506945 A7 B7 五、發明説明（/ ) 發明領域 本發明是利用觸媒氧化系統減少水中或空氣中氨及/或 酚類污染物，於溫和條件下，可將此類污染物轉化成氮、 二氧化碳、水等無害性最終產物。所使用的氧化觸媒特色 係將貴重金屬類活性金屬附著於疏水性擔體上。 背景說明 來自煉油、石化、肥料、食品加工等工業的廢水或廢 氣，常含有氨、酚…等污染物，由於環保法規日趨嚴格， 此類污染源排放前必須先行處理。 生物法是常見去除水中氨的方法，其去除機制如下：506945 A7 B7 V. Description of the Invention (/) Field of the Invention The invention uses a catalyst oxidation system to reduce ammonia and / or phenol pollutants in water or air. Under mild conditions, such pollutants can be converted into nitrogen and carbon dioxide. , Water and other harmless end products. The oxidation catalyst used is characterized in that precious metal active metals are attached to a hydrophobic support. Background note Wastewater or waste gas from oil refining, petrochemical, fertilizer, food processing and other industries often contain pollutants such as ammonia, phenol, etc. Due to the increasingly strict environmental protection regulations, such pollution sources must be treated before discharge. Biological method is a common method to remove ammonia in water, and its removal mechanism is as follows:
Nitrosomonas Nitrobactor 氧 -► ν〇2· -► νο3· 即利用硝化菌撕加5〇777⑽烈、將氨轉化成硝酸根· 離子，再於無氧狀態下，利用脫硝菌乃⑽而7770/7於， 你αΤ/Μ…等將硝酸根離子(N〇〇轉成無害性氮氣(N〇。但硝 化菌活性易被進料水中之酚類、硫氰酸（SCN·)、胺類…等 污染物所抑制，使此類微生物無法發揮其去除水中氨的功 能。爲降低廢水毒性，常利用化學氧化法先將含有氨、酚 類...等污染物之廢水先行前處理，再排入生物處理單元。 而所用的化學氧化法包括觸媒氧化、非觸媒氧化。 V.S. Mishira，V.V. Mahajani 及 J.B. Joshi 所撰之文獻回 顧“溼式空氣氧化法”（34 Ind. Eng· Chem· Res· 2-48 (1995) ，提及利用非觸媒氧化法去除水中酚類、氰酸及含氮化合 物，所使用的反應條件爲150-225°C，.20·69 M Pa，於此高 4 —— _____ 本纸張尺度適用中國國家標準（CNS ) A4規格（210X297公釐） (请先Μ讀背面之注意事項鼻填寫本'κ ) ^衣---- 訂· 經濟部智慧財產局員工消費合作社印製 506945 A7 B7 [ --------- i五、發明説明（7) 1Nitrosomonas Nitrobactor Oxygen-► ν〇2 · -► νο3 · That is, the use of nitrifying bacteria to tear 〇777⑽⑽, transform ammonia into nitrate · ions, and then in an anaerobic state, using denitrifying bacteria ⑽ and 7770/7 Therefore, your αT / M, etc. will convert nitrate ions (N00 to harmless nitrogen (N0). But the activity of nitrifying bacteria is easily affected by phenols, thiocyanate (SCN ·), amines, etc. in the feed water) Suppression of pollutants prevents such microorganisms from performing their function of removing ammonia from water. To reduce the toxicity of wastewater, chemical oxidation is often used to first treat wastewater containing ammonia, phenols, and other pollutants before it is discharged. Biological treatment unit. The chemical oxidation methods used include catalytic oxidation and non-catalytic oxidation. A review of the literature by VS Mishira, VV Mahajani, and JB Joshi on "Wet Air Oxidation" (34 Ind. Eng · Chem · Res · 2-48 (1995), mentioning the use of non-catalytic oxidation to remove phenols, cyanic acid and nitrogen-containing compounds in water, the reaction conditions used are 150-225 ° C, .20 · 69 M Pa, which is higher than 4 —— _____ This paper size applies to China National Standard (CNS) A4 specification (21 0X297 mm) (Please read the notes on the back first and fill out this 'κ') ^ Order ---- Order · Printed by the Intellectual Property Bureau of the Ministry of Economic Affairs and Consumer Cooperatives 506945 A7 B7 [--------- i. Description of the invention (7) 1
