活性炭改(gai)性后處(chu)理磺(huang)胺(an)廢(fei)水

　　磺胺(an)廢(fei)水(shui)經活(huo)性(xing)(xing)炭(tan)改(gai)性(xing)(xing)后處(chu)理(li)，活(huo)性(xing)(xing)炭(tan)經氯(lv)(lv)化鐵改(gai)性(xing)(xing)。并進行批量(liang)實驗以評估廢(fei)水(shui)中(zhong)的(de)磺胺(an)二(er)甲嘧(mi)啶(ding)吸附(fu)到(dao)活(huo)性(xing)(xing)炭(tan)和改(gai)性(xing)(xing)活(huo)性(xing)(xing)炭(tan)上的(de)平衡，分別分析(xi)動(dong)力(li)學和熱力(li)學特(te)征。結果表明，氯(lv)(lv)化鐵處(chu)理(li)后，活(huo)性(xing)(xing)炭(tan)改(gai)變了(le)表面積(ji)、孔隙(xi)體積(ji)和表面zeta電位還增(zeng)加了(le)表面含氧官能團的(de)數量(liang)。經試(shi)驗發現，磺胺(an)二(er)甲啶(ding)在改(gai)性(xing)(xing)活(huo)性(xing)(xing)炭(tan)上的(de)吸附(fu)得到(dao)了(le)顯著改(gai)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(you)效去除顏色、氣味、無機化合物(wu)和大(da)多數有(you)機污(wu)(wu)染物(wu)。但其(qi)在(zai)實(shi)際(ji)應用中的(de)使用受其(qi)吸(xi)(xi)(xi)(xi)附(fu)(fu)(fu)效率和成(cheng)本(ben)低的(de)限制(zhi)。金屬(shu)離(li)子(zi)改(gai)性(xing)(xing)(xing)后(hou)的(de)活(huo)(huo)性(xing)(xing)(xing)炭(tan)生產簡單便宜(yi)，能(neng)顯著(zhu)提高活(huo)(huo)性(xing)(xing)(xing)炭(tan)的(de)吸(xi)(xi)(xi)(xi)附(fu)(fu)(fu)性(xing)(xing)(xing)能(neng)。然而，活(huo)(huo)性(xing)(xing)(xing)炭(tan)中磺(huang)(huang)胺類廢水的(de)吸(xi)(xi)(xi)(xi)附(fu)(fu)(fu)機制(zhi)尚不清(qing)楚(chu)，對磺(huang)(huang)胺類的(de)吸(xi)(xi)(xi)(xi)附(fu)(fu)(fu)能(neng)力(li)及(ji)其(qi)理(li)化性(xing)(xing)(xing)質知之(zhi)甚少(shao)。本(ben)研(yan)究(jiu)采用鐵離(li)子(zi)改(gai)性(xing)(xing)(xing)活(huo)(huo)性(xing)(xing)(xing)炭(tan)。用于探索吸(xi)(xi)(xi)(xi)附(fu)(fu)(fu)機制(zhi)的(de)批量吸(xi)(xi)(xi)(xi)附(fu)(fu)(fu)實(shi)驗。磺(huang)(huang)胺二甲啶對活(huo)(huo)性(xing)(xing)(xing)炭(tan)和改(gai)性(xing)(xing)(xing)活(huo)(huo)性(xing)(xing)(xing)炭(tan)的(de)吸(xi)(xi)(xi)(xi)附(fu)(fu)(fu)特(te)性(xing)(xing)(xing)通過吸(xi)(xi)(xi)(xi)附(fu)(fu)(fu)動力(li)學(xue)(xue)、吸(xi)(xi)(xi)(xi)附(fu)(fu)(fu)熱力(li)學(xue)(xue)和吸(xi)(xi)(xi)(xi)附(fu)(fu)(fu)等溫線進行了研(yan)究(jiu)，為去除廢水中的(de)磺(huang)(huang)胺污(wu)(wu)染物(wu)提供了科學(xue)(xue)依據。

　　活性(xing)(xing)炭改性(xing)(xing)后(hou)的特性(xing)(xing)

