TWI317648B

TWI317648B - Method and apparatus for processing nitrogen oxide and sulfur oxide

Info

Publication number: TWI317648B
Application number: TW095125957A
Authority: TW
Inventors: Shiao-Shing Chen; Chung-Cheng Wei; Chih-Yu Cheng
Original assignee: Univ Nat Taipei Technology
Priority date: 2006-07-14
Filing date: 2006-07-14
Publication date: 2009-12-01
Also published as: TW200803963A

Description

1317648 九、發明說明：【發明所屬之技術領域】本發明係一種關於處理氮氧化物及硫氧化物之方法聽置1別是-種_零價鐵之還原特性，併同處理煙道氣中氣氧化物及硫氧化物之方法及褒置。【先前技術】空氣污染物中的氮氧化物主要是指一氧化氮（No)及一氧化氮（N〇2)’而在人為產生的氮氡化物，主要以一氧化氮的形式排放，因此，一氧化氮遂成為氮氧化物控制的主要污染物。氮氧化物在大氣中易與碳氫化合物反應，形成酸雨、光化學煙霧及造成溫室效應，對人體及環境造成損壞。現行煙道氣脫确處理技術可分乾式及濕式兩大類，乾式法包括 SCR(Selective Catalytic Reduction)及 SNCR(Selective Non- Catalytic Reduction)等，濕式法則有氧化/吸收法、吸收/還原法、及氧化/吸收/還原法等。然因濕式法吸收NOx後會產生水污染的問題，因此目前大型污染源(如發電用鍋爐、煉鋼爐等）所採行的方法多為SCR，茲針對SCR處理技術及SNCR處理技術說明如下： (1 )選擇性觸媒還原法（SCR，Selective Catalytic Reduction) SCR處理技術由於去除效率較高（70〜90%)，因此為目前廣泛應用的廢氣脫硝技術，由於化學反應之活 1317648 化能較高，因此使用v2〇5_Ti〇2或添加其他特殊成分製成觸’以加速反應的進行。但因燃燒廢氣中含有S〇2，其會與過剩之丽3反應生成(nh4)2so4 及NEUHS04沉積於觸媒表面造成腐钱（李天財、薛人象，燃煤鍋爐使用選擇性觸媒還原反應器（SCR) 之問題探討，燃燒季刊，第十三卷第四期，2004)，且廢氣中如含有粉塵，亦將磨蝕觸媒，造成觸媒阻基或注氨阻塞等問題，使觸媒使用年限減少，產生觸媒更新問題。 (2)選擇性非觸媒還原法(SNCR，Selective Non-Catalytic Reduction) SNCR處理技術是將含氮溶液(尿素或液氨）直接喷入高溫煙道氣中（900〜1200。〇，將NOx還原為N2及 HzO。SNCR雖然設備及操作費用較便宜，但去除率比 SCR差，在理想情況下，仍有20〜30%的NOx無法去除，作為還原劑的NH3可能造成鍋爐腐蝕，如NH3反應不完全，亦可能隨著煙道氣排放造成環境二次污染。空氣污染物中的硫氧化物係二氧化硫（S02)及三氧化硫（S〇3)之總稱，二氧化硫是含硫的煤及燃油燃燒時所產生，二氧化硫會繼續與氧反應生成三氧化硫，當大氣中有水氣存在時，二氧化硫、三氧化硫會與水作用形成亞硫酸及硫酸’造成酸雨，不僅對人體健康造成傷害且危害生態環境。目前對於so2排放之控制方法，除採用低含硫燃料以 1317648 降低S〇2排放量，對煙道氣排放之s〇2之處理方法主要為煙道氣除硫法(Flue Gas Desulfurization, FGD)，依其副產物之處置方式可分為產物拋棄式(throwaway product)及產物可售式(saleable product)二種，再由其反應劑投入方式又可區分為濕式、乾式及半乾式。產物拋棄式FGD為最普遍被採用的系統，但無論是採濕式、乾式或半乾式之型式，均有二次污染物（污泥或固體廢棄物）之處置問題。產物可售式 $ FGD處理後雖可回收硫磺或硫酸等有價產物，但其設置成本高’設備系統複雜，產品市場不大等因素，所以尚無法被廣泛接受。 FGD主要是為處理大型燃煤（油）火力發電廠之煙道氣而設計，用於其他工業鍋爐燃燒設備較不經濟。有關FGD 以外之除硫技術之研究，以觸媒氧化法(Catalytic oxidation process)最為普遍。觸媒氧化法通常以r -A1203、Ce203、 Si〇2、Zr02等擔體來擔持貴重金屬或過渡金屬氧化物，氧；化金屬在有氧情況下，會與so2作用將其氧化生成金屬硫酸鹽。亦有文獻中指出以六種不同金屬氧化物擔持於Zr〇2 去除S〇2發現以Cll〇2效果最好’而pt> Zr〇2- AI2O3能夠耐受金屬硫酸鹽之毒化（Kikuyama, S.，Miura，A., Kikuchi，R.， Takeguchi, T. and Eguchi, K., "SOx sorption-desorption characteristics by Zr02-based mixed oxides," Applied Catalysis, Applied catalysis A:General 259, 2003, pp.191-197.)。研究發現在無氧狀況下，Ce02也可以吸附氧化S02,而由Ti〇2、Al203、 MgO、BaO、Zr02生成之金屬硫酸鹽，高溫時可分解，並 1317648 • 可以CO或H2還原氣體還原再生（Limousy,L.，Mahzoul，H.，1317648 IX. Description of the invention: [Technical field to which the invention pertains] The present invention relates to a method for treating nitrogen oxides and sulfur oxides, which is to be used in the treatment of flue gas. Methods and apparatus for gas oxides and sulfur oxides. [Prior Art] Nitrogen oxides in air pollutants mainly refer to nitric oxide (No) and nitric oxide (N〇2)', which are produced in the form of nitrogen monoxide, which is mainly produced in the form of nitric oxide. Nitric oxide is the main pollutant controlled by nitrogen oxides. Nitrogen oxides are easily reacted with hydrocarbons in the atmosphere to form acid rain, photochemical smog and cause greenhouse effects, causing damage to humans and the environment. The current flue gas decontamination treatment technology can be divided into dry and wet types. The dry method includes SCR (Selective Catalytic Reduction) and SNCR (Selective Non- Catalytic Reduction). The wet method includes oxidation/absorption method and absorption/reduction method. And oxidation/absorption/reduction methods, etc. However, the problem of water pollution is caused by the absorption of NOx by the wet method. Therefore, the methods adopted by large-scale pollution sources (such as boilers for power generation, steel-making furnaces, etc.) are mostly SCR. The SCR processing technology and SNCR processing technology are explained below. : (1) Selective Catalytic Reduction (SCR) SCR treatment technology is a widely used exhaust gas denitration technology due to high removal efficiency (70~90%), due to the chemical reaction activity 1317648 It can be higher, so use v2〇5_Ti〇2 or add other special ingredients to make a touch to accelerate the reaction. However, due to the presence of S〇2 in the combustion exhaust gas, it will react with the excess 丽3 to form (nh4)2so4 and NEUHS04 deposited on the surface of the catalyst to cause rot (Liang Tiancai, Xue Renxiang, coal-fired boilers using selective catalyst reduction reaction) Discussion on the problem of the device (SCR), Burning Quarterly, Vol. 13 (4), 2004), and if the exhaust gas contains dust, it will also abrade the catalyst, causing problems such as catalyst blockage or ammonia injection blocking. Reduced service life, resulting in catalyst update issues. (2) Selective Non-Catalytic Reduction (SNCR) The SNCR treatment technique is to directly spray a nitrogen-containing solution (urea or liquid ammonia) into a high-temperature flue gas (900 to 1200. 〇, NOx Reduced to N2 and HzO. Although the equipment and operation cost is cheaper, the removal rate is worse than SCR. Under ideal conditions, 20~30% of NOx cannot be removed. NH3 as a reducing agent may cause corrosion of the boiler, such as NH3. Incomplete reaction may also cause secondary pollution of the environment with flue gas emissions. The sulfur oxides in air pollutants are the general term for sulfur dioxide (S02) and sulfur trioxide (S〇3). Sulfur dioxide is sulfur-containing coal and When fuel is burned, sulfur dioxide will continue to react with oxygen to form sulfur trioxide. When there is moisture in the atmosphere, sulfur dioxide and sulfur trioxide will react with water to form sulfurous acid and sulfuric acid, causing acid rain, which not only harms human health. And it is harmful to the ecological environment. At present, for the control method of so2 emission, in addition to using low-sulfur fuel to reduce S〇2 emissions by 1317648, the treatment method for flue gas emissions is mainly flue. Flue Gas Desulfurization (FGD) can be divided into two types: the throwaway product and the saleable product according to the disposal method of its by-products, which can be distinguished by the reactant input method. It is wet, dry and semi-dry. Product-disposable FGD is the most commonly used system, but whether it is wet, dry or semi-dry, there are secondary pollutants (sludge or solid waste). Disposal problem. Although the product can be sold at a price of $ FGD, although valuable products such as sulfur or sulfuric acid can be recovered, but the installation cost is high, the equipment system is complicated, and the product market is not large, so it is not widely accepted. FGD is mainly for processing. It is designed to be used as a flue gas for large coal-fired (oil) thermal power plants, and it is less economical for other industrial boilers. The research on desulfurization technology other than FGD is most common with the Catalytic oxidation process. Catalytic oxidation method usually carries precious metals or transition metal oxides, such as r-A1203, Ce203, Si〇2, Zr02, etc., in the case of oxygen, in the case of aerobic conditions, The action of o2 oxidizes it to form metal sulfate. It is also pointed out in the literature that six different metal oxides are supported in Zr〇2. S〇2 is removed and it is found that Cll〇2 has the best effect while pt> Zr〇2-AI2O3 can Tolerance to metal sulfate (Kikuyama, S., Miura, A., Kikuchi, R., Takeguchi, T. and Eguchi, K., "SOx sorption-desorption characteristics by Zr02-based mixed oxides," Applied Catalysis, Applied catalysis A: General 259, 2003, pp. 191-197.). It is found that under anaerobic conditions, Ce02 can also adsorb and oxidize S02, while the metal sulfate produced by Ti〇2, Al203, MgO, BaO, Zr02 can be decomposed at high temperature, and 1317648 • can be reduced by CO or H2 reducing gas. (Limousy, L., Mahzoul, H.,

