From grape bagasse to graphene-like porous carbon nanosheets for CO2 capture.

Graphene-based materials have increasingly attracted attention in recent years. It is a material is recognized worldwide due to its numerous applications in several sectors. However, graphene production involves several challenges: scalability, high costs, and high-quality production. This study synthesized graphene-like porous carbon nanosheets (GPCNs) through a thermochemical process under a nitrogen atmosphere using grape bagasse as a precursor. Three temperatures (700, 800, and 900 ºC) of the pyrolysis process were studied. Chemical graphitization and activation were used to form high-specific surface area materials: FeCl3.6H2O(aq) and ZnCl2(s) in a simultaneous activation-graphitization (SAG) method. The materials obtained (GPCN700, GPCN800, and GPCN900) were compared to previously produced chars (C700, C800, and C900). A high specific surface area and total pore volume were obtained for GPCN materials, and GPCN900 presented the highest values: 1062.7 m2g-1 and 0.635 cm3 g-1, respectively. The GPCN and char materials were classified as mesoporous and applied as adsorbents for CO2(g). The GPCN800 presented the best CO2(g) adsorbent, with a CO2(g) adsorption capacity of 168.71 mg g-1.

Preparation of carbonaceous materials from flotation-sludge of the poultry industry and its application in the methylene blue adsorption.

In this work, different carbonaceous materials based on floated sludge from a poultry industry wastewater treatment plant (PI-WTP) were synthesized. These materials were characterized and investigated in methylene blue dye (MB) adsorption. The influences of the initial pH solution, adsorbent dosage, kinetics, equilibrium, and thermodynamics were evaluated in the adsorption experiments. A simulation of a real textile effluent was also carried out to evaluate the adsorbent. The results of the adsorbents' characterization demonstrated that adding ZnCl2 + lime, followed by pyrolysis and acid leaching, significantly improved the material's properties, leading to abundant porosity and high surface area. The adsorption experiments indicated that the natural pH of the solution (8.0) and the AC-II dosage of 0.75 g L-1 are optimal for MB removal. Elovich and Sips' models (with a maximum adsorption capacity of 221.02 mg g-1 at 328 K) best fitted the experimental kinetic and equilibrium data, respectively. The adsorption process is spontaneous and endothermic according to thermodynamic parameters. The discoloration efficiency of the simulated effluent was 67.8%. In conclusion, the floated sludge, a residue produced on a large scale that needs to be disposed of correctly, can be converted into a value-added material (carbonaceous adsorbent) and applied to treat colored effluents.

Citrus fruit residues as alternative precursors to developing H2O and CO2 activated carbons and its application for Cu(II) adsorption.

Due to its toxicity, the presence of Cu(II) ions released in aquatic environments presents a serious threat to the environment and human health. In search of sustainable and low-cost alternatives, there are citrus fruit residues, which are generated in large quantities by the juice industries and can be used to produce activated carbons. Therefore, the physical route was investigated for producing activated carbons to reuse citrus wastes. In this work, eight activated carbons were developed, varying the precursor (orange peel-OP, mandarine peel-MP, rangpur lime peel-RLP, and sweet lime peel-SLP) and the activating agent (CO2 and H2O) to remove Cu(II) ions of the aqueous medium. Results revealed promising activated carbons with a micro-mesoporous structure, a specific surface area of around 400 m2 g-1, and a pore volume of around 0.25 cm3 g-1. In addition, Cu (II) adsorption was favored at pH 5.5. The kinetic study showed that the equilibrium was reached within 60 min removing about 80% of Cu(II) ions. The Sips model was the most suitable for the equilibrium data, providing maximum adsorption capacities (qmS) values of 69.69, 70.27, 88.04, 67.83 mg g-1 for activated carbons (AC-CO2) from OP, MP, RLP, and SLP, respectively. The thermodynamic behavior showed that the adsorption process of Cu(II) ions was spontaneous, favorable, and endothermic. It was suggested that the mechanism was controlled by surface complexation and Cu2+-π interaction. Desorption was possible with an HCl solution (0.5 mol L-1). From the results obtained in this work, it is possible to infer that citrus residues could be successfully converted into efficient adsorbents to remove Cu(II) ions from aqueous solutions.

