The influence of sample mass (scaling effect) on the synthesis and structure of non-graphitizing carbon (biochar) during the analytical pyrolysis of biomass.

The porous non-graphitizing carbon (NGC) known as biochar is derived from the pyrolytic conversion of organic precursors and is widely investigated due to its multifunctional applications. At present, biochar is predominantly synthesized in custom lab-scale reactors (LSRs) to determine the properties of carbon, while a thermogravimetric reactor (TG) is utilized for pyrolysis characterization. This results in inconsistencies in the correlation between the structure of biochar carbon and the pyrolysis process. If a TG reactor can also be used as an LSR for biochar synthesis, then the process characteristics and the properties of the synthesized NGC can be simultaneously investigated. It also eliminates the need for expensive LSRs in the laboratory, improves the reproducibility, and correlatability of pyrolysis characteristics with the properties of the resulting biochar carbon. Furthermore, despite numerous TG studies on the kinetics and characterization of biomass pyrolysis, none have questioned how the properties of biochar carbon vary due to the influence of the starting sample mass (scaling) in the reactor. Herein, with a lignin-rich model substrate (walnut shells), TG is utilized as an LSR, for the first time, to investigate the scaling effect starting from the pure kinetic regime (KR). The changes in the pyrolysis characteristics and the structural properties of the resultant NGC with scaling are concurrently traced and comprehensively studied. It is conclusively proven that scaling influences the pyrolysis process and the NGC structure. There is a gradual shift in pyrolysis characteristics and NGC properties from the KR until an inflection mass of ∼200 mg is reached. After this, the carbon properties (aryl-C%, pore characteristics, defects in nanostructure, and biochar yield) are similar. At small scales (≲100 mg), and especially near the KR (≤10 mg) carbonization is higher despite the reduced char formation reaction. The pyrolysis is more endothermic near KR with increased emissions of CO2 and H2O. For a lignin-rich precursor, at masses above inflection point, TG can be employed for concurrent pyrolysis characterization and biochar synthesis for application-specific NGC investigations.

Biochar Synthesis from Mineral- and Ash-Rich Waste Biomass, Part 1: Investigation of Thermal Decomposition Mechanism during Slow Pyrolysis.

Synthesizing biochar from mineral- and ash-rich waste biomass (MWB), a by-product of human activities in urban areas, can result in renewable and versatile multi-functional materials, which can also cater to the need of solid waste management. Hybridizing biochar with minerals, silicates, and metals is widely investigated to improve parent functionalities. MWB intrinsically possesses such foreign materials. The pyrolysis of such MWB is kinetically complex and requires detailed investigation. Using TGA-FTIR, this study investigates and compares the kinetics and decomposition mechanism during pyrolysis of three types of MWB: (i) mineral-rich banana peduncle (BP), (ii) ash-rich sewage sludge (SS), and (iii) mineral and ash-rich anaerobic digestate (AD). The results show that the pyrolysis of BP, SS, and AD is exothermic, catalyzed by its mineral content, with heat of pyrolysis 5480, 4066, and 1286 kJ/kg, respectively. The pyrolysis favors char formation kinetics mainly releasing CO2 and H2O. The secondary tar reactions initiate from ≈318 °C (BP), 481 °C (SS), and 376 °C (AD). Moreover, negative apparent activation energies are intrinsic to their kinetics after 313 °C (BP), 448 °C (SS), and 339 °C (AD). The results can support in tailoring and controlling sustainable biochar synthesis from slow pyrolysis of MWB.

Modern Carbon-Based Materials for Adsorptive Removal of Organic and Inorganic Pollutants from Water and Wastewater.

