Valentin V. Sychev, Angelina V. Miroshnikova, Aleksandr S. Kazachenko, Andrey M. Skripnikov, Oxana P. Taran, Valery E. Tarabanko
{"title":"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","authors":"Valentin V. Sychev, Angelina V. Miroshnikova, Aleksandr S. Kazachenko, Andrey M. Skripnikov, Oxana P. Taran, Valery E. Tarabanko","doi":"10.1007/s13399-024-06365-9","DOIUrl":null,"url":null,"abstract":"<div><p>Nanoscale nickel particles formed <i>in situ</i> 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 Ni<sup>0</sup> (111), (200), (220) at 2θ angles of 44, 52, and 76, respectively, are present in the X-ray diffraction patterns, hinting at the metal <i>in situ</i> reduction. The presence of Ni oxides was also confirmed via XPS (signals 855.8 and 874.3 eV, Ni<sup>0</sup>/Ni<sub>ox</sub> = 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 Ni<sup>0</sup>, Ni<sup>2+</sup>, Ni<sup>3+</sup> at the surface (Ni<sup>0</sup>/Ni<sub>ox</sub> = 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 <i>in situ</i> 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 H<sub>2</sub> 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 H<sub>2</sub>. 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%.</p></div>","PeriodicalId":488,"journal":{"name":"Biomass Conversion and Biorefinery","volume":"15 10","pages":"15417 - 15426"},"PeriodicalIF":3.5000,"publicationDate":"2024-11-25","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":"0","resultStr":"{\"title\":\"Reductive catalytic fractionation of flax shives by using nickel formate for in situ catalyst generation and the shives as a support for the metal\",\"authors\":\"Valentin V. Sychev, Angelina V. Miroshnikova, Aleksandr S. Kazachenko, Andrey M. Skripnikov, Oxana P. Taran, Valery E. Tarabanko\",\"doi\":\"10.1007/s13399-024-06365-9\",\"DOIUrl\":null,\"url\":null,\"abstract\":\"<div><p>Nanoscale nickel particles formed <i>in situ</i> 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 Ni<sup>0</sup> (111), (200), (220) at 2θ angles of 44, 52, and 76, respectively, are present in the X-ray diffraction patterns, hinting at the metal <i>in situ</i> reduction. The presence of Ni oxides was also confirmed via XPS (signals 855.8 and 874.3 eV, Ni<sup>0</sup>/Ni<sub>ox</sub> = 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 Ni<sup>0</sup>, Ni<sup>2+</sup>, Ni<sup>3+</sup> at the surface (Ni<sup>0</sup>/Ni<sub>ox</sub> = 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 <i>in situ</i> 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 H<sub>2</sub> 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 H<sub>2</sub>. 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%.</p></div>\",\"PeriodicalId\":488,\"journal\":{\"name\":\"Biomass Conversion and Biorefinery\",\"volume\":\"15 10\",\"pages\":\"15417 - 15426\"},\"PeriodicalIF\":3.5000,\"publicationDate\":\"2024-11-25\",\"publicationTypes\":\"Journal Article\",\"fieldsOfStudy\":null,\"isOpenAccess\":false,\"openAccessPdf\":\"\",\"citationCount\":\"0\",\"resultStr\":null,\"platform\":\"Semanticscholar\",\"paperid\":null,\"PeriodicalName\":\"Biomass Conversion and Biorefinery\",\"FirstCategoryId\":\"5\",\"ListUrlMain\":\"https://link.springer.com/article/10.1007/s13399-024-06365-9\",\"RegionNum\":4,\"RegionCategory\":\"工程技术\",\"ArticlePicture\":[],\"TitleCN\":null,\"AbstractTextCN\":null,\"PMCID\":null,\"EPubDate\":\"\",\"PubModel\":\"\",\"JCR\":\"Q3\",\"JCRName\":\"ENERGY & FUELS\",\"Score\":null,\"Total\":0}","platform":"Semanticscholar","paperid":null,"PeriodicalName":"Biomass Conversion and Biorefinery","FirstCategoryId":"5","ListUrlMain":"https://link.springer.com/article/10.1007/s13399-024-06365-9","RegionNum":4,"RegionCategory":"工程技术","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":null,"EPubDate":"","PubModel":"","JCR":"Q3","JCRName":"ENERGY & FUELS","Score":null,"Total":0}
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%.
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.