改性锡丝光沸石催化混合糖脱水制备5-羟甲基糠醛  

Dehydration of sugar mixtures to 5-hydroxymethylfurfural catalyzed by modified tin-mordenite

作　　者：张若楠 李钢[1] 麻忠敏 吕强 ZHANG Ruonan;LI Gang;MA Zhongmin;LÜQiang(State Key Laboratory of Fine Chemicals,School of Chemical Engineering,Dalian University of Technology,Dalian 116024,China;Qingdao Sanli Benno New Materials Co.,Ltd.,Qingdao 266000,China)

机构地区：[1]大连理工大学化工学院精细化工国家重点实验室,辽宁大连116024 [2]青岛三力本诺新材料股份有限公司,山东青岛266000

出　　处：《燃料化学学报（中英文）》2024年第8期1070-1078,共9页Journal of Fuel Chemistry and Technology

摘　　要：采用酸处理脱铝补位两步法对丝光沸石(MOR)锡改性制备了系列Sn-MOR催化剂,用X射线衍射(XRD)、紫外-可见漫反射光谱(UV-vis)、氨程序升温脱附(NH3-TPD)、X射线荧光光谱(XRF)对其进行表征。结果表明,改性后催化剂仍保持丝光沸石的晶体结构,酸中心强度与酸量有改变,同时在沸石骨架中引入了锡。研究了改性丝光沸石催化单糖(葡萄糖、果糖)及混合糖生成5-羟甲基糠醛(HMF),结果表明,改性后的Sn-MOR仍保持MOR对果糖脱水为HMF的较高催化活性,同时引入的锡物种对葡萄糖具有异构化活性,因此,Sn-MOR可以同时催化葡萄糖和果糖脱水生成HMF。以商品果葡糖浆作为反应底物,在果葡糖浆质量1.94 g,催化剂用量0.3 g,反应温度170℃,反应时间3 h的较优反应条件下,以3.76-Sn-MOR1为催化剂,果葡糖浆转化率91.82%,HMF产率63.76%,HMF选择性69.43%;催化剂循环使用五次,仍保持了一定的催化活性,HMF产率仍有49.5%。5-hydroxymethylfurfural(HMF)is a versatile compound that has great market potential in the future chemical industry.HMF production from fructose has a problem of higher cost,while HMF production from glucose has a problem of lower yield.Therefore,the use of relatively inexpensive biomass-derived syrup to produce HMF in order to achieve industrial production is currently a research hotspot.A series of Sn-MOR catalysts were prepared by using mordenite zeolite(H-MOR)as a carrier,which was modified with acid treatment and adding tin to remove Al and replenish Sn.The Sn-MOR catalysts were characterized by X-ray diffraction(XRD),diffuse reflectance ultraviolet-visible spectra(UV-vis),ammonia temperature programmed desorption(NH3-TPD),and X-ray fluorescence spectroscopy(XRF).The characterization results showed that the Sn-MOR still maintained the crystal structure of mordenite,with changes in strength and content of acid centers,and Sn was inserted into the zeolite skeleton.Glucose and fructose were used as substrates in the catalytic reaction of unmodified H-MOR and modified Sn-MOR,and the experimental results showed that H-MOR catalyzed the dehydration reaction of glucose poorly,with a HMF yield of only 7.08%,but its catalytic performance in dehydration of fructose was better,with a HMF yield of 76.78%.The modified Sn-MOR possessed isomerization activity,which improved the reactivity of glucose dehydration with a HMF yield of 38.65%,while the modified Sn-MOR still maintained the high catalytic activity of MOR for fructose dehydration to HMF.Using sugar mixtures(mhydrated glucose∶mfructose=1∶1)as the substrate,the reaction performance of the catalysts with different tin metal additions to H-MOR was firstly investigated,and the results showed that 3.76-Sn-MOR with 3.76%tin addition catalyzed the dehydration of the sugar mixtures better.The reaction performance of the catalyst prepared by adding tin after H-MOR acid treatment was further investigated,and the results showed that the 3.76-Sn-MOR1 prepared by acid treat

关 键 词：混合糖 5-羟甲基糠醛 锡-丝光沸石 脱铝补位 脱水反应 

分 类 号：O643.36[理学—物理化学]