304188 A7 B7 經濟部中央棣準局員工消費合作社印装 五、發明説明（） 1 .發明背景 煉油及石化工業產生之廢鹼液’含有高濃度丑j及少量 硫醇、酚、油份，除產生惡臭外，並會造成廢水處理場活性 污泥單元之pH失控問題，由於環保法規趨於嚴格，以傳 統之深井注入法或海洋放流，已無法符合要求，必須以其它 方法前處理，已知之處理方法有硫酸中和汽提法、中低壓澄 式氧化法、高壓溼式氧化法、焚化法、超臨界水氧化法等。 硫酸中和汽提法，由於汽提塔操作溫度高（塔底12〇 °C、塔頂112 °C)，將廢鹼液中之碳氫化合物一併汽提至塔 頂’曾現場取樣實測，其〇6含量高達5.9%，而C7含量為 0.67%，由於此股被汽提出之硫化氫酸氣，含有高濃度碳氩 化合物，硫磺回收不易，一般引入廢氣燃燒塔燃燒，造成 排放污染。中低壓溼式氧化法係僅將///氧化成//2&03， 排入廢水處理場，仍會造成pH失控，活性污泥死亡。高壓 溼式氧化法則屬於高溫高壓操作，反應器需要特殊材質，設 備及操作費高。焚化法則設備價格高昂，操作維持費高，且 排氣亦有*S02污染及飛灰等問題。另超臨界水氧化法腐蝕性 極強，設備及操作費非常昂貴。 本發明係先將廢驗液進行加酸中和，由於加酸中和時， 並無汽提操作，故中和後所產生之硫化氩酸氣，其碳氫化合 物含量可低於0 . 5 % (實驗室實測結果），因此可直接引入硫 磺回收工場回收硫磺。中和液再利用強氧化劑進行氧化處 理0 3 ----------^------1T------.it (請先聞讀背面之注意事項再填寫本頁) 本紙張尺度適用中國國家橾準（CNS ) A4規格（210X297公釐） 83. 3.10,000 A7304188 A7 B7 Printed by the Consumers ’Cooperative of the Central Department of Economics of the Ministry of Economic Affairs V. Description of the invention () 1. Background of the invention The waste lye produced in the oil refining and petrochemical industries contains high concentrations of ugly j and a small amount of mercaptans, phenols, and oil, except It produces odor and will cause the pH of the activated sludge unit of the wastewater treatment plant to be out of control. Due to the stricter environmental protection regulations, the traditional deep well injection method or ocean discharge cannot meet the requirements. It must be pre-treated by other methods. Treatment methods include sulfuric acid neutralization stripping method, medium and low pressure clarification oxidation method, high pressure wet oxidation method, incineration method, supercritical water oxidation method, etc. Sulfuric acid neutralization stripping method, due to the high operating temperature of the stripping tower (12 ° C at the bottom of the tower and 112 ° C at the top of the tower), the hydrocarbons in the waste lye are stripped to the top of the tower together. The content of 〇6 is as high as 5.9%, and the content of C7 is 0.67%. Because this steamed hydrogen sulfide acid gas contains high concentration of carbon argon compounds, sulfur recovery is not easy. Generally, it is introduced into the exhaust gas combustion tower for combustion, causing emission pollution. The medium and low pressure wet oxidation system only oxidizes /// to // 2 & 03 and discharges it into the wastewater treatment plant, which will still cause pH runaway and the activated sludge will die. The high-pressure wet oxidation method belongs to high-temperature and high-pressure operation. The reactor requires special materials, and the equipment and operation costs are high. The incineration law equipment is expensive, the operation and maintenance costs are high, and the exhaust also has problems such as * S02 pollution and fly ash. In addition, the supercritical water oxidation method is extremely corrosive, and the equipment and operation costs are very expensive. The present invention first neutralizes the waste test solution with acid. Since the acid is added to neutralize, there is no stripping operation, so the hydrogen sulfide gas produced after neutralization can have a hydrocarbon content of less than 0.5 % (Laboratory measurement results), so it can be directly introduced into the sulfur recovery plant to recover sulfur. Neutralization solution is then oxidized with a strong oxidizer 0 3 ---------- ^ ------ 1T------.it (please read the precautions on the back before filling in this Page) This paper scale is applicable to China National Standard (CNS) A4 (210X297mm) 83. 3.10,000 A7
