摘要：綜述了(le)化(hua)(hua)學催(cui)化(hua)(hua)氧(yang)(yang)(yang)(yang)化(hua)(hua)法(fa)(fa)(fa)、光催(cui)化(hua)(hua)氧(yang)(yang)(yang)(yang)化(hua)(hua)法(fa)(fa)(fa)、電催(cui)化(hua)(hua)氧(yang)(yang)(yang)(yang)化(hua)(hua)法(fa)(fa)(fa)、超(chao)臨界水催(cui)化(hua)(hua)氧(yang)(yang)(yang)(yang)化(hua)(hua)法(fa)(fa)(fa)幾種(zhong)典型的(de)催(cui)化(hua)(hua)氧(yang)(yang)(yang)(yang)化(hua)(hua)技術(shu)的(de)原理(li)及其在印染(ran)廢水處理(li)中的(de)應用，并對其發展前景和存在問題進行了(le)簡要(yao)評(ping)述。

關鍵詞：印染廢水(shui)；催化氧化；水(shui)處理

印(yin)染(ran)(ran)廢(fei)(fei)水具有(you)(you)(you)水量大(da)(da)、色度高(gao)(gao)(gao)、堿(jian)性(xing)強、有(you)(you)(you)機(ji)(ji)物(wu)含量高(gao)(gao)(gao)等特點(dian)。廢(fei)(fei)水中(zhong)常含有(you)(you)(you)染(ran)(ran)料、助劑(ji)、油劑(ji)、酸堿(jian)、纖維雜質及無(wu)機(ji)(ji)鹽[1]等。隨著現代(dai)工業的發展(zhan)和印(yin)染(ran)(ran)加工技(ji)術(shu)(shu)的進(jin)步，大(da)(da)量新型(xing)印(yin)染(ran)(ran)助劑(ji)、染(ran)(ran)料、PVA漿料等難(nan)以生(sheng)物(wu)降解的有(you)(you)(you)機(ji)(ji)物(wu)在印(yin)染(ran)(ran)行業中(zhong)的廣泛應用，致(zhi)使印(yin)染(ran)(ran)廢(fei)(fei)水中(zhong)染(ran)(ran)料的穩定性(xing)得到強化(hua)，有(you)(you)(you)機(ji)(ji)物(wu)成分越來(lai)越復雜多(duo)變，BOD5/CODcr比值下降，可(ke)生(sheng)化(hua)性(xing)降低。如何消除印(yin)染(ran)(ran)廢(fei)(fei)水中(zhong)高(gao)(gao)(gao)色度和高(gao)(gao)(gao)COD值，已成為長期困擾印(yin)染(ran)(ran)廢(fei)(fei)水治理(li)的兩個關鍵問題(ti)。目前國內外處(chu)理(li)印(yin)染(ran)(ran)廢(fei)(fei)水多(duo)以生(sheng)化(hua)法(fa)(fa)和物(wu)化(hua)法(fa)(fa)為主，但都存在處(chu)理(li)效(xiao)率(lv)不高(gao)(gao)(gao)，投資費用大(da)(da)、運行成本(ben)高(gao)(gao)(gao)、CODcr和色度去除率(lv)低等缺點(dian)。針對上述(shu)問題(ti)，近年來(lai)國內外采用催(cui)化(hua)氧化(hua)技(ji)術(shu)(shu)處(chu)理(li)印(yin)染(ran)(ran)廢(fei)(fei)水的研究十分活(huo)躍，并(bing)取得一(yi)定進(jin)展(zhan)。

催化(hua)氧(yang)化(hua)技術是(shi)一(yi)(yi)(yi)種高(gao)級(ji)氧(yang)化(hua)技術，具有(you)降(jiang)解完全、無(wu)(wu)二次污(wu)染、能耗和(he)(he)原材料消耗低的(de)優點。高(gao)級(ji)氧(yang)化(hua)技術處理有(you)機污(wu)染物的(de)一(yi)(yi)(yi)般機理是(shi)：有(you)機物和(he)(he)高(gao)級(ji)氧(yang)化(hua)技術體(ti)系的(de)·OH自由(you)(you)(you)基(ji)反應生成(cheng)有(you)機自由(you)(you)(you)基(ji)（R·），有(you)機自由(you)(you)(you)基(ji)（R·）與(yu)氧(yang)氣分子相撞生成(cheng)過氧(yang)化(hua)物自由(you)(you)(you)基(ji)（ROO-），過氧(yang)化(hua)物自由(you)(you)(you)基(ji)（ROO-）再(zai)進一(yi)(yi)(yi)步分解或與(yu)其它自由(you)(you)(you)基(ji)反應生成(cheng)一(yi)(yi)(yi)系列中間產(chan)物或最(zui)終(zhong)被礦化(hua)為H2O、CO2和(he)(he)無(wu)(wu)機鹽。一(yi)(yi)(yi)般認為其歷程是(shi)：

催(cui)化(hua)氧(yang)化(hua)技術(shu)是在有機物污(wu)染物的反應體系中(zhong)加入氧(yang)化(hua)劑和催(cui)化(hua)劑并(bing)在一定的外在激發(fa)條件下(xia)，打破染料(liao)分子中(zhong)的不飽和原(yuan)子發(fa)色團，從而降解為小(xiao)分子。如下(xia)對(dui)近年來印染廢水催(cui)化(hua)氧(yang)化(hua)處(chu)理技術(shu)進行綜述，重點介紹了該技術(shu)的原(yuan)理及其在印染廢水處(chu)理中(zhong)的應用(yong)，并(bing)對(dui)其發(fa)展前景和存在問題(ti)進行了簡要評述。

1·化學催(cui)化氧化法（CCO）

化(hua)(hua)學催化(hua)(hua)氧化(hua)(hua)法(fa)是印染廢水脫色較(jiao)為成熟的(de)方法(fa)，該技術的(de)核心在于催化(hua)(hua)劑(ji)和氧化(hua)(hua)劑(ji)的(de)選(xuan)擇(ze)。化(hua)(hua)學催化(hua)(hua)氧化(hua)(hua)法(fa)主要包(bao)括Fenton法(fa)、二氧化(hua)(hua)氯催化(hua)(hua)氧化(hua)(hua)法(fa)以及臭(chou)氧催化(hua)(hua)氧化(hua)(hua)法(fa)。

1.1 Fenton催化氧化法

Fenton催化(hua)(hua)氧化(hua)(hua)法(fa)是在酸性(xing)條(tiao)(tiao)件(jian)(jian)下(xia)，Fe2+催化(hua)(hua)H2O產生(sheng)(sheng)氧化(hua)(hua)能力更強的(de)(de)·OH自由基(ji)（僅次(ci)于F2），再(zai)加上(shang)Fe3+的(de)(de)絮凝作用從而有效降(jiang)(jiang)解(jie)有機(ji)物(wu)。Fenton試劑(ji)(ji)中的(de)(de)FeSO·47H2O和H2O2都是常用的(de)(de)廉(lian)價(jia)藥品，因(yin)此對實(shi)際(ji)印染廢水(shui)的(de)(de)處理(li)具(ju)有較(jiao)大的(de)(de)應用和研究價(jia)值。魯璐[2]用Fenton試劑(ji)(ji)預(yu)處理(li)實(shi)際(ji)印染廢水(shui)最后正交實(shi)驗得出最佳操作條(tiao)(tiao)件(jian)(jian)：30%H2O2投加5mL/L，FeSO4·7H2O投加800 mg/L，pH值為3.45，此時H2O2/Fe2+的(de)(de)摩(mo)爾比(bi)為15.5，COD去除(chu)率為33.14%，BOD5/CODcr值從0.139增加到0.321，可(ke)生(sheng)(sheng)化(hua)(hua)性(xing)能的(de)(de)提高為后續生(sheng)(sheng)物(wu)處理(li)階(jie)段(duan)提供了良好條(tiao)(tiao)件(jian)(jian)。目前，Fenton試劑(ji)(ji)常與(yu)其他技術(shu)如電(dian)、光、超聲、吸附(fu)、微波、絮凝法(fa)如生(sheng)(sheng)物(wu)法(fa)等聯合(he)運(yun)用來降(jiang)(jiang)低成本或提高氧化(hua)(hua)效率。A.Wang等[3]以活(huo)性(xing)炭纖維為陰極，RuO2/Ti為陽(yang)極，采用Electro-Fenton法(fa)對偶氮(dan)染料酸性(xing)紅(hong)14進行降(jiang)(jiang)解(jie)研究，在酸性(xing)紅(hong)14質量濃度(du)為200mg/L，Fe2+濃度(du)為1.0×10-3mol/L，pH為3.0，電(dian)流(liu)密度(du)為180A/m2，電(dian)解(jie)時間為6h條(tiao)(tiao)件(jian)(jian)下(xia)，水(shui)樣的(de)(de)TOC去除(chu)率為70%。