　　活(huo)(huo)(huo)(huo)(huo)(huo)(huo)(huo)(huo)性(xing)(xing)(xing)(xing)(xing)(xing)炭(tan)(tan)(tan)(tan)(tan)(tan)(tan)和(he)(he)(he)(he)(he)改(gai)(gai)性(xing)(xing)(xing)(xing)(xing)(xing)活(huo)(huo)(huo)(huo)(huo)(huo)(huo)(huo)(huo)性(xing)(xing)(xing)(xing)(xing)(xing)炭(tan)(tan)(tan)(tan)(tan)(tan)(tan)的(de)(de)(de)化(hua)學結(jie)(jie)構(gou)和(he)(he)(he)(he)(he)物理(li)化(hua)學性(xing)(xing)(xing)(xing)(xing)(xing)質差(cha)異很大。鐵(tie)離子改(gai)(gai)性(xing)(xing)(xing)(xing)(xing)(xing)后(hou)，活(huo)(huo)(huo)(huo)(huo)(huo)(huo)(huo)(huo)性(xing)(xing)(xing)(xing)(xing)(xing)炭(tan)(tan)(tan)(tan)(tan)(tan)(tan)的(de)(de)(de)表(biao)(biao)面(mian)(mian)積(ji)、總(zong)孔(kong)(kong)容量(liang)、微孔(kong)(kong)體積(ji)和(he)(he)(he)(he)(he)中孔(kong)(kong)體積(ji)都有一(yi)定(ding)(ding)程度的(de)(de)(de)增(zeng)加(jia)(jia)，可以為(wei)磺胺(an)二(er)甲啶(ding)提供更多(duo)的(de)(de)(de)吸附點。由于(yu)改(gai)(gai)性(xing)(xing)(xing)(xing)(xing)(xing)，活(huo)(huo)(huo)(huo)(huo)(huo)(huo)(huo)(huo)性(xing)(xing)(xing)(xing)(xing)(xing)炭(tan)(tan)(tan)(tan)(tan)(tan)(tan)的(de)(de)(de)微孔(kong)(kong)結(jie)(jie)構(gou)可能會產生較大的(de)(de)(de)比表(biao)(biao)面(mian)(mian)積(ji)。在(zai)活(huo)(huo)(huo)(huo)(huo)(huo)(huo)(huo)(huo)化(hua)過程中，鐵(tie)離子主要沉積(ji)在(zai)介孔(kong)(kong)中，擴大孔(kong)(kong)徑并進(jin)入(ru)微孔(kong)(kong)。將金屬鹽釋放的(de)(de)(de)氧化(hua)氣體引(yin)入(ru)微孔(kong)(kong)，并與(yu)微孔(kong)(kong)碳壁(bi)反應。活(huo)(huo)(huo)(huo)(huo)(huo)(huo)(huo)(huo)性(xing)(xing)(xing)(xing)(xing)(xing)炭(tan)(tan)(tan)(tan)(tan)(tan)(tan)和(he)(he)(he)(he)(he)改(gai)(gai)性(xing)(xing)(xing)(xing)(xing)(xing)活(huo)(huo)(huo)(huo)(huo)(huo)(huo)(huo)(huo)性(xing)(xing)(xing)(xing)(xing)(xing)炭(tan)(tan)(tan)(tan)(tan)(tan)(tan)SEM圖(tu)1顯(xian)(xian)示(shi)圖(tu)像(a)和(he)(he)(he)(he)(he)(b)中。活(huo)(huo)(huo)(huo)(huo)(huo)(huo)(huo)(huo)性(xing)(xing)(xing)(xing)(xing)(xing)炭(tan)(tan)(tan)(tan)(tan)(tan)(tan)的(de)(de)(de)形狀表(biao)(biao)明(ming)(ming)具有規則(ze)孔(kong)(kong)結(jie)(jie)構(gou)的(de)(de)(de)光(guang)滑表(biao)(biao)面(mian)(mian)。與(yu)活(huo)(huo)(huo)(huo)(huo)(huo)(huo)(huo)(huo)性(xing)(xing)(xing)(xing)(xing)(xing)炭(tan)(tan)(tan)(tan)(tan)(tan)(tan)相比，改(gai)(gai)性(xing)(xing)(xing)(xing)(xing)(xing)活(huo)(huo)(huo)(huo)(huo)(huo)(huo)(huo)(huo)性(xing)(xing)(xing)(xing)(xing)(xing)炭(tan)(tan)(tan)(tan)(tan)(tan)(tan)表(biao)(biao)面(mian)(mian)粗(cu)(cu)糙不(bu)規則(ze)。孔(kong)(kong)隙(xi)結(jie)(jie)構(gou)受損(sun)，孔(kong)(kong)隙(xi)率增(zeng)加(jia)(jia)。這可能是(shi)由于(yu)鐵(tie)離子引(yin)入(ru)活(huo)(huo)(huo)(huo)(huo)(huo)(huo)(huo)(huo)性(xing)(xing)(xing)(xing)(xing)(xing)炭(tan)(tan)(tan)(tan)(tan)(tan)(tan)內孔(kong)(kong)，導致碳壁(bi)氧化(hua)和(he)(he)(he)(he)(he)孔(kong)(kong)徑增(zeng)加(jia)(jia)。活(huo)(huo)(huo)(huo)(huo)(huo)(huo)(huo)(huo)性(xing)(xing)(xing)(xing)(xing)(xing)炭(tan)(tan)(tan)(tan)(tan)(tan)(tan)中磺胺(an)二(er)甲啶(ding)的(de)(de)(de)擴散有利(li)于(yu)粗(cu)(cu)糙的(de)(de)(de)表(biao)(biao)面(mian)(mian)結(jie)(jie)構(gou)和(he)(he)(he)(he)(he)多(duo)孔(kong)(kong)特性(xing)(xing)(xing)(xing)(xing)(xing)。