生物质与油浆共热解产物分布及相互作用

Product distribution and interaction of co-pyrolysis of biomass and oil slurry

  • 摘要: 生物质作为一种全生命周期碳近零排放的可再生资源,从生物质中提取轻质燃料和化学品是实现碳达峰和碳中和的终极方向。将化石能源与生物质共转化是符合我国的基本国情、寻求化石能源和新能源优化组合的可行之路。以玉米秆(CS)与催化裂化油浆(FCC)为原料,研究了2者共热解过程中的相互作用及生物质内在矿物质对产物分布和产物特性的影响。结果表明,不同比例的CS与FCC油浆共热解过程中的相互作用以聚合反应为主,导致所得半焦产率均有所增加,进一步分析发现反应过程中的相互作用增强了热解焦油中含氧化合物的脱除,促进了烃类物质的生成,提高了焦油产物的品质。其中,酚类物质含量明显降低,芳香烃中3~4个环的稠环芳烃增加较多,脂肪烃中碳原子数量大于13的烃类含量有所增加。当添加30%FCC时,共热解油中酚类物质较计算值减少约7%,芳香烃和脂肪烃含量分别高出约2%和9%。与脱矿CS相比,未脱矿的CS与FCC油浆共热解促进了焦油的生成,抑制了半焦和气体的产生。矿物质的存在对2者的相互作用具有增强效果,不仅促进了油浆的裂解,增强了生物质的脱氧反应,产生更多的烃类,而且减缓了自由基的聚合反应,改善了共热解体系中稠环化合物的缩聚程度。焦油中蓖系物含量减少,脂肪烃含量增加。热重实验评价表明,共热解所得的半焦气化反应活性明显提高,有利于后续的利用。

     

    Abstract: Biomass is a renewable resource with nearly zero carbon emissions in the whole life cycle. The extraction of light fuels and chemicals from biomass is the ultimate direction to achieve carbon peak and carbon neutrality. Co-conversion of fossil energy and biomass is a feasible way to seek optimal combination of fossil energy and new energy in accordance with basic national conditions. In this paper, the interaction between corn stalk (CS) and fluid catalytic cracking slurry (FCC) during co-pyrolysis and the effect of biomass intrinsic minerals on product distribution and product characteristics were studied.The results show that there was obvious interaction between CS and FCC slurry in different proportions during the co-pyrolysis process, the polymerization reaction played a dominant role in the process,and the yield of semi coke increased. The interaction during co-pyrolysis enhanced the removal of oxygen containing compounds, promoted the generation of hydrocarbons, and finally improved the quality of the tar products. Among them, the content of phenolic substances decreased significantly, the polycyclic aromatic hydrocarbons of 3~4 rings in aromatic hydrocarbon increased, and the hydrocarbon with more than 13 carbon atoms in aliphatic hydrocarbons also increased. For the co-pyrolysis of 30%FCC with 70% CS, the phenolic compounds in the co-pyrolysis oil decreased by about 7% compared with the calculated values, and the contents of aromatic hydrocarbons and aliphatic hydrocarbons increased by about 2% and 9%, respectively. Compared with demineralized CS, the co-pyrolysis of un-demineralized CS and FCC promoted the formation of tar, and inhibited the generation of semi coke and gas. The presence of minerals could enhanced the interaction between CS and FCC, which not only promoted the cracking of oil slurry, strengthened the deoxidation reaction of biomass and produced more hydrocarbons, but also relieved the polymerization of free radicals and improved the condensation degree of polycyclic compounds in the co-pyrolysis system. The content of pyrene in tar was reduced and the amount of aliphatic hydrocarbon increased.Thermogravimetric experiment evaluation showed that the gasification reactivity of the char produced from co-pyrolysis was obviously improved, which was beneficial to the subsequent utilization.

     

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