Acid-activated and WO_x-loaded montmorillonite catalysts and their catalytic behaviors in glycerol dehydration  

催化甘油脱水反应的酸活化蒙脱石负载WO_x催化剂的研究（英文）

作　　者：Weihua Yu Pengpeng Wang Chunhui Zhou Hanbin Zhao Dongshen Tong Hao Zhang Huimin Yang Shengfu Ji Hao Wang 俞卫华;王朋朋;周春晖;赵汉彬;童东绅;张浩;杨慧敏;季生福;王浩(浙江工业大学之江学院,浙江杭州310024;浙江工业大学化学工程学院,绿色化学合成技术国家重点实验室培育基地,浙江杭州310032;南昆士兰大学未来材料研究所,澳大利亚图文巴4350;浙江省地质矿产研究所,浙江省非金属矿物工程研究中心,浙江杭州310007;国家林业局竹子研究开发中心,浙江省竹子高效加工重点实验室,浙江杭州310012;北京化工大学,化工资源有效利用国家重点实验室,北京100029)

机构地区：[1]Zhijiang College, Zhejiang University of Technology, Hangzhou 310024, Zhejiang, China [2]Research Group for Advanced Materials & Sustainable Catalysis (AMSC), Research Center for Clay Minerals, State Key Laboratory Breeding Base of Green Chemistry Synthesis Technology, Discipline of Industrial Catalysis, College of Chemical Engineering, Zhejiang University of Technology, Hangzhou 310 [3]Centre for Future Materials, University of Southern Queensland, Toowoomba, Queensland 4350, Australia [4]Engineering Research Center of Non‐metallic Minerals of Zhejiang Province, Zhejiang Institute of Geology and Mineral Resource, Hangzhou 310007, Zhejiang, China [5]Key Laboratory of High Efficient Processing of Bamboo of Zhejiang Province, China National Bamboo Research Center, Hangzhou 310012, Zhejiang,China [6]State Key Laboratory of Chemical Resource Engineering, Beijing University of Chemical Technology, Beijing 100029, China

出　　处：《Chinese Journal of Catalysis》2017年第6期1087-1100,共14页催化学报（英文）

基　　金：supported by the National Natural Science Foundation of China(21373185,41672033,21506188,21404090);the Open Project Programs of Engineering Research Center of Non-metallic Minerals of Zhejiang Province(ZD2015k07);of State Key Laboratory Breeding Base of Green Chemistry-Synthesis Technology(GCTKF2014006);of Key Laboratory of High Efficient Processing of Bamboo of Zhejiang Province(2016);of State Key Laboratory of Chemical Resource Engineering,Beijing University of Chemical Technology(CRE-2016-C-303)~~

摘　　要：The use of H2SO4‐,HCl‐,H3PO4‐,and CH3COOH‐activated montmorillonite(Mt)and WOx/H3PO4‐activated Mt as catalysts for the gas‐phase dehydration of glycerol was investigated.The WOx/H3PO4‐activated Mt catalysts were prepared by an impregnation method using H3PO4‐activated Mt(Mt‐P)as the support.The catalysts were characterized using powder X‐ray diffraction,Fourier‐transform infrared spectroscopy,N2adsorption‐desorption,diffuse reflectance ultraviolet‐visible spectroscopy,temperature‐programmed desorption of NH3,and thermogravimetric analysis.The acid activation of Mt and WOx loaded on Mt‐P affected the strength and number of acid sites arising from H+exchange,the leaching of octahedral Al3+cations from Mt octahedral sheets,and the types of WOx(2.7≤x≤3)species(i.e.,isolated WO4/WO6‐containing clusters,two‐dimensional[WO6]polytungstates,or three‐dimensional WO3crystals).The strong acid sites were weakened,and the weak and medium acid sites were strengthened when the W loading on Mt‐P was12wt%(12%W/Mt‐P).The12%W/Mt‐P catalyst showed the highest catalytic activity.It gave a glycerol conversion of89.6%and an acrolein selectivity of81.8%at320°C.Coke deposition on the surface of the catalyst led to deactivation.甘油是一种可由生物资源生产、可持续的、可降解的平台化学品,是生物柴油、肥皂化工等工业生产过程中的主要副产物.催化甘油脱水反应生产丙烯醛,有望能替代丙烯等石油裂解产物合成丙烯醛的传统工业路线.丙烯醛是一种重要的化工中间体,被用于合成蛋氨酸、丙烯酸、3-甲基吡啶和1,3-丙二醇,并被广泛地应用于农药、医药、高分子材料等领域.随着全球可持续能源发展,生物柴油生产迅速发展,将产生大量的副产物甘油.利用甘油为原料,通过合适的催化剂的催化脱水反应生成丙烯醛,是近十多年来国内外工业催化的研究热点之一.用于催化甘油脱水合成丙烯醛的酸催化剂有杂多酸、金属氧化物、沸石与酸性粘土矿物等.钨磷杂多酸(H_3PW_(12)O_(40))负载的催化剂虽然具有较强的酸性,有利于催化甘油脱水,但容易导致结焦,而且热稳定差,容易失活.钨磷杂多酸负载于SiO_2,TiO_2,Al_2O_3,SiO_2-Al_2O_3,K-10蒙脱石上表现出不同的催化活性,表明催化剂和载体的表面酸性和孔结构影响催化性能.近来研究发现,负载于ZrO_2,Al_2O_3的钨氧化物(WO_x)催化剂热稳定性好、酸性高,在甘油脱水反应生成丙烯醛中表现出良好的催化性能.但有关钨氧化物(WO_x)结构、催化活性受载体组成、酸性影响的本质和规律一直不清楚.本文采用20 wt%的硫酸、盐酸、磷酸和乙酸对蒙脱石进行酸改性,并在磷酸改性的蒙脱石上负载W含量为4–16 wt%的WO_x作为催化剂,用于甘油气相脱水反应.X-射线衍射(XRD)、热重-差热法(TG-DTG)、氨程序升温脱附(NH_(3^-)TPD)、红外光谱(FT-IR)和紫外漫反射可见光谱(DR UV-vis)等表征,探讨了酸改性和负载WO_x的蒙脱石对催化剂催化性能的影响.蒙脱石经过20wt%的硫酸、盐酸、磷酸和乙酸的活化,酸性增加.四种酸改性的蒙脱石对甘油气相脱水反应均有催化活性,这是因为在蒙脱石酸活化

关 键 词：GLYCEROL ACROLEIN DEHYDRATION WOx Acid‐activated nanoclay Catalyst 

分 类 号：O643.36[理学—物理化学]