經濟部中央梂準局貞工消費合作社印製 而國内習用之高溫高壓濕式氧化法，係於25〇t、 60ato«下，直接以高壓空氣將污染物氧化，排放水中 COD(化學需氧量）仍高於i〇〇〇mg/L，且其操作費用每處理 一公噸廢鹼液約3500元。而本發明係採低溫低壓處理程 序，操作安全性較高，操作費用較便宜，初估約25〇〇元/公 秉，且排放水中COD含量可低於2〇〇mg/L。 衡諸各種處理方法，均有其不足處。而本處理程序可改 善以往之造成二次污染、操作不安全、設備及操作費高等缺 失。 2 .發明概述： 本發明為一種新的煉油廢鹼液處理程序，此處理程序為 先將煉油廢鹼液加酸中和處理，產生的硫化氫酸氣引入硫磺 回收工場回收硫磺，中和液再利用強氧化劑進行氧化處理， 所使用的強氧化劑為0H.自由基，0H·自由基的來源為斐 頓試液（Fenton’s Reagent)或利用紫外光（U.V.)照射 H2〇2溶液。斐頓試液（Fenton’s Reagent)之製備程序 係將F e S04或F e C 12. . ·等鐵離子溶液與Η202溶液混合即可。 作用原理係於ρΗ<4 . 5下，利用亞鐵或鐵離予（Fe + 2或 Fe + 3)催化過氧化氫（H2〇2)溶液產生〇H.自由基。中和液 中之硫化氫、硫醇類等幾可被0H·自由基完全氧化，有效解 決煉油廢鹼液所造成的污染問題。 本發明可應用於煉油廠處理各煉油製程所產生的廢鹼 液，一般煉油廠皆設置有硫磺回收工場，而本發明之加酸中 ^------ir------^ (請先閱讀背面之注意事項再填寫本K ) 本紙張尺度適用中國國家標準（CNS > A4規格（210 X 297公釐） 83. 3.10,000 經濟部中央樣準局貝工消费合作社印装 304188 A7 - —~— ------B7 五、發明説明（） ~~ ~ 和處理階段所產生的硫化氫酸氣可引入硫磺回收工場回收硫 磺，達到資源化目的。 除可回收硫磺外，本發明亦具有低溫低壓操作、處理安 全性高、操作費用較低、處理效果佳等優點。處理後排放液 化學需氧値（C0D)可降至200mg/l以下，得以直接排放。 3 .發明的詳細説明： 以附圖一説明本發明之處理流程。進料廢鯰液的成份為： 5’000~50,000mg/l、NaOH 5-15 wt%、化學需氧 値（（：0〇)1〇,〇〇0~100,0〇〇11^/1、非硫化物部份之（；〇1) 値為l，000~5,000mg/l，pH値大於13。此廢鹼液先經加 酸中和處理，所使用的酸液為破酸或鹽酸。中和的反應條件 為pHl〜6，最適的反應範圍為5〜6 ;溫度40〜90 °C，較適的 溫度範圍在60〜8 0°C ;中和槽滞留時間為5〜50分鐘，一般 約25分鐘，反應即可達到平衡。中和反應之化學反應式如 下： N a 2S + . H 2S 0 4一 N a 2S 0 4 + H 2S ^ ( p H = 5 . 0 ) 在pH = 5下，H2S大部份以分子態存在，氣液平衡後，大部份 H2S進入氣相。此加酸中和步驟產生的酸氣硫化氫（H2S)含 量92¾以上，破氫化合物（hydrocarbon)含量則低於 0.5%，可引入硫磺回收工場回收硫磺。 中和反應後排出之中和液，碗化氫濃度僅餘i，〇〇〇〜 1,500 mg/1、C0D値則為 3,000~6,500mg/l。將此中和 液再引入可瞬間完全混合的反應器内進行氧化反應’所使用 5 本纸張尺度逋用中國國家揲準（CNS ) A4规格（210X297公釐） 83. 3.1〇,〇〇〇 ^------訂------m C請先閲讀背面之注意事3再填寫本夏) 304188 A7 B7 經濟部中央揉準局負工消费合作社印装 五、發明説明（） 的強氧化劑為0H .自由基’ 0H .自由基的來源為斐頓試液 (Fenton's Reagent)或利用紫外光（ϋ ν.)照射H2〇2溶 液。氧化反應時，廢鹼/雙氧水（3 5wt%)體積流量比為 20〜40 ;亞鐵及鐵離子（Fe + 2&Fe + 3)濃度為 50〜300mg/l，反應溫度60〜l〇〇°c，較佳的溫度範圍為 70〜95 C ;反應落液於氧化槽中之滯留時間為〜丨2〇分 鐘’較佳的滞留時間為20~60分鐘。有關〇Η·自由基之產生 反應式及0 Η _與污染物成份如齡 ( p h e n 〇 1，c 5〇 Η )之氧化反 應式如下： H202 幵2〇2 + Fe — OH + OH + Fe 3(Fenton’s"Rsagent) C^OH + 280fT — 6C02 + 而2〇(氧 i匕反應) 依廢鹼成份及濃度之不同，於上述之反應條件範圍内，調整 其最適反應條件，所得最終排放液C0D値皆可低於 2 0 0 m g / 1。此排放液p Η約1 · 8 - 2 . 4，仍需加人鹼液調至中 性再放流。加鹼中和過程會有氫氧化鐵（F e ( Ο Η) 3 )沈澱物 產生，經固液分離後，氫氧化鐵沈澱物部份則再回流至氧化 槽内，繼續其催化作用。 依硫化氫氣液平衡原理，於硫化氫分壓為一大氣壓、pH 5 . 0、溫度7 0 °C時，液相中硫化氫濃度的理論平衡値為 1，4 0 0 m g / 1，而溫度4 0 °C時，液相中硫化氫濃度則為 2,450 mg/1。提升溫度可有效移除液相中硫化氫，本發明 之加酸中和處理階段，試驗結果顯示，於適當的反應時間 内，中和液中殘留之硫化氫濃度即已接近理論平衡値。 6 ^------ίτ------0 (請先閱讀背面之注意事項再填寫本頁) 本紙張尺度逋用中國國家揉準（CNS ) Α4规格（210Χ 297公釐） 83. 