膠管柱及/或酸性氧化鋁管柱淨化，並利用正己烷、 二氣甲烷、正己烷/二氯甲烷之混合液或上述之任意組合， 流洗此淨化管柱至少一次，以獲得流洗液。在進行管柱淨 化步驟之前，更可包括進行管柱預洗步驟，以利用例如正 己烷預洗此淨化管柱。 另一種方式，前述之管柱淨化步驟則使經酸洗之粗萃 溶液通過例如活性碳/矽藻土管柱淨化，並利用曱醇、甲 ® 苯、二氯曱烷、二氣甲烷/曱醇/甲苯之混合液、環己烷/二 氣甲烷之混合液、正己烷或上述之任意組合，流洗此淨化 管柱至少一次，以獲得流洗液。在進行管柱淨化步驟之前， 亦可包括進行管柱預洗步驟，以利用例如甲醇、甲苯、二 氯甲烷/甲醇/甲苯之混合液、環己烷/二氯曱烷之混合液、 正己烷或上述之任意組合，預洗此淨化管柱。 然後，進行第二減壓濃縮步驟，其係利用惰性氣體， 例如氮氣，去除前述有機溶劑，獲得戴奥辛類化合物。補 •充說明的是，在前述萃取步驟以及淨化步驟中，並未添加 13c12-同位素標誌、内標準品。 之後，進行配製步驟，以將前述戴奥辛類化合物溶解 於例如約10 mL之正己烷中，而配置成所需戴奥辛濃度的 淨化液。在進行後續裂解步驟之前，可另進行定量步驟， 利用例如高解析質譜儀(HRMS)，測定多氣二聯苯戴奥辛 (PCDDs)以及多氣二聯苯呋喃(PCDFs)的含量。 隨後，進行後續裂解步驟，其係利用例如第2圖之戴 奥辛類流連續產生設備100，裂解淨化液中之正己烷，而[s] 14 201215869 仵、辛類測試樣品。在-例子中，當氣體流量為約〇 ^ 時’偶若戴奥辛於注入口的濃度為約2 ng-TEQ/Nm3 時’注射筒式幫浦的供應流速為約8fiL/h 試樣品於正己烧注入溶液之組成，則可例如第i表：= 17種多氣二聯苯戴奥辛（pCDDs)以及多氣二聯笨呋喃 (PCDFs)的異構物。 °月參閱第1表，其係顯示本發明一實施例之戴奥辛類 測S式樣品之組成。 第1表 配製濃度 (pg〜L) 注入總 量(ng) TEQ 毒性當量濃度 (ng-TEQ/Nm3) 2,3,7,8-TCDD 0.224 0.002 1.0 0.093 1,2,3,7,8-PeCDD 0.626 0.005 0.5 0.131 1,2,3,4,7,8-HxCDD 0.687 0.005 0.1 0.029 1,2,3,6,7,8-HxCDD 0.982 0.008 0.1 0.041 1,2,3,7,8,9-HxCDD 0.725 0.006 0.1 0.030 1,2,3,4,6,7,8-HpCDD 4.523 0.036 0.01 0.019 OCDD 7.256 0.058 0.001 0.003 2,3,7,8-TCDF 1.516 0.012 0.1 0.063 1,2,3,7,8-PeCDF 1.545 0.012 0.05 0.032 2,3,4,7,8-PeCDF 5.531 0.044 0.5 1.152 1,2,3,4,7,8-HxCDF 3.332 0.027 0.1 0.139 1,2,3,6,7,8-HxCDF 3.182 0.025 0.1 0.133 1,2,3,7,8,9-HxCDF 0.908 0.007 0.1 0.038 2,3,4,6,7,8-HxCDF 3.296 0.026 0.1 0.137 1,2,3,4,6,7,8-HpCDF 8.888 0.071 0.01 0.037 1,2,3,4,7,8,9-HpCDF 1.701 0.014 0.01 0.007 OCDF 3.906 0.031 0.001 0.002 [S] 15 201215869 PCDD/Fs — (採樣體積：0.0192 Nm3) 2.086 實施例〜：評估正己烧之破壞效率 此實施例係進行裂解步驟， 溫度(約2叫，例如於_至5 : 例如第2圖之# ώ * 50 C之▲度下，並利用 中例如85百八戴奥辛類流連續產生設備刚，裂解淨化液 測試樣品。如"百刀比之正己燒，而獲得戴奥辛類 L/—時，倘:之製程條件’當氣體流量為約〇·32 時，注射筒式j奥辛於/主入口的滚度為約2阶项胸3 入溶液的戴奥在浦的供應流速為約8 ^/hr時，則正己烷注 且正己、類測試樣品之組成可例如第1表之所示， 壞效率可如第2表之所示。 烧的“效^二其根據本發日卜實施例之正己 第攔為實施例2]於不同裂解溫度、空間流速(space l6〇〇/hT^M^^^ 4 π ，率（百分比；。/ο)。第3襴為實施例2-2於不同裂解 孤度SV為i6〇〇/hr、供應流速為約8叫加時正己燒的破 壞效率(％)。帛4攔為實施例2-3於不同裂解溫度、8乂為 3000/hr、供應流速為約4 μυΐπ>時正己烧的破壞效率(％)。 第5欄為實施例2_4於不同裂解溫度、8¥為3〇〇〇/hr、供 應流速為約8 pL/hr時正己烷的破壞效率（％)。以上每組樣 本値係重複至少三個獨立實驗而得出。 ， 第2表 201215869 裂解正己烷 的溫度（°c) 實施例2_1 實施例2-2 實施例2_3 實施例2-4 450〇C 23.2 29.6 36.6 41.3 500°C 30.1 40.4 78.2 87.6 525〇C 48.4 58.9 84.8 94.7 550〇C 63.6 71.5 90.4 97.4 575〇C 84.4 86.5 96.1 98.7 由第2表之結果可知，在500°C至550°C之溫度下，利 用例如戴奥辛類流連續產生設備，裂解淨化液中例如85百 分比至99百分比之正己烷。其次，裂解溫度越高或空間流 速(SV)越小，則正己烷於石英爐管内停留時間越長，可增 加正己烷之破壞效率。而裂解溫度越高，正己烷之破壞效 率亦越高。 實施例三：評估連續戴奥辛氣流之穩定性 此實施例係於實施例二之裂解過程中，藉由例如第2 圖之三向閥104的切換，於預設間隔時間收集石英爐管110 出口的戴奥辛類化合物，配合氣相層析儀/火焰離子化偵測 器（GC/FID)130即時偵測，藉此評估連續戴奥辛氣流之穩 定性，其結果如第3圖之所示。 請參閱第3圖，其係繪示本發明一實施例之戴奥辛類 化合物之出口煙道氣流之濃度曲線圖，藉此評估連續戴奥 辛氣流之穩定性，其中縱軸為戴奥辛類化合物之出口煙道 氣流的濃度(ng-TEQ/Nm3)，橫軸為利用第2圖之戴奥辛類 [s] 17 201215869 流連續產生設備刚之操作時間（分鐘），圖 表溫度在5坑時、出口·的戴奥辛類化合代 圖號之曲線代表溫度在咖時、出口測 ：：， 化合物之濃度，圖號▲之曲線代表溫度在575。匸時、員 測得的戴奥辛類化合物之濃度，而圖中之上限與下限=二 別代表自行預設之上限值及下限值。 乂 ’、、Analysis; NIEA) Announcement No. NIEAA 808.73B, "Methods for the Determination of Dioxin and Furan in Emission Pipelines". Briefly, the purifying step can include performing a pickling purification step, a column purification step, and a second reduced pressure concentration step. The foregoing pickling and purifying step may dissolve the crude extract by using an aliphatic hydrocarbon or n-hexane having a carbon number of 1 to 1 Torr to form a crude extract solution, and purify the 13 201215869 coarse extract by using