但是(shi)(shi)，Fenton試劑催化氧化法因(yin)H2O2利用率低(di)、有(you)機物礦(kuang)化不充分等不足，限(xian)制了其發展和工業化推(tui)廣(guang)應用。目(mu)前大多數研(yan)究尚處(chu)于實驗室和理論探索階段。另(ling)外，經Fenton試劑處(chu)理過的(de)廢水顯弱酸性，是(shi)(shi)此工藝的(de)不足之處(chu)。

1.2二(er)氧化氯催(cui)化氧化法(fa)

二氧化氯(lv)（ClO）2不(bu)僅具有高(gao)效的殺菌能力，又具有滅藻、剝泥、防(fang)腐、抗霉(mei)、保鮮、除臭(chou)和漂白(bai)脫色多方面的功(gong)能。在PH≤7時二氧化氯(lv)的分(fen)解產物對印染(ran)廢(fei)水發(fa)色基(ji)團有取代作(zuo)用，并能夠(gou)與染(ran)料分(fen)子(zi)結構中的雙鍵進行加(jia)成，從(cong)而(er)破(po)壞染(ran)料分(fen)子(zi)中的發(fa)色基(ji)團達到脫色的目的。

二氧(yang)(yang)(yang)化(hua)(hua)(hua)(hua)(hua)(hua)(hua)(hua)氯催(cui)化(hua)(hua)(hua)(hua)(hua)(hua)(hua)(hua)氧(yang)(yang)(yang)化(hua)(hua)(hua)(hua)(hua)(hua)(hua)(hua)法(fa)一(yi)般是在常溫常壓下(xia)(xia)以過渡金屬氧(yang)(yang)(yang)化(hua)(hua)(hua)(hua)(hua)(hua)(hua)(hua)物為(wei)(wei)催(cui)化(hua)(hua)(hua)(hua)(hua)(hua)(hua)(hua)劑(ji)。謝(xie)少雄等(deng)(deng)[4]以NaClO為(wei)(wei)氧(yang)(yang)(yang)化(hua)(hua)(hua)(hua)(hua)(hua)(hua)(hua)劑(ji)，NiO2為(wei)(wei)催(cui)化(hua)(hua)(hua)(hua)(hua)(hua)(hua)(hua)劑(ji)模(mo)擬處(chu)理(li)(li)(li)印(yin)(yin)染廢(fei)(fei)水(shui)(shui)(shui)(shui)，廢(fei)(fei)水(shui)(shui)(shui)(shui)的(de)色度(du)去除(chu)(chu)(chu)率(lv)(lv)可達99%以上，COD去除(chu)(chu)(chu)率(lv)(lv)50%以上。施(shi)來順等(deng)(deng)[5]研究比較了二氧(yang)(yang)(yang)化(hua)(hua)(hua)(hua)(hua)(hua)(hua)(hua)氯直接氧(yang)(yang)(yang)化(hua)(hua)(hua)(hua)(hua)(hua)(hua)(hua)和催(cui)化(hua)(hua)(hua)(hua)(hua)(hua)(hua)(hua)氧(yang)(yang)(yang)化(hua)(hua)(hua)(hua)(hua)(hua)(hua)(hua)處(chu)理(li)(li)(li)鉻(ge)黑T模(mo)擬水(shui)(shui)(shui)(shui)，單純(chun)用(yong)二氧(yang)(yang)(yang)化(hua)(hua)(hua)(hua)(hua)(hua)(hua)(hua)氯化(hua)(hua)(hua)(hua)(hua)(hua)(hua)(hua)學氧(yang)(yang)(yang)化(hua)(hua)(hua)(hua)(hua)(hua)(hua)(hua)處(chu)理(li)(li)(li)COD為(wei)(wei)2928mg/L的(de)鉻(ge)黑T廢(fei)(fei)水(shui)(shui)(shui)(shui)時，最(zui)佳pH值為(wei)(wei)1.8，二氧(yang)(yang)(yang)化(hua)(hua)(hua)(hua)(hua)(hua)(hua)(hua)氯投加量為(wei)(wei)1200mg/L，反應時間60min，COD去除(chu)(chu)(chu)率(lv)(lv)為(wei)(wei)24.1%，BOD去除(chu)(chu)(chu)率(lv)(lv)為(wei)(wei)21.8%，脫(tuo)色率(lv)(lv)為(wei)(wei)70.0%.而經過1200mg/L二氧(yang)(yang)(yang)化(hua)(hua)(hua)(hua)(hua)(hua)(hua)(hua)氯和0.25gTiO2催(cui)化(hua)(hua)(hua)(hua)(hua)(hua)(hua)(hua)氧(yang)(yang)(yang)化(hua)(hua)(hua)(hua)(hua)(hua)(hua)(hua)60min后，COD去除(chu)(chu)(chu)率(lv)(lv)33.6%，BOD去除(chu)(chu)(chu)率(lv)(lv)為(wei)(wei)53.2%，脫(tuo)色率(lv)(lv)為(wei)(wei)75.2%。通(tong)常二氧(yang)(yang)(yang)化(hua)(hua)(hua)(hua)(hua)(hua)(hua)(hua)氯催(cui)化(hua)(hua)(hua)(hua)(hua)(hua)(hua)(hua)氧(yang)(yang)(yang)化(hua)(hua)(hua)(hua)(hua)(hua)(hua)(hua)法(fa)與混凝、氣浮、吸附、過濾和生化(hua)(hua)(hua)(hua)(hua)(hua)(hua)(hua)法(fa)等(deng)(deng)聯(lian)用(yong)組合處(chu)理(li)(li)(li)印(yin)(yin)染廢(fei)(fei)水(shui)(shui)(shui)(shui)。賀啟(qi)環等(deng)(deng)[6]對(dui)經微電(dian)解預處(chu)理(li)(li)(li)后的(de)酸(suan)性大紅染料廢(fei)(fei)水(shui)(shui)(shui)(shui)進行以自制(zhi)載銅(tong)活性炭為(wei)(wei)催(cui)化(hua)(hua)(hua)(hua)(hua)(hua)(hua)(hua)劑(ji)的(de)二氧(yang)(yang)(yang)化(hua)(hua)(hua)(hua)(hua)(hua)(hua)(hua)氯催(cui)化(hua)(hua)(hua)(hua)(hua)(hua)(hua)(hua)氧(yang)(yang)(yang)化(hua)(hua)(hua)(hua)(hua)(hua)(hua)(hua)實驗，結(jie)果(guo)(guo)表(biao)明：在最(zui)佳工藝條件(jian)下(xia)(xia)對(dui)酸(suan)性大紅GR染料廢(fei)(fei)水(shui)(shui)(shui)(shui)的(de)COD及色度(du)去除(chu)(chu)(chu)率(lv)(lv)分別達80%和97.8%，BOD5/COD由(you)0.072上升到0.41。采用(yong)二氧(yang)(yang)(yang)化(hua)(hua)(hua)(hua)(hua)(hua)(hua)(hua)氯處(chu)理(li)(li)(li)印(yin)(yin)染廢(fei)(fei)水(shui)(shui)(shui)(shui)，具有(you)設備(bei)簡單、投資少、能耗小(xiao)、操作管理(li)(li)(li)方便(bian)等(deng)(deng)優點，但是二氧(yang)(yang)(yang)化(hua)(hua)(hua)(hua)(hua)(hua)(hua)(hua)氯對(dui)含(han)淀(dian)粉、PVA漿料廢(fei)(fei)水(shui)(shui)(shui)(shui)的(de)處(chu)理(li)(li)(li)效(xiao)果(guo)(guo)不理(li)(li)(li)想。