3. !0,〇〇〇 A7The high-temperature, high-pressure, and wet-type oxidation method, which is printed by the Central Engineering Bureau of the Ministry of Economic Affairs and used by the domestic high-temperature and high-pressure wet oxidation system, is directly oxidized with high-pressure air to discharge COD (chemical oxygen demand) under 25〇t, 60ato Amount) is still higher than 1000mg / L, and its operating cost is about 3500 yuan per metric ton of waste lye. However, the present invention adopts a low-temperature and low-pressure treatment process, which has high operation safety and relatively low operation cost. The initial estimate is about 2500 yuan / square meter, and the COD content in the discharged water can be less than 200 mg / L. All kinds of treatment methods have their shortcomings. And this processing procedure can improve the past defects such as secondary pollution, unsafe operation, high equipment and operation costs. 2. Summary of the invention: The present invention is a new treatment process of waste lye for oil refining. This treatment process is to add acid to neutralize the waste lye for oil refining. The generated hydrogen sulfide acid gas is introduced into the sulfur recovery plant to recover sulfur and neutralize the liquid. The strong oxidant is then used for oxidation treatment. The strong oxidant used is 0H. Free radical, and the source of 0H · free radical is Fenton's Reagent or ultraviolet light (UV) is used to irradiate the H202 solution. The preparation procedure of Fenton's Reagent is to mix Fe e S04 or Fe C 12.... And other ferric ion solution with Η202 solution. The principle of action is under ρΗ <4.5, using ferrous or iron ion (Fe + 2 or Fe + 3) to catalyze hydrogen peroxide (H2〇2) solution to generate OH. Radicals. Hydrogen sulfide, mercaptans, etc. in the neutralization liquid can be completely oxidized by 0H · free radicals, effectively solving the pollution problem caused by the waste lye of oil refining. The invention can be applied to oil refineries to process waste alkali liquor produced by various oil refining processes. Generally, oil refineries are equipped with sulfur recovery plants, and the acid addition of the invention ^ ------ ir ------ ^ (Please read the precautions on the back before filling in this K) The paper size is in accordance with Chinese National Standard (CNS> A4 size (210 X 297 mm) 83. 3.10,000 Printed by Beigong Consumer Cooperative, Central Bureau of Standards, Ministry of Economic Affairs 304188 A7-— ~ — --B7 V. Description of the invention () ~~ ~ and the hydrogen sulfide acid gas generated in the treatment stage can be introduced into the sulfur recovery plant to recover sulfur, so as to achieve the purpose of resource utilization. In addition to recoverable sulfur The present invention also has the advantages of low temperature and low pressure operation, high processing safety, low operating cost, and good processing effect. After treatment, the chemical oxygen demand value (C0D) of the discharged liquid can be reduced to less than 200mg / l and can be directly discharged. 