活(huo)(huo)(huo)(huo)(huo)(huo)(huo)(huo)(huo)性(xing)(xing)(xing)(xing)(xing)(xing)炭(tan)(tan)(tan)(tan)(tan)(tan)(tan)和(he)(he)(he)(he)(he)改(gai)(gai)性(xing)(xing)(xing)(xing)(xing)(xing)活(huo)(huo)(huo)(huo)(huo)(huo)(huo)(huo)(huo)性(xing)(xing)(xing)(xing)(xing)(xing)炭(tan)(tan)(tan)(tan)(tan)(tan)(tan)TEM圖(tu)像如圖(tu)1(c)和(he)(he)(he)(he)(he)(d)所(suo)示(shi)。這些圖(tu)片(pian)表(biao)(biao)明(ming)(ming)活(huo)(huo)(huo)(huo)(huo)(huo)(huo)(huo)(huo)性(xing)(xing)(xing)(xing)(xing)(xing)炭(tan)(tan)(tan)(tan)(tan)(tan)(tan)是(shi)無(wu)(wu)定(ding)(ding)形的(de)(de)(de)。與(yu)活(huo)(huo)(huo)(huo)(huo)(huo)(huo)(huo)(huo)性(xing)(xing)(xing)(xing)(xing)(xing)炭(tan)(tan)(tan)(tan)(tan)(tan)(tan)相比，改(gai)(gai)性(xing)(xing)(xing)(xing)(xing)(xing)活(huo)(huo)(huo)(huo)(huo)(huo)(huo)(huo)(huo)性(xing)(xing)(xing)(xing)(xing)(xing)炭(tan)(tan)(tan)(tan)(tan)(tan)(tan)表(biao)(biao)現(xian)出許多(duo)孔(kong)(kong)隙(xi)和(he)(he)(he)(he)(he)透明(ming)(ming)點，進(jin)一(yi)步表(biao)(biao)明(ming)(ming)表(biao)(biao)面(mian)(mian)積(ji)增(zeng)加(jia)(jia)。活(huo)(huo)(huo)(huo)(huo)(huo)(huo)(huo)(huo)性(xing)(xing)(xing)(xing)(xing)(xing)炭(tan)(tan)(tan)(tan)(tan)(tan)(tan)和(he)(he)(he)(he)(he)改(gai)(gai)性(xing)(xing)(xing)(xing)(xing)(xing)活(huo)(huo)(huo)(huo)(huo)(huo)(huo)(huo)(huo)性(xing)(xing)(xing)(xing)(xing)(xing)炭(tan)(tan)(tan)(tan)(tan)(tan)(tan)EDS圖(tu)像如圖(tu)1(e)和(he)(he)(he)(he)(he)(f)所(suo)示(shi)。與(yu)活(huo)(huo)(huo)(huo)(huo)(huo)(huo)(huo)(huo)性(xing)(xing)(xing)(xing)(xing)(xing)炭(tan)(tan)(tan)(tan)(tan)(tan)(tan)相比，改(gai)(gai)性(xing)(xing)(xing)(xing)(xing)(xing)活(huo)(huo)(huo)(huo)(huo)(huo)(huo)(huo)(huo)性(xing)(xing)(xing)(xing)(xing)(xing)炭(tan)(tan)(tan)(tan)(tan)(tan)(tan)的(de)(de)(de)元素O和(he)(he)(he)(he)(he)Fe含量(liang)顯(xian)(xian)著增(zeng)加(jia)(jia)，C活(huo)(huo)(huo)(huo)(huo)(huo)(huo)(huo)(huo)性(xing)(xing)(xing)(xing)(xing)(xing)炭(tan)(tan)(tan)(tan)(tan)(tan)(tan)上鐵(tie)離子負荷的(de)(de)(de)含量(liang)降低。此外，進(jin)一(yi)步證明(ming)(ming)表(biao)(biao)面(mian)(mian)含氧量(liang)增(zeng)加(jia)(jia)，有利(li)于(yu)磺胺(an)二(er)甲啶(ding)的(de)(de)(de)吸附。活(huo)(huo)(huo)(huo)(huo)(huo)(huo)(huo)(huo)性(xing)(xing)(xing)(xing)(xing)(xing)炭(tan)(tan)(tan)(tan)(tan)(tan)(tan)和(he)(he)(he)(he)(he)改(gai)(gai)性(xing)(xing)(xing)(xing)(xing)(xing)活(huo)(huo)(huo)(huo)(huo)(huo)(huo)(huo)(huo)性(xing)(xing)(xing)(xing)(xing)(xing)炭(tan)(tan)(tan)(tan)(tan)(tan)(tan)XRD圖(tu)如圖(tu)1(g)和(he)(he)(he)(he)(he)(h)所(suo)示(shi)。而且(qie)沒有活(huo)(huo)(huo)(huo)(huo)(huo)(huo)(huo)(huo)性(xing)(xing)(xing)(xing)(xing)(xing)炭(tan)(tan)(tan)(tan)(tan)(tan)(tan)和(he)(he)(he)(he)(he)改(gai)(gai)性(xing)(xing)(xing)(xing)(xing)(xing)活(huo)(huo)(huo)(huo)(huo)(huo)(huo)(huo)(huo)性(xing)(xing)(xing)(xing)(xing)(xing)炭(tan)(tan)(tan)(tan)(tan)(tan)(tan)的(de)(de)(de)明(ming)(ming)顯(xian)(xian)特征峰值，說明(ming)(ming)它們是(shi)無(wu)(wu)形的(de)(de)(de)。這與(yu)TEM照片(pian)結(jie)(jie)果一(yi)致。

