活性(xing)炭改性(xing)后處理磺胺廢水(shui)

　　磺(huang)胺(an)(an)廢水經(jing)活(huo)性(xing)(xing)炭改(gai)(gai)(gai)(gai)性(xing)(xing)后處理，活(huo)性(xing)(xing)炭經(jing)氯化鐵改(gai)(gai)(gai)(gai)性(xing)(xing)。并進行批量(liang)(liang)實驗(yan)以評估廢水中的(de)磺(huang)胺(an)(an)二(er)甲(jia)嘧啶吸附到活(huo)性(xing)(xing)炭和改(gai)(gai)(gai)(gai)性(xing)(xing)活(huo)性(xing)(xing)炭上的(de)平衡，分別分析動力(li)學和熱(re)力(li)學特(te)征。結果表(biao)明，氯化鐵處理后，活(huo)性(xing)(xing)炭改(gai)(gai)(gai)(gai)變了表(biao)面積(ji)(ji)、孔(kong)隙體積(ji)(ji)和表(biao)面zeta電位還(huan)增加了表(biao)面含氧官能團(tuan)的(de)數量(liang)(liang)。經(jing)試驗(yan)發現，磺(huang)胺(an)(an)二(er)甲(jia)啶在改(gai)(gai)(gai)(gai)性(xing)(xing)活(huo)性(xing)(xing)炭上的(de)吸附得到了顯著改(gai)(gai)(gai)(gai)善(shan)。

　　磺胺二甲啶是一種新型污染物，主要用于治療各種細菌感染引起的疾病。大多數磺胺二甲嘧啶以磺胺或代謝物的形式通過動物糞便和尿液釋放到環境中。這些磺胺或代謝物可能長期存在于環境中，可通過農場徑流和城市污水處理廠進入土壤、地表水、地下水甚至飲用水。傳統的污水處理技術只能去除廢水中的一些抗生素。這促使研究人員開發簡單高效的新技術，有效處理磺胺廢水。由于比表面積大，孔結構復雜，活性炭能有(you)效去(qu)除顏色、氣味、無機化合物(wu)(wu)和(he)大多數有(you)機污染物(wu)(wu)。但其(qi)在實際應用中(zhong)的(de)(de)使(shi)用受其(qi)吸(xi)(xi)附(fu)(fu)(fu)(fu)效率和(he)成本低(di)的(de)(de)限制。金屬離子改(gai)性(xing)(xing)(xing)后的(de)(de)活性(xing)(xing)(xing)炭(tan)生產簡單便宜(yi)，能顯著提(ti)高活性(xing)(xing)(xing)炭(tan)的(de)(de)吸(xi)(xi)附(fu)(fu)(fu)(fu)性(xing)(xing)(xing)能。然而，活性(xing)(xing)(xing)炭(tan)中(zhong)磺胺(an)(an)類廢水的(de)(de)吸(xi)(xi)附(fu)(fu)(fu)(fu)機制尚不清楚，對(dui)(dui)磺胺(an)(an)類的(de)(de)吸(xi)(xi)附(fu)(fu)(fu)(fu)能力(li)及其(qi)理化性(xing)(xing)(xing)質知之(zhi)甚(shen)少。本研究采(cai)用鐵離子改(gai)性(xing)(xing)(xing)活性(xing)(xing)(xing)炭(tan)。用于探(tan)索吸(xi)(xi)附(fu)(fu)(fu)(fu)機制的(de)(de)批量吸(xi)(xi)附(fu)(fu)(fu)(fu)實驗。磺胺(an)(an)二甲啶對(dui)(dui)活性(xing)(xing)(xing)炭(tan)和(he)改(gai)性(xing)(xing)(xing)活性(xing)(xing)(xing)炭(tan)的(de)(de)吸(xi)(xi)附(fu)(fu)(fu)(fu)特性(xing)(xing)(xing)通過吸(xi)(xi)附(fu)(fu)(fu)(fu)動(dong)力(li)學(xue)、吸(xi)(xi)附(fu)(fu)(fu)(fu)熱(re)力(li)學(xue)和(he)吸(xi)(xi)附(fu)(fu)(fu)(fu)等溫線進(jin)行(xing)了研究，為(wei)去(qu)除廢水中(zhong)的(de)(de)磺胺(an)(an)污染物(wu)(wu)提(ti)供(gong)了科學(xue)依(yi)據。

