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Co-firing of biomass and coal may increase short-term renewable fuel usage. However, the lower heating value and higher reactivity (at lower temperatures) of raw biomass can result in fuel segregation in boilers, causing burnout at lower temperatures, lower steam generation efficiency and fouling. In addition, the relatively high water content of some biomasses requires extensive drying prior to combustion. These issues may be addressed by hydrothermally carbonizing moist biomasses to produce hydrochars that more closely resemble coal’s properties prior to co-firing. In the present work, we probe the co-oxidation behavior of a series of hydrothermally carbonized biomass samples over a range of hydrochar-coal blend ratios to determine the degree of carbonization necessary to reduce fuel segregation. However, due to the presence of an extractable amorphous secondary char, even highly carbonized hydrochars have considerably higher oxidative reactivity than a representative bituminous coal sample. When blended, the hydrochars and coal display distinct derivative thermogravimetric oxidation ranges, in which a low-temperature peak is dominated by the secondary char oxidation, followed by a high-temperature char oxidation peak of the primary solid hydrochar. After extraction of the secondary char, the primary char displays a lower reactivity than the coal. As a co-fired fuel, it appears that blending hydrochars up to 10 wt% with a bituminous coal is possible as a partial fuel substitution. To increase the percentage of hydrochars blended with coal, it may be necessary to extract this secondary char (which contains valuable biofuels and platform chemicals) before blending.

Opuntia ficus-indica cladodes are a potential source of solid biofuel from marginal, dry land. Experiments assessed the effects of temperature (180-250°C), reaction time (0.5-3h) and biomass to water ratio (B/W; 0.07-0.30) on chars produced via hydrothermal carbonization. Multivariate linear regression demonstrated that the three process parameters are critically important to hydrochar solid yield, while B/W drives energy yield. Heating value increased together with temperature and reaction time and was maximized at intermediate B/W (0.14-0.20). Microscopy shows evidence of secondary char formed at higher temperatures and B/W ratios. X-ray diffraction, thermogravimetric data, microscopy and inductively coupled plasma mass spectrometry suggest that calcium oxalate in the raw biomass remains in the hydrochar; at higher temperatures, the mineral decomposes into CO2 and may catalyze char/tar decomposition.

Hydrothermal carbonisation was used to upgrade fuels from two types of agro-industrial wastes: olive tree trimmings and olive pulp. Hydrochar yield, elemental and proximate analyses, thermal stability, higher heating value (HHV), and energy yield at different reaction temperatures (120, 150, 180, 200, 220, 235 and 250 °C) and solid load (biomass to water ratios − B/W − equal to 7, 10, 15 and 25%) were assessed for a fixed reaction time of 30 min. HHV varied linearly with hydrochar mass yield and reaction temperature in the temperature range 180–250 °C. Solid load proved to be a crucial parameter in determining the energy properties of hydrochars. The higher B/W, the higher were the degree of carbonisation (in terms of fixed and total carbon), the hydrochar HHV, and the hydrochar yield. Elemental analysis showed that during HTC, olive pulp samples underwent a greater degree of carbonisation when compared to the corresponding olive tree trimmings residues. High solid load and high reaction temperature promoted secondary char formation. Secondary char showed a sphere-like structure formed by overlapping layers. EDS microanalysis showed that secondary char is characterised by a significantly higher carbon content than parent primary char, thus confirming its contribution towards enhancing the HHV of hydrochars.

Olive trimmings (OT) were used as feedstock for an in-depth experimental study on the reaction kinetics controlling hydrothermal carbonization (HTC). OT were hydrothermally carbonized for a residence time τ of up to 8 h at temperatures between 180 and 250 °C to systematically investigate the chemical and energy properties changes of hydrochars during HTC. Additional experiments at 120 and 150 °C at τ = 0 h were carried out to analyze the heat-up transient phase required to reach the HTC set-point temperature. Furthermore, an original HTC reaction kinetics model was developed. The HTC reaction pathway was described through a lumped model, in which biomass is converted into solid (distinguished between primary and secondary char), liquid, and gaseous products. The kinetics model, written in MATLABTM, was used in best fitting routines with HTC experimental data obtained using OT and two other agro-wastes previously tested: grape marc and Opuntia Ficus Indica. The HTC kinetics model effectively predicts carbon distribution among HTC products versus time with the thermal transient phase included; it represents an effective tool for R&D in the HTC field. Importantly, both modeling and experimental data suggest that already during the heat-up phase, biomass greatly carbonizes, in particular at the highest temperature tested of 250 °C.

