Experimental studies of hydrothermal liquefaction of kitchen waste with H+, OH- and Fe3+ additives for bio-oil upgrading.

Kitchen waste (KW) has gradually become a prominent problem in municipal solid waste treatment. Hydrothermal liquefaction (HTL) is a promising method used to make fuel oil from food and KW. However, the upgrading of bio-oil is particularly important for the sake of industrial reuse. In this study, the KW from university restaurants was subjected to HTL experiments in order to study theoretical feasibility. With the change of conversion temperature and residence time, the optimal conversion working conditions in this study were determined according to the quality and yield of the bio-oil. Moreover, the bio-oil upgrading effects of different additives (hydrogen chloride, sodium hydroxide, and iron(III) chloride) on the HTL of KW were studied. Alkaline additives have an inhibitory effect on the bio-oil yield and positive effect on coke yield. Acidic additives and iron (Fe)-containing additives can promote bio-oil yield. As an important aspect of upgrading, the effect on the nitrogen content of bio-oil with additives was revealed. The alkaline and Fe-containing additives have little effect on reducing the viscosity of the bio-oil while with the appropriate ratio (2.5 mol•kg-1) of acidic additives to the raw material, the static and dynamic fluidity of the oil phase products are reduced to about 0.1 Pa•s.

The mechanisms of calcium-catalyzed graphenization of cellulose and lignin biochars uncovered.

A recent study has shown that highly crystalline graphene-based materials can be obtained from poorly organized carbon precursors using calcium as a non-conventional catalyst. XRD and TEM analyses of calcium-impregnated cellulose and lignin biochars showed the formation of well-ordered graphenic structures (Lc > 7 nm, d002 < 0.345 nm) above 1200 °C, far below the standard graphenization temperatures (T > 2000 °C). Herein, we propose new insights on the mechanism controlling the formation of highly graphenic biochars using Ca as a catalyst. We postulate that the calcium-catalyzed graphenization occurs through the formation of a metastable calcium carbide by reaction between CaO particles and amorphous carbon between 1000 and 1200 °C. CaC2 decomposes into calcium vapor and a graphenic shell covering the CaC2 particles as confirmed by TEM analysis. The thickness and planarity of the graphenic shell increase with the CaC2 initial particle size (between 20 and 200 nm), and its growth is controlled by the diffusion of the calcium vapor through the graphene layer. A much effective graphenization was obtained for the lignin biochars compared to cellulose, with Lc > 10 nm and d002 < 0.340 nm, attributed to the insertion of sulfur in the graphenic shells, which favors their ruptures and the decomposition of CaC2 into graphene. We believe that these findings would enable the reduction of costs and environmental impact of graphene-based materials synthesis using cheap and abundant renewable feedstocks and catalysts as well.

Calcium as an innovative and effective catalyst for the synthesis of graphene-like materials from cellulose.

Pyrolysis of lignocellulosic biomass (hard carbon) produces poorly graphitic biochar. In this study, nano-structured biochars were produced from microcrystalline cellulose using calcium as a non-conventional catalyst. Calcium is abundant, environmental-friendly and widely accessible. Graphitization of calcium-impregnated cellulose was carried out at 1800 °C, a temperature below 2000 °C where the graphitization usually occurs. XRD, Raman spectroscopy, high-resolution TEM together with the in-house numerical tool developed enable the quantification of the graphene fringes in the biochars. The non-impregnated cellulose biochar was composed of short and poorly stacked graphene fringes. The impregnation with 2 wt.% of calcium led to the conversion of the initial structure into a well-organized and less defective graphene-like one. The graphene-like structures obtained were composed of tens of stacked graphene fringes with a crystallite size up to 20 nm and an average interlayer spacing equal to 0.345 nm, close to the reference value of standard hexagonal graphite (0.3354 nm). The increase of the calcium concentration did not significantly improve the crystallite sizes of the graphene-like materials but rather drastically improved their rate. Our results propose a mechanism and provide new insights on the synthesis of graphene-like materials from bio-feedstocks using calcium where the literature is focused on transition metals such as iron and nickel among others. The decrease of the graphitization temperature below 2000 °C should lower the production cost as well as the environmental impact of the thermal graphene-like materials synthesis using biomass. This finding should stimulate further research in the field and broaden the application perspectives.

Hydrogen-Rich and Clean Fuel Gas Production from Co-pyrolysis of Biomass and Plastic Blends with CaO Additive.

The treatment and disposal of waste biomass and plastics are of great importance to achieve both waste management and resource recycling. In this work, pyrolysis of biomass and plastic blends were investigated to identify the influence of temperature and in situ CaO addition on the production of hydrogen-rich, HCl-free, and low tar content fuel gases. The results show that the increase in temperature and the use of CaO significantly improved both the quantity and quality of the fuel gas and mitigated the formation of tar compounds and HCl. Moreover, H2 yield was significantly improved from 0.30 to 3.68 mmol/g with the increase in temperature from 550 to 850 °C. Also, the use of in situ CaO significantly increased the H2 yield by 28-88%. The H2/CO ratio was also enhanced from 0.35 to 1.50 with the temperature increase and CaO addition. Tar removal efficiency reached approximately 70.09% with the use of CaO at 850 °C. The produced HCl gas could be effectively absorbed by CaO through dechlorination reactions to form CaClOH at a highest mitigation efficiency of 92.37%. The results could be used to develop clean and efficient treatment technologies of waste biomass and plastics.

