Holistic biorefinery approach for biogas and hydrogen production: Integration of anaerobic digestion with hydrothermal carbonization and steam gasification.

Recently, the integration of biochemical and thermochemical processes is recognized as a promising strategy for the valorization of lignocellulosic biomass into renewable energy production. In this study, different routes for the valorization of hemp hurd for biohydrogen and biomethane production were proposed, including anaerobic digestion (AD), hydrothermal carbonization, and steam gasification. AD results revealed that NaOH pre-treatment of hemp hurd improved biomethane production yield by 164%. Comparing hydrochars from raw hemp, digestate derived hydrochars had higher mass yield due to changes in composition during AD as well as high ash content of digestates. It was found that high ash content of digestates originated from inorganic compounds in inoculum that accumulated over hemp hurd during anaerobic digestion process. Among feedstocks (hydrochars and raw hemp hurd), hemp hurd derived hydrochar at 200 °C showed the best performance in terms of H2 yield (1278 mL/g) whereas carbon efficiency reached % 92 in case of digestate derived hydrochar at 200 °C. HTC improved the steam gasification performance of hemp hurd whereas hydrochars from NaOH pretreated digestate yielded lowest hydrogen production due to the high content of inorganics, particularly phosphorus (P) and aluminum (Al). According to BMP test, spent liquor obtained at the lowest HTC temperature (200 °C) exhibited the highest BMP, reaching 213 mL CH4/g COD. Considering the overall gas products of four different routes, it is concluded that HTC as a post-treatment exhibits slightly better performance than HTC as pre-treatment. Although alkali pretreatment enhanced the anaerobic digestion performance, the resulting hydrochars exhibited low gasification activity.

NO and SO2 emissions from combustion of raw and torrefied biomasses and their blends with lignite.

The impact of torrefaction on the NO and SO2 emissions from combustion of biomass was investigated. Combustion experiments were carried out with two torrefied biomass fuels, i.e., poultry litter and olive tree pruning and their blends with lignite using a bench scale single particle reactor. For comparison, NO and SO2 emissions from tests with untorrefied biomasses and their blends with lignite were also investigated. The total release of SO2 and NO for each fuel was determined at three different temperatures: 900, 1000, and 1100 °C. The NO release from the untorrefied biomasses was found to be lower than those from torrefied biomasses, despite their higher fuel- N content. In case of co-combustion of both raw and torrefied biomass with lignite, the NO release was lower than the anticipated one. On the other hand, in the co-combustion experiments, blends with torrefied biomass showed a larger reduction in SO2 release than the blends with raw biomass. The study revealed that the SO2 emissions from blends are not proportional to the mixing ratio of the fuels and to the emissions properties of the respective fuels. No clear correlation was detected between the NOx emissions and fuel-N content. In addition to the NO and SO2 emissions, the sintering propensity of the ash residue were investigated using scanning electron microscopy (SEM).

Evaluation of Poultry Manure: Combination of Phosphorus Recovery and Activated Carbon Production.

Intensive growth of poultry production leads to generation of a large-scale accumulation of wastes, which is a critical concern for poultry farming. An environmentally friendly and effective solution is still being sought for sustainable management of poultry manure. In this study, evaluation of poultry manure both as a carbon source for production of solid fuels and activated carbon and as a phosphorus source has been investigated. The study focuses on the following: (1) biochar and hydrochar production under different process conditions for production of carbon-rich fuel from poultry manure; (2) phosphorus recovery by acid leaching-alkali precipitation from manure ash, biochar, and hydrochar; and (3) activated carbon production from acid-leached hydrochar and biochar. The results reveal that production of biochar and hydrochar is not a promising method for upgrading laying hen manure into an energy-dense solid fuel. Phosphorus in ash and chars was recovered as amorphous calcium phosphate with yields of 57.3-48.5% by acid leaching-alkali precipitation. Untreated and acid-leached chars were subjected to a chemical activation process with KOH and ZnCl2 to produce activated carbon. Due to the catalytic effect of inorganics in chars, the KOH activation resulted in a very low yield of activated carbon. The surface areas of activated carbons prepared using ZnCl2 were comparable to activated carbons derived from typical biomass using ZnCl2.

Plasma-Catalytic Reforming of Naphthalene and Toluene as Biomass Tar over Honeycomb Catalysts in a Gliding Arc Reactor.

