
活性炭的(de)環己烷氧化(hua)
今天,我(wo)想介(jie)紹一下(xia)環(huan)己(ji)(ji)(ji)烷無(wu)溶劑氧化(hua)活(huo)(huo)性炭。活(huo)(huo)性炭的原料是磷酸(suan)鹽浸泡在(zai)380中℃在(zai)惰性氣體下(xia)碳化(hua),然(ran)后(hou)用(yong)過氧化(hua)氫激活(huo)(huo)。活(huo)(huo)性炭通過SEM,EDX,FTIR,TGA和BET表(biao)面積和孔徑分析儀(yi)表(biao)征。在(zai)自制(zhi)雙壁三頸批量中,活(huo)(huo)性炭作為環(huan)己(ji)(ji)(ji)烷無(wu)環(huan)氧化(hua)成環(huan)己(ji)(ji)(ji)醇和環(huan)己(ji)(ji)(ji)酮(這種混合物稱(cheng)為KA油)催化(hua)劑的潛(qian)能(neng)反(fan)應堆。優化(hua)了(le)不(bu)同反(fan)應參(can)數(shu)/添加劑的影(ying)響。
19世紀初,活性炭首次被報道為(wei)有(you)效催(cui)(cui)化(hua)(hua)(hua)劑。19世紀初,活(huo)(huo)(huo)性(xing)(xing)(xing)(xing)炭(tan)(tan)通常由不(bu)同(tong)農(nong)業原料的(de)(de)(de)(de)(de)熱活(huo)(huo)(huo)化(hua)(hua)(hua)法(fa)制備,作為(wei)過(guo)氧(yang)化(hua)(hua)(hua)氫(qing)降解(jie)的(de)(de)(de)(de)(de)催(cui)(cui)化(hua)(hua)(hua)劑。活(huo)(huo)(huo)性(xing)(xing)(xing)(xing)炭(tan)(tan)對過(guo)氧(yang)化(hua)(hua)(hua)氫(qing)分解(jie)有(you)很好的(de)(de)(de)(de)(de)催(cui)(cui)化(hua)(hua)(hua)活(huo)(huo)(huo)性(xing)(xing)(xing)(xing),但持續時間短。催(cui)(cui)化(hua)(hua)(hua)活(huo)(huo)(huo)性(xing)(xing)(xing)(xing)消失的(de)(de)(de)(de)(de)*有(you)可能原因(yin)(yin)是(shi)活(huo)(huo)(huo)性(xing)(xing)(xing)(xing)炭(tan)(tan)表面氧(yang)化(hua)(hua)(hua)基團的(de)(de)(de)(de)(de)失活(huo)(huo)(huo)。近幾十年來,研究人員成功地解(jie)決了(le)活(huo)(huo)(huo)性(xing)(xing)(xing)(xing)炭(tan)(tan)耐久(jiu)性(xing)(xing)(xing)(xing)的(de)(de)(de)(de)(de)主(zhu)要問題(ti)。活(huo)(huo)(huo)性(xing)(xing)(xing)(xing)炭(tan)(tan)通過(guo)物(wu)理、物(wu)理、化(hua)(hua)(hua)學和(he)(he)(he)化(hua)(hua)(hua)學活(huo)(huo)(huo)化(hua)(hua)(hua)進行調(diao)整(zheng),在(zai)光氣和(he)(he)(he)硫化(hua)(hua)(hua)氫(qing)的(de)(de)(de)(de)(de)生產中顯(xian)示出良好的(de)(de)(de)(de)(de)催(cui)(cui)化(hua)(hua)(hua)活(huo)(huo)(huo)性(xing)(xing)(xing)(xing),氫(qing)化(hua)(hua)(hua)、聚(ju)合和(he)(he)(he)鹵化(hua)(hua)(hua)去除SO 2 和(he)(he)(he)NO x 氧(yang)化(hua)(hua)(hua)苯二醇。由于其孔隙度(du)、活(huo)(huo)(huo)性(xing)(xing)(xing)(xing)位點和(he)(he)(he)高表面積(ji),活(huo)(huo)(huo)性(xing)(xing)(xing)(xing)炭(tan)(tan)的(de)(de)(de)(de)(de)這種(zhong)性(xing)(xing)(xing)(xing)能。因(yin)(yin)此,通過(guo)控制這些參數,活(huo)(huo)(huo)性(xing)(xing)(xing)(xing)炭(tan)(tan)可以調(diao)整(zheng)為(wei)有(you)效的(de)(de)(de)(de)(de)催(cui)(cui)化(hua)(hua)(hua)劑,用于選擇有(you)機轉化(hua)(hua)(hua)。
