香料廢水的化學處理法論述
由于合成香料廢水中含(han)有(you)(you)大量對微生物(wu)(wu)具(ju)有(you)(you)毒害作用(yong)的(de)難降(jiang)解的(de)有(you)(you)機(ji)物(wu)(wu),又缺乏營養(yang)元素磷。直接采用(yong)生化(hua)法處(chu)理這類廢水效果極低,有(you)(you)時(shi)甚(shen)至無法運行。目前合成香料廢水的(de)化(hua)學處(chu)理方法主(zhu)要為化(hua)學氧(yang)化(hua)法。通過化(hua)學氧(yang)化(hua),可(ke)以將廢水中許多有(you)(you)毒有(you)(you)害難降(jiang)解的(de)有(you)(you)機(ji)物(wu)(wu)轉化(hua)為微毒、無毒、易降(jiang)解的(de)物(wu)(wu)質,另外還可(ke)以起到消毒殺(sha)菌的(de)作用(yong),比較適合于該類廢水的(de)處(chu)理。
濕(shi)式氧(yang)(yang)(yang)(yang)(yang)(yang)化(hua)(hua)(hua)技術(WA0)是(shi)(shi)從(cong)20世紀50年(nian)代發展起來的(de)(de)(de)(de)(de)一(yi)種重要的(de)(de)(de)(de)(de)處(chu)(chu)(chu)理(li)(li)(li)(li)(li)(li)(li)有(you)(you)(you)(you)毒有(you)(you)(you)(you)害、高(gao)(gao)濃(nong)(nong)度(du)有(you)(you)(you)(you)機(ji)(ji)廢(fei)(fei)(fei)(fei)水(shui)(shui)(shui)(shui)(shui)的(de)(de)(de)(de)(de)有(you)(you)(you)(you)效(xiao)(xiao)(xiao)方(fang)法(fa)(fa)(fa)。它是(shi)(shi)在(zai)(zai)(zai)(zai)(zai)高(gao)(gao)溫(wen)(125~320oC)和高(gao)(gao)壓(ya)(O.5~20MPa)條(tiao)件(jian)下(xia),以(yi)(yi)空氣中(zhong)的(de)(de)(de)(de)(de)氧(yang)(yang)(yang)(yang)(yang)(yang)氣為(wei)(wei)(wei)(wei)氧(yang)(yang)(yang)(yang)(yang)(yang)化(hua)(hua)(hua)劑(ji)(現在(zai)(zai)(zai)(zai)(zai)也(ye)(ye)有(you)(you)(you)(you)使(shi)用(yong)(yong)臭氧(yang)(yang)(yang)(yang)(yang)(yang)、過(guo)(guo)氧(yang)(yang)(yang)(yang)(yang)(yang)化(hua)(hua)(hua)氫等(deng)(deng)其(qi)他氧(yang)(yang)(yang)(yang)(yang)(yang)化(hua)(hua)(hua)劑(ji)),在(zai)(zai)(zai)(zai)(zai)液相中(zhong)將(jiang)有(you)(you)(you)(you)機(ji)(ji)物(wu)氧(yang)(yang)(yang)(yang)(yang)(yang)化(hua)(hua)(hua)為(wei)(wei)(wei)(wei)C0,和水(shui)(shui)(shui)(shui)(shui)等(deng)(deng)無機(ji)(ji)物(wu)或小(xiao)分子(zi)有(you)(you)(you)(you)機(ji)(ji)物(wu)的(de)(de)(de)(de)(de)化(hua)(hua)(hua)學(xue)過(guo)(guo)程。該方(fang)法(fa)(fa)(fa)已經開始應(ying)(ying)(ying)用(yong)(yong)于城市污泥的(de)(de)(de)(de)(de)處(chu)(chu)(chu)置和活(huo)性(xing)炭的(de)(de)(de)(de)(de)再生(sheng)(sheng),以(yi)(yi)及造紙黑液、酒精(jing)廢(fei)(fei)(fei)(fei)水(shui)(shui)(shui)(shui)(shui)處(chu)(chu)(chu)理(li)(li)(li)(li)(li)(li)(li)等(deng)(deng),并(bing)取(qu)得(de)了很(hen)(hen)好的(de)(de)(de)(de)(de)效(xiao)(xiao)(xiao)果(guo)。