Biomass gasification is a promising and sustainable process to produce renewable and CO2-neutral syngas (H2 and CO). However, the contamination of syngas with tar is one of the major challenges to limit the deployment of biomass gasification on a commercial scale. Here, we propose a hybrid plasma-catalytic system for steam reforming of tar compounds over honeycomb-based catalysts in a gliding arc discharge (GAD) reactor. The reaction performances were evaluated using the blank substrate and coated catalytic materials (γ-Al2O3 and Ni/γ-Al2O3). Compared with the plasma alone process, introducing the honeycomb materials in GAD prolonged the residence time of reactant molecules for collision with plasma reactive species to promote their conversions. The presence of Ni/γ-Al2O3 gave the best performance with the high conversion of toluene (86.3%) and naphthalene (75.5%) and yield of H2 (35.0%) and CO (49.1%), while greatly inhibiting the formation of byproducts. The corresponding highest overall energy efficiency of 50.9 g/kWh was achieved, which was 35.4% higher than that in the plasma alone process. Characterization of the used catalyst and long-term running indicated that the honeycomb material coated with Ni/γ-Al2O3 had strong carbon resistance and excellent stability. The superior catalytic performance of Ni/γ-Al2O3 can be mainly ascribed to the large specific surface area and the in situ reduction of nickel oxide species in the reaction process, which promoted the interaction between plasma reactive species and catalysts and generated the plasma-catalysis synergy.

Assessing the Importance of Pyrolysis Process Conditions and Feedstock Type on the Combustion Performance of Agricultural-Residue-Derived Chars.

The combustion performance of chars derived from vine shoots, wheat straw, and corn stover was investigated to assess the influence of both the biomass precursor and pyrolysis operating conditions. Chars were produced through slow pyrolysis at different peak temperatures (350 and 500 °C), pressures (0.1 and 0.5 MPa), and residence times of the vapor phase (50 and 150 s). From the thermogravimetric curves obtained under air, the combustion performance index (S) was calculated for each char. Apparent kinetics were also estimated using the Coats-Redfern method and assuming an F3/2 reaction model. Results show that the combustion patterns of chars were more influenced by the type of feedstock than by the pyrolysis conditions. Corn stover appeared to be the most interesting feedstock in order to produce chars with tuned reactivity. Results from partial least-squares (PLS) regression revealed that the most important factors affecting S were the contents of potassium (negative effect) and cellulose (positive effect) in the original biomass.

Sandpaper Wastes as Adsorbent for the Removal of Brilliant Green and Malachite Green Dye.

Sandpaper wastes were used as adsorbent after pyrolysis at 500 °C and calcination at 800 °C for the removal of brilliant green and malachite green cationic dye from an aqueous solution. The effects of the pH, the adsorbent dose, the contact time, and the initial dye concentration on the removal efficiencies were investigated. The isotherm studies were conducted by using the Langmuir, Freundlich, and Dubinin-Radushkevich models, and thermodynamic studies were also performed. The adsorption of the Brilliant green and malachite green were found to comply with the Langmuir isotherm model and the Freundlich isotherm model, respectively. The thermodynamic studies showed that the adsorption of dyes were endothermic. The E values obtained from the Dubinin-Radushkevich isotherm showed that the adsorption mechanism was chemical in nature. Furthermore, the three kinetic models (pseudo first-order, pseudo second-order, and intraparticle diffusion) were investigated. It was found that the pseudo second-order kinetic model fitted well for adsorption of dyes.

Sustainable valorization of food wastes into solid fuel by hydrothermal carbonization.

The aim of this study was to comparatively evaluate the effect of hydrothermal carbonization (HTC) conditions on the yield and the fuel properties of hydrochar obtained from food waste (FW) and its digestate (FD). The mass yield of hydrochars from FW and FD were found between 47.0 and 69.8%, 43.0 and 58.2%, respectively, under tested conditions. Based on both mass and energy yields, optimum temperature and duration were selected as 200 °C and 60 min for FW and 200 °C and 30 min for FD. FW and FD hydrochars produced optimum conditions had similar properties to lignite. The selected hydrochars were also subjected to steam gasification and combustion experiments. The combustion reactivity of hydrochars was found to be higher than that of lignite. Steam gasification produced 57-59 mol H2/kg hydrochar. The overall results emphasize the potential of H2 production by integrated systems of dark fermentation, HTC and steam gasification, besides production of solid fuel.

Influences of feedstock type and process variables on hydrochar properties.

In this study, the effect of process variables, such as temperature, biomass:water ratio and reaction time, in hydrothermal carbonization (HTC) has been studied for different type biomasses. Response surface methodology was used to study the influence of each factors as well as their combined interactive effect on the mass yield and energy density of hydrochars. The results showed that the temperature and time were significant factors effecting the mass yield and energy densification ratio in HTC of the sunflower stalk and algae, whereas temperature was only significant factor in HTC of poultry litter. The biomass:water ratio was found insignificant for all tested biomasses. In addition, the fuel properties of hydrochars were compared with the properties of biochar derived from torrefaction at 300 °C. The results showed that for all tested biomass, the biochars had lower volatile matter and fixed carbon than hydrochars.