I t ! _ ； 溫局壓之嚴苛條件下，其最終產物爲二氧化碳、低分子有 丨 機酸及氨。在此劇烈之反應條件下，氨仍無法進一步被氧 I 化成％。 而有關觸媒氧化部份，T.Y. Yan (U.S. Pat.No.5,552,063, 1996)曾硏發出一反應條件較爲溫和的處理方法，以去除水 中氨及酚。所用的觸媒爲沁~1〇，犯界及（：〇“〇雙金屬觸 媒’觸媒擔體爲活性碳，反應條件是8(M45°C，0.2-3.5 Μ Pa ’反應條件溫和，但於每小時空間流速（LHSV，Liquid Hourly Space Velocity, v/v hr·1)爲 2，進料水含氨 80 毫克/升 ’其氨去除率低於60%，且處理大約15(3倍觸媒體積之進 料水後，觸媒活性已開始衰退。而處理約500倍觸媒體積 之進料水後，去除率更低於15%。另酚亦無法完全被氧化 ’僅被氧化成乙酸(Acetic acid)。 一般而言，利用傳統親水性觸媒去除水中氨或有機污 染物，反應速率低，主要原因是水中氧氣溶解度低，於觸 媒孔洞內存有液態水的情況，造成氧化速率受限於反應物 之質傳限制。此外，若廢水中含有有機污染物，觸媒孔洞 內積碳是另一嚴重問題。 直接利用燃燒法氧化空氣中的氨污染物，氮氧化物是 高溫氧化的主要產物，此方法仍會造成二次空氣污染。就 本發明案作者所知，尙未有文獻提及利用觸媒氧化法可有 效將水中或空氣中之氨、酚轉化成n2, c〇2及出〇 ° 因此，開發一有效且符合經濟效益之處理程序’於溫 和條件下去除水中氨及酚類污染物，爲本發明目的所在。 _^_________：_ 本紙張尺度適用中國國家標準（CNS ) A4規格（210X 297公釐） (請先閱讀背面之注意事項再填寫本頁) , -- - —I- I. I !· I 一 = = _ Γ,) » —i- -i ? 1 1 · 、γ5 經濟部智慧財產局員工消費合作社印製 506945 經濟部智慧財產局員工消費合作社印製 A7 B7 ___ 五、發明説明（飞） 出乎意料之外’本發明利用疏水性觸媒’於溫和反應條件 下，發現可將水中或空氣中之氨、酚污染物氧化成無害性 N2, C〇2及H2〇。 發明槪要 本發明係一種處理方法，於溫和反應條件下，可氧化 去除水中氨、酚類污染物，不造成二次污染。 本發明是利用疏水性觸媒氧化去除廢水或廢氣中之氨 及揮發性污染物。此疏水性觸媒是將第νπΙ族金屬或該 族金屬化合物或兩者同時附著於疏水性擔體上，如styrene divmyl benzene co-polymer，氟化碳、氟化一氧化石夕’此類 疏水性觸媒是由 Karl T. Chuang (U.S. Pat. No. 5,009,872)所 發展。本案處理程序是先將水中氨、酚汽提出來，而後於 氣相中，將氨、酚氧化成無害性N2, c〇2及H2〇。汽提及氧. 化兩種作用可在同一反應器中進行，或是在不同的反應器 中進行。 本發明是一種處理程序，主要作用如下： (d) 提供一塡充床，由惰性塡充材料及疏水性觸媒混合 充塡而成，或提供各別兩個塡充床，其中之一充塡惰性物 質（汽提用），另一個塡充床則充塡疏水性觸媒（氧化反應用） 〇 (e) 導入氧氣及含有氨、酚之廢水、廢氣，流經塡充床 ’於適當反應條件下，將廢水或廢氣中之氨、酚類污染物 去除。 (f) 塡充床之操作條件爲50-250T：，氧氣分壓0.02-5 Μ 本紙張尺度適用標準（CNS ) Α4規格（ (請先閱讀背面之注意事項再填寫本頁 η 訂 ο 506945 A7 B7 五、發明説明（十I t! _; Under severe conditions of temperature and pressure, the final products are carbon dioxide, low molecular organic acids and ammonia. Under these severe reaction conditions, ammonia cannot be further converted to% by oxygen. Regarding the catalyst oxidation part, T.Y. Yan (U.S. Pat. No. 5,552,063, 1996) once issued a treatment method with milder reaction conditions to remove ammonia and phenol from water. The catalyst used is Qin ~ 10, and the crime boundary and (: 〇〇〇 bimetal catalyst 'catalyst carrier is activated carbon, the reaction conditions are 8 (M45 ° C, 0.2-3.5 MPa' reaction conditions are mild, But at an hourly space velocity (LHSV, Liquid Hourly Space Velocity, v / v hr · 1) of 2, the feed water contains 80 mg / L of ammonia, its ammonia removal rate is less than 60%, and the treatment is about 15 (3 times After the feed water of the catalyst volume, the catalyst activity has begun to decline. After about 500 times of the feed water of the catalyst volume, the removal rate is even lower than 15%. In addition, the phenol cannot be completely oxidized. Acetic acid. In general, traditional hydrophilic catalysts are used to remove ammonia or organic pollutants in water, and the reaction rate is low, mainly due to the low solubility of oxygen in the water and the presence of liquid water in the catalyst holes, resulting in the oxidation rate. Limited by the mass transfer of the reactants. In addition, if the wastewater contains organic pollutants, carbon deposition in the catalyst holes is another serious problem. The ammonia pollutants in the air are oxidized directly by combustion, and nitrogen oxides are oxidized at high temperatures. The main product of this method will still cause secondary empty Pollution. As far as the author of the present invention knows, there is no literature mentioning that the catalytic oxidation method can be used to effectively convert ammonia and phenol in water or air to n2, c02 and 0 °. Therefore, the development of an effective and consistent The economical treatment procedure 'removing ammonia and phenolic pollutants in water under mild conditions is the purpose of this invention. _ ^ _________: _ This paper size applies to China National Standard (CNS) A4 (210X 297 mm) (please (Please read the notes on the back before filling this page),----I- I. I! · I 一 = = _ Γ,) »—i- -i? 1 1 · γ5 Employees’ Intellectual Property Bureau, Ministry of Economic Affairs Printed by the cooperative 506945 Printed by the Consumers ’Cooperative of the Intellectual Property Bureau of the Ministry of Economic Affairs Printed A7 