3. Detailed description of the invention: The processing flow of the present invention will be explained with the first drawing. The composition of the feed catfish liquid is: 5'000 ~ 50,000mg / l, NaOH 5-15 wt%, chemical oxygen demand value ((: 0〇 ) 1〇, 〇〇0 ~ 100, 〇〇〇11 ^ / 1, non-sulfide part (; 〇1) The value is 1, 00 0 ~ 5,000mg / l, pH value is greater than 13. This waste lye is first neutralized by adding acid, and the acid used is acid or hydrochloric acid. The neutralization reaction conditions are pHl ~ 6, and the most suitable reaction range is 5 ~ 6; temperature 40 ~ 90 ° C, the suitable temperature range is 60 ~ 80 ° C; the residence time of the neutralization tank is 5 ~ 50 minutes, generally about 25 minutes, the reaction can reach equilibrium. Neutralization reaction The chemical reaction formula is as follows: N a 2S +. H 2S 0 4-N a 2S 0 4 + H 2S ^ (p H = 5. 0) At pH = 5, most of the H2S exists in molecular state, and the gas-liquid equilibrium After that, most of the H2S enters the gas phase. The acid gas produced in the acid neutralization step has a hydrogen sulfide (H2S) content of more than 92¾, and a hydrogen breaking compound (hydrocarbon) content of less than 0.5%. Sulfur recovery plants can be introduced to recover sulfur. After the neutralization reaction, the neutralized liquid is discharged, and the concentration of the hydrogenation in the bowl is only 10,000 to 1,500 mg / 1, and the COD value is 3,000 to 6,500 mg / l. This neutralized liquid is reintroduced into the completely mixed instantaneously. The oxidation reaction used in the reactor 'uses 5 paper scales that use the Chinese National Standard (CNS) A4 specification (210X297mm) 83.3.1〇, 〇〇〇 ^ ------ ------ m C, please read the notes on the back 3 before filling in this summer) 304188 A7 B7 Printed by the Central Ministry of Economic Affairs Bureau of Labor and Consumer Cooperatives V. The description of invention () The strong oxidant is 0H. Free radical '0H. The source of free radicals is Fenton's Reagent (Fenton's Reagent) or the use of ultraviolet light (ϋ ν.) Irradiate H2〇2 solution. During the oxidation reaction, the waste alkali / hydrogen peroxide (35 wt%) volume flow ratio is 20 ~ 40; the concentration of ferrous iron and iron ions (Fe + 2 & Fe + 3) is 50 ~ 300mg / l, and the reaction temperature is 60 ~ 100. ° C, the preferred temperature range is 70 ~ 95 C; the residence time of the reaction solution in the oxidation tank is ~ 丨 20 minutes', the preferred residence time is 20 ~ 60 minutes. The reaction formula for the generation of 〇Η · free radicals and the oxidation reaction formula of 0 Η _ with pollutant components such as age (phen 〇1, c 5〇Η) are as follows: H202 and 2〇2 + Fe — OH + OH + Fe 3 (Fenton's " Rsagent) C ^ OH + 280fT — 6C02 + and 2〇 (oxygen reaction) According to the difference of waste alkali composition and concentration, within the range of the above reaction conditions, adjust the optimal reaction conditions to obtain the final discharge liquid C0D Values can be less than 200 mg / 1. The effluent p Η is about 1. 