Brilhac,J.F., Gilot,P., Garin,F. and Maire,G., "S02 sorption on fresh and aged SOx traps," Applied Catalysis, Applied catalysis B:Environmental 42, 2003, pp.237-249 ；Brilhac, J.F., Gilot, P., Garin, F. and Maire, G., "S02 sorption on fresh and aged SOx traps," Applied Catalysis, Applied catalysis B: Environmental 42, 2003, pp. 237-249;

Limousy,L.,Mahzoul,H.,Brilhac,J.R,Gilot,R,Garin,F. and Maire,G., , "A study of the regeneration of fresh and aged SOx adsorbers under , reducing condition," Applied Catalysis, Applied catalysis B:Enviromnental 45, 2003, pp. 169-179.)。近年來觸媒氧化法之研究’逐漸朝向併同處理SOx及NOx的趨勢，其採用的氧扣觸媒有天然錳礦、鈣鎂醋酸鹽及Cu02等，其中天然猛 . 礦耐磨性佳，還可採流動床方式處理。觸媒氧化法係利用貝重金屬或過渡金屬乳化物為催化劑，雖可將S 轉化為硫酸鹽或硫酸回收，但有觸媒價格昂貴及酸性腐钱問題等缺點。現今對於氮氧化物與硫氧化物的併同處理仍以濕式處理或觸媒反應等方式為主，尤其，近年來觸媒氧化法之研究，已逐漸朝向併同處理N〇x&S〇x的趨勢，其採用的氧化觸媒有天然猛礦、舞镁錯酸鹽及Cu〇2等。但上述處理方式仍有缺點，如濕式處理有廢水、廢棄物處置等二次污染處理問題，觸媒氧化法則有成本高、酸腐蝕、觸媒毒化及使用後觸媒處理等問題。【發明内容】基於上述’本發明的目的之一係提供一種處理氮氧化 1317648 物/硫氧化物之方法，此方法是經由使用零價鐵將氮氧化物/ 硫氧化物還原，而達減低污染之目的。零價鐵因其價格低且有強還原能力，並具有取得容易，使用後鐵粉為無害且 '可回收再利用等特性，符合目前零廢棄之環保趨勢等優點。且目前尚未見以零價鐵粉併同處理一氧化氮、二氧化硫之方法併同處理氮氧化物及硫氧化物的方法，此併同處理的方法可簡化處理流程，並減少處理設施的設置及操作費用。本發明的方法係包含將含有氮氧化物及硫氧化物之氣體與零價鐵粉接觸，並於至少623K的溫度下反應。藉由 '在高溫下使氮氧化物及硫氧化物與零價鐵粉產生氧化還原 I 反應’而有效降低經處理後氣體中的氮氧化物及硫氧化物含量。 • ->· 本發明的方法之另一種實施樣態，其包含下列步驟：G) 提供一反應器，該反應器包含一反應槽體、一設於該反應槽體之進料端、一設於該反應槽體i出料端，以及一加熱裝置；（2)將足夠處理該些氮氧化物及硫氧化物之零價鐵粉 ' 置入該反應槽體中，並以加熱裝置使該反應槽體之溫度到、達並維持在至少623K; (3)以及使含有該些氮氧化物及硫氧化物之氣體由該進料端通入，接觸該零價鐵粉，使該些氣體中之氮氧化物及硫氧化物降低後，再由該出料端排出。上述反應槽體之溫度應維持在至少623K，且越高的溫度T以使單位零價鐵粉處理更尚量的氮氧化物及硫氧化物。較佳的溫度為至少723K，更佳者為至少773κ。 10 1317648 上述之反應器可進一步包含一流量控制器控制該進料端之進料速率。另外，上述之反應器亦可為一習用的流體化床反應器。在化學工業裝置中，經常利用流體流經填充床，以增加兩相之接觸面積，提高均勻性及反應速率。諸如氣涂气乾燥器、氣體吸收填充塔、異相觸媒反應器、固粒氣流輪送裝置等。簡單之填充床是在一中空導管下端裝置—筛網 )(或多孔板），其上堆積固體粒子而成。流速再增加時，則所有之固體粒子被懸浮在往上流動之流體中，而呈現约勺之狀態，此時稱之為開始流體化床（或最小流體化床）。此時，流體與固體粒子間之摩擦力和固體粒子所受之浮力與粒子之重量相等。此刻之流體速度稱為最小流體化速产 (minium fluidization velocity)。若再繼續增加流體之令速’則粒子床慢慢升高，而得十分均勻之流體化床，稱為顆粒流體化床。當產生流體化床後，流體之流速再增加時， ' 壓力落差仍保持不變，但粒子床之高度增加，空隙度亦增加，若再增加流體之流速，則粒子會被流體挾帶流出導管，不再有流體化床而輸出輸送區域。同時，尚可利用一氣體排放監測系統監測該出料端排出之氣體中所含之氮氧化物及硫氧化物的含量，以調整處理的條件或適時更換零價鐵粉。本發明之另一目的為提供一種處理氮氧化物及硫氧化物之裝置，其包含：一反應槽體，該反應槽體中具有足夠處理該些氮氧化物及硫氧化物之零價鐵粉；一進料端，其 11 1317648 係設於該反應槽體上，作為含有氮氧化物及硫氧化物之氣體之進入端；一加熱裝置，其係用以使該反應槽體的溫度到達並維持在至少623K;以及一出料端，其係設於該反應槽體上’作為經處理氣體之排出端。因為越局的溫度可以使單位零價鐵粉處理更高量的氮氧化物及硫氧化物，因此，上述之加熱裝置需使該反應槽體的溫度到達並維持在至少623K，較隹者為至少723K，更佳者為至少773Κ。且該加熱裝置可環設於該反應槽體之外。上述裝置尚可進-步包含一流量控制器控制該進料端之進料速率。另外’上㈣置可為—習用的流體化床反應器。同時，上述該裝置可進一步包含一氣體排放監測系統監測該出料端翻之氣射所含之氮氧化物及硫氧化物的含量。以下將以實施例進一步說明本發明的實施方式，下列實施例僅係供:乍例示及說明，並非用以限定本發日㈣圍。應瞭解的是，本領域中且古太細^ 通常知識者#可在不脫離本發明的精神及乾疇下進行些許、… 後附之申請專利範圍而定。 ^ 乾圍當視【實施方式】 12 1317648 示’取一内徑為0.8 cm，總長度為76 cm之反應管柱17，於該反應管柱17之靠近一端部處，設有一 4 cm的束縮段 12，此束縮段12可加快氣體進流速度，使鐵粉易於流體化。於束縮段12之端部，置入玻璃棉Η，此段玻璃棉14可作為支稽鐵粉及平均分配進流氣體外，並可延長進流氣體預熱時間。由該反應管柱17的上方開口填入零價鐵粉，並於開口端置入玻璃棉15。反應管柱17的外圍設有加熱器is，其係藉由溫度控制器20所控制’此溫度控制器2〇可偵測反應區13之反應溫度，再經由反應套組1〇中之加熱器18 加熱控制反應溫度。反應套组1〇外包覆有一保溫絕熱層 19,該保溫絕熱層19可降低反應管柱之溫度散逸，減少加熱耗能。反應管柱17的下方設有進料端5〇，其係藉由管路4〇與氣體流1：控制ϋ 30連接，藉以控制進人氣體的流量及流速。另外，於反應管柱17的上方設有排氣端⑼，排氣端 60 .經由管路連接至氣体連續排放監測系統⑽ Emission Monit()ring System，CEMs)7()，其可進行連續監測分析氮氧化物及硫氧化物的濃度。此監測线可將分析結果連接個人電腦之數賴㈣儲存，亦可依此回潮控制 =體之進氣速度及反m以魏體處歡最佳效率，或可作為維修或更換耗材之數據參考。 …利用上述裝置處理氮氧化物及硫氧化物時，是將含有氣氧化物及硫氧化物之欲虚 .# 欲處理乳體猎由官路4〇與氣體流量 13 1317648 控制器30 I入已預熱至特定溫度，並包含零價鐵粉i6的反應套組10 ’於此區段中，零價鐵粉16與欲處理氣體反應 -後’可降低該氣體中之氮氧化物及硫氧化物，再由排氣端 60排出。、，· 、反應管柱之進料端50設有一預熱區11，可將欲處理氣體賴後再進人反應區I3，如此將更有财反應溫度之控制。反應溫度較佳控制在673K以上，更佳為773K以上。 , 關於本發明之處理氮氧化物及硫氧化物之裝置，可以包含更多的反應套組10,而反應套組10可串聯或並聯連接。即欲處理氣體通過-組反應套組後，由排氣端排放出 :之氣體可再連接另一組反應套組之.進氣端而連續處理廢 : 氣。或者是，欲處理氣體以歧管同時導入數個反應套之進料端而同時處理。因此，可視需要而增加或減少反應套組之數量’以達處理廢氣之最佳效率。以中小型規模的柴油發電機或鍋爐為例，本發明同時可以處理氮氧化物及硫氧化物，處理效率在溫度以上時，氮氧化物達80%以上，而硫氧化物可達7〇%以上，並且無 . 二次污物產生。本發明所提供的裝置利用零價鐵之還原特. -；性，併同處理煙道氣中氮氧化物及硫氧化物。除了不會有現有處理氮氧化物及硫氧化物之缺點之外，以一套設備同步處理氮氧化物及硫氧化物來取代使用兩套設備分別處理氮氧化物及硫氧化物，因此更有其經濟價值。實施例2 利用本發明之方法處理氮氧化物及硫氧化物組裝如實施例1所述之裝置，但係使用下述之材料及 14 1317648 設備。材料· 1.零價鐵粉(iron p〇wder):粒徑<212# m(70 mesh)，純度99.9 % ’比表面積為0.183 m2/g，廢牌：德國 Riedel-deHagn(RdH)。 2·高純度氮氣：純度99.999 %，廠牌：三福氣體或聯華氣體。 ) 3. —氧化氣“準氧體：NO濃度為6000 ppm，Balanced with Ns gas，±2%，廠牌：僑泰氣體有限公司。 4. 一氧化硫標準氟體：s〇2濃度為6000 ppm，Balanced with N2 gas ’ 土2%，廠牌：僑泰氣體有限公司。 5. NIST標準氣體：S02濃度為861 ppm，CO濃度為853 ppm ’ Balanced with N2 gas，士1 〇/0，廠牌： SCOTT-MARRIN,INC.。 6. 管柱：採用内徑8 mm的破璃管製作。 ) 設備： 1.連續自動監測儀器：Limousy, L., Mahzoul, H., Brilhac, JR, Gilot, R, Garin, F. and Maire, G., , "A study of the regeneration of fresh and aged SOx adsorbers under , reducing condition," Applied Catalysis, Applied catalysis B: Enviromnental 45, 2003, pp. 169-179.). In recent years, the research on catalyst oxidation method has gradually moved toward the same trend of SOx and NOx. The oxygen-catalyzing catalysts used are natural manganese ore, calcium-magnesium acetate and Cu02, among which natural minerals have good wear resistance. It can be treated by flow bed method. Catalyst oxidation uses a heavy metal or transition metal emulsion as a catalyst. Although S can be converted to sulfate or sulfuric acid, there are disadvantages such as high catalyst cost and acid decay. Nowadays, the simultaneous treatment of nitrogen oxides and sulfur oxides is still mainly in the form of wet treatment or catalytic reaction. In particular, in recent years, studies on catalytic oxidation have gradually approached N〇x&S〇. The trend of x is that the oxidizing catalysts used are natural smear, magnesium sulphate and Cu 〇 2 . However, the above treatment methods still have disadvantages, such as wet treatment with secondary pollution treatment such as waste water and waste disposal, and the catalyst oxidation method has problems such as high cost, acid corrosion, catalytic poisoning and catalyst treatment after use. SUMMARY OF THE INVENTION One of the objects of the present invention is to provide a method for treating nitrogen oxide 1317648/sulfur oxide by reducing nitrogen oxide/sulfur oxide by using zero-valent iron to reduce pollution. The purpose. Due to its low price and strong reducing ability, zero-valent iron has the advantages of easy to obtain, and the iron powder is harmless and can be recycled and reused after use, which is in line with the current environmental trends of zero waste. At present, there is no method for treating nitrogen oxides and sulfur oxides with zero-valent iron powder and treating nitrogen monoxide and sulfur dioxide, and the same treatment method can simplify the treatment process and reduce the setting of treatment facilities. Operating costs. The process of the present invention comprises contacting a gas containing nitrogen oxides and sulfur oxides with zero-valent iron powder and reacting at a temperature of at least 623K. The content of nitrogen oxides and sulfur oxides in the treated gas is effectively reduced by 'reacting redox I with nitrogen oxides and sulfur oxides at low temperatures to produce zero-valent iron powders'. • ->· Another embodiment of the method of the present invention comprises the steps of: G) providing a reactor comprising a reaction tank body, a feed end disposed at the reaction tank body, and a Provided in the discharge end of the reaction tank body i, and a heating device; (2) placing a zero-valent iron powder sufficient to treat the nitrogen oxides and sulfur oxides into the reaction tank body, and heating the device The temperature of the reaction tank reaches, reaches and is maintained at at least 623 K; (3) and the gas containing the nitrogen oxides and sulfur oxides is introduced from the feed end to contact the zero-valent iron powder to make the After the nitrogen oxides and sulfur oxides in the gas are lowered, they are discharged from the discharge end. The temperature of the above reaction tank should be maintained at at least 623 K, and the higher temperature T is such that more zero amount of nitrogen oxides and sulfur oxides are treated by the unit zero-valent iron powder. The preferred temperature is at least 723 K, more preferably at least 773 K. 10 1317648 The reactor described above may further comprise a flow controller for controlling the feed rate of the feed end. Alternatively, the reactor described above may be a conventional fluidized bed reactor. In chemical industrial plants, fluids are often used to flow through a packed bed to increase the contact area of the two phases, increasing uniformity and reaction rate. Such as gas-coated gas dryers, gas absorption packed towers, heterogeneous catalyst reactors, solid-grain