an acidic solution such as concentrated sulfuric acid. Solution at least once. The above-mentioned column purification step is performed by purifying the acid-washed crude extract solution through, for example, an acid gel column and/or an acidic alumina column, and using a mixture of n-hexane, di-methane, n-hexane/dichloromethane or Any combination of the above, the purge column is flow washed at least once to obtain a flow wash. Prior to performing the column purification step, a column pre-washing step may be included to pre-wash the purge column with, for example, n-hexane. Alternatively, the above-described column purification step purifies the acid-washed crude extract solution through, for example, an activated carbon/diatomaceous earth column, and utilizes decyl alcohol, methyl benzene, dichloro decane, and di-methane/decanol. The mixture of /toluene, a mixture of cyclohexane/diqimethane, n-hexane or any combination thereof is used to wash the purge column at least once to obtain a flow wash. Before the column purification step, the column pre-washing step may be included to utilize a mixture of, for example, methanol, toluene, dichloromethane/methanol/toluene, cyclohexane/dichlorodecane, n-hexane. Or any combination of the above, pre-wash the purification string. Then, a second vacuum concentration step is carried out which removes the aforementioned organic solvent using an inert gas such as nitrogen to obtain a dioxin compound. Supplementary Note: In the above extraction step and purification step, 13c12-isotope label and internal standard were not added. Thereafter, a preparation step is carried out to dissolve the aforementioned dioxin compound in, for example, about 10 mL of n-hexane, and to prepare a purification liquid having a desired concentration of dioxin. Prior to the subsequent lysis step, a further quantification step can be performed to determine the levels of poly-diphenyldiphenyl dioxin (PCDDs) and poly-diphenyldiphenylfurans (PCDFs) using, for example, a high resolution mass spectrometer (HRMS). Subsequently, a subsequent cleavage step is carried out which utilizes, for example, the dioxin-like stream continuous production apparatus 100 of Fig. 2 to cleave n-hexane in the purification liquid, and [s] 14 201215869 仵, 辛-type test sample. In the example, when the gas flow rate is about 〇^, the supply flow rate of the syringe pump is about 8fiL/h when the concentration of the dioxin is about 2 ng-TEQ/Nm3. The composition of the infusion solution can be, for example, the i-th table: = 17 kinds of poly-pure diphenyl dioxin (pCDDs) and polyisomers of dipyridamole (PCDFs). For the month of the month, reference is made to the first table, which shows the composition of the dioxin-like S-type sample according to an embodiment of the present invention. Table 1 Formulation Concentration (pg~L) Total Injection (ng) TEQ Toxic Equivalent Concentration (ng-TEQ/Nm3) 2,3,7,8-TCDD 0.224 0.002 1.0 0.093 1,2,3,7,8- PeCDD 0.626 0.005 0.5 0.131 1,2,3,4,7,8-HxCDD 0.687 0.005 0.1 0.029 1,2,3,6,7,8-HxCDD 0.982 0.008 0.1 0.041 1,2,3,7,8,9 -HxCDD 0.725 0.006 0.1 0.030 1,2,3,4,6,7,8-HpCDD 4.523 0.036 0.01 0.019 OCDD 7.256 0.058 0.001 0.003 2,3,7,8-TCDF 1.516 0.012 0.1 0.063 1,2,3,7 ,8-PeCDF 1.545 0.012 0.05 0.032 2,3,4,7,8-PeCDF 5.531 0.044 0.5 1.152 