B7 ___ V. Explanation of the invention (flying) Unexpectedly, the present invention uses a hydrophobic catalyst under mild reaction conditions and found that it can be used in water or air The ammonia and phenol pollutants are oxidized into harmless N2, Co2 and H2O. The invention is a treatment method, under mild reaction conditions, it can oxidize and remove ammonia and phenol pollutants in water without causing two Secondary pollution. Oxidation of ammonia and volatile pollutants in waste water or exhaust gas with a hydrophobic catalyst. This hydrophobic catalyst is a group νπΙ metal or a metal compound or both attached to a hydrophobic support, such as styrene divmyl Benz co-polymer, fluorinated carbon, fluorinated monoxide, and other such hydrophobic catalysts were developed by Karl T. Chuang (US Pat. No. 5,009,872). The treatment procedure in this case is to first remove ammonia and phenol vapor from water. It is proposed, and then in the gas phase, ammonia and phenol are oxidized to harmless N2, co2 and H20. Oxygen is mentioned. The two reactions can be performed in the same reactor or in different reactors. The present invention is a processing program, the main functions of which are as follows: (d) Provide a filling bed made of a mixture of an inert filling material and a hydrophobic catalyst, or provide two separate filling beds, one of which is charged.塡 Inert substances (for stripping), and the other 塡 filled bed is filled with hydrophobic catalyst (for oxidation reaction) 〇 (e) Introduce oxygen, waste water and waste gas containing ammonia and phenol, flow through the 塡 filled bed 'as appropriate Under the reaction conditions, ammonia and phenol pollutants in waste water or waste gas are removed. (f) 塡 The operating conditions of the filling bed are 50-250T :, the partial pressure of oxygen is 0.02-5 Μ Applicable standards (CNS) Α4 specifications of this paper ((Please read the precautions on the back before filling in this page η Order 506945 A7 B7 V. Description of invention (ten)
Pa。處理過的廢水或氣體直接自反應區排放即可。 圖示說明： 圖一：本發明之流程說明’應用於去除水中氨及酣類 污染物。 圖二：本發明之流程說明，應用於去除空氣中氨污染 物。 圖三：氨去除率與廢水累積處理量之關係圖。 圖四：pH値對於氨去除率之影響。 圖五：反應壓力對於在不同流量下，氨去除率之影響 圖六：反應溫度對於氨去除率之影響。 圖七：利用疏水性觸媒Pt/SDB (Pt附著於疏水性載體 Styrene Divinyl Benzene Co-polymer 上）氧化處理酚之最終 產物。 圖八:疏水性觸媒Pt/SDB去除空氣中氨之觸媒活性。 本發明較佳實施例的詳細說明： 本發明係一種處理程序，以氧氣爲氧化劑來源，利用 疏水性觸媒將廢水或廢氣中之氨及酚氧化去除。觸媒組成 是將第VIII族金屬或該族金屬化合物，或兩者混合物，特 別是鉑（Pt)或鈀(Pd)，附著於不具任何反應活性的疏水性擔 體上。此類擔體如 SDB(Styrene Divmyl Benzene Co-polymer) 、氟化碳、氟化二氧化砂(Fluorinated silicalite)。本發明之 處理程序，具有經濟效益，因觸媒活性持久，且在溫和的 反應條件下，即能有效氧化去除氨、酚及揮發性有機污染 本紙浪尺度適用中國國家標準（CNS ) A4規格（21〇Χ 297公釐） (請先閲績背面之注意事項再填寫本頁) 愛-- 訂 經濟部智慧財產局員工消費合作社印製 506945 A7 B7 五、發明説明（(） 物。 圖一所不，塡充床是由疏水性氧化觸媒及惰性物質混 合塡充而成。惰性物質是用於提昇水中氨的汽提效果，爲 增進質傳效果，坡璃、陶瓷、氧化鋁類等親水性材質較適 合。而疏水性觸媒及增進汽提效果的親水性惰性物質，可 分別充塡於不同的反應器內，在此情況下，進料水先流經 親水性惰性物質所充塡之反應器，利用氧氣或空氣進行汽 提作用，汽提後含有氨、酚之氣體則導入疏水性氧化觸媒 塡充床進行氧化作用，產生N2，C〇2及H2〇等無害性產物。 被汽提後之廢水則逕予排放。 若含有氨、酚等污染物之進料水，導入混合床，則汽 提和氧化作用於同一反應器內同時進行。氨、酚等污染物 被汽提後直接以氣相反應方式氧化成N2,（：〇2及沁0。疏水. 性觸媒使得氨、酚污染物及氧氣能夠以氣相方式進行催化 反應，而氣相之質傳效率是液相擴散之103- 104倍，質傳效 率之大幅增進爲本發明高反應效率的主要原因。 本處理程序所需的反應條件甚爲溫和，反應範圍如下: 壓力 5-5〇〇psig,溫度 50-20(TC，LHSV 0.1-20 v/v hi··1。 處理水可直接由塡充床排放，經冷卻後，排入環境中 。由於反應產物爲N2, CCh及HUO，對環境完全不會造成任 .何危害。爲詳述本發明對於氨及酚類等污染物之處理效果 ’特以下列闡述性而非限制性之試驗實例說明： 例一：觸媒活性及觸媒壽命 人工合成廢水是由硫酸銨（（NH〇2S〇4)配製含氨 _ —____ 8 本紙張尺度適用中國國家標準（CNS ) A4規格（210X297公釐） (請先閱讀背面之注意事項再填寫本頁) 訂 經濟部智慧財產局員工消費合作社印製 506945 A7 B7 經濟部智慧財產局員工消費合作社印製 五、發明説明（k) 12〇mg/L於0.1M NaHC〇3 ρΗ8·5的溶液中而成，反應器爲 內徑1.5公分不繡鋼管，充塡15ml Pt/SDB疏水性觸媒及 15ml壓碎之陶瓷碎屑（徑約0.5-0.8mm)。廢水以流速 3.5ml/nmi.、向下流經反應器，氧氣亦以相同方式流經反應 暑I ， ΰίίΜ l〇〇ml/mm.。 本例試驗結果示於圖三，可知於130°C、90psig及 LHSV 7v/v hfl之反應條件下，氨去除率約72%。