　　活性(xing)(xing)炭改性(xing)(xing)后的特性(xing)(xing)

　　活(huo)(huo)(huo)(huo)(huo)(huo)性(xing)(xing)(xing)(xing)(xing)炭(tan)(tan)(tan)(tan)和(he)(he)改(gai)(gai)(gai)(gai)性(xing)(xing)(xing)(xing)(xing)活(huo)(huo)(huo)(huo)(huo)(huo)性(xing)(xing)(xing)(xing)(xing)炭(tan)(tan)(tan)(tan)的(de)(de)(de)化(hua)學結構(gou)和(he)(he)物理化(hua)學性(xing)(xing)(xing)(xing)(xing)質差異很大(da)(da)。鐵(tie)(tie)離(li)子(zi)(zi)改(gai)(gai)(gai)(gai)性(xing)(xing)(xing)(xing)(xing)后，活(huo)(huo)(huo)(huo)(huo)(huo)性(xing)(xing)(xing)(xing)(xing)炭(tan)(tan)(tan)(tan)的(de)(de)(de)表(biao)(biao)(biao)面(mian)(mian)積(ji)(ji)、總孔(kong)(kong)容量(liang)、微孔(kong)(kong)體積(ji)(ji)和(he)(he)中(zhong)(zhong)孔(kong)(kong)體積(ji)(ji)都有(you)(you)(you)一(yi)定程度的(de)(de)(de)增(zeng)加(jia)，可以為磺胺二(er)甲啶(ding)提(ti)供更多(duo)的(de)(de)(de)吸附(fu)點(dian)。由于(yu)改(gai)(gai)(gai)(gai)性(xing)(xing)(xing)(xing)(xing)，活(huo)(huo)(huo)(huo)(huo)(huo)性(xing)(xing)(xing)(xing)(xing)炭(tan)(tan)(tan)(tan)的(de)(de)(de)微孔(kong)(kong)結構(gou)可能會產生較(jiao)大(da)(da)的(de)(de)(de)比表(biao)(biao)(biao)面(mian)(mian)積(ji)(ji)。在(zai)(zai)活(huo)(huo)(huo)(huo)(huo)(huo)化(hua)過程中(zhong)(zhong)，鐵(tie)(tie)離(li)子(zi)(zi)主(zhu)要(yao)沉積(ji)(ji)在(zai)(zai)介孔(kong)(kong)中(zhong)(zhong)，擴大(da)(da)孔(kong)(kong)徑(jing)并進入(ru)微孔(kong)(kong)。將(jiang)金屬鹽(yan)釋(shi)放(fang)的(de)(de)(de)氧(yang)化(hua)氣體引(yin)入(ru)微孔(kong)(kong)，并與微孔(kong)(kong)碳(tan)壁反應。活(huo)(huo)(huo)(huo)(huo)(huo)性(xing)(xing)(xing)(xing)(xing)炭(tan)(tan)(tan)(tan)和(he)(he)改(gai)(gai)(gai)(gai)性(xing)(xing)(xing)(xing)(xing)活(huo)(huo)(huo)(huo)(huo)(huo)性(xing)(xing)(xing)(xing)(xing)炭(tan)(tan)(tan)(tan)SEM圖(tu)(tu)(tu)1顯(xian)(xian)示圖(tu)(tu)(tu)像(xiang)(a)和(he)(he)(b)中(zhong)(zhong)。