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Lignin is a potential sustainable alternative to polyacrylonitrile (PAN) precursor for the production of carbon fibers. The high purity lignin extracted from residual forest biomass via organosolv process undergoes stabilization and carbonization treatment to produce carbon fibers. Recent developments suggest the potential of producing organosolv lignin carbon fibers (OLCF) with competing mechanical properties similar to PAN carbon fibers. This is likely to enable the use of OLCF in structurally demanding applications such as wind turbine blades. In this work, a life cycle assessment (LCA) is performed with a threefold objective. First, the environmental footprint of OLCF is quantified and results are compared with PAN-CF produced in Sweden and elsewhere in Europe i.e., electricity demands met by European average electrical grid (RER). Second, the environmental performance of OLCF reinforced wind turbine blades (referred as BIOMAT) to be installed in 0.8 MW capacity is evaluated against incumbent variants: glass fiber turbine blade (GFTB), PAN-CF based turbine blades manufactured in Sweden (CFTB-SE), and other parts of Europe (CFTB-RER). Finally, the total environmental externality costs (EEC) of these blades and corresponding lifetime electricity generation when they are installed in 0.8 MW capacity wind turbine blade are calculated. Our results indicate that the environmental impacts of OLCF are lower by 71–94% than PAN-CF-RER in nine, and lower by 43–90% than PAN-CF-SE in six out of ten impact categories quantified respectively. BIOMAT blades also have better overall environmental performance than existing blade variants and particularly lucrative because of their negative total climate change impact. The total EEC of BIOMAT blades is 74%, 83% and 88% lower than GFTB, CFTB-SE and CFTB-RER respectively. Correspondingly, the total EEC of lifetime electricity generated by wind turbine equipped with BIOMAT blades is 11%, 17% and 23% lower than the respective blade variants.

Hydrothermal carbonization (HTC) offers significant potential for converting residual waste streams into advanced carbon materials with diverse applications. However, a key challenge in scaling up HTC is managing the large volumes of organic-rich filtrate produced during the process. Through a resting process, the filtrate can be repurposed to produce self-generated carbon (SGC). The spontaneously formed SGC exhibited a spherical morphology and low ash content, even when derived from complex, ash-rich precursors such as anaerobic digestate. SGC production from HTC filtrate may open up a new valorization route for industrial and municipal side-streams. In this study, we investigate how temperature, time, and agitation influence SGC yield, morphology, and particle size distribution. The cumulative yield was measured at intervals (days 2, 5, 7, 9, 26). The average cumulative yield after 26 days increased by 102 % at 50 °C compared to 20 °C, but decreased by 42 % at 4 °C. Agitated samples had the highest yield, increasing by over 260 % at 20 °C. The products showed variations in morphology and size distribution, with agitated samples producing more uniform and smaller particles. SEM imaging indicated a distinct product at 4 °C, with no visible spherical material being generated. Our results imply that changes in temperature and agitation are highly influential in the formation of SGC and may be used in optimizing product yield, sphere size and uniformity. The consistent formation rate over the 26-day period suggests that extending the experimental duration could further increase material yield. This is supported by mass balance calculations.

Herein, we have investigated how pure lignin extracted from birch and spruce via a hybrid organosolv/steam explosion method reacts under hydrothermal carbonization (HTC) to produce hydrochar, a product that has found applications in environmental remediation, energy storage and catalysis. We subjected thirteen lignin samples obtained from birch and spruce under different extraction conditions to HTC at 260 ℃ for four hours. The yield of hydrochar varied between the different extraction conditions and source, although no clear correlation between extraction conditions and yield could be observed. For instance, lignin from birch pretreated in 60%v/v ethanol for 15 min resulted in a hydrochar yield of 39 wt%. Increasing the time to 30 and 60 resulted in a hydrochar yield of 27 wt% and 23 wt%, respectively. This suggested that small changes in the organosolv reaction conditions might produce highly structurally different lignin, resulting in the difference in HTC yield. Thus, we chose a subset of four lignin samples to investigate in-depth, subjecting these samples to a range of hydrothermal reaction temperatures and residence times. Solid State NMR and FTIR analysis indicated that the most significant structural changes occurred below 230 ℃ resulting in the breaking of C-O- linkages. Increasing the temperature or time had minimal impact, with no further C-O- linkages broken and no changes to the ring structure of C-C groups. Size exclusion chromatography indicated that the degree of micro and macromolecules in the liquid product varied significantly with lignin source and HTC reaction conditions. Overall, this study demonstrated that lignin has a large reaction range where it produces a very chemically similar solid product, with the only major difference being the yield of material. This is important for industry, as it indicates that a similar solid product can be easily achieved independently of extraction conditions allowing the HTC reaction to be tuned towards extracting the maximum benefit from products contained in the liquid.