Characteristics and synergistic effects of co-combustion of carbonaceous wastes with coal.

This study presents combustion behavior and emission results obtained for different fuels: poultry litter (PL) and its char (PLC), scrap tires (ST) and its char (STC) and blends of char/lignite (PLC/LIG and STC/LIG). The combustion parameters and emissions were investigated via a non-isothermal thermogravimetric method and experiments in a lab-scale reactor. Fuel indexes were used for the prediction of high temperature corrosion risks and slagging potentials of the fuels used. The addition of chars to lignite caused a lowering of the combustion reactivity (anti-synergistic effect). There was a linear correlation between the NOx emissions and the N content of the fuel. The form of S and the concentrations of alkali metals in the fuel had a strong effect on the extent of SO2 emissions. The use of PL and PLC in blends reduced SO2 emissions and sulphur compounds in the fly ash. The 2S/Cl ratio in the fuel showed that only PLC and STC/PLC would show a risk of corrosion during combustion. The ratio of basic to acidic oxides in fuel indicated that ST, STC and STC/LIG have low slagging potential. The molar (Si+P+K)/(Ca+Mg) ratio, which was used for PL, PLC and PLC containing blends, showed that the ash melting temperatures of these fuels would be higher than 1000 °C.

Effects of spent liquor recirculation in hydrothermal carbonization.

In this study, the effect of the recirculation of spent liquor from hydrothermal carbonization was investigated depending on the biomass type (grape pomace, orange pomace and poultry litter). The yield and fuel properties of hydrochars and spent liquor characteristics were determined for each recirculation step. By recirculation, mass and energy yields of the hydrochar increased, but their combustion characteristics changed: the ignition temperature and combustion reactivity decreased. The organic and inorganic load of liquor was increased with recirculation number, but not as much as would be expected after the first recycle. It was concluded that the load of organic and inorganic species in spent liquor decreased the leaching of some inorganics and diffusion of the degraded soluble fragments from biomass in the subsequent hydrothermal carbonization. Overall, this study showed that spent liquor recirculation makes the overall hydrothermal carbonization process environmentally friendly.

Conversion of poultry wastes into energy feedstocks.

In this study, conversion of wastes from poultry farming and industry into biochar and bio-oil via thermochemical processes was investigated. Fuel characteristics and chemical structure of biochars and bio-oils have been investigated using standard fuel analysis and spectroscopic methods. Biochars were produced from poultry litter through both hydrothermal carbonization (sub-critical water, 175-250°C) and pyrolysis over a temperature range between 250 and 500°C. In comparison to hydrothermal carbonization, pyrolysis at lower temperatures produced biochar with greater energy yield due to the higher mass yield. Biochars obtained by both processes were comparable to coal. Hydrothermal liquefaction of poultry meal at different temperatures (200-325°C) was conducted and compared to optimize its process conditions. Higher temperatures favored the formation of bio-crude oil, with a maximum yield of 35wt.% at 300°C. The higher heating values of bio-oils showed that bio-oil could be a potential source of synthetic fuels. However, elemental analysis demonstrated the high nitrogen content of bio-oils. Therefore, bio-oils obtained from hydrothermal liquefaction of poultry meal should be upgraded for utilization as a transport and heating fuel.

Combustion behavior of different kinds of torrefied biomass and their blends with lignite.

In this study, the combustion behavior of different kinds of torrefied biomass (lignocellulosic and animal wastes) and their blends with lignite was investigated via non-isothermal thermogravimetric method under air atmosphere. For comparison, combustion characteristics of raw biomasses were also determined. Torrefaction process improved the reactivity of char combustion step of biomasses. Characteristic combustion parameters for blends showed non-additivity behavior. It was found that the mixture of torrefied biomasses and lignite at a ratio of 1:1 had a lower ignition and burnout temperature than the coal-only sample. Although no interactions were observed between the lignite and torrefied biomass at initial step of combustion, a certain degree of interaction between the components occurred at char combustion step. Kinetic parameters of combustion were calculated by using the Coats Redfern model. Overall, this study showed that poultry litters can be used as a substitute fuel in coal/biomass co-firing systems by blending with lignocellulosic biomass.

Characterization of products from hydrothermal carbonization of orange pomace including anaerobic digestibility of process liquor.