1,2,3,4,7,8-HxCDF 3.332 0.027 0.1 0.139 1,2,3,6,7, 8-HxCDF 3.182 0.025 0.1 0.133 1,2,3,7,8,9-HxCDF 0.908 0.007 0.1 0.038 2,3,4,6,7,8-HxCDF 3.296 0.026 0.1 0.137 1,2,3,4,6 ,7,8-HpCDF 8.888 0.071 0.01 0.037 1,2,3,4,7,8,9-HpCDF 1.701 0.014 0.01 0.007 OCDF 3.906 0.031 0.001 0.002 [S] 15 201215869 PCDD/Fs — (Sampling volume: 0.0192 Nm3) 2.086 Example ~: Assessing the Destructive Efficiency of Positive Burning This example is a cracking step, temperature (about 2, for example, _ to 5: for example, # ώ * 50 C of Figure 2, and utilized, for example 85 Eight pairs of Aoxin flow continuous generating equipment, cracking and purifying liquid test samples. If the "Hundred Knife is more than the burned, and get the Dyson type L / -, if the process conditions 'when the gas flow is about 〇 · 32, The rotation of the syringe type j Osing at the main inlet is about 2 steps. The supply of the liquid to the solution is about 8 ^ / hr, and the composition of the test sample is the positive hexane injection. For example, as shown in the first table, the bad efficiency can be as shown in the second table. The "effectiveness" of the burning method according to the embodiment of the present invention is the same as that of the example 2] at different cracking temperatures and space flow rates (space l6〇〇/hT^M^^^ 4 π, rate (percentage; /ο). The third example is the destruction efficiency (%) of Example 2-2 at different cracking degree of SV of i6〇〇/hr, and the supply flow rate is about 8 times plus time. The 拦4 block is the second embodiment. -3 at a different cracking temperature, 8 乂 is 3000/hr, and the supply flow rate is about 4 μυΐπ> the destruction efficiency (%) of the burned. The fifth column is Example 2_4 at different cracking temperatures, 8¥ is 3〇〇〇 /hr, the destruction efficiency (%) of n-hexane at a supply flow rate of about 8 pL/hr. The above series of samples were repeated for at least three independent experiments. Table 2, 201215869 Pyrolysis of n-hexane (°c) Example 2_1 Example 2-2 Example 2_3 Example 2-4 450〇C 23.2 29.6 36.6 41.3 500°C 30.1 40.4 78.2 87.6 525〇C 48.4 58.9 84.8 94.7 550〇C 63.6 71.5 90.4 97.4 575〇C 84.4 86.5 96.1 98.7 As can be seen from the results of Table 2, at a temperature of 500 ° C to 550 ° C, using a continuous generation equipment such as a dioxin stream, pyrolysis purification For example, 85 to 99 percent of n-hexane in the liquid. Secondly, the higher the pyrolysis temperature or the smaller the space velocity (SV), the longer the residence time of n-hexane in the quartz furnace tube can increase the destruction efficiency of n-hexane. The higher the efficiency of the destruction of n-hexane, the higher the stability of the hexane. Example 3: Evaluation of the stability of the continuous dioxin flow. This embodiment is in the cracking process of the second embodiment, by switching the three-way valve 104, for example, in FIG. The dioxin compound at the outlet of the quartz furnace tube 110 is collected at a preset interval, and is immediately detected by a gas chromatograph/flame ionization detector (GC/FID) 130, thereby evaluating the stability of the continuous dioxin flow. The results are shown in Fig. 3. Please refer to Fig. 3, which is a graph showing the concentration of the outlet flue gas stream of the dioxin-like compound