　　兩種吸附劑(ji)的代表(biao)性(xing)(xing)(xing)(xing)SEM，TEM和EDS圖像。(a)活(huo)性(xing)(xing)(xing)(xing)炭(tan)的SEM(比(bi)(bi)例(li)尺為(wei)(wei)2μm)，(b)活(huo)性(xing)(xing)(xing)(xing)炭(tan)的TEM(比(bi)(bi)例(li)尺為(wei)(wei)100nm)，(c)活(huo)性(xing)(xing)(xing)(xing)炭(tan)的EDS，(d)改性(xing)(xing)(xing)(xing)活(huo)性(xing)(xing)(xing)(xing)炭(tan)SEM(比(bi)(bi)例(li)尺為(wei)(wei)2μm)，(e)改性(xing)(xing)(xing)(xing)活(huo)性(xing)(xing)(xing)(xing)炭(tan)TEM(比(bi)(bi)例(li)尺為(wei)(wei)100nm)，(f)改性(xing)(xing)(xing)(xing)活(huo)性(xing)(xing)(xing)(xing)炭(tan)EDS，(g)活(huo)性(xing)(xing)(xing)(xing)炭(tan)的XRD，(h)改性(xing)(xing)(xing)(xing)活(huo)性(xing)(xing)(xing)(xing)炭(tan)XRD。

