|Place of Conferral||北京|
|Keyword||双环戊二烯 氢甲酰化反应 加氢反应 三环癸烷不饱和单醛 三环癸烷二甲醛 三环癸烷二甲醇|
双环戊二烯（DCPD）主要来源于石油裂解制乙烯的副产物C5馏分和煤炭炼焦副产物轻苯馏分，通过氢甲酰化和加氢反应DCPD可以合成一系列的高附加值精细化学品，如三环癸烷不饱和单醛（MFTD），三环癸烷二甲醛（DFTD），三环癸烷二甲醇（TDDMO）等。本文首先综述了DCPD在主要领域的应用与现状，介绍了烯烃氢甲酰化反应工艺及其催化剂的发展历程以及双环戊二烯氢甲酰化反应的研究进展及现实意义。随后，在DCPD氢甲酰化反应和加氢反应合成高附加值精细化学品的研究方面，做了如下研究：（1）采用吸附—沉淀法制备了纳米粉体ZnO、Al2O3、CeO2、TiO2（金红石）和TiO2（钙钛矿）担载的超低铑负载量催化剂。测试了这5种催化剂对DCPD氢甲酰化合成MFTD的活性效果，筛选出最优催化剂载体并进一步考察合成气压力、反应温度、反应时间、膦配体/催化剂质量比等因素对反应体系的影响。通过在不同温度不同反应时间对反应液取样分析，得到了一系列反应动力学数据。结果表明超低Rh负载量0.006%（质量百分比，下同） Rh/ZnO 在反应中表现出较高的催化性能，获得了94.10% MFTD产率和100% MFTD 选择性。而在相同反应条件下在0.006%Rh/Al2O3(CeO2、TiO2（金红石）和TiO2（钙钛矿）上只获得了10.82～57.59% MFTD选择性，这表明DCPD高效合成MFTD选择合适的催化剂载体是非常有必要的。DCPD氢甲酰化反应的动力学数据表明适宜的温度对提高DCPD的转化率有利，过高的温度可能会引起催化剂表面Rh活性位点的凝聚与烧结从而使催化剂的活性大大降低。0.006% Rh/ZnO催化剂的重复使用结果表明催化剂重复使用4次后催化活性不会有太大的变化，说明制备的催化剂有较好的稳定性。（2）采用共沉淀法制备了6种Fe3O4负载的Rh、Co-Rh催化剂，测试了其在DCPD氢甲酰化合成DFTD中的催化性能。DCPD合成DFTD反应过程分两步进行：第一步DCPD先生成MFTD；第二步改变反应条件使MFTD转化为DFTD。在Rh/Fe3O4上，当DCPD的转化率接近于100%时产物DFTD的选择性只有21.3%，但是当使用Co/Rh 为2：1的Co-Rh /Fe3O4时DFTD的选择性高达90.6%。为了弄清Co的引入对催化活性的影响，对这6种催化剂进行了TPR，TPD 和TG-DTA表征。TPR表征结果表明Co的引入在催化剂表面产生了活性更高的铑物种。H2-TPD分析结果表明随着引入一定量的Co可以增加Rh物种的分散度。TG-DTA结果表明钴含量影响Rh-P的强度，而Rh-P键的强度又会影响生成产物MFTD和DFTD的反应速率和选择性。其次考察了钴负载量对DCPD合成DFTD两步反应过程的动力学的影响。对于MFTD合成的影响，随着钴引入量的增加MFTD的生成速率逐渐加快，当Co/Rh为2时MFTD的生成速率达到最快，进一步增加钴的引入量MFTD的生成速率基本保持不变；对于DFTD合成的影响，随着钴的引入量的增加DFTD的生成速率逐渐加快，当Co/Rh为2时DFDT的生成速率达到最快，进一步增加钴的引入量DFTD的生成速率呈现下降的趋势，确定了较合适的催化剂为4Co-2Rh/Fe3O4。（3）以铁磁性氧化物Fe3O4为载体，RuCl3·xH2O及Ni(NO3)2·6H2O为活性组分前驱体，采用共沉淀法制备了一系列Ru-Ni/Fe3O4催化剂。以DFTD的催化加氢合成三环癸烷二甲醇为探针反应，在Ni为主催化剂的前提下，考察了Ru的添加量对催化剂性能的影响。测试结果表明Ru/Fe3O4能更大程度地提高反应物DCPD的转化率，Ni/Fe3O4能更大程度地提高产物TDDMO的选择性，而制备的Ru-Ni/Fe3O4既能提高DCPD的转化率又能提高产物TDDMO的选择性。即便在Ru的负载量很低的情况下，在钌改性的Ni/Fe3O4 上，DFTD的最高转化率达98%，TDDMO的选择性接近于97%。随Ru负载量的升高，Ru-Ni双金属催化剂的活性呈现先升高后降低的趋势，在Ru/Ni的原子比为1：9时催化剂活最高。 结合催化剂XRD、TPR表征深入研究了Ru的加入对催化剂性能影响的原因。XRD表征结果表明不论是钌物种还是镍物种在催化剂的表面均呈现高的分散性。TPR表征结果说明，对于一系列的RuOx-NiOy/FeOx催化剂，随着钌含量的增加，钌的还原峰温度发生了改变向高温移动，说明钌与镍存在协同作用，这是既能提高反应转化率又能提高目标产物选择性的主要原因。
Dicyclopentadiene (DCPD) mostly comes from both the C5 fraction by-product of ethylene cracking process and light benzene fraction of the coal-coking process. A series of value-added fine chemicals such as monoformyltricyclodecenes(MFTD), diformyltricyclodecanes(DFTD) and tricyclodecanedimethylol(TDDMO) will be synthesized with DCPD as the main feed. In this thesis, the development of the catalyst and the reaction process of the olefin hydroformylation, the practical significance and the recent development of the DCPD hydroformylation are reviewed and put study on the synthesis of value-added fine chemicals from DCPD. The main contents and conclusions are listed as follows:(1) The fabrication of 0.006%Rh/ZnO (Al2O3, CeO2, TiO2(rutile) and TiO2(anatase)) involved the use of nano powder ZnO (Al2O3, CeO2, TiO2(rutile), and TiO2(anatase)) as a support and rhodium chloride as the Rh precursor and the prepared catalysts were tested for DCPD hydroformylation to MFTD. 94.1% MFTD yield with 100% MFTD selectivity could be achieved over 0.006% Rh/ZnO catalyst, while only 10.82～57.59% MFTD yield were obtained over others under the same reaction conditions of 0.006% Rh/ZnO catalyst, suggesting that it is necessary to select an appropriate carrier for DCPD hydroformylation. The kinetics was systematically studied by examining reaction temperatures. Kinetic analysis suggested that an appropriate reaction temperature might be needed to obtain a higher MFTD yield; a higher reaction temperature might be brought out some