Hydrothermal carbonization (HTC) and pyrolysis are two promising thermochemical conversion strategies to valorize agricultural wastes, yet neither process can be implemented alone to sustainably upgrade both wet and dry feedstocks. HTC is ideal for wet feedstocks, such as manure, but its solid hydrochars suffer from low surface area and stability. Pyrolysis is well suited to dry agricultural residues, but pyrolysis biochars have low nutrient contents and bio-oils are often highly oxygenated. We propose an integrated process that co-pyrolyzes a nutrient-rich cow manure hydrochar with raw agricultural residues, which effectively reduces the environmental impact of these wastes while producing value-added bioproducts. Biochars produced from the proposed process are more suitable for soil amendments due to their enhancement in bioavailable nutrients and surface area than the manure hydrochars and raw biomass. Co-pyrolysis of blends enriched with cow manure yield oils higher in alkanes and alkenes with fewer oxygenated compounds.

Research around hydrothermal carbonization (HTC) has seen a huge development in recent years, materializing in the first pilot and industrial plants. Even though HTC reactions are slightly exothermic, the overall process entails energy consumption to both reach operating conditions and tackle heat losses. To face this issue and to develop a zero-energy process, this work proposes an innovative solution: the coupling of an HTC reactor with a solar concentrator, designed to fully cover the HTC energy needs. A 300 ml stainless steel HTC reactor was constructed and positioned on the focus of a parabolic dish concentrator (PDC), consisting of one parabolic mirror of 0.8 m2. To maximize the light absorption, the illuminated side of the HTC reactor was coated with a thin layer of nanostructured copper oxide, realized via electron beam deposition. Then, the effectiveness of the hybrid solar-HTC solution was demonstrated by carrying out an experimental campaign on a residual agro-biomass (grape seeds), which was treated at 180, 220, and 250 °C for 2 h. The coating confers excellent absorbing performances to the system, exhibiting an absorptance of up to 95.6% (at 300 nm wavelength). Heating times, yields, composition, and energy properties of “solar hydrochars” resemble those of studies performed in traditional HTC systems. This research work proves the feasibility of the solar-HTC prototype apparatus and opens the way to the development of a zero-energy solar-HTC technology.

An olive waste stream mixture, coming from a three phase-continuous centrifugation olive oil mill industry, with a typical wet basis mass composition of olive pulp 39 wt%, kernels 5 wt% and olive mill waste water 56 wt%, was subjected to hydrothermal carbonisation (HTC) at 180, 220 and 250 °C for a 3-hour residence time in a 2-litre stainless steel electrically heated batch reactor. The raw feedstock and corresponding hydrochars were characterised in terms of proximate and ultimate analyses, higher heating values and energy properties. Results showed an increase in carbonisation of samples with increasing HTC severity and an energy densification ratio up to 142% (at 250 °C). Hydrochar obtained at 250 °C was successfully pelletised using a lab scale pelletiser without binders or expensive drying procedures. Energy characterisation (HHV, TGA), ATR-FTIR analysis, fouling index evaluation and pelletisation results suggested that olive mill waste hydrochars could be used as energy dense and mechanical stable bio-fuels. Characterisation of HTC residues in terms of mineral content via induced coupled plasma optical emission spectroscopy (ICP-OES) as well as Total and Dissolved Organic Carbon enabled to evaluate their potential use as soil improvers. Nutrients and polyphenolic compounds in HTC liquid fractions were evaluated for the estimation of their potential use as liquid fertilisers. Results showed that HTC could represent a viable route for the valorisation of olive mill industry waste streams.

Supercritical water gasification (SCWG) of biomass was studied by means of a stoichiometric thermodynamic model. Such approach is based on reaction equilibria and it allows calculating the extent of the single reactions involved. A very simple model was proposed, involving only 6 components and 3 independent reactions. The model was validated against literature experimental data for different feedstock and it was used to understand the influence of biomass and operating conditions. The analyses allowed calculating the values of the reaction extent of water-gas shift (WGS) and CO methanation at equilibrium: a graphical approach was proposed in order to interpret the outcomes. Results showed that the influence of pressure is very limited. Moreover, it was observed that the maximum H 2 production is linked to a parameter ψ , function of the H/C and O/C ratios of the feedstock. Finally, considerations about the role of WGS and methanation in the production of H 2 were traced.

