活性炭改(gai)性后(hou)處理磺胺廢水(shui)

　　磺胺廢水經(jing)(jing)活(huo)性(xing)(xing)(xing)(xing)炭改性(xing)(xing)(xing)(xing)后(hou)處(chu)理，活(huo)性(xing)(xing)(xing)(xing)炭經(jing)(jing)氯(lv)(lv)化鐵(tie)改性(xing)(xing)(xing)(xing)。并進(jin)行(xing)批量(liang)實(shi)驗以評估廢水中(zhong)的(de)磺胺二甲嘧(mi)啶(ding)吸附到活(huo)性(xing)(xing)(xing)(xing)炭和改性(xing)(xing)(xing)(xing)活(huo)性(xing)(xing)(xing)(xing)炭上(shang)的(de)平(ping)衡(heng)，分別分析(xi)動力學和熱(re)力學特征。結果表明，氯(lv)(lv)化鐵(tie)處(chu)理后(hou)，活(huo)性(xing)(xing)(xing)(xing)炭改變了(le)表面積(ji)(ji)、孔隙體(ti)積(ji)(ji)和表面zeta電位(wei)還增加了(le)表面含氧官能團(tuan)的(de)數量(liang)。經(jing)(jing)試驗發現(xian)，磺胺二甲啶(ding)在改性(xing)(xing)(xing)(xing)活(huo)性(xing)(xing)(xing)(xing)炭上(shang)的(de)吸附得到了(le)顯著改善。

　　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(neng)有效去(qu)除(chu)(chu)顏色、氣味、無(wu)機(ji)化合(he)物和(he)(he)大多數有機(ji)污(wu)染物。但(dan)其在實際應用中(zhong)的(de)(de)使用受(shou)其吸(xi)附(fu)(fu)效率和(he)(he)成本(ben)低的(de)(de)限制(zhi)。金屬離子改性(xing)(xing)后的(de)(de)活性(xing)(xing)炭(tan)(tan)(tan)生產簡(jian)單(dan)便(bian)宜，能(neng)顯著提(ti)(ti)高活性(xing)(xing)炭(tan)(tan)(tan)的(de)(de)吸(xi)附(fu)(fu)性(xing)(xing)能(neng)。然而，活性(xing)(xing)炭(tan)(tan)(tan)中(zhong)磺胺(an)類廢(fei)水(shui)的(de)(de)吸(xi)附(fu)(fu)機(ji)制(zhi)尚(shang)不(bu)清楚，對磺胺(an)類的(de)(de)吸(xi)附(fu)(fu)能(neng)力及其理化性(xing)(xing)質(zhi)知之甚少。本(ben)研究采用鐵離子改性(xing)(xing)活性(xing)(xing)炭(tan)(tan)(tan)。用于探索吸(xi)附(fu)(fu)機(ji)制(zhi)的(de)(de)批量吸(xi)附(fu)(fu)實驗。磺胺(an)二甲啶對活性(xing)(xing)炭(tan)(tan)(tan)和(he)(he)改性(xing)(xing)活性(xing)(xing)炭(tan)(tan)(tan)的(de)(de)吸(xi)附(fu)(fu)特(te)性(xing)(xing)通過吸(xi)附(fu)(fu)動力學、吸(xi)附(fu)(fu)熱力學和(he)(he)吸(xi)附(fu)(fu)等溫線進行了(le)研究，為去(qu)除(chu)(chu)廢(fei)水(shui)中(zhong)的(de)(de)磺胺(an)污(wu)染物提(ti)(ti)供了(le)科學依據。

　　活(huo)性(xing)炭改性(xing)后的特性(xing)