而於120 °C，60psig及LHSV 7v/v hf之反應條件下，氨去除率約 50%。且由圖三可知，累積處理量達1000倍觸媒體積時， 觸媒活性仍未有降低的趨勢。 例二：pH對於水中氨去除效率的影響 如前所述，本發明之處理程序涉及汽提、氧化兩種作 用，而只有分子態氨才具揮發性，方可被汽提至氣相中，. 進而被氧化成Nh。而水相中分子態氨（NHb)及離子態氨 (NHO之存在比率是取決於pH，其相關式如下：pH= pKa + log(NH3/NH〇，25°C下，pKa二9.2。於此實例中，探討 pH 對 於氨去除率的影響。PH 5.9，6.8及7.7之緩衝液由0.1M KH2P〇4、0.1M Na〇H兩種水溶液分另IJ配製。而pH 8.5之緩 衝液則由0.0251^免434〇7.1服2〇(3(^$)及0.05以11123〇4水溶 液配製，另ρΗΙΟ.Ο之緩衝液則由0.025MNa4B4〇7.10H2〇(Borax)及 〇.1M NaOH水溶液配製。各pH緩衝液再加入(NH〇2S〇4，使 其氨含量爲125mg/L。利用圖一所示之系統進行本試驗， 所用的疏水性觸媒爲Pt/SDB。反應條件爲120°C，60psig， 氧氣流速爲 l〇〇ml/min, LHSV 則爲 7 v/v hr·1。 _；___9 _ 本紙張尺度適用中國國家標準（CNS ) A4規格（21 OX 297公釐） (請先閱讀背面之注意事項再填寫本頁) rvr—Pa. The treated wastewater or gas can be discharged directly from the reaction zone. Schematic illustration: Figure 1: Process description of the present invention is applied to remove ammonia and tritium pollutants in water. Figure 2: The process of the present invention is illustrated and applied to remove ammonia pollutants from the air. Figure 3: Relationship between ammonia removal rate and cumulative wastewater treatment capacity. Figure 4: Effect of pH 値 on ammonia removal rate. Figure 5: Effect of reaction pressure on ammonia removal rate at different flow rates Figure 6: Effect of reaction temperature on ammonia removal rate. Figure 7: The final product of phenol oxidation treatment using hydrophobic catalyst Pt / SDB (Pt attached to hydrophobic carrier Styrene Divinyl Benzene Co-polymer). Figure 8: The catalytic activity of hydrophobic catalyst Pt / SDB to remove ammonia from air. Detailed description of the preferred embodiment of the present invention: The present invention is a treatment program that uses oxygen as a source of oxidant and uses a hydrophobic catalyst to oxidize and remove ammonia and phenol in wastewater or waste gas. The catalyst composition consists of a Group VIII metal or a metal compound of the group, or a mixture of the two, especially platinum (Pt) or palladium (Pd), attached to a hydrophobic support that does not have any reactivity. Such supports are, for example, SDB (Styrene Divmyl Benzene Co-polymer), carbon fluoride, and fluorinated silicalite. The processing procedure of the invention has economic benefits, because the catalyst has long-lasting activity, and under mild reaction conditions, it can effectively remove ammonia, phenol and volatile organic pollution by oxidative removal. The paper scale is applicable to Chinese National Standard (CNS) A4 specifications ( 21〇 × 297 mm) (please read the notes on the back of the results before filling out this page) Love-Order the printed copy of 506945 A7 B7 by the Consumer Cooperatives of the Intellectual Property Bureau of the Ministry of Economic Affairs 5. Description of the invention ((). Figure 1 No, the packed bed is a mixture of a hydrophobic oxidation catalyst and an inert substance. The inert substance is used to enhance the stripping effect of ammonia in water. To improve the mass transfer effect, slope glass, ceramics, alumina and other hydrophilic The suitable materials are suitable. The hydrophobic catalyst and the hydrophilic inert materials that enhance the stripping effect can be filled in different reactors. In this case, the feed water first flows through the hydrophilic inert materials. The reactor uses oxygen or air for stripping. After the stripping, the gas containing ammonia and phenol is introduced into the hydrophobic oxidation catalyst and packed into the bed for oxidation, producing non-hazardous products such as N2, Co2 and H20. Wastewater after stripping is discharged in advance. If feed water containing pollutants such as