Co-hydrothermal carbonization of pine residual sawdust and non-dewatered sewage sludge - effect of reaction conditions on hydrochar characteristics.

Waste valorization is mandatory to develop and consolidate a circular bioeconomy. It is necessary to search for appropriate processes to add value to different wastes by utilizing them as feedstocks to provide energy, chemicals, and materials. For instance, hydrothermal carbonization (HTC) is an alternative thermochemical process that has been suggested for waste valorization aiming at hydrochar production. Thus, this study proposed the Co-HTC of pine residual sawdust (PRS) with non-dewatered sewage sludge (SS) - two wastes largely produced in sawmills and wastewater treatment plants, respectively - without adding extra water. The influence of temperature (180, 215, and 250 °C), reaction time (1, 2, and 3 h), and PRS/SS mass ratio (1/30, 1/20, and 1/10) on the yield and characteristics of the hydrochar were evaluated. The hydrochars obtained at 250 °C had the best coalification degree, showing the highest fuel ratio, high heating value (HHV), surface area, and N, P, and K retention, although presenting the lowest yields. Conversely, hydrochar functional groups were generally reduced by increasing Co-HTC temperatures. Regarding the Co-HTC effluent, it presented acidic pH (3.66-4.39) and high COD values (6.2-17.3 g·L-1). In general, this new approach could be a promising alternative to conventional HTC, in which a high amount of extra water is required. Besides, the Co-HTC process can be an option for managing lignocellulosic wastes and sewage sludges while producing hydrochar. This carbonaceous material has the potential for several applications, and its production is a step towards a circular bioeconomy.

Innovative process for sulphur recovery from waste incineration flue gases: production of marketable sodium bisulphite solution.

This study presents an innovative process for recovering sulphur from hazardous waste incineration flue gases, designed to produce a marketable sodium bisulphite solution while ensuring complete SO2 removal. This new process is characterized by a double absorption strategy at two different pH levels. The first step, at an acidic pH, generates the desired bisulphite solution, while the second step, at a basic pH, produces the sulphite solution for recycling into the first step and ensures total SO2 removal. The process's performance and feasibility were evaluated on a laboratory scale using a batch reactor with synthetic gas. The parametric study focused on the initial sulphite concentration in the absorption solution and the reactor temperature. A removal efficiency exceeding 95% was achieved across all initial sulphite concentrations and temperature ranges, when the pH was maintained above 6. At pH 5, where bisulphites are the predominant sulphur species, the removal efficiency remained substantial at approximately 70%. The oxidation of sulphites/bisulphites by oxygen in the flue gases was minimal, with less than 5% conversion to sulphate. Additionally, pH-controlled experiments were conducted to optimize plant start-up procedures. For the basic reactor, starting with water and adjusting the pH to 8 during SO2 absorption effectively minimized sodium hydroxide consumption. In contrast, for the acidic reactor at pH 5, initiating the process with a concentrated sulphite solution resulted in more stable absorption rates. These findings underscore the process's potential for efficient sulphur recovery and highlight the importance of pH management in optimizing operational stability and chemical consumption.

Hydrochar from sawdust and sewage sludge - a potential media for retaining heavy metals in sustainable drainage systems (SuDS).

Waste valorization is an essential aspect of sustainable development. From this perspective, co-hydrothermal carbonization (Co-HTC) is a promising thermochemical process for converting organic waste into hydrochar. Hydrochar is a solid material whose physicochemical properties could make it suitable for adsorbing pollutants such as heavy metals. Accordingly, this work evaluated the hydrochar from Co-HTC of sawdust and non-dewatered sewage sludge as a potential adsorbent of heavy metals at low concentrations. In the context of sustainable drainage systems (SuDS), it is notable that heavy metals are present at very low but still potentially harmful concentrations, which presents a potential opportunity for the application of hydrochar. Thus, three hydrochars (H-180, H-215, and H-250), produced by Co-HTC at 180, 215, and 250 °C, were tested herein for their ability to retain lead (Pb2+). The H-180 presented better performance than other hydrochars (H-215 and H-250), suggesting that chemisorption could be the main adsorption mechanism. Interestingly, the presence of other cationic heavy metals (Cu2+, Zn2+, Cd2+, Cr6+, and Ni2+) did not hinder the Pb2+ adsorption, for which the removal efficiency remained close to 100%. In fact, in such a multi-metal system, hydrochar can be suitable for capturing both lead and cadmium. Therefore, the hydrochar from Co-HTC of sawdust and non-dewatered sewage sludge can be useful for removing heavy metals at low concentrations, such as those found in urban runoff waters. Although further studies are required, these findings suggest hydrochar as a potential material for application in SuDS.