gas flow devices, and the like. A simple packed bed is a hollow conduit lower end device - a screen (or a perforated plate) from which solid particles are deposited. When the flow rate is increased again, all of the solid particles are suspended in the upward flowing fluid to assume a state of about scoop, which is referred to as starting a fluidized bed (or a minimum fluidized bed). At this time, the friction between the fluid and the solid particles and the buoyancy of the solid particles are equal to the weight of the particles. The fluid velocity at this moment is called the minimum fluidization velocity. If the speed of the fluid is further increased, the particle bed is slowly raised, and a fluidized bed which is very uniform is called a fluidized bed of particles. When the fluidized bed is generated, the flow rate of the fluid increases again, the pressure drop remains unchanged, but the height of the particle bed increases, and the voidage also increases. If the flow velocity of the fluid is increased, the particles will be carried out of the conduit by the fluid. , no more fluidized bed and output delivery area. At the same time, a gas emission monitoring system can be used to monitor the content of nitrogen oxides and sulfur oxides contained in the gas discharged from the discharge end to adjust the processing conditions or to replace the zero-valent iron powder in a timely manner. Another object of the present invention is to provide an apparatus for treating nitrogen oxides and sulfur oxides, comprising: a reaction tank body having sufficient zero-valent iron powder for treating the nitrogen oxides and sulfur oxides; a feed end, 11 1317648 is disposed on the reaction tank as an entry end of a gas containing nitrogen oxides and sulfur oxides; a heating device is used to bring the temperature of the reaction tank to and Maintained at least 623K; and a discharge end, which is disposed on the reaction tank as the discharge end of the treated gas. Because the temperature of the end office can make the unit zero-valent iron powder process a higher amount of nitrogen oxides and sulfur oxides, the above heating device needs to make the temperature of the reaction tank reach and maintain at least 623K, which is better. At least 723K, and even better at least 773Κ. And the heating device can be disposed outside the reaction tank body. The apparatus described above may further comprise a flow controller for controlling the feed rate of the feed end. In addition, the upper (four) arrangement can be a conventional fluidized bed reactor. At the same time, the apparatus may further comprise a gas emission monitoring system for monitoring the content of nitrogen oxides and sulfur oxides contained in the gas jet of the discharge end. The embodiments of the present invention will be further described by the following examples, which are merely intended to illustrate and illustrate, and are not intended to limit the scope of the present invention. It should be understood that the present invention may be practiced in the art without departing from the spirit and scope of the invention. ^干围视视 [Embodiment] 12 1317648 shows 'take an inner diameter of 0.8 cm, a total length of 76 cm of the reaction column 17, near the end of the reaction column 17, with a 4 cm bundle The constricted section 12, which accelerates the gas inflow velocity, makes the iron powder easy to fluidize. At the end of the bundled section 12, a glass wool quilt is placed, and the glass wool 14 can be used as the iron powder and the average distribution of the inflow gas, and the inflowing gas preheating time can be extended. Zero-valent iron powder is filled in from the upper opening of the reaction column 17, and glass wool 15 is placed at the open end. A heater is is disposed on the periphery of the reaction column 17, which is controlled by the temperature controller 20. The temperature controller 2 detects the reaction temperature of the reaction zone 13 and passes through the heater in the reaction set 1 18 Heating controls the reaction temperature. The reaction jacket 1 is covered with a heat insulating layer 19, which can reduce the temperature dissipation of the reaction column and reduce the heating energy consumption. Below the reaction column 17, a feed end 5 is provided which is connected to the gas stream 1: control port 30 by a line 4, thereby controlling the flow rate and flow rate of the incoming gas. In addition, an exhaust end (9) is provided above the reaction column 17, and the exhaust end 60 is connected to the gas continuous emission monitoring system (10) Emission Monit () ring system, CEMs) 7 () via a pipeline, which can be continuously monitored. Analyze the concentration of nitrogen oxides and sulfur oxides. This monitoring line can be used to connect the analysis results to the personal computer (4) storage, or according to the resurgence control = body intake speed and anti-m to the best efficiency of the Wei body, or as a data reference for repair or replacement of consumables . ... When using the above device to treat nitrogen oxides and sulfur oxides, it will contain gas oxides and sulfur oxides. #要处理乳猎猎由官路4〇 and gas flow 13 1317648 controller 30 I Preheating to a specific temperature, and containing a zero-valent iron powder i6 reaction set 10 'in this section, zero-valent iron powder 16 reacts with the gas to be treated - after 'reducing nitrogen oxides and sulfur oxidation in the gas The object is then discharged by the exhaust end 60. The feed end 50 of the reaction column is provided with a preheating zone 11 for allowing the gas to be treated to enter the reaction zone I3, which will control the reaction temperature. The reaction temperature is preferably controlled to be 673 K or more, more preferably 773 K or more. Regarding the apparatus for treating nitrogen oxides and sulfur oxides of the present invention, more reaction kits 10 may be contained, and the reaction jackets 10 may be connected in series or in parallel. That is, after the gas passes through the group reaction set, the gas discharged from the exhaust end can be connected to the intake end of the other set of reaction sets to continuously treat the waste: gas. Alternatively, the gas to be treated is simultaneously processed by a manifold simultaneously introduced into the feed ends of the plurality of reaction jackets. Therefore, the number of reaction sets can be increased or decreased as needed to achieve optimum efficiency in treating the exhaust gases. Taking small and medium-sized diesel generators or boilers as an example, the present invention can simultaneously treat nitrogen oxides and sulfur oxides. When the treatment efficiency is above temperature, the nitrogen oxides are more than 80%, and the sulfur oxides can reach 7〇%. Above, and no. Secondary dirt is produced. The device provided by the invention utilizes the reduction of zero-valent iron and treats nitrogen oxides and sulfur oxides in the flue gas. In addition to the shortcomings of the existing treatment of nitrogen oxides and sulfur oxides, a series of equipment is used to simultaneously treat nitrogen oxides and sulfur oxides instead of using two sets of equipment to treat nitrogen oxides and sulfur oxides separately. Its economic value. Example 2 Treatment of Nitrogen Oxides and Sulfur Oxides by the Method of the Invention The apparatus described in Example 1 was assembled using the materials described below and 14 1317648 equipment. Materials · 1. Iron p〇wder: particle size <212# m (70 mesh), purity 99.9 % 'specific surface area is 0.183 m2 / g, waste brand: Germany Riedel-deHagn (RdH). 2. High purity nitrogen: purity 99.999%, label: Sanfu gas or Lianhua gas. 3. Oxidation gas “Phosphorus: NO concentration is 6000 ppm, Balanced with Ns gas, ±2%, label: Qiaotai Gas Co., Ltd. 4. Sulfur oxide standard fluorine: s〇2 concentration is 6000 Ppm, Balanced with N2 gas ' soil 2%, label: Qiaotai Gas Co., Ltd. 5. NIST standard gas: S02 concentration is 861 ppm, CO concentration is 853 ppm ' Balanced with N2 gas, 士1 〇/0, factory Brand: SCOTT-MARRIN, INC. 6. Pipe column: made of glass tube with inner diameter of 8 mm.) Equipment: 1. Continuous automatic monitoring instrument:

a、量測原理：NDIR b、量測範圍：Ν〇=〇〜400 ppm最大1000 ppm S〇2=〇〜400 ppm 最大 1000 ppm CO=〇〜500 ppm 最大 1000 ppm 〇2=0〜25 % H2〇=〇〜28000 ppm c、廠牌：德國 SICK MAIHAK AG (Modular System 15 1317648 S710) 2. 質量流量控制器： a、量測最大範圍：NO : 80 mL/min N2 : 400 mL/min S〇2 : 80 mL/min b、薇牌：章嘉 3. 分析天平： a、量測範圍：0.〜200.g/min b、量測精度：O.lmg c、廠牌：德國 SCALTEC (SBC-32) 4·加熱器：以50x50mm之鋁材、加熱管、耐熱膠帶、矽鐵龍隔熱帶、岩棉管及電熱線圈等組合而成。 5. PID溫度控制器：a, measurement principle: NDIR b, measurement range: Ν〇 = 〇 ~ 400 ppm maximum 1000 ppm S 〇 2 = 〇 ~ 400 ppm maximum 1000 ppm CO = 〇 ~ 500 ppm maximum 1000 ppm 〇 2 = 0 ~ 25% H2〇=〇~28000 ppm c, label: Germany SICK MAIHAK AG (Modular System 15 1317648 S710) 2. Mass flow controller: a. Measurement range: NO: 80 mL/min N2 : 400 mL/min S 〇 2 : 80 mL / min b, Wei brand: Zhang Jia 3. Analytical balance: a, measurement range: 0. ~ 200.g / min b, measurement accuracy: O.lmg c, label: Germany SCALTEC ( SBC-32) 4·Heater: It is made up of 50x50mm aluminum, heating tube, heat-resistant tape, Nippon-iron insulation tape, rock wool tube and electric heating coil. 5. PID temperature controller:

a、量測範圍：0.0.〜999.9°Ca, measurement range: 0.0. ~ 999.9 ° C

b、控制範圍：0.0·〜999.9°Cb, control range: 0.0·~999.9 °C

c、量測精度：0.1°C d、量測誤差：±1%c, measurement accuracy: 0.1 ° C d, measurement error: ± 1%

e、熱電偶：K-TYPE f、廠牌：國產 VERTEX (VT 4800) 6. X光粉末繞射光譜儀（XRD，X-Ray powder Diffraction) 廠牌：曰本 RigakuCo.(DMAX 2200 VK) 進料氣體係由6000 ppmNO、S02標準氣體與純N2氣體經質量流量控制器稀釋調配所供應。進料氣體引入實驗 16 1317648 管柱前，先通過流量控制器，調整質量流量控制器，再導入填充零價鐵粉之反應管柱。管柱之鐵粉反應區外部以鋁質電熱管加熱，電熱管外層以岩綿隔離包覆保溫。進行處理前，先預熱約二十分鐘使溫度穩定，在氣體處理過程中，電熱器之加熱係以比例式積分微分(proportional integral derivative，PID)溫控器控制’使反應溫度維持在設定溫度 ±1.5 °C範圍内，以進行定溫反應。進料氣體與鐵粉反應後，通入氣體連續排放監測系統（Continuous Emissioiie, thermocouple: K-TYPE f, label: domestic VERTEX (VT 4800) 6. X-ray powder Diffraction (XRD) X-Ray powder Diffraction label: Sakamoto RigakuCo. (DMAX 2200 VK) feed The gas system is supplied by 6000 ppm NO, S02 standard gas and pure N2 gas diluted by a mass flow controller. Feed gas introduction experiment 16 1317648 Before the column, the mass flow controller is adjusted through the flow controller, and then the reaction column filled with zero-valent iron powder is introduced. The outside of the iron powder reaction zone of the pipe column is heated by an aluminum electric heating pipe, and the outer layer of the electric heating pipe is insulated and covered with rock wool. Before the treatment, preheating for about 20 minutes to stabilize the temperature. During the gas treatment, the heating of the electric heater is controlled by a proportional integral derivative (PID) thermostat to keep the reaction temperature at the set temperature. Within a range of ±1.5 °C, a constant temperature reaction is carried out. After the feed gas reacts with the iron powder, it is introduced into the continuous gas emission monitoring system (Continuous Emissioii)

MonitoringSystem，CEMS)進行連續監測並分析 NO、S02 濃度，並將分析結果連接個人電腦之數據擷取器儲存。分析方法 1. NO檢測方法：排放管道中氮氧化物自動檢測方法為儀器分析法（NIEAA411.72C)。 2. S〇2檢測方法：排放管道中二氧化硫抽取式自動檢測方法為非分散性紅外光法、紫外光法’以及螢光法（NffiA A413.72C)。 3. C0檢測方法：排放管道中一氧化碳自動檢測方法為非分散性紅外線法（ΝΙΕΑ A704.02C )。 4. 〇2檢測方法：排放管道中氧自動檢測方法為電極法 (NIEAA432.71B)。 <反應溫度> 反應溫度的測試是以五組不同反應溫度穿透試驗，以測定溫度對鐵粉去除NO、S〇2之能力及單位重量零價鐵去除NO、S02量，其條件如表1所示。 17 1317648 表1不同反應溫度的測試條件MonitoringSystem, CEMS) continuously monitors and analyzes the concentration of NO and S02, and connects the analysis results to the data grabber of the personal computer for storage. Analytical method 1. NO detection method: The automatic detection method of nitrogen oxides in the discharge pipeline is the instrumental analysis method (NIEAA411.72C). 2. S〇2 detection method: The automatic detection method of sulfur dioxide extraction in the discharge pipeline is non-dispersive infrared light method, ultraviolet light method and fluorescent method (NffiA A413.72C). 3. C0 detection method: The automatic detection method of carbon monoxide in the discharge pipeline is non-dispersive infrared method (ΝΙΕΑ A704.02C). 4. 〇2 detection method: The automatic detection method of oxygen in the discharge pipe is the electrode method (NIEAA432.71B). <Reaction temperature> The test of the reaction temperature is carried out by five different reaction temperature penetration tests to determine the ability of the temperature to remove NO and S〇2 from the iron powder and the amount of zero-valent iron per unit weight to remove NO and S02. Table 1 shows. 17 1317648 Table 1 Test conditions for different reaction temperatures

反應溫度：（1)573 K ; (2)623 K ; (3) 673 K ; (4)723 K ; (5)773 K NO進流濃度：500 ppm S〇2進流濃度：500 ppm 進流率：300 mL/min 鐵粉量：0.5 g 本測試之“穿透”，NO是以零價鐵流體化床之NO 處理效率低於80%時，視為NO穿透。S02則以零價鐵流體化床之S02處理效率低於80%時，視為S02穿透。當 NO、S02排放濃度皆超過進流濃度90%以上時，則結束測試。有關如何由NO、S02穿透時間來求得NO、S02累積去除量、單位鐵粉去除能力及鐵粉利用率，其計算方式分述如下： NO、S02累積去除量（r卯、豕仍2，mg)定義為自反應系統開始至NO、S02穿透之總去除NO、S02重量。其計算方式是從穿透實驗所得數據先求得NO、S02總去除體積，用理想氣體方程式求得常態條件下的NO、S02去除莫爾數，再乘以分子量，即可得到NO、S02累積去除量。其計算式如下： [Ch f I \ time -Tbi WmorSO, ~ Σ 2 time =0 C〇ut\pPm、x Q X MW x time (min ) _yrnin J_ 0.082 ( atm'L lx 298( K)Reaction temperature: (1) 573 K; (2) 623 K; (3) 673 K; (4) 723 K; (5) 773 K NO influent concentration: 500 ppm S〇2 influent concentration: 500 ppm inflow Rate: 300 mL/min Iron powder: 0.5 g The "penetration" of this test, NO is considered to be NO penetration when the NO treatment efficiency of the zero-valent iron fluidized bed is less than 80%. S02 is regarded as S02 penetration when the S02 treatment efficiency of the zero-valent iron fluidized bed is less than 80%. When the NO and S02 emission concentrations exceed 90% of the influent concentration, the test is terminated. The calculation method of how to obtain NO, S02 cumulative removal, unit iron powder removal capacity and iron powder utilization rate from NO and S02 breakthrough time is as follows: NO, S02 cumulative removal amount (r卯, 豕 still 2 , mg) is defined as the total removal of NO, S02 weight from the beginning of the reaction system to NO, S02 penetration. The calculation method is to obtain the total removal volume of NO and S02 from the data obtained from the penetration experiment, and obtain the NO and S02 removal moir number under the normal condition by the ideal gas equation, and then multiply the molecular weight to obtain the accumulation of NO and S02. Removal amount. The calculation formula is as follows: [Ch f I \ time -Tbi WmorSO, ~ Σ 2 time =0 C〇ut\pPm, x Q X MW x time (min ) _yrnin J_ 0.082 ( atm'L lx 298( K)

