Hydrothermal carbonization (HTC): Near infrared spectroscopy and partial least-squares regression for determination of selective components in HTC solid and liquid products derived from maize silage

Near-infrared (NIR) spectroscopy was evaluated as a rapid method of predicting fiber components (hemicellulose, cellulose, lignin, and ash) and selective compounds of hydrochar and corresponding process liquor produced by hydrothermal carbonization (HTC) of maize silage. Several HTC reaction times and temperatures were applied and NIR spectra of both HTC solids and liquids were obtained and correlated with concentration determined from van-Soest fiber analysis, IC, and UHPLC. Partial least-squares regression was applied to calculate models for the prediction of selective substances. The model developed with the spectra had the best performance in 3–7 factors with a correlation coefficient, which varied between 0.9275–0.9880 and 0.9364–0.9957 for compounds in solid and liquid, respectively. Calculated root mean square errors of prediction (RMSEP) were 0.42–5.06 mg/kg. The preliminary results indicate that NIR, a widely applied technique, might be applied to determine chemical compounds in HTC solid and liquid

Ash reduction of corn stover by mild hydrothermal preprocessing

Lignocellulosic biomass such as corn stover can contain high ash content, which may act as an inhibitor in downstream conversion processes. Most of the structural ash in biomass is located in the cross-linked structure of lignin, which is mildly reactive in basic solutions. Four organic acids (formic, oxalic, tartaric, and citric) were evaluated for effectiveness in ash reduction, with limited success. Because of sodium citrate’s chelating and basic characteristics, it is effective in ash removal. More than 75 % of structural and 85 % of whole ash was removed from the biomass by treatment with 0.1 g of sodium citrate per gram of biomass at 130 °C and 2.7 bar. FTIR, fiber analysis, and chemical analyses show that cellulose and hemicellulose were unaffected by the treatment. ICP–AES showed that all inorganics measured were reduced within the biomass feedstock, except sodium due to the addition of Na through the treatment. Sodium citrate addition to the preconversion process of corn stover is an effective way to reduced physiological ash content of the feedstock without negatively impacting carbohydrate and lignin content

Algal Remediation of Wastewater Produced from Hydrothermally Treated Septage

Hydrothermal carbonization (HTC) is a promising technology to convert wet wastes like septic tank wastes, or septage, to valuable platform chemical, fuels, and materials. However, the byproduct of HTC, process liquid, often contains large amount of nitrogen species (up to 2 g/L of nitrogen), phosphorus, and a variety of organic carbon containing compounds. Therefore, the HTC process liquid is not often treated at wastewater treatment plant. In this study, HTC process liquid was treated with algae as an alternative to commercial wastewater treatment. The HTC process liquid was first diluted and then used to grow Chlorella sp. over a short period of time (15 days). It was found that the algae biomass concentration increased by 644 mg/L over the course of 10 days, and which subsequently removed a majority of the nutrients in the HTC process liquid. Around 600 mg/L of algal biomass was collected in the process liquid at the end of treatment (day 15). Meanwhile, chemical oxygen demand (COD), total phosphorous, total Kheldjal nitrogen, and ammonia were reduced by 70.0, 77.7, 82.2, and 99.0% by fifteen days compared to the untreated wastewater, respectively. This study demonstrates that HTC process liquid can be treated by growing algae creating a potential replacement for expensive synthetic nutrient feeds for algal production

Hydrothermal Carbonization

Over the past decade, hydrothermal carbonization (HTC) has emerged as a promising thermochemical pathway for treating and converting wet wastes into fuel, materials, and chemicals [...

Carbon Capture from Biogas by Deep Eutectic Solvents: A COSMO Study to Evaluate the Effect of Impurities on Solubility and Selectivity