A review on hydrothermal carbonization of potential biomass wastes, characterization and environmental applications of hydrochar, and biorefinery perspectives of the process.

It is imperative to search for appropriate processes to convert wastes into energy, chemicals, and materials to establish a circular bio-economy toward sustainable development. Concerning waste biomass valorization, hydrothermal carbonization (HTC) is a promising route given its advantages over other thermochemical processes. From that perspective, this article reviewed the HTC of potential biomass wastes, the characterization and environmental utilization of hydrochar, and the biorefinery potential of this process. Crop and forestry residues and sewage sludge are two categories of biomass wastes (lignocellulosic and non-lignocellulosic, respectively) readily available for HTC or even co-hydrothermal carbonization (Co-HTC). The temperature, reaction time, and solid-to-liquid ratio utilized in HTC/Co-HTC of those biomass wastes were reported to range from 140 to 370 °C, 0.05 to 48 h, and 1/47 to 1/1, respectively, providing hydrochar yields of up to 94 % according to the process conditions. Hydrochar characterization by different techniques to determine its physicochemical properties is crucial to defining the best applications for this material. In the environmental field, hydrochar might be suitable for removing pollutants from aqueous systems, ameliorating soils, adsorbing atmospheric pollutants, working as an energy carrier, and performing carbon sequestration. But this material could also be employed in other areas (e.g., catalysis). Regarding the effluent from HTC/Co-HTC, this byproduct has the potential for serving as feedstock in other processes, such as anaerobic digestion and microalgae cultivation. These opportunities have aroused the industry interest in HTC since 2010, and the number of industrial-scale HTC plants and patent document applications has increased. The hydrochar patents are concentrated in China (77.6 %), the United States (10.6 %), the Republic of Korea (3.5 %), and Germany (3.5 %). Therefore, considering the possibilities of converting their product (hydrochar) and byproduct (effluent) into energy, chemicals, and materials, HTC or Co-HTC could work as the first step of a biorefinery. And this approach would completely agree with circular bioeconomy principles.

Temperature phased anaerobic digestion (TPAD) of organic fraction of municipal solid waste (OFMSW) and digested sludge (DS): Effect of different hydrolysis conditions.

Hydrolysis is the most critical stage in high solids Temperature Phased Anaerobic Digestion (TPAD). In this paper two different Organic Fraction of Municipal Solid Waste (OFMSW) types were tested in co-digestion with Digested Sludge (DS) at different temperatures: 37, 55 and 65 °C. Volatile fatty acids (VFAs), soluble chemical oxygen demand (CODs) and Biochemical Methane Production (BMP) were measured and calculated after 0, 24, 48 and 72 h hydrolysis. The results showed that both the BMP and the methane production rate improved. A Solids Retention Time (SRT) of 72 h at a temperature of 55 °C gave the best results: the reaction rate constant k was 0.34 d-1 and the BMP was 250 mLCH4/gMV, which were 47% and 19% higher compared to the reference (0 h hydrolysis). The CODs and VFAs profiles during hydrolysis showed how OFMSW initial characteristics can affect the performance of temperature phased anaerobic digestion.

Sewage sludge ash-derived materials for H2S removal from a landfill biogas.

H2S removal is a key step for biogas cleaning because this component can lead to premature corrosion of the equipment and its cleaning has a significant cost. The aim of the present work was to assess the use of sewage sludge derived ash (SSA)-materials for H2S removal from a landfill biogas. SSA and mixtures made with SSA, activated carbon (AC) and sand were tested for H2S removal. The best removal efficiency was obtained with the mixture 80%m SSA and 20%m AC, while SSA alone was not a good adsorbent under tested experimental conditions. The materials characterization helped the adsorption mechanism understanding. Indeed, results highlighted that SSA presence stabilizes the pH on a basic range, favorable for H2S dissociation into HS- then its chemisorption. On the other hand, with the microporosity of AC, the contact surface between H2S and oxygen was sufficiently large for chemisorption kinetics. It also appeared that the mixture with sand and AC adorbs non selectively H2S but also other volatile organic pollutants present in biogas. Contrariwise, with SSA/AC mixtures, H2S seems to be selectively chemisorbed.

