活性(xing)炭改性(xing)后處(chu)理磺(huang)胺廢水

　　磺(huang)胺(an)廢水(shui)經(jing)(jing)活性(xing)(xing)(xing)炭(tan)改(gai)性(xing)(xing)(xing)后處(chu)理(li)(li)，活性(xing)(xing)(xing)炭(tan)經(jing)(jing)氯(lv)化鐵(tie)改(gai)性(xing)(xing)(xing)。并進行(xing)批量(liang)實(shi)驗(yan)以評估(gu)廢水(shui)中的磺(huang)胺(an)二甲嘧啶吸附到活性(xing)(xing)(xing)炭(tan)和改(gai)性(xing)(xing)(xing)活性(xing)(xing)(xing)炭(tan)上(shang)的平衡，分別分析(xi)動力學和熱力學特征。結果表明，氯(lv)化鐵(tie)處(chu)理(li)(li)后，活性(xing)(xing)(xing)炭(tan)改(gai)變(bian)了表面積、孔(kong)隙體(ti)積和表面zeta電位還增加了表面含(han)氧官能團(tuan)的數量(liang)。經(jing)(jing)試(shi)驗(yan)發現，磺(huang)胺(an)二甲啶在改(gai)性(xing)(xing)(xing)活性(xing)(xing)(xing)炭(tan)上(shang)的吸附得到了顯(xian)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)有效(xiao)去除顏(yan)色、氣味、無機(ji)化合物和(he)(he)大多數(shu)有機(ji)污染物。但(dan)其(qi)(qi)在實(shi)際應用中(zhong)的(de)使用受其(qi)(qi)吸(xi)(xi)附(fu)(fu)(fu)(fu)(fu)效(xiao)率和(he)(he)成本低的(de)限制。金屬離子改性(xing)(xing)(xing)(xing)后(hou)的(de)活(huo)性(xing)(xing)(xing)(xing)炭生產(chan)簡單(dan)便宜，能(neng)顯著提高活(huo)性(xing)(xing)(xing)(xing)炭的(de)吸(xi)(xi)附(fu)(fu)(fu)(fu)(fu)性(xing)(xing)(xing)(xing)能(neng)。然而，活(huo)性(xing)(xing)(xing)(xing)炭中(zhong)磺(huang)胺(an)類(lei)廢(fei)水(shui)的(de)吸(xi)(xi)附(fu)(fu)(fu)(fu)(fu)機(ji)制尚(shang)不清楚，對磺(huang)胺(an)類(lei)的(de)吸(xi)(xi)附(fu)(fu)(fu)(fu)(fu)能(neng)力(li)及其(qi)(qi)理化性(xing)(xing)(xing)(xing)質知之(zhi)甚少(shao)。本研(yan)究(jiu)采用鐵離子改性(xing)(xing)(xing)(xing)活(huo)性(xing)(xing)(xing)(xing)炭。用于探索吸(xi)(xi)附(fu)(fu)(fu)(fu)(fu)機(ji)制的(de)批(pi)量吸(xi)(xi)附(fu)(fu)(fu)(fu)(fu)實(shi)驗。磺(huang)胺(an)二甲啶(ding)對活(huo)性(xing)(xing)(xing)(xing)炭和(he)(he)改性(xing)(xing)(xing)(xing)活(huo)性(xing)(xing)(xing)(xing)炭的(de)吸(xi)(xi)附(fu)(fu)(fu)(fu)(fu)特性(xing)(xing)(xing)(xing)通過(guo)吸(xi)(xi)附(fu)(fu)(fu)(fu)(fu)動力(li)學、吸(xi)(xi)附(fu)(fu)(fu)(fu)(fu)熱(re)力(li)學和(he)(he)吸(xi)(xi)附(fu)(fu)(fu)(fu)(fu)等溫線進行了(le)研(yan)究(jiu)，為去除廢(fei)水(shui)中(zhong)的(de)磺(huang)胺(an)污染物提供(gong)了(le)科學依(yi)據。

　　活性(xing)炭改性(xing)后的特性(xing)