ammonia and phenol is introduced into the mixed bed, stripping and oxidation are performed simultaneously in the same reactor. Pollutants such as ammonia and phenol are After stripping, it is directly oxidized to N2 in the gas phase reaction mode. (: 〇2 and Qin 0. Hydrophobic catalysts enable ammonia, phenol pollutants and oxygen to conduct catalytic reactions in the gas phase, and the mass transfer efficiency It is 103-104 times of liquid phase diffusion, and the substantial increase in mass transfer efficiency is the main reason for the high reaction efficiency of the present invention. The reaction conditions required for this process are very mild, and the reaction range is as follows: pressure 5-50 psig, Temperature 50-20 (TC, LHSV 0.1-20 v / v hi ·· 1. The treated water can be discharged directly from the radon filling bed, and after cooling, it is discharged into the environment. Because the reaction products are N2, CCh and HUO, the environment It will not cause any harm at all. In order to elaborate the treatment effect of the present invention on pollutants such as ammonia and phenols, the following illustrative and non-limiting test examples are illustrated: Example 1: Catalyst activity and catalyst life Synthetic wastewater is prepared from ammonium sulfate ((NH〇2S〇4) Ammonia _ —____ 8 This paper size applies to Chinese National Standard (CNS) A4 (210X297 mm) (Please read the notes on the back before filling this page) Order printed by the Intellectual Property Bureau of the Ministry of Economic Affairs and the Consumer Cooperatives 506945 A7 B7 Economy Printed by the Consumer Cooperatives of the Ministry of Intellectual Property Bureau. 5. Description of the invention (k) 120 mg / L in a solution of 0.1M NaHC〇3 ρΗ8.5. The reactor is a non-embossed steel pipe with an inner diameter of 1.5 cm and is filled with 15 ml. Pt / SDB hydrophobic catalyst and 15ml crushed ceramic chips (about 0.5-0.8mm in diameter). Wastewater flows through the reactor at a flow rate of 3.5ml / nmi. Oxygen also flows through the reaction heat in the same way. ΰίΜ 100ml / mm. The test results of this example are shown in Figure 3. It can be seen that under the reaction conditions of 130 ° C, 90 psig and LHSV 7v / v hfl, the ammonia removal rate is about 72%. Under 120 ° C, 60 psig and LHSV 7v / v hf reaction conditions, the ammonia removal rate is about 50%. Moreover, it can be seen from Fig. 3 that when the cumulative processing amount reaches 1000 times the volume of the catalyst, the catalyst activity has not yet decreased. Example 2: The effect of pH on the efficiency of ammonia removal in water. As mentioned earlier, the treatment procedure of the present invention involves two effects: stripping and oxidation, and only molecular ammonia is volatile before it can be stripped into the gas phase. It is further oxidized to Nh. The presence ratio of molecular ammonia (NHb) and ionic ammonia (NHO) in the water phase depends on the pH, and the correlation is as follows: pH = pKa + log (NH3 / NH0, pKa 9.2 at 25 ° C. In this example, the effect of pH on ammonia removal rate is discussed. The buffer solutions of pH 5.9, 6.8, and 7.7 are prepared from two aqueous solutions of 0.1M KH2P04 and 0.1M NaOH. The buffer solution of pH 8.5 is prepared by 0.0251 ^ free 434〇7.1 serving 20 (3 ($) and 0.05) was prepared with an aqueous solution of 11123304, and the other buffer solution was prepared with 0.025M Na4B4〇7.10H2O (Borax) and 0.1M NaOH aqueous solution. Each pH buffer was further added with (NHO2S04) to make the ammonia content of 125mg / L. This test was performed using the system shown in Figure 1. The hydrophobic catalyst used was Pt / SDB. The reaction conditions were 120 ° C , 60 psig, oxygen flow rate is 100 ml / min, LHSV is 7 v / v hr · 1. _; _9 _ This paper size applies to China National Standard (CNS) A4 (21 OX 297 mm) (please first Read the notes on the back and fill out this page) rvr—
