Catalytic Hydroprocessing of White Pine Pyrolysis Bio-Oil over Cobalt-Molybdenum Carbide in a Continuous Packed-Bed Reac
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Catalytic Hydroprocessing of White Pine Pyrolysis Bio-Oil over Cobalt-Molybdenum Carbide in a Continuous Packed-Bed Reactor Rui Li 1 & Zhixin Zhao 1 & Bo Zhang 2 & Xiaozheng Sun 1 & Zhen Zhang 3 & Ying Zhang 1 & Haitao Chen 1 & Qiangu Yan 4 Received: 1 August 2020 / Accepted: 18 November 2020 # Springer Science+Business Media, LLC, part of Springer Nature 2020
Abstract Catalytic hydroprocessing of white pine pyrolysis bio-oil over cobalt-molybdenum (CoMo) carbide supported on biochar was carried out in a continuous fixed-bed reactor at a temperature between 350 and 425 °C, hydrogen pressure between 7 and 12.5 MPa, and liquid hourly space velocity (LHSV) of 0.1–1.0 h−1 with a hydrogen flow rate of 500 mL/min. The results showed that the CoMo carbide catalyst can effectively improve the yield and qualities of hydrotreated bio-oil. Under the preferred reaction conditions of 400–425 °C, 10 MPa H2, and LHSV 0.3 h−1, the yield, the carbon content, the carbon recovery ratio, and the higher heating value of the upgraded bio-oil reached 24.2–25.7% of the feed, 86.5–87.4%, 48.1–52.1%, and 41.8– 43.9 MJ/kg, respectively. The oxygen content, total acid number, and moisture of the hydrotreated bio-oil decreased to 0.1– 1.6 wt%, < 1.2 mg of KOH/g, and < 0.2 wt%, respectively. Hydrocarbons in the hydrotreated bio-oil accounted for 84.5– 84.9 mol% of the total organic products and were mainly composed of C7, C8, C9, C10, and C11 molecules. The components of the upgraded bio-oil showed the following order: i-paraffins > aromatics > olefins > paraffins > naphthenes. Keywords Hydrodeoxygenation . Fast pyrolysis oil . Biomass . Bio-oil . Thermochemical process
Introduction Pyrolysis is a thermochemical technology performed at temperatures between 400 and 550 °C in the absence of oxygen. The pyrolysis technology has merits such as high heating rate, short vapor residence time, well controllable operation, and high product yield. It has therefore been considered an economic way to convert lignocellulosic biomass into liquid products (known as the bio-oil with CAS registry number 1207435-39-9) [1, 2]. The pyrolytic bio-oil is a potential alternative fuel resource. Compared with petroleum-derived * Qiangu Yan [email protected]; [email protected] 1
College of Engineering, Northeast Agricultural University, Harbin 150030, Heilongjiang, China
2
Key Laboratory for Green Chemical Process of Ministry of Education, School of Chemical Engineering and Pharmacy, Wuhan Institute of Technology, Wuhan, Hubei, China
3
Key Laboratory of Coarse Cereal Processing (Ministry of Agriculture and Rural Affairs), College of Pharmacy and Biological Engineering, Chengdu University, Chengdu 610041, People’s Republic of China
4
Ligsteel LLC, Madison, WI 53705, USA
fuels, it has some unique characteristics including high density (specific gravity of 1.1–1.3), low pH (2–3.7), a moderate heating value (16–19 MJ/kg), and a high moisture content (15–35%). The direct use of the bio-oil as a transportation fuel is problematic, which is mainly due to the hig
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