　　活(huo)(huo)(huo)(huo)性(xing)(xing)(xing)(xing)(xing)(xing)(xing)(xing)(xing)炭(tan)(tan)(tan)和(he)(he)改(gai)(gai)(gai)性(xing)(xing)(xing)(xing)(xing)(xing)(xing)(xing)(xing)活(huo)(huo)(huo)(huo)性(xing)(xing)(xing)(xing)(xing)(xing)(xing)(xing)(xing)炭(tan)(tan)(tan)的(de)(de)(de)(de)(de)(de)化學結(jie)構和(he)(he)物理化學性(xing)(xing)(xing)(xing)(xing)(xing)(xing)(xing)(xing)質差異很大。鐵(tie)離子改(gai)(gai)(gai)性(xing)(xing)(xing)(xing)(xing)(xing)(xing)(xing)(xing)后，活(huo)(huo)(huo)(huo)性(xing)(xing)(xing)(xing)(xing)(xing)(xing)(xing)(xing)炭(tan)(tan)(tan)的(de)(de)(de)(de)(de)(de)表(biao)面(mian)積(ji)(ji)(ji)、總孔(kong)容量、微(wei)孔(kong)體積(ji)(ji)(ji)和(he)(he)中(zhong)(zhong)孔(kong)體積(ji)(ji)(ji)都有一定程(cheng)度的(de)(de)(de)(de)(de)(de)增加(jia)(jia)，可以為磺(huang)(huang)胺二甲啶提供(gong)更多(duo)的(de)(de)(de)(de)(de)(de)吸附(fu)點。由(you)于改(gai)(gai)(gai)性(xing)(xing)(xing)(xing)(xing)(xing)(xing)(xing)(xing)，活(huo)(huo)(huo)(huo)性(xing)(xing)(xing)(xing)(xing)(xing)(xing)(xing)(xing)炭(tan)(tan)(tan)的(de)(de)(de)(de)(de)(de)微(wei)孔(kong)結(jie)構可能(neng)會產(chan)生較(jiao)大的(de)(de)(de)(de)(de)(de)比表(biao)面(mian)積(ji)(ji)(ji)。在活(huo)(huo)(huo)(huo)化過程(cheng)中(zhong)(zhong)，鐵(tie)離子主要(yao)沉積(ji)(ji)(ji)在介(jie)孔(kong)中(zhong)(zhong)，擴大孔(kong)徑并進入微(wei)孔(kong)。將金(jin)屬鹽釋放的(de)(de)(de)(de)(de)(de)氧(yang)化氣體引入微(wei)孔(kong)，并與微(wei)孔(kong)碳壁反(fan)應。活(huo)(huo)(huo)(huo)性(xing)(xing)(xing)(xing)(xing)(xing)(xing)(xing)(xing)炭(tan)(tan)(tan)和(he)(he)改(gai)(gai)(gai)性(xing)(xing)(xing)(xing)(xing)(xing)(xing)(xing)(xing)活(huo)(huo)(huo)(huo)性(xing)(xing)(xing)(xing)(xing)(xing)(xing)(xing)(xing)炭(tan)(tan)(tan)SEM圖1顯(xian)(xian)示圖像(xiang)(a)和(he)(he)(b)中(zhong)(zhong)。活(huo)(huo)(huo)(huo)性(xing)(xing)(xing)(xing)(xing)(xing)(xing)(xing)(xing)炭(tan)(tan)(tan)的(de)(de)(de)(de)(de)(de)形(xing)(xing)狀表(biao)明(ming)具有規則孔(kong)結(jie)構的(de)(de)(de)(de)(de)(de)光滑表(biao)面(mian)。與活(huo)(huo)(huo)(huo)性(xing)(xing)(xing)(xing)(xing)(xing)(xing)(xing)(xing)炭(tan)(tan)(tan)相比，改(gai)(gai)(gai)性(xing)(xing)(xing)(xing)(xing)(xing)(xing)(xing)(xing)活(huo)(huo)(huo)(huo)性(xing)(xing)(xing)(xing)(xing)(xing)(xing)(xing)(xing)炭(tan)(tan)(tan)表(biao)面(mian)粗(cu)糙(cao)不規則。孔(kong)隙結(jie)構受損，孔(kong)隙率增加(jia)(jia)。這可能(neng)是由(you)于鐵(tie)離子引入活(huo)(huo)(huo)(huo)性(xing)(xing)(xing)(xing)(xing)(xing)(xing)(xing)(xing)炭(tan)(tan)(tan)內孔(kong)，導致碳壁氧(yang)化和(he)(he)孔(kong)徑增加(jia)(jia)。活(huo)(huo)(huo)(huo)性(xing)(xing)(xing)(xing)(xing)(xing)(xing)(xing)(xing)炭(tan)(tan)(tan)中(zhong)(zhong)磺(huang)(huang)胺二甲啶的(de)(de)(de)(de)(de)(de)擴散有利于粗(cu)糙(cao)的(de)(de)(de)(de)(de)(de)表(biao)面(mian)結(jie)構和(he)(he)多(duo)孔(kong)特性(xing)(xing)(xing)(xing)(xing)(xing)(xing)(xing)(xing)。