8-2.4, still need to add human lye to adjust to neutral and then release. During the alkali neutralization process, iron hydroxide (F e (Ο Η) 3) precipitates will be generated. After solid-liquid separation, the part of the iron hydroxide precipitates will be returned to the oxidation tank to continue its catalytic effect. According to the principle of hydrogen sulfide liquid equilibrium, when the partial pressure of hydrogen sulfide is atmospheric pressure, pH 5.0, and temperature 70 ° C, the theoretical equilibrium value of the concentration of hydrogen sulfide in the liquid phase is 1, 4 0 0 mg / 1, and the temperature At 40 ° C, the concentration of hydrogen sulfide in the liquid phase is 2,450 mg / 1. Increasing the temperature can effectively remove the hydrogen sulfide in the liquid phase. In the neutralization treatment stage of adding acid in the present invention, the test results show that within an appropriate reaction time, the concentration of residual hydrogen sulfide in the neutralizing liquid is close to the theoretical equilibrium value. 6 ^ ------ ίτ ------ 0 (please read the precautions on the back before filling in this page) This paper uses the Chinese National Standard (CNS) Α4 specification (210Χ 297 mm) 83 . 3.! 0, 〇〇〇A7
經濟部中央揉準局負工消费合作社印11Printed by the Ministry of Economic Affairs Central Bureau of Accreditation and Consumer Cooperatives 11
中和反應所產生的酸氣，硫化氫（H2S)含量高於 9 2%(v/v)、碳氫化合物（Hydrocarb〇n)含量低於〇 .5% (v/v)，適合引入硫磺回收工場回收硫磺，每處理一公秉廢 鹼可回收43公斤硫磺。 中和處理後之中和液，再引入可瞬間完全混合之反應器 内進行氧化反應，所使用強氧化劑為.自由基。〇H •自 由基具備極強的氧化特性，常溫常壓下，與有機物的反應速 率，為臭氧的1 倍以上。另外0H.不像其它強氧化劑，如 KMn〇4、HC102等，氧化後會產生重金屬、氣化物等毒性物 質，為一極佳之氧化劑。 處理後之排放液’ COD低於200mg/i，且已無硫臭， Η 2 S及Η 2 S 2 〇 3測定結果均為微量。此排放液ρ η約1 § 一 2 _ 4，需經加鹼中和後再予以排放，中和時，氫氧化鐵 (F e ( 0 Η ) 3 )沈澱物會伴隨生成，經固液分離後，再泵送回 乳化槽繼續其催化作用，除了減少鐵鹽之消耗量外，更可完 全免除氫氧化鐵固體廢棄物之處置困擾。 為詳述本發明對於廢鹼液之處理效果，以下列闡述性 而非限制性之試驗實例説明： 例一：煉油廢鹼液樣品A ( c 0 D 1 3 , 1 5 0 m g /丨、s -2 5 , 9 4 0 mg/1 - NaOH 5.1\»^%、非硫化合物（：〇〇1，2(7〇11^/1、 pH>13.5)利用本發明處理，其加酸中和處理條件為溫度？！ 、ρ Η = 4 . 8上0 · 2、中和槽滯留時間2 5分鐘、濃硫酸添加 量34.5cc/L廢驗。而氧化處理條件為：溫度、氧化槽 83. 3. !〇,〇〇〇 裝 訂 · 線 (請先閲讀背面之注意事項再填寫本頁) 五、發明説明（ A7 B7 滞留時間30min.、亞鐵離子濃度i95mg/l、廢鹼/雙氧水 (3 5 w t % )體積流量比3 4 · 2。處理結果如表一所示。 表一：煉油Θ 1驗樣品A之中和氧化處理結罢 反應階段 分析項目 加酸中和 中和前中和後 氧化處理 COD(mg/l) 13,146 3,830 —一 __— -一 2 0 3 H9S(mg/l) 5,940 1,346 _ <1 例一：煉油廢驗樣品 B(COD 94，110mg/l、45 000 m g/1、N a Ο Η 1 Ο · 2 w t %、非硫化合物 C O D 4 ’ 1 1 〇 m g/!、 pH>14.0)利用本發明處理，其加酸中和處理條件為：溫度 4 6 °C、中和槽滞留時間2 5分鐘、濃硫酸添加量6 8 c c / L廢 鹼。而氧化處理條件為：溫度8 4 X、氧化槽滯留時間5 〇分 鐘、廢鹼/雙氧水（3 5 w t % )體積流量比2 4 · 4。另探討不同 亞鐵離子濃度對氧化處理效果之影響，其試驗結果如表二所 示0 (請先閱讀背面之注意事項再填寫本頁) -装· 訂 纸 -1___I 本 經濟部中央橾準局貞工消费合作社印装 表二：不同亞鐵離子濃度對氧化處理效果之吾4狻 分析項目 反應階段 COD(mg/l) H2 S( mg/1) 加酸中和前 94,110 45,000 加酸中和後 6,253 1,472 氧化反應 Fe + z 9 5 mg/1 233 <1 Fe + ^ 1 90mg/l 1 70 <1 Fe + ^ 2 8 5mg/l 16 1 <1 例三：煉油廢鹼樣品 C ( C 0 D 9 2，4 0 0 m g / 1、s - 2 4 4 , 7 6 〇 m g / 1 > N a 0 Η 10.2wt%、非硫化合物 COD 2,8 8 0 mg/l、 8 83· 3. !〇,〇〇〇 • —^1 ^04188 A7 --------- B7 五、發明説明（） '" ――-- .pH>14.0)利用本發明處理，其加酸中和處理條件為、 中和槽滯留時間25分鐘、濃硫酸添加量68cc/L廢鹼。而氧 處理條件為：亞鐵離子濃度95fflg/i、氧化槽滯留時間5〇分 鐘、廢鹼/雙氧水（35wt%)流量比24.4。另探討氧化階段 不同反應溫度對處理效果之影響，其試驗結果表三所示。 参三：不巧反應溫度對氧化處理效果之积塑 分析項目 反應階·段 C 0 D ( m g / 1 ) f从不^ <於箐 H2 s( mg/ 1 ) 加酸中和前 92,440 _ 44,760 加酸中和後 5,840 Γ 1,188 轧化反應 ----- 反應溫度了 (TC 36fi < \ 反應溫度8 4 °C 266 <1 例四：煉油廢驗樣品C(COD 9 2,4 0 0>ng/l、S-2 44)7 6 q mg/l、NaOH 10.2wt%、非硫化合物 C0I) 2,8 8 0 mg/ι、 p H > 1 4 . a)利用本發明處理，其加酸中和處理條件為7 〇 t、 中和槽滯留時間25分鐘、濃硫酸添加量68cc/l廢鹼。