活(huo)(huo)(huo)(huo)(huo)(huo)性(xing)(xing)(xing)(xing)(xing)炭(tan)(tan)(tan)(tan)的(de)(de)(de)形(xing)狀表(biao)(biao)(biao)明(ming)(ming)(ming)(ming)具有(you)(you)(you)規(gui)則(ze)孔(kong)(kong)結構(gou)的(de)(de)(de)光滑(hua)表(biao)(biao)(biao)面(mian)(mian)。與活(huo)(huo)(huo)(huo)(huo)(huo)性(xing)(xing)(xing)(xing)(xing)炭(tan)(tan)(tan)(tan)相比，改(gai)(gai)(gai)(gai)性(xing)(xing)(xing)(xing)(xing)活(huo)(huo)(huo)(huo)(huo)(huo)性(xing)(xing)(xing)(xing)(xing)炭(tan)(tan)(tan)(tan)表(biao)(biao)(biao)面(mian)(mian)粗(cu)糙不規(gui)則(ze)。孔(kong)(kong)隙(xi)結構(gou)受損(sun)，孔(kong)(kong)隙(xi)率增(zeng)加(jia)。這(zhe)可能是由于(yu)鐵(tie)(tie)離(li)子(zi)(zi)引(yin)入(ru)活(huo)(huo)(huo)(huo)(huo)(huo)性(xing)(xing)(xing)(xing)(xing)炭(tan)(tan)(tan)(tan)內孔(kong)(kong)，導致(zhi)碳(tan)壁氧(yang)化(hua)和(he)(he)孔(kong)(kong)徑(jing)增(zeng)加(jia)。活(huo)(huo)(huo)(huo)(huo)(huo)性(xing)(xing)(xing)(xing)(xing)炭(tan)(tan)(tan)(tan)中(zhong)(zhong)磺胺二(er)甲啶(ding)的(de)(de)(de)擴散有(you)(you)(you)利(li)于(yu)粗(cu)糙的(de)(de)(de)表(biao)(biao)(biao)面(mian)(mian)結構(gou)和(he)(he)多(duo)孔(kong)(kong)特(te)性(xing)(xing)(xing)(xing)(xing)。活(huo)(huo)(huo)(huo)(huo)(huo)性(xing)(xing)(xing)(xing)(xing)炭(tan)(tan)(tan)(tan)和(he)(he)改(gai)(gai)(gai)(gai)性(xing)(xing)(xing)(xing)(xing)活(huo)(huo)(huo)(huo)(huo)(huo)性(xing)(xing)(xing)(xing)(xing)炭(tan)(tan)(tan)(tan)TEM圖(tu)(tu)(tu)像(xiang)如(ru)圖(tu)(tu)(tu)1(c)和(he)(he)(d)所(suo)示。這(zhe)些圖(tu)(tu)(tu)片表(biao)(biao)(biao)明(ming)(ming)(ming)(ming)活(huo)(huo)(huo)(huo)(huo)(huo)性(xing)(xing)(xing)(xing)(xing)炭(tan)(tan)(tan)(tan)是無(wu)定形(xing)的(de)(de)(de)。與活(huo)(huo)(huo)(huo)(huo)(huo)性(xing)(xing)(xing)(xing)(xing)炭(tan)(tan)(tan)(tan)相比，改(gai)(gai)(gai)(gai)性(xing)(xing)(xing)(xing)(xing)活(huo)(huo)(huo)(huo)(huo)(huo)性(xing)(xing)(xing)(xing)(xing)炭(tan)(tan)(tan)(tan)表(biao)(biao)(biao)現出許多(duo)孔(kong)(kong)隙(xi)和(he)(he)透明(ming)(ming)(ming)(ming)點(dian)，進一(yi)步表(biao)(biao)(biao)明(ming)(ming)(ming)(ming)表(biao)(biao)(biao)面(mian)(mian)積(ji)(ji)增(zeng)加(jia)。