活(huo)(huo)(huo)(huo)性(xing)(xing)(xing)(xing)(xing)(xing)(xing)(xing)(xing)炭(tan)(tan)(tan)和(he)(he)改(gai)(gai)(gai)性(xing)(xing)(xing)(xing)(xing)(xing)(xing)(xing)(xing)活(huo)(huo)(huo)(huo)性(xing)(xing)(xing)(xing)(xing)(xing)(xing)(xing)(xing)炭(tan)(tan)(tan)TEM圖像(xiang)如(ru)圖1(c)和(he)(he)(d)所示。這些圖片表(biao)明(ming)活(huo)(huo)(huo)(huo)性(xing)(xing)(xing)(xing)(xing)(xing)(xing)(xing)(xing)炭(tan)(tan)(tan)是無定形(xing)(xing)的(de)(de)(de)(de)(de)(de)。與活(huo)(huo)(huo)(huo)性(xing)(xing)(xing)(xing)(xing)(xing)(xing)(xing)(xing)炭(tan)(tan)(tan)相比，改(gai)(gai)(gai)性(xing)(xing)(xing)(xing)(xing)(xing)(xing)(xing)(xing)活(huo)(huo)(huo)(huo)性(xing)(xing)(xing)(xing)(xing)(xing)(xing)(xing)(xing)炭(tan)(tan)(tan)表(biao)現(xian)出許多(duo)孔(kong)隙和(he)(he)透明(ming)點，進一步(bu)表(biao)明(ming)表(biao)面(mian)積(ji)(ji)(ji)增加(jia)(jia)。活(huo)(huo)(huo)(huo)性(xing)(xing)(xing)(xing)(xing)(xing)(xing)(xing)(xing)炭(tan)(tan)(tan)和(he)(he)改(gai)(gai)(gai)性(xing)(xing)(xing)(xing)(xing)(xing)(xing)(xing)(xing)活(huo)(huo)(huo)(huo)性(xing)(xing)(xing)(xing)(xing)(xing)(xing)(xing)(xing)炭(tan)(tan)(tan)EDS圖像(xiang)如(ru)圖1(e)和(he)(he)(f)所示。與活(huo)(huo)(huo)(huo)性(xing)(xing)(xing)(xing)(xing)(xing)(xing)(xing)(xing)炭(tan)(tan)(tan)相比，改(gai)(gai)(gai)性(xing)(xing)(xing)(xing)(xing)(xing)(xing)(xing)(xing)活(huo)(huo)(huo)(huo)性(xing)(xing)(xing)(xing)(xing)(xing)(xing)(xing)(xing)炭(tan)(tan)(tan)的(de)(de)(de)(de)(de)(de)元(yuan)素O和(he)(he)Fe含(han)(han)量顯(xian)(xian)著增加(jia)(jia)，C活(huo)(huo)(huo)(huo)性(xing)(xing)(xing)(xing)(xing)(xing)(xing)(xing)(xing)炭(tan)(tan)(tan)上(shang)鐵(tie)離子負荷的(de)(de)(de)(de)(de)(de)含(han)(han)量降低。此(ci)外，進一步(bu)證明(ming)表(biao)面(mian)含(han)(han)氧(yang)量增加(jia)(jia)，有利于磺(huang)(huang)胺二甲啶的(de)(de)(de)(de)(de)(de)吸附(fu)。活(huo)(huo)(huo)(huo)性(xing)(xing)(xing)(xing)(xing)(xing)(xing)(xing)(xing)炭(tan)(tan)(tan)和(he)(he)改(gai)(gai)(gai)性(xing)(xing)(xing)(xing)(xing)(xing)(xing)(xing)(xing)活(huo)(huo)(huo)(huo)性(xing)(xing)(xing)(xing)(xing)(xing)(xing)(xing)(xing)炭(tan)(tan)(tan)XRD圖如(ru)圖1(g)和(he)(he)(h)所示。而且沒有活(huo)(huo)(huo)(huo)性(xing)(xing)(xing)(xing)(xing)(xing)(xing)(xing)(xing)炭(tan)(tan)(tan)和(he)(he)改(gai)(gai)(gai)性(xing)(xing)(xing)(xing)(xing)(xing)(xing)(xing)(xing)活(huo)(huo)(huo)(huo)性(xing)(xing)(xing)(xing)(xing)(xing)(xing)(xing)(xing)炭(tan)(tan)(tan)的(de)(de)(de)(de)(de)(de)明(ming)顯(xian)(xian)特征峰值，說明(ming)它們(men)是無形(xing)(xing)的(de)(de)(de)(de)(de)(de)。這與TEM照片結(jie)果一致。