1.3臭氧催化氧化法

臭(chou)(chou)氧(yang)(yang)(yang)（O）3能有(you)(you)(you)效(xiao)(xiao)打破染(ran)料(liao)(liao)(liao)(liao)發色(se)基團(tuan)，又因印染(ran)廢(fei)水多呈堿性(xing)[1]，有(you)(you)(you)利于O3轉化(hua)(hua)(hua)為(wei)·OH。O3既可(ke)直接與有(you)(you)(you)機(ji)物(wu)反應(ying)，也可(ke)通過反應(ying)過程(cheng)中產(chan)生(sheng)的(de)(de)(de)(de)(de)·OH氧(yang)(yang)(yang)化(hua)(hua)(hua)有(you)(you)(you)機(ji)物(wu)，具有(you)(you)(you)很(hen)(hen)好的(de)(de)(de)(de)(de)降解(jie)(jie)有(you)(you)(you)機(ji)物(wu)、開環脫色(se)和(he)(he)消毒效(xiao)(xiao)果(guo)，而(er)且多余的(de)(de)(de)(de)(de)O3在水中自動分(fen)(fen)解(jie)(jie)成O2，無二次污染(ran)。Y.Dong[7]采(cai)用天(tian)然(ran)礦(kuang)物(wu)水鎂石作(zuo)為(wei)催(cui)化(hua)(hua)(hua)劑催(cui)化(hua)(hua)(hua)臭(chou)(chou)氧(yang)(yang)(yang)氧(yang)(yang)(yang)化(hua)(hua)(hua)處理活(huo)性(xing)艷紅X—3B染(ran)料(liao)(liao)(liao)(liao)廢(fei)水，結果(guo)表(biao)明(ming)，染(ran)料(liao)(liao)(liao)(liao)的(de)(de)(de)(de)(de)降解(jie)(jie)率、COD的(de)(de)(de)(de)(de)去(qu)除(chu)率分(fen)(fen)別由單獨(du)臭(chou)(chou)氧(yang)(yang)(yang)氧(yang)(yang)(yang)化(hua)(hua)(hua)時的(de)(de)(de)(de)(de)47%、9.0%提高到(dao)89%、32.5%。通常臭(chou)(chou)氧(yang)(yang)(yang)催(cui)化(hua)(hua)(hua)氧(yang)(yang)(yang)化(hua)(hua)(hua)和(he)(he)其他技(ji)術(shu)如UV、超聲、電化(hua)(hua)(hua)學法、活(huo)性(xing)炭吸附等聯(lian)合以強化(hua)(hua)(hua)廢(fei)水處理效(xiao)(xiao)果(guo)。光的(de)(de)(de)(de)(de)照射可(ke)進一(yi)步激活(huo)O3分(fen)(fen)子產(chan)生(sheng)更多的(de)(de)(de)(de)(de)·OH，從而(er)強化(hua)(hua)(hua)O3的(de)(de)(de)(de)(de)氧(yang)(yang)(yang)化(hua)(hua)(hua)效(xiao)(xiao)率。I.Peternel等[8]研究了在UV存在條件(jian)下臭(chou)(chou)氧(yang)(yang)(yang)催(cui)化(hua)(hua)(hua)氧(yang)(yang)(yang)化(hua)(hua)(hua)活(huo)性(xing)染(ran)料(liao)(liao)(liao)(liao)，結果(guo)發現，溶(rong)液TOC的(de)(de)(de)(de)(de)去(qu)除(chu)率達到(dao)40.1%，色(se)度去(qu)除(chu)率達到(dao)100%。P.C.C.Faria等[9]采(cai)用臭(chou)(chou)氧(yang)(yang)(yang)/活(huo)性(xing)炭協同(tong)降解(jie)(jie)染(ran)料(liao)(liao)(liao)(liao)廢(fei)水，結果(guo)表(biao)明(ming)，單靠活(huo)性(xing)炭的(de)(de)(de)(de)(de)吸附作(zuo)用不能完全去(qu)除(chu)染(ran)料(liao)(liao)(liao)(liao)的(de)(de)(de)(de)(de)色(se)度，單獨(du)臭(chou)(chou)氧(yang)(yang)(yang)氧(yang)(yang)(yang)化(hua)(hua)(hua)雖可(ke)以很(hen)(hen)好地(di)去(qu)除(chu)色(se)度，但TOC的(de)(de)(de)(de)(de)去(qu)除(chu)率不高；而(er)臭(chou)(chou)氧(yang)(yang)(yang)/活(huo)性(xing)炭聯(lian)用技(ji)術(shu)可(ke)以很(hen)(hen)好地(di)去(qu)除(chu)染(ran)料(liao)(liao)(liao)(liao)的(de)(de)(de)(de)(de)色(se)度和(he)(he)TOC。

O.S.G.P.Soares等繼續研究(jiu)了臭(chou)氧/活性(xing)炭連續運(yun)行處理(li)染料廢水(shui)，結果表明，臭(chou)氧/活性(xing)炭聯(lian)用技術(shu)中活性(xing)炭起到了吸附(fu)劑和催化劑的作用。

臭氧(yang)催(cui)化(hua)氧(yang)化(hua)技術(shu)對印(yin)染廢(fei)(fei)水(shui)(shui)的(de)(de)(de)處(chu)理(li)國內已有比較成熟的(de)(de)(de)工藝，具有良好(hao)(hao)的(de)(de)(de)前(qian)景，但建設投資大(da)，運行費用(yong)高。應(ying)加大(da)催(cui)化(hua)臭氧(yang)氧(yang)化(hua)處(chu)理(li)染料廢(fei)(fei)水(shui)(shui)的(de)(de)(de)研究力度，研制出催(cui)化(hua)效果好(hao)(hao)、壽(shou)命長、重復性好(hao)(hao)的(de)(de)(de)催(cui)化(hua)劑，使臭氧(yang)氧(yang)化(hua)法在染料廢(fei)(fei)水(shui)(shui)處(chu)理(li)領(ling)域得到廣泛的(de)(de)(de)應(ying)用(yong)。

2·光催化氧化法(fa)（PCO）

光催(cui)(cui)(cui)化(hua)(hua)氧(yang)化(hua)(hua)技術（PCO）始于(yu)20世紀70年(nian)代，光催(cui)(cui)(cui)化(hua)(hua)氧(yang)化(hua)(hua)是(shi)在光照(zhao)射下，催(cui)(cui)(cui)化(hua)(hua)劑(ji)(ji)價帶上的(de)(de)電子(zi)被激(ji)發(fa)躍遷到導帶，在價帶上產(chan)生相應的(de)(de)空穴。空穴將其表面吸(xi)(xi)附的(de)(de)OH-和(he)H2O氧(yang)化(hua)(hua)成(cheng)·OH，被激(ji)發(fa)的(de)(de)電子(zi)與O2結(jie)合(he)成(cheng)·O2-，·OH和(he)·O2-將有機(ji)污染物最終氧(yang)化(hua)(hua)為CO2、H2O和(he)無機(ji)離(li)子(zi)。同時因染料(liao)是(shi)一種光敏(min)化(hua)(hua)劑(ji)(ji)，能夠吸(xi)(xi)收(shou)較長(chang)(chang)波長(chang)(chang)的(de)(de)光，自(zi)身電子(zi)被激(ji)發(fa)而首(shou)先產(chan)生躍遷。躍遷后(hou)具有高能量(liang)的(de)(de)激(ji)態(tai)電子(zi)又被傳(chuan)遞到催(cui)(cui)(cui)化(hua)(hua)劑(ji)(ji)的(de)(de)導帶上，協助(zhu)催(cui)(cui)(cui)化(hua)(hua)劑(ji)(ji)被較長(chang)(chang)波長(chang)(chang)的(de)(de)光間接激(ji)發(fa)，大大擴大了(le)其應用范圍。光催(cui)(cui)(cui)化(hua)(hua)氧(yang)化(hua)(hua)法（PCO）處理印染廢水就是(shi)利用染料(liao)化(hua)(hua)合(he)物對光的(de)(de)吸(xi)(xi)收(shou)，且光有助(zhu)于(yu)催(cui)(cui)(cui)化(hua)(hua)劑(ji)(ji)的(de)(de)激(ji)發(fa)和(he)加速光反應的(de)(de)進行(xing)。光催(cui)(cui)(cui)化(hua)(hua)劑(ji)(ji)主要有半導體型、鈣鈦礦型、天然錳礦、雜(za)多酸（鹽）類。其中以半導體光催(cui)(cui)(cui)化(hua)(hua)劑(ji)(ji)為主的(de)(de)研究是(shi)熱點。

