Kinetic Analysis of Digestate Slow Pyrolysis with the Application of the Master-Plots Method and Independent Parallel Reactions Scheme.

The solid fraction obtained by mechanical separation of digestate from anaerobic digestion plants is an attractive feedstock for the pyrolysis process. Especially in the case of digestate obtained from biogas plants fed with energy crops, this can be considered a lignin rich residue. The aim of this study is to investigate the pyrolytic kinetic characteristics of solid digestate. The Starink model-free method has been used for the kinetic analysis of the pyrolysis process. The average Activation Energy value is about 204.1 kJ/mol, with a standard deviation of 25 kJ/mol, which corresponds to the 12% of the average value. The activation energy decreased along with the conversion degree. The variation range of the activation energy is about 99 kJ/mol, this means that the average value cannot be used to statistically represent the whole reaction. The Master-plots method was used for the determination of the kinetic model, obtaining that n-order was the most probable one. On the other hand, the process cannot be modeled with a single-step reaction. For this reason it has been used an independent parallel reactions scheme to model the complete process.

Response surface optimization of product yields and biofuel quality during fast hydrothermal liquefaction of a highly CO2-tolerant microalgae.

The effects of biochemical components and processing variables (e.g., temperatures, solid-liquid ratio, ethanol concentration, and time) during fast hydrothermal liquefaction of a highly CO2-tolerant microalgae (Micractinium sp.) on the product yields and biofuel quality were explored using response surface methodology coupled with central composite design. Results showed that the maximum bio-oil yield (51.4 %) was obtained at 321 °C for 49 min at ethanol concentration of 75 % and solid-liquid ratio of 15.3 %. Among different studied parameters, ethanol concentration showed the highest significant impact on the bio-oil yield due to the low P-value and high F-value in ANOVA analysis. Furthermore, the chemical compositions of bio-oils were determined, which showed that the increase of ethanol concentration in the solvent not only increased the bio-oil yield but also promoted the bio-oil quality by reduction of carboxylic acids and nitrogen-containing compounds with simultaneous enhancement of esters in the bio-oil. The present results show that fast hydrothermal liquefaction is a promising approach to convert the microalgae into high quality biofuels rich in esters.

Effect of support type and crystal form of support in the catalytic gasification of old corrugated containers using Fe-based catalysts.

Catalytic gasification of old corrugated containers with Fe-based catalysts is a promising way to produce renewable H2 along with the utilization of solid waste. In this study, the effect of support type and crystal form of support in Fe-based catalysts on the catalytic gasification of old corrugated containers was systematically investigated. The results show that, the introduction of Fe/γ-Al2O3, Fe/TiO2, Fe/SiO2, and Fe/ZSM5-30 promote H2 production. Among them, Fe/TiO2 has the highest catalytic activity on H2 yield (25.10 mmol/g) related to the formation of Fe2TiO5 solid-melt material. Fe/γ-Al2O3 shows the best H2 selectivity (46.34 %) and good H2 yield (24.19 mmol/g) due to good dispersity of Fe. Further, the order of catalytic effect on H2 selectivity is Fe/amorphous Al2O3 (51.46 %) > Fe/α-Al2O3 (46.98 %) > Fe/γ-Al2O3 (46.34 %). With the increase in cycle index, Fe/amorphous Al2O3 shows the best catalytic effect on H2 yield (25.56 mmol/g) after 11 indexes due to the formation of Al2FeO4. Fe/γ-Al2O3 shows the best stability on H2 selectivity (∼43 %) after 11 indexes.

High-value products from ex-situ catalytic pyrolysis of polypropylene waste using iron-based catalysts: the influence of support materials.