The effect of the origin of MSWI bottom ash on the H2S elimination from landfill biogas.

Municipal Solid Waste Incineration (MSWI) Bottom Ash (BA) is a potential alternative adsorbent for biogas treatment due to its reactivity with hydrogen sulfide (H2S). The quality of BA depends however on the nature of the waste and the process technology of the waste incineration facility. To determine whether the origin of the BA could have an influence on its H2S elimination efficiency, comparative experimental tests were conducted in a landfill site with six bottom ashes from different MSW incinerators. Results showed that one of the BAs (A) had a much higher adsorption capacity than the rest (B-F), with 37g H2S/kg dry BA, compared to 11-16g H2S/kg dry BA for the other bottom ashes. Detailed physico-chemical analyses of the six BA were performed and complemented by principal component analysis to understand the different behaviors. BA iron content and specific surface area provided by the quench product stood out as key factors that promote the elimination of H2S.

Valorization of MSWI bottom ash for biogas desulfurization: Influence of biogas water content.

In this study an alternative valorization of Municipal Solid Waste Incineration (MSWI) Bottom Ash (BA) for H2S elimination from landfill biogas was evaluated. Emphasis was given to the influence of water content in biogas on H2S removal efficiency by BA. A small-scale pilot was developed and implemented in a landfill site located in France. A new biogas analyzer was used and allowed real-time continuous measurement of CH4, CO2, O2, H2S and H2O in raw and treated biogas. The H2S removal efficiency of bottom ash was evaluated for different inlet biogas humidities: from 4 to 24gwater/m3. The biogas water content was found to greatly affect bottom ash efficiency regarding H2S removal. With humid inlet biogas the H2S removal was almost 3 times higher than with a dry inlet biogas. Best removal capacity obtained was 56gH2S/kgdryBA. A humid inlet biogas allows to conserve the bottom ash moisture content for a maximum H2S retention.

Liquid mixing and solid segregation in high-solid anaerobic digesters.

An experimental procedure (Residence Time Distribution technique) was used to characterize the macro-mixing of both liquid and solid phases of a laboratory-scale dry anaerobic digester using appropriate tracers. The effects of the waste origin and total solid content were studied. An increase in TS content from 22% to 30% TS (w/w) induced a macro-mixing mode closer to a theoretical Plug Flow Reactor. The segregation of particles having different densities was investigated regarding the RTD of the solid phase. Segregation of dense particles occurred at low TS content. By using different TS content and waste origins, it was also determined that the yield stress was a key parameter in the mechanism of segregation. At high yield stress, dense particles were more stable and thus less subjected to settling. As a consequence, operating at high TS content may permit to prevent the sedimentation of the denser particles.

Influence of substrate concentration and moisture content on the specific methanogenic activity of dry mesophilic municipal solid waste digestate spiked with propionate.

The objective of this study was to evaluate the influence of substrate concentration and moisture content on the specific methanogenic activity (SMA) of a fresh dry mesophilic digestate from a municipal solid waste digester plant. For this purpose, SMA tests were performed under mesophilic conditions into glass bottles of 500 mL volume used as batch reactors, during a period of 20-25 days. Propionate was used as substrate at concentrations ranging from 1 to 10 gCOD/kg. Four moisture contents were studied: 65%, 75%, 80% and 82%. Experimental results showed that propionate concentration and moisture content strongly influenced the SMA. The highest SMA was observed at a substrate concentration of 10 gCOD/kg (11.3 mgCOD gVS(-1) d(-1) for the second dose of propionate) and at a moisture content of 82% (7.8 mgCOD gVS(-1) d(-1) for the second dose of propionate, at a concentration of 5 gCOD/kg). SMA was found to decrease linearly when decreasing the moisture content.