活性炭實驗條(tiao)件和工藝條(tiao)件
在(zai)目前的(de)工作中,在(zai)溫和的(de)反應(ying)條件下,活性炭被(bei)用作無金(jin)屬催化劑和無環氧(yang)環己(ji)烷KA油。優化了反應(ying)參數(shu),并在(zai)生產率方面發現了催化效率。活性炭成(cheng)為(wei)環己(ji)烷無溶劑氧(yang)化的(de)有用催化劑,方便、活性、低成(cheng)本、可回收、不滲透(tou)、環保。

活(huo)性(xing)炭(tan)(tan)的(de)表(biao)(biao)(biao)面(mian)形(xing)態是通(tong)過(guo)掃描電子顯微鏡進(jin)(jin)行研究的(de)。活(huo)性(xing)炭(tan)(tan)的(de)元素組成通(tong)過(guo)能(neng)量(liang)色散X射線(xian)(xian)光(guang)譜記(ji)錄。通(tong)過(guo)X射線(xian)(xian)衍(yan)射儀進(jin)(jin)行X射線(xian)(xian)分(fen)析(xi)。活(huo)性(xing)炭(tan)(tan)表(biao)(biao)(biao)面(mian)的(de)官能(neng)團通(tong)過(guo)傅里葉(xie)紅(hong)外光(guang)譜儀檢查。通(tong)過(guo)TGA0/10000熱(re)分(fen)析(xi)儀℃溫度范圍內 以10℃/ min的(de)速率在N 2流下熱(re)量(liang)重量(liang)損失(shi)百分(fen)比 。活(huo)性(xing)炭(tan)(tan)面(mian)積分(fen)析(xi)儀測(ce)量(liang)活(huo)性(xing)炭(tan)(tan)的(de)表(biao)(biao)(biao)面(mian)積。
將環己烷(12.5mL)和活性炭(0.4g)裝載到自設雙(shuang)壁三口式(shi)間歇式(shi)反(fan)(fan)應(ying)器中。在分子氧(40mL / min)存在下(xia),在75℃攪拌混合物14小時 。堿性在同(tong)一(yi)組反(fan)(fan)應(ying)參數中NaOH:0.2 mmole的存在下(xia)也進行(xing)反(fan)(fan)應(ying)。環自烷通(tong)過氣相色譜分析轉化為KA油,使用(yong)交聯甲基硅氧烷毛細(xi)管柱(30μm,內徑0.32mm, 米 m膜厚),火焰離子化檢測器(FID)相連。
通過SEM分析(xi)活性(xing)炭的(de)表面形態。SEM圖(tu)為(wei)多孔(kong)(kong)結構(gou)、微孔(kong)(kong)/中(zhong)孔(kong)(kong)與活性(xing)炭內表面連接的(de)交(jiao)聯通道(dao)的(de)混(hun)合 1 。高放(fang)大倍(bei)率(lv)顯(xian)示2-10腔的(de)存在μ 米(mi) ,內部微孔(kong)(kong)和中(zhong)孔(kong)(kong)可以(yi)很容(rong)易地訪(fang)問。EDX分析(xi)(圖(tu) 2 )磷和二氧化硅顯(xian)示痕跡, 這些是(shi)花(hua)生殼的(de)主要(yao)內容(rong)。
討論活(huo)性炭實驗結(jie)果
含(han)(han)氧(yang)(yang)(yang)(yang)官(guan)(guan)能(neng)(neng)團(tuan)(tuan)(tuan)(tuan)(tuan)負責將環(huan)(huan)己烷(wan)(wan)氧(yang)(yang)(yang)(yang)化成(cheng)環(huan)(huan)己醇和環(huan)(huan)己酮(tong)(tong)(tong)(tong)。據廣泛(fan)報道,活性(xing)炭(tan)(tan)表(biao)(biao)面(mian)和分(fen)子氧(yang)(yang)(yang)(yang)通過(guo)(guo)含(han)(han)氧(yang)(yang)(yang)(yang)官(guan)(guan)能(neng)(neng)團(tuan)(tuan)(tuan)(tuan)(tuan),如堿、酮(tong)(tong)(tong)(tong)和醌。