國內(nei)一(yi)些學(xue)者也(ye)(ye)嘗試(shi)將(jiang)濕(shi)式氧(yang)(yang)(yang)(yang)(yang)(yang)化(hua)(hua)(hua)技術應(ying)(ying)(ying)用(yong)(yong)于合(he)成(cheng)香料(liao)(liao)(liao)廢(fei)(fei)(fei)(fei)水(shui)(shui)(shui)(shui)(shui)的(de)(de)(de)(de)(de)處(chu)(chu)(chu)理(li)(li)(li)(li)(li)(li)(li)。楊(yang)琦等(deng)(deng)的(de)(de)(de)(de)(de)研究結(jie)果(guo)表(biao)明(ming),在(zai)(zai)(zai)(zai)(zai)中(zhong)溫(wen)(160℃)、中(zhong)壓(ya)(2.8MPa)條(tiao)件(jian)下(xia),采用(yong)(yong)濕(shi)式氧(yang)(yang)(yang)(yang)(yang)(yang)化(hua)(hua)(hua)處(chu)(chu)(chu)理(li)(li)(li)(li)(li)(li)(li)高(gao)(gao)濃(nong)(nong)度(du)的(de)(de)(de)(de)(de)香料(liao)(liao)(liao)廢(fei)(fei)(fei)(fei)水(shui)(shui)(shui)(shui)(shui),原(yuan)水(shui)(shui)(shui)(shui)(shui)COD、TOC、色(se)(se)度(du)分別(bie)為(wei)(wei)(wei)(wei)65lllmg/L、35000mg/L、ll260倍。廢(fei)(fei)(fei)(fei)水(shui)(shui)(shui)(shui)(shui)經30min濕(shi)式氧(yang)(yang)(yang)(yang)(yang)(yang)化(hua)(hua)(hua)處(chu)(chu)(chu)理(li)(li)(li)(li)(li)(li)(li)后(hou)。其(qi)COD、TOC、色(se)(se)度(du)的(de)(de)(de)(de)(de)去(qu)除(chu)(chu)(chu)率分別(bie)為(wei)(wei)(wei)(wei)48%、5l%、95%,而且BOD/COD值從(cong)原(yuan)來的(de)(de)(de)(de)(de)0.195增(zeng)加(jia)(jia)到0.419。可(ke)生(sheng)(sheng)化(hua)(hua)(hua)性(xing)得(de)到明(ming)顯(xian)改善。另外(wai)發現WAO處(chu)(chu)(chu)理(li)(li)(li)(li)(li)(li)(li)后(hou)的(de)(de)(de)(de)(de)中(zhong)間產物(wu)主(zhu)要為(wei)(wei)(wei)(wei)低級(ji)有(you)(you)(you)(you)機(ji)(ji)酸、醇、酮等(deng)(deng),它們(men)難(nan)(nan)以(yi)(yi)進一(yi)步被(bei)化(hua)(hua)(hua)學(xue)氧(yang)(yang)(yang)(yang)(yang)(yang)化(hua)(hua)(hua),但它們(men)很(hen)(hen)容易(yi)被(bei)生(sheng)(sheng)物(wu)降(jiang)解(jie)。楊(yang)琦等(deng)(deng)采用(yong)(yong)催化(hua)(hua)(hua)濕(shi)式氧(yang)(yang)(yang)(yang)(yang)(yang)化(hua)(hua)(hua)處(chu)(chu)(chu)理(li)(li)(li)(li)(li)(li)(li)香料(liao)(liao)(liao)廢(fei)(fei)(fei)(fei)水(shui)(shui)(shui)(shui)(shui),原(yuan)水(shui)(shui)(shui)(shui)(shui)COD、TOC、色(se)(se)度(du)依次為(wei)(wei)(wei)(wei)7l600mg/L、28100m、12000倍。用(yong)(yong)ABO稀(xi)土類催化(hua)(hua)(hua)劑(ji),在(zai)(zai)(zai)(zai)(zai)160oC和0.98MPa條(tiao)件(jian)下(xia)進行(xing)試(shi)驗(yan),經30min氧(yang)(yang)(yang)(yang)(yang)(yang)化(hua)(hua)(hua)反(fan)應(ying)(ying)(ying)后(hou),COD、TOC、色(se)(se)度(du)的(de)(de)(de)(de)(de)去(qu)除(chu)(chu)(chu)率分別(bie)為(wei)(wei)(wei)(wei)69.1%、74.8%、79.5%,BOD/COD從(cong)0.184提高(gao)(gao)到0.354。