【作者】 李小玉；

【导师】 石秋杰；

【作者基本信息】 南昌大学 ， 工业催化， 2007， 硕士

【摘要】 本文第一部分采用正交实验法优化海泡石的改性条件，包括盐酸溶液中HCl的质量分数、酸处理时间、焙烧温度和焙烧时间。以改性后的海泡石和工业上常用γ-Al₂O₃为载体，采用浸渍和化学还原法制备了Ni-B-Mo／Sep（Sep：不同改性条件制备的海泡石）和Ni-B-Mo／γ-Al₂O₃催化剂。以糠醛液相加氢制糠醇为探针反应，考察了催化剂的性能。实验结果表明：海泡石的最佳改性条件为，盐酸溶液中HCl的质量分数10％、酸处理时间48h、焙烧温度400℃、焙烧时间6h。经最佳条件改性后的海泡石(记为Sep（opt）的比表面积为112.5 m²／g，是未改性海泡石的2.38倍；Ni-B-Mo／Sep（opt）催化剂的活性比表面积为17.61 m²／g。具有较好的催化性能，糠醛转化率和糠醇选择性分别为83.8％和98.7％，均优于Ni-B-Mo／γ-Al₂O₃催化剂。采用电感耦合等离子发射光谱（ICP）、差热分析技术（DTA）、NH₃吸附红外光谱法（IR）、比表面积测试（BET）、程序升温还原（TPR）和程序升温脱附（TPD）等表征手段，考察了载体对Ni-B-Mo合金催化剂性能的影响。研究结果表明，Ni-B-Mo／sep表现出高活性主要是由于其独特的合金组成、较高的Ni含量、适量的L酸中心，以及海泡石本身含有的Fe元素能修饰Ni-B-Mo合金，Ni-B-Mo／sep催化剂对反应物具有更多数量的中等强度吸附中心，对产物具有更少数量的吸附中心。Ni-B-Mo／Sep选择性更高主要是由于其对糠醇吸附的强度较弱不易发生深度加氢所致。本文第二部分采用超声-浸渍方法制备Ni／γ-Al₂O₃催化剂，并用以催化糠醛加氢制2-甲基呋喃。分别采用稀土元素、过渡金属元素和对Ni／γ-Al₂O₃催化剂进行了改性，取得了较好的效果。用稀土元素改性时，Nd和Eu可以提高了催化剂的选择性，对2-甲基呋喃的选择性从93.1％分别提高到96.2％和97.4％。用过渡金属元素改性时，Mo、W元素和Ni存在协同作用，均能使催化剂的选择性大幅度提高，选择性从93.1％分别提高到96.8％、98.8％。所有催化剂的活性为100％。更多还原

【Abstract】 In the first part of this paper, orthogonal test design was applied to optimizesepiolite modification conditions such as acid concentration, acid treatment time,calcination temperature and calcination time. Supported Ni-B-Mo amorphous alloycatalysts were prepared by impregnation combined with chemical reduction methodusing treated sepiolite andγ-Al₂O₃ as carriers. The liquid phase hydrogenation offurfural （FFR） to furfural alcohol （FFA） was selected as probe reaction. Catalyticperformance of Ni-B-Mo carried by diffirent modificated Sepiolites were investigatedto identify the best modification condition. The results show that Sepiolite treated by10％（mass fraction） HCl for 48 h and calcined at 400℃for 6 h exhibit optimalcatalytic performance.Specific surface area of the sepiolite modificated with optimium condition is112.5 m²/g, which is 2.38 times of that of unmodified sepiolite. Active specificsurface area of catalyst with the optimal carder is 17.61 m²/g tested by H₂-TPD. Itsconversion of furfural and selectivity to furfural alcohol is 83.8％and 98.7％,respectively. The conversion and selectivity of Ni-B-Mo/Sep（O） are higher than thoseof Ni-B-Mo/γ-Al₂O₃.Effects of carriers on the the properties of the catalyst were investigated byInductively Coupled Plasma-Atomic Emission Spectroscopy, differential thermalanalysis, NH₃-adsorption infrared spectra, BET surface area, temperatureprogrammed reduction, temperature programmed desorption of hydrogen, furfural andfurfural alcohol. The results show that Ni-B-Mo/Sep exhibits high activity and highselectivity to furfural alcohol. The high activity was attributed to the unique structureof amorphous alloy, more loading of Ni, lewis acid, the promoting effect of Fe insepiolite, more middle-strength adsorption center to H₂ or FFR and less adsorptioncenter to FFA. The superior selectivity to furfural alcohol was mainly due to theweaker adsorption of FFA on Ni-B-Mo/Sep, thus further hydrogenation of FFA wasprevented.In the second part of this paper, Supported Ni/γ-Al₂O₃ catalysts for thehydrogenation of furfural to 2-methylfuran were prepared by impregnation combinedwith ultrasound. The addition of Nd or Eu can make the selectivity to 2-methylfuranof Ni/γ-Al₂O₃ increased from 93.1％to 96.2％or 97.4％, respectively. While Mo andW can also enhance the selectivity of the catalyst and the selectivity increased from93.1％to 96.8％or 98.8％. The catalytic activity of all the catalysts is 100％更多还原