　　活(huo)(huo)(huo)(huo)(huo)(huo)(huo)性(xing)(xing)(xing)(xing)(xing)(xing)炭(tan)(tan)(tan)(tan)(tan)和(he)(he)改(gai)(gai)性(xing)(xing)(xing)(xing)(xing)(xing)活(huo)(huo)(huo)(huo)(huo)(huo)(huo)性(xing)(xing)(xing)(xing)(xing)(xing)炭(tan)(tan)(tan)(tan)(tan)的(de)(de)(de)(de)(de)化學(xue)結(jie)(jie)(jie)構和(he)(he)物理化學(xue)性(xing)(xing)(xing)(xing)(xing)(xing)質差異(yi)很(hen)大。鐵離(li)子(zi)改(gai)(gai)性(xing)(xing)(xing)(xing)(xing)(xing)后(hou)，活(huo)(huo)(huo)(huo)(huo)(huo)(huo)性(xing)(xing)(xing)(xing)(xing)(xing)炭(tan)(tan)(tan)(tan)(tan)的(de)(de)(de)(de)(de)表(biao)(biao)面(mian)(mian)積、總(zong)孔(kong)(kong)(kong)(kong)容量(liang)(liang)、微(wei)(wei)孔(kong)(kong)(kong)(kong)體積和(he)(he)中(zhong)孔(kong)(kong)(kong)(kong)體積都(dou)有(you)一(yi)(yi)(yi)定程度(du)的(de)(de)(de)(de)(de)增加，可以為(wei)磺胺二甲啶提供更多的(de)(de)(de)(de)(de)吸附點(dian)。由(you)于(yu)改(gai)(gai)性(xing)(xing)(xing)(xing)(xing)(xing)，活(huo)(huo)(huo)(huo)(huo)(huo)(huo)性(xing)(xing)(xing)(xing)(xing)(xing)炭(tan)(tan)(tan)(tan)(tan)的(de)(de)(de)(de)(de)微(wei)(wei)孔(kong)(kong)(kong)(kong)結(jie)(jie)(jie)構可能會產(chan)生(sheng)較大的(de)(de)(de)(de)(de)比(bi)表(biao)(biao)面(mian)(mian)積。在活(huo)(huo)(huo)(huo)(huo)(huo)(huo)化過(guo)程中(zhong)，鐵離(li)子(zi)主(zhu)要沉(chen)積在介(jie)孔(kong)(kong)(kong)(kong)中(zhong)，擴大孔(kong)(kong)(kong)(kong)徑并(bing)(bing)進(jin)入微(wei)(wei)孔(kong)(kong)(kong)(kong)。將金屬(shu)鹽釋放(fang)的(de)(de)(de)(de)(de)氧化氣(qi)體引入微(wei)(wei)孔(kong)(kong)(kong)(kong)，并(bing)(bing)與(yu)微(wei)(wei)孔(kong)(kong)(kong)(kong)碳(tan)壁(bi)反應(ying)。活(huo)(huo)(huo)(huo)(huo)(huo)(huo)性(xing)(xing)(xing)(xing)(xing)(xing)炭(tan)(tan)(tan)(tan)(tan)和(he)(he)改(gai)(gai)性(xing)(xing)(xing)(xing)(xing)(xing)活(huo)(huo)(huo)(huo)(huo)(huo)(huo)性(xing)(xing)(xing)(xing)(xing)(xing)炭(tan)(tan)(tan)(tan)(tan)SEM圖(tu)(tu)(tu)1顯(xian)(xian)示(shi)(shi)(shi)圖(tu)(tu)(tu)像(a)和(he)(he)(b)中(zhong)。