Supercritical water gasification (SCWG) is an interesting technology for the production of energy from wet and residual biomass. To date, the complete understanding of the fundamental phenomena involved in SCWG is still an open issue. An interesting aspect to be investigated is represented by the interactions among the single constituents of biomass, such as cellulose and lignin. This can be accomplished by using glucose and phenol as model compounds. In the present study, four glucose/phenol mixtures were utilized. All mixtures presented a constant organics mass fraction of 5%, where the relative fraction of phenol ranged from 0% (pure glucose) to 30%. The mixtures were gasified at 400 °C and 25.0 MPa in a continuous tubular reactor, with a residence time between 10 and 240 s. Results showed that, at the considered reaction conditions, phenol mostly behaves as a sort of inert in terms of total gas production, although it plays an inhibitory action towards H 2 . The analysis of the liquid phase revealed that phenol likely inhibits Cannizzaro and de-carbonylation reactions and it advantages the pathways involving de-hydration reactions.

Supercritical water gasification (SCWG) is an emerging technology for the valorization of (wet) biomass into a valuable fuel gas composed of hydrogen and/or methane. The harsh temperature and pressure conditions involved in SCWG (T > 375 °C, p > 22 MPa) are definitely a challenge for the manufacturing of the reactors. Metal surfaces are indeed subject to corrosion under hydrothermal conditions, and expensive special alloys are needed to overcome such drawbacks. A ceramic reactor could be a potential solution to this issue. Finding a suitable material is, however, complex because the catalytic effect of the material can influence the gas yield and composition. In this work, a research reactor featuring an internal alumina inlay was utilized to conduct long-time (16 h) batch tests with real biomasses and model compounds. The same experiments were also conducted in batch reactors made of stainless steel and Inconel 625. The results show that the three devices have similar performance patterns in terms of gas production, although in the ceramic reactor higher yields of C2+ hydrocarbons were obtained. The SEM observation of the reacted alumina surface revealed a good resistance of such material to supercritical conditions, even though some intergranular corrosion was observed. View Full-Text

Hydrochar is the product of the hydrothermal carbonization process, which is able to convert biomass into a carbon-rich material at mild hydrothermal conditions. This article is aimed at exploring a novel possibility, that is converting hydrochar into a valuable fuel gas by means of another hydrothermal technology: supercritical water gasification (SCWG), which operates at higher temperatures and pressures. Tests were performed in 5 ml micro-autoclaves with a hydrochar concentration of 15 wt.%. Residence times between 1 h and 16 h were adopted. The results showed that hydrochar derived from maize silage can still be gasified, producing a gas rich in CO2 and CH4. The data here obtained were also compared with literature data concerning the SCWG of glucose and beech sawdust, highlighting the main differences in terms of solid, liquid and gaseous yields. The solid material obtained after SCWG was observed by means of scanning electron microscopy after different residence times, highlighting the formation of coke spheres. Finally, the effect of the addition of an alkali catalyst (K2CO3) was tested and discussed.

Batch reactors made of stainless steel and Inconel® 625 were used for the hydrothermal gasification of glucose and beech sawdust under both subcritical (350 °C) and supercritical (400 °C) conditions at a pressure of 30 MPa. These tests were executed over residence times ranging from 60 to 300 min. The amounts of solid, liquid and gas produced and the composition of the resulting gas phase were measured. The results showed that a higher H 2 output was achieved in the stainless steel reactors, while the Inconel® 625 reactors were more effective for the synthesis of CH 4 and light hydrocarbons. A visual observation of the metal surfaces was performed using scanning electron microscopy to explain the persistence of catalytic activity even after an aging treatment and many hours of operation.

The supercritical water gasification (SCWG) of biomass for H2 production is analyzed in terms of process development and energetic self-sustainability. The conceptual design of a plant is proposed and the SCWG process involving several substrates (glycerol, microalgae, sewage sludge, grape marc, phenol) is simulated by means of AspenPlus™. The influence of various parameters – biomass concentration and typology, reaction pressure and temperature – is analyzed. The process accounts for the possibility of exploiting the mechanical energy of compressed syngas (later burned to sustain the SCWG reaction) through expansion in turbines, while purified H2 is fed to fuel cells. Results show that the SCWG reaction can be energetically self-sustained if minimum feed biomass concentrations of 15–25% are adopted. Interestingly, the H2 yields are found to be maximal at similar feed concentrations. Finally, an energy balance is performed showing that the whole process could provide a net power of about 150 kWe/(1000 kgfeed/h).

Thermo-gravimetric analysis (TGA) was performed on grape seeds, skins, stalks, marc, vine-branches, grape seed oil and grape seeds depleted of their oil. The TGA data was modeled through Gaussian, logistic and Miura–Maki distributed activation energy models (DAEMs) and a simpler two-parameter model. All DAEMs allowed an accurate prediction of the TGA data; however, the Miura–Maki model could not account for the complete range of conversion for some substrates, while the Gaussian and logistic DAEMs suffered from the interrelation between the pre-exponential factor k0 and the mean activation energy E0 – an obstacle that can be overcome by fixing the value of k0 a priori. The results confirmed the capabilities of DAEMs but also highlighted some drawbacks in their application to certain thermodegradation experimental data.