活(huo)(huo)(huo)(huo)(huo)(huo)性(xing)(xing)(xing)(xing)(xing)炭(tan)(tan)(tan)(tan)和(he)(he)改(gai)(gai)(gai)(gai)性(xing)(xing)(xing)(xing)(xing)活(huo)(huo)(huo)(huo)(huo)(huo)性(xing)(xing)(xing)(xing)(xing)炭(tan)(tan)(tan)(tan)EDS圖(tu)(tu)(tu)像(xiang)如(ru)圖(tu)(tu)(tu)1(e)和(he)(he)(f)所(suo)示。與活(huo)(huo)(huo)(huo)(huo)(huo)性(xing)(xing)(xing)(xing)(xing)炭(tan)(tan)(tan)(tan)相比，改(gai)(gai)(gai)(gai)性(xing)(xing)(xing)(xing)(xing)活(huo)(huo)(huo)(huo)(huo)(huo)性(xing)(xing)(xing)(xing)(xing)炭(tan)(tan)(tan)(tan)的(de)(de)(de)元素O和(he)(he)Fe含(han)(han)量(liang)顯(xian)(xian)著增(zeng)加(jia)，C活(huo)(huo)(huo)(huo)(huo)(huo)性(xing)(xing)(xing)(xing)(xing)炭(tan)(tan)(tan)(tan)上(shang)鐵(tie)(tie)離(li)子(zi)(zi)負荷的(de)(de)(de)含(han)(han)量(liang)降(jiang)低。此外，進一(yi)步證明(ming)(ming)(ming)(ming)表(biao)(biao)(biao)面(mian)(mian)含(han)(han)氧(yang)量(liang)增(zeng)加(jia)，有(you)(you)(you)利(li)于(yu)磺胺二(er)甲啶(ding)的(de)(de)(de)吸附(fu)。活(huo)(huo)(huo)(huo)(huo)(huo)性(xing)(xing)(xing)(xing)(xing)炭(tan)(tan)(tan)(tan)和(he)(he)改(gai)(gai)(gai)(gai)性(xing)(xing)(xing)(xing)(xing)活(huo)(huo)(huo)(huo)(huo)(huo)性(xing)(xing)(xing)(xing)(xing)炭(tan)(tan)(tan)(tan)XRD圖(tu)(tu)(tu)如(ru)圖(tu)(tu)(tu)1(g)和(he)(he)(h)所(suo)示。而且沒有(you)(you)(you)活(huo)(huo)(huo)(huo)(huo)(huo)性(xing)(xing)(xing)(xing)(xing)炭(tan)(tan)(tan)(tan)和(he)(he)改(gai)(gai)(gai)(gai)性(xing)(xing)(xing)(xing)(xing)活(huo)(huo)(huo)(huo)(huo)(huo)性(xing)(xing)(xing)(xing)(xing)炭(tan)(tan)(tan)(tan)的(de)(de)(de)明(ming)(ming)(ming)(ming)顯(xian)(xian)特(te)征峰值，說明(ming)(ming)(ming)(ming)它們是無(wu)形(xing)的(de)(de)(de)。這(zhe)與TEM照片結果一(yi)致(zhi)。