　　活性(xing)炭吸(xi)附磺(huang)胺的三個階段

　　活性(xing)(xing)炭(tan)(tan)和(he)(he)改性(xing)(xing)活性(xing)(xing)炭(tan)(tan)和(he)(he)改性(xing)(xing)活性(xing)(xing)炭(tan)(tan)上的吸(xi)附和(he)(he)擴(kuo)散過程(cheng)可分三(san)個(ge)階段描述，如圖2所示。由于**階段吸(xi)附在活性(xing)(xing)炭(tan)(tan)表(biao)面(mian)，吸(xi)附率*初很高。然后，在顆(ke)粒(li)內(nei)快速擴(kuo)散的過程(cheng)中，磺胺二甲啶逐漸(jian)吸(xi)附在活性(xing)(xing)炭(tan)(tan)上，吸(xi)附率常數逐漸(jian)降低。在第三(san)階段，邊界層和(he)(he)傳質阻力的影(ying)響增加，導(dao)致顆(ke)粒(li)擴(kuo)散減慢。所有(you)三(san)個(ge)階段的擬合方程(cheng)都沒有(you)通過坐標的原點，這表(biao)明顆(ke)粒(li)的擴(kuo)散并不(bu)是(shi)控制(zhi)吸(xi)附率的**步驟。因此，吸(xi)附過程(cheng)也(ye)受膜(mo)擴(kuo)散和(he)(he)表(biao)面(mian)吸(xi)附的影(ying)響。

　　磺胺二甲(jia)啶在(zai)活性炭上吸附的顆粒中擴散。

　　改性(xing)活性(xing)炭的表面(mian)顯(xian)示出(chu)許多孔隙和透明(ming)度，大量(liang)含氧(yang)官能團被(bei)改性(xing)，導致(zhi)磺胺二甲啶吸附(fu)機(ji)制的變化。根(gen)據本研(yan)究(jiu)的相關研(yan)究(jiu)結果(guo)，活性(xing)炭表面(mian)磺胺二甲啶的吸附(fu)機(ji)制總結如(ru)下（圖(tu)3）：

　　1.微孔捕獲

　　SEM圖像顯示，活性(xing)炭(tan)的(de)規則孔結構受損，孔隙率增(zeng)加。TEM圖像顯示，改性(xing)活性(xing)炭(tan)表面(mian)含有(you)許多透明點，表明孔結構更發達，修改后可(ke)獲得更多的(de)吸(xi)附點。這(zhe)有(you)利(li)于磺胺二甲啶吸(xi)附到黑碳分子層的(de)孔中。此外，經鐵(tie)離子改性(xing)后，活性(xing)炭(tan)的(de)表面(mian)積(ji)(ji)、總孔容量、微孔體積(ji)(ji)和中孔體積(ji)(ji)都有(you)一定程度的(de)增(zeng)加。

　　2.氫鍵相互作用

　　通(tong)過FTIR通(tong)過促(cu)(cu)進改(gai)性(xing)(xing)活(huo)性(xing)(xing)炭表面(mian)與磺(huang)胺(an)二(er)甲啶(ding)之間(jian)(jian)氫鍵(jian)的相(xiang)互作用，促(cu)(cu)進磺(huang)胺(an)二(er)甲啶(ding)的吸附。從數據圖(tu)中發現，3400和2850cm-1處寬吸收峰(feng)表明改(gai)性(xing)(xing)活(huo)性(xing)(xing)炭表面(mian)存在-OH。這些分(fen)子(zi)間(jian)(jian)氫鍵(jian)增強了磺(huang)胺(an)二(er)甲啶(ding)與活(huo)性(xing)(xing)炭的表面(mian)相(xiang)互作用，預計(ji)將有(you)助于活(huo)性(xing)(xing)炭與異磺(huang)胺(an)二(er)甲啶(ding)之間(jian)(jian)的親和力吸附。