半(ban)導體光(guang)催(cui)化(hua)(hua)劑(ji)主要有氧化(hua)(hua)物（如(ru)TiO2、ZnO和WO3等(deng)(deng)）和硫(liu)化(hua)(hua)物（如(ru)CdS、ZnS等(deng)(deng)），硫(liu)化(hua)(hua)物雖然有較小的禁帶寬度(du)(du)，但容易(yi)發生光(guang)腐蝕現(xian)象，較氧化(hua)(hua)物而(er)(er)言，穩定性差(cha)。銳鈦TiO2以(yi)其(qi)(qi)無毒(du)(du)、催(cui)化(hua)(hua)活(huo)性高、氧化(hua)(hua)能力和穩定性強、太陽光(guang)照射下(xia)即可(ke)反應、且價(jia)格相對(dui)(dui)便宜(yi)最(zui)為常(chang)用(yong)(yong)(yong)。懸(xuan)浮(fu)(fu)型TiO2在(zai)液相中結構簡單，比表面積(ji)大(da)能與有機污(wu)染物充分接觸，受光(guang)充分，故光(guang)解(jie)(jie)效(xiao)率高。王成國[10]采用(yong)(yong)(yong)納米(mi)級TiO2懸(xuan)浮(fu)(fu)態光(guang)催(cui)化(hua)(hua)氧化(hua)(hua)處(chu)理直接耐曬翠藍染液（染料(liao)(liao)濃度(du)(du)100mg/L，用(yong)(yong)(yong)量1000mg/L），當光(guang)照時(shi)間大(da)于200min時(shi)，色(se)(se)度(du)(du)去(qu)除率達93%，TOC去(qu)除率達50%。Sylwia Mozia等(deng)(deng)[11]考察(cha)了TiO2光(guang)催(cui)化(hua)(hua)劑(ji)對(dui)(dui)含氮的紅色(se)(se)酸(suan)性染料(liao)(liao)的降解(jie)(jie)性能，通過對(dui)(dui)染料(liao)(liao)初(chu)始濃度(du)(du)、催(cui)化(hua)(hua)劑(ji)用(yong)(yong)(yong)量及反應動力學(xue)的探討(tao)，發現(xian)在(zai)可(ke)見(jian)光(guang)下(xia)TiO2對(dui)(dui)此種(zhong)染料(liao)(liao)也(ye)有很好的降解(jie)(jie)效(xiao)果。但大(da)量的實(shi)驗(yan)研究表明(ming)，懸(xuan)浮(fu)(fu)體系中存在(zai)納米(mi)TiO2顆粒難以(yi)回收，有容易(yi)中毒(du)(du)等(deng)(deng)缺點，而(er)(er)負(fu)載型TiO2能克服此缺點。負(fu)載型是指將TiO2固(gu)定在(zai)載體上，可(ke)以(yi)將TiO2負(fu)載于適宜(yi)的載體上，也(ye)可(ke)在(zai)其(qi)(qi)表面負(fu)載少量的金(jin)屬雜質(zhi)，以(yi)提高催(cui)化(hua)(hua)活(huo)性。

負(fu)載型(xing)光催(cui)化劑所用(yong)載體(ti)主要是(shi)玻(bo)(bo)璃，金屬，吸(xi)附(fu)劑，陶瓷類等(deng)[12]。郭新章等(deng)[13]用(yong)TiO2、WO3對活性染料(liao)水溶(rong)液(ye)進行(xing)光催(cui)化降解(jie)，結(jie)果(guo)(guo)表(biao)明TiO2對活性艷藍X-BR染料(liao)的(de)降解(jie)能力(li)比WO3強。譚湘萍(ping)等(deng)[14]比較了載銀TiO2和單(dan)一TiO2催(cui)化劑降解(jie)印染廢水，發現載銀TiO2效(xiao)果(guo)(guo)明顯好(hao)于單(dan)一TiO2催(cui)化劑，COD去(qu)除率大(da)幅(fu)提高(gao)。陳(chen)俊(jun)等(deng)[15]用(yong)兩步溶(rong)膠(jiao)凝膠(jiao)制備了TiO2/SiO2復合(he)(he)材料(liao)并(bing)研究了其催(cui)化活性，結(jie)果(guo)(guo)表(biao)明，經高(gao)溫(wen)處理后，TiO2/SiO2復合(he)(he)物的(de)降解(jie)率遠(yuan)遠(yuan)大(da)于TiO2粉體(ti)。Sandra Parra等(deng)[16]將TiO2負(fu)載于玻(bo)(bo)璃珠和玻(bo)(bo)璃環等(deng)惰性的(de)玻(bo)(bo)璃制品上用(yong)來去(qu)處理阿(a)特拉(la)津，取得(de)了很好(hao)的(de)效(xiao)果(guo)(guo)。

光(guang)(guang)催化(hua)氧化(hua)技術具有能(neng)耗底、操作簡單(dan)，反應條件溫和，無二次污染等特點。目(mu)前光(guang)(guang)催化(hua)技術和超聲波(bo)、電場(chang)、磁場(chang)、微波(bo)等物理(li)場(chang)聯合應用(yong)，處理(li)有毒(du)、生(sheng)物難(nan)以(yi)降(jiang)解的(de)(de)(de)有機污染物。這種(zhong)聯合光(guang)(guang)催化(hua)技術雖處于(yu)研究探索階段，但這種(zhong)聯合技術將會極大(da)地促進高(gao)級氧化(hua)技術的(de)(de)(de)發展和應用(yong)，還會進一步促進水處理(li)技術的(de)(de)(de)發展。然而作為近(jin)年來發展起來的(de)(de)(de)新型的(de)(de)(de)水處理(li)技術，光(guang)(guang)催化(hua)降(jiang)解現在還基本(ben)上停留在理(li)論研究階段，實際應用(yong)很少。未來應著重解決廉價(jia)高(gao)活性催化(hua)劑的(de)(de)(de)制(zhi)備、分離(li)回收(shou)及(ji)(ji)固定化(hua)問題(ti)，以(yi)及(ji)(ji)光(guang)(guang)催化(hua)反應器的(de)(de)(de)設(she)計及(ji)(ji)提(ti)高(gao)太陽光(guang)(guang)能(neng)利用(yong)率等問題(ti)。