此(ci)外,通過(guo)(guo)含(han)(han)氧(yang)(yang)(yang)(yang)表(biao)(biao)面(mian)官(guan)(guan)能(neng)(neng)團(tuan)(tuan)(tuan)(tuan)(tuan)活性(xing)炭(tan)(tan)氧(yang)(yang)(yang)(yang)化反應,這些官(guan)(guan)能(neng)(neng)團(tuan)(tuan)(tuan)(tuan)(tuan)通過(guo)(guo)分(fen)子氧(yang)(yang)(yang)(yang)再生(sheng)。酚基是(shi)(shi)環(huan)(huan)己烷(wan)(wan)氧(yang)(yang)(yang)(yang)化*穩(wen)(wen)定(ding)、*主要的(de)來源,除(chu)其它(ta)含(han)(han)氧(yang)(yang)(yang)(yang)基團(tuan)(tuan)(tuan)(tuan)(tuan)外。對苯二(er)酚系統的(de)芬(fen)頓樣機(ji)制(zhi)是(shi)(shi)環(huan)(huan)己烷(wan)(wan)氧(yang)(yang)(yang)(yang)化傳播*有(you)可(ke)能(neng)(neng)的(de)方(fang)式。喹諾酮(tong)(tong)(tong)(tong)通過(guo)(guo)連續氧(yang)(yang)(yang)(yang)氣在(zai)反應混合物中(zhong)再生(sheng)。化學/熱處理(li)可(ke)用于表(biao)(biao)面(mian)官(guan)(guan)能(neng)(neng)團(tuan)(tuan)(tuan)(tuan)(tuan)(品種/密度)。例如,在(zai)*近的(de)研究中(zhong)TGA活性(xing)炭(tan)(tan)表(biao)(biao)面(mian)產生(sheng)的(de)氧(yang)(yang)(yang)(yang)官(guan)(guan)能(neng)(neng)團(tuan)(tuan)(tuan)(tuan)(tuan)通過(guo)(guo)熱處理(li)進行調整。高溫580活性(xing)炭(tan)(tan)℃下處理(li);。因此(ci),**現有(you)的(de)含(han)(han)氧(yang)(yang)(yang)(yang)官(guan)(guan)能(neng)(neng)團(tuan)(tuan)(tuan)(tuan)(tuan)將是(shi)(shi)醌。確認高溫(700°C)下醌官(guan)(guan)能(neng)(neng)團(tuan)(tuan)(tuan)(tuan)(tuan)的(de)穩(wen)(wen)定(ding)性(xing)。同樣,喹諾酮(tong)(tong)(tong)(tong)官(guan)(guan)能(neng)(neng)團(tuan)(tuan)(tuan)(tuan)(tuan)的(de)穩(wen)(wen)定(ding)性(xing)高達800°C。因此(ci),綜上(shang)所(suo)述(shu),環(huan)(huan)己烷(wan)(wan)氧(yang)(yang)(yang)(yang)化成(cheng)環(huan)(huan)己醇和環(huan)(huan)己酮(tong)(tong)(tong)(tong)遵循方(fang)案所(suo)示的(de)機(ji)制(zhi) 。
活(huo)性(xing)炭(tan)(tan)通過(guo)化(hua)學方法合成(cheng),環己(ji)烷中無(wu)溶劑(ji)氧(yang)(yang)化(hua)低分(fen)子(zi)氧(yang)(yang)。活(huo)性(xing)炭(tan)(tan)通過(guo)熱處理進行調節(jie),以發(fa)展表面上的(de)酚(fen)官能團(tuan)。*佳反(fan)應參數如下:反(fan)應物115.56mmol、活(huo)性(xing)炭(tan)(tan)0.4g、 溫(wen)度75℃、時間14小時。將催(cui)(cui)化(hua)劑(ji)的(de)催(cui)(cui)化(hua)活(huo)性(xing)與當前(qian)研究重要性(xing)生(sheng)產率報告的(de)文獻進行比較。催(cui)(cui)化(hua)劑(ji)重復使用幾(ji)次,說(shuo)明(ming)催(cui)(cui)化(hua)劑(ji)的(de)耐久性(xing)。結果表明(ming),醌基官能團(tuan)是(shi)分(fen)子(zi)氧(yang)(yang)化(hua)環己(ji)烷再生(sheng)的(de)*佳反(fan)應核心。發(fa)現活(huo)性(xing)炭(tan)(tan)是(shi)真(zhen)正具有延長(chang)壽命的(de)異相(xiang)催(cui)(cui)化(hua)劑(ji)。
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