Catalytic pyrolysis of rape straw for upgraded bio-oil production using HZSM-5 zeolite

Abstract: Catalytic upgrading of the vapors from rape straw vacuum pyrolysis was conducted over HZSM-5 zeolite in a fixed bed reactor. Univariate analysis was employed in this study to investigate the effects of the operating parameters, including catalyst quality, Si/Al ratio of catalyst, and catalyzing temperature, on the product yields and the composition of upgraded bio-oil. Based on the univariate analysis, the preliminary operating parameters of catalytic reactor were optimized. The results showed that, when the catalyzing temperature was 500℃ and HZSM-5 (Si/Al=50) quality was 60 g, a lower oxygen content (27.97 percent), higher heating value (30.14kJ/kg-1), and a lower hydrogen-to-carbon ratio (0.12) were obtained. Moreover, the components of the obtained bio-oil contained a small amount of high oxygen contents, such as aldehydes, acids, and ketones. Meanwhile, phenols and aromatic hydrocarbons obviously increased. Product distribution and yield between upgraded bio-oil and crude bio-oil was also compared to study the catalytic refining effects and catalytic deoxygenation performance of HZSM-5 zeolite. This capacity of HZSM-5 zeolite was the key to make up for the two shortcomings of crude bio-oil, which were corrosivity and instability. The catalyst quality had significant effects on the properties of the upgraded bio-oil. Catalytic upgrading of pyrolysis vapors was incomplete when the catalyst quality was not high enough. However, when the catalyst quality was excessive, a decreased yield of upgraded oil resulted due to excessive secondary cracking reactions. In this study, the quality ratio of the catalyst to biomass was about 0.4. Catalyzing temperature also had an important effect on the properties of upgraded oil. When the catalyzing temperature was lower, the activation energy could not meet the needs of cracking reactions, and the catalytic effect was poor. When the catalyzing temperature was higher than optimal value, deactivation of the catalyst resulted because the structure of the catalyst was destroyed. Accordingly, the upgraded bio-oil with a higher gross heating value and lower oxygen content was obtained when the catalyzing temperature was about 500℃. The Si/Al ratio of the catalyst, which determined its density of acid sites and acid strength, had a great impact on catalytic product distribution. Four different Si/Al ratios of HZSM-5 were investigated. Upgraded bio-oil with a higher gross heating value and lower oxygen content was obtained when the Si/Al ratio of HZSM-5 was 50. Also, there were significant differences between upgraded bio-oil and crude bio-oil in product distribution and yield. The yield of crude bio-oil was 43.98 percent while the yield of upgraded bio-oil was 36.12 percent. Oxygenated components in the upgraded bio-oil, such as aldehydes, carboxylic acids, and ketones, which were 13.71 percent, 11.75 percent, and 13.59 percent, dropped significantly to 3.38 percent, 1.68 percent, and 4.48 percent, respectively. However, phenols containing lower oxygen and non-oxygenated hydrocarbons increased observably. These results showed that the HZSM-5 catalyst had a strong catalytic refining and catalytic deoxygenation capacity. Based on the results of this study, a catalytic reaction mechanism of HZSM-5 was proposed by comparing non-catalytic and catalytic bio-oil compositions. HZSM-5 was highly active in catalytic deoxidation. However, the online catalytic upgrading mechanism of bio-oil vapors was complex and it needs to be further studied in the future.