用甲酸镍原位催化生成麻片,麻片作为金属载体进行还原催化分馏

IF 3.5 4区 工程技术 Q3 ENERGY & FUELS
Valentin V. Sychev, Angelina V. Miroshnikova, Aleksandr S. Kazachenko, Andrey M. Skripnikov, Oxana P. Taran, Valery E. Tarabanko
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引用次数: 0

摘要

提出了以甲酸镍为前驱体原位制备纳米级镍颗粒,用于还原催化分离亚麻片。用XRD对亚麻片RCF固体产物进行了检测,发现在2θ角44,52和76处分别存在Ni0(111),(200),(220)的特征反射,表明金属在原位还原。通过XPS(信号855.8和874.3 eV, Ni0/Niox = 0.0)也证实了Ni氧化物的存在。采用肼还原甲酸镍的方法,在亚麻片上预沉积了替代镍催化剂。经XRD分析发现,预沉积的Ni颗粒呈非晶状,分布较细;XPS分析证实,表面既有金属态,也有氧化态Ni0, Ni2+, Ni3+ (Ni0/Niox = 0.14)。单体化合物,如4-丙基愈创木酚、4-丙基愈创木酚和4-丙基愈创木酚,在原位形成的Ni存在下,总收率为6.92 wt.%。从反应器中排除氢分子使木质素单体产率从6.92%下降到3.80 wt.%,但后者的值超过了与H2非催化加氢的单体产率的3倍(1.44 wt.%)。镍颗粒催化甲酸离子加氢木质素的研究在保持甲酸离子浓度不变的情况下,降低反应质量中Ni的含量,使单体产率下降到与利用H2分子进行非催化加氢反应相对应的水平。通过肼还原镍预沉积的工艺提供了更高的总酚单体收率,高达9.12 wt.%,相当于在已知的Ni/C催化剂存在下的收率。酚类单体的主要产物- 4-丙醇愈创木酚选择性达42%。
本文章由计算机程序翻译,如有差异,请以英文原文为准。
Reductive catalytic fractionation of flax shives by using nickel formate for in situ catalyst generation and the shives as a support for the metal

Nanoscale nickel particles formed in situ using nickel formate as a precursor are proposed for the reductive catalytic fractionation (RCF) of flax shives. The examination of solid products of flax shives RCF by XRD revealed that characteristic reflections for Ni0 (111), (200), (220) at 2θ angles of 44, 52, and 76, respectively, are present in the X-ray diffraction patterns, hinting at the metal in situ reduction. The presence of Ni oxides was also confirmed via XPS (signals 855.8 and 874.3 eV, Ni0/Niox = 0.0). The alternative Ni-catalyst was pre-deposited on flax shives via reduction of nickel formate by hydrazine. The pre-deposited Ni particles were found to be XRD amorphous hinting at fine distribution and XPS confirmed both metallic and oxidized states Ni0, Ni2+, Ni3+ at the surface (Ni0/Niox = 0.14). Monomeric compounds, such as 4-propylguaiacol, 4-propenylguaiacol, and 4-propanolguaiacol, were obtained with a total yield of 6.92 wt.% in the presence of in situ formed Ni. Excluding the molecular hydrogen from the reactor drops the lignin monomers yield from 6.92 to 3.80 wt.%, but the latter value exceeds the yield of the monomers of non-catalytic hydrogenation with H2 by a factor of 3 (1.44 wt.%). Ni particles catalyze the process of lignin hydrogenation by formate ion; decreasing the Ni content in the reaction mass while keeping formate ion concentration at the same level drops the monomers yield down to the level corresponding to the non-catalytic hydrogenation with using molecular H2. The process over nickel pre-deposited via reduction by hydrazine provided a higher total phenolic monomers yield of up to 9.12 wt.% equaled to the yields in the presence of the known Ni/C catalysts. The selectivity on the main product among phenolic monomers – 4-propanolguaiacol reached 42%.

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来源期刊
Biomass Conversion and Biorefinery
Biomass Conversion and Biorefinery Energy-Renewable Energy, Sustainability and the Environment
CiteScore
7.00
自引率
15.00%
发文量
1358
期刊介绍: Biomass Conversion and Biorefinery presents articles and information on research, development and applications in thermo-chemical conversion; physico-chemical conversion and bio-chemical conversion, including all necessary steps for the provision and preparation of the biomass as well as all possible downstream processing steps for the environmentally sound and economically viable provision of energy and chemical products.
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