Currently, a serious threat for living organisms and human life in particular, is water contamination with persistent organic and inorganic pollutants. To date, several techniques have been adopted to remove/treat organics and toxic contaminants. Adsorption is one of the most effective and economical methods for this purpose. Generally, porous materials are considered as appropriate adsorbents for water purification. Conventional adsorbents such as activated carbons have a limited possibility of surface modification (texture and functionality), and their adsorption capacity is difficult to control. Therefore, despite the significant progress achieved in the development of the systems for water remediation, there is still a need for novel adsorptive materials with tunable functional characteristics. This review addresses the new trends in the development of new adsorbent materials. Herein, modern carbon-based materials, such as graphene, oxidized carbon, carbon nanotubes, biomass-derived carbonaceous matrices-biochars as well as their composites with metal-organic frameworks (MOFs) and MOF-derived highly-ordered carbons are considered as advanced adsorbents for removal of hazardous organics from drinking water, process water, and leachate. The review is focused on the preparation and modification of these next-generation carbon-based adsorbents and analysis of their adsorption performance including possible adsorption mechanisms. Simultaneously, some weak points of modern carbon-based adsorbents are analyzed as well as the routes to conquer them. For instance, for removal of large quantities of pollutants, the combination of adsorption and other methods, like sedimentation may be recommended. A number of efficient strategies for further enhancing the adsorption performance of the carbon-based adsorbents, in particular, integrating approaches and further rational functionalization, including composing these adsorbents (of two or even three types) can be recommended. The cost reduction and efficient regeneration must also be in the focus of future research endeavors. The targeted optimization of the discussed carbon-based adsorbents associated with detailed studies of the adsorption process, especially, for multicomponent adsorbate solution, will pave a bright avenue for efficient water remediation.

Bio-reserves inventory-improving substrate management for anaerobic waste treatment in a fast-growing Indian urban city, Chennai.

India is one among the Asia's newly industrialized countries, in which urban centres generate large amount of municipal solid wastes due to the rapid urbanization. To demonstrate urban waste potentials for biogas production by anaerobic digestion, a comprehensive analysis on the availability of organic waste hotspots and its biogas potential for the exemplary case of Chennai, India, was undertaken. The identified hotspots and their biogas potential were plotted with Geographical Information System as thematic maps. The results of biogas potential tests revealed strong variations in the biogas potentials of individual waste streams from 240.2 to 514.2 mLN/g oDM (organic dry matter) with oDM reduction in the range of 36.4-61.5 wt.-%. Major waste generation hotspots were identified from the surveyed urban bio-reserves and the biogas potentials within an effective area of 5 km radius surrounding the hotspot were estimated. It was found that the biogas potential of individual hotspots ranged between 38.0-5938.7 m3/day. Further results revealed that the biogas potential during anaerobic co-digestion, by considering nearby bio-reserves in the effective areas of major hotspots, with and without residential organic waste, ranged between 4110.4-18-106.1 m3/day and 253.2-5969.5 m3/day, originating from 144.0-620.0 tons and 3.1-170.5 tons, respectively. Despite variations in the composition of the wastes, the Carbon/Nitrogen ratio, oDM reduction, biogas production and substrate availability were improved during co-digestion of nearby bio-reserves within the major hotspots, thereby improving the prevailing barriers in substrate management during anaerobic digestion of wastes.

Multi-stage optimization approach for sustainable municipal solid waste collection systems in urban areas of Asia's newly industrialized countries.

A multi-stage optimization approach for sustainable collection system design for urban municipal solid waste is developed for megacities in Asia's newly industrialized countries. The approach combines four methods-analysis of waste and area characteristics, data acquisition and evaluation by GIS, mathematical projection of existing and future collection systems, and identification of most suitable alternatives through comparative multi-criteria decision analysis (MCDA). The approach is applied in Bangalore, India with 1.66 million inhabitants and 46.7-km2 area of investigation, and stratified based on population density. Two possible collection mechanisms (door-to-door (D2D) and community bin (CB)) are analyzed with a varied combination of collection coverage and waste segregation level. The study results confirm that both operational and investment expenses of the collection system decrease with an increasing rate of CB collection. Moreover, overall CO2 emissions of waste collection from the entire area of investigation decrease from 5.2 to 3.1 tons per day if the present 100% D2D collection is replaced with 100% CB collection system. Also, the increase of segregation at source contributes to the reduction of operational expenses and CO2 emissions; for example, a 20% increase of segregation level for D2D collection system leads to a 6% reduction of CO2 emissions. Considering all decision parameters through MCDA, a collection system comprising only CB with one separate compartment for wet waste and another combined compartment for dry and mixed waste is determined to be the most favorable approach.

