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Biomass pyrolysis within the alkaline molten salt is attractive due to its ability to achieve high hydrogen yield under relatively mild conditions. However, poor contact between biomass, especially the biomass pellet, and hydroxide during the slow heating process, as well as low reaction temperatures, become key factors limiting the hydrogen production. To address these challenges, fast pyrolysis of the algae pellet in molten NaOH-Na 2 CO 3 was conducted at 550, 650, and 750 °C. Algae were chosen as feedstock for their high photosynthetic efficiency and growth rate, and the concept of coupling molten salt with concentrated solar energy was proposed to address the issue of high energy consumption at high temperatures. At 750 °C, the pollutant gases containing Cl and S were completely removed, and the HCN removal rate reached 44.92%. During the continuous pyrolysis process, after a slight increase, the hydrogen yield remained stable at 71.48 mmol/g-algae and constituted 86.10% of the gas products, and a minimum theoretical hydrogen production efficiency of algae can reach 84.86%. Most importantly, the evolution of physicochemical properties of molten NaOH-Na 2 CO 3 was revealed for the first time. Combined with the conversion characteristics of feedstock and gas products, this study provides practical guidance for large-scale application of molten salt including feedstock, operation parameters, and post-treatment process.

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. N 1-3 compounds account for over 60% in lipid and protein-rich samples, while N 0 and N 4 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 kinetic rate laws of heavy metal (HM) vaporization from municipal solid waste during its incineration were studied. Realistic artificial waste (RAW) samples spiked with Pb, Zn, and Cd were injected into a fluidized bed reactor. Metal vaporization wastracked by continuous measure ofthe above metals in exhaust gases. An inverse model of the reactor was used to calculate the metal vaporization rates from the concentration vs time profiles in the outlet gas. For each metal, experiments were carried out at several temperatures in order to determine the kinetic parameters and to obtain specific rate laws as functions of temperature. Temperature has a strong influence on the HM vaporization dynamics, especially on the vaporization kinetics profile. This phenomenon was attributed to internal diffusion control of the HM release. Two types of kinetic rate laws were established based on temperature: a fourth- or fifth-order polynomial rate law (r(x) = k0e(-E(A)/RT)p(x)) for temperatures lower than 740 degrees C and a first-order polynomial (r(x) = k0e(-E(A)/ RT(q-q(f) for temperatures higher than 740 degrees C.

Accumulation of toxic metals generated by thermal treatment of municipal solid waste presents a serious threat to the environment. A study was carried out to investigate the kinetic law of toxic metal release from municipal solid waste during their thermal treatment. Both direct and inverse models were developed in transient conditions. The direct mathematical model of the fluid-bed reactor is based on Kunii and Levenspiel's two-phase flow model for Geldart Group B particles. The inverse model intends to predict the metal's rate of vaporization from its concentration in the outlet gas. The derived models were found to predict reasonably well the experimental observations. A method to derive the kinetic law of toxic metals release during fluidized bed thermal treatment of model waste from the global model and the experimental measurements is derived and illustrated. A first-order law was fitted for the mineral matrix, and a second-order law (simplified) was fitted for the realistic model waste. The kinetic law obtained in this way could be integrated in a global model of combustion of municipal solid waste in order to simulate the effects of operating parameters on the metal's behavior.

Metal vaporization experiments were carried out in an atmospheric fluidized bed to study the influence of operating conditions on the extent of heavy metal (HM) release in fumes from municipal solid waste incinerators. Modelwastes spiked with compounds of Pb, Cd, and Zn were used. The parameters studied were temperature, treatment duration, matrix of the model waste (mineral and organic), HM initial speciation, and gas composition (N2, air, air + HCl, gas mixture simulating the incinerators). The extent of vaporization was measured by solid sample analysis and on-line analysis of the gaseous effluent, after customization of the ICP technique for gas analysis. The results indicate the metal vaporization rate is very high initially and then slows. The results with mineral matrices give the decreasing order of volatility Cd > Pb > Zn, but in industrial incinerators Zn volatilizes slightly more than Pb. Temperature (especially for porous alumina) and mineral matrix have a strong influence on the HM vaporization, but HCl concentration and HM initial speciation do not. The gas composition and the initial metal concentration are significant parameters. The matrix influence clearly denoted the mass transfer limitations in the vaporization process from mineral matrix.

In light of Title I of the Clean Air Act Amendments of 1990, selenium will most probably be considered for regulation in the electric power industry. This has generated interest for removing this element from fossil-fired flue gas. This study deals with coal combustion: selenium volatilization and its speciation in the cooled flue gas were investigated to better understand its chemical behavior to validate the thermodynamic approach to such complex systems and to begin developing emission control strategies. Se volatility is influenced by several factors such as temperature, residence time, fuel type, particle size, and Se speciation of the fuels, as well as the forms of the Se inthe spiked coal/coke. Spiked coke and coal samples were burned in a thermobalance, and atomic Se and its dioxide were identified in the cooled combustion flue gas by X-ray photoelectron spectroscopy (XPS). A thermodynamic calculation was applied to a complex system including 54 elements and 3,200 species that describes the coal combustion. Several theoretical predictions concerning Se behavior, such as its speciation in flue gas, agreed well with experiments, which supports using thermodynamics for predicting trace element chemistry in combustion systems.