3·電催(cui)化氧(yang)化法（ECO）

電(dian)(dian)(dian)(dian)催(cui)(cui)化(hua)(hua)(hua)(hua)(hua)(hua)(hua)(hua)氧(yang)(yang)(yang)(yang)化(hua)(hua)(hua)(hua)(hua)(hua)(hua)(hua)法(fa)(fa)(fa)（ECO）是(shi)(shi)一種(zhong)頗有發(fa)展前景(jing)的電(dian)(dian)(dian)(dian)化(hua)(hua)(hua)(hua)(hua)(hua)(hua)(hua)學廢水(shui)處(chu)(chu)理(li)(li)(li)(li)方法(fa)(fa)(fa)。電(dian)(dian)(dian)(dian)催(cui)(cui)化(hua)(hua)(hua)(hua)(hua)(hua)(hua)(hua)氧(yang)(yang)(yang)(yang)化(hua)(hua)(hua)(hua)(hua)(hua)(hua)(hua)法(fa)(fa)(fa)（ECO）主要是(shi)(shi)通過(guo)電(dian)(dian)(dian)(dian)極和(he)催(cui)(cui)化(hua)(hua)(hua)(hua)(hua)(hua)(hua)(hua)材(cai)料(liao)(liao)(liao)的作用產生超氧(yang)(yang)(yang)(yang)自(zi)由基(ji)(ji)（·O）2、H2O2、羥基(ji)(ji)自(zi)由基(ji)(ji)（·OH）等(deng)活(huo)性(xing)(xing)基(ji)(ji)團來氧(yang)(yang)(yang)(yang)化(hua)(hua)(hua)(hua)(hua)(hua)(hua)(hua)水(shui)體中(zhong)的有機物[17]。陽(yang)極材(cai)料(liao)(liao)(liao)是(shi)(shi)影(ying)響該法(fa)(fa)(fa)降解(jie)有機物的效(xiao)率(lv)(lv)(lv)和(he)能(neng)耗的關鍵因素(su)，研(yan)制綜合性(xing)(xing)能(neng)好的陽(yang)極材(cai)料(liao)(liao)(liao)是(shi)(shi)該領域(yu)的熱點和(he)難點[18]。電(dian)(dian)(dian)(dian)極的催(cui)(cui)化(hua)(hua)(hua)(hua)(hua)(hua)(hua)(hua)活(huo)性(xing)(xing)和(he)穩定性(xing)(xing)可以(yi)(yi)通過(guo)摻雜其(qi)(qi)他(ta)金屬(shu)和(he)非金屬(shu)得到加強。電(dian)(dian)(dian)(dian)催(cui)(cui)化(hua)(hua)(hua)(hua)(hua)(hua)(hua)(hua)氧(yang)(yang)(yang)(yang)化(hua)(hua)(hua)(hua)(hua)(hua)(hua)(hua)法(fa)(fa)(fa)在(zai)(zai)印染廢水(shui)處(chu)(chu)理(li)(li)(li)(li)方面有著(zhu)廣泛的應用前景(jing)。王(wang)愛民(min)等(deng)[19]用電(dian)(dian)(dian)(dian)催(cui)(cui)化(hua)(hua)(hua)(hua)(hua)(hua)(hua)(hua)氧(yang)(yang)(yang)(yang)化(hua)(hua)(hua)(hua)(hua)(hua)(hua)(hua)法(fa)(fa)(fa)降解(jie)酸(suan)(suan)(suan)性(xing)(xing)紅B，表(biao)明(ming)在(zai)(zai)酸(suan)(suan)(suan)性(xing)(xing)條件(jian)下(xia)酸(suan)(suan)(suan)性(xing)(xing)紅B以(yi)(yi)分(fen)子(zi)狀態存在(zai)(zai)更有利于(yu)電(dian)(dian)(dian)(dian)催(cui)(cui)化(hua)(hua)(hua)(hua)(hua)(hua)(hua)(hua)氧(yang)(yang)(yang)(yang)化(hua)(hua)(hua)(hua)(hua)(hua)(hua)(hua)。申哲民(min)等(deng)[20]電(dian)(dian)(dian)(dian)催(cui)(cui)化(hua)(hua)(hua)(hua)(hua)(hua)(hua)(hua)三種(zhong)催(cui)(cui)化(hua)(hua)(hua)(hua)(hua)(hua)(hua)(hua)劑降解(jie)酸(suan)(suan)(suan)性(xing)(xing)紅B，結(jie)果(guo)(guo)表(biao)明(ming)，稀土材(cai)料(liao)(liao)(liao)在(zai)(zai)ECO體系中(zhong)呈負催(cui)(cui)化(hua)(hua)(hua)(hua)(hua)(hua)(hua)(hua)效(xiao)應；軟猛礦(kuang)石的色(se)度(du)去(qu)(qu)除(chu)(chu)效(xiao)果(guo)(guo)明(ming)顯(xian)；TiO2的催(cui)(cui)化(hua)(hua)(hua)(hua)(hua)(hua)(hua)(hua)效(xiao)果(guo)(guo)最顯(xian)著(zhu)，其(qi)(qi)色(se)度(du)和(he)COD去(qu)(qu)除(chu)(chu)效(xiao)果(guo)(guo)比(bi)無催(cui)(cui)化(hua)(hua)(hua)(hua)(hua)(hua)(hua)(hua)劑時(shi)(shi)的效(xiao)果(guo)(guo)分(fen)別提高60%和(he)75%。尹紅霞等(deng)[21]用鈦基(ji)(ji)體二氧(yang)(yang)(yang)(yang)化(hua)(hua)(hua)(hua)(hua)(hua)(hua)(hua)鉛電(dian)(dian)(dian)(dian)極（Ti/SnO2+Sb2O3/PbO2）對含60mg/L甲基(ji)(ji)橙的模擬廢水(shui)處(chu)(chu)理(li)(li)(li)(li)2h，脫色(se)率(lv)(lv)(lv)82.21%，COD去(qu)(qu)除(chu)(chu)率(lv)(lv)(lv)為76.75%。李慶新等(deng)[22]采用RuO2-Ti板(ban)作為陽(yang)極，不銹鋼(gang)板(ban)為陰極，電(dian)(dian)(dian)(dian)催(cui)(cui)化(hua)(hua)(hua)(hua)(hua)(hua)(hua)(hua)氧(yang)(yang)(yang)(yang)化(hua)(hua)(hua)(hua)(hua)(hua)(hua)(hua)處(chu)(chu)理(li)(li)(li)(li)酸(suan)(suan)(suan)性(xing)(xing)蒽醌綠2Ж廢水(shui)。結(jie)果(guo)(guo)表(biao)明(ming)處(chu)(chu)理(li)(li)(li)(li)酸(suan)(suan)(suan)性(xing)(xing)蒽醌綠2Ж模擬染料(liao)(liao)(liao)廢水(shui)的最佳(jia)電(dian)(dian)(dian)(dian)催(cui)(cui)化(hua)(hua)(hua)(hua)(hua)(hua)(hua)(hua)氧(yang)(yang)(yang)(yang)化(hua)(hua)(hua)(hua)(hua)(hua)(hua)(hua)條件(jian)為槽(cao)電(dian)(dian)(dian)(dian)壓10V、初始pH值為4、NaCl濃度(du)為2.0g/L；在(zai)(zai)此條件(jian)下(xia)連續電(dian)(dian)(dian)(dian)解(jie)50min，COD去(qu)(qu)除(chu)(chu)率(lv)(lv)(lv)和(he)脫色(se)率(lv)(lv)(lv)分(fen)別為61.46%和(he)83.14%。研(yan)究表(biao)明(ming)脈沖電(dian)(dian)(dian)(dian)催(cui)(cui)化(hua)(hua)(hua)(hua)(hua)(hua)(hua)(hua)氧(yang)(yang)(yang)(yang)化(hua)(hua)(hua)(hua)(hua)(hua)(hua)(hua)可以(yi)(yi)明(ming)顯(xian)提高能(neng)量(liang)效(xiao)率(lv)(lv)(lv)和(he)電(dian)(dian)(dian)(dian)流效(xiao)率(lv)(lv)(lv)，降低處(chu)(chu)理(li)(li)(li)(li)成本。各(ge)類染料(liao)(liao)(liao)在(zai)(zai)電(dian)(dian)(dian)(dian)催(cui)(cui)化(hua)(hua)(hua)(hua)(hua)(hua)(hua)(hua)氧(yang)(yang)(yang)(yang)化(hua)(hua)(hua)(hua)(hua)(hua)(hua)(hua)處(chu)(chu)理(li)(li)(li)(li)時(shi)(shi)，其(qi)(qi)去(qu)(qu)除(chu)(chu)率(lv)(lv)(lv)的大小順序是(shi)(shi)：硫化(hua)(hua)(hua)(hua)(hua)(hua)(hua)(hua)染料(liao)(liao)(liao)＞酸(suan)(suan)(suan)性(xing)(xing)染料(liao)(liao)(liao)＞中(zhong)性(xing)(xing)染料(liao)(liao)(liao)＞陽(yang)離子(zi)染料(liao)(liao)(liao)[23]。

電(dian)催化(hua)(hua)氧化(hua)(hua)技(ji)術是(shi)一種有效(xiao)環保的(de)(de)有機廢(fei)(fei)水處理方法(fa)，它(ta)操作簡單(dan)易控(kong)制(zhi)，是(shi)生物法(fa)和化(hua)(hua)學(xue)法(fa)處理廢(fei)(fei)水無與倫比的(de)(de)，但在(zai)該領域還存在(zai)析氧、析氫副反應，成本高、能耗大等(deng)缺點。此(ci)外高性能電(dian)極的(de)(de)研(yan)制(zhi)開發和電(dian)化(hua)(hua)學(xue)反應器(qi)的(de)(de)選擇和設(she)計以(yi)及如(ru)何提高電(dian)流效(xiao)率是(shi)亟待解決的(de)(de)問(wen)題。

