Strategic use of crop residue biochars for removal of hazardous compounds in wastewater.

Crop residues are affordable lignocellulosic waste in the world, and a large portion of the waste has been burned, releasing toxic pollutants into the environment. Since the crop residue is a carbon and ingredient rich material, it can be strategically used as a sorptive material for (in)organic pollutants in the wastewater after thermo-chemical valorization (i.e., biochar production). In this review, applications of crop residue biochars to adsorption of non-degradable synthetic dyes, antibiotics, herbicides, and inorganic heavy metals in wastewater were discussed. Properties (porosity, functional groups, heteroatom, and metal(oxide)s, etc.) and adsorption capacity relationships were comprehensively reviewed. The current challenges of crop residue biochars and guidelines for development of efficient adsorbents were also provided. In the last part, the future research directions for practical applications of the crop residue biochars in wastewater treatment plants have been suggested.

Environmental benefits from the use of CO2 in the thermal disposal of cigarette butts.

As the global consumption of cigarettes has increased, the massive generation of cigarette butts (CBs) has led to critical environmental and health problems. Landfilling or incineration of CBs has been conventionally carried out, but such disposal protocols have suffered from the potential risks of the unwanted/uncontrolled release of leachates, carcinogens, and toxic chemicals into all environmental media. Thus, this study focuses on developing an environmentally dependable method for CB disposal. Littered CBs from filtered/electronic cigarettes were valorized into syngas (H2/CO). To seek a greener approach for the valorization of CBs, CO2 was intentionally considered as a reaction intermediate. Prior to multiple pyrolysis studies, the toxic chemicals in the CBs were qualitatively determined. This study experimentally proved that the toxic chemicals in CBs were detoxified/valorized into syngas. Furthermore, this work demonstrated that CO2 was effective in thermally destroying toxic chemicals in CBs via a gas-phase reaction. The reaction features and CO2 synergistically enhance syngas production. With the use of a supported Ni catalyst and CO2, syngas production from the catalytic pyrolysis of CBs was greatly enhanced (approximately 4 times). Finally, the gas-phase reaction by CO2 was reliably maintained owing to the synergistic mechanistic/reaction feature of CO2 for coke formation prevention on the catalyst surface.

Applications of agricultural residue biochars to removal of toxic gases emitted from chemical plants: A review.

Crop residues are representative agricultural waste materials, massively generated in the world. However, a large fraction of them is currently being wasted, though they have a high potential to be used as a value-added carbon-rich material. Also, the applications of carbon-rich materials from agricultural waste to industries can have economic benefit because waste-derived carbon materials are considered inexpensive waste materials. In this review, valorization methods for crop residues as carbon-rich materials (i.e., biochars) and their applications to industrial toxic gas removals are discussed. Applications of crop residue biochars to toxic gas removal can have significant environmental benefits and economic feasibility. As such, this review discussed the technical advantages of the use of crop residue biochars as adsorbents for hazardous gaseous pollutants and greenhouse gases (GHGs) stemmed from combustion of fossil fuels and the different refinery processes. Also, the practical benefits from the activation methods in line with the biochar properties were comprehensively discussed. The relationships between the physico-chemical properties of biochars and the removal mechanisms of gaseous pollutants (H2S, SO2, Hg0, and CO2) on biochars were also highlighted in this review study. Porosity controls using physical and chemical activations along with the addition of specific functional groups and metals on biochars have significantly contributed to the enhancement of flue gas adsorption. The adsorption capacity of biochar for each toxic chemical was in the range of 46-76 mg g-1 for H2S, 40-182 mg g-1 for SO2, 80-952 µg g-1 for Hg0, and 82-308 mg g-1 CO2, respectively. This helps to find suitable activation methods for adsorption of the target pollutants. In the last part, the benefits from the use of biochars and the research directions were prospectively provided to make crop residue biochars more practical materials in adsorption of pollutant gases.

Disposal of plastic mulching film through CO2-assisted catalytic pyrolysis as a strategic means for microplastic mitigation.