　　兩種(zhong)吸附(fu)劑的(de)代(dai)表性(xing)(xing)(xing)(xing)SEM，TEM和EDS圖像。(a)活(huo)性(xing)(xing)(xing)(xing)炭的(de)SEM(比例(li)尺(chi)為(wei)2μm)，(b)活(huo)性(xing)(xing)(xing)(xing)炭的(de)TEM(比例(li)尺(chi)為(wei)100nm)，(c)活(huo)性(xing)(xing)(xing)(xing)炭的(de)EDS，(d)改(gai)性(xing)(xing)(xing)(xing)活(huo)性(xing)(xing)(xing)(xing)炭SEM(比例(li)尺(chi)為(wei)2μm)，(e)改(gai)性(xing)(xing)(xing)(xing)活(huo)性(xing)(xing)(xing)(xing)炭TEM(比例(li)尺(chi)為(wei)100nm)，(f)改(gai)性(xing)(xing)(xing)(xing)活(huo)性(xing)(xing)(xing)(xing)炭EDS，(g)活(huo)性(xing)(xing)(xing)(xing)炭的(de)XRD，(h)改(gai)性(xing)(xing)(xing)(xing)活(huo)性(xing)(xing)(xing)(xing)炭XRD。

　　活(huo)性炭吸附磺(huang)胺的三個(ge)階(jie)段

　　活性(xing)炭和(he)(he)改性(xing)活性(xing)炭和(he)(he)改性(xing)活性(xing)炭上的(de)吸附(fu)(fu)(fu)和(he)(he)擴(kuo)(kuo)散(san)(san)過程(cheng)(cheng)可分三個階段描述，如(ru)圖2所示。由(you)于**階段吸附(fu)(fu)(fu)在(zai)活性(xing)炭表面(mian)，吸附(fu)(fu)(fu)率(lv)*初很高。然后，在(zai)顆粒內快(kuai)速擴(kuo)(kuo)散(san)(san)的(de)過程(cheng)(cheng)中，磺(huang)胺二甲啶(ding)逐漸吸附(fu)(fu)(fu)在(zai)活性(xing)炭上，吸附(fu)(fu)(fu)率(lv)常數逐漸降低(di)。在(zai)第(di)三階段，邊界層和(he)(he)傳質阻力(li)的(de)影響增(zeng)加(jia)，導致顆粒擴(kuo)(kuo)散(san)(san)減(jian)慢。所有(you)三個階段的(de)擬合方(fang)程(cheng)(cheng)都沒有(you)通過坐標的(de)原點，這(zhe)表明顆粒的(de)擴(kuo)(kuo)散(san)(san)并不是控(kong)制吸附(fu)(fu)(fu)率(lv)的(de)**步驟。因此，吸附(fu)(fu)(fu)過程(cheng)(cheng)也受膜擴(kuo)(kuo)散(san)(san)和(he)(he)表面(mian)吸附(fu)(fu)(fu)的(de)影響。

　　磺胺二甲啶(ding)在活性炭上吸附(fu)的顆(ke)粒(li)中擴散。

　　改(gai)性(xing)(xing)(xing)活(huo)性(xing)(xing)(xing)炭的表面顯示出許多孔隙和(he)透明(ming)度(du)，大量含氧官能團被改(gai)性(xing)(xing)(xing)，導(dao)致磺胺(an)二(er)甲啶吸(xi)(xi)附機制的變(bian)化(hua)。根(gen)據本研究的相(xiang)關研究結(jie)果，活(huo)性(xing)(xing)(xing)炭表面磺胺(an)二(er)甲啶的吸(xi)(xi)附機制總(zong)結(jie)如下（圖3）：

　　1.微孔捕獲

　　SEM圖像顯(xian)(xian)示(shi)(shi)，活(huo)性(xing)(xing)(xing)炭(tan)的(de)(de)規則孔結構受損，孔隙率(lv)增加。TEM圖像顯(xian)(xian)示(shi)(shi)，改(gai)性(xing)(xing)(xing)活(huo)性(xing)(xing)(xing)炭(tan)表面含有許(xu)多透明點，表明孔結構更(geng)發(fa)達，修(xiu)改(gai)后可獲(huo)得更(geng)多的(de)(de)吸(xi)附(fu)點。這有利于(yu)磺胺二甲啶吸(xi)附(fu)到黑碳分子層的(de)(de)孔中(zhong)。此外，經鐵(tie)離子改(gai)性(xing)(xing)(xing)后，活(huo)性(xing)(xing)(xing)炭(tan)的(de)(de)表面積(ji)、總孔容量、微孔體(ti)積(ji)和中(zhong)孔體(ti)積(ji)都有一定程度的(de)(de)增加。

　　2.氫鍵(jian)相互作用(yong)

　　通過FTIR通過促(cu)(cu)進(jin)改性(xing)活(huo)性(xing)炭表(biao)(biao)面與(yu)(yu)磺胺(an)二甲啶(ding)之間氫(qing)鍵的相互作用，促(cu)(cu)進(jin)磺胺(an)二甲啶(ding)的吸附。從數據(ju)圖中發現(xian)，3400和2850cm-1處(chu)寬吸收(shou)峰表(biao)(biao)明改性(xing)活(huo)性(xing)炭表(biao)(biao)面存在-OH。這些(xie)分子間氫(qing)鍵增強了磺胺(an)二甲啶(ding)與(yu)(yu)活(huo)性(xing)炭的表(biao)(biao)面相互作用，預(yu)計(ji)將有助(zhu)于活(huo)性(xing)炭與(yu)(yu)異磺胺(an)二甲啶(ding)之間的親(qin)和力吸附。

