Characteristics and Evolution of Nitrogen in the Heavy Components of Algae Pyrolysis Bio-Oil.

Algae pyrolytic bio-oil contains a large quantity of N-containing components (NCCs), which can be processed as valuable chemicals, while the harmful gases can also be released during bio-oil upgrading. However, the characteristics of NCCs in the bio-oil, especially the composition of heavy NCCs (molecular weight ≥200 Da), have not been fully studied due to the limitation of advanced analytical methods. In this study, three kinds of algae rich in lipids, proteins, and carbohydrates were rapidly pyrolyzed (10-25 °C/s) at different temperatures (300-700 °C). The bio-oil was analyzed using a Fourier transform ion cyclotron resonance mass spectrometer equipped with electrospray ionization, and the characteristics and evolution of nitrogen in heavy components were first obtained. The results indicated that the molecular weight of most heavy NCCs was distributed in the 200-400 Da range. N1-3 compounds account for over 60% in lipid and protein-rich samples, while N0 and N4 components are prominent in carbohydrate-rich samples. As temperature increases, most NCCs become more aromatic and contain less O due to the strong Maillard and deoxygenation reactions. Moreover, the heavier NCCs were promoted to form lighter compounds with more nitrogen atoms through decomposition (mainly denitrogenation and deoxygenation). Finally, some strategies to deal with the NCCs for high-quality bio-oil production were proposed.

The effect of combined pretreatments on the pyrolysis of corn stalk.

Untreated corn stalk (CS), deionized water washed CS (WCS), aqueous phase bio-oil washed CS (LCS), and 5% acetic acid washed CS (CCS) were torrefied at 230, 260, and 290 °C. The influences of washing, torrefaction, and combined washing-torrefaction pretreatments on corn stalk pyrolysis were investigated. The combined pretreatments, especially aqueous phase bio-oil washing-torrefaction improved fuel properties of pretreated samples largely by increasing their volatile and hydrogen contents. Absorption peaks of O-H and CO groups in combined pretreatment samples increased when torrefaction temperature increased. In addition, CO, H2, and CH4 contents of pyrolysis gas increased, while CO2 decreased after combined pretreatments. The bio-oil yields from WCS290, LCS290, and CCS290 increased by 134.04%, 127.66%, and 129.79% respectively, compared with that from CS290. Similarly, their relative sugar contents (rich in levoglucosan) increased to 36.63%, 45.89%, and 52.34%, respectively. Aqueous phase oil washing-torrefaction is a promising pretreatment and acetic acid plays the most important role.

Influence of physicochemical properties of metal modified ZSM-5 catalyst on benzene, toluene and xylene production from biomass catalytic pyrolysis.

Biomass catalytic pyrolysis with various metals (Zn, Fe, Ca, Ce and La) modified ZSM-5 catalysts were analyzed, in order to investigate the relationship between the physicochemical properties of catalysts and the benzene, toluene and xylene (BTX) products. Results revealed that the BTX products were positively correlated with the strong acid site contents of the catalysts. Appropriate amount (0.5-4 wt%) of loaded Zn species increased the strong acid site contents of the catalysts as well as BTX yields, and the highest yield of BTX was observed under Zn loading amount of 2 wt%. While excessive metal loading amount (10 wt%) decreased both the acidity and the physical properties of the catalyst, resulting in poor diffusion of reactants and products in the channel and decreased the BTX yield. It is recommended that ZSM-5 catalyst with higher strong acid site content and pore volume should be used for BTX production.