而 礼化處理條件為·亞鐵離子濃度mg/1、溫度71。^、廢 鹼/雙氧水（3 5 w t % )流量比2 4 . 4。另探討氧化階段不同反 應時間對處理效果之影響，其試驗結果如表四所示。 請 先 聞 讀 背 面 之 注The acid gas produced by the neutralization reaction has a hydrogen sulfide (H2S) content higher than 92% (v / v) and a hydrocarbon (Hydrocarb〇n) content lower than 0.5% (v / v), suitable for introducing sulfur The recycling workshop recycles sulfur, and 43 kg of sulfur can be recovered for every waste alkali treated. After the neutralization treatment, the neutralized liquid is introduced into the reactor which can be completely mixed in an instant to carry out the oxidation reaction. The strong oxidant used is free radicals. 〇H • Free radicals have extremely strong oxidizing properties. At room temperature and pressure, the reaction rate with organic substances is more than double that of ozone. In addition, 0H. Unlike other strong oxidants, such as KMn〇4, HC102, etc., it will produce toxic substances such as heavy metals and vapors after oxidation, which is an excellent oxidant. The COD of the discharged liquid after the treatment is less than 200 mg / i, and it has no sulfur odor. The measurement results of Η 2 S and Η 2 S 2 O 3 are both trace amounts. This discharge liquid ρ η is about 1 § 1 2 _ 4, and it needs to be discharged after neutralization with alkali. During neutralization, precipitates of iron hydroxide (F e (0 Η) 3) will be generated and separated by solid-liquid separation After that, it is pumped back to the emulsifying tank to continue its catalytic function. In addition to reducing the consumption of iron salts, it can completely eliminate the trouble of the disposal of solid waste of iron hydroxide. To elaborate on the treatment effect of the present invention on waste lye, the following illustrative and non-limiting test examples are used to illustrate: Example 1: Sample A (c 0 D 1 3, 1 50 mg / 丨, s -2 5, 9 4 0 mg / 1-NaOH 5.1%, non-sulfur compounds (: 〇〇1,2, (7〇11 ^ / 1, pH> 13.5) treated by the present invention, which is acid-neutralized The processing conditions are temperature?!, Ρ Η = 4.8 on 0. 2. The residence time of the neutralization tank is 2 5 minutes, the concentration of concentrated sulfuric acid is 34.5cc / L. The oxidation treatment conditions are: temperature, oxidation tank 83. 3.! 〇, 〇〇〇 binding · thread (please read the precautions on the back before filling in this page) 5. Description of the invention (A7 B7 retention time 30min., Ferrous ion concentration i95mg / l, waste alkali / hydrogen peroxide (3 5 wt%) The volume flow ratio is 3 4 · 2. The processing results are shown in Table 1. Table 1: Oil refining Θ 1 Analysis of the sample A during the oxidation reaction and the reaction phase of the oxidation reaction before and after neutralization Oxidation treatment COD (mg / l) 13,146 3,830-one __--one 2 0 3 H9S (mg / l) 5,940 1,346 _ < 1 Example 1: Sample B for oil refining waste inspection (COD 94, 110mg / l, 45,000 mg / 1 N a Ο Η 1 Ο · 2 wt%, non-sulfur compound COD 4 '1 1 〇mg / !, pH> 14.0) using the