活(huo)(huo)(huo)(huo)(huo)(huo)(huo)性(xing)(xing)(xing)(xing)(xing)(xing)炭(tan)(tan)(tan)(tan)(tan)的(de)(de)(de)(de)(de)形狀表(biao)(biao)明(ming)具有(you)規(gui)則(ze)孔(kong)(kong)(kong)(kong)結(jie)(jie)(jie)構的(de)(de)(de)(de)(de)光滑表(biao)(biao)面(mian)(mian)。與(yu)活(huo)(huo)(huo)(huo)(huo)(huo)(huo)性(xing)(xing)(xing)(xing)(xing)(xing)炭(tan)(tan)(tan)(tan)(tan)相比(bi)，改(gai)(gai)性(xing)(xing)(xing)(xing)(xing)(xing)活(huo)(huo)(huo)(huo)(huo)(huo)(huo)性(xing)(xing)(xing)(xing)(xing)(xing)炭(tan)(tan)(tan)(tan)(tan)表(biao)(biao)面(mian)(mian)粗糙不(bu)規(gui)則(ze)。孔(kong)(kong)(kong)(kong)隙(xi)結(jie)(jie)(jie)構受損(sun)，孔(kong)(kong)(kong)(kong)隙(xi)率增加。這可能是由(you)于(yu)鐵離(li)子(zi)引入活(huo)(huo)(huo)(huo)(huo)(huo)(huo)性(xing)(xing)(xing)(xing)(xing)(xing)炭(tan)(tan)(tan)(tan)(tan)內孔(kong)(kong)(kong)(kong)，導致碳(tan)壁(bi)氧化和(he)(he)孔(kong)(kong)(kong)(kong)徑增加。活(huo)(huo)(huo)(huo)(huo)(huo)(huo)性(xing)(xing)(xing)(xing)(xing)(xing)炭(tan)(tan)(tan)(tan)(tan)中(zhong)磺胺二甲啶的(de)(de)(de)(de)(de)擴散(san)有(you)利(li)于(yu)粗糙的(de)(de)(de)(de)(de)表(biao)(biao)面(mian)(mian)結(jie)(jie)(jie)構和(he)(he)多孔(kong)(kong)(kong)(kong)特性(xing)(xing)(xing)(xing)(xing)(xing)。活(huo)(huo)(huo)(huo)(huo)(huo)(huo)性(xing)(xing)(xing)(xing)(xing)(xing)炭(tan)(tan)(tan)(tan)(tan)和(he)(he)改(gai)(gai)性(xing)(xing)(xing)(xing)(xing)(xing)活(huo)(huo)(huo)(huo)(huo)(huo)(huo)性(xing)(xing)(xing)(xing)(xing)(xing)炭(tan)(tan)(tan)(tan)(tan)TEM圖(tu)(tu)(tu)像如圖(tu)(tu)(tu)1(c)和(he)(he)(d)所示(shi)(shi)(shi)。這些圖(tu)(tu)(tu)片表(biao)(biao)明(ming)活(huo)(huo)(huo)(huo)(huo)(huo)(huo)性(xing)(xing)(xing)(xing)(xing)(xing)炭(tan)(tan)(tan)(tan)(tan)是無定形的(de)(de)(de)(de)(de)。與(yu)活(huo)(huo)(huo)(huo)(huo)(huo)(huo)性(xing)(xing)(xing)(xing)(xing)(xing)炭(tan)(tan)(tan)(tan)(tan)相比(bi)，改(gai)(gai)性(xing)(xing)(xing)(xing)(xing)(xing)活(huo)(huo)(huo)(huo)(huo)(huo)(huo)性(xing)(xing)(xing)(xing)(xing)(xing)炭(tan)(tan)(tan)(tan)(tan)表(biao)(biao)現出許多孔(kong)(kong)(kong)(kong)隙(xi)和(he)(he)透明(ming)點(dian)，進(jin)一(yi)(yi)(yi)步表(biao)(biao)明(ming)表(biao)(biao)面(mian)(mian)積增加。