Conventional disposal processes (incineration and landfilling) of agricultural plastic wastes release harmful chemicals and microplastics into our ecosystems. To provide a disposal platform not releasing harmful chemicals, pyrolysis of a representative agricultural plastic waste was proposed in this study. Spent plastic mulching film (SMF) was used as a model waste compound. To make pyrolysis process more environmentally benign, CO2 was used as a raw material in pyrolysis of SMF. H2 and hydrocarbons were produced from pyrolysis of SMF under the inert (N2) and CO2 conditions, because SMF is composed of polyethylene. To enhance conversion of hydrocarbons into H2, catalytic pyrolysis of SMF was conducted over Ni/SiO2. Compared to non-catalytic pyrolysis, total concentration of pyrolytic gases was enhanced up to 3.1 and 11.3 times under N2 and CO2 conditions, respectively. The gas phase reactions between CO2 and hydrocarbons led to formation of CO, which enhanced production of pyrolytic gases under the CO2 condition. Moreover, gas phase reactions resulted in less production of pyrolytic oil from CO2 condition (15.9 wt%) in reference to the N2 condition (22.6 wt%). All experimental results confirmed that CO2 and SMF can be used as useful feedstocks to produce value-added products. ENVIRONMENTAL IMPLICATION: Plastic waste used from a sector of agriculture is incinerated or/and landfilled, generating hazardous microplastic and volatile compounds into the environment. Thus, an environmentally friendly process for plastic waste materials in the agricultural industry is required. This study converted a spent plastic mulching film (SMF), broadly used for plastic greenhouse, into value-added syngas through catalytic pyrolysis. CO2 was used as a reactant. We found that concentration of CO2 was key to improve syngas formation from pyrolysis of SMF. Thus, this study suggested that CO2/SMF are used as useful feedstocks through catalytic pyrolysis, while they were previously discarded as waste materials.

CO2-assisted catalytic pyrolysis of cellulose acetate using Ni-based catalysts.

Cellulose acetate (CA) is one of widely used polymers for chemical and medical applications due to its versatile physico-chemical functionalities. Although its recycle is available after a deacetylation process, the recycle process releases a huge amount of wastewater. Thus, this study investigated a direct disposal process of CA with its valorization to syngas (H2 and CO) through pyrolysis. To construct more environmentally benign process, CO2 was used as a co-feedstock with CA to simultaneously convert them into syngas. Pyrolysis of CA in N2 was performed as a reference study to examine the effectiveness of CO2 on valorization of CA. Acetic acid and methyl acetate were main volatile pyrolysates (VPs) from CA pyrolysis, and the further thermal cracking of VPs resulted in syngas and CH4 formations under both N2 and CO2 conditions. To expedite syngas formations, multi-stage pyrolysis (two-stage pyrolysis) and catalytic pyrolysis were employed. With the increased thermal energy through two-stage pyrolysis, four times more production of syngas was shown, comparing to the result of a single-stage pyrolysis. With Ni catalysts, the syngas formation was the two orders of magnitude higher than the single-stage pyrolysis, and the significant enhancement of CO formation was shown in the presence of CO2 due to combined effects of CO2 and the Ni-based catalysts. This CO enhancement resulted from catalytically expedited gas phase reactions between CO2 and VPs evolved from CA. In addition, the CO2 contributed to the suppression of coke deposition on the catalyst, thereby suggesting more technical and environmental benefits of CO2 as a reactive co-feedstock of pyrolysis in reference to N2. Therefore, this study proved the direct and versatile technical platform to convert CA and CO2 into syngas.

Carbon dioxide assisted thermal decomposition of cattle excreta.

To develop the environmentally benign thermo-chemical process, this study placed great emphasis on the influence of CO2 on pyrolysis of cattle excreta for energy recovery. To this end, this study evaluates the possible enhanced energy recovery from cattle excreta using CO2 as reaction medium/feedstock in the thermal degradation of cattle excreta. The enhanced generation of CO in the presence of CO2 reached up to 15.15mol% (reference value: 0.369mol%) at 690°C, which was equivalent to ~4000 times more generation of CO. In addition to the enhanced generation of CO, the enhanced generation of H2 and CH4 in the thermal degradation of cattle excreta in CO2. Thus, the findings of this study revealed two genuine roles of CO2: 1) enhanced thermal cracking of volatile organic carbons (VOCs) evolved from the thermal degradation of cattle excreta and 2) direct reaction between VOCs and CO2 via gas phase reaction.

Quantification of volatile fatty acids from cattle manure via non-catalytic esterification for odour indication.