Catalytic pyrolysis is considered a promising strategy for the utilisation of plastic waste from the economic and environmental perspectives. As such, the supporting materials play a critical role in the properties of the catalyst. This study clarified this influence on the dispersion of the iron (Fe) within an experimental context. Four different types of typical supports with different physical structures were introduced and explored in a two-stage fixed-bed reactor; these included metallic oxides (Al2O3, TiO2), a non-metallic oxide (SiO2), and molecular sieves (ZSM-5). The results show that the liquid products were converted into carbon deposits and lighter gaseous products, such as hydrogen. The Al2O3-supported catalyst with a relatively moderate specific surface areas and average pore diameter exhibited improved metal distribution with higher catalytic activity. In comparison, the relatively low specific surface areas of TiO2 and small average pore diameters of ZSM-5 had a negative impact on metal distribution and the subsequent catalytic reformation process; this was because of the inadequate reaction during the catalytic process. The Fe/Al2O3 catalyst produced a higher yield of carbon deposits (30.2 wt%), including over 65% high-value carbon nanotubes (CNTs) and hydrogen content (58.7 vol%). Additionally, more dispersive and uniform CNTs were obtained from the Fe/SiO2 catalyst. The Fe/TiO2 catalyst promoted the formation of carbon fibre twisted like fried dough twist. Notably, there was interesting correspondence between the size of the reduced Fe nanoparticles and the product distribution. Within certain limits, the smaller Fe particle size facilitates the catalytic activity. The smaller and better dispersed Fe particles over the support materials were observed to be essential for hydrocarbon cracking and the subsequent formation of carbon deposits. The findings from this study may provide specific guidance for the preparation of different forms of carbon materials.

Prospective contributions of biomass pyrolysis to China's 2050 carbon reduction and renewable energy goals.

Recognizing that bioenergy with carbon capture and storage (BECCS) may still take years to mature, this study focuses on another photosynthesis-based, negative-carbon technology that is readier to implement in China: biomass intermediate pyrolysis poly-generation (BIPP). Here we find that a BIPP system can be profitable without subsidies, while its national deployment could contribute to a 61% reduction of carbon emissions per unit of gross domestic product in 2030 compared to 2005 and result additionally in a reduction in air pollutant emissions. With 73% of national crop residues used between 2020 and 2030, the cumulative greenhouse gas (GHG) reduction could reach up to 8620 Mt CO2-eq by 2050, contributing 13-31% of the global GHG emission reduction goal for BECCS, and nearly 4555 Mt more than that projected for BECCS alone in China. Thus, China's BIPP deployment could have an important influence on achieving both national and global GHG emissions reduction targets.

LCA analysis of food waste co-digestion.

The i-REXFO LIFE project designs an innovative business model with the objective of reducing significantly the amount of landfilled food waste. Given the availability of supermarket food waste in the Umbria region (Italy), the logistics is optimized using a Vehicle Routing Problem Solver, mass and energy balances of the biogas plant are partly calculated and partly measured from a real biogas plant. The data obtained from food waste transport and anaerobic co-digestion process are used as input for LCA analysis. The aim of the methodology is to assess the environmental and economic benefit of the substitution of energy crops (like corn silage) with food waste in anaerobic digestion. Two approaches are adopted: consequential LCA and attributional LCA. Only one impact category is taken into account: climate change. This decision has been taken to focus on two decision making criteria (economic feasibility and GHG emissions reduction). The results show that a reduction of 42% in the carbon footprint of the electricity produced from the biogas plant can be obtained by substituting about 9900 t of corn silage with 6600 t of food waste. Through the combined use of economic analysis and consequential LCA it has been possible to identify an optimized scenario in which: food waste produced from food industries is collected and used to produce energy in Expired Food Energy chains (EFE), while the food obtained from supermarkets is used to promote charity initiatives in actions aiming at the Reduction of Expired Food waste (REF).

Bioenergy in China: Evaluation of domestic biomass resources and the associated greenhouse gas mitigation potentials.

As bioenergy produces neutral or even negative carbon emissions, the assessment of biomass resources and associated emissions mitigation is a key step toward a low carbon future. However, relevant comprehensive estimates lack in China. Here, we measure the energy potential of China's domestic biomass resources (including crop residues, forest residues, animal manure, municipal solid waste and sewage sludge) from 2000 to 2016 and draw the spatial-temporal variation trajectories at provincial resolution. Scenario analysis and life cycle assessment are also applied to discuss the greenhouse gas mitigation potentials. Results show that the collectable potential of domestic biomass resources increased from 18.31 EJ in 2000 to 22.67 EJ in 2016 with overall uncertainties fluctuating between (-26.6%, 39.7%) and (-27.6%, 39.5%). Taking energy crops into account, the total potential in 2016 (32.69 EJ) was equivalent to 27.6% of China's energy consumption. If this potential can be realized in a planned way to displace fossil fuels during the period 2020-2050, cumulative greenhouse gas emissions mitigation would be in the range of 1652.73-5859.56 Mt CO2-equivalent, in which the negative greenhouse gas emissions due to the introduction of bioenergy with carbon capture and storage would account for 923.78-1344.13 Mt CO2-equivalent. Contrary to increasing bioenergy potentials in most provinces, there are declining trends in Tibet, Beijing, Shanghai and Zhejiang. In addition, Yunnan, Sichuan and Inner Mongolia would have the highest associated greenhouse gas mitigation potentials. This study can provide valuable guidance on the exploitation of China's untapped biomass resources for the mitigation of global climate change.

