为了获得高质量生物质燃料油,需要对生物质直接裂解得到的生物质油进行催化裂解精制;精制过程中催化剂容易结焦,对精制反应产生很大影响。今采用热重,红外,核磁等分析手段,对生物质油催化裂解精制中所使用的催化剂HZSM-5上的焦炭前驱物进行了表征,从而对焦炭的生成以及催化剂再生进行深入研究。结果表明沉积在催化剂表面上的焦炭前驱物主要是短链饱和烃类化合物,沸点在200℃以下;催化剂内部的结焦前驱物主要为芳香族碳氢化合物,这些化合物的沸程范围在350-650℃。此外还对催化剂HZSM-5采用在空气中600℃焙烧的方式再生以及再生次数对产物量和催化活性的影响进行了研究。结果表明:再生前三次,催化剂活性变化不大,随着再生次数的增加,催化剂活性受到影响程度也增大。
In preparation of motor fuel, the bio-oil from pyrolysis of biomass must be further upgraded (catalytic cracking ) so as to improve its quality. However the catalyst used in the cracking reaction is easy to lose its activity due to being coked, so that it is important to study the coke formation and its effects on the catalyst activity in the cracking process. TGA, FTIR and CNMR were used to analyze the precursor of coke on the catalyst HZSM-5 used in upgrading and based on it the mechanism of coking was discussed too. The results indicates that precursors of coke deposited inside the pore of the molecular sieve are mainly aromatic hydrocarbons with the boiling points ranging from 350 ℃ to 650 ℃. Those precursors on the outer surface of the catalyst were identified as saturated aliphatic hydrocarbons with the boiling points below 200 ℃. The effect of regenerating the deactivated HZSM-5 through calcining it in air at 600℃ was also studied. In terms of the yield of organic distillate and the formation rate of coke, the results show that reused catalytic activity changes moderately during the first 3 times of regeneration, while the reused catalyst is gradually deactivated after repeated regenerations more than 3 times.