【作者】 彭琥；

【导师】 俞斌； 朱毅青；

【作者基本信息】 南京工业大学 ， 应用化学， 2004， 硕士

【摘要】 本课题的前期研究工作已取得了实验室研究的良好进展，实验结果表明，本课题用溶胶-凝胶法制备的NiO／SiO₂-TiO₂催化剂是一种新型的优良的加氢催化剂。目前正在进行中试工业放大研究。在工业放大试验中，催化剂的成型是一个瓶颈问题。目前，关于超细镍基负载型催化剂的中试成型尚未见有文献报道。 因此，本课题主要在实验室研究的基础上，侧重于催化剂的中试成型工艺条件研究，通过小试、中试评价，考察中试成型条件对催化剂性能的影响，这一工作，对该催化剂的工业化应用具有十分重要的意义。 本文围绕这一中心问题工作，作了以下几方面的研究考察。 1 首先采用热脉冲的方法对比了3种不同的催化剂的热稳定性（三种催化剂分别为第一次挤条成型催化剂长岭2#，NCG型苯加氢催化剂，涂膜型催化剂JZ007），近似推算出3种催化剂的热失活速率方程。催化剂前驱体的物化性能用BET、TPR、XRD、TG—DTA、TEM及强度测定仪进行表征。用固定床连续流动微反装置，以苯加氢生成环己烷的反应对催化剂的催化性能进行实验室评价。 2 考察了催化剂组成对镍基负载型催化剂性能的影响，制备了8个催化剂，实验从3种途径考察了催化剂的性能：（1）氢苯比为3.1：1，3.5：1催化剂的反应活性温度，（2）当反应温度为160℃，220℃，氢苯比为3.1：1，3.5：1催化剂的反应空速范围，（3）通过飞温实验考察催化剂的热稳定性。 3 为解决催化剂侧压强度的不足，我们在实验室进行了超细镍基负载型催化剂实验室小试成型工艺条件研究，用硅溶胶及Ni²⁺-硅溶胶两种不同的胶粘剂进行挤条成型，通过BET、FT-IR、XRD、TPR等技术考察了催化剂在成型过程中，胶粘剂的浓度、粘度，湿／干粉比，催化剂老化时间，以及焙烧温度等因素对催化剂的强度以及催化剂的比表面积和孔结构的影响。结果表明：胶粘剂的性质、胶粘剂浓度、湿／干粉比对催化剂的比表面积、强度，有较大的影响。合适的成型工艺条件下，催化剂不但有较高的强度，而且催化剂的孔径分布很均匀，分布范围在1.1nm到3.3nm。 4 在实验室小试成型工艺条件的研究基础上，放大制备10公斤NiO／SiO₂-TiO₂工业中试用催化剂粉料，加胶粘剂A进行挤条成型，着重考察成型过程中加入胶粘剂后对催化剂性能的影响。研究结果表明，溶胶—凝胶法制备南京工业大学硕士学位论文得到的催化体系有大的比表面（>3 00m2/g），孔径分布单一。加入胶粘剂A时，催化剂的强度随着胶粘剂含量的增大而增大，当胶粘剂含量达到18%的时候，Nio/s 102一Tio:体系产生了新的晶相。胶粘剂的含量对催化剂的性能并无较大的影响，用固定床连续流动微反装置，考察催化剂苯加氢生成环己烷的催化性能，苯转化率均为100%，环己烷的选择性均达到99.0%以上。 5催化剂的中试评价结果与实验室小试评价结果非常接近，催化剂在只12=1.oMPa，LHSv=2.Oh一，，2200C，氢油比3.3:l的条件下，苯转化率100%，环己烷选择性99.92%，显示出优异的性能，与0510镍基催化剂的催老对比实验可以看出，300℃;2 .0/h;1 .OMPa氢苯比3.3:1条件下，运转70小时后，超细镍基负载型催化剂苯转化率仍然有，96.75%，而0510催化剂已经下降到58.56%，由此可以看出在比较苛刻的条件下，超细镍基负载型催化剂的热稳定性能更佳，这对以后工业侧线试验提供有利的保证。更多还原