建(jian)立(li)了經驗(yan)反(fan)應(ying)(ying)(ying)動力學(xue)模型.結(jie)果(guo)表(biao)明(ming)在(zai)(zai)(zai)(zai)(zai)90min內(nei)反(fan)應(ying)(ying)(ying)呈一(yi)級(ji)反(fan)應(ying)(ying)(ying)。此(ci)外(wai)用(yong)(yong)色(se)(se)譜一(yi)質(zhi)(zhi)譜技術鑒定(ding)廢(fei)(fei)(fei)(fei)水(shui)(shui)(shui)(shui)(shui)中(zhong)有(you)(you)(you)(you)機(ji)(ji)污染物(wu),從(cong)鑒定(ding)結(jie)果(guo)看.有(you)(you)(you)(you)機(ji)(ji)物(wu)沒有(you)(you)(you)(you)被(bei)完全氧(yang)(yang)(yang)(yang)(yang)(yang)化(hua)(hua)(hua),例如尚(shang)有(you)(you)(you)(you)苯甲醇、苯甲醛等(deng)(deng)存在(zai)(zai)(zai)(zai)(zai)。WAO技術具有(you)(you)(you)(you)啟動時(shi)(shi)(shi)間短、氧(yang)(yang)(yang)(yang)(yang)(yang)化(hua)(hua)(hua)速度(du)快、占(zhan)地少,當(dang)COD質(zhi)(zhi)量(liang)(liang)濃(nong)(nong)度(du)>2時(shi)(shi)(shi),能量(liang)(liang)可(ke)回收等(deng)(deng)優點,但也(ye)(ye)存在(zai)(zai)(zai)(zai)(zai)著需(xu)耐(nai)中(zhong)溫(wen)、耐(nai)中(zhong)壓(ya)的(de)(de)(de)(de)(de)設備,一(yi)次投資大等(deng)(deng)缺點。雖然(ran)(ran)它對香料(liao)(liao)(liao)廢(fei)(fei)(fei)(fei)水(shui)(shui)(shui)(shui)(shui)中(zhong)的(de)(de)(de)(de)(de)色(se)(se)度(du)有(you)(you)(you)(you)很(hen)(hen)好的(de)(de)(de)(de)(de)去(qu)除(chu)(chu)(chu)效(xiao)(xiao)(xiao)果(guo),但對COD去(qu)除(chu)(chu)(chu)率不高(gao)(gao),處(chu)(chu)(chu)理(li)(li)(li)(li)(li)(li)(li)后(hou)出(chu)水(shui)(shui)(shui)(shui)(shui)仍然(ran)(ran)要結(jie)合(he)其(qi)他工(gong)藝進行(xing)處(chu)(chu)(chu)理(li)(li)(li)(li)(li)(li)(li)。在(zai)(zai)(zai)(zai)(zai)工(gong)業廢(fei)(fei)(fei)(fei)水(shui)(shui)(shui)(shui)(shui)處(chu)(chu)(chu)理(li)(li)(li)(li)(li)(li)(li)中(zhong)。Fenton試(shi)劑(ji)也(ye)(ye)是(shi)(shi)一(yi)種經常使(shi)用(yong)(yong)的(de)(de)(de)(de)(de)強氧(yang)(yang)(yang)(yang)(yang)(yang)化(hua)(hua)(hua)劑(ji)。Fenton試(shi)劑(ji)是(shi)(shi)由(you)過(guo)(guo)氧(yang)(yang)(yang)(yang)(yang)(yang)化(hua)(hua)(hua)氫與(yu)催化(hua)(hua)(hua)劑(ji)Fe構成(cheng)的(de)(de)(de)(de)(de)氧(yang)(yang)(yang)(yang)(yang)(yang)化(hua)(hua)(hua)體系,其(qi)作用(yong)(yong)機(ji)(ji)理(li)(li)(li)(li)(li)(li)(li)是(shi)(shi)在(zai)(zai)(zai)(zai)(zai)酸性(xing)條(tiao)件(jian)下(xia)過(guo)(guo)氧(yang)(yang)(yang)(yang)(yang)(yang)化(hua)(hua)(hua)氫被(bei)Fe催化(hua)(hua)(hua)產生(sheng)(sheng)反(fan)應(ying)(ying)(ying)活(huo)性(xing)很(hen)(hen)高(gao)(gao)的(de)(de)(de)(de)(de)羥基自(zi)由(you)基,使(shi)有(you)(you)(you)(you)機(ji)(ji)物(wu)和還原(yuan)性(xing)物(wu)質(zhi)(zhi)發生(sheng)(sheng)氧(yang)(yang)(yang)(yang)(yang)(yang)化(hua)(hua)(hua)。