Nicole D. Berge

Hydrothermal carbonization of biomass residuals: a comparative review of the chemistry, processes and applications of wet and dry pyrolysis

The carbonization of biomass residuals to char has strong potential to become an environmentally sound conversion process for the production of a wide variety of products. In addition to its traditional use for the production of charcoal and other energy vectors, pyrolysis can produce products for environmental, catalytic, electronic and agricultural applications. As an alternative to dry pyrolysis, the wet pyrolysis process, also known as hydrothermal carbonization, opens up the field of potential feedstocks for char production to a range of nontraditional renewable and plentiful wet agricultural residues and municipal wastes. Its chemistry offers huge potential to influence product characteristics on demand, and produce designer carbon materials. Future uses of these hydrochars may range from innovative materials to soil amelioration, nutrient conservation via intelligent waste stream management and the increase of carbon stock in degraded soils.

Hydrothermal Carbonization of Municipal Waste Streams

Hydrothermal carbonization (HTC) is a novel thermal conversion process that can be used to convert municipal waste streams into sterilized, value-added hydrochar. HTC has been mostly applied and studied on a limited number of feedstocks, ranging from pure substances to slightly more complex biomass such as wood, with an emphasis on nanostructure generation. There has been little work exploring the carbonization of complex waste streams or of utilizing HTC as a sustainable waste management technique. The objectives of this study were to evaluate the environmental implications associated with the carbonization of representative municipal waste streams (including gas and liquid products), to evaluate the physical, chemical, and thermal properties of the produced hydrochar, and to determine carbonization energetics associated with each waste stream. Results from batch carbonization experiments indicate 49-75% of the initially present carbon is retained within the char, while 20-37% and 2-11% of the carbon is transferred to the liquid- and gas-phases, respectively. The composition of the produced hydrochar suggests both dehydration and decarboxylation occur during carbonization, resulting in structures with high aromaticities. Process energetics suggest feedstock carbonization is exothermic.

The Fate of Nitrogen in Bioreactor Landfills

Although bioreactor landfills have many advantages associated with them, challenges remain, including the persistence of ammonia-nitrogen in the leachate. It has been suggested that ammonia-nitrogen is one of the most significant long-term pollution problem in landfills and is likely a parameter that will determine when landfill postclosure monitoring may end. The fate of nitrogen in bioreactor landfills is not well understood. As more landfills transition operation to bioreactors, more attention must be paid to how operating the landfill as a bioreactor may affect the fate of nitrogen. Processes such as sorption, volatilization, nitrification, denitrification, anaerobic ammonium oxidation, and dissimilatory nitrate reduction may all occur.

Influence of reaction time and temperature on product formation and characteristics associated with the hydrothermal carbonization of cellulose

Studies have demonstrated that hydrothermal carbonization of biomass and waste streams results in the formation of beneficial materials/resources with minimal greenhouse gas production. Data necessary to understand how critical process conditions influence carbonization mechanisms, product formation, and associated environmental implications are currently lacking. The purpose of this work is to hydrothermally carbonize cellulose at different temperatures and to systematically sample over a 96-h period to determine how changes in reaction temperature influence product evolution. Understanding cellulose carbonization will provide insight to carbonization of cellulosic biomass and waste materials. Results from batch experiments indicate that the majority of cellulose conversion occurs between the first 0.5-4h, and faster conversion occurs at higher temperatures. Data collected over time suggest cellulose solubilization occurs prior to conversion. The composition of solids recovered after 96h is similar at all temperatures, consisting primarily of sp(2) carbons (furanic and aromatic groups) and alkyl groups.