Life cycle assessment of pyrolysis, gasification and incineration waste-to-energy technologies: Theoretical analysis and case study of commercial plants.

Municipal solid waste (MSW) pyrolysis and gasification are in development, stimulated by a more sustainable waste-to-energy (WtE) option. Since comprehensive comparisons of the existing WtE technologies are fairly rare, this study aims to conduct a life cycle assessment (LCA) using two sets of data: theoretical analysis, and case studies of large-scale commercial plants. Seven systems involving thermal conversion (pyrolysis, gasification, incineration) and energy utilization (steam cycle, gas turbine/combined cycle, internal combustion engine) are modeled. Theoretical analysis results show that pyrolysis and gasification, in particular coupled with a gas turbine/combined cycle, have the potential to lessen the environmental loadings. The benefits derive from an improved energy efficiency leading to less fossil-based energy consumption, and the reduced process emissions by syngas combustion. Comparison among the four operating plants (incineration, pyrolysis, gasification, gasification-melting) confirms a preferable performance of the gasification plant attributed to syngas cleaning. The modern incineration is superior over pyrolysis and gasification-melting at present, due to the effectiveness of modern flue gas cleaning, use of combined heat and power (CHP) cycle, and ash recycling. The sensitivity analysis highlights a crucial role of the plant efficiency and pyrolysis char land utilization. The study indicates that the heterogeneity of MSW and syngas purification technologies are the most relevant impediments for the current pyrolysis/gasification-based WtE. Potential development should incorporate into all process aspects to boost the energy efficiency, improve incoming waste quality, and achieve efficient residues management.

Agro-industrial waste to solid biofuel through hydrothermal carbonization.

In this paper, the use of grape marc for energy purposes was investigated. Grape marc is a residual lignocellulosic by-product from the winery industry, which is present in every world region where vine-making is addressed. Among the others, hydrothermal carbonization was chosen as a promising alternative thermochemical process, suitable for the treatment of this high moisture substrate. Through a 50 mL experimental apparatus, hydrothermal carbonization tests were performed at several temperatures (namely: 180, 220 and 250 °C) and residence times (1, 3, 8 h). Analyses on both the solid and the gaseous phases obtained downstream of the process were performed. In particular, solid and gas yields versus the process operational conditions were studied and the obtained hydrochar was evaluated in terms of calorific value, elemental analysis, and thermal stability. Data testify that hydrochar form grape marc presents interesting values of HHV (in the range 19.8-24.1 MJ/kg) and physical-chemical characteristics which make hydrochar exploitable as a solid biofuel. In the meanwhile, the amount of gases produced is very small, if compared to other thermochemical processes. This represents an interesting result when considering environmental issues. Statistical analysis of data allows to affirm that, in the chosen range of operational conditions, the process is influenced more by temperature than residence time. These preliminary results support the option of upgrading grape marc toward its energetic valorisation through hydrothermal carbonization.

Hydrothermal carbonization of off-specification compost: a byproduct of the organic municipal solid waste treatment.

The possibility to apply the hydrothermal carbonization (HTC) process to off-specification compost (EWC 19.05.03) at present landfilled was investigated in this work. The aim was to produce a carbonaceous solid fuel for energy valorization, with the perspective of using HTC as a complementary technology to common organic waste treatments. Thus, samples of EWC 19.05.03 produced by a composting plant were processed through HTC in a batch reactor. Analytical activities allowed to characterize the HTC products and their yields. The hydrochar was characterized in terms of heating value, thermal stability and C, H, O, N, S and ash content. The liquid phase was characterized in terms of total organic carbon and mineral content. The composition of the gas phase was measured. Results show that the produced hydrochar has a great potentiality for use as solid fuel.

The effect of temperature and heating rate on char properties obtained from solar pyrolysis of beech wood.

Char samples were produced from pyrolysis in a lab-scale solar reactor. The pyrolysis of beech wood was carried out at temperatures ranging from 600 to 2000°C, with heating rates from 5 to 450°C/s. CHNS, scanning electron microscopy analysis, X-ray diffractometry, Brunauer-Emmett-Teller adsorption were employed to investigate the effect of temperature and heating rate on char composition and structure. The results indicated that char structure was more and more ordered with temperature increase and heating rate decrease (higher than 50°C/s). The surface area and pore volume firstly increased with temperature and reached maximum at 1200°C then reduced significantly at 2000°C. Besides, they firstly increased with heating rate and then decreased slightly at heating rate of 450°C/s when final temperature was no lower than 1200°C. Char reactivity measured by TGA analysis was found to correlate with the evolution of char surface area and pore volume with temperature and heating rate.