4·光(guang)電催化氧化法（EAPCO）

光(guang)(guang)(guang)(guang)(guang)(guang)電(dian)(dian)(dian)(dian)(dian)(dian)(dian)催(cui)(cui)(cui)(cui)化(hua)(hua)(hua)(hua)氧(yang)(yang)化(hua)(hua)(hua)(hua)技(ji)術(shu)(shu)(shu)（EAPCO）是(shi)(shi)一(yi)種電(dian)(dian)(dian)(dian)(dian)(dian)(dian)化(hua)(hua)(hua)(hua)學(xue)(xue)(xue)(xue)(xue)輔助的(de)(de)(de)(de)(de)(de)光(guang)(guang)(guang)(guang)(guang)(guang)催(cui)(cui)(cui)(cui)化(hua)(hua)(hua)(hua)氧(yang)(yang)化(hua)(hua)(hua)(hua)技(ji)術(shu)(shu)(shu)，以(yi)光(guang)(guang)(guang)(guang)(guang)(guang)催(cui)(cui)(cui)(cui)化(hua)(hua)(hua)(hua)劑(ji)(ji)(ji)作為(wei)陽極(ji)(ji)，通過(guo)(guo)(guo)外加陽極(ji)(ji)偏壓(ya)使(shi)光(guang)(guang)(guang)(guang)(guang)(guang)激發產(chan)生的(de)(de)(de)(de)(de)(de)電(dian)(dian)(dian)(dian)(dian)(dian)(dian)子(zi)(zi)通過(guo)(guo)(guo)外電(dian)(dian)(dian)(dian)(dian)(dian)(dian)路流向(xiang)陰(yin)(yin)(yin)極(ji)(ji)，有(you)(you)(you)效(xiao)(xiao)(xiao)促進(jin)(jin)(jin)光(guang)(guang)(guang)(guang)(guang)(guang)生電(dian)(dian)(dian)(dian)(dian)(dian)(dian)子(zi)(zi)與(yu)空(kong)(kong)穴(xue)分離，使(shi)體(ti)(ti)系中(zhong)有(you)(you)(you)更(geng)(geng)多的(de)(de)(de)(de)(de)(de)空(kong)(kong)穴(xue)存在(zai)，從而生成(cheng)更(geng)(geng)多的(de)(de)(de)(de)(de)(de)羥基(ji)(ji)自由基(ji)(ji)（·OH），提(ti)高(gao)(gao)光(guang)(guang)(guang)(guang)(guang)(guang)量子(zi)(zi)的(de)(de)(de)(de)(de)(de)效(xiao)(xiao)(xiao)率(lv)(lv)(lv)(lv)，達到提(ti)高(gao)(gao)光(guang)(guang)(guang)(guang)(guang)(guang)催(cui)(cui)(cui)(cui)化(hua)(hua)(hua)(hua)效(xiao)(xiao)(xiao)率(lv)(lv)(lv)(lv)的(de)(de)(de)(de)(de)(de)目(mu)(mu)的(de)(de)(de)(de)(de)(de)。安太(tai)成(cheng)等[24]在(zai)TiO2光(guang)(guang)(guang)(guang)(guang)(guang)催(cui)(cui)(cui)(cui)化(hua)(hua)(hua)(hua)劑(ji)(ji)(ji)和(he)(he)電(dian)(dian)(dian)(dian)(dian)(dian)(dian)催(cui)(cui)(cui)(cui)化(hua)(hua)(hua)(hua)劑(ji)(ji)(ji)同(tong)時(shi)存在(zai)的(de)(de)(de)(de)(de)(de)條件下(xia)(xia)(xia)，將(jiang)三相(xiang)電(dian)(dian)(dian)(dian)(dian)(dian)(dian)極(ji)(ji)技(ji)術(shu)(shu)(shu)與(yu)光(guang)(guang)(guang)(guang)(guang)(guang)催(cui)(cui)(cui)(cui)化(hua)(hua)(hua)(hua)技(ji)術(shu)(shu)(shu)結合，構成(cheng)了(le)一(yi)種很(hen)具特色的(de)(de)(de)(de)(de)(de)多相(xiang)三維(wei)電(dian)(dian)(dian)(dian)(dian)(dian)(dian)極(ji)(ji)電(dian)(dian)(dian)(dian)(dian)(dian)(dian)助光(guang)(guang)(guang)(guang)(guang)(guang)催(cui)(cui)(cui)(cui)化(hua)(hua)(hua)(hua)體(ti)(ti)系，在(zai)通電(dian)(dian)(dian)(dian)(dian)(dian)(dian)的(de)(de)(de)(de)(de)(de)情況下(xia)(xia)(xia)填入電(dian)(dian)(dian)(dian)(dian)(dian)(dian)解池中(zhong)的(de)(de)(de)(de)(de)(de)電(dian)(dian)(dian)(dian)(dian)(dian)(dian)催(cui)(cui)(cui)(cui)化(hua)(hua)(hua)(hua)劑(ji)(ji)(ji)被(bei)誘導(dao)(dao)成(cheng)為(wei)復(fu)極(ji)(ji)性(xing)(xing)粒(li)(li)子(zi)(zi)電(dian)(dian)(dian)(dian)(dian)(dian)(dian)極(ji)(ji)，使(shi)得陰(yin)(yin)(yin)陽極(ji)(ji)的(de)(de)(de)(de)(de)(de)反應不但(dan)在(zai)主電(dian)(dian)(dian)(dian)(dian)(dian)(dian)極(ji)(ji)上(shang)進(jin)(jin)(jin)行(xing)。還(huan)分別(bie)在(zai)粒(li)(li)子(zi)(zi)電(dian)(dian)(dian)(dian)(dian)(dian)(dian)極(ji)(ji)的(de)(de)(de)(de)(de)(de)兩(liang)端進(jin)(jin)(jin)行(xing)，對(dui)亞(ya)甲基(ji)(ji)藍的(de)(de)(de)(de)(de)(de)降(jiang)(jiang)(jiang)解表(biao)明(ming)(ming)，在(zai)光(guang)(guang)(guang)(guang)(guang)(guang)電(dian)(dian)(dian)(dian)(dian)(dian)(dian)催(cui)(cui)(cui)(cui)化(hua)(hua)(hua)(hua)體(ti)(ti)系中(zhong)亞(ya)甲基(ji)(ji)藍的(de)(de)(de)(de)(de)(de)脫色率(lv)(lv)(lv)(lv)與(yu)COD去除率(lv)(lv)(lv)(lv)分別(bie)為(wei)95%和(he)(he)87%，而單獨(du)電(dian)(dian)(dian)(dian)(dian)(dian)(dian)催(cui)(cui)(cui)(cui)化(hua)(hua)(hua)(hua)體(ti)(ti)系分別(bie)為(wei)78%和(he)(he)68%，單獨(du)光(guang)(guang)(guang)(guang)(guang)(guang)催(cui)(cui)(cui)(cui)化(hua)(hua)(hua)(hua)體(ti)(ti)系分別(bie)為(wei)89%和(he)(he)71%。鄭(zheng)保戰等[25]采用(yong)(yong)傳統的(de)(de)(de)(de)(de)(de)溶膠(jiao)—凝膠(jiao)法以(yi)導(dao)(dao)電(dian)(dian)(dian)(dian)(dian)(dian)(dian)玻(bo)璃(li)為(wei)載(zai)體(ti)(ti)制備了(le)二氧(yang)(yang)化(hua)(hua)(hua)(hua)鈦(tai)薄膜作為(wei)光(guang)(guang)(guang)(guang)(guang)(guang)催(cui)(cui)(cui)(cui)化(hua)(hua)(hua)(hua)劑(ji)(ji)(ji)，在(zai)光(guang)(guang)(guang)(guang)(guang)(guang)、電(dian)(dian)(dian)(dian)(dian)(dian)(dian)、化(hua)(hua)(hua)(hua)學(xue)(xue)(xue)(xue)(xue)的(de)(de)(de)(de)(de)(de)協(xie)同(tong)作用(yong)(yong)下(xia)(xia)(xia)，考察了(le)催(cui)(cui)(cui)(cui)化(hua)(hua)(hua)(hua)劑(ji)(ji)(ji)對(dui)模擬工業廢水的(de)(de)(de)(de)(de)(de)光(guang)(guang)(guang)(guang)(guang)(guang)催(cui)(cui)(cui)(cui)化(hua)(hua)(hua)(hua)降(jiang)(jiang)(jiang)解能力(li)。研究(jiu)結果(guo)表(biao)明(ming)(ming)，此方法制備的(de)(de)(de)(de)(de)(de)二氧(yang)(yang)化(hua)(hua)(hua)(hua)鈦(tai)薄膜在(zai)光(guang)(guang)(guang)(guang)(guang)(guang)、電(dian)(dian)(dian)(dian)(dian)(dian)(dian)、化(hua)(hua)(hua)(hua)學(xue)(xue)(xue)(xue)(xue)等方法的(de)(de)(de)(de)(de)(de)協(xie)同(tong)作用(yong)(yong)下(xia)(xia)(xia)可以(yi)有(you)(you)(you)效(xiao)(xiao)(xiao)地降(jiang)(jiang)(jiang)解模擬廢水中(zhong)的(de)(de)(de)(de)(de)(de)有(you)(you)(you)機(ji)染(ran)料—甲基(ji)(ji)紫。李(li)明(ming)(ming)玉等[26]設計研制出了(le)新(xin)型(xing)光(guang)(guang)(guang)(guang)(guang)(guang)-電(dian)(dian)(dian)(dian)(dian)(dian)(dian)-化(hua)(hua)(hua)(hua)學(xue)(xue)(xue)(xue)(xue)催(cui)(cui)(cui)(cui)化(hua)(hua)(hua)(hua)集(ji)成(cheng)反應器.在(zai)紫外光(guang)(guang)(guang)(guang)(guang)(guang)和(he)(he)外加電(dian)(dian)(dian)(dian)(dian)(dian)(dian)場的(de)(de)(de)(de)(de)(de)作用(yong)(yong)下(xia)(xia)(xia)，對(dui)酸性(xing)(xing)大紅(hong)3R進(jin)(jin)(jin)行(xing)光(guang)(guang)(guang)(guang)(guang)(guang)電(dian)(dian)(dian)(dian)(dian)(dian)(dian)催(cui)(cui)(cui)(cui)化(hua)(hua)(hua)(hua)降(jiang)(jiang)(jiang)解脫色，實(shi)現了(le)在(zai)陽、陰(yin)(yin)(yin)兩(liang)極(ji)(ji)同(tong)時(shi)對(dui)染(ran)料進(jin)(jin)(jin)行(xing)降(jiang)(jiang)(jiang)解脫色處(chu)理，達到了(le)“雙(shuang)極(ji)(ji)雙(shuang)效(xiao)(xiao)(xiao)”的(de)(de)(de)(de)(de)(de)目(mu)(mu)的(de)(de)(de)(de)(de)(de)。實(shi)驗(yan)表(biao)明(ming)(ming)，當用(yong)(yong)0.02 mol/L硫(liu)酸鈉為(wei)支持電(dian)(dian)(dian)(dian)(dian)(dian)(dian)解質(zhi)、初始pH=3和(he)(he)陰(yin)(yin)(yin)極(ji)(ji)電(dian)(dian)(dian)(dian)(dian)(dian)(dian)位－Ec=0.66V的(de)(de)(de)(de)(de)(de)條件下(xia)(xia)(xia)，陰(yin)(yin)(yin)極(ji)(ji)槽和(he)(he)陽極(ji)(ji)槽對(dui)30 mg/L酸性(xing)(xing)大紅(hong)3R溶液的(de)(de)(de)(de)(de)(de)脫色降(jiang)(jiang)(jiang)解率(lv)(lv)(lv)(lv)分別(bie)達到92%和(he)(he)60%，與(yu)雙(shuang)極(ji)(ji)單效(xiao)(xiao)(xiao)的(de)(de)(de)(de)(de)(de)光(guang)(guang)(guang)(guang)(guang)(guang)電(dian)(dian)(dian)(dian)(dian)(dian)(dian)催(cui)(cui)(cui)(cui)化(hua)(hua)(hua)(hua)相(xiang)比，效(xiao)(xiao)(xiao)率(lv)(lv)(lv)(lv)顯(xian)著提(ti)高(gao)(gao)。事(shi)實(shi)證明(ming)(ming)，光(guang)(guang)(guang)(guang)(guang)(guang)電(dian)(dian)(dian)(dian)(dian)(dian)(dian)催(cui)(cui)(cui)(cui)化(hua)(hua)(hua)(hua)技(ji)術(shu)(shu)(shu)是(shi)(shi)一(yi)種比光(guang)(guang)(guang)(guang)(guang)(guang)催(cui)(cui)(cui)(cui)化(hua)(hua)(hua)(hua)更(geng)(geng)為(wei)有(you)(you)(you)效(xiao)(xiao)(xiao)的(de)(de)(de)(de)(de)(de)降(jiang)(jiang)(jiang)解有(you)(you)(you)機(ji)污染(ran)物的(de)(de)(de)(de)(de)(de)技(ji)術(shu)(shu)(shu)。但(dan)是(shi)(shi)目(mu)(mu)前對(dui)電(dian)(dian)(dian)(dian)(dian)(dian)(dian)助光(guang)(guang)(guang)(guang)(guang)(guang)催(cui)(cui)(cui)(cui)化(hua)(hua)(hua)(hua)技(ji)術(shu)(shu)(shu)的(de)(de)(de)(de)(de)(de)研究(jiu)主要集(ji)中(zhong)在(zai)對(dui)電(dian)(dian)(dian)(dian)(dian)(dian)(dian)化(hua)(hua)(hua)(hua)學(xue)(xue)(xue)(xue)(xue)輔助作用(yong)(yong)的(de)(de)(de)(de)(de)(de)驗(yan)證上(shang)，對(dui)該過(guo)(guo)(guo)程(cheng)的(de)(de)(de)(de)(de)(de)影(ying)響(xiang)因素(su)，半導(dao)(dao)體(ti)(ti)電(dian)(dian)(dian)(dian)(dian)(dian)(dian)極(ji)(ji)的(de)(de)(de)(de)(de)(de)電(dian)(dian)(dian)(dian)(dian)(dian)(dian)化(hua)(hua)(hua)(hua)學(xue)(xue)(xue)(xue)(xue)測定(ding)和(he)(he)分析，高(gao)(gao)活性(xing)(xing)、高(gao)(gao)穩(wen)定(ding)性(xing)(xing)光(guang)(guang)(guang)(guang)(guang)(guang)催(cui)(cui)(cui)(cui)化(hua)(hua)(hua)(hua)劑(ji)(ji)(ji)的(de)(de)(de)(de)(de)(de)制備、電(dian)(dian)(dian)(dian)(dian)(dian)(dian)助光(guang)(guang)(guang)(guang)(guang)(guang)催(cui)(cui)(cui)(cui)化(hua)(hua)(hua)(hua)過(guo)(guo)(guo)程(cheng)機(ji)理的(de)(de)(de)(de)(de)(de)深(shen)入研究(jiu)，以(yi)及開(kai)發實(shi)用(yong)(yong)性(xing)(xing)的(de)(de)(de)(de)(de)(de)固定(ding)膜式反應器是(shi)(shi)今后(hou)研究(jiu)工作的(de)(de)(de)(de)(de)(de)方向(xiang)。