\ mole K J 18 1317648 其中：r&為NO或S02穿透時間，Cb為NO或so2之. 進流濃度’（^如為NO或S02排放濃度，2為進流率，為分子量。單位鐵粉去除能力（TA，mg NO/g Fe or mg S02/g Fe)其定義為每克零價鐵可去除N0、S02之重量，其計算式如下： TA _ Wm〇rso2(ms) ~~ wfM) 其中為鐵粉重。鐵粉利用率（Utilization of ZVI，t/oZ，％，W/W% ) 其定義為與NO、s〇2累積去除量反應消耗鐵粉重量與參與反應鐵粉總重量之比值。 u〇z=^{m8) ^Fe (m8 ) 其中灰為參與反應消耗的鐵量，為鐵粉重。上述測試的結果顯示，在反應溫度573 Κ時，無任何的NO、S〇2累積去除量，顯示此溫度下並無no、8〇2的去除效果。心皿度623K ’鐵粉量〇.5 g，進流率3〇〇 mL/min時， NO排放*度在操作初細彳可得完全去除，時間達⑽秒，而S02排放處度在操作初期雖然無法獲得完全去除，但在 40 ppm附#近可維持約3〇〇秒的穩定排放濃度。隨後，Μ。、 S〇2排放辰度均隨操作時間增加逐漸升高。穿透時間為 530和S〇2穿透時間為480秒。鐵粉NO、S02去除能力分別為33 mg N〇/g Fe及n.43 mg S〇2/g Fe。由上述可 19 1317648 知，此反應溫度對於NO、S02的去除能力處理優於在反應溫度573 K時。反應 >孤度673K，鐵粉量〇.5 g，進流率3〇〇 mL/min時， NO、S〇2排放濃度在操作初期可得完全去除，no完全去除時間達1180秒，S〇2完全去除時間達280秒。隨後，NO、 S〇2排放濃度均隨操作時間增加而升高。no穿透時間為 1870秒，S〇2穿透時間為1230秒。單位鐵粉NO、S02去除能力分別為 22.65 mg NO/g Fe 及 30.03 mg S02/g Fe。反應溫度723K，鐵粉量0.5 g，進流率3〇〇 mL/min時， NO、S〇2排放濃度在操作初期可得完全去除，N〇完全去除時間達2320秒，S〇2完全去除時間達217〇秒。隨後， NO、S〇2排放濃度·均隨操作時間增加而急速升高。N〇穿透時間為3840秒，S〇2穿透時間為254〇秒。單位鐵粉no、 S02 去除能力分別為 46.28 mg NO/g Fe 及 65.55 mg S02/g\ mole KJ 18 1317648 where: r& is NO or S02 penetration time, Cb is NO or so2. Influent concentration '(^ is NO or S02 emission concentration, 2 is inflow rate, is molecular weight. Unit iron powder The removal ability (TA, mg NO/g Fe or mg S02/g Fe) is defined as the weight of N0 and S02 can be removed per gram of zero-valent iron. The calculation formula is as follows: TA _ Wm〇rso2(ms) ~~ wfM) Among them is iron powder weight. The utilization rate of iron powder (Utilization of ZVI, t/oZ, %, W/W%) is defined as the ratio of the weight of the iron powder consumed by the cumulative removal of NO and s〇2 to the total weight of the participating iron powder. U〇z=^{m8) ^Fe (m8 ) where ash is the amount of iron consumed in the reaction and is iron powder. The results of the above tests showed that at the reaction temperature of 573 ,, there was no cumulative removal of NO and S〇2, indicating that there was no no, 8〇2 removal effect at this temperature. The heart degree is 623K 'iron powder amount 〇.5 g, when the inflow rate is 3〇〇mL/min, the NO emission* degree can be completely removed at the beginning of operation, the time is up to (10) seconds, and the S02 emission degree is operating. Although it is not possible to obtain complete removal at the beginning, it can maintain a stable emission concentration of about 3 sec at 40 ppm. Subsequently, hehe. The emission intensity of S〇2 increased gradually with the increase of operation time. The penetration time was 530 and the S〇2 penetration time was 480 seconds. The removal capacities of iron powder NO and S02 were 33 mg N〇/g Fe and n.43 mg S〇2/g Fe, respectively. It is known from the above-mentioned pp. 13 1317648 that this reaction temperature is superior to the removal ability of NO and S02 at a reaction temperature of 573 K. Reaction > 673K, iron powder 〇.5 g, inflow rate 3〇〇mL/min, NO, S〇2 emission concentration can be completely removed at the beginning of the operation, no complete removal time of 1180 seconds, S 〇2 completely removed for 280 seconds. Subsequently, the NO and S〇2 emission concentrations increased with increasing operating time. The no penetration time is 1870 seconds and the S〇2 penetration time is 1230 seconds. The removal capacity of unit iron powder NO and S02 was 22.65 mg NO/g Fe and 30.03 mg S02/g Fe, respectively. When the reaction temperature is 723K, the amount of iron powder is 0.5 g, and the inflow rate is 3〇〇mL/min, the NO and S〇2 emission concentrations can be completely removed at the initial stage of operation. The complete removal time of N〇 is 2320 seconds, and S〇2 is completely removed. The time is 217 seconds. Subsequently, the NO and S〇2 emission concentrations all increased rapidly with the increase of the operation time. The N〇 penetration time was 3840 seconds and the S〇2 penetration time was 254 seconds. The removal capacity of unit iron powder no and S02 is 46.28 mg NO/g Fe and 65.55 mg S02/g, respectively.

Fe ° 反應溫度773K，鐵粉量0.5 g進流率3〇〇 mL/min時， NO、S〇2排放濃度在操作初期均可完全去除，N〇完全去除時間達3910秒，S〇2完全去除時間達37〇〇秒。隨後， NO、S〇2排放濃度均隨操作時間增加而急速升高。N〇穿透時間為4730秒，S〇2穿透時間為424〇秒。經計算所得的單位鐵粉NO、S〇2去除能力分別為57 52 mg N〇/g以及 109.47 mg S〇2/g Fe。從單位鐵粉處理量的觀點而言，反應溫度與單位鐵粉處理 NO、S02 能力（mg NO/g Fe、mg s〇2/g Fe)關係圖 20 1317648When the Fe ° reaction temperature is 773K and the iron powder volume is 0.5 g, the inflow rate is 3〇〇mL/min, the NO and S〇2 emission concentrations can be completely removed at the initial stage of operation. The complete removal time of N〇 is 3910 seconds, and S〇2 is completely The removal time is 37 seconds. Subsequently, the NO and S〇2 emission concentrations increased rapidly with the increase of the operation time. The N〇 penetration time was 4730 seconds and the S〇2 penetration time was 424 〇 seconds. The calculated removal capacity of NO and S〇2 per unit iron powder was 57 52 mg N〇/g and 109.47 mg S〇2/g Fe, respectively. From the viewpoint of unit iron powder treatment, the reaction temperature is related to the unit metal powder treatment NO, S02 capacity (mg NO / g Fe, mg s 〇 2 / g Fe) 20 1317648