Valorization of Different Fractions from Butiá Pomace by Pyrolysis: H2 Generation and Use of the Biochars for CO2 Capture.

This work valorizes butiá pomace (Butia capitata) using pyrolysis to prepare CO2 adsorbents. Different fractions of the pomace, like fibers, endocarps, almonds, and deoiled almonds, were characterized and later pyrolyzed at 700 °C. Gas, bio-oil, and biochar fractions were collected and characterized. The results revealed that biochar, bio-oil, and gas yields depended on the type of pomace fraction (fibers, endocarps, almonds, and deoiled almonds). The higher biochar yield was obtained by endocarps (31.9%wt.). Furthermore, the gas fraction generated at 700 °C presented an H2 content higher than 80%vol regardless of the butiá fraction used as raw material. The biochars presented specific surface areas reaching 220.4 m2 g-1. Additionally, the endocarp-derived biochar presented a CO2 adsorption capacity of 66.43 mg g-1 at 25 °C and 1 bar, showing that this material could be an effective adsorbent to capture this greenhouse gas. Moreover, this capacity was maintained for 5 cycles. Biochars produced from butiá precursors without activation resulted in a higher surface area and better performance than some activated carbons reported in the literature. The results highlighted that pyrolysis could provide a green solution for butiá agro-industrial wastes, generating H2 and an adsorbent for CO2.

Pyrolysis of citrus wastes for the simultaneous production of adsorbents for Cu(II), H2, and d-limonene.

A route based on pyrolysis and physical activation with H2O and CO2 was proposed to reuse citrus waste traditionally discarded. The citrus wastes were orange peel (OP), mandarine peel (MP), rangpur lime peel (RLP), and sweet lime peel (SLP). The main aim was to use the solid products of this new route as adsorbents for Cu(II) ions. Copper ions are among the most important water pollutants due to their non-degradability, toxicity, and bioaccumulation, facilitating their inclusion and long persistence in the food chain. Besides the solid products, the liquid and gaseous fractions were evaluated for possible applications. Results showed that the citrus waste composition favored the thermochemical treatment. In addition, the following yields were obtained from the pyrolysis process: approximately 30 % wt. of biochar, 40 % wt. of non-condensable gases, and 30 % wt. of bio-oil. The biochars did not present a high specific surface area. Nevertheless, activated carbons with CO2 and H2O presented specific surface areas of 212.4 m2/g and 399.4 m2/g, respectively, and reached Cu(II) adsorption capacities of 28.2 mg g-1 and 27.8 mg g-1. The adsorption kinetic study revealed that the equilibrium was attained at 60 min and the pseudo-second-order model presented a better fit to the experimental data. The main generated gases were CO2, which could be employed as an activating agent for activated carbon production. d-limonene, used for food and medicinal purposes, was the main constituent of the bio-oil.

Pyrolysis of grape bagasse to produce char for Cu(II) adsorption: a circular economy perspective.

Based on cleaner production and circular economy concepts, chars were produced through thermochemical conversion of grape bagasse and then used as adsorbents to uptake Cu(II) from aqueous media since Cu(II) is a common element found in fungicides to treat grapevines. The grape bagasse and char characteristics were investigated through several analytical techniques (TGA, SEM, XRD, FTIR, and BET). Three chars were obtained using different pyrolysis temperatures: 700, 800, and 900 °C. The materials had similar removal percentages and adsorption capacity. The char produced at 700 °C was chosen due to its lower production cost. Studies were conducted on the adsorbent dosage and pH effect, adsorption kinetics, isotherms, and thermodynamics. The most efficient dosage was 1.5 g L-1, and the pH was 5.5. The kinetic study showed that the equilibrium was reached in 60 min and the pseudo-second-order model presents the best fit. After the temperature influence study (25, 35, 45, and 55 °C), it was possible to verify that Cu(II) adsorption through char was favored at 55 °C. The Freundlich model showed the best fit for the experimental data. The highest removal percentage was 96.56%, and the high maximum adsorption capacity was 42 mg g-1. The thermodynamic study shows the adsorption as a spontaneous process, favorable, and endothermic. Supplementary Information: The online version contains supplementary material available at 10.1007/s13399-022-02792-8.

