催化学报
催化學報
최화학보
CHINESE JOURNAL OF CATALYSIS
2015年
3期
400-407
,共8页
王正宝%张琪%路晓飞%陈双佳%刘春杰
王正寶%張琪%路曉飛%陳雙佳%劉春傑
왕정보%장기%로효비%진쌍가%류춘걸
共沉淀法%低碱度%苯%选择加氢%钌锌催化剂
共沉澱法%低堿度%苯%選擇加氫%釕鋅催化劑
공침정법%저감도%분%선택가경%조자최화제
Coprecipitation%Low alkalinity%Benzene%Selective hydrogenation%Ru-Zn catalyst
在低碱度下采用共沉淀法成功制备了非负载型Ru-Zn催化剂,用于苯选择加氢制环己烯反应.固定氢氧化钠沉淀剂的量,考察了不同氯化锌加入量对催化剂结构和催化性能的影响,采用N2吸附、X射线衍射和程序升温还原等手段对催化剂进行了表征.同时考察了选用具有最佳锌含量的Ru-Zn催化剂时搅拌速度和硫酸锌添加剂等对催化反应性能的影响,最后考察了催化剂多次使用时的反应性能.研究表明, Zn含量16.7%(质量分数)的Ru-Zn催化剂具有最佳的催化性能;在ZnSO4水溶液(0.45 mol/L)中,优化反应条件(哈氏合金釜,1200 r/min,150oC, H2压5 MPa)下反应45 min,苯转化率57%时环己烯选择性可达80%(收率超过45%).钌催化剂中ZnO晶体对于环己烯选择性达到80%非常重要.催化剂回收循环反应5次时反应性能基本不变,表明低碱度下制备的催化剂具有良好的稳定性,显示了工业化应用前景.
在低堿度下採用共沉澱法成功製備瞭非負載型Ru-Zn催化劑,用于苯選擇加氫製環己烯反應.固定氫氧化鈉沉澱劑的量,攷察瞭不同氯化鋅加入量對催化劑結構和催化性能的影響,採用N2吸附、X射線衍射和程序升溫還原等手段對催化劑進行瞭錶徵.同時攷察瞭選用具有最佳鋅含量的Ru-Zn催化劑時攪拌速度和硫痠鋅添加劑等對催化反應性能的影響,最後攷察瞭催化劑多次使用時的反應性能.研究錶明, Zn含量16.7%(質量分數)的Ru-Zn催化劑具有最佳的催化性能;在ZnSO4水溶液(0.45 mol/L)中,優化反應條件(哈氏閤金釜,1200 r/min,150oC, H2壓5 MPa)下反應45 min,苯轉化率57%時環己烯選擇性可達80%(收率超過45%).釕催化劑中ZnO晶體對于環己烯選擇性達到80%非常重要.催化劑迴收循環反應5次時反應性能基本不變,錶明低堿度下製備的催化劑具有良好的穩定性,顯示瞭工業化應用前景.
재저감도하채용공침정법성공제비료비부재형Ru-Zn최화제,용우분선택가경제배기희반응.고정경양화납침정제적량,고찰료불동록화자가입량대최화제결구화최화성능적영향,채용N2흡부、X사선연사화정서승온환원등수단대최화제진행료표정.동시고찰료선용구유최가자함량적Ru-Zn최화제시교반속도화류산자첨가제등대최화반응성능적영향,최후고찰료최화제다차사용시적반응성능.연구표명, Zn함량16.7%(질량분수)적Ru-Zn최화제구유최가적최화성능;재ZnSO4수용액(0.45 mol/L)중,우화반응조건(합씨합금부,1200 r/min,150oC, H2압5 MPa)하반응45 min,분전화솔57%시배기희선택성가체80%(수솔초과45%).조최화제중ZnO정체대우배기희선택성체도80%비상중요.최화제회수순배반응5차시반응성능기본불변,표명저감도하제비적최화제구유량호적은정성,현시료공업화응용전경.
Several unsupported Ru‐Zn catalysts were successfully prepared using the coprecipitation method under low alkaline conditions, and their catalytic performance was evaluated for the selective liq‐uid‐phase hydrogenation of benzene. The effect of the amount of ZnCl2 added to the coprecipitation solution on the physical and catalytic properties of the Ru‐Zn catalysts was studied whilst keeping the amount of the NaOH precipitant constant. The properties of the resulting catalysts were charac‐terized by N2 adsorption, X‐ray diffraction, and temperature‐programmed reduction. The effects of the stirring rate and the amount of ZnSO4 additive on the catalytic properties of the Ru‐Zn catalysts were investigated using the optimal Zn content. The recyclability of the optimal Ru‐Zn catalyst was also explored. The results revealed that the optimal Zn content for the Ru‐Zn catalysts was 16.7 wt%, and the selectivity for cyclohexene could reach up to 80%(yield>45%) when the benzene conversion was 57%in an aqueous solution of ZnSO4 (0.45 mol/L) under the optimal reaction con‐ditions (i.e., hastelloy reactor, 1200 r/min, 150 °C and 5 MPa of H2 pressure). The presence of ZnO crystals in the Ru catalysts was found to be critical to obtaining high selectivity for cyclohexene (>80%). The Ru‐Zn catalysts prepared under the low alkaline conditions also showed good stability, which indicates that they could potentially be used for industrial application.