Deep eutectic solvents (DES) are compounds of a hydrogen bond donor (HBD) and a hydrogen bond acceptor (HBA) that contain a depressed melting point compared to their individual constituents. DES have been studied for their use as carbon capture media and biogas upgrading. However, contaminants’ presence in biogas might affect the carbon capture by DES. In this study, conductor-like screening model for real solvents (COSMO-RS) was used to determine the effect of temperature, pressure, and selective contaminants on five DES’ namely, choline chloride-urea, choline chloride-ethylene glycol, tetra butyl ammonium chloride-ethylene glycol, tetra butyl ammonium bromide-decanoic acid, and tetra octyl ammonium chloride-decanoic acid. Impurities studied in this paper are hydrogen sulfide, ammonia, water, nitrogen, octamethyltrisiloxane, and decamethylcyclopentasiloxane. At infinite dilution, CO2 solubility dependence upon temperature in each DES was examined by means of Henry’s Law constants. Next, the systems were modeled from infinite dilution to equilibrium using the modified Raoults’ Law, where CO2 solubility dependence upon pressure was examined. Finally, solubility of CO2 and CH4 in the various DES were explored with the presence of varying mole percent of selective contaminants. Among the parameters studied, it was found that the HBD of the solvent is the most determinant factor for the effectiveness of CO2 solubility. Other factors affecting the solubility are alkyl chain length of the HBA, the associated halogen, and the resulting polarity of the DES. It was also found that choline chloride-urea is the most selective to CO2, but has the lowest CO2 solubility, and is the most polar among other solvents. On the other hand, tetraoctylammonium chloride-decanoic acid is the least selective, has the highest maximum CO2 solubility, is the least polar, and is the least affected by its environment

Liquid-Liquid Equilibrium of Deep Eutectic Solvent-Aromatic-Aliphatic Ternary Systems: Experimental Study with COSMO Model Predictions

Common solvents used for aromatic extraction from aliphatics typically degrade into toxic compounds, while green alternatives perform poorly compared to the state-of-the-art solvents. Deep eutectic solvents (DES) are a novel solvent type made of hydrogen bond donors (HBD) and hydrogen bond acceptors (HBA). DES have been applied in various applications, including advanced separations. In this study, DES were studied experimentally and using the Conductor-like Screening Model (COSMO) to separate benzene from cyclohexane as model compounds for an aromatic:aliphatic system. Both equilibrium and kinetic studies were performed to determine the liquid liquid equilibrium (LLE) and mass transfer rate for the DES-based separation. Selected HBAs including tetrabutylammonium bromide (N4444Br), tetrahexylammonium bromide (N6666Br), choline chloride (ChCl), and methyltriphenylphosphonium bromide (METPB) were paired with HBDs including ethylene glycol (EG) and glycerol (Gly). COSMO was used, with adjustments to reflect DES specific interactions, to predict the liquid-liquid equilibrium (LLE). COSMO results showed that ChCl and N6666Br-based DES extracted too little benzene or too much cyclohexane, respectively, to be considered for experimental evaluation. Overall, the COSMO model predictions for LLE of EG-based DES were very accurate, with root-mean-square deviations (RMSD) below 1% for both N4444Br:EG and METPB:EG. The glycerol systems were less accurately modeled, with RMSD’s of 4% for N4444Br:Gly and 6% for METPB:Gly. The lower accuracy of glycerol system predictions fmay be due to limitations in COSMO for handling glycerol’s influence on polarizability in the DES that is not seen in EG-based DES. Mass transfer kinetics were determined experimentally for DES and the results were fit to a first order kinetics model. METPB:Gly had the highest mass transfer coefficient at 0.180 min−1, followed by N4444Br:EG at 0.143 min−1. N4444Br:Gly and METPB:EG had the lowest mass transfer coefficients at 0.096 min−1 and 0.084 min−1, respectively. It was found that mass transfer rate was not directly related to maximum benzene solubility, as N4444Br:EG and METPB:Gly had the highest and lowest benzene removal, respectively, but had similar mass transfer coefficients

Techno-Economic Assessment of Co-Hydrothermal Carbonization of a Coal-Miscanthus Blend

Co-Hydrothermal Carbonization (Co-HTC) is a thermochemical process, where coal and biomass were treated simultaneously in subcritical water, resulting in bulk-homogenous hydrochar that is carbon-rich and a hydrophobic solid fuel with combustion characteristics like coal. In this study, technoeconomic analysis of Co-HTC was performed for a scaled-up Co-HTC plant that produces fuel for 110 MWe coal-fired power plant using Clarion coal #4a and miscanthus as starting feedstocks. With precise mass and energy balance of the Co-HTC process, sizing of individual equipment was conducted based on various systems equations. Cost of electricity was calculated from estimated capital, manufacturing, and operating and maintenance costs. The breakeven selling price of Co-HTC hydrochar was $117 per ton for a 110 MWe. Sensitivity analysis indicates that this breakeven selling price could be as low as$106 per ton for a higher capacity plant. Besides plant size, the price of solid fuel is sensitive to the feedstock costs and hydrochar yield