On-site treatment of flowback and produced water from shale gas hydraulic fracturing: A review and economic evaluation.

On-site flowback treatment systems are typically rated and selected based on three fundamental categories: satisfying customer needs (e.g. meeting effluent quality, capacity, delivery time and time required to reach stable and steady effluent quality), common features comparison (e.g. treatment costs, stability of operation, scalability, logistics, and maintenance frequency) and through substantial product differentiation such as better service condition, overcoming current market limitations (e.g. fouling, salinity limit), and having lower environmental footprints and emissions. For treatment of flowback, multiple on-site treatment systems are available for primary separation (i.e. reducing TSS concentrations and particle size below 25 µm for disposal), secondary separation (i.e. removing TSS, iron and main scaling ions, and reducing particle size up to 5 µm for reuse), or tertiary treatment (i.e. reducing TDS concentration in the permeate/distillate to below 500 mg/L) for recycling or discharge. Depending on geographic features, frac-fluid characteristics, and regulatory aspects, operators may choose disposal or reuse of flowback water. Among these approaches, desalination is the least utilized option while in the majority of cases on-site basic separation is selected which can result in savings up to $306,800 per well. Compared to desalination systems, basic separation systems (e.g. electrocoagulation, dissolved air floatation) have higher treatment capacity (159-4133 m3/d) and specific water treatment production per occupied space (8.9-58.8 m3/m2), lower treatment costs ($2.90 to $13.30 per m3) and energy demand, and finally generate less waste owing to their high recovery of 98-99.5%, which reduces both operator costs and environmental burdens.

Removal of inert COD and trace metals from stabilized landfill leachate by granular activated carbon (GAC) adsorption.

Landfills in Germany are currently approaching stabilization phase; as a result removal of inert organics and potentially toxic elements in the leachate is becoming a primary concern. Dissolved air floatation (DAF) at the secondary stage reduces only 27% of the residual chemical oxygen demand (COD) in the investigated treatment systems; downstream granular activated carbon (GAC) units are required to further reduce COD concentration by 40-56% to meet indirect discharge or direct discharge limits respectively. Therefore, in this study performance in terms of COD and trace metals adsorption of different types of granular activated carbon were compared over different contact times and dosages. GAC 1 with Brunauer-Emmett-Teller (BET) surface area of 719.5 ±â€¯2.1 m2/g and average pore diameter (D) of 4.81 nm was identified to be inappropriate for treatment of leachate from this landfill. GAC 2 (with BET of 1513.7 ±â€¯6.4 m2/g and D of 3.50 nm) was feasible for COD reduction from DAF-pretreated leachate, while GAC 3 (with BET of 644.5 ±â€¯2.6 m2/g and D of 5.65 nm) can be coupled either with biological step alone, or as a tertiary step after the DAF unit. Moreover, as COD is the primary remaining contaminant of interest after secondary and tertiary treatment, spectrometer probes provide a close estimation of COD concentration for use in online monitoring. Beside COD removal, GAC 3 also confirmed the effectiveness of trace metals adsorption even at trace level, as it removed 66, 64, 48, 47, 43, and 25% of copper, cobalt, chromium, manganese, nickel, and zinc, respectively.

High-rate anaerobic treatment of wastewater from soft drink industry: Methods, performance and experiences.

