Advancing hydrogen generation: Kinetic insights and process refinement for sorption-enhanced steam gasification of biomass utilizing waste carbide slag.

Sorption enhanced steam gasification of biomass (SESGB) presents a promising approach for producing high-purity H2 with potential for zero or negative carbon emissions. This study investigated the effects of gasification temperature, CaO to carbon in biomass molar ratio [CaO/C], and steam flow on the SESGB process, employing carbide slag (CS) and its modifications, CSSi2 (mass ratio of CS to SiO2 is 98:2) and CSCG5 (mass ratio of CS to coal gangue (CG) is 95:5), as CaO-based sorbents. The investigation included non-isothermal and isothermal gasification experiments and kinetic analyses using corn cob (CC) in a macro-weight thermogravimetric setup, alongside a fixed-bed pyrolysis-gasification system to assess operational parameter effects on gas product. The results suggested that CO2 capture by CaO reduced the mass loss during the main gasification as the [CaO/C] increased. The appropriate temperature for SESGB process should be selected between 550 and 700 °C at atmospheric pressure. The appropriate amount of sorbent or steam could facilitate the gasification reaction, but excessive addition led to adverse effects. Operational parameters influenced the apparent activation energy (Ea) by affecting various gasification reactions. For each test, Ea at the char gasification stage was significantly higher than that at the rapid pyrolysis stage. The addition of CS notably increased H2 concentration and yield, while sharply reducing CO2 levels. H2 concentration initially rose and then fell with greater steam flow, peaking at 76.11 vol% for a steam flow of 1.0 g/min. H2 yield peaked at 298 mL/g biomass with a steam flow of 1.5 g/min, a gasification temperature of 600 °C and a [CaO/C] of 1.0. Increasing gasification temperature remarkably boosted the H2 and CO2 yields. Optimal conditions for the SESGB using CS as a sorbent, determined via response surface methodology (RSM), include a gasification temperature of 666 °C, a [CaO/C] of 1.99, and a steam flow of 0.5 g/min, under which H2 and CO2 yields were 464 and 48 mL/g biomass, respectively. CSSi2 and CSCG5 demonstrated excellent cyclic H2 production stability, maintaining H2 yields around 440 mL/g biomass and low CO2 yields (∼60 mL/g biomass) across five cycles. The study results offer new insights for the high-value utilization of agroforestry biomass and the reduction and resource utilization of industrial waste.

Co-pyrolysis of peanut shell with municipal sludge: reaction mechanism, product distribution, and synergy.

Biomass/sludge co-pyrolysis contributes to the high-efficiency resource utilization, harmless treatment, and reduction in volume of sludge. Due to the complexity of co-pyrolysis reaction, it is essential to evaluate the thermodynamic behavior, synergy, and reaction mechanism of this process to make it commercially viable. In this work, the pyrolysis properties, thermodynamic analysis and product distribution of municipal sludge (MS), peanut shell (PS), and their blends with various sludge mass ratios (SMRs) were investigated by a thermogravimetric analyzer and a fixed bed reactor. There was a considerable synergy existing in the process of PS/MS co-pyrolysis, and the synergy occurred mainly at the devolatilization phase, accelerating the mixture pyrolysis. When the conversion rate α was less than 0.7, the apparent activation energy decreased continuously with SMR at the same α; however, it increased dramatically with SMR when α was greater than 0.7. Reactants and reaction stages greatly affected the kinetic mechanism of fuel pyrolysis, and this finding was beneficial for the numerical simulation of mixture pyrolysis. Based on the conclusions and precision of this work, the mass ratio of PS to MS was recommended to be 6:4, which had the strongest synergy, with a gas yield of 26.69 wt.% at 600°C and a lower heating value (LHV) of pyrolysis gas of 14.89 MJ/Nm3.

Co-combustion of high alkali coal with municipal sludge: Thermal behaviour, kinetic analysis, and micro characteristic.

Blending sludge rich in protein and aliphatic hydrocarbons into the high alkali coal (HAC) has been demonstrated to reduce the ash melting temperature of the HAC/sludge mixture, thereby increasing the effectiveness and efficiency of liquid slagging. However, whether the incorporation of sludge can affect the combustion stability of the original coal-fired boiler is still debatable. As the combustion stability of the fuel can directly affect the operational safety of the boiler, it is of great practical value for exploring the effect of sludge incorporation on the combustion performance of HAC. In this work, the thermal behaviour and microscopic properties of individual HAC, municipal sludge (MS) and HAC/MS mixtures were tested using a Thermogravimetric analyser (TGA) and a Fourier transform infrared (FTIR) spectrometer, respectively. The exothermic, thermodynamic and functional group evolution patterns during the combustion of these samples were also evaluated. Ignition temperatures (Ti) of the HAC/MS mixtures were relatively lower than that of individual HAC, and decreased with the increase in sludge mass ratio (SMR). The synergistic effect of the co-combustion of HAC and MS resulted in a slightly higher total heat release during the combustion of MS10HAC90 (i.e., the mass percentage of MS and HAC is 1:9) than HAC alone, however, the total heat release of the blend decreased progressively with increasing SMR. The experimental values of the average Eα for all four mixtures were lower than the theoretical values, indicating that the addition of MS lowered the reaction energy barriers of the mixtures. Consumption rates of the principal groups in samples during the oxidation and combustion all tended to increase progressively with increasing SMR. There are three major synergistic effects existing during co-combustion of HAC and MS: (1) the reaction of free radicals with benzene molecules; (2) the interaction of free radicals; and (3) the catalytic effect of alkali and alkaline earth metals. These findings can provide theoretical guidance for the determination of key parameters (mixing ratio) for the blending of HAC and MS, and can fill the research gap in terms of microscopic reactivity and synergistic effects during the co-combustion of HAC and MS.

Research on Thermal Behaviors and NO x Release Properties during Combustion of Sewage Sludge, Sawdust, and Their Blends.

To investigate the thermal behaviors and NO x emission properties during combustion of sewage sludge (SS), sawdust (SD), and their blends (SS5SD5, SS3SD7, and SS1SD9 with SD proportions of 50, 70, and 90 wt %, respectively), tests were conducted using thermogravimetry-mass spectrometry (TG-MS), Fourier transform infrared spectroscopy (FTIR), and a tube furnace in this study. Results indicated that hydrogen in the fuel was mainly released during volatile combustion, and carbon conversion proceeded during the whole combustion process. With the SD proportion increasing, samples exhibited better combustion characteristics. Compared to SD, SS emitted more NO x due to its higher nitrogen content but showed lower conversion ratios from fuel nitrogen to NO x , and the NO x yields decreased significantly with the increase in SD proportion. NO x emissions of higher volatile samples were more sensitive to temperature, and NO x yields of SD and SS1SD9 continued to decrease from 800 to 1000 °C, whereas NO x yields of SS, SS5SD5, and SS3SD7 changed slightly from 800 to 900 °C and decreased significantly from 900 to 1000 °C. Synergistic effects of cocombustion on NO x emission varied with the blending ratio and temperature. SS5SD5 and SS3SD7 always presented a positive NO x reduction performance, and SS1SD9 exhibited opposite NO x reduction effects at different temperatures. Synthetically considering the SS disposal capacity, combustion characteristic, and NO x yield, an SS proportion of around 30% in blends is more recommended in practical applications.