present invention, its acid addition and neutralization treatment conditions are: temperature 4 6 ° C, neutralization The dwell time of the tank is 25 minutes, the amount of concentrated sulfuric acid added is 6 8 cc / L. The oxidation treatment conditions are: temperature 8 4 X, dwell time of the oxidation tank 50 minutes, waste alkali / hydrogen peroxide (35 wt%) volume flow Ratio 2 4 · 4. In addition, the effect of different ferrous ion concentrations on the oxidation treatment effect is discussed. The test results are shown in Table 2 0 (please read the precautions on the back and then fill out this page) -installed · bound paper -1 ___ I Printed by the Ministry of Economic Affairs, Central Bureau of Prefectural Affairs, Zhengong Consumer Cooperatives Table 2: The effect of different ferrous ion concentrations on the oxidation treatment. The reaction phase COD (mg / l) H2 S (mg / 1) before acid neutralization 94,110 45,000 Acid addition neutralization 6,253 1,472 Oxidation reaction Fe + z 9 5 mg / 1 233 < 1 Fe + ^ 1 90mg / l 1 70 < 1 Fe + ^ 2 8 5mg / l 16 1 < 1 Example 3 ： Sample C of refining waste alkali (C 0 D 9 2, 4 0 0 mg / 1, s-2 4 4, 7 6 0 mg / 1 > N a 0 Η 10.2wt%, non-sulfur compound COD 2, 8 8 0 mg / l, 8 83 · 3.! 〇, 〇〇〇 • — ^ 1 ^ 04188 A7 --------- B7 V. Description of invention () '" -------- .pH & gt 14.0) Using the treatment of the present invention, the acid-adding neutralization treatment conditions are: the neutralization tank residence time is 25 minutes, and the concentration of concentrated sulfuric acid is 68 cc / L spent alkali. The oxygen treatment conditions are: ferrous ion concentration 95fflg / i, oxidation tank residence time 50 minutes, waste alkali / hydrogen peroxide (35wt%) flow ratio 24.4. In addition, the effect of different reaction temperatures on the treatment effect in the oxidation stage is discussed. The test results are shown in Table 3. Reference three: Accumulative analysis of the effect of accidental reaction temperature on the oxidation treatment reaction stage · stage C 0 D (mg / 1) f never ^ & Yu Jing H2 s (mg / 1) before acid neutralization 92,440 _ 44,760 After acid addition and neutralization 5,840 Γ 1,188 Rolling reaction ----- reaction temperature (TC 36fi < \ reaction temperature 8 4 ° C 266 < 1 Example 4: Refinery waste test sample C (COD 9 2,4 0 0> ng / l, S-2 44) 7 6 q mg / l, NaOH 10.2 wt%, non-sulfur compound COI) 2,8 8 0 mg / ι, p H > 1 4. a) Use of the present invention For the treatment, the acid addition and neutralization treatment conditions were 70 t, the neutralization tank residence time was 25 minutes, and the concentration of concentrated sulfuric acid was 68 cc / l spent alkali. The etiquette treatment conditions are: ferrous ion concentration mg / 1, temperature 71. ^, Waste alkali / hydrogen peroxide (35wt%) flow ratio of 24.4. In addition, the effect of different reaction time on the treatment effect in the oxidation stage is discussed. The test results are shown in Table 4. Please read the back notes first