　　3.π-π電(dian)子(zi)供體-受體(EDA)相(xiang)互作用。

　　磺(huang)胺二甲啶與改性(xing)活性(xing)炭合理相互作(zuo)用的示意(yi)圖。1.微孔捕(bu)獲。2.氫鍵相互作(zuo)用。.π-πEDA相互作(zuo)用。4.靜(jing)電(dian)相互作(zuo)用。5.配位(wei)相互作(zuo)用。

　　鐵離子改性后(hou)，活(huo)性炭(tan)(tan)活(huo)性炭(tan)(tan)的(de)表面積(ji)、總孔容量(liang)、微孔體積(ji)和(he)中孔體積(ji)。含(han)氧加(jia)了活(huo)性炭(tan)(tan)表面含(han)氧官能(neng)團(tuan)的(de)數量(liang)，可以大大提高吸(xi)(xi)附(fu)(fu)(fu)(fu)能(neng)力。磺(huang)(huang)(huang)胺(an)(an)(an)二(er)甲嘧啶(ding)(ding)在(zai)改性活(huo)性炭(tan)(tan)上(shang)去除磺(huang)(huang)(huang)胺(an)(an)(an)廢水中顯(xian)著增加(jia)，并在(zai)25℃下磺(huang)(huang)(huang)胺(an)(an)(an)二(er)甲嘧啶(ding)(ding)在(zai)改性活(huo)性炭(tan)(tan)上(shang)的(de)*大吸(xi)(xi)附(fu)(fu)(fu)(fu)量(liang)為17.261mg/g。然(ran)而，吸(xi)(xi)附(fu)(fu)(fu)(fu)平衡時(shi)間(jian)幾(ji)乎保(bao)持不變(bian)。磺(huang)(huang)(huang)胺(an)(an)(an)二(er)甲啶(ding)(ding)在(zai)原始和(he)改性活(huo)性炭(tan)(tan)上(shang)的(de)吸(xi)(xi)附(fu)(fu)(fu)(fu)動力學分為快(kuai)速和(he)慢速吸(xi)(xi)附(fu)(fu)(fu)(fu)階段，磺(huang)(huang)(huang)胺(an)(an)(an)二(er)甲啶(ding)(ding)吸(xi)(xi)附(fu)(fu)(fu)(fu)在(zai)12小時(shi)內快(kuai)速完成。pH該(gai)值對磺(huang)(huang)(huang)胺(an)(an)(an)二(er)甲啶(ding)(ding)的(de)吸(xi)(xi)附(fu)(fu)(fu)(fu)有顯(xian)著影響(xiang)。當pH磺(huang)(huang)(huang)胺(an)(an)(an)二(er)甲啶(ding)(ding)的(de)吸(xi)(xi)附(fu)(fu)(fu)(fu)量(liang)在(zai)3-10之(zhi)間(jian)增加(jia)，然(ran)后(hou)減少。微孔捕獲，靜電相互(hu)作(zuo)用(yong)，氫鍵相互(hu)作(zuo)用(yong)，π-πEDA相互(hu)作(zuo)用(yong)和(he)配位相互(hu)作(zuo)用(yong)是吸(xi)(xi)附(fu)(fu)(fu)(fu)的(de)可能(neng)機制。降低(di)溫度促(cu)進吸(xi)(xi)附(fu)(fu)(fu)(fu)反應。pH該(gai)值對磺(huang)(huang)(huang)胺(an)(an)(an)二(er)甲啶(ding)(ding)的(de)吸(xi)(xi)附(fu)(fu)(fu)(fu)有顯(xian)著影響(xiang)。當pH磺(huang)(huang)(huang)胺(an)(an)(an)二(er)甲啶(ding)(ding)的(de)吸(xi)(xi)附(fu)(fu)(fu)(fu)量(liang)在(zai)3-10之(zhi)間(jian)增加(jia)，然(ran)后(hou)減少。