Seven different lignin samples, three from Kraft extraction and four from organosolv extraction, were subjected to hydrothermal treatment at 260℃ for four hours to assess the impact of lignin type on the physicochemical properties of the hydrothermal material. The ¹³C Solid state NMR, XPS, FTIR and SEM analysis revealed that the different sources of lignin and the extraction conditions created variations in the degree of syringyl and guaiacyl subunits, inter-unit bonding arrangements, morphology and surface composition. Hydrothermal carbonization appeared to “normalize” the differences between each of the lignin samples, via breaking β-O-4 or α-O-4 linkages, removal of methoxy and syringyl subunits, and creation of C–C and 4-O-5 linkages to polymerization into large 100−200 μm amorphous carbon particles. Overall, this study indicates that the source and extraction type have minimal influence on the physicochemical structure and morphology of the final hydrothermal product.

Ammonium has been successfully utilized to nitrogen dope carbon structures via hydrothermal carbonization, although the influence of different attached counter ions (anions) on the resultant carbon physicochemical properties and electrochemical performance has not been examined before. Four different counter ions (SO42-, PO43-, Cl-, and Fe(SO4)(2)) attached to ammonium were seen to influence the hydrothermal reaction, nitrogen incorporation levels, physicochemical properties, activation ability and supercapacitor performance. For instance, nitrogen K-edge NEXAFS found differences in the levels of pyridinic and pyrrolic groups with PO43- incorporating predominately pyridinic nitrogen groups. PO43- also achieved the highest surface area (2132.6 m(2) g(-1)), however this material was unstable as a supercapacitor, losing almost 50% of its performance over 500 cycles. SO42- resulted in the highest level of nitrogen incorporation (5.53 at%) and hydrothermal yield (45.5%), while Fe(SO4)(2)(2-) resulted in the lowest (2.92 at%). However, Fe(SO4)(2)(2-) produced unique flower like structures not seen in any of the other anions. Cl- produced the highest performing material, achieving 190 F g(-1) at 10 mV s(-1) in 1 M KOH and had moderate nitrogen incorporation (3.42 at%). Overall, this study indicates that the anion has substantial influence on the physicochemical properties of the material, allowing an additional level of tailoring.

This work provides the first observations of and insights into the self-generation of carbon microspheres from the supernatant after hydrothermal carbonization of anaerobic digestate has been completed and the hydrochar removed. Solid State NMR and XPS revealed that the carbon microspheres were comprised of decomposed fragments of proteins, carbohydrates and lignin. The carbon microspheres were significantly lower in ash content (3.1%), compared to the hydrothermal solid (41.2%) and precursor (25.2%) and their formation reduced the total organic carbon load of the supernatant. The low ash content allowed them to be easily activated, achieving a surface area of 1711.0 m2 g−1, compared to 51.4 m2 g−1 for the activated hydrothermal solid and 12.8 m2 g−1 for the activated precursor. The microcarbon spheres achieved a specific capacitance from cyclic voltammetry of 86 F g−1 at 100 mV s−1 to 176 F g−1 at 1 mV s−1, while the gravimetric capacitance was 42 F g−1 at 25 A g−1 and 140 F g−1 at 0.5 A g−1 in 0.5 M Li2SO4 and a 1.8V potential window. Overall, this study highlights the importance of exploring this new product and its valorisation potential for the hydrothermal carbonization of ash-rich precursors.