活(huo)(huo)(huo)(huo)(huo)(huo)(huo)性(xing)(xing)(xing)(xing)(xing)(xing)炭(tan)(tan)(tan)(tan)(tan)和(he)(he)改(gai)(gai)性(xing)(xing)(xing)(xing)(xing)(xing)活(huo)(huo)(huo)(huo)(huo)(huo)(huo)性(xing)(xing)(xing)(xing)(xing)(xing)炭(tan)(tan)(tan)(tan)(tan)EDS圖(tu)(tu)(tu)像如圖(tu)(tu)(tu)1(e)和(he)(he)(f)所示(shi)(shi)(shi)。與(yu)活(huo)(huo)(huo)(huo)(huo)(huo)(huo)性(xing)(xing)(xing)(xing)(xing)(xing)炭(tan)(tan)(tan)(tan)(tan)相比(bi)，改(gai)(gai)性(xing)(xing)(xing)(xing)(xing)(xing)活(huo)(huo)(huo)(huo)(huo)(huo)(huo)性(xing)(xing)(xing)(xing)(xing)(xing)炭(tan)(tan)(tan)(tan)(tan)的(de)(de)(de)(de)(de)元素O和(he)(he)Fe含量(liang)(liang)顯(xian)(xian)著增加，C活(huo)(huo)(huo)(huo)(huo)(huo)(huo)性(xing)(xing)(xing)(xing)(xing)(xing)炭(tan)(tan)(tan)(tan)(tan)上鐵離(li)子(zi)負荷的(de)(de)(de)(de)(de)含量(liang)(liang)降(jiang)低(di)。此外，進(jin)一(yi)(yi)(yi)步證(zheng)明(ming)表(biao)(biao)面(mian)(mian)含氧量(liang)(liang)增加，有(you)利(li)于(yu)磺胺二甲啶的(de)(de)(de)(de)(de)吸附。活(huo)(huo)(huo)(huo)(huo)(huo)(huo)性(xing)(xing)(xing)(xing)(xing)(xing)炭(tan)(tan)(tan)(tan)(tan)和(he)(he)改(gai)(gai)性(xing)(xing)(xing)(xing)(xing)(xing)活(huo)(huo)(huo)(huo)(huo)(huo)(huo)性(xing)(xing)(xing)(xing)(xing)(xing)炭(tan)(tan)(tan)(tan)(tan)XRD圖(tu)(tu)(tu)如圖(tu)(tu)(tu)1(g)和(he)(he)(h)所示(shi)(shi)(shi)。而且沒有(you)活(huo)(huo)(huo)(huo)(huo)(huo)(huo)性(xing)(xing)(xing)(xing)(xing)(xing)炭(tan)(tan)(tan)(tan)(tan)和(he)(he)改(gai)(gai)性(xing)(xing)(xing)(xing)(xing)(xing)活(huo)(huo)(huo)(huo)(huo)(huo)(huo)性(xing)(xing)(xing)(xing)(xing)(xing)炭(tan)(tan)(tan)(tan)(tan)的(de)(de)(de)(de)(de)明(ming)顯(xian)(xian)特征峰值，說明(ming)它們(men)是無形的(de)(de)(de)(de)(de)。這與(yu)TEM照片結(jie)(jie)(jie)果一(yi)(yi)(yi)致。