according to an embodiment of the present invention, thereby evaluating the stability of the continuous dioxin flow, wherein The axis is the concentration of the flue gas stream of the dioxin-like compound (ng-TEQ/Nm3), and the horizontal axis is the operating time (minutes) of the continuous generation device using the dioxin class [s] 17 201215869 When the temperature of the chart is at 5 pits, the curve of the Dioxin type of the export is represented by the temperature at the coffee time, the export test::, the concentration of the compound, and the curve of the figure ▲ represents the temperature at 575. The concentration of the dioxin compound, and the upper and lower limits in the figure = two represent the upper limit and the lower limit.乂 ’,
由第3圖之結果可知，經裂解所得之的戴奥辛類化入 物之煙道氣流的濃度’大致可為約0.1 ng_TEQ/Nrn3至： 48.5ng-TEQ/Nm3，可連續產生穩定的戴奥辛氣流。更進j 步而言，戴奥辛類測試樣品之煙道氣流的濃度例如可為約 11.0ng-TEQ/Nm3 至約 13.0ng-TEQ/Nm3。舉例而言，告^ 有戴奥辛類化合物之正己烧的供應流速為約4 pL/hr、氣體 流量為約0.8 L/min時，戴奥辛類化合物之進流濃产為約 12.140 ng-TEQ/Nm3。除了溫度在575°C的條件的前約3〇 分鐘、戴奥辛類化合物之回收率為約84.6%之外，在 烷的破壞溫度為525T：、550°C及575°C時，隨著操作時門 的增加，戴奥辛類化合物之回收率均大致維持在約90百分 比至約110百分比。其次，隨著破壞溫度的提高，戴奥辛 類化合物之回收率有偏低的趨勢。 此外’需補充的是，本發明雖以特定的戴奧辛類化合 物、萃取方式、溶劑、氣體、反應條件或裂解設備等作為 例示’說明本發明戴奥辛類測試樣品之製造方法，惟本發 明所屬技術領域中任何具有通常知識者可知，本發明並不 限於此，在不脫離本發明之精神和範圍内，本發明之戴奧 辛類測試樣品之製造方法亦可使用其他的戴奧辛類化合 201215869 物、萃取方式、溶劑、氣體、反應條件或裂解設備等進行。 由上述本發明實施例可知，本發明之戴奥辛類測試樣 品之製造方法，其優點在於利用含氯之金屬進行高溫製程 伴隨產生的飛灰，從中萃取出組成與製程現場廢氣相似之 戴奧辛類測試樣品。因此，所得之戴奥辛類測試樣品可作 為測試戴奥辛脫除能力的反應物，更可降低購買戴奥辛標 準品之成本。 雖然本發明已以實施例揭露如上，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内，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。 【圖式簡單說明】 為讓本發明之上述和其他目的、特徵、優點與實施例 Φ 能更明顯易懂，所附圖式之詳細說明如下： 第1圖係繪示根據本發明一實施例的戴奥辛類測試樣 品之製造方法的部分流程圖。 第2圖係繪示根據本發明一實施例之戴奥辛類流連續 產生設備的示意圖。 第3圖係繪示根據本發明一實施例之戴奥辛類化合物 之出口煙道氣流之濃度曲線圖。 [s] 【主要元件符號說明】 19 201215869As is apparent from the results of Fig. 3, the concentration of the flue gas stream of the dioxin-like derivative obtained by the cleavage can be approximately from about 0.1 ng_TEQ/Nrn3 to: 48.5 ng-TEQ/Nm3, and a stable dioxin gas flow can be continuously produced. Further, in step j, the concentration of the flue gas stream of the dioxin-like test sample may be, for example, about 11.0 ng-TEQ/Nm3 to about 13.0 ng-TEQ/Nm3. For example, when the supply flow rate of the dioxin-like compound is about 4 pL/hr and the gas flow rate is about 0.8 L/min, the influent concentration of the dioxin-like compound is about 12.140 ng-TEQ/Nm3. Except for the temperature of 575 ° C before the conditions of about 3 〇, the recovery of the dioxin-like compound is about 84.6%, when the destruction temperature of the alkane is 525T:, 550 ° C and 575 ° C, with the operation With the increase in the gate, the recovery of the dioxin-like compound is maintained generally at about 90 percent to about 110 percent. Secondly, with the increase in the destruction temperature, the recovery rate of the dioxin-like compound tends to be low. In addition, it is to be noted that the present invention describes the manufacturing method of the dioxin test sample of the present invention by using a specific dioxin compound, extraction method, solvent, gas, reaction conditions or cracking equipment as an example, but the technical field to which the present invention pertains It is to be understood that the invention is not limited thereto, and