　　兩種吸(xi)附劑的(de)代表(biao)性(xing)(xing)SEM，TEM和EDS圖像。(a)活(huo)性(xing)(xing)炭(tan)的(de)SEM(比例(li)尺(chi)為2μm)，(b)活(huo)性(xing)(xing)炭(tan)的(de)TEM(比例(li)尺(chi)為100nm)，(c)活(huo)性(xing)(xing)炭(tan)的(de)EDS，(d)改性(xing)(xing)活(huo)性(xing)(xing)炭(tan)SEM(比例(li)尺(chi)為2μm)，(e)改性(xing)(xing)活(huo)性(xing)(xing)炭(tan)TEM(比例(li)尺(chi)為100nm)，(f)改性(xing)(xing)活(huo)性(xing)(xing)炭(tan)EDS，(g)活(huo)性(xing)(xing)炭(tan)的(de)XRD，(h)改性(xing)(xing)活(huo)性(xing)(xing)炭(tan)XRD。

　　活性炭吸附磺(huang)胺的(de)三個階段(duan)

　　活(huo)性(xing)(xing)(xing)炭(tan)和(he)改(gai)性(xing)(xing)(xing)活(huo)性(xing)(xing)(xing)炭(tan)和(he)改(gai)性(xing)(xing)(xing)活(huo)性(xing)(xing)(xing)炭(tan)上的(de)(de)吸(xi)(xi)附(fu)(fu)和(he)擴(kuo)(kuo)散(san)過(guo)程可分三(san)個階(jie)段(duan)(duan)(duan)描(miao)述，如(ru)圖2所示(shi)。由于(yu)**階(jie)段(duan)(duan)(duan)吸(xi)(xi)附(fu)(fu)在(zai)(zai)活(huo)性(xing)(xing)(xing)炭(tan)表(biao)面，吸(xi)(xi)附(fu)(fu)率(lv)(lv)*初很高。然后，在(zai)(zai)顆(ke)粒內(nei)快速擴(kuo)(kuo)散(san)的(de)(de)過(guo)程中(zhong)，磺(huang)胺二甲啶逐(zhu)漸吸(xi)(xi)附(fu)(fu)在(zai)(zai)活(huo)性(xing)(xing)(xing)炭(tan)上，吸(xi)(xi)附(fu)(fu)率(lv)(lv)常數逐(zhu)漸降低(di)。在(zai)(zai)第三(san)階(jie)段(duan)(duan)(duan)，邊界層和(he)傳質阻力(li)的(de)(de)影(ying)響(xiang)增加，導致顆(ke)粒擴(kuo)(kuo)散(san)減慢。所有(you)三(san)個階(jie)段(duan)(duan)(duan)的(de)(de)擬合方程都沒(mei)有(you)通過(guo)坐標(biao)的(de)(de)原(yuan)點，這表(biao)明顆(ke)粒的(de)(de)擴(kuo)(kuo)散(san)并不是控制吸(xi)(xi)附(fu)(fu)率(lv)(lv)的(de)(de)**步驟。因此(ci)，吸(xi)(xi)附(fu)(fu)過(guo)程也(ye)受膜擴(kuo)(kuo)散(san)和(he)表(biao)面吸(xi)(xi)附(fu)(fu)的(de)(de)影(ying)響(xiang)。