Fenton試(shi)劑(ji)特別(bie)適用(yong)(yong)于生(sheng)(sheng)物(wu)難(nan)(nan)降(jiang)解(jie)或一(yi)般化(hua)(hua)(hua)學(xue)方(fang)法(fa)(fa)(fa)難(nan)(nan)以(yi)(yi)奏(zou)效(xiao)(xiao)(xiao)的(de)(de)(de)(de)(de)有(you)(you)(you)(you)機(ji)(ji)廢(fei)(fei)(fei)(fei)水(shui)(shui)(shui)(shui)(shui)的(de)(de)(de)(de)(de)處(chu)(chu)(chu)理(li)(li)(li)(li)(li)(li)(li)。熊燕蘋等(deng)(deng)采用(yong)(yong)Fenton試(shi)劑(ji)法(fa)(fa)(fa)處(chu)(chu)(chu)理(li)(li)(li)(li)(li)(li)(li)COD質(zhi)(zhi)量(liang)(liang)濃(nong)(nong)度(du)為(wei)(wei)(wei)(wei)23.2L的(de)(de)(de)(de)(de)洋茉莉醛香料(liao)(liao)(liao)廢(fei)(fei)(fei)(fei)水(shui)(shui)(shui)(shui)(shui),通(tong)過(guo)(guo)試(shi)驗(yan)確(que)定(ding)的(de)(de)(de)(de)(de)最(zui)佳條(tiao)件(jian):pH為(wei)(wei)(wei)(wei)3.0,n(HO):n(Fe2+)=10:1,每200mL廢(fei)(fei)(fei)(fei)水(shui)(shui)(shui)(shui)(shui)需(xu)HO2(質(zhi)(zhi)量(liang)(liang)分數(shu)為(wei)(wei)(wei)(wei)30%)的(de)(de)(de)(de)(de)最(zui)佳用(yong)(yong)量(liang)(liang)為(wei)(wei)(wei)(wei)20mL,反(fan)應(ying)(ying)(ying)2.0h后(hou)COD的(de)(de)(de)(de)(de)去(qu)除(chu)(chu)(chu)率達到80%以(yi)(yi)上(考(kao)慮(lv)到工(gong)程實際運行(xing)成(cheng)本,質(zhi)(zhi)量(liang)(liang)分數(shu)為(wei)(wei)(wei)(wei)30%的(de)(de)(de)(de)(de)H0投加(jia)(jia)量(liang)(liang)為(wei)(wei)(wei)(wei)25mL/L,其(qi)他條(tiao)件(jian)不變,COD去(qu)除(chu)(chu)(chu)率為(wei)(wei)(wei)(wei)62%)。色(se)(se)譜一(yi)質(zhi)(zhi)譜分析表(biao)明(ming)Fenton試(shi)劑(ji)對該香料(liao)(liao)(liao)廢(fei)(fei)(fei)(fei)水(shui)(shui)(shui)(shui)(shui)有(you)(you)(you)(you)很(hen)(hen)好的(de)(de)(de)(de)(de)降(jiang)解(jie)作用(yong)(yong),成(cheng)功(gong)地將(jiang)大分子(zi)洋茉莉醛分解(jie)為(wei)(wei)(wei)(wei)較小(xiao)的(de)(de)(de)(de)(de)烷烴分子(zi),有(you)(you)(you)(you)利于廢(fei)(fei)(fei)(fei)水(shui)(shui)(shui)(shui)(shui)的(de)(de)(de)(de)(de)后(hou)續(xu)處(chu)(chu)(chu)理(li)(li)(li)(li)(li)(li)(li)。黃益宏研究了UV/Fenton光助(zhu)催化(hua)(hua)(hua)氧(yang)(yang)(yang)(yang)(yang)(yang)化(hua)(hua)(hua)法(fa)(fa)(fa)處(chu)(chu)(chu)理(li)(li)(li)(li)(li)(li)(li)高(gao)(gao)濃(nong)(nong)度(du)香料(liao)(liao)(liao)廢(fei)(fei)(fei)(fei)水(shui)(shui)(shui)(shui)(shui)(氣浮處(chu)(chu)(chu)理(li)(li)(li)(li)(li)(li)(li)后(hou)出(chu)水(shui)(shui)(shui)(shui)(shui)COD為(wei)(wei)(wei)(wei)27314mg/L)的(de)(de)(de)(de)(de)新(xin)技術以(yi)(yi)及有(you)(you)(you)(you)關影響(xiang)因素(su)。