Effective adsorptive removal of atrazine herbicide in river waters by a novel hydrochar derived from Prunus serrulata bark.

In this work, a novel and effective hydrochar was prepared by hydrothermal treatment of Prunus serrulata bark to remove the pesticide atrazine in river waters. The hydrothermal treatment has generated hydrochar with a rough surface and small cavities, favoring the atrazine adsorption. The adsorption equilibrium time was not influenced by different atrazine concentrations used, being reached after 240 min. The Elovich adsorption kinetic model presented the best adjustment to the kinetic data. The Langmuir model presented the greatest compliance to the isotherm data and indicated a higher affinity between atrazine and hydrochar, reaching a maximum adsorption capacity of 63.35 mg g-1. Thermodynamic parameters showed that the adsorption process was highly spontaneous, endothermic, and favorable, with a predominance of physical attraction forces. In treating three real river samples containing atrazine, the adsorbent showed high removal efficiency, being above 70 %. The hydrochar from Prunus serrulata bark waste proved highly viable to remove atrazine from river waters due to its high efficiency and low precursor material cost.

Development of activated carbon from Schizolobium parahyba (guapuruvu) residues employed for the removal of ketoprofen.

Schizolobium parahyba species can be found in all of South America, producing several residues that can be a major opportunity to develop activated carbon. This work presents the investigation regarding the development of a high specific surface activated carbon (981.55 m2 g-1) and its application in the adsorption of ketoprofen from the aqueous media. The ketoprofen molecules were better adhered to the adsorbent surface under acidic conditions (pH = 2), being the ideal adsorbent dosage determined as 0.7 g L-1, resulting in satisfactory values. It was found that the system reached equilibrium in 200 to 250 min depending on the initial concentration studied, achieving an adsorption capacity of 229 mg g-1. The general order was the most suitable model for describing the experimental data, with an R2 ≥ 0.9985 and MSR ≤ 63.40 (mg g-1)2. The equilibrium adsorption found that the temperature increases the adsorption capacity, achieving 447.35 mg g-1 at 328 K. Besides that, the Tóth model was the most suitable for describing the isotherms R2 ≥ 0.9990 and MSR ≤ 25.67 (mg g-1)2, indicating a heterogeneous adsorbent. The thermodynamic values found that the adsorption of ketoprofen is spontaneous (average ΔG0 of - 32.79 kJ mol-1) and endothermic (ΔH0 10.44 kJ mol-1). The treatment of simulated effluent with the developed adsorbent was efficient, removing 90% of ketoprofen, ibuprofen, and salts. It was found that the adsorbent is reaming its adsorption capacity up to the 5th cycle, progressively decreasing the adsorption capacity until the adsorption does not occur past the 12th cycle. Overall, the results demonstrated that the activated carbon from residual biomass of the Schizolobium parahyba species could be an excellent alternative in obtaining an effective adsorbent to treat wastewater-containing drugs.

Graywater treatment of emerging pollutant linear alkylbenzene sulfonate by adsorption with leather shave waste activated carbon.