In the present work, the supercritical water gasification (SCWG) of biomass is analyzed with a view to outlining the possible thermodynamic constraints that must be taken into account to develop this new process. In particular, issues concerning the formation of solid carbon and the process heat duty are discussed. The analysis is conducted by means of a two-phase non-stoichiometric thermodynamic model, based on Gibbs free energy minimization. Results show that char formation at equilibrium only occurs at high biomass concentrations, with a strong dependence on biomass composition. As regards the process heat duty, SCWG is mostly endothermic when biomass concentration is low, although a very small amount of oxidizing agent is able to make the process exothermic, with only a small loss in the heating value of the syngas produced.

The winery industry produces every year in the world about 270 millions of hectolitres of wine. A consequent amount of grape marc is then generated that has to be somehow treated and processed. For this reason a technique to treat grape marc (bio-drying) was studied and applied at the University of Trento. Grape marc, as is, is not suitable for direct combustion because of its high water content. By bio-drying the lower heating value has been increased up to the limit for a good combustion. This result allows a decentralized management of a grape marc drying differently from the conventional solutions.

In this paper, a hydrothermal carbonization (HTC) process is designed and modeled on the basis of experimental data previously obtained for two representative organic waste materials: off-specification compost and grape marc. The process accounts for all the steps and equipment necessary to convert raw moist biomass into dry and pelletized hydrochar. By means of mass and thermal balances and based on common equations specific to the various equipment, thermal energy and power consumption were calculated at variable process conditions: HTC reactor temperature T: 180, 220, 250 °C; reaction time θ: 1, 3, 8 h. When operating the HTC plant with grape marc (65% moisture content) at optimized process conditions (T = 220 °C; θ = 1 h; dry biomass to water ratio = 0.19), thermal energy and power consumption were equal to 1170 kWh and 160 kWh per ton of hydrochar produced, respectively. Correspondingly, plant efficiency was 78%. In addition, the techno-economical aspects of the HTC process were analyzed in detail, considering both investment and production costs. The production cost of pelletized hydrochar and its break-even point were determined to be 157 €/ton and 200 €/ton, respectively. Such values make the use of hydrochar as a CO2 neutral biofuel attractive.

Thermodynamic equilibrium modeling is important in order to understand which are the expected yields and the energy needs of the supercritical water gasification (SCWG) process. A thermodynamic equilibrium model allows calculating which is the system composition at equilibrium. Equilibrium composition can allow calculating, with good approximation, the overall process yields, especially when high temperatures and/or catalysts are used. In this Chapter, the current state of the art in the field of thermodynamic equilibrium modeling of SCWG is reviewed. The most common modeling approaches are presented, highlighting their advantages and disadvantages. Then, the practical implementation of a non-stoichiometric thermodynamic equilibrium model, based on Gibbs energy minimization, is performed. Finally, it is shown how thermodynamic modeling can be used to build a process model for SCWG, which is a fundamental tool to evaluate the process energy sustainability and its practical feasibility.

In the present work an equilibrium model (gas-solid), based on the minimization of the Gibbs energy, has been used in order to estimate the theoretical yield and the equilibrium composition of the reaction products (syngas and char) of biomass thermochemical conversion processes (pyrolysis and gasification). The data obtained from this model have also been used to calculate the heating value of the fuel gas, in order to evaluate the overall energy efficiency of the thermal conversion stage. The proposed model has been applied both to partial oxidation and steam gasification processes with varying air to biomass (ER) and steam to carbon (SC) ratio values and using different feedstocks; the obtained results have been compared with experimental data and with other model predictions obtaining a satisfactory agreement.

The growing importance of bio-based products, combined with the desire to decrease the production of wastes, boosts the necessity to use wastes as raw materials for bio-based products. A waste material with a large potential is spent sugar beets, which are mainly used as animal feeds or fertilizers. After hydrothermal treatment, the produced chars exhibited an H/C ratio of 1.2 and a higher heating value of 22.7 MJ/kg, which were similar to that of subbituminous coal and higher than that of lignite. Moreover, the treatment of 25 g/L of glucose and 22 g/L of fructose by heating up to 160 &deg, C led to a possible application of spent sugar beets for the production of 5-hydroxymethylfurfural. In the present study, the maximum concentration of 5-hydroxymethylfurfural was 3.4 g/L after heating up to 200 &deg, C.