IT I©___ 506945 A7. B7IT I © ___ 506945 A7. B7
經濟部智慧財產局員工消費合作社印製 試驗結果示於圖四，可淸楚看出pH大於8時，氨去 除率顯著增加，於ρΗ=8·0時，水溶液中NIL/NH/之存在比 率約0.06 ’即總氨之6%是以分子態氨存在，處理過程中， 分子態氨不斷地被汽提氧化，離子態胺(NIi〇即不斷轉成分 子態氨(NIL)，以維持一平衡狀態。爲得到一較佳之氨去除 效率，反應液之pH値必需維持7以上。 例三：操作壓力對於在不同流量下，氨去除效率之影響 ^於0.1M NaHC〇3, PH8.5水溶液中’加入硫酸胺，使其 氨含量爲130mg/L ’以此當作含有氨之人工合成廢水。內 徑〇.9Cm不鏽鋼管充塡12.5ml Pt/SDB觸媒及12.5mi粉碎 的陶瓷碎屑（直徑〇.5-〇.8mm)。廢水分別以流速丄〇、2 〇、 3’〇ml/min.、向下流經反應益’氧熟亦以相同方向流經反應 器’丨沉速75ml/mm·，反應溫度爲130C。試驗結果（圖五）顯 不’高操作壓力有利於氨去除率，低流裊可得到較高之氨 轉化率，於130。(：，40pslg及LHSV 2.4Wv hf之反應條件下 ’氨轉化率可高達95%。 例四：反應溫度對於氨去除率之影響 於〇·1Μ NaHCO、pH8.5水溶液中，加入硫酸胺，使其 氨含量爲130mg/L，以此當作含有氨之人工合成廢水。內 徑〇.9cm不鏽鋼管充塡12.5ml Pt/SDB觸媒及i2.5ml粉碎 的陶瓷碎屑（直徑0.5-0.8mm)。廢水以流速2.〇mi/min.、向 下k經反應器，氧氣亦以相同方向流經反應器，流速 75ml/min.，反應溫度爲12(rc、13(rc。試驗結果示於圖六 ’可知高溫有利於氨之去除率。 — —___10___ 本紙張尺度適用準（CNS ) 格（210X 297公釐1 - (請先閱讀背面之注意事項再填寫本頁) —衣----- 、1T- Ρ. 506945 7;- A7 發明説明（f) 例五：利用疏水性觸媒Pt/SDB於相同反應條件下，同時 去除水中氨及酚 於〇.1M NaHC〇3, ρΗ8·5水溶液中，加入硫酸胺，使其 氨含量爲125mg/L，同時亦加入酚500mg/L，以此當作人工 合成廢水。反應器爲內徑1.5cm不鏽鋼管，充塡15ml Pt/SDB觸媒及15ml粉碎的陶瓷碎屑（直徑〇.5_〇,8mm)。廢 水以流速3.5ml/mm.(LHSV 7v/v hr’、向下流經反應器，氧 氣亦由相同方向流經反應器，流速分別爲1〇〇，300ml/min. 。反應條件爲130C ’ 90psig。試驗結果不於表一*。 (請先閱讀背面之注意事項再填寫本頁) 表一 氧氣流速（ml/mm.) 氨去除率(％) 酚去除率(％) 300 44.4 45.4 100 35.7 41.1 訂 經濟部智慈財產局員工消費合作社印製 本試驗結果顯示，於相同反應條件下，Pt/SDB疏水性 觸媒可同時催化氨及酚之氧化反應，且酚係被氧化成CO: 及H2◦，未累積其它中間產物(如圖七所示）。 例六：氧氣分壓對於氨去除率之影響 於〇.1M NaHCCX pH8.5水溶液中，加入硫酸胺，使其 氨含量爲125mg/L，以此當作含有氨之人工合成廢水。反 應器爲內徑1.5cm不鏽鋼管，充塡15ml Pt/SDB觸媒及 15ml粉碎的陶瓷碎屑（直徑0.5-0.8mm)。廢水以流速 3.5ml/min.(LHSV 7.0v/v hr’、向下流經反應器，氧氣亦由 相同方向流經反應器。相關反應條件及試驗結果示於表二 ，如預期般，高氧氣分壓及高溫皆有利於氨轉化成％及 11 本纸張尺度適用中國國家標準（CNS ) A4規格（210X 297公釐） 506945 A7 B7 五、發明説明（’） H2〇。The results of the printing test of the Consumer Cooperative of the Intellectual Property Bureau of the Ministry of Economic Affairs are shown in Figure 4. It can be clearly seen that when the pH is greater than 8, the ammonia removal rate significantly increases. About 0.06 ', that is, 6% of total ammonia is molecular ammonia. During the process, molecular ammonia is continuously stripped and oxidized, and ionic amine (NIi〇 is continuously converted into molecular ammonia (NIL) to maintain a Equilibrium state. In order to obtain a better ammonia removal efficiency, the pH of the reaction solution must be maintained above 7. Example 3: The effect of operating pressure on ammonia removal efficiency under different flow rates ^ in 0.1M NaHC〇3, PH8.5 aqueous solution "Add ammonium sulfate to make ammonia content 130mg / L" as the artificial synthetic wastewater containing ammonia. Inside diameter 0.9Cm stainless steel tube filled with 12.5ml Pt / SDB catalyst and 12.5mi crushed ceramic debris (Diameter 0.5-0.8 mm). Wastewater flows through the reactor at a flow rate of 丄 〇, 20, 3'ml / min., And the oxygen is also passed through the reactor in the same direction. The sinking speed is 75ml. / mm ·, the reaction temperature is 130C. The test results (Figure 5) show that 'high operating pressure is conducive to Removal rate, low flow rate can get higher ammonia conversion rate, under 130. (:, 40pslg and LHSV 2.4Wv hf reaction conditions, the ammonia conversion rate can be as high as 95%. Example 4: reaction temperature for ammonia removal rate Affects 0.1M NaHCO, pH8.5 aqueous solution, amine sulfate is added to make ammonia content 130mg / L, which is regarded as artificial synthetic wastewater containing ammonia. Inside diameter 0.9cm stainless steel tube is filled with 12.5ml Pt / SDB catalyst and i2.5ml crushed ceramic chips (diameter 0.5-0.8mm). Wastewater flows through the reactor at a flow rate of 2.0 mi / min., And oxygen flows through the reactor in the same direction with a flow rate of 75ml. / min., the reaction temperature is 12 (rc, 13 (rc.). The test results are shown in Figure 6. 