Hydrothermal carbonization (HTC) is an energy-efficient thermochemical process for converting wet waste products into value added materials for water treatment. Understanding how HTC influences the physicochemical properties of the resultant materials is critical in optimizing the process for water treatment, where surface functionality and surface area play a major role. In this study, we have examined the HTC of four wet waste streams, sewage sludge, biosludge, fiber sludge, and horse manure at three different temperatures (180 degrees C, 220 degrees C, and 260 degrees C). The physicochemical properties of these materials were examined via FTIR, SEM and BET with their adsorption capacity were assessed using methylene blue. The yield of solid material after hydrothermal carbonization (hydrochar) decreased with increasing temperature for all samples, with the largest impact on horse manure and fiber sludge. These materials also lost the highest degree of oxygen, while HTC had minimal impact on biosludge and sewage sludge. The differences here were due to the varying compositions of each waste material, FTIR identified resonances related to cellulose in horse manure and fiber sludge, which were not detected in biosludge and sewage sludge. Adsorption capacities varied between 9.0 and 68 mg g(-1) with biosludge HTC at 220 degrees C adsorbing the highest amount. Adsorption also dropped drastically at the highest temperature (260 degrees C), indicating a correlation between adsorption capacity and HTC conditions. This was attributed to the loss of oxygen functional groups, which can contribute to adsorption. These results suggest that adsorption properties can be tailored both by selection of HTC temperature and feedstock.

In this study, we have examined how the activation of hydrothermally carbonized sewage sludge and horse manure influences the inorganic component of these materials and surface chemistry. This was examined through statistical correlations between kinetic tests using trimethoprim, fluconazole, perfluorooctanoic acid, and copper, zinc, and arsenic and physicochemical properties. Yield and inorganic content varied considerably, with potassium hydroxide-activated materials producing lower yields with higher inorganic content. Phosphoric acid activation incorporated inorganically bound phosphorus into the material, although this showed no statistically relevant benefit. A maximum surface area of 1363 m(2)g(-1)and 343 m(2)g(-1)was achieved for the horse manure and sewage sludge. Statistical analysis found positive correlations between carbon-oxygen functionalities and trimethoprim, fluconazole, perfluorooctanoic acid, and copper removal, while inorganic content was negatively correlated. Conversely, arsenic removal was positively correlated with inorganic content. This research provides insight into the interactions with the organic/inorganic fraction of activated waste materials for water treatment.

In this work, the influence of (NH4)(2)SO4 and (NH4)(2)HPO4 as well as temperature is examined on the hydrothermal carbonization of glucose, fructose and sucrose. Increasing the temperature from 160 to 220 degrees C increased the yield of hydrothermal carbon for each saccharide for the (NH4)(2)SO4 solution, whereas (NH4)(2)HPO4 produced a yield that was independent of temperature. The addition of (NH4)(2)SO4 increased the yield obtained at 220 degrees C by 4.27, 7.03 and 2.01 wt% for glucose, fructose and sucrose over the baseline salt free solution, respectively. (NH4)(2)SO4 also increased the quantity of acid produced and the average size of the hydrothermal carbon spheres. Conversely, (NH4)(2)HPO4 produced carbon structures consisting of interlocked spherical shapes and produced almost no acidic products. XPS analysis revealed that (NH4)(2)SO4 incorporated nitrogen and sulfur into the hydrothermal structure, while (NH4)(2)HPO4 only allowed nitrogen to be incorporated. It was assessed that NH4(+) enhances the production of hydrothermal carbon, except in the presence of PO43-, which prevents the reaction from effectively forming hydrothermal carbon and organic acids. [GRAPHICS] .

Humic acids (HAs) represent an economic and environmental challenge in water treatment, as they have the propensity to foul membranes and create toxic byproducts when interacting with chlorine. To overcome this, HAs were submitted to hydrothermal carbonization to convert them into an easy to remove, valuable carbon material. The result was a carbonaceous material which was easy to filter/dewater compared to HAs with a char yield of 49 +/- 1.8 wt %, and with 46.6 1.4 wt % ending up in the water phase, 2.2 +/- 0.2 wt % in the tar, and the rest in the gaseous fraction. The molecular weight distribution of the organic matter in the water pre-and post-HTC indicated that the structure was broken into several different fragments with a lower molecular weight than that initially present. Physicochemical analysis of the material via elemental analysis, X-ray photoelectron spectroscopy, diffuse reflectance infrared Fourier transform spectroscopy, and solid-state nuclear magnetic resonance indicated that under hydrothermal carbonization, the aromatic structure of HAs condensed. Carboxylic acids groups were also lost from the surface of HAs, with ether and alcohols increasing because of their loss. The morphology of the obtained material had an amorphous macrostructure consisting of many smaller light lamellar carbon fragments. Finally, the hydrothermal treatment increased the surface area from 0.4 to 103.0 m(2) g(-1).The porosity is located in the mesoporous range of 10-80 nm with a maximum peak at 50 nm.