Synopsis of Factors Affecting Hydrogen Storage in Biomass-Derived Activated Carbons

Hydrogen (H2) is largely regarded as a potential cost-efficient clean fuel primarily due to its beneficial properties, such as its high energy content and sustainability. With the rising demand for H2 in the past decades and its favorable characteristics as an energy carrier, the escalating USA consumption of pure H2 can be projected to reach 63 million tons by 2050. Despite the tremendous potential of H2 generation and its widespread application, transportation and storage of H2 have remained the major challenges of a sustainable H2 economy. Various efforts have been undertaken by storing H2 in activated carbons, metal organic frameworks (MOFs), covalent organic frameworks (COFs), etc. Recently, the literature has been stressing the need to develop biomass-based activated carbons as an effective H2 storage material, as these are inexpensive adsorbents with tunable chemical, mechanical, and morphological properties. This article reviews the current research trends and perspectives on the role of various properties of biomass-based activated carbons on its H2 uptake capacity. The critical aspects of the governing factors of H2 storage, namely, the surface morphology (specific surface area, pore volume, and pore size distribution), surface functionality (heteroatom and functional groups), physical condition of H2 storage (temperature and pressure), and thermodynamic properties (heat of adsorption and desorption), are discussed. A comprehensive survey of the literature showed that an “ideal” biomass-based activated carbon sorbent with a micropore size typically below 10 Å, micropore volume greater than 1.5 cm3/g, and high surface area of 4000 m2/g or more may help in substantial gravimetric H2 uptake of >10 wt% at cryogenic conditions (−196 °C), as smaller pores benefit by stronger physisorption due to the high heat of adsorption

Ion Selective Electrodes for Flue Gas Desulfurization Wastewater Monitoring: Effects of Ionic Strength on Selective Ions

Ion selective electrodes (ISE) were evaluated for use in a flue gas desulfurization (FGD) wastewater monitoring system. Calcium, chloride, nitrate, and nitrite ISE’s were calibrated in a broad range of concentrations that were designed to model an actual FGD wastewater sample that was obtained from an industrial partner. Ideal Nernst, Modified Nernst, and a multiparameter regression analysis was performed for each electrode and evaluated on general fit and sensitivity at anticipated operating conditions. The Ideal Nernst equation, even with correction for ionic strength, was not able to properly model actual electrode performance. The multiparameter regression was able to model the electrode performance with relative errors of 10–25% when ionic strengths were below 0.1 M. Through the evaluation of real-time sensor usage at real conditions, a methodology of washing and sampling rate is suggested to minimize error in the readings

Synopsis of Factors Affecting Hydrogen Storage in Biomass-Derived Activated Carbons

Hydrogen (H2) is largely regarded as a potential cost-efficient clean fuel primarily due to its beneficial properties, such as its high energy content and sustainability. With the rising demand for H2 in the past decades and its favorable characteristics as an energy carrier, the escalating USA consumption of pure H2 can be projected to reach 63 million tons by 2050. Despite the tremendous potential of H2 generation and its widespread application, transportation and storage of H2 have remained the major challenges of a sustainable H2 economy. Various efforts have been undertaken by storing H2 in activated carbons, metal organic frameworks (MOFs), covalent organic frameworks (COFs), etc. Recently, the literature has been stressing the need to develop biomass-based activated carbons as an effective H2 storage material, as these are inexpensive adsorbents with tunable chemical, mechanical, and morphological properties. This article reviews the current research trends and perspectives on the role of various properties of biomass-based activated carbons on its H2 uptake capacity. The critical aspects of the governing factors of H2 storage, namely, the surface morphology (specific surface area, pore volume, and pore size distribution), surface functionality (heteroatom and functional groups), physical condition of H2 storage (temperature and pressure), and thermodynamic properties (heat of adsorption and desorption), are discussed. A comprehensive survey of the literature showed that an “ideal” biomass-based activated carbon sorbent with a micropore size typically below 10 Å, micropore volume greater than 1.5 cm3/g, and high surface area of 4000 m2/g or more may help in substantial gravimetric H2 uptake of >10 wt% at cryogenic conditions (−196 °C), as smaller pores benefit by stronger physisorption due to the high heat of adsorption