Removal of bisphenol A and 17α-ethinyl estradiol from landfill leachate using single-walled carbon nanotubes

In this study, the adsorption of bisphenol A (BPA) and 17α-ethinyl estradiol (EE2) from landfill leachate onto single-walled carbon nanotubes (SWCNTs) was investigated. Different leachate solutions were prepared by altering the pH, ionic strength, and dissolved organic carbon (DOC) in the solutions to mimic the varying water conditions that occur in leachate during the various stages of waste decomposition. The youngest and oldest leachate solutions contained varying DOC and background chemistry and were represented by leachate Type A (pH = 5.0; DOC = 2500 mg/L; conductivity = 12,500 μS/cm; [Ca(2+)] = 1200 mg/L; [Mg(2+)] = 470 mg/L) and Type E (pH = 7.5; DOC = 250 mg/L; conductivity = 3250 μS/cm; [Ca(2+)] = 60 mg/L; [Mg(2+)] = 180 mg/L). These solutions were subsequently combined in different ratios to produce intermediate solutions, labeled B-D, to replicate time-dependent changes in leachate composition. Overall, a larger fraction of EE2 was removed as compared to BPA, consistent with its higher log K(OW) value. The total removal of BPA and EE2 decreased in older leachate solutions, with the adsorptive capacity of SWCNTs decreasing in the order of leachate Type A > Type B > Type C > Type D > Type E. An increase in the pH from 3.5 to 11 decreased the adsorption of BPA by 22% in young leachate and by 10% in old leachate. The changes in pH did not affect the adsorption of EE2 in the young leachate, but did reduce adsorption by 32% in the old leachate. Adjusting the ionic strength using Na(+) did not significantly impact adsorption, while increasing the concentration of Ca(2+) resulted in a 12% increase in the adsorption of BPA and a 19% increase in the adsorption of EE2. DOC was revealed to be the most influential parameter in this study. In the presence of hydrophilic DOC, represented by glucose in this study, adsorption of the endocrine disrupting compounds (EDCs) onto the SWCNTs was not affected. In the absence of SWCNTs, hydrophobic DOC (i.e., humic acid) adsorbed 15-20% of BPA and EE2. However, when the humic acid and SWCNTs were both present, the overall adsorptive capacity of the SWCNTs was reduced. Hydrophobic (π-π electron donor-acceptor) interactions between the EDCs and the constituents in the leachate, as well as interactions between the SWCNTs and the EDCs, are proposed as potential adsorption mechanisms for BPA and EE2 onto SWCNTs.

Thermal conversion of municipal solid waste via hydrothermal carbonization: Comparison of carbonization products to products from current waste management techniques

Hydrothermal carbonization (HTC) is a novel thermal conversion process that may be a viable means for managing solid waste streams while minimizing greenhouse gas production and producing residual material with intrinsic value. HTC is a wet, relatively low temperature (180-350 °C) thermal conversion process that has been shown to convert biomass to a carbonaceous residue referred to as hydrochar. Results from batch experiments indicate HTC of representative waste materials is feasible, and results in the majority of carbon (45-75% of the initially present carbon) remaining within the hydrochar. Gas production during the batch experiments suggests that longer reaction periods may be desirable to maximize the production of energy-favorable products. If using the hydrochar for applications in which the carbon will remain stored, results suggest that the gaseous products from HTC result in fewer g CO(2)-equivalent emissions than the gases associated with landfilling, composting, and incineration. When considering the use of hydrochar as a solid fuel, more energy can be derived from the hydrochar than from the gases resulting from waste degradation during landfilling and anaerobic digestion, and from incineration of food waste. Carbon emissions resulting from the use of the hydrochar as a fuel source are smaller than those associated with incineration, suggesting HTC may serve as an environmentally beneficial alternative to incineration. The type and extent of environmental benefits derived from HTC will be dependent on hydrochar use/the purpose for HTC (e.g., energy generation or carbon storage).