5·催化超臨界水氧(yang)化法（CSCWO）

超(chao)臨(lin)界(jie)水氧(yang)化(hua)(hua)法（SCWO）是(shi)一種新(xin)型的(de)(de)水處理技術(shu)。它(ta)是(shi)利用(yong)(yong)超(chao)臨(lin)界(jie)水（tc=374.4℃，Pc=22.05MPa）對有(you)(you)機物的(de)(de)良(liang)好溶(rong)解性(xing)（甚至于可以(yi)任意比(bi)例與(yu)SCW混合），使99%以(yi)上(shang)的(de)(de)有(you)(you)機物被降解。它(ta)是(shi)一種在不產生(sheng)有(you)(you)害副(fu)產物情況(kuang)下，徹(che)底有(you)(you)效降解廢物的(de)(de)好方法[27]。為(wei)了(le)加快反應(ying)(ying)速(su)度(du)，減少反應(ying)(ying)時間，降低反應(ying)(ying)溫度(du)，將適宜的(de)(de)催(cui)化(hua)(hua)劑(ji)(ji)引入SCWO，開(kai)發了(le)超(chao)臨(lin)界(jie)水催(cui)化(hua)(hua)氧(yang)化(hua)(hua)技術(shu)（CSCWO）。該技術(shu)的(de)(de)關鍵是(shi)研(yan)制耐(nai)高溫、高活性(xing)、高穩定(ding)性(xing)的(de)(de)催(cui)化(hua)(hua)劑(ji)(ji)。一般應(ying)(ying)用(yong)(yong)的(de)(de)催(cui)化(hua)(hua)劑(ji)(ji)主(zhu)要有(you)(you)貴(gui)金屬(shu)、過渡金屬(shu)、稀土金屬(shu)及(ji)其氧(yang)化(hua)(hua)物、復(fu)合氧(yang)化(hua)(hua)物和鹽(yan)類。SCWO所用(yong)(yong)氧(yang)化(hua)(hua)劑(ji)(ji)主(zhu)要有(you)(you)空氣(qi)、O2、H2O2、KMnO4及(ji)KMnO4+O2等。