This report proposes a new approach to evaluate the odour nuisance of cattle manure samples from three different cattle breeds (i.e., native cattle, beef cattle, and milk cow) by means of quantification and speciation of volatile fatty acids (VFAs). To this end, non-catalytic esterification thermally induced in the presence of a porous material (silica) was undertaken, and the optimal operational parameters such as the derivatizing temperature (330°C) for the maximum yield (≥99±0.4%) of volatile fatty acid methyl esters (VFAMEs) were established. Among the VFA species in cattle manure based on quantification of VFAs, the major species were acetic, butyric and valeric acid. Considering the odour threshold of each VFA, our experimental results suggested that the major contributors to odour nuisance were C4-5 VFA species (i.e., butyric and valeric acid). Hydrothermal treatment was performed at 150°C for 0-40min to correlate the formation of VFAs with different types of cattle feed formulations. Our experimental data demonstrated that the formation of total VFAs is linearly proportional to the hydrothermal treatment duration and the total content of VFAs in native cattle, beef cattle, and milk cow manure samples reached up to ~1000, ~3200, and ~2800ppm, respectively. Thus, this study demonstrated that the degree of VFA formation is highly dependent on cattle feed formulations, which rely significantly on the protein content. Furthermore, the hydrothermal treatment provides a favourable condition for generating more VFAs. In this context, producing cattle manure into refused derived fuel (RDF) via a hydrothermal treatment is not a viable option to control odour.

Pyrolysis of microalgal biomass in carbon dioxide environment.

This work mechanistically investigated the influence of CO2 in the thermo-chemical process of microalgal biomass (Chlorella vulgaris and Microcystis aeruginosa) to achieve a fast virtuous cycle of carbon via recovering energy. This work experimentally justified that the influence of CO2 in pyrolysis of microalgal biomass could be initiated at temperatures higher than 530 °C, which directly led to the enhanced generation of syngas. For example, the concentration of CO from pyrolysis of M. aeruginosa increased up to ∼ 3000% at 670 °C in the presence of CO2. The identified universal influence of CO2 could be summarized by the expedited thermal cracking of VOCs evolved from microalgal biomass and by the unknown reaction between VOCs and CO2. This identified effectiveness of CO2 was different from the Boudouard reaction, which was independently occurred with dehydrogenation. Thus, microalgal biomass could be a candidate for the thermo-chemical process (pyrolysis and gasification).

Carbon dioxide assisted sustainability enhancement of pyrolysis of waste biomass: A case study with spent coffee ground.

This work mainly presents the influence of CO2 as a reaction medium in the thermo-chemical process (pyrolysis) of waste biomass. Our experimental work mechanistically validated two key roles of CO2 in pyrolysis of biomass. For example, CO2 expedited the thermal cracking of volatile organic compounds (VOCs) evolved from the thermal degradation of spent coffee ground (SCG) and reacted with VOCs. This enhanced thermal cracking behavior and reaction triggered by CO2 directly led to the enhanced generation of CO (∼ 3000%) in the presence of CO2. As a result, this identified influence of CO2 also directly led to the substantial decrease (∼ 40-60%) of the condensable hydrocarbons (tar). Finally, the morphologic change of biochar was distinctive in the presence of CO2. Therefore, a series of the adsorption experiments with dye were conducted to preliminary explore the physico-chemical properties of biochar induced by CO2.

Synergetic sustainability enhancement via utilization of carbon dioxide as carbon neutral chemical feedstock in the thermo-chemical processing of biomass.

This study investigated the utilization of CO2 as carbon neutral chemical feedstock in the thermo-chemical processing (i.e., pyrolysis and gasification) of biomass to enhance sustainability via modification of the composition of end products. To justify the universal function of CO2 in the thermo-chemical process, the biomass experimented on in this work was not limited to ligno-cellulosic biomass; seaweed (i.e., red macroalgae) was used to expand biofuel feedstock beyond terrestrial biomass. Our experimental results validated the achieved enhanced generation of ∼200% for H2 and ∼1000% for CO by means of adopting CO2 in the thermo-chemical process, as compared to the case in N2. This can be explained by the enhanced thermal cracking of volatile organic carbons (VOCs) evolved from the thermal degradation of biomass and the reaction between CO2 and VOCs. Considering mass balance under our experimental conditions, we confirmed reaction between CO2 and VOCs, which was universally observed in pyrolysis of all biomass samples used in this work. Thus, the identified influence of CO2 in the thermo-chemical process can be directly applied in a variety of research and industrial fields, which would be environmentally desirable.