化学研究与应用
化學研究與應用
화학연구여응용
CHEMICAL RESEARCH AND APPLICATION
2014年
7期
1066-1073
,共8页
成咏澜%张文华%廖学品%石碧
成詠瀾%張文華%廖學品%石碧
성영란%장문화%료학품%석벽
胶原纤维%模板%TiO2-ZrO2 复合氧化物%载体%酯化
膠原纖維%模闆%TiO2-ZrO2 複閤氧化物%載體%酯化
효원섬유%모판%TiO2-ZrO2 복합양화물%재체%지화
collagen fiber%template%TiO2-ZrO2 mixed oxides%support%esterification reaction
本文以胶原纤维为模板,制备了多孔纤维状TiO2-ZrO2复合氧化物,并以此为载体制备了多孔纤维状SO42-/TiO2-ZrO2固体酸。 SEM观察发现TiO2-ZrO2和SO42-/TiO2-ZrO2均复制了胶原纤维独特的纤维结构, TiO2-ZrO2氧化物的比表面积达到77．51 m2·g-1；XRD分析发现,Ti-Zr摩尔比对TiO2-ZrO2的晶相结构有重要影响,当Ti/Zr摩尔比为0．67∶1时,TiO2-ZrO2以TiZrO4晶相为主；NH3-TPD分析表明SO42-/TiO2-ZrO2的酸量及酸强度与Ti-Zr摩尔比以及活化温度有着密切关系。在乙酸与正丁醇的酯化反应中,多孔纤维状SO42-/TiO2-ZrO2固体酸表现出优良的催化性能。当催化剂用量为6．5wt%,反应时间为60min时,乙酸的转化率高达98．1%；该固体酸催化剂重复使用性优良,循环使用5次时,转化率仍然保持在85%以上。
本文以膠原纖維為模闆,製備瞭多孔纖維狀TiO2-ZrO2複閤氧化物,併以此為載體製備瞭多孔纖維狀SO42-/TiO2-ZrO2固體痠。 SEM觀察髮現TiO2-ZrO2和SO42-/TiO2-ZrO2均複製瞭膠原纖維獨特的纖維結構, TiO2-ZrO2氧化物的比錶麵積達到77．51 m2·g-1；XRD分析髮現,Ti-Zr摩爾比對TiO2-ZrO2的晶相結構有重要影響,噹Ti/Zr摩爾比為0．67∶1時,TiO2-ZrO2以TiZrO4晶相為主；NH3-TPD分析錶明SO42-/TiO2-ZrO2的痠量及痠彊度與Ti-Zr摩爾比以及活化溫度有著密切關繫。在乙痠與正丁醇的酯化反應中,多孔纖維狀SO42-/TiO2-ZrO2固體痠錶現齣優良的催化性能。噹催化劑用量為6．5wt%,反應時間為60min時,乙痠的轉化率高達98．1%；該固體痠催化劑重複使用性優良,循環使用5次時,轉化率仍然保持在85%以上。
본문이효원섬유위모판,제비료다공섬유상TiO2-ZrO2복합양화물,병이차위재체제비료다공섬유상SO42-/TiO2-ZrO2고체산。 SEM관찰발현TiO2-ZrO2화SO42-/TiO2-ZrO2균복제료효원섬유독특적섬유결구, TiO2-ZrO2양화물적비표면적체도77．51 m2·g-1；XRD분석발현,Ti-Zr마이비대TiO2-ZrO2적정상결구유중요영향,당Ti/Zr마이비위0．67∶1시,TiO2-ZrO2이TiZrO4정상위주；NH3-TPD분석표명SO42-/TiO2-ZrO2적산량급산강도여Ti-Zr마이비이급활화온도유착밀절관계。재을산여정정순적지화반응중,다공섬유상SO42-/TiO2-ZrO2고체산표현출우량적최화성능。당최화제용량위6．5wt%,반응시간위60min시,을산적전화솔고체98．1%；해고체산최화제중복사용성우량,순배사용5차시,전화솔잉연보지재85%이상。
In the present study,a novel porous and fibrous composite oxide of TiO2-ZrO2 was prepared using collagen fiber as tem-plate,and the composite oxide was further used as support to prepare SO4 2-/TiO2-ZrO2 solid acid. SEM observation showed that the morphology of collagen fiber has been successfully duplicated by TiO2-ZrO2 and SO4 2-/TiO2-ZrO2 ,and the specific surface area of as-prepared TiO2-ZrO2 was as high as 77. 51 m2·g-1 . XRD analysis indicated that the mole ratio of Ti/Zr would greatly influence the crystalline phases of TiO2-ZrO2. When the mole ratio of Ti/Zr was 0. 67∶1,TiZrO4 was the main crystalline phase of TiO2-ZrO2 composite oxide. NH3-TPD determination results showed that the acid content and acid strength of porous fibrous SO4 2-/TiO2-ZrO2 solid acid was greatly related with mole ratio of Ti/Zr and activation temperature. In the esterification reaction of acetic acid and n-butyl alcohol,porous and fibrous SO4 2-/TiO2-ZrO2 solid acid exhibited excellent catalytic activity. It was found that when the dosage of SO4 2-/TiO2-ZrO2 was 6. 5 wt%,the conversion extent of acetic acid was 98. 1%at 60 minutes. In addition,the as-prepared solid acid catalyst also has good reusability,the conversion extent was still higher than 85%at the 5th recycling.