I 旁 裝 訂 經*部中央梂準局貝工消费合作社印製 表四：不同f應時間對氧化處理效果之影響 分析項目 反應階段 COD(mg/l) Η 2 S ( m g/1) 加酸中和前 92,440 44,760 加酸中和後 5,840 1,188 氧化反應 反應時間5 0 m i η 260 <1 反應時間80min 17 0 <1 9 本纸法尺度適用中國國家捸準（CNS ) A4^( 210X297^*7-'~~ ----- 83. 3.10,000 ^04188 A7I. Bookbinding and Economic Development Department * Central Bureau of Industry and Engineering, Beigong Consumer Cooperative Printed Table 4: Analysis of the effect of different f time on the oxidation treatment effect. COD (mg / l) Η 2 S (mg / 1) in the reaction stage of the project And before 92,440 44,760 Neutralization with acid 5,840 1,188 Oxidation reaction time 5 0 mi η 260 < 1 Reaction time 80min 17 0 < 1 9 The standard of this paper method is applicable to the Chinese National Standard of Practice (CNS) A4 ^ (210X297 ^ * 7- '~~ ----- 83. 3.10,000 ^ 04188 A7
订 線. 經濟部中央揉準局貝工消費合作社印製 ο 1 本纸張尺度逍用尹國蹰家採準（〇^〉八4规格（210：<297公釐） 83. 3. 10,000 A7 發明説明（ 圖式簡單説明： 圖一為煉油廢鹼液中和氧化處理流程，將煉油廢鹼液導入中 和槽，經加酸中和所產生的硫化氫酸氣直接引入硫磺工場回 收硫磺，中和液則導入氧化槽進行氧化反應，同時注入過氧 化氫（Η"2)及硫酸亞鐵（f e S〇4)溶液，以產生〇 η自由基進 行氧化反應。氧化處理去除大部份之污染物後，其排放液再 導入加鹼中和單元，本單元操作時會產生氩氧化鐵 (F e ( Ο Η )3)沈澱物，固液分離後，氫氧化鐵（F e ( 〇 Η ) 3)沈 殿物回流至氧化槽，上澄液則予以排放。本處理方法之每— 單元均為連績式操作。 圖二為煉油廢檢液經本處理方法處理前後之外觀差異，處理 前之廢鹼液呈黃褐色，處理後則呈無色透明狀。 裝------,玎------.it (請先聞讀背面之注意事項再填寫本頁) 經濟部中央棣準局—工消費合作杜印製Lined. Printed by the Beigong Consumer Cooperative of the Central Bureau of Economic Development of the Ministry of Economic Affairs. 1 This paper standard is used in the Yin Guoge family standard (〇 ^> 84 specifications (210: < 297 mm) 83. 3. 10,000 A7 Invention Description (Simple illustration: Figure 1 is the process of neutralizing and oxidizing the waste lye for refining. The waste lye for refining is introduced into the neutralization tank, and the hydrogen sulfide acid gas generated by acid neutralization is directly introduced into the sulfur factory to recover sulfur. The liquid is introduced into the oxidation tank for oxidation reaction, and at the same time, hydrogen peroxide (H " 2) and ferrous sulfate (fe S〇4) solutions are injected to generate 〇η free radicals for oxidation reaction. The oxidation treatment removes most of the pollution After the material is discharged, the discharge liquid is then introduced into the alkali addition neutralization unit. During the operation of this unit, iron oxyhydroxide (F e (Ο Η) 3) precipitates are generated. After solid-liquid separation, the iron hydroxide (F e (〇Η) 3) Shen Dianwu returns to the oxidation tank, and the Shangcheng liquid is discharged. Each unit of this treatment method is a continuous operation. Figure 2 shows the difference in appearance of the refining waste test liquid before and after treatment by this treatment method. The lye is yellow-brown, and after treatment is colorless and transparent . ------ loaded like, Ding ------.it (please read smell precautions to fill out the back of this page) Ministry of Economic Affairs Bureau of the Central Di quasi - Workers consumer cooperatives printed
83· 3· 10,000 本紙張尺度適用宁國國家棣率（CNS) A4规格（21〇χ297公簸）83 · 3 · 10,000 This paper scale is applicable to the Ningguo National Atomic Rate (CNS) A4 specification (21〇 × 297 hectares)