Catalytic upgrading of penicillin fermentation residue bio-oil by metal-supported HZSM-5.

Antibiotic fermentation residue (AR) is composed of hazardous organic waste produced by the pharmaceutical industry. AR can be effectively converted into bio-oil by fast pyrolysis, but its high nitrogen content limits the prospect of bio-oil as a fuel resource. In order to further reduce the nitrogen content of AR bio-oil, we have examined the catalytic removal of N and O from penicillin fermentation residue (PR) bio-oil under fast pyrolysis conditions. We have used M/HZSM-5 (M = Fe, Co, Ni, Cu, Zn, Zr, Mo, Ag and Ce) metal catalysts, with a metal oxide content of 10%. Additionally, the effect of mixed and separated catalytic forms on catalytic upgrading were analyzed, and changes in the catalyst itself before and after pyrolysis under separated catalytic conditions were specifically investigated. Our results show that the metal elements in the fresh catalyst will exist in the form of oxides, ions and simple metals. In-situ reduction caused by pyrolysis gas in the catalytic pyrolysis process makes some ionic metals (e.g., Co, Cu and Ag) in the catalyst transform into oxides, and some metal oxides are reduced to simple metals or suboxides (including Fe, Ni, Cu and Mo). The N content in the mixed catalytic bio-oil decreased from 10.09 wt% to Zn/HZSM-5 (6.98 wt%), Co/HZSM-5 (7.1 wt%), Cu/HZSM-5 (7.18 wt%) and Ce/HZSM-5 (7.18 wt%). We also observed significant reduction in the O content (9.77 wt%) with Ag/HZSM-5 (3.75 wt%), Mo/HZSM-5 (6.86 wt%), Ce/HZSM-5 (8.39 wt%) and Fe/HZSM-5 (8.54 wt%) in the separated catalytic bio-oil. The Ni/HZSM-5 catalystcan reduce the organic acid content in bio-oil from 22.9% to 10.8%. The separated catalysis methodology also promoted an increase of hydrocarbons in the bio-oil: Zn/HZSM-5, Ag/HZSM-5, Mo/HZSM-5, Zr/HZSM-5 and Ce/HZSM-5 reached 11.6%, 11.5%, 11.1%, 10.1%, and 8.8%, respectively. Carbon deposition formed by aromatic carbon/graphite carbon, pyrrole and pyridine compounds leads to deactivation of the catalyst.