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Biofuels and Biomass
Magnetically recoverable Ni/NiO catalyst for hydrogenation of cashew nut shell oil to value-added products Anil Kumar Sinha, Hari Singh, Rajkumar Yadav, Parasmani Rajput, Dibyendu Bhattacharyya, and Sambhu Nath Jha Energy Fuels, Just Accepted Manuscript • DOI: 10.1021/acs.energyfuels.9b00663 • Publication Date (Web): 09 May 2019 Downloaded from http://pubs.acs.org on May 12, 2019
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Energy & Fuels
Magnetically recoverable Ni/NiO catalyst for hydrogenation of cashew nut shell oil to value-added products Hari Singha, Rajkumar Yadava, Parasmani Rajputb, D. Bhattacharyyab, S. N. Jhab, and A. K. Sinha*a aCSIR-
Indian Institute of Petroleum, Dehradun – 248005, India,
Academy of Scientific and Innovative Research (AcSIR) New Delhi-110001, India. bAtomic
& Molecular Physics Division, Bhabha Atomic Research Centre Trombay, Mumbai -
400 085. *Corresponding author. E-mail:
[email protected], Fax: +91-135-266-203; Tel: +91\1352525842 Abstract A Ni/NiO catalyst is reported for converting phenolic compound such as guaiacol and (CNSL) cashew nut shell liquid into a different hydrocarbon. High guaiacol conversion (80%) and higher cyclohexane selectivity (23%) over Ni/NiO catalyst are reported compared to the other reported Ni-based catalysts at a temperature of 300 °C and 50 bar H2 pressure. The CNSL hydrodeoxygenation (HDO) activity increased with the temperature and reached a maximum conversion (100%) at 300 °C temperature. The high total acidic sites of Ni/NiO favored the high conversion (100%) with 15% cyclohexane selectivity, 30% phenol selectivity, and maximum selectivity for tetradecane (45%) in CNSL hydrodeoxygenation. This is the first such report to the best of our knowledge. The Ni/NiO catalyst was characterized by XRD, TEM, XPS, NH3TPD, N2-sorption, XANES and XAFS. The products were analyzed by FTIR, 1H NMR, GC, and GC-MS. XRD analysis showed that NiO crystallinity decreased while Ni crystallinity increased after reduction. XAFS analysis confirmed that the metallic Ni nature increased after reduction as indicated by a decrease in the Ni-Ni1Ni bond distance from 2.596 Å for the unreduced Ni/NiO to 1 ACS Paragon Plus Environment
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2.519 Å (closer to that for metallic Ni FCC phase) for the reduced sample, which would result in improved hydrogenation activity of the reduced catalyst. Spent Ni/NiO catalyst showed good stability without any phase change during the reaction and retained its original structure. Keywords: Guaiacol, CNSL, Hydrogenation, Ni/NiO, Tetradecane, Cyclohexane, Cyclohexanol 1. Introduction The biomass-derived materials can be a viable source for the manufacture of different hydrocarbon fuels and chemicals via catalytic routes [1, 2]. The non-edible vegetable oils such as castor oil, rapeseed oil, jatropha oil, and waste cashew nut shell liquid have an abundant range of applications for value-added products [2-5]. The cashew nut shell liquid (CNSL) has long-chain hydrocarbon phenols [5, 6] in its structure and constitutes about 1/4 of the cashew weight [1, 47]. CNSL is an agricultural side product of cashew and is released as agriculture waste after cashew nut processed [5-7]. It is a dark yellow colored viscous waste liquid product of the cashew industry [7]. The main constituents of cashew nut shell liquid are anacardic acid, cardanol, and cardol [9] Technically CNSL contains its 3/4 part cardanol, 1/10 part cardol, and remaining polymeric compounds [9, 10]. All these phenolic compounds of the CNSL are a mixture of saturated, mono, di, and trienes. Heterogeneous catalysts play a major role in the hydrogenation of lignin-model compounds [3, 8-11] such as guaiacol. The cardanol-rich cashew nut shell liquid, a lignin-model compound has been explored for oxidation reactions [7, 12]. CNSL has the potential to produce a vast number of synthetic compounds and chemical products by exploiting the different reactive sites, to be a specific, phenolic hydroxyl group, unsaturation in the side chain and aromatic ring. The complete reduction of the aromatic rings by hydrogenation into saturated hydrocarbons over the surface of the metal catalyst is much desired [13, 15]. The catalytic activity of the supported metal catalyst 2 ACS Paragon Plus Environment
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Energy & Fuels
for the reduction of aromatic rings via hydrogenation route is in the order of Co