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

　　磺胺二甲啶與改(gai)性(xing)活性(xing)炭(tan)合理相(xiang)互作(zuo)用(yong)(yong)(yong)的(de)示意圖。1.微(wei)孔捕(bu)獲。2.氫鍵(jian)相(xiang)互作(zuo)用(yong)(yong)(yong)。.π-πEDA相(xiang)互作(zuo)用(yong)(yong)(yong)。4.靜電相(xiang)互作(zuo)用(yong)(yong)(yong)。5.配位相(xiang)互作(zuo)用(yong)(yong)(yong)。

　　鐵離子改性(xing)(xing)(xing)(xing)后，活性(xing)(xing)(xing)(xing)炭(tan)(tan)活性(xing)(xing)(xing)(xing)炭(tan)(tan)的(de)表面積(ji)(ji)、總孔容量、微孔體積(ji)(ji)和(he)中孔體積(ji)(ji)。含氧加(jia)了(le)活性(xing)(xing)(xing)(xing)炭(tan)(tan)表面含氧官能團的(de)數量，可(ke)以(yi)大(da)大(da)提高吸附(fu)能力(li)。磺(huang)(huang)(huang)胺(an)(an)二(er)(er)(er)甲(jia)嘧啶(ding)(ding)在(zai)改性(xing)(xing)(xing)(xing)活性(xing)(xing)(xing)(xing)炭(tan)(tan)上(shang)去(qu)除(chu)磺(huang)(huang)(huang)胺(an)(an)廢水中顯著(zhu)增(zeng)加(jia)，并(bing)在(zai)25℃下磺(huang)(huang)(huang)胺(an)(an)二(er)(er)(er)甲(jia)嘧啶(ding)(ding)在(zai)改性(xing)(xing)(xing)(xing)活性(xing)(xing)(xing)(xing)炭(tan)(tan)上(shang)的(de)*大(da)吸附(fu)量為17.261mg/g。然(ran)而，吸附(fu)平衡時(shi)間(jian)幾乎保持不變。磺(huang)(huang)(huang)胺(an)(an)二(er)(er)(er)甲(jia)啶(ding)(ding)在(zai)原始和(he)改性(xing)(xing)(xing)(xing)活性(xing)(xing)(xing)(xing)炭(tan)(tan)上(shang)的(de)吸附(fu)動力(li)學分為快速(su)和(he)慢速(su)吸附(fu)階段，磺(huang)(huang)(huang)胺(an)(an)二(er)(er)(er)甲(jia)啶(ding)(ding)吸附(fu)在(zai)12小時(shi)內快速(su)完成。pH該值對(dui)磺(huang)(huang)(huang)胺(an)(an)二(er)(er)(er)甲(jia)啶(ding)(ding)的(de)吸附(fu)有顯著(zhu)影(ying)響。當(dang)pH磺(huang)(huang)(huang)胺(an)(an)二(er)(er)(er)甲(jia)啶(ding)(ding)的(de)吸附(fu)量在(zai)3-10之(zhi)間(jian)增(zeng)加(jia)，然(ran)后減少(shao)。微孔捕獲，靜電相(xiang)互作用，氫鍵相(xiang)互作用，π-πEDA相(xiang)互作用和(he)配位相(xiang)互作用是吸附(fu)的(de)可(ke)能機制(zhi)。降低溫度促(cu)進吸附(fu)反應。pH該值對(dui)磺(huang)(huang)(huang)胺(an)(an)二(er)(er)(er)甲(jia)啶(ding)(ding)的(de)吸附(fu)有顯著(zhu)影(ying)響。當(dang)pH磺(huang)(huang)(huang)胺(an)(an)二(er)(er)(er)甲(jia)啶(ding)(ding)的(de)吸附(fu)量在(zai)3-10之(zhi)間(jian)增(zeng)加(jia)，然(ran)后減少(shao)。