In this study, the effect of the temperature and reaction time on hydrothermal carbonization (HTC) of orange pomace was investigated. In addition, a set of anaerobic batch tests were performed to determine the resulting biogas and methane potential of the spent liquor. Hydrochar yields followed a decreasing trend with the increasing temperature, whereas reaction time had no considerably effect on the yield. The evolution of the H/C and O/C atomic ratios from the raw material to the hydrochars suggested that dehydration reactions prevail during HTC. The hydrochars tended to become enriched in Ca, Mg and P minerals by increasing HTC temperature. The heavy metal contents in hydrochars were found below limits and no PAH compound was detected. Anaerobic digestion tests showed that the aqueous phase from HTC can be used as feedstocks for biogas production.

Hydrogen production from algal biomass via steam gasification.

Algal biomasses were tested as feedstock for steam gasification in a dual-bed microreactor in a two-stage process. Gasification experiments were carried out in absence and presence of catalyst. The catalysts used were 10% Fe2O3-90% CeO2 and red mud (activated and natural forms). Effects of catalysts on tar formation and gasification efficiencies were comparatively investigated. It was observed that the characteristic of algae gasification was dependent on its components and the catalysts used. The main role of the catalyst was reforming of the tar derived from algae pyrolysis, besides enhancing water gas shift reaction. The tar reduction levels were in the range of 80-100% for seaweeds and of 53-70% for microalgae. Fe2O3-CeO2 was found to be the most effective catalyst. The maximum hydrogen yields obtained were 1036 cc/g algae for Fucus serratus, 937 cc/g algae for Laminaria digitata and 413 cc/g algae for Nannochloropsis oculata.

Hydrothermal carbonization and torrefaction of grape pomace: a comparative evaluation.

Grape pomace was treated by hydrothermal carbonization (sub-critical water, 175-275°C) and torrefaction (nitrogen atmosphere, 250 and 300°C), with mass yield of solid product (char) ranging between 47% and 78%, and energy densification ratio to 1.42-1.15 of the original feedstock. The chars were characterised with respect to their fuel properties, morphological and structural properties and combustion characteristics. The hydrothermal carbonization produced the char with greater energy density than torrefaction. The chars from torrefaction were found to be more aromatic in nature than that from hydrothermal carbonization. Hydrothermal carbonization process produced the char having high combustion reactivity. Most interesting was the finding that aqueous phase from hydrothermal carbonization had antioxidant activity. The results obtained in this study showed that HTC appears to be promising process for a winery waste having high moisture content.

The slow and fast pyrolysis of cherry seed.

The slow and fast pyrolysis of cherry seeds (CWS) and cherry seeds shells (CSS) was studied in fixed-bed and fluidized bed reactors at different pyrolysis temperatures. The effects of reactor type and temperature on the yields and composition of products were investigated. In the case of fast pyrolysis, the maximum bio-oil yield was found to be about 44 wt% at pyrolysis temperature of 500 °C for both CWS and CSS, whereas the bio yields were of 21 and 15 wt% obtained at 500 °C from slow pyrolysis of CWS and CSS, respectively. Both temperature and reactor type affected the composition of bio-oils. The results showed that bio-oils obtained from slow pyrolysis of CWS and CSS can be used as a fuel for combustion systems in industry and the bio-oil produced from fast pyrolysis can be evaluated as a chemical feedstock.

Activated carbon from leather shaving wastes and its application in removal of toxic materials.

In this study, utilization of a solid waste as raw material for activated carbon production was investigated. For this purpose, activated carbons were produced from chromium and vegetable tanned leather shaving wastes by physical and chemical activation methods. A detailed analysis of the surface properties of the activated carbons including acidity, total surface area, extent of microporosity and mesoporosity was presented. The activated carbon produced from vegetable tanned leather shaving waste produced has a higher surface area and micropore volume than the activated carbon produced from chromium tanned leather shaving waste. The potential application of activated carbons obtained from vegetable tanned shavings as adsorbent for removal of water pollutants have been checked for phenol, methylene blue, and Cr(VI). Adsorption capacities of activated carbons were found to be comparable to that of activated carbons derived from biomass.

Pyrolysis of the tetra pak.

This study deals with pyrolysis of tetra pak which is widely used as an aseptic beverage packaging material. Pyrolysis experiments were carried out under inert atmosphere in a batch reactor at different temperatures and by different pyrolysis modes (one- and two-step). The yields of char, liquid and gas were quantified. Pyrolysis liquids produced were collected as three separate phases; aqueous phase, tar and polyethylene wax. Characterization of wax and the determination of the total amount of phenols in aqueous phase were performed. Chemical compositions of gas and char products relevant to fuel applications were determined. Pure aluminum can be also recovered by pyrolysis.