The purpose of this research is to evaluate the use of leather shave waste activated carbon (ACLW) as an alternative for the treatment of wastewater containing linear alkylbenzene sulfonate (LAS). Batch adsorption tests were carried out (pH effect, isotherms, kinetics). The activated carbon was tested for its life cycle by desorption with solvent and it was further evaluated as real wastewater treatment for bath graywater. Under the optimum pH of 2.5, kinetic studies showed a better correlation with the pseudo-second order model, with an activation energy of 27.5 kJ mol-1. Equilibrium isotherms correlated better with the double layer model, indicating hemi-micelle formation and performing a high-affinity isotherm. Adsorption was shown to be endothermic (∆H0 = + 73.89 kJ mol-1), entropy driven (∆S0 = + 0.46 kJ mol-1 K-1), and occurring spontaneously. The use of ethanol solution was effective for the regeneration of the adsorbent. Adsorption was applied in real wastewater, removing contaminants from bath graywater, especially anionic surfactants with up to 95% removal efficiency.

Synergistic effect of the activated carbon addition from leather wastes in chitosan/alginate-based composites.

In this work, chitosan/alginate composites were developed by the gelation method with the addition of different amounts of activated carbon produced from tannery waste (ACTW). The performance of these composites was verified through the adsorption of the textile dye Remazol Brilliant Blue R (RBBR). A synergistic effect was observed by the addition of ACTW; with a specific surface area up to 45.584 m2/g, the maximum adsorption capacity was 300.96 mg/g. The synergy was due to the reduction in steric hindrance, with the adsorption capacity 1.2 times higher than expected. The material was regenerated with sodium hydroxide for 10 cycles. The composite containing 30% ACTW (AC30) was applied in the treatment of real textile effluent, with 30% reductions in the biochemical oxygen demand (BOD), 39% in the chemical oxygen demand (COD), 78% in turbidity, and 67% in color.

Simultaneous production of mesoporous biochar and palmitic acid by pyrolysis of brewing industry wastes.

Pyrolysis of malt bagasse was carried out to obtain simultaneously a mesoporous biochar and an oil fraction rich in palmitic acid. The best result for biochar production was at 500 °C with holding time of 10 min. The yields of biochar and pyrolytic oil in this condition were, 29.7 and 33.9 wt%, respectively. The pyrolysis temperature and holding time influenced the yields of the products. An increase in pyrolysis temperature (from 500 to 700 °C) and holding time (from 10 to 50 min) caused a decrease in biochar yield, a reduction in the volatile matter content and an increase in the amount of ash. Additionally, in the range studied in this work, the increase of the pyrolysis temperature caused a decrease in the specific surface area and total pore volume of the biochar. Meanwhile, the biochar presented interesting functional groups and a mesoporous character, which can be a precursor to obtain adsorbents, or even, be used as adsorbent. The pyrolytic oil was composed of oxygenated aromatic compounds, the main fraction being palmitic acid (27.3%), which can be used in a number of applications, including biodiesel production. This work demonstrated that an available and problematic waste, malt bagasse, can be converted simultaneously into a mesoporous biochar and, into a pyrolytic oil rich in palmitic acid. Biochar and pyrolytic oil, in turn, are products of great value and can be applied in several fields.

Ultrasonication-promoted synthesis of Ni/mayenite for catalytic reforming of biomass tar.

Ultrasound-assisted approach was successfully applied for the synthesis of mayenite from calcium and aluminum hydroxides and then subsequently impregnated with Ni by the wet impregnation method. The synthesis was performed with a 13 mm probe-type ultrasound, operating under an acoustic power of 30.5 W and a frequency of 20 kHz. Ultrasound application was studied in detail from a 3k experimental design, where the variables studied were ultrasound time (10-50 min) and calcination temperature (900-1200 °C). Ultrasound promoted an effective dispersion of the precursors in a short time of 10 min leading to a high conversion to mayenite after calcination at 1200 °C. Ultrasound treatment also had a positive effect on Ni impregnation, increasing the dispersion of the metal in the support and leading to a stronger interaction of nickel-containing species with mayenite support. The use of ultrasound application has proved to be attractive both for catalyst properties and for facilitating catalyst synthesis.

Development of high quality activated carbon from biological sludge and its application for dyes removal from aqueous solutions.

