Upgrading of derived pyrolysis vapors for the production of biofuels from corncobs

doi:10.1007/s11705-017-1685-4

Front. Chem. Sci. Eng.

2018, Vol. 12

Issue (1) : 50-58 https://doi.org/10.1007/s11705-017-1685-4

RESEARCH ARTICLE

Upgrading of derived pyrolysis vapors for the production of biofuels from corncobs

Liaoyuan Mao, Yanxin Li, Z. Conrad Zhang(

)

State Key Laboratory of Catalysis, Dalian National Laboratory for Clean Energy, Dalian Institute of Chemical Physics, Chinese Academy of Sciences, Dalian 116023, China

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Abstract

A bubbling fluidized bed pyrolyzer was integrated with an in-situ honeycomb as a catalytic upgrading zone for the conversion of biomass to liquid fuels. In the upgrading zone, zeolite coated ceramic honeycomb (ZCCH) catalysts consisting of ZSM-5 (Si/Al=25) were stacked and N₂ or recycled non-condensable gas was used as a carrier gas. Ground corncob particles were fast pyrolyzed in the bubbling bed using fine sand particles as a heat carrier and the resulting pyrolysis vapors were passed on-line over the catalytic upgrading zone. The influence of carrier gas, temperature, and weight hourly space velocity (WHSV) of catalyst on the oil product properties, distribution and mass balance were studied. Using ZCCH effectively increased the hydrocarbon yield and the heating value of the dry oil, especially in the presence of the recycled noncondensable gas. Even a low usage of zeolite catalyst at WSHV of 180 h⁻¹ was effective in upgrading the pyrolysis oil and other light olefins. The highest hydrocarbon (≥C2) and liquid aromatics yields reached to 14.23 and 4.17 wt-%, respectively. The undesirable products including light oxygenates, furans dramatically decreased in the presence of the ZCCH catalyst.

Keywords corncob monolith upgrading pyrolysis

Corresponding Author(s): Z. Conrad Zhang

Just Accepted Date: 25 September 2017 Online First Date: 23 January 2018 Issue Date: 26 February 2018

Cite this article:

Liaoyuan Mao,Yanxin Li,Z. Conrad Zhang. Upgrading of derived pyrolysis vapors for the production of biofuels from corncobs[J]. Front. Chem. Sci. Eng., 2018, 12(1): 50-58.

URL:

https://academic.hep.com.cn/fcse/EN/10.1007/s11705-017-1685-4
https://academic.hep.com.cn/fcse/EN/Y2018/V12/I1/50

Fig.1 Schematic view of the bubbling bed reactor system for pyrolysis of biomass and in-situ upgrading of pyrolysis vapor

Tab.1 Product yields as a function of temperature and WHSV for ZCCH catalyzed pyrolysis of corncob

Fig.2 Yields as a function of WHSV for the ZCCH catalyzed pyrolysis of corncob. Yields refer to the mass of product divided by the mass of feedstock. Reaction conditions: TP= 500 °C; feeding rate of corncob is 15 g·min^?¹; 450 g silica sand was used as solid heat carrier in the fluidized bed; and 200 g biomass was fed per experiment. The residence time of stream flow in pyrolysis zone is 1.3 s (with a velocity of 0.8 m·s^?¹). The WHSV in the ZCCH upgrading zone was varied from 45 to 180 h^?¹. The WHSV was calculated according to a biomass feeding rate of 0.9 kg·h^?¹ and a weight of catalyst coated on ZCCH (5, 10, 15 and 20 g, respectively). A blank experiment was run in the absence of ZCCH or any other catalyst. Carrier gas: Pure N₂. Key: (a) catalytic temperature at ZCCH is 500 °C, (b) temperature at ZCCH is 550 °C, (c) temperature at ZCCH is 600 °C. ■Light oxygenates, ●Furans, ▲Phenols, ▾Aromatics, ◆Benzofurans, ★CO, ▿CO₂, △CH₄, ◇C2-C6, □hydrocarbons (≥C2)

Tab.2 Product yields and properties of dry oil as a function of catalyst exposure time on stream with or without regeneration

Fig.3 Effects of thermal regeneration of ZCCH on the product distribution. (a) Pyrolysis without catalyst regeneration; (b) ZCCH was regenerated at 550 °C every 40 min in air medium. Key: ■Light oxygenates, ● Furans, ▲Phenols, ▾Aromatics, ◆Benzofurans, ★ Total yield of dry oil

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