　　兩(liang)種(zhong)吸附劑的(de)(de)代表性(xing)(xing)SEM，TEM和(he)EDS圖像(xiang)。(a)活(huo)性(xing)(xing)炭(tan)的(de)(de)SEM(比例(li)尺(chi)(chi)為(wei)(wei)2μm)，(b)活(huo)性(xing)(xing)炭(tan)的(de)(de)TEM(比例(li)尺(chi)(chi)為(wei)(wei)100nm)，(c)活(huo)性(xing)(xing)炭(tan)的(de)(de)EDS，(d)改性(xing)(xing)活(huo)性(xing)(xing)炭(tan)SEM(比例(li)尺(chi)(chi)為(wei)(wei)2μm)，(e)改性(xing)(xing)活(huo)性(xing)(xing)炭(tan)TEM(比例(li)尺(chi)(chi)為(wei)(wei)100nm)，(f)改性(xing)(xing)活(huo)性(xing)(xing)炭(tan)EDS，(g)活(huo)性(xing)(xing)炭(tan)的(de)(de)XRD，(h)改性(xing)(xing)活(huo)性(xing)(xing)炭(tan)XRD。

　　活(huo)性(xing)炭吸(xi)附磺胺(an)的三個階段(duan)

　　活(huo)性炭(tan)和(he)改性活(huo)性炭(tan)和(he)改性活(huo)性炭(tan)上的(de)吸(xi)附(fu)和(he)擴散(san)(san)過程可分三個(ge)階段(duan)描述，如圖2所(suo)示(shi)。由于**階段(duan)吸(xi)附(fu)在(zai)(zai)活(huo)性炭(tan)表面，吸(xi)附(fu)率(lv)*初很高。然后，在(zai)(zai)顆(ke)粒(li)內快速擴散(san)(san)的(de)過程中，磺(huang)胺二甲啶逐漸(jian)吸(xi)附(fu)在(zai)(zai)活(huo)性炭(tan)上，吸(xi)附(fu)率(lv)常數逐漸(jian)降(jiang)低。在(zai)(zai)第三階段(duan)，邊界層和(he)傳質阻(zu)力的(de)影響(xiang)增加，導致(zhi)顆(ke)粒(li)擴散(san)(san)減(jian)慢。所(suo)有(you)三個(ge)階段(duan)的(de)擬合(he)方程都沒有(you)通過坐標(biao)的(de)原點，這表明(ming)顆(ke)粒(li)的(de)擴散(san)(san)并不是控制(zhi)吸(xi)附(fu)率(lv)的(de)**步驟(zou)。因此(ci)，吸(xi)附(fu)過程也(ye)受膜擴散(san)(san)和(he)表面吸(xi)附(fu)的(de)影響(xiang)。

　　磺胺(an)二甲啶在(zai)活性(xing)炭上(shang)吸附的(de)顆粒(li)中擴散。

　　改(gai)性活(huo)性炭的表面顯(xian)示出(chu)許多孔隙(xi)和透明度，大量含氧官能團被改(gai)性，導致磺胺二(er)甲啶吸附機制的變化。根據本研究的相關(guan)研究結果，活(huo)性炭表面磺胺二(er)甲啶的吸附機制總結如下（圖3）：

　　1.微孔捕獲

　　SEM圖像(xiang)顯示，活(huo)性(xing)(xing)(xing)(xing)炭的(de)規則孔(kong)結構(gou)受損，孔(kong)隙率增(zeng)(zeng)加。TEM圖像(xiang)顯示，改性(xing)(xing)(xing)(xing)活(huo)性(xing)(xing)(xing)(xing)炭表面含有許(xu)多(duo)透明點(dian)，表明孔(kong)結構(gou)更發達，修改后可獲得更多(duo)的(de)吸(xi)附點(dian)。這(zhe)有利于磺(huang)胺二甲(jia)啶吸(xi)附到黑碳分(fen)子(zi)層的(de)孔(kong)中。此外，經鐵離(li)子(zi)改性(xing)(xing)(xing)(xing)后，活(huo)性(xing)(xing)(xing)(xing)炭的(de)表面積(ji)、總孔(kong)容(rong)量、微孔(kong)體(ti)積(ji)和(he)中孔(kong)體(ti)積(ji)都有一定程度的(de)增(zeng)(zeng)加。

　　2.氫鍵相互作(zuo)用(yong)

　　通(tong)過FTIR通(tong)過促進(jin)(jin)改性(xing)活(huo)(huo)性(xing)炭(tan)(tan)表(biao)面與磺胺(an)二(er)甲啶(ding)之(zhi)間(jian)氫鍵的相互作用，促進(jin)(jin)磺胺(an)二(er)甲啶(ding)的吸(xi)附。從數據(ju)圖中發(fa)現(xian)，3400和2850cm-1處寬吸(xi)收峰表(biao)明(ming)改性(xing)活(huo)(huo)性(xing)炭(tan)(tan)表(biao)面存在(zai)-OH。這些分(fen)子間(jian)氫鍵增強(qiang)了磺胺(an)二(er)甲啶(ding)與活(huo)(huo)性(xing)炭(tan)(tan)的表(biao)面相互作用，預計將有(you)助于活(huo)(huo)性(xing)炭(tan)(tan)與異磺胺(an)二(er)甲啶(ding)之(zhi)間(jian)的親和力吸(xi)附。

　　3.π-π電(dian)子供(gong)體-受體(EDA)相互(hu)作用。

　　磺(huang)胺二甲啶(ding)與改性活(huo)性炭合理相(xiang)互(hu)(hu)作用(yong)的示意圖。1.微孔捕獲。2.氫(qing)鍵相(xiang)互(hu)(hu)作用(yong)。.π-πEDA相(xiang)互(hu)(hu)作用(yong)。4.靜電相(xiang)互(hu)(hu)作用(yong)。5.配(pei)位相(xiang)互(hu)(hu)作用(yong)。