試(shi)驗(yan)表(biao)明(ming):pH在(zai)(zai)(zai)(zai)(zai)2—4,n(COD):n(H2O2)=1:1.5,Fe質(zhi)(zhi)量(liang)(liang)濃(nong)(nong)度(du)為(wei)(wei)(wei)(wei)1.7g/L的(de)(de)(de)(de)(de)條(tiao)件(jian)下(xia),反(fan)應(ying)(ying)(ying)時(shi)(shi)(shi)間90min,COD去(qu)除(chu)(chu)(chu)率可(ke)達99.6%。并(bing)通(tong)過(guo)(guo)對比(bi)實驗(yan)證明(ming),UV/Fenton法(fa)(fa)(fa)比(bi)傳(chuan)統(tong)Fenton法(fa)(fa)(fa)的(de)(de)(de)(de)(de)處(chu)(chu)(chu)理(li)(li)(li)(li)(li)(li)(li)效(xiao)(xiao)(xiao)果(guo)好很(hen)(hen)多,同時(shi)(shi)(shi)可(ke)以(yi)(yi)節省藥劑(ji)用(yong)(yong)量(liang)(liang)。
石芳(fang)等用(yong)(yong)(yong)WAO法處理合(he)成(cheng)香料生產中(zhong)的高濃度白水(shui)(shui)廢(fei)(fei)(fei)水(shui)(shui),該廢(fei)(fei)(fei)水(shui)(shui)含COD質量濃度高達(da)10000mg/L,并有(you)(you)強(qiang)烈刺(ci)激性(xing)氣(qi)味(wei)。其(qi)(qi)工(gong)藝特點:先(xian)加絮(xu)凝(ning)劑和殺菌劑進行預(yu)處理,絮(xu)凝(ning)劑采(cai)用(yong)(yong)(yong)聚丙(bing)烯酰胺,殺菌劑采(cai)用(yong)(yong)(yong)C10,用(yong)(yong)(yong)攪拌(ban)器(qi)攪拌(ban)一段時問(wen),砂濾,將(jiang)(jiang)廢(fei)(fei)(fei)水(shui)(shui)中(zhong)的部(bu)分(fen)(fen)有(you)(you)機(ji)物(wu)去除(chu)。然后采(cai)用(yong)(yong)(yong)負(fu)載硅鈦化(hua)(hua)(hua)合(he)物(wu)活(huo)性(xing)炭,對(dui)廢(fei)(fei)(fei)水(shui)(shui)中(zhong)的有(you)(you)機(ji)物(wu)進行吸附.以去除(chu)部(bu)分(fen)(fen)難降(jiang)(jiang)解(jie)的大分(fen)(fen)子(zi)物(wu)質,減少(shao)后續吸附池的有(you)(you)機(ji)負(fu)荷(he)。最后采(cai)用(yong)(yong)(yong)自制催(cui)化(hua)(hua)(hua)劑(載體為(wei)工(gong)業(ye)用(yong)(yong)(yong)y—A1O,,其(qi)(qi)外型為(wei)條形,負(fu)載Mn、Ni、Ce、Co、Fe等活(huo)性(xing)組分(fen)(fen))與雙氧(yang)水(shui)(shui)進行催(cui)化(hua)(hua)(hua)氧(yang)化(hua)(hua)(hua),雙氧(yang)水(shui)(shui)具有(you)(you)很強(qiang)的氧(yang)化(hua)(hua)(hua)性(xing)能,在氧(yang)化(hua)(hua)(hua)催(cui)化(hua)(hua)(hua)劑作用(yong)(yong)(yong)下,將(jiang)(jiang)白水(shui)(shui)中(zhong)的難降(jiang)(jiang)解(jie)有(you)(you)機(ji)物(wu)分(fen)(fen)解(jie)成(cheng)小的分(fen)(fen)子(zi),再由負(fu)載活(huo)性(xing)組分(fen)(fen)的活(huo)性(xing)炭將(jiang)(jiang)其(qi)(qi)吸附。整個(ge)處理過(guo)程COD去除(chu)率(lv)為(wei)95%,出水(shui)(shui)水(shui)(shui)質達(da)到(dao)國家(jia)二(er)級排放標(biao)準。

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