如第二圖，由圖中可以觀察到反應溫度與單位鐵粉處理 NO能力呈現線性關係，隨著反應溫度上升，處理能力也急速增加，反應溫度623 K時，單位鐵粉去除能力較低僅有6.33 mgNO/gFe，當溫度升高至673 K時，單位鐵粉去除能力上升至22.65 mg NO/g Fe，上升幅度達2.58倍，而 723 K及773 K之單位鐵粉去除能力則分別為46.28及 57.52 mg NO/g Fe，顯示在溫度673〜723 K範圍，鐵粉活性增加，約增加1.04倍，但當溫度持續增加至773 K時，鐵粉活性又上升，鐵粉單位處理能力增加幅度約為24 %。另由第二圖可知，反應溫度與單位鐵粉處理S〇2能力也呈現線性正相關。反應溫度在623 K時，單位鐵粉去除能力較低僅有11.43 mg SCVg Fe，當溫度升高至673 K時，單位鐵粉去除能力上升至30.03 mg S02/g Fe，上升幅度達 1.63倍’而723 K及773 K之單位鐵粉去除8〇2能力則分別為 65·55 及 109.47 mg S02/g Fe，顯示在溫度 673〜723 K ) 範圍，鐵粉活性增加，約增加1.18倍，當溫度持續增加至 773 K時’鐵粉活性持續上升，鐵粉單位處理能力增加幅度約為67 %。第二圖中並顯示’單位鐵粉NO、8〇2處理量隨反應溫度增加而增加’且兩者均為迴歸係數大於〇97的線性關係。因在分子量上，S〇2遠大於N〇，使得在每一反應溫度的單位鐵粉S〇2處理量均大於單位鐵粉no處理量。另外趨勢線的斜率，S〇2較大，顯示零價鐵在反應溫度更高時，對S〇2的去除效果會更好。 21 1317648 由前面不同反應溫度之測試結果可知，反應溫度愈高其單位重量鐵粉去除NO量及單位重量鐵粉去除S02量愈高。如反應溫度於723 K及773 K時，其單位重量鐵粉去除NO量分別為46.28 mg及57.52 mg，相當於反應溫度623 K之NO量6.33 mg的6.31倍及8.09倍；而在相同溫度的單位重量鐵粉去除S02量分別為65.55 mg及109.47 mg，相當於反應溫度623 K單位鐵粉去除S02量11.43 mg之 4.73倍及8.58倍。 <氣體進流率> 根據表2測試氣體進流率（流通量）及鐵粉重量對於處理 NO、S02的影響，每種影響因子均選定四組不同變數，依上述操作進行。當NO、S02兩者去除率皆低於40 %時，即NO、S02排放濃度皆超過進流濃度60 %以上時，即結束操作。 22 1317648 表2氣體進流率（流通量）條件及鐵粉重量之試驗變數及控制影響因子（各有四組變數）控制條件氣體進流率（mL/min): 反應溫度：773 K (1)250，（2) 300，（3)350， NO進流濃度：500 ppm (4)400 S〇2進流濃度：500 ppm 鐵粉量：0.5 g 鐵粉量（g): 反應溫度：773 K (1)0.25，（2)0.5，（3)0.75， NO進流濃度：500 ppm (4)1.0 S〇2進流濃度：500 ppm 進流率：300 mL/min 爲了比較不同影響因子對NO、S02去除效果之影響，因實際應用上爲達到符合排放標準之處理效果，工程設計所採用之去除率都不會太低，故本節NO穿透研究選擇以 NO去除率降為80 %時之鐵粉累積去除NO量作為比較基準；S02穿透研究則選擇以S02去除率降為80 %時之鐵粉累積去除802量作為比較基準，其計算方式同上所述。計算流通量時是以氣體進流率除以流體化床的截面積來求得，本試驗中的進流率分別為250、300、350及400 mL/min，其流通量依序為 0.5、0.6、0.7 及 0.8 L/cm2.min。第三圖為鐵粉量為0.5 g下不同流通量（0.5、0.6、0.7、 0.8 L/cm2 . min )與穿透時間關係圖，由圖可知，在四種不同流通量的NO穿透時間均大於S02穿透時間，且NO穿透時間與S〇2穿透時間均隨流通量增加而降低，兩者呈線 23 1317648 增加而降 S〇2與鐵性關係。NO穿透時間與叫穿透時間隨流通量低的原因，歧流通量愈大，將帶人更多的n〇、粉反應，讓參舆反應的鐵粉較快消耗。第四圖為鐵粉量〇5 g時不同流通量與加量、S02累積去除量關係圖，由圖可知，在四種不同、=去旦除 S02累積去除量均較N。累積去除量大。當流通量:J ’ 〇·6、0.7、0.8 !W . min 時，N。累積去除量 7As shown in the second figure, it can be observed from the figure that the reaction temperature has a linear relationship with the NO capacity per unit of iron powder. As the reaction temperature increases, the processing capacity increases rapidly. When the reaction temperature is 623 K, the unit iron powder removal capacity is low. There is 6.33 mg NO/gFe. When the temperature rises to 673 K, the unit iron powder removal capacity increases to 22.65 mg NO/g Fe, which increases by 2.58 times, while the 723 K and 773 K unit iron powder removal capacities are respectively 46.28 and 57.52 mg NO/g Fe, showing an increase in iron powder activity at a temperature of 673 to 723 K, an increase of about 1.04 times, but when the temperature continues to increase to 773 K, the iron powder activity increases again, and the iron powder unit treatment capacity increases. The amplitude is about 24%. In addition, as shown in the second figure, the reaction temperature is also linearly positively correlated with the ability of unit iron powder to treat S〇2. When the reaction temperature is 623 K, the unit iron powder removal capacity is only 11.43 mg SCVg Fe. When the temperature is raised to 673 K, the unit iron powder removal capacity rises to 30.03 mg S02/g Fe, which increases by 1.63 times. The ability to remove 8〇2 of 723 K and 773 K units of iron powder is 65.55 and 109.47 mg S02/g Fe, respectively, which is shown in the range of 673~723 K. The activity of iron powder increases, about 1.18 times. When the temperature continues to increase to 773 K, the activity of iron powder continues to rise, and the unit capacity of iron powder increases by about 67%. In the second figure, it is shown that the 'unit iron powder NO, 8〇2 treatment amount increases as the reaction temperature increases' and both have a linear relationship with a regression coefficient greater than 〇97. Since S 〇 2 is much larger than N 分子量 in terms of molecular weight, the treatment amount per unit iron powder S 〇 2 at each reaction temperature is larger than the treatment amount per unit iron powder no. In addition, the slope of the trend line, S〇2 is larger, indicating that the zero-valent iron will have a better removal effect on S〇2 when the reaction temperature is higher. 21 1317648 It can be seen from the test results of different reaction temperatures that the higher the reaction temperature, the higher the amount of NO removed per unit weight of iron powder and the higher the amount of S02 removed per unit weight of iron powder. For example, when the reaction temperature is 723 K and 773 K, the amount of NO removed per unit weight of iron powder is 46.28 mg and 57.52 mg, respectively, which is equivalent to 6.31 times and 8.09 times the amount of NO of 6.33 mg at a reaction temperature of 623 K; The amount of S02 removed per unit weight of iron powder was 65.55 mg and 109.47 mg, respectively, which was equivalent to 4.73 times and 8.58 times that of the reaction temperature of 623 K unit iron powder to remove S02 11.43 mg. <Gas inflow rate> According to Table 2, the influence of the gas inflow rate (flow amount) and the weight of the iron powder on the treatment of NO and S02 was selected, and each of the influence factors was selected from four different variables, and the above operation was carried out. When both NO and S02 removal rates are less than 40%, that is, if the NO and S02 emission concentrations exceed 60% of the influent concentration, the operation is completed. 22 1317648 Table 2 Gas inflow rate (flow rate) conditions and test variables of iron powder weight and control influence factors (each with four sets of variables) Control condition gas inflow rate (mL/min): Reaction temperature: 773 K (1 ) 250, (2) 300, (3) 350, NO Influent concentration: 500 ppm (4) 400 S〇2 Influent concentration: 500 ppm Iron powder: 0.5 g Iron powder (g): Reaction temperature: 773 K (1) 0.25, (2) 0.5, (3) 0.75, NO influent concentration: 500 ppm (4) 1.0 S〇2 Influent concentration: 500 ppm Inflow rate: 300 mL/min To compare different impact factors The effect of NO and S02 removal effect, because the actual application is to achieve the treatment effect of meeting the emission standard, the removal rate adopted by the engineering design is not too low, so the NO penetration study in this section chooses to reduce the NO removal rate to 80%. The amount of NO accumulated by the iron powder was used as a comparison standard; the S02 penetration study selected the amount of iron powder cumulative removal 802 when the S02 removal rate was reduced to 80% as a comparison reference, and the calculation method was the same as above. Calculating the flow rate is obtained by dividing the gas inflow rate by the cross-sectional area of the fluidized bed. The inflow rates in this test are 250, 300, 350, and 400 mL/min, respectively, and the flow rate is 0.5. 0.6, 0.7 and 0.8 L/cm2.min. The third figure shows the relationship between the different fluxes (0.5, 0.6, 0.7, 0.8 L/cm2. min) and the penetration time under the iron powder amount of 0.5 g. It can be seen from the figure that the NO penetration time in four different fluxes Both were larger than the S02 breakthrough time, and the NO breakthrough time and the S〇2 penetration time decreased with the increase of the flux. The two increased the line 23 1317648 and decreased the relationship between S〇2 and iron. The reason why the NO penetration time and the penetration time are low with the circulation amount is that the larger the flow rate, the more n〇, the powder reaction will be brought, and the iron powder reacted by the Shenqi will be consumed faster. The fourth figure shows the relationship between the different fluxes and the additions and the cumulative removal of S02 when the amount of iron powder is g5 g. It can be seen from the figure that the cumulative removals of S02 are better than N in the four different types. The cumulative removal is large. When the flow rate: J 〇 6 · 6, 0.7, 0.8 ! W . min, N. Cumulative removal 7

28·76'29·50^30·46- 54.73、55.63 與 55.72 mg。 · 由上述可知，NO累積去除量、％累積量 0.5、0.6、0.7、0.8 IW ·如置“通 min打，並未隨流通量增加而^明顯的差異，所以’在此流通量區間時，可藉提高流通1來減少操作時間，且不會損失零價鐵的去除能力。 <鐵粉量效應> 為便於比較同-進流率下不同鐵粉量的鐵粉去除能力’以NO累積去除量、s〇2累積去除量來做比較，並以零價鐵流體化床之NO處理效率低於8〇 %時，視為N〇穿透(breakthrough)，S〇2處理效率低於8〇 %時，視為s〇2 穿透時間，來計算NO累積去除量、S〇2累積去除量。第五圖為進流率300 mL/min下，不同鐵粉量（0.25 g、 0.50 g、0.75 g、1.0 g)與穿透時間關係圖，由圖可知，在不同鐵粉量均呈現NO穿透時間大於S02穿透時間，且NO 穿透時間與S02穿透時間均隨鐵粉量增加而增加，兩者呈線性關係。 24 1317648 第六圖為進流率是300 mL/min下，不同鐵粉量（0.25 g、〇.5〇g、0.75 g、l.Og)與NO累積去除量、S02累積去除量關係圖，觀察圖4.15可知，在四種不同鐵粉量，S02 累積去除量均較NO累積去除量大。鐵粉量0.25 g的NO 累積去除量為14.16 mg，S02累積去除量為24.14 mg是四種不同鐵粉量中NO累積去除量、S02累積去除量最小者。隨著鐵粉量的增加，NO累積去除量與S02累積去除量均呈增加情形，如0.5 g鐵粉量的NO累積去除量為28.76 mg ’ s〇2累積去除量為54.73 mg，0.75 g鐵粉量的NO累積去除量為47.92 mg，S02累積去除量為94.47 mg，而1.0 §鐵粉量的NO累積去除量為66.71 mg，S02累積去除量為 132·54 mg。由此可知，1.〇 g鐵粉量的NO累積去除量與 S〇2累積去除量皆是四種不同鐵粉量中最多者，且從圖 4/15可知，NO累積去除量、S02累積去除量均隨鐵粉量增加而增加，兩者呈線性關係。實施例3 XRD試驗爲確定鐵粉與NO、S02反應後之可能產物’本發明把與NO、S02反應過後之鐵粉檢取樣本進行XRD試驗，主要針對鐵粉與NO、S02反應可能產物包括：FeS、FeSz、 FeO、Fe203、Fe304及FeS04等物質加以確認分析。分析的結果顯示零價鐵與NO、S02反應之產物有下列所示之幾種可能性：28·76'29·50^30·46- 54.73, 55.63 and 55.72 mg. · As can be seen from the above, the NO accumulation removal amount and the % accumulation amount are 0.5, 0.6, 0.7, and 0.8 IW. If the "through min is hit, there is no significant difference with the increase in the flow rate, so in the flow range, It is possible to reduce the operation time by increasing the circulation 1 without losing the removal ability of zero-valent iron. <Iron powder amount effect> In order to compare the iron powder removal ability of different iron powder amounts under the same-inflow rate, The cumulative removal amount and the cumulative removal amount of s〇2 are compared, and when the NO treatment efficiency of the zero-valent iron fluidized bed is less than 8〇%, it is regarded as N〇 breakthrough, and the treatment efficiency of S〇2 is lower than that. At 8〇%, it is regarded as the s〇2 penetration time to calculate the cumulative removal of NO and the cumulative removal of S〇2. The fifth figure shows the amount of different iron powder (0.25 g, 0.50) at an inflow rate of 300 mL/min. g, 0.75 g, 1.0 g) and penetration time diagram, it can be seen from the figure that the NO penetration time is greater than the S02 breakthrough time in different iron powder quantities, and the NO penetration time and S02 penetration time are both with iron powder. The amount increases and increases, and the two are linear. 24 1317648 The sixth figure shows the difference in the amount of iron powder at an inflow rate of 300 mL/min. 0.25 g, 〇.5〇g, 0.75 g, l.Og) and NO accumulation removal, S02 cumulative removal relationship diagram, observe Figure 4.15 shows that in four different iron powder quantities, S02 cumulative removal is more than NO accumulation The removal amount is large. The cumulative removal of NO with an amount of 0.25 g of iron powder is 14.16 mg, and the cumulative removal of S02 is 24.14 mg, which is the minimum cumulative removal of NO in the four different iron powders, and the smallest cumulative removal of S02. The increase of NO cumulative removal and S02 cumulative removal increased, such as the cumulative removal of NO of 0.5 g iron powder was 28.76 mg ' s 〇 2 cumulative removal was 54.73 mg, 0.75 g of iron powder amount of NO accumulation The removal amount was 47.92 mg, the cumulative removal of S02 was 94.47 mg, and the cumulative removal of NO of 1.0 § iron powder was 66.71 mg, and the cumulative removal of S02 was 132·54 mg. It is known that 1. 〇g iron powder The cumulative removal of NO and the cumulative removal of S〇2 are the most common among the four different iron powders, and it can be seen from Fig. 4/15 that the cumulative removal of NO and the cumulative removal of S02 increase with the increase of iron powder. The two are linear. Example 3 XRD test is to determine the possible product of iron powder reacting with NO and S02' Invented the iron powder sample after the reaction with NO, S02, XRD test, mainly for the reaction of iron powder with NO, S02 possible products including: FeS, FeSz, FeO, Fe203, Fe304 and FeS04 and other substances to confirm the analysis. The results show that the products of the reaction of zero-valent iron with NO and S02 have the following possibilities:

Fe 十 NO + S02 一 FeS , FeS2，FeO , Fe203，Fe304，FeS04 把和NO、S02反應過之鐵粉取樣做XRD試驗，所得的X 25 1317648 光繞射分析圖譜如第七圖所示，由此XRD分析圖譜可得知’使用過的鐵粉大部分轉換為FeS、Fe304，但仍有相每數量零價鐵未參與反應，另有少部分轉換為Fe2〇3、Fe X NO + S02 - FeS , FeS2 , FeO , Fe203 , Fe304 , FeS04 The iron powder reacted with NO and S02 was sampled for XRD test. The obtained X 25 1317648 light diffraction analysis spectrum is shown in the seventh figure. This XRD analysis shows that most of the used iron powder is converted to FeS and Fe304, but there are still some zero-valent irons in the phase, and a small part is converted to Fe2〇3.

FeS〇4，因此其可能之反應式為： 4Fe + 2N0+S02 < FeS + N2+Fe30A ⑴ 6Fe + 2N0 + 2S02 < -^2FeS + N2 +2Fe203 (2)FeS〇4, so its possible reaction formula is: 4Fe + 2N0+S02 < FeS + N2+Fe30A (1) 6Fe + 2N0 + 2S02 < -^2FeS + N2 +2Fe203 (2)

Fe + 2N0 + S02 <-，—一 ·» 似04 +N2 (3) 實施例4零價鐵併同處理NO、S02與單獨處理NO、之比較利用實施例1之裝置進行併同處理NO、S〇2與單獨處理NO、s〇2之比較。第八圖為反應溫度773 K進流率25〇 mL/min零價鐵〇·5 g單獨處理NO、S02與併同處理N0、s〇2的N〇、s〇排放濃度穿透曲線圖，由圖可知，零價鐵單獨處理N〇、 S〇2與併同處理NO、S〇2,在操作初期均能獲得完全去除，其π全去除時間，單獨處理N〇約為349〇秒，單獨處理 S〇2約為2410秒；併同處理的N〇約為44〇〇秒，併同声理的S〇2約為4250秒。隨後，不管是零價鐵單獨處理购、 S〇2或零價鐵併同處理N〇、s〇2，其N〇、s〇2排放心均隨操作時間增加而急劇上升。今以N〇、sQ2去除率= 义為基準’將汁异所得的單位鐵粉的N〇、去除量、、、 =乍為比較零價鐵單獨處理N〇、叫與零價鐵併同處理 S〇2的優劣。计算結果如表3，零償鐵單獨處理⑽、 26 1317648 S02的單位鐵粉NO、S02去除量分別為47.11 mgNO/gFe 及71.86 mg S02/ g Fe ;零價鐵併同處理NO、S02的單位鐵粉NO、S02去除量分別為54.55 mgNO/gFe及112.91 mg S02/ g Fe。表3零價鐵單獨處理NO、S02與零價鐵併同處理NO、S02 單位零價鐵粉NO、S02去除量之比較（NO、S02去除率為 80%) 項目單獨處理 NO 單獨處理 S〇2 併同處理NO、S02 NO S02 單位鐵粉去除量 (mg NO/ g Fe) 或 (mg S02/ g Fe) 47.11 71.86 54.55 112.91 由此可知，在去除率為80%時，零價鐵併同處理NO、 S02較零價鐵單獨處理NO、S02效果佳。其原因可從X光繞射分析圖譜得知，第九、十圖分別為零價鐵粉單獨處理 ) NO、S〇2的鐵粉X光繞射分析圖譜，由圖可知，其使用後的鐵粉大部分仍為未反應的零價鐵。零價鐵粉單獨處理 S02的鐵粉僅有少部分轉換為FeS、Fe203及Fe304，顯示 S02完全走還原反應。而零價鐵粉單獨處理NO的鐵粉則轉換為Fe203及Fe304。第七圖為零價鐵併同處理N0、S02 的鐵粉X光繞射分析圖譜，從圖可知，使用過的鐵粉大部分為高氧化態的FeS、Fe304,少部分轉換為Fe203、FeS04, 未參與反應的零價鐵不像零價鐵單獨處理NO、S02多。且因圖譜中有FeS04的出現，可確認S02在零價鐵併同處理 27 1317648 NO S〇2日$ ’有部分走氧化路線，不像在零價鐵單獨處理奶2時’S02S全走還原路線。從上述反應式(3)可知生成工莫耳FeSCV須消耗2莫耳舶及i莫耳s〇2，因此，Μα 的生成可增加單位鐵粉N〇、s〇2去除量。另從熱力學得矣零彳貝鐵及％的洽為零，NO、S〇2的捨分別為90.3 a K】/mGl[37]、-296.8 KJ/m()1[37]，而反應後的產物為％〇4、 Fe203、FeS 及 FeS〇4，分別為_1115 7[37]、领 6間、 _85·4[38]及159’2[38]Kj/_’經計算可得反應式⑴、⑺、 (3)的反應熱分別為-1084.9、-1407、275.4 1^/111〇1。由反應熱可知，反應式（1)、（2)為放熱反應，反應式（3)為吸熱反 : 應。由Van 1 Hoff方程式可知，當反應為吸熱反應，反應；溫度增加較有利反應進行。所以反應溫度增加，有利於Fe + 2N0 + S02 <-, -1·like 04 + N2 (3) Example 4 Comparison of zero-valent iron and treatment of NO, S02 and NO treatment alone, using the apparatus of Example 1 and treating NO together , S〇2 and the comparison of NO, s〇2 alone. The eighth figure shows the N 〇 and 〇〇 emission concentration breakthrough curves of the reaction temperature 773 K inflow rate 25 〇 mL / min zero-valent iron 〇 · 5 g separately treated NO, S02 and the same treatment N0, s〇2, It can be seen from the figure that the zero-valent iron alone treats N〇, S〇2 and the same treatment of NO and S〇2, and can be completely removed at the beginning of the operation, and the π total removal time is N 〇 about 349 〇 seconds. S〇2 is treated separately for about 2410 seconds; the same N〇 is about 44 〇〇 seconds, and the same S声2 is about 4250 seconds. Subsequently, regardless of whether the zero-valent iron is separately processed, S〇2 or zero-valent iron, and the same treatment N〇, s〇2, the N〇, s〇2 discharge hearts rise sharply with the increase of the operation time. Now N〇, sQ2 removal rate = meaning as the benchmark 'N, the amount of removal, the amount of the iron powder of the unit iron powder obtained by the juice is compared with the zero-valent iron, and the treatment is treated separately with zero-valent iron. The advantages and disadvantages of S〇2. The calculation results are shown in Table 3. The removals of NO and S02 per unit iron powder of the zero-compensated iron alone (10) and 26 1317648 S02 are 47.11 mgNO/gFe and 71.86 mg S02/ g Fe respectively; the units with zero-valent iron and the same treatment of NO and S02 The removal of iron powder NO and S02 was 54.55 mg NO/gFe and 112.91 mg S02/g Fe, respectively. Table 3: Zero-valent iron treatment of NO, S02 and zero-valent iron separately and treatment with NO, S02 unit zero-valent iron powder NO, S02 removal (NO, S02 removal rate is 80%) Item Separate treatment NO Separate treatment S〇 2 and treatment with NO, S02 NO S02 unit iron powder removal (mg NO / g Fe) or (mg S02 / g Fe) 47.11 71.86 54.55 112.91 It can be seen that at the removal rate of 80%, zero-valent iron It is better to treat NO and S02 with zero price iron alone to treat NO and S02 separately. The reason can be seen from the X-ray diffraction analysis spectrum, the ninth and tenth graphs are treated separately as zero-valent iron powder. The iron powder X-ray diffraction analysis map of NO and S〇2 can be seen from the figure. Most of the iron powder is still unreacted zero-valent iron. Zero-valent iron powder treatment alone S02 iron powder was only converted to FeS, Fe203 and Fe304, indicating that S02 completely went through the reduction reaction. The iron powder treated with zero-valent iron powder alone is converted to Fe203 and Fe304. The seventh figure is the zero-valent iron and the X-ray diffraction analysis of the iron powder of N0 and S02. It can be seen from the figure that most of the used iron powder is FeS and Fe304 in high oxidation state, and a small part is converted into Fe203 and FeS04. The zero-valent iron that is not involved in the reaction is not treated with zero-valent iron alone. And because of the presence of FeS04 in the map, it can be confirmed that S02 is in the zero-valent iron and treated with 27 1317648 NO S〇2, and there is a partial oxidation route, unlike when the zero-valent iron is treated separately for milk 2 'S02S full-reduction route. From the above reaction formula (3), it is known that the production of Moer FeSCV consumes 2 moles and i moles s2, and therefore, the formation of Μα can increase the removal amount of unit iron powders N〇 and s〇2. In addition, from the thermodynamics, the zero-boiled iron and % are zero, and the values of NO and S〇2 are 90.3 a K]/mGl[37] and -296.8 KJ/m()1[37], respectively. The products are %〇4, Fe203, FeS and FeS〇4, which are calculated by _1115 7[37], collar 6 , _85·4[38] and 159'2[38]Kj/_'. The heat of reaction of the formulae (1), (7), and (3) is -1084.9, -1407, and 275.4 1^/111〇1, respectively. It is known from the reaction heat that the reaction formulas (1) and (2) are exothermic reactions, and the reaction formula (3) is endothermic. It can be seen from the Van 1 Hoff equation that when the reaction is an endothermic reaction, the reaction is carried out with an increase in temperature. Therefore, the reaction temperature increases, which is beneficial to