A high quality activated carbon was developed from biological sludge of a beverage wastewater treatment plant (BWTP). The material was characterized and its adsorption potential to remove Allura Red AC and Crystal Violet dyes from aqueous media was verified. The ACBS (activated carbon from beverage sludge) revealed mesoporous features, presenting average pore diameter of 6.32 nm, pore volume of 0.5098 cm3 g-1 and surface area of 631.8 m2 g-1. Adsorption was adequate using 0.25 g L -1 of ACBS, and, the process was favored at pH 2.0 for Allura Red AC and pH 8.0 for Crystal Violet. From the kinetic viewpoint, the data were satisfactorily represented by the pseudo-second order model. Freundlich and Sips models were suitable to represent the adsorption equilibrium of the Allura Red and Crystal Violet, respectively. The maximum values for adsorption capacities were 287.1 mg g-1 for Allura Red and 640.7 mg g-1 for Crystal Violet. The adsorption of both dyes was thermodynamically spontaneous, favorable and endothermic. In brief, the residual sludge of a wastewater treatment plant may be used as an eco-friendly precursor for ACBS production. ACBS was an efficient adsorbent material able to uptake dyes from aqueous solutions.

Adsorption of leather dyes on activated carbon from leather shaving wastes: kinetics, equilibrium and thermodynamics studies.

In this work, the adsorption of Acid Black 210 (AB210) and Acid Red 357 (AR357) onto activated carbon prepared from leather shaving wastes (ACLW) was investigated. The activated carbon presented a surface area of 800.4 m²/g with an average pore size of 1.27 nm. The kinetic study showed that the adsorption of both dyes followed the Elovich kinetic model while the AB210 and AR357 isotherm data were well described by the Langmuir and BET models, respectively. Furthermore, the Boyd plot revealed that the adsorption of the leather dyes on activated carbon was mainly governed by film diffusion. The pH had a strong influence on the adsorption, and the higher amounts of dye adsorbed were obtained at pH 2. The obtained activated carbon exhibited a high monolayer adsorption capacity of 573.9 and 204.4 mg/g for AB210 and AR357, respectively. Its high capacity is mainly attributed to its basicity (0.17 mmol/g) and high surface area. Desorption efficiency of the spent activated carbon was found to be 54.3% and 43.0% for AB210 and AR357, respectively. The spontaneity of the process was demonstrated by the negative values of the Gibbs free energy change.

A Dual-mode model interpretation of CO2/CH4 permeability in polysulfone membranes at low pressures.

An asymmetric membrane of polysulfone (PSf) was synthesized by phase inversion method. Permeation experiments were carried out between 2 to 5 bar pressure, and at temperatures 20 to 45°C. The dense-selective layer of PSf membrane presents regular thickness (about 5 µm), and was not possible to observe the formation of macrovoids in porous layer. The CO2 permeability through membrane was 18.8 Barrer at 35°C and 2 bar pressure, and this relationship between the pressure and the CO2 permeability was described adequately by Dual-mode model. The absence of CH4 permeability at 2 and 3 bar pressure, qualifies the PSf membrane for gases separation with high selectivity in this range.

Fodder radish seed cake biochar for soil amendment.

In this work, fodder radish seed cake (FRSC) was pyrolyzed in a rotary kiln reactor at 0, 3, and 6 rpm, at final temperature of 500 °C. Maximum biochar yield was observed at 0 rpm (≈ 26 wt.%). Increase of the rotary speed decreased the volatile matter content and increased the ash content of the biochars. Biochars exhibited alkaline pH (≈ 9.0), low electrical conductivity (< 105.6 dS m-1), and high cation exchange capacity (69 to 78 cmolc kg-1), as well as high nitrogen contents (≈ 80 g kg-1). FTIR analysis presented biochars with similar spectra, with carboxyl and carbonyl groups within the structure, along with aromatic rings and nitrogen containing functions (amides). Biochar incubation experiments in an acrisol at different biochar doses (5 g L-1 soil to 40 g L-1 soil) were performed in order to evaluate changes in soil fertility parameters caused by FRSC biochar application. Results indicated that most of macro (N, P, K, Ca, Mg) and micronutrients (S, Cu, Zn, Mn, B, Na) increased with increase of the dosage, along with the decrease in Al and H+ Al contents. An increase in pH (from 4.25 to 5.33) was also observed, in electric conductivity (from 30.0 to 45.7 dS m-1), and a decrease in soil real density (from 3.67 to 2.99 kg L-1) at the dosage of 40 g char L-1 soil.