　　磺胺二甲(jia)啶(ding)在活(huo)性炭上吸附的顆粒中擴散。

　　改(gai)性(xing)活(huo)性(xing)炭的(de)表面(mian)顯示出許多孔(kong)隙和(he)透明度(du)，大(da)量含(han)氧官(guan)能團被改(gai)性(xing)，導致磺胺二(er)甲(jia)啶吸附機制的(de)變化。根據本研究(jiu)的(de)相關研究(jiu)結果，活(huo)性(xing)炭表面(mian)磺胺二(er)甲(jia)啶的(de)吸附機制總結如下(xia)（圖3）：

　　1.微孔捕獲

　　SEM圖像顯(xian)示(shi)，活(huo)性(xing)炭(tan)的(de)規則孔(kong)結(jie)構(gou)(gou)受損，孔(kong)隙率增加(jia)。TEM圖像顯(xian)示(shi)，改(gai)性(xing)活(huo)性(xing)炭(tan)表面(mian)含(han)有(you)許多透明點(dian)，表明孔(kong)結(jie)構(gou)(gou)更發達，修改(gai)后可(ke)獲得更多的(de)吸附(fu)點(dian)。這有(you)利于磺胺二甲(jia)啶(ding)吸附(fu)到黑碳(tan)分子層的(de)孔(kong)中。此(ci)外(wai)，經鐵離子改(gai)性(xing)后，活(huo)性(xing)炭(tan)的(de)表面(mian)積(ji)、總孔(kong)容量、微孔(kong)體(ti)積(ji)和中孔(kong)體(ti)積(ji)都有(you)一(yi)定程度的(de)增加(jia)。

　　2.氫鍵相互作用

　　通過FTIR通過促進(jin)改(gai)性(xing)活性(xing)炭(tan)(tan)表面與(yu)(yu)磺胺(an)二(er)(er)甲啶之間(jian)(jian)氫鍵(jian)的(de)相(xiang)互(hu)作用(yong)，促進(jin)磺胺(an)二(er)(er)甲啶的(de)吸(xi)附。從(cong)數據圖(tu)中發(fa)現(xian)，3400和2850cm-1處(chu)寬吸(xi)收峰(feng)表明改(gai)性(xing)活性(xing)炭(tan)(tan)表面存在-OH。這(zhe)些分子(zi)間(jian)(jian)氫鍵(jian)增(zeng)強了磺胺(an)二(er)(er)甲啶與(yu)(yu)活性(xing)炭(tan)(tan)的(de)表面相(xiang)互(hu)作用(yong)，預計將有助于活性(xing)炭(tan)(tan)與(yu)(yu)異磺胺(an)二(er)(er)甲啶之間(jian)(jian)的(de)親和力吸(xi)附。

　　3.π-π電子供體-受(shou)體(EDA)相互(hu)作用。

　　磺胺二甲啶(ding)與改性(xing)(xing)活性(xing)(xing)炭合(he)理相(xiang)互(hu)(hu)作(zuo)用的示意(yi)圖。1.微孔(kong)捕獲。2.氫鍵相(xiang)互(hu)(hu)作(zuo)用。.π-πEDA相(xiang)互(hu)(hu)作(zuo)用。4.靜電(dian)相(xiang)互(hu)(hu)作(zuo)用。5.配位相(xiang)互(hu)(hu)作(zuo)用。