　　鐵(tie)離子(zi)改(gai)性(xing)后(hou)，活(huo)性(xing)炭(tan)活(huo)性(xing)炭(tan)的(de)(de)表面(mian)積、總(zong)孔(kong)容量(liang)、微孔(kong)體積和中(zhong)(zhong)孔(kong)體積。含氧加了活(huo)性(xing)炭(tan)表面(mian)含氧官能團(tuan)的(de)(de)數量(liang)，可以大(da)大(da)提高吸(xi)(xi)(xi)(xi)(xi)(xi)(xi)附能力。磺(huang)(huang)胺(an)(an)(an)二(er)甲(jia)(jia)(jia)嘧啶在(zai)(zai)(zai)改(gai)性(xing)活(huo)性(xing)炭(tan)上(shang)去除磺(huang)(huang)胺(an)(an)(an)廢(fei)水中(zhong)(zhong)顯著增加，并在(zai)(zai)(zai)25℃下磺(huang)(huang)胺(an)(an)(an)二(er)甲(jia)(jia)(jia)嘧啶在(zai)(zai)(zai)改(gai)性(xing)活(huo)性(xing)炭(tan)上(shang)的(de)(de)*大(da)吸(xi)(xi)(xi)(xi)(xi)(xi)(xi)附量(liang)為(wei)17.261mg/g。然而，吸(xi)(xi)(xi)(xi)(xi)(xi)(xi)附平衡時(shi)間幾乎保持不變。磺(huang)(huang)胺(an)(an)(an)二(er)甲(jia)(jia)(jia)啶在(zai)(zai)(zai)原(yuan)始(shi)和改(gai)性(xing)活(huo)性(xing)炭(tan)上(shang)的(de)(de)吸(xi)(xi)(xi)(xi)(xi)(xi)(xi)附動力學分(fen)為(wei)快速(su)(su)和慢速(su)(su)吸(xi)(xi)(xi)(xi)(xi)(xi)(xi)附階(jie)段，磺(huang)(huang)胺(an)(an)(an)二(er)甲(jia)(jia)(jia)啶吸(xi)(xi)(xi)(xi)(xi)(xi)(xi)附在(zai)(zai)(zai)12小時(shi)內(nei)快速(su)(su)完成。pH該(gai)值對磺(huang)(huang)胺(an)(an)(an)二(er)甲(jia)(jia)(jia)啶的(de)(de)吸(xi)(xi)(xi)(xi)(xi)(xi)(xi)附有顯著影響。當pH磺(huang)(huang)胺(an)(an)(an)二(er)甲(jia)(jia)(jia)啶的(de)(de)吸(xi)(xi)(xi)(xi)(xi)(xi)(xi)附量(liang)在(zai)(zai)(zai)3-10之間增加，然后(hou)減少。微孔(kong)捕獲，靜(jing)電相(xiang)互作(zuo)(zuo)用(yong)，氫(qing)鍵(jian)相(xiang)互作(zuo)(zuo)用(yong)，π-πEDA相(xiang)互作(zuo)(zuo)用(yong)和配位相(xiang)互作(zuo)(zuo)用(yong)是吸(xi)(xi)(xi)(xi)(xi)(xi)(xi)附的(de)(de)可能機制。降低溫(wen)度(du)促進吸(xi)(xi)(xi)(xi)(xi)(xi)(xi)附反(fan)應。pH該(gai)值對磺(huang)(huang)胺(an)(an)(an)二(er)甲(jia)(jia)(jia)啶的(de)(de)吸(xi)(xi)(xi)(xi)(xi)(xi)(xi)附有顯著影響。當pH磺(huang)(huang)胺(an)(an)(an)二(er)甲(jia)(jia)(jia)啶的(de)(de)吸(xi)(xi)(xi)(xi)(xi)(xi)(xi)附量(liang)在(zai)(zai)(zai)3-10之間增加，然后(hou)減少。