FeSCU的生成’因此零價鐵可與更多的no、s〇2反應，使得零價鐵併同處理NO、S〇2,在反應溫度愈高時有更長的穿透時間。再加上零價鐵併同處理NO、S〇2的鐵粉氧化程；；!度較零價鐵單獨處理N〇、S〇2徹底，即零價鐵併同處理 NO、S〇2的鐵粉反應較徹底，遂有零價鐵併同處理N〇、 S〇2所得的單位鐵粉NO、S〇2去除量較零價鐵單獨處理 ' NO、S02多的情形。 ; 綜前所述，零價鐵因其價格低且有強還原能力，並具 — 有取得容易，使用後鐵粉為無害且可回收再利用等特性，符合目前零廢棄之環保趨勢等優點，並僅利用同一套設備即可併同處续氮氧化物及硫氧化物。因此，本發明利用零價鐵粉處理氣氧化物及硫氧化物之方法及裝置具有顯著效The formation of FeSCU 'so zero-valent iron can react with more no, s〇2, so that zero-valent iron can be treated with NO, S〇2, and the penetration time is longer when the reaction temperature is higher. In addition, the zero-valent iron is treated with the iron powder oxidation process of NO and S〇2; the degree is less than that of zero-valent iron alone, and N〇 and S〇2 are completely treated, that is, zero-valent iron is treated with NO and S〇2. The reaction of iron powder is more thorough. The removal of NO and S〇2 per unit iron powder obtained by zero-valent iron and the treatment of N〇 and S〇2 is more than that of zero-valent iron alone. As mentioned above, due to its low price and strong reducing ability, zero-valent iron has the advantage of being easy to obtain, and the iron powder is harmless and recyclable after use, which is in line with the current environmental trends of zero waste. Nitrogen oxides and sulfur oxides can be reconciled in the same place using only the same equipment. Therefore, the method and apparatus for treating gaseous oxides and sulfur oxides using zero-valent iron powder have significant effects

28 1317648 果。【圖式簡單說明】第一圖為本發明之裝置概示圖。第二圖為不同反應溫度與單位鐵粉處理NO、S02能力關係圖’條件為]Si0=500 ppm，S〇2=500 ppm， Fe =0·5 g，Fl〇w=300 mL/min，T=623〜773 K。第三圖為鐵粉量0.5 g時不同流通量與穿透時間關係圖，條件為 T=773 K，N0=500 ppm，S02=500 ppm，Fe =0.5 g，Flux=0.5 〜0.8 L/cm2 · min (Flowrate=250〜400 mL/min)。第四圖為鐵粉量0.5g時不同流通量與N0、S02累積去除量關係圖，條件為T=773 K，NO=500 ppm， S〇2=500 ppm ’ Fe =0.5 g ’ Flux=0.5〜0.8 L/cm2 · min 〜400 mL/min)下。第五圖為不同鐵粉量與穿透時間關係圖，條件為T=773 K，NO=500 ppm，S〇2=500 ppm，Flowrate=300 mL/min，Fe=0.25〜1.0 g，進流率 300 mL/min 下。第六圖為不同鐵粉量與NO、S02累積去除量關係圖，條件為 T=773 K，NO=500 ppm，S02=500 ppm， Flowrate=300 mL/min，Fe=0.25〜1.0 g 進流率 300 mL/min 下。第七圖為零價鐵併同處理NO、S02後鐵粉之X光繞射 29 1317648 分析圖議。第八圖為零價鐵單獨處理NO、S02與零價鐵併同處理 _ NO、S02的NO、S02排放濃度穿透曲線圖，條件為 T=773 K，Flowrate=250 mL/min，Fe =0.5 η - g，NO =550 ppm，S〇2=550 ppm 下。 • 第九圖為零價鐵單獨處理NO後鐵粉之X光繞射分析。圖譜。第十圖為零價鐵單獨處理S02後鐵粉之X光繞射分析 5 圖譜。 . 【主要元件符號說明】 10 反應套組 11預熱區 12 束縮段 13反應區 14 玻璃棉 15玻璃棉 16 鐵粉 17反應管柱 18 加熱器 19保溫絕熱層 20 溫度控制器 30氣體流量控制器 40 管路 50進氣端 60 排氣端 70氣体連續排放監測系統 3028 1317648 fruit. BRIEF DESCRIPTION OF THE DRAWINGS The first figure is an overview of the apparatus of the present invention. The second graph shows the relationship between different reaction temperatures and the capacity of NO and S02 treated by unit iron powder. The conditions are as follows: Si0=500 ppm, S〇2=500 ppm, Fe=0.5 g, Fl〇w=300 mL/min, T=623~773 K. The third graph is the relationship between the different flux and penetration time when the amount of iron powder is 0.5 g. The conditions are T=773 K, N0=500 ppm, S02=500 ppm, Fe=0.5 g, Flux=0.5 ～0.8 L/cm2 · min (Flowrate=250~400 mL/min). The fourth graph shows the relationship between the different fluxes and the cumulative removal of N0 and S02 when the amount of iron powder is 0.5g. The condition is T=773 K, NO=500 ppm, S〇2=500 ppm 'Fe =0.5 g ' Flux=0.5 ~0.8 L/cm2 · min ~ 400 mL/min). The fifth graph shows the relationship between the amount of iron powder and the penetration time. The conditions are T=773 K, NO=500 ppm, S〇2=500 ppm, Flowrate=300 mL/min, Fe=0.25~1.0 g, inflow. The rate is 300 mL/min. The sixth figure shows the relationship between the amount of different iron powder and the cumulative removal of NO and S02. The conditions are T=773 K, NO=500 ppm, S02=500 ppm, Flowrate=300 mL/min, Fe=0.25~1.0 g inflow. The rate is 300 mL/min. Figure 7: Zero-valent iron and X-ray diffraction of iron powder after treatment of NO and S02 29 1317648 Analysis. The eighth figure is the zero-valent iron treatment of NO, S02 and zero-valent iron separately and the same treatment _ NO, S02 NO, S02 emission concentration breakthrough curve, the condition is T = 773 K, Flowrate = 250 mL / min, Fe = 0.5 η - g, NO = 550 ppm, S〇2 = 550 ppm. • Figure 9 shows the X-ray diffraction analysis of iron powder after zero-valent iron treatment of NO alone. Map. The tenth figure shows the X-ray diffraction analysis of iron powder after zero-valent iron treatment of S02 alone. [Main component symbol description] 10 reaction kit 11 preheating zone 12 bundle section 13 reaction zone 14 glass wool 15 glass wool 16 iron powder 17 reaction column 18 heater 19 insulation layer 20 temperature controller 30 gas flow control 40 conduit 50 intake end 60 exhaust end 70 gas continuous discharge monitoring system 30

Claims

1317648 X. Patent Application Range: 1. A method for treating nitrogen oxides and sulfur oxides comprising contacting a gas containing nitrogen oxides and sulfur oxides with zero-valent iron powder and reacting at a temperature of at least 623K. 2. A method for treating nitrogen oxides and sulfur oxides, comprising the following steps: (1) providing a reactor comprising a reaction tank body, a feed end disposed at the reaction tank body, and a Provided at the discharge end of the reaction tank body and a heating device; (2) placing zero-valent iron powder sufficient to treat the nitrogen oxides and sulfur oxides into the reaction tank body, and using the heating device The temperature of the reaction tank reaches and is maintained at at least 623 K; and (3) the gas containing the nitrogen oxides and sulfur oxides is introduced from the feed end to contact the zero-valent iron powder to make the gases After the nitrogen oxides and sulfur oxides are lowered, they are discharged from the discharge end. 3. The method of treating nitrogen oxides and sulfur oxides as described in claim 2, wherein the temperature of the step (2) is at least 773K. 4. The method for treating nitrogen oxides and sulfur oxides as described in claim 3, wherein the ratio of the amount of zero-valent iron powder to the amount of nitrogen oxides and sulfur oxides treated in the step (2) is 1 g : 6-60 mg and 1 g . 10-120 mg. 5. The method of treating nitrogen oxides and sulfur oxides as described in claim 2 wherein the reactor further comprises a flow controller for controlling the feed rate of the feed end. 31 1317648 6. A method of treating nitrogen oxides and sulfur oxides as described in claim 2, wherein the reactor is a fluidized bed reactor. 7. The method for treating nitrogen oxides and sulfur oxides as described in claim 2, wherein the nitrogen oxides and sulfur oxides contained in the gas discharged from the discharge end are further monitored by a gas emission monitoring system. The content. 8. The method for treating nitrogen oxides and sulfur oxides according to claim 2, further comprising using a complex array of the reactors described in the step (1), and the reactors are connected in parallel or in series Connected in a way. A device for treating nitrogen oxides and sulfur oxides, comprising: a reaction tank body having a zero-valent iron powder sufficient for treating the nitrogen oxides and sulfur oxides; and a feed end, It is disposed in the reaction tank and is in contact with the inlet end of the gas containing nitrogen oxides and sulfur oxides; a heating device for bringing the temperature of the reaction tank to reach and maintain at least 623K; The material end is disposed on the reaction tank body as the discharge end of the treated gas. 10. The apparatus for treating nitrogen oxides and sulfur oxides according to claim 9, wherein the heating means is for bringing the temperature of the reaction tank to and maintained at at least 773K. 11. The apparatus for treating milk oxides and sulfur oxides according to claim 9, wherein the heating means is disposed outside the reaction tank. 12. The apparatus for treating nitrogen oxides and sulfur oxides according to claim 9, wherein the apparatus further comprises a flow controller for controlling the 32