【Abstract】 It has made the good progress of laboratory research in earlier stage of this subject, the result show that, the catalyst(NiO/SiO2-TiO2) prepared by Sol-Gel, is a kind of new-type fine hydro-catalysts . It is being enlarged and studies that carrying on pilot scale industry at present. In industry enlarges and tests, the form of the catalyst is a bottleneck question. At present, we have not found about the pilot scale shaping of ultrafine nickel base catalyst in document reportsSo, based on the laboratory research, the main work of this subject is get technological conditions of the pilot scale shaping process conditions of catalyst. This work, have very important meanings to use to the industrialization of this catalyst Around this central issue, we have done the researches of the following aspectsFirst, adopt by the methods of the thermal pulse, compare with three kinds different heat stability in catalyst of it is the approximate to calculate and publish 3 kinds catalyst hot to last living speed equation. The materialization performance of forerunner’s body of catalyst determines the appearance to signify with BET, TPR, XRD, TG-DTA, TEM and intensity. Flow littly in succession with fixed bed and add hydrogen turn into ring carry on laboratory appraise by own the response catalysis performance in catalyst s of alkenes with benzeneSecond, we has observed that the catalyst forms the impact on base catalyst performance of load type of nickel, Have prepared 8 pieces of catalyst, has observed the performance of the catalyst through threr kinds of ways in experiment : (l)The hydrogen benzene is to 3.1:1,3.5: l,The active temperature of response of catalyst,( 2) to act as temperature of reacting as 160癈, 220 癈, The hydrogen benzene is to 3.1:1,3. The LSHV range of catalyst of 3.5:1,( 3) observing heat stability of the catalyst through thermal pulse experiment.To improve the intensity of catalyst, we used the ultrafine particle NiO/TiOi-SiOi catalysts which were prepared by Sol-Gel method and two different adhesives: SiO2 and Ni2+-SiO2 adhesive. By wring the raw materials we had the catalysts extrusion molding. We used BET,FT-IR,XRD,TPR techniques to investigate the compression strength, the BET and the pore structure of catalysts by changing some factors such as the glutinousness and concentration of adhesive ,the ageing time and temperature and so on. The results showed that : the properties of adhesive and the concentration of adhesive have relatively great influence on the BET and pore structure of catalysts.Under the suitable condition, not only the compression strength of catalysts is relatively high,but also NiO particles of the supported ultrafine Ni catalysts disperse uniformly in the catalysts and their diameters arrange from 1.1 nm to 3.3nm.On the basis of research of the lab scale shaping process conditions of the catalyst, 10kg NiO/TiO2-SiO2 catalyst powder that used for industrial experiment was prepared by sol-gel method with the tetraethyl silicate N butyltitanate and nickel nitrate. Adhesive A was used for extrusion. The physical and chemical properties of the catalyst precursors were investigated by BE. XRD . TG-DTA . TEM and intensity test.The results show that, with the increase of the Adhesive content, the intensity of catalyst increases. XRD show NiO/SiO2-TiO2 has a new phases when the content of adhesive is 13%wt. The content of adhesive has little effect to the activity of catalyst. The results showed that these catalysts had good reaction activity and good cyclohexane selectivity in the Benzene hydrogenation reaction, the benzene conversion and cyclohexane selectivity kept 100% and 99.0% at 0.80Mpa> LVSH=1.0h"1 > and the ratio of benzene: H2=3.3:lThe pilot scales of catalyst appraise and laboratory lab scale appraise result result close very much, The catalyst is in PH2=1.0MPa , LHSV=2.0h’1, 220, the ratio of benzene and hydrogen is 3.3:1.benzene conversion ratio 100%, the own alkane alternative 99 of the ring . 92%, demonstrate excellent performance , one that is with 0510 nickel ba更多还原