Catalytic cracking of crude bio-oil from glycerol-assisted liquefaction of swine manure

The crude bio-oil produced from the glycerol-assisted liquefaction of swine manure which had large amount of long chain esters, was upgraded by thermal cracking over a modified zeolite catalyst. The effects of thermal cracking temperature (350-425 °C), reaction time (15-60 min) and catalyst loading (0-10 wt%) on the yield and quality of the upgraded oil were analyzed. The yield of upgraded bio-oil decreased with the increase of reaction temperature, reaction time and catalyst loading, but the viscosity, heating value and composition of the upgraded bio-oil became more desirable. Taking into the consideration both the yield and quality of the upgraded bio-oil, the optimal thermal cracking could be achieved over 5 wt% catalyst at 400 °C for 30 min. Under this condition, the yield of upgraded bio-oil was 46.14 wt% of the crude bio-oil, and 62.5% of the energy stored in the crude bio-oil was recovered. The oxygen content of the upgraded bio-oil was 15.04%, which was less than half of the original value of 33.98%. The viscosity of the upgraded bio-oil was 3.6 cP, compared with 188.9 cP for the crude bio-oil. The heating value of the upgraded bio-oil was 41.4 MJ/kg, compared with 30.54 MJ/kg for the crude bio-oil. Both the viscosity and heating value of the upgraded bio-oil were comparable to those of commercial diesel. The GC-MS analysis showed that the catalytic upgrading resulted in the increased cracking of long-chain acid methyl esters (such as hexadecanoic acid methyl ester), forming various alkanes, alkenes and their isomers, and short-chain acid methyl esters (such as heptanoic acid methyl ester). Elevated temperature and high catalyst loading enhanced the selectivity of thermal cracking towards alkanes and alkenes in the upgraded bio-oil.