'It can be seen that high temperature is beneficial to the removal rate of ammonia. — —___ 10___ This paper is applicable to the standard (CNS) grid (210X 297 mm 1- (Please read the precautions on the back before filling in this page) — clothing -----, 1T-P. 506945 7;-A7 Description of the invention (f) Example 5: Use hydrophobic catalyst Pt / SDB under the same reaction conditions At the same time, remove ammonia and phenol in water at the same time in 0.1M NaHC〇3, ρΗ8.5 · 5 aqueous solution, add amine sulfate to make ammonia content of 125mg / L, at the same time, 500mg / L of phenol was also added to treat it as artificial wastewater. The reactor was a 1.5cm inner diameter stainless steel tube filled with 15ml Pt / SDB catalyst and 15ml crushed ceramic debris (diameter 0.5_〇 , 8mm). Wastewater flows through the reactor at a flow rate of 3.5ml / mm. (LHSV 7v / v hr ', and oxygen also flows through the reactor in the same direction with flow rates of 100, 300ml / min., Respectively. The reaction conditions were 130C '90 psig. The test results are not in Table 1 *. (Please read the notes on the back before filling this page.) Table 1 Oxygen flow rate (ml / mm.) Ammonia removal rate (%) Phenol removal rate (%) 300 44.4 45.4 100 35.7 41.1 Ordered by the Intellectual Property Office of the Ministry of Economic Affairs The test results printed by the cooperative show that under the same reaction conditions, the Pt / SDB hydrophobic catalyst can simultaneously catalyze the oxidation reaction of ammonia and phenol, and the phenol system is oxidized to CO: and H2. No other intermediate products (such as Figure 7). Example 6: Effect of partial pressure of oxygen on ammonia removal rate In 0.1M NaHCCX pH8.5 aqueous solution, amine sulfate was added to make the ammonia content to 125mg / L, which was regarded as artificial synthetic wastewater containing ammonia. The reactor was a stainless steel tube with an inner diameter of 1.5 cm, filled with 15 ml of Pt / SDB catalyst and 15 ml of crushed ceramic chips (0.5-0.8 mm in diameter). Wastewater flows through the reactor at a flow rate of 3.5ml / min. (LHSV 7.0v / v hr ', and oxygen also flows through the reactor in the same direction. The relevant reaction conditions and test results are shown in Table 2. As expected, high oxygen Partial pressure and high temperature are favorable for the conversion of ammonia into% and 11 This paper size is applicable to Chinese National Standard (CNS) A4 specification (210X 297 mm) 506945 A7 B7 V. Description of the invention (') H2〇.
(請先閲讀背面之注意事項再填寫本頁} 衣-- 訂 經濟部智慧財產局員工消費合作社印製 於0.1M NaHC〇3, PH8.5水溶液中，加入硫酸胺，使g 氨含量爲125mg/L，同時亦加入酚500mg/L，以此當作人工 合成廢水。反應器爲內徑1.5cm之不鏽鋼管，充塡15ml Pt/SDB觸媒及15ml粉碎的陶瓷碎屑（直徑0.5-0.8mm)。廢 水以流速3.5ml/min.(LHSV 7v/v hf1)、向下流經反應器，氧 氣亦以相同方向流經反應器。反應條件及試驗結果示於表 三，可知高氧氣分壓及高溫有利於酸轉化成C〇2, H2〇。 _ —___ 12 本紙張尺度適用中國國家榡隼（c叫八视格（21〇>< 297公麓） 506945 A7 B7 五、發明説明（丨0 ) -* 衣二 溫度(°c) 氧氣流量 (ml/mm) 氧氣分壓(psi) 酚去除率(％) 100 100 24.7 13.4 100 100 64.7 24.4 100 300 24.7 10.7 100 300 64.7 24.3 130 .100 24.7 27.5 130 100 64.7 45.4 130 300 24.7 29.6 130 300 64.7 41.1 (請先閲讀背面之注意事項再填寫本頁) 例八：以空氣爲氧化劑 經濟部智慧財產局員工消費合作社印製 以氨水配製人工合成廢水，氨含量爲140mg/L， ρΗΙΟ.5。