Bimetallic carbon nanotube encapsulated Fe-Ni catalysts from fast pyrolysis of waste plastics and their oxygen reduction properties.

Carbon-based bimetallic electrocatalysts were obtained by catalytic pyrolysis of waste plastics with Fe-Ni-based catalysts and were used as efficient oxygen reduction reaction (ORR) catalysts in this study. The prepared iron-nickel alloy nanoparticles encapsulated in oxidized carbon nanotubes (FeNi-OCNTs) are solid products with a unique structure. Moreover, the chemical composition and structural features of FeNi-OCNTs were determined. The iron-nickel alloy nanoparticles were wrapped in carbon layers, and the carbon nanotubes had an outer diameter of 20-50 nm and micron-scale lengths. FeNi-OCNT with a Fe/Ni ratio of 1:2 (FeNi-OCNT12) exhibited remarkable electrochemical performance as an ORR catalyst with a positive onset potential of 1.01 V (vs. RHE) and a half-wave potential of 0.87 V (vs. RHE), which were comparable to those of a commercial 20% Pt/C catalyst. Furthermore, FeNi-OCNT12 exhibited promising long-term stability and higher tolerance to methanol than the commercial 20% Pt/C catalyst in an alkaline medium. These properties were attributable to the protective OCNT coating of the iron-nickel alloy nanoparticles.

Preparation of Iron- and Nitrogen-Codoped Carbon Nanotubes from Waste Plastics Pyrolysis for the Oxygen Reduction Reaction.

A novel method for the preparation of iron- and nitrogen-codoped carbon nanotubes (Fe-N-CNTs) is proposed, based on the catalytic pyrolysis of waste plastics. First, carbon nanotubes are produced from pyrolysis of plastic waste over Fe-Al2 O3 ; then, Fe-CNTs and melamine are heated together in an inert atmosphere. Different co-pyrolysis temperatures are tested to optimize the electrocatalyst production. A high doping temperature improves the degree of graphite formation and promotes the conversion of nitrogen into a more stable form. Compared with commercial Pt/C, the electrocatalyst obtained from pyrolysis at 850 °C shows remarkable properties, with an onset potential of 0.943 V versus RHE and a half-wave potential of 0.811 V versus RHE, and even better stability and anti-poisoning properties. In addition, zinc-air battery tests are performed, and the optimized catalyst exhibits a high maximum power density.

Scaled-up biodiesel synthesis from Chinese Tallow Kernel oil catalyzed by Burkholderia cepacia lipase through ultrasonic assisted technology: A non-edible and alternative source of bio energy.

In East Asia, for thousands of years, the fruit of Chinese tallow tree (Sapium sebiferum) has been used for multiple purposes because of its chemical composition; the presence of high amounts of lipids is remarkable, showing potential to be used as substrate for biodiesel synthesis. Previously have been reported the use of alkaline and enzymatic catalysts, microwave technology and the use of ionic liquids as co-solvents with the lipids of this tree species to produce biodiesel. This study shows the results of the use of Burkholderia cepacia lipase as enzymatic catalyst for transesterification of Chinese Tallow Kernel oil (CTK), extracted from the fruit of Chinese tallow tree, into biodiesel, with the use of ultrasonic assisted technology and without the usage of solvents. The optimal operational parameters were determined and the reactions were developed in a batch reactor with the use of ultrasonic irradiation and emulsification to enhance the mass transfer. The scaled-up experiments, in an especially designed 3 L capacity reactor, showed promising results, obtaining 55.20% biodiesel and a kinematic viscosity of 10.31 mm2.s-1 in only 4 h, in comparison with previously published (in vitro) methods. The valorization of this non-edible source of oil represents an opportunity to use as an alternative source for bioenergy and also to tackle the uncontrolled expansion of this oleaginous tree species in some ecologically fragile ecosystems.