　　鐵離(li)子(zi)改(gai)性(xing)(xing)(xing)后(hou)，活性(xing)(xing)(xing)炭(tan)活性(xing)(xing)(xing)炭(tan)的(de)表面積(ji)、總(zong)孔(kong)容量、微(wei)孔(kong)體(ti)積(ji)和(he)中孔(kong)體(ti)積(ji)。含氧(yang)加(jia)了(le)活性(xing)(xing)(xing)炭(tan)表面含氧(yang)官(guan)能團的(de)數量，可以大大提(ti)高(gao)吸(xi)(xi)附(fu)(fu)(fu)(fu)能力。磺(huang)(huang)(huang)胺(an)二(er)甲(jia)(jia)嘧啶(ding)在(zai)(zai)改(gai)性(xing)(xing)(xing)活性(xing)(xing)(xing)炭(tan)上(shang)(shang)去除磺(huang)(huang)(huang)胺(an)廢水中顯(xian)(xian)著增加(jia)，并在(zai)(zai)25℃下磺(huang)(huang)(huang)胺(an)二(er)甲(jia)(jia)嘧啶(ding)在(zai)(zai)改(gai)性(xing)(xing)(xing)活性(xing)(xing)(xing)炭(tan)上(shang)(shang)的(de)*大吸(xi)(xi)附(fu)(fu)(fu)(fu)量為(wei)17.261mg/g。然而，吸(xi)(xi)附(fu)(fu)(fu)(fu)平衡(heng)時間(jian)幾乎保持不變。磺(huang)(huang)(huang)胺(an)二(er)甲(jia)(jia)啶(ding)在(zai)(zai)原始和(he)改(gai)性(xing)(xing)(xing)活性(xing)(xing)(xing)炭(tan)上(shang)(shang)的(de)吸(xi)(xi)附(fu)(fu)(fu)(fu)動力學分為(wei)快速和(he)慢速吸(xi)(xi)附(fu)(fu)(fu)(fu)階(jie)段，磺(huang)(huang)(huang)胺(an)二(er)甲(jia)(jia)啶(ding)吸(xi)(xi)附(fu)(fu)(fu)(fu)在(zai)(zai)12小時內快速完成(cheng)。pH該(gai)值對磺(huang)(huang)(huang)胺(an)二(er)甲(jia)(jia)啶(ding)的(de)吸(xi)(xi)附(fu)(fu)(fu)(fu)有(you)顯(xian)(xian)著影響。當pH磺(huang)(huang)(huang)胺(an)二(er)甲(jia)(jia)啶(ding)的(de)吸(xi)(xi)附(fu)(fu)(fu)(fu)量在(zai)(zai)3-10之間(jian)增加(jia)，然后(hou)減(jian)(jian)少。微(wei)孔(kong)捕(bu)獲(huo)，靜電相(xiang)互作(zuo)用，氫鍵相(xiang)互作(zuo)用，π-πEDA相(xiang)互作(zuo)用和(he)配(pei)位相(xiang)互作(zuo)用是(shi)吸(xi)(xi)附(fu)(fu)(fu)(fu)的(de)可能機制。降低溫度促(cu)進吸(xi)(xi)附(fu)(fu)(fu)(fu)反應。pH該(gai)值對磺(huang)(huang)(huang)胺(an)二(er)甲(jia)(jia)啶(ding)的(de)吸(xi)(xi)附(fu)(fu)(fu)(fu)有(you)顯(xian)(xian)著影響。當pH磺(huang)(huang)(huang)胺(an)二(er)甲(jia)(jia)啶(ding)的(de)吸(xi)(xi)附(fu)(fu)(fu)(fu)量在(zai)(zai)3-10之間(jian)增加(jia)，然后(hou)減(jian)(jian)少。