Knowledge Management System Of Institute of process engineering,CAS
|导师||宋文立 ; 王泽|
|关键词||生物质 发酵渣 酚醛树脂 催化 热解|
With depletion of coal and petroleum fossil fuels, the utilization of biomass as an important resource of renewable energy is urgently demanded. Among the biomass materials, the resource of lignin rich biomass, including the black liquid and the lignocellulose fermentation residue is abundant, but has not been utilized high efficiently. However, whatever the type of biomass is, the unavoidable shortcomings of the pryolytic liquid such as the complexity of the composition and the low heat value extremely restricted the application of the pyrolytic liquid. The two methods of catalytic pyrolysis and co-pyrolysis with plastics were thereby frequently used for upgrading of the pyrolytic liquid. On another hand, waste circuit board discarded every year in large amount is an important issue related to environment, energy, and materials. Therefore, the pyrolysis of phenolic resin, as a major component of circuit, is a potential way to recover energy materials (fuel gas and char) and other high value chemicals. Based on the above reasons, the individual pyrolysis of phenolic resin and corn straw fermentation residue, the co-pyrolysis of their mixture, and the catalytic pyrolsis of the fermentation residue were investigated, through the TG and Py-GC/MS method. Additionally, kinetic analyses were conducted on the individual pyrolytic behaviors of the two materials of phenolic resin and fermentation residue with a similar phenolic structure by the Coats-Redfern method. Some of the major results are as follows:The initial pyrolytic temperature of phenolic resin is higher, indicating a higher stability of the material. The pyrolytic liquid product mainly consists of phenol, methylphenol, dimethylphenol, and their derivatives, accompanied with a low amount of aromatics and some special structure related products. On the contrary, the initial pyrolytic temperature is rather low and the products are broadly scattered in the types of small acids, alkyl phenols, alkoxy phenols, aromatics, etc. Particularly, 2,3-dihydro-benzofuran is a major and specific product from pyrolysis of fermentation residue. Under the synergistic effect by co-pyrolysis of fermentation residue and phenolic resin, the formation of aromatics is restricted while alkyl phneols are more generated; the content of alkoxy phenol appears a maximum value varied with increasing temperature, and the formation of alkoxy phenol is promoted at low temperatures but hindered at high temperatures; the gas products of CH4 and CO are more generated, while the formation of H2 is hindered severely.Under the catalysis of ZSM-5 and Y zeolite, the content of aromatics is increased and comparatively the effect of ZSM-5 is more distinct, while the content of alkyl phenols is decreased, except that phenol is more generated, and comparatively the effect of Y zeolite is more remarkable. Under the influences of SAPO-34 and ZSM-5, alkoxy phenols are more generated at lower temperatures but are reduced at higher temperatures. Comparatively, Y zeolite has a strongest effect in promoting the conversion of alkoxy phenols, while the influence of SAPO-34 is weakest to all product components. Kinetic analysis illustrated that the pyrolysis of phenolic resin is a diffusion controlled process in the conversion range of 25% - 75%. The pyrolysis of fermentation reside is much more complex than that of phenolic resin, and thus the whole process has to be analyzed by stages: in the conversion range of 10%-50%, the pyrolysis of fermentation residue is also predominantly controlled by diffusion process; in the higher conversion range of 50% to 75%, no mechanic function was found qualified in description of the reaction stage, while relatively a second order reaction model has a higher correlation level with the experimental results, with a much lower activation energy value.
|马蕊. 秸秆发酵渣的催化热解及其与酚醛树脂的共热解研究[D]. 北京. 中国科学院研究生院,2016.|