反應器爲內徑1.5cm之不鏽鋼管，充塡15ml Pt/SDB觸媒及15ml粉碎的陶瓷碎屑（直徑0.5-0.8mm)。廢 水以流速3.5ml/mm.(LHSV 7v/v hf1)、向下流經反應器，空 氣或氧氣亦以相同方向流經反應器，流速爲100ml/mm.。 試驗結果示於表四，結果顯示以空氣爲氧化劑者，其氨去 除效率較低。考量操作成本，工業界仍以空氣爲優先考量 的氧化劑來源。 表四 LHSV (v/v hr'1) 氨去除率 (%，空氣爲氧化劑） 氨去除率 (%，純氧:ί氧化劑） 5 46.5 56.5 3 67.8 75.7 13 本紙張尺度適用中國國家標準（CNS ) A4規格（210X297公釐） 506945 A7 _____B7 五、發明説明（（/ ) 例九：自空氣中去除氨 以圖二所示之試驗裝置處理混合均勻含有3500-73〇0ppmv氨之氣體，處理條件爲i〇〇-i32°C、空間流速 176001^1。試驗結果示於圖八，結果顯示觸媒活性可達 〇.91mg/min/g catalyst。 (請先閲讀背面之注意事項再填寫本頁 —C3裝----- 訂- 經濟部智慧財產局員工消費合作社印製 A Ns c /—\ 一準 一標 -家 -國 ，國 f中 用 適 X ο 4 釐 公(Please read the precautions on the back before filling in this page.) Clothing-Ordered by the Intellectual Property Bureau of the Ministry of Economic Affairs, the Consumer Cooperatives printed in 0.1M NaHC〇3, PH8.5 aqueous solution, adding amine sulfate to make the ammonia content of 125mg / L, and also added phenol 500mg / L as artificial wastewater. The reactor is a stainless steel tube with an inner diameter of 1.5cm, filled with 15ml Pt / SDB catalyst and 15ml crushed ceramic chips (0.5-0.8 in diameter) mm). Wastewater flows through the reactor at a flow rate of 3.5ml / min. (LHSV 7v / v hf1), and oxygen also flows through the reactor in the same direction. The reaction conditions and test results are shown in Table 3. It can be seen that the high oxygen partial pressure And high temperature is favorable for the conversion of acid into C02, H2〇. _ —___ 12 This paper size is applicable to the Chinese national standard (c is called eight-vision grid (21〇 > < 297)) 506945 A7 B7 V. Description of the invention (丨 0)-* clothing temperature (° c) oxygen flow rate (ml / mm) oxygen partial pressure (psi) phenol removal rate (%) 100 100 24.7 13.4 100 100 64.7 24.4 100 300 24.7 10.7 100 300 64.7 24.3 130. 100 24.7 27.5 130 100 64.7 45.4 130 300 24.7 29.6 130 300 64.7 41.1 (Please read the notes on the back first (Fill in this page) Example 8: Using air as an oxidant, the Consumers' Cooperative of the Intellectual Property Bureau of the Ministry of Economic Affairs prints a synthetic wastewater prepared with ammonia, the ammonia content is 140mg / L, ρΗΙ0.5. The reactor is a stainless steel tube with an inner diameter of 1.5cm Fill 15ml Pt / SDB catalyst and 15ml crushed ceramic chips (0.5-0.8mm in diameter). Wastewater flows through the reactor at a flow rate of 3.5ml / mm. (LHSV 7v / v hf1), and air or oxygen is also added to Flow through the reactor in the same direction with a flow rate of 100ml / mm. The test results are shown in Table 4. The results show that the efficiency of ammonia removal is lower for those using air as the oxidant. Considering the operating cost, the industry still considers air as the oxidant. Source: Table 4 LHSV (v / v hr'1) Ammonia removal rate (%, air is oxidant) Ammonia removal rate (%, pure oxygen: oxidant) 5 46.5 56.5 3 67.8 75.7 13 This paper size applies to Chinese national standards ( CNS) A4 specification (210X297 mm) 506945 A7 _____B7 V. Description of the invention (/) Example 9: Remove ammonia from the air and treat it with the test device shown in Figure 2 to mix and evenly contain the gas containing 3500- 730,000 ppmv ammonia. Conditions are i〇〇-i32 ° C A space velocity of 176,001 ^ 1. The test results are shown in Figure 8. The results show that the catalyst activity can reach 0.91 mg / min / g catalyst. (Please read the precautions on the back before filling in this page—C3 Pack ----- Order-Printed by the Consumer Cooperatives of the Intellectual Property Bureau of the Ministry of Economic Affairs A Ns c / — \ One quasi-one bid-Home-Country, Country f Middle Use X ο 4 centimeters