B3LYP/6-31G(d,p) method was used to investigate the catalytic cracking mechanism of biomass tar model compound.Phenol,toluene and benzene were selected as the tar model compounds and CaO was selected as the catalyst.T...B3LYP/6-31G(d,p) method was used to investigate the catalytic cracking mechanism of biomass tar model compound.Phenol,toluene and benzene were selected as the tar model compounds and CaO was selected as the catalyst.The pathways of tar compound radical absorbed by CaO were determined firstly through comparing enthalpy changes of the absorption,and then Mulliken population changes were analyzed.The results show that the absorption of tar model compound radical and CaO is an exothermic reaction.Formation of C—O—Ca is more easily than that of C—Ca—O and formation of Caromatic—Caromatic—Ca—O is more easily than that of Caromatic—C(O)—Ca—O.The C—C bond Mulliken populations in tar model compound radicals are reduced by 11.9%,10.5% and 15.5% in the case of a hydrogen atom removed,and those are 15.7%,14.3% and 16.3% in the case of two hydrogen atoms removed through the absorption of CaO.Catalytic ability of CaO acting on the tar model compound is in an order of phenol>benzene>toluene.展开更多
Catalytic steam reforming is a promising route for tar conversion to high energy syngas in the process of biomass gasification. However, the catalyst deactivation caused by the deposition of residual carbon is still a...Catalytic steam reforming is a promising route for tar conversion to high energy syngas in the process of biomass gasification. However, the catalyst deactivation caused by the deposition of residual carbon is still a major challenge. In this paper, a modified Ni-based Ni-Co/Al2O3-CaO (Ni-Co/AC) catalyst and a conventional Ni/Al2O3 (Ni/A) catalyst were prepared and tested for tar catalytic removal in which toluene was selected as the model component. Experiments were conducted to reveal the influences of the reaction temperature and the ratio between steam to carbon on the toluene conversion and the hydrogen yield. The physicochemical properties of the modified Ni-based catalyst were determined by a series of characterization methods. The results indicated that the Ni-Co alloy was determined over the Ni-Co/AC catalyst. The doping of CaO and the presence of Ni-Co alloy promoted the performance of toluene catalytic dissociation over Ni-Co/AC catalyst compared with that over Ni/A catalyst. After testing in steam for 40 h, the carbon conversion over Ni-Co/AC maintained above 86% and its resistance to carbon deposition was superior to Ni/A catalyst.展开更多
针对生物质气化再燃技术路线中焦油的价值及利用开展研究。通过热重-质谱联用仪分析典型农业废弃物在热解、气化过程中焦油组分的析出情况,并在管式流动实验台上研究焦油在生物质气化气还原NO中的作用以及焦油还原NO受当量比、温度等因...针对生物质气化再燃技术路线中焦油的价值及利用开展研究。通过热重-质谱联用仪分析典型农业废弃物在热解、气化过程中焦油组分的析出情况,并在管式流动实验台上研究焦油在生物质气化气还原NO中的作用以及焦油还原NO受当量比、温度等因素的影响规律,最后建立了甲苯还原NO的机制模型,并以停流动实验台的实验结果进行了验证。结果表明:苯、甲苯、苯乙烯和苯酚是具有代表性的焦油组分;焦油对生物质气化气还原NO有积极的作用;焦油组分还原NO存在最佳的当量比,并要求合适的温度窗口,需要关注聚合反应;甲苯还原NO机制(NO reduction by toluene,NRT)模型与实验结果拟合良好,模型的生成速率和消耗速率分析显示HCCO和C2H在焦油还原NO中具有重要作用。展开更多
基金Project(51276023)supported by the National Natural Science Foundation of China
文摘B3LYP/6-31G(d,p) method was used to investigate the catalytic cracking mechanism of biomass tar model compound.Phenol,toluene and benzene were selected as the tar model compounds and CaO was selected as the catalyst.The pathways of tar compound radical absorbed by CaO were determined firstly through comparing enthalpy changes of the absorption,and then Mulliken population changes were analyzed.The results show that the absorption of tar model compound radical and CaO is an exothermic reaction.Formation of C—O—Ca is more easily than that of C—Ca—O and formation of Caromatic—Caromatic—Ca—O is more easily than that of Caromatic—C(O)—Ca—O.The C—C bond Mulliken populations in tar model compound radicals are reduced by 11.9%,10.5% and 15.5% in the case of a hydrogen atom removed,and those are 15.7%,14.3% and 16.3% in the case of two hydrogen atoms removed through the absorption of CaO.Catalytic ability of CaO acting on the tar model compound is in an order of phenol>benzene>toluene.
基金This work was financially supported by the National Nature Science Foundation of China(Grant Nos.51922040 and 51821004)the Fok Ying Tung Education Foundation(Grant No.161051)the Fundamental Research Funds for the Central Universities(Nos.2018ZD08 and 2020DF01).
文摘Catalytic steam reforming is a promising route for tar conversion to high energy syngas in the process of biomass gasification. However, the catalyst deactivation caused by the deposition of residual carbon is still a major challenge. In this paper, a modified Ni-based Ni-Co/Al2O3-CaO (Ni-Co/AC) catalyst and a conventional Ni/Al2O3 (Ni/A) catalyst were prepared and tested for tar catalytic removal in which toluene was selected as the model component. Experiments were conducted to reveal the influences of the reaction temperature and the ratio between steam to carbon on the toluene conversion and the hydrogen yield. The physicochemical properties of the modified Ni-based catalyst were determined by a series of characterization methods. The results indicated that the Ni-Co alloy was determined over the Ni-Co/AC catalyst. The doping of CaO and the presence of Ni-Co alloy promoted the performance of toluene catalytic dissociation over Ni-Co/AC catalyst compared with that over Ni/A catalyst. After testing in steam for 40 h, the carbon conversion over Ni-Co/AC maintained above 86% and its resistance to carbon deposition was superior to Ni/A catalyst.
文摘针对生物质气化再燃技术路线中焦油的价值及利用开展研究。通过热重-质谱联用仪分析典型农业废弃物在热解、气化过程中焦油组分的析出情况,并在管式流动实验台上研究焦油在生物质气化气还原NO中的作用以及焦油还原NO受当量比、温度等因素的影响规律,最后建立了甲苯还原NO的机制模型,并以停流动实验台的实验结果进行了验证。结果表明:苯、甲苯、苯乙烯和苯酚是具有代表性的焦油组分;焦油对生物质气化气还原NO有积极的作用;焦油组分还原NO存在最佳的当量比,并要求合适的温度窗口,需要关注聚合反应;甲苯还原NO机制(NO reduction by toluene,NRT)模型与实验结果拟合良好,模型的生成速率和消耗速率分析显示HCCO和C2H在焦油还原NO中具有重要作用。