經(jing)過(guo)20多(duo)年的(de)(de)(de)(de)(de)(de)(de)研究，超(chao)臨(lin)(lin)(lin)(lin)界(jie)水(shui)催(cui)(cui)(cui)化(hua)(hua)(hua)(hua)(hua)(hua)(hua)氧化(hua)(hua)(hua)(hua)(hua)(hua)(hua)已成(cheng)功用于(yu)(yu)有(you)(you)毒廢(fei)水(shui)、難降(jiang)解(jie)印染(ran)(ran)廢(fei)水(shui)的(de)(de)(de)(de)(de)(de)(de)處理(li)。目前已有(you)(you)報道印染(ran)(ran)廢(fei)水(shui)中含(han)有(you)(you)的(de)(de)(de)(de)(de)(de)(de)苯胺、硝基(ji)苯、鄰苯二(er)(er)(er)(er)甲(jia)(jia)酸類等(deng)(deng)含(han)有(you)(you)苯環、胺基(ji)、偶氮等(deng)(deng)基(ji)團的(de)(de)(de)(de)(de)(de)(de)有(you)(you)毒有(you)(you)機污染(ran)(ran)物的(de)(de)(de)(de)(de)(de)(de)催(cui)(cui)(cui)化(hua)(hua)(hua)(hua)(hua)(hua)(hua)超(chao)臨(lin)(lin)(lin)(lin)界(jie)水(shui)處理(li)文(wen)獻。Savage等(deng)(deng)[28]以CuO為(wei)催(cui)(cui)(cui)化(hua)(hua)(hua)(hua)(hua)(hua)(hua)劑(ji)(ji)，對苯酚進(jin)行了(le)超(chao)臨(lin)(lin)(lin)(lin)界(jie)水(shui)氧化(hua)(hua)(hua)(hua)(hua)(hua)(hua)機理(li)研究，表明催(cui)(cui)(cui)化(hua)(hua)(hua)(hua)(hua)(hua)(hua)劑(ji)(ji)提(ti)(ti)高了(le)苯酚的(de)(de)(de)(de)(de)(de)(de)轉(zhuan)化(hua)(hua)(hua)(hua)(hua)(hua)(hua)率(lv)(lv)和(he)二(er)(er)(er)(er)氧化(hua)(hua)(hua)(hua)(hua)(hua)(hua)碳(tan)的(de)(de)(de)(de)(de)(de)(de)產(chan)量，催(cui)(cui)(cui)化(hua)(hua)(hua)(hua)(hua)(hua)(hua)劑(ji)(ji)的(de)(de)(de)(de)(de)(de)(de)添加增大了(le)苯酚自(zi)由基(ji)的(de)(de)(de)(de)(de)(de)(de)生成(cheng)速(su)率(lv)(lv)，從而(er)提(ti)(ti)高了(le)苯酚的(de)(de)(de)(de)(de)(de)(de)轉(zhuan)化(hua)(hua)(hua)(hua)(hua)(hua)(hua)率(lv)(lv)。郭小華(hua)等(deng)(deng)[29]利用Mn2+為(wei)催(cui)(cui)(cui)化(hua)(hua)(hua)(hua)(hua)(hua)(hua)劑(ji)(ji)、H2O2為(wei)氧化(hua)(hua)(hua)(hua)(hua)(hua)(hua)劑(ji)(ji)進(jin)行了(le)催(cui)(cui)(cui)化(hua)(hua)(hua)(hua)(hua)(hua)(hua)超(chao)臨(lin)(lin)(lin)(lin)界(jie)水(shui)氧化(hua)(hua)(hua)(hua)(hua)(hua)(hua)偏(pian)(pian)二(er)(er)(er)(er)甲(jia)(jia)肼實驗(yan)(yan)。結果表明，在超(chao)臨(lin)(lin)(lin)(lin)界(jie)水(shui)中偏(pian)(pian)二(er)(er)(er)(er)甲(jia)(jia)肼能被有(you)(you)效去除(chu)。偏(pian)(pian)二(er)(er)(er)(er)甲(jia)(jia)肼的(de)(de)(de)(de)(de)(de)(de)去除(chu)率(lv)(lv)隨反應(ying)溫(wen)度(du)和(he)壓力的(de)(de)(de)(de)(de)(de)(de)升高、停留時間的(de)(de)(de)(de)(de)(de)(de)延長(chang)和(he)Mn2+濃度(du)增大而(er)提(ti)(ti)高。當Mn2+濃度(du)為(wei)30mg/L時，偏(pian)(pian)二(er)(er)(er)(er)甲(jia)(jia)肼的(de)(de)(de)(de)(de)(de)(de)去除(chu)率(lv)(lv)與(yu)無催(cui)(cui)(cui)化(hua)(hua)(hua)(hua)(hua)(hua)(hua)劑(ji)(ji)時相比(bi)有(you)(you)了(le)較大的(de)(de)(de)(de)(de)(de)(de)提(ti)(ti)高。當處理(li)條(tiao)件為(wei)：30MPa、500℃、3.6s和(he)Mn2+濃度(du)為(wei)30mg/L時，COD去除(chu)率(lv)(lv)高達99.6%。葛紅光等(deng)(deng)[30]以CuO/γ-Al2O3和(he)MnO2/Al2O3為(wei)催(cui)(cui)(cui)化(hua)(hua)(hua)(hua)(hua)(hua)(hua)劑(ji)(ji)、H2O2為(wei)氧化(hua)(hua)(hua)(hua)(hua)(hua)(hua)劑(ji)(ji)，在一(yi)個(ge)連(lian)續流固定床反應(ying)器中進(jin)行了(le)超(chao)臨(lin)(lin)(lin)(lin)界(jie)水(shui)氧化(hua)(hua)(hua)(hua)(hua)(hua)(hua)對氨(an)基(ji)苯酚實驗(yan)(yan)。實驗(yan)(yan)結果表明，CuO和(he)MnO催(cui)(cui)(cui)化(hua)(hua)(hua)(hua)(hua)(hua)(hua)劑(ji)(ji)對于(yu)(yu)對氨(an)基(ji)苯酚的(de)(de)(de)(de)(de)(de)(de)氧化(hua)(hua)(hua)(hua)(hua)(hua)(hua)降(jiang)解(jie)具有(you)(you)顯著(zhu)的(de)(de)(de)(de)(de)(de)(de)促進(jin)作用對氨(an)基(ji)苯酚的(de)(de)(de)(de)(de)(de)(de)去除(chu)率(lv)(lv)隨反應(ying)溫(wen)度(du)和(he)壓力的(de)(de)(de)(de)(de)(de)(de)升高、停留時間的(de)(de)(de)(de)(de)(de)(de)延長(chang)而(er)提(ti)(ti)高，在24～26MPa和(he)400～450℃條(tiao)件下，數秒鐘內COD去除(chu)率(lv)(lv)可達到99%以上(shang)，催(cui)(cui)(cui)化(hua)(hua)(hua)(hua)(hua)(hua)(hua)劑(ji)(ji)CuO/γ-Al2O3的(de)(de)(de)(de)(de)(de)(de)催(cui)(cui)(cui)化(hua)(hua)(hua)(hua)(hua)(hua)(hua)效果優于(yu)(yu)MnO2/Al2O3。證明了(le)催(cui)(cui)(cui)化(hua)(hua)(hua)(hua)(hua)(hua)(hua)超(chao)臨(lin)(lin)(lin)(lin)界(jie)水(shui)氧化(hua)(hua)(hua)(hua)(hua)(hua)(hua)技術的(de)(de)(de)(de)(de)(de)(de)高效性。

CSCWO技(ji)(ji)(ji)術(shu)能徹底礦(kuang)化(hua)(hua)有機(ji)物，但(dan)它(ta)的(de)(de)(de)處(chu)(chu)理過程還是存在一些(xie)(xie)技(ji)(ji)(ji)術(shu)難(nan)題，如高溫、高壓(ya)(ya)的(de)(de)(de)苛刻反應(ying)條件，反應(ying)過程中對(dui)反應(ying)器(qi)的(de)(de)(de)強腐(fu)蝕(shi)性(xing)、無(wu)機(ji)鹽的(de)(de)(de)堵塞問(wen)題及(ji)運行費(fei)用等問(wen)題都是阻(zu)礙超(chao)臨界水(shui)(shui)氧化(hua)(hua)技(ji)(ji)(ji)術(shu)工業化(hua)(hua)的(de)(de)(de)挑戰性(xing)問(wen)題。目前，SCWO在美國(guo)、德國(guo)、瑞(rui)士、日本等國(guo)已有工業化(hua)(hua)的(de)(de)(de)處(chu)(chu)理裝置，且日處(chu)(chu)理能力可觀。而SCWO在我國(guo)起步(bu)晚(wan)還處(chu)(chu)于實(shi)驗階(jie)段。為(wei)了(le)克服SCWO的(de)(de)(de)這些(xie)(xie)難(nan)題，目前的(de)(de)(de)研究工作主(zhu)要(yao)集中在催化(hua)(hua)劑的(de)(de)(de)選擇以(yi)及(ji)設備防腐(fu)蝕(shi)等方面。隨著超(chao)臨界水(shui)(shui)氧化(hua)(hua)技(ji)(ji)(ji)術(shu)研究的(de)(de)(de)深入，催化(hua)(hua)劑和高溫、高壓(ya)(ya)條件下耐腐(fu)蝕(shi)新材料的(de)(de)(de)開發(fa)以(yi)及(ji)工藝系統的(de)(de)(de)優化(hua)(hua)設計，會使(shi)超(chao)臨界水(shui)(shui)催化(hua)(hua)氧化(hua)(hua)技(ji)(ji)(ji)術(shu)的(de)(de)(de)優勢更加(jia)明顯，它(ta)將成為(wei)未(wei)來(lai)污水(shui)(shui)處(chu)(chu)理技(ji)(ji)(ji)術(shu)的(de)(de)(de)主(zhu)流。

6·結語

隨(sui)著社會(hui)經(jing)濟的發展人(ren)們對環境(jing)問題(ti)越(yue)(yue)來(lai)(lai)越(yue)(yue)重視，廢(fei)水排放標準要求也越(yue)(yue)來(lai)(lai)越(yue)(yue)嚴格(ge)。催(cui)(cui)化(hua)氧(yang)(yang)化(hua)法通過多種途徑強化(hua)傳統化(hua)學氧(yang)(yang)化(hua)法的處理效果(guo)，促(cu)進催(cui)(cui)化(hua)劑產生(sheng)高活性的基團(tuan)或離子(zi)發生(sheng)鏈(lian)式(shi)反應(ying)，降解水中的有機污染物，使生(sheng)物難降解的有機物徹底(di)氧(yang)(yang)化(hua)分(fen)解成小分(fen)子(zi)而不造成二次污染。因(yin)此，隨(sui)著催(cui)(cui)化(hua)劑制(zhi)備技(ji)術的不斷(duan)完(wan)善(shan)，新材料的研制(zhi)開(kai)發，催(cui)(cui)化(hua)氧(yang)(yang)化(hua)法處理印染廢(fei)水技(ji)術將會(hui)得到更加(jia)廣(guang)泛的應(ying)用(yong)。

參考文獻：略

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