Hydrothermal carbonization of food waste and associated packaging materials for energy source generation

Hydrothermal carbonization (HTC) is a thermal conversion technique that converts food wastes and associated packaging materials to a valuable, energy-rich resource. Food waste collected from local restaurants was carbonized over time at different temperatures (225, 250 and 275°C) and solids concentrations to determine how process conditions influence carbonization product properties and composition. Experiments were also conducted to determine the influence of packaging material on food waste carbonization. Results indicate the majority of initial carbon remains integrated within the solid-phase at the solids concentrations and reaction temperatures evaluated. Initial solids concentration influences carbon distribution because of increased compound solubilization, while changes in reaction temperature imparted little change on carbon distribution. The presence of packaging materials significantly influences the energy content of the recovered solids. As the proportion of packaging materials increase, the energy content of recovered solids decreases because of the low energetic retention associated with the packaging materials. HTC results in net positive energy balances at all conditions, except at a 5% (dry wt.) solids concentration. Carbonization of food waste and associated packaging materials also results in net positive balances, but energy needs for solids post-processing are significant. Advantages associated with carbonization are not fully realized when only evaluating process energetics. A more detailed life cycle assessment is needed for a more complete comparison of processes.

Effects of Biomass Types and Carbonization Conditions on the Chemical Characteristics of Hydrochars

Effects of biomass types (bark mulch versus sugar beet pulp) and carbonization processing conditions (temperature, residence time, and phase of reaction medium) on the chemical characteristics of hydrochars were examined by elemental analysis, solid-state ¹³C NMR, and chemical and biochemical oxygen demand measurements. Bark hydrochars were more aromatic than sugar beet hydrochars produced under the same processing conditions. The presence of lignin in bark led to a much lower biochemical oxygen demand (BOD) of bark than sugar beet and increasing trends of BOD after carbonization. Compared with those prepared at 200 °C, 250 °C hydrochars were more aromatic and depleted of carbohydrates. Longer residence time (20 versus 3 h) at 250 °C resulted in the enrichment of nonprotonated aromatic carbons. Both bark and sugar beet pulp underwent deeper carbonization during water hydrothermal carbonization than during steam hydrothermal carbonization (200 °C, 3 h) in terms of more abundant aromatic C but less carbohydrate C in water hydrochars.

An assessment of bioreactor landfill costs and benefits

Because effective operation of bioreactor landfills involves careful operation and construction of infrastructure beyond that necessary in traditional landfills, upfront capital and operating costs are greater than those associated with traditional landfills. Prior to investing in bioreactor landfills, landfill owners must be convinced that larger short-term expenses (e.g., liquid and/or air injection infrastructure) will be balanced by future economic benefits (e.g., extension of landfill life, reduced leachate treatment costs, etc.). The purpose of this paper is to describe an economic model developed to evaluate the impact of various operational (anaerobic, aerobic, or hybrid) and construction (retrofit and as-built) bioreactor landfill strategies on project economics. Model results indicate retrofit bioreactor landfills are more expensive than traditional landfills, while both the as-built and aerobic bioreactor landfills are less costly. Simulation results indicate the parameters that influence bioreactor economics most significantly are airspace recovery, gas recovery and subsequent use to generate electricity, and savings resulting from reduced leachate treatment costs.

Assessing the environmental impact of energy production from hydrochar generated via hydrothermal carbonization of food wastes.

Although there are numerous studies suggesting hydrothermal carbonization is an environmentally advantageous process for transformation of wastes to value-added products, a systems level evaluation of the environmental impacts associated with hydrothermal carbonization and subsequent hydrochar combustion has not been conducted. The specific objectives of this work are to use a life cycle assessment approach to evaluate the environmental impacts associated with the HTC of food wastes and the subsequent combustion of the generated solid product (hydrochar) for energy production, and to understand how parameters and/or components associated with food waste carbonization and subsequent hydrochar combustion influence system environmental impact. Results from this analysis indicate that HTC process water emissions and hydrochar combustion most significantly influence system environmental impact, with a net negative GWP impact resulting for all evaluated substituted energy-sources except biomass. These results illustrate the importance of electricity production from hydrochar particularly when it is used to offset coal-based energy sources. HTC process water emissions result in a net impact to the environment, indicating a need for developing appropriate management strategies. Results from this analysis also highlight a need for additional exploration of liquid and gas-phase composition, a better understanding of how changes in carbonization conditions (e.g., reaction time and temperature) influence metal and nutrient fate, and the exploration of liquid-phase treatment.