the method for producing a dioxin test sample of the present invention may also use other dioxin compounds 201215869, extraction methods, and without departing from the spirit and scope of the present invention. The solvent, gas, reaction conditions or cracking equipment are carried out. It can be seen from the above embodiments of the present invention that the manufacturing method of the dioxin test sample of the present invention has the advantages of using the chlorine-containing metal to carry out the fly ash accompanying the high-temperature process, and extracting the dioxin test sample having the composition similar to the process site exhaust gas. . Therefore, the resulting dioxin test sample can be used as a reaction to test the dioxin removal ability, and the cost of purchasing the dioxin standard can be reduced. Although the present invention has been disclosed in the above embodiments, it is not intended to limit the present invention, and any one of ordinary skill in the art to which the present invention pertains may 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. BRIEF DESCRIPTION OF THE DRAWINGS The above and other objects, features, advantages and embodiments of the present invention will become more apparent and understood. Part of the flow chart for the manufacturing method of the dioxin test sample. Fig. 2 is a schematic view showing a dioxin-like flow continuous generating apparatus according to an embodiment of the present invention. Figure 3 is a graph showing the concentration of the exit flue gas stream of a dioxin-like compound according to an embodiment of the present invention. [s] [Key component symbol description] 19 201215869
ίο:方法 11 :進行萃取步驟，以利用第 一有機溶劑萃取飛灰而獲得 粗萃溶液，且此飛灰係由含氣 之金屬進行高溫製程伴隨產 生之步驟 13 :進行淨化步驟，以從前述 之粗萃物獲得戴奥辛類化合 物之步驟 15 :進行配製步驟，以將前述 之戴奥辛類化合物溶解於第 四有機溶劑中，而形成淨化液 之步驟 17 :進行裂解步驟，以於500 它至550°C之溫度下，裂解淨 化液中85百分比至99百分比 之第四有機溶劑，而獲得戴奥 辛類測試樣品之步驟 100 :戴奥辛類流連續產生設 備 101 :注入口 102/104/106 :三向閥 103 :空氣筒 105 :氣體流量控制計 107 :預熱區 110 :石英爐管 111 :玻璃珠混合設備 120 :溫度控制器 130:氣相層析儀/火焰離子化 偵測器 131/132/133/134/135/136/137 /138 :管路 141a/141b/142a/142b:吸收管 柱 143a/143b :空置管柱 161 :矽膠管柱 170 :冷凝箱 180 :真空幫浦 [S] 20Οο: Method 11: performing an extraction step of extracting fly ash with a first organic solvent to obtain a crude extraction solution, and the fly ash is subjected to a high temperature process accompanied by a gas-containing metal. Step 13: performing a purification step to Step 15 of obtaining a dioxin-like compound from the crude extract: performing a preparation step of dissolving the aforementioned dioxin-like compound in a fourth organic solvent to form a purification liquid, step 17: performing a lysis step, at 500 to 550 ° At a temperature of C, cleavage of 85 to 99% of the fourth organic solvent in the purification liquid, and obtaining a dioxin-like test sample, step 100: dioxin-like flow continuous production apparatus 101: injection port 102/104/106: three-way valve 103 Air cylinder 105: gas flow controller 107: preheating zone 110: quartz furnace tube 111: glass bead mixing device 120: temperature controller 130: gas chromatograph/flame ionization detector 131/132/133/ 134/135/136/137 /138: line 141a/141b/142a/142b: absorption column 143a/143b: empty column 161: rubber column 170: condensation box 180: vacuum pump [S] 20