Development of CO2 activated biochar from solid wastes of a beer industry and its application for methylene blue adsorption.

An alternative activated biochar was developed from barley malt bagasse (BMB) through pyrolysis followed by CO2 activation. The materials BMB, biochar and activated biochar (CO2-biochar) were characterized and tested as adsorbents for the removal of methylene blue (MB) from aqueous solutions. Adsorption kinetics, equilibrium and thermodynamics were studied. It was found that BMB and biochar presented surface area values lower than 1 m2 g-1, while CO2-biochar was a typical mesoporous material with surface area around 80 m2 g-1. As consequence, the adsorption potential for methylene blue was in the following order CO2-biochar ≫ biochar > BMB. Adsorption kinetics of MB on CO2-biochar followed the pseudo-second order model. Langmuir presented the best fit with the equilibrium adsorption isotherms. The maximum adsorption capacity was 161 mg g-1. MB adsorption on CO2-biochar was spontaneous, favorable and exothermic. Pyrolysis followed by CO2 activation was a suitable route to produce an alternative mesoporous adsorbent from barley malt bagasse.

Nanofibrillated cellulose from tobacco industry wastes.

Tobacco stems waste underwent steam explosion pulping for nanofibrillated cellulose (NFC) production. In order to obtain NFC hydrogels, the pulp obtained by steam explosion was bleached and refined in a grinder employing specific energy of up to 5067kWh/t. Eucalyptus kraft pulp was processed under the same conditions to produce NFC hydrogels, later used in order to compare with NFC hydrogels from tobacco stems waste. According to statistical analysis, the optimum tobacco stems pulping condition was obtained with a severity index of log3.0 and active alkali of 16.25%. These conditions allowed obtaining a bleached pulp with Schopper Riegler degree of 46. Electronic microscopy with field emission showed a higher presence of nanofibers in the tobacco stems pulp than in commercial eucalyptus kraft pulp, both after refining. Thermal analysis indicated that tobacco stems pulp degrade at lower temperatures than eucalyptus kraft pulp. FTIR analysis did not indicate chemical bonding differences between the two pulps.

Formation of PCDD and PCDF in the thermal treatment of footwear leather wastes.

The leather waste generated by the footwear industry is considered dangerous due to the presence of trivalent chromium, derived from the salt utilized to tan hides. In Brazil, the majority of this waste is disposed on landfills and only about 3% are recycled. The thermal treatment is an alternative method for purification of such residues. By using this technique it is possible to generate energy and recover the chromium present in the ash for the production of basic chromium sulfate (tanning industry), high carbon ferrochromium or carbon-free ferrochromium (steel industry). In the last 10 years, the gasification and combustion of footwear leather waste have been intensively studied at the Federal University of Rio Grande do Sul. The research experiment for characterization of the emissions of polychlorinated dibenzo-p-dioxins and dibenzofurans (PCDD/F) were carried out in a semi-pilot unit (350 kW(th)). From new investments the thermal capacity of the unit will increase to 600 kW(th). The unit will produce power from the heat generated in the combustion. The experimental results indicated that during the thermal treatment of footwear leather wastes, the formation mechanism of PCDD/F is the de novo synthesis. Most of PCDD/F were found in the particulate phase (>95%). A kinetic model was used for discussion of the achieved experimental results. The model is based in the carbon gasification, PCDD/F formation, desorption and degradation. From the conclusions obtained in this work will be possible minimize the PCDD/F formation in process of combustion of footwear leather wastes.