agglomeration of the active site. (2) Six different Rh-based catalysts were prepared on Fe3O4 supports by co-precipitation and their catalytic performances in DCPD hydroformylation were evaluated. The overall hydroformylation of DCPD could be divided into two stages: Stage1, the hydroformylation of DCPD to MFTD; stage2, the further hydroformylation of MFTD to DFTD. When the DCPD conversion over the monometallic Rh/Fe3O4 catalyst was nearly complete, the selectivity to the desired DFTD product was only 21.3%, but the DFTD selectivity increased to 90.6% when cobalt was introduced into the system at a Co/Rh ratio of 2:1. In order to understand the effect of the introduction of Co on the catalytic activity, the TPR, TPD and TG-DTA characterizations of these 6 catalysts were performed. The TPR results indicated that the added cobalt likely enhanced the catalytic performance by giving rise to a more reactive Rh surface species. H2-TPD analysis showed that the Rh dispersion was improved with increasing cobalt loading. TG-DTA analysis showed that the cobalt loading affected the Rh–P interaction strength, which resulted in different reaction rates and product distributions.In addition, the effect of cobalt loading on the kinetics of the two-step reaction of DFTD synthesis from DCPD was investigated. For the effect of MFTD synthesis, the formation rate of MFTD is gradually increased with the increase of cobalt loading. When Co/Rh is 2, the formation rate of MFTD is the fastest. However, when further increasing the amount of cobalt loading, the formation rate of MFTD remains basically unchanged; For the effect of DFTD synthesis, the formation rate of DFTD increases gradually with the increase of the amount of cobalt loading. When Co/Rh is 2, the generation rate of DFDT is the fastest. When further increasing the amount of cobalt introduced, the generation rate of DFTD tends to decrease. A suitable catalyst was determined to be 4Co-2Rh/Fe3O4. (3) A series of Ru-Ni/Fe3O4 catalysts were prepared via coprecipitation method, using Fe3O4 as the support and RuCl3·xH2O and Ni(NO3)2·6H2O as precursors. The effects of Ru addition on catalytic performance were studied using hydrogenation of DFTD to TDDMO as the probe reaction.The test results show that monometallic Ru/Fe3O4 catalyst is conducive to the conversion of the reaction and Ni/Fe3O4 catalyst is contribute to selectivity of the product TDDMO. However, the prepared Ru-Ni/Fe3O4 can not only improve the conversion rate of DCPD but also improve the TDDMO selectivity. The conversion of DFTD was greatly increased to 98% but the selectivity of TDDMO was remarkly enhanced to 97% using the modifying Ni/Fe3O4 catalysts with ruthenium catalyst, even at a very lowing Ru loading. With the increase of Ru loading, the activity of Ru-Ni bimetallic catalysts first increases and then decreases. The catalyst activity is highest when the Ru/Ni atomic ratio is 1:9.In combination with the XRD and TPR characterizations, the influence of the addition of Ru on the performance of the catalyst was thoroughly studied. XRD results revealed that the Ru and Ni species were highly dispersed on magnetic iron oxide matrix. The TPR results indicated that there is a synergetic effect between ruthenium and nickel species and that the added ruthenium likely enhanced the catalytic performance by giving rise to a more reactive nickel surface species.
|李成阳. 双环戊二烯合成高附加值精细化学品的研究[D]. 北京. 中国科学院大学,2018.|
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