At an Austrian soft drink company, an expanded granular sludge bed reactor for anaerobic wastewater treatment was inoculated with sludge from paper and food industries. Detailed online monitoring and laboratory examinations were carried out during startup and subsequent phases, which included a period of inhibition after ca. 80 days during which reactor degradative performance diminished suddenly, following a period of increased effluent VFA. After dosing iron chloride (FeCl2) and micronutrients and reducing organic loading to startup levels, the reactor eventually reached efficient operation (>85% COD degradation) after a gradual recovery phase. In this work performance data both at lab and full scale are elaborated along startup, adaptation, pre-inhibition, recovery and stable phases, and correlated between scales. High rate anaerobic treatment of soft drink industry wastewater was successful in terms of COD removal efficiency and final effluent COD (∼300 mg l-1), with a startup period (including inhibition) of ca. 5 months.

Municipal landfill leachate characteristics and feasibility of retrofitting existing treatment systems with deammonification - A full scale survey.

Leachate characteristics, applied technologies and energy demand for leachate treatment were investigated through survey in different states of Germany. Based on statistical analysis of leachate quality data from 2010 to 2015, almost half of the contaminants in raw leachate satisfy direct discharge limits. Decrease in leachate pollution index of current landfills is mainly related to reduction in concentrations of certain heavy metals (Pb, Zn, Cd, Hg) and organics (biological oxygen demand (BOD5), chemical oxygen demand (COD), and adsorbable organic halogen (AOX)). However, contaminants of concern remain COD, ammonium-nitrogen (NH4N) and BOD5 with average concentrations in leachate of about 1850, 640, and 120 mg/L respectively. Concentrations of COD and NH4N vary seasonally, mainly due to temperature changes; concentrations during the first quarter of the year are mostly below the annual average value. Electrical conductivity (EC) of leachate may be used as a time and cost saving alternative to monitor sudden changes in concentration of these two parameters, due to high correlations of around 0.8 with both COD and NH4N values which are possibly due to low heavy metal concentrations in leachate. The decreased concentrations of heavy metals and BOD5 favor the retrofitting of an existing biological reactor (nitrification/denitrification) with the deammonification process and post denitrification, as this lowers average annual operational cost (in terms of energy and external carbon source) and CO2 emission by €25,850 and 15,855 kg CO2,eq respectively.

Uptake and biodegradation of the antimicrobial sulfadimidine by the species Tripolium pannonicum acting as biofilter and its further biodegradation by anaerobic digestion and concomitant biogas production.

This project analyses the uptake and biodegradation of the antimicrobial sulfadimidine (SDI) from the culture medium and up to the anaerobic digestion. Tripolium pannonicum was grown under hydroponic conditions with different concentrations of SDI (0, 5 and 10mg·L(-1)) and the fresh biomass, containing different amounts of SDI taken up, was used as substrate for biogas production. SDI was analyzed by liquid chromatography coupled to positive ion electrospray mass spectrometry (ESI LC-MS). Based on the findings, T. pannonicum is able to uptake SDI. The more SDI is in the culture medium, the higher the SDI content in the plant tissue. According to this study, it is possible to produce high yields of biogas using biomass of T. pannonicum containing SDI and at the same time biodegradation of SDI is carried out. The highest specific biogas yield is obtained using shoots as substrate of the plants cultivated at 5mg·L(-1) SDI.

Potential use of the facultative halophyte Chenopodium quinoa Willd. as substrate for biogas production cultivated with different concentrations of sodium chloride under hydroponic conditions.

This project analyses the biogas potential of the halophyte Chenopodium quinoa Willd. In a first approach C. quinoa was grown with different concentrations of NaCl (0, 10 and 20 ppt NaCl) and the crop residues were used as substrate for biogas production. In a second approach, C. quinoa was grown with 0, 10, 20 and 30 ppt NaCl under hydroponic conditions and the fresh biomass was used as substrate. The more NaCl is in the culture medium, the higher the sodium, potassium, crude ash and hemicellulose content in the plant tissue whereas the calcium, sulfur, nitrogen and carbon content in the biomass decrease. According to this study, it is possible to produce high yields of methane using biomass of C. quinoa. The highest specific methane yields were obtained using the substrate from the plants cultivated at 10 and 20 ppt NaCl in both experiments.