Recycling of Industrial Waste as Soil Binding Additives-Effects on Soil Mechanical and Hydraulic Properties during Its Stabilisation before Road Construction.

To improve the in situ soil stabilization, different chemical additives are used (ion exchange compounds, additives based on H2SO4 or vinyl polymers, and organic additives using lignosulfonates). One interesting alternative is the production of additives from various waste materials. The extensive testing of waste-based blends with soil was performed; the mechanical (unconfined compressive strength (UCS)) and hydraulic (capillary rise, water absorption, and frost resistance (FR)) soil properties were measured. The optimization process led to obtaining additive compositions ensuring high strength and sealing properties: by-pass ash from the ceramics industry, waste H2SO4, pyrolytic waxes/oils from waste mixed plastics, waste tires and HDPE, and emulsion from chewing gum waste. For sandy soil, the following additives were the most promising: emulsion from pyrolytic wax (EPW) from waste PE foil (WPEF) with the addition of waste H2SO4, pyrolytic-oil emulsion from waste tires, EPW from waste mixed plastics with the addition of "by-pass" waste ash and NaOH, EPW from WPEF with the addition of NaOH, and EPW from WPEF reaching up to 93% FR, a 79.6% 7-day UCS increase, and a 27.6% of 28-day UCS increase. For clay: EPW from WPEF with the addition of NaOH, EPW from WPEF with the addition of waste H2SO4, and solely EPW from WPEF reaching up to 7.5% FR, an 80.7% 7-day UCS increase, and a 119.1% 28-day UCS increase.

Comparison of the Efficiency of Hetero- and Homogeneous Catalysts in Cellulose Liquefaction.

Biomass liquefaction is a well-known and extensively described process. Hydrothermal processes are well understood and can be used in the fuel industry. The use of organic solvents can result in full-fledged products for use in the synthesis of polyurethanes. The plastics industry, including polyurethanes, is targeting new, more environmentally friendly solutions. One of these is the replacement of petrochemical polyols with compounds obtained from renewable sources. It is common in biomass liquefaction to use sulfuric acid (VI) as a catalyst. The purpose of the present study was to test the effectiveness of a heterogeneous catalyst such as Nafion ion-exchange resin on the cellulose liquefaction process. The results obtained were compared with the bio-polyols obtained in a conventional way, using a homogeneous catalyst (sulfuric acid (VI)). Depending on the catalyst used and the temperature of the process, bio-polyols characterized, among other things, by a hydroxyl number in the range of 740-400 mgKOH/g were obtained. The research provides new information on the possibility of using heterogeneous catalysts in cellulose liquefaction.

Exploring synergistic effects in physical-chemical activation of Acorus calamus for water treatment solutions.

The research proposed a novel method of obtaining sorption material from readily available Acorus calamus biomass through a combination of physical and chemical activation processes. The material with the highest specific surface area (1652 m2 g-1) was obtained by physical activation with CO2, followed by chemical activation with KOH. Reversing the order of activation methods resulted in a lower specific surface area (1014 m2 g-1) of the carbon sample. Chemical activation produced activated carbon with a surface area of 1066 m2 g-1-, while physical activation produced 390 m2 g-1. This confirms the synergistic effect of combining the two activation methods for biocarbon. It was observed that physical activation with CO2 generates a diverse range of pores, including meso- and macropores, while chemical activation induces the formation of micropores. In contrast, reversing the order of these processes leads to the degradation of the porous structure. The application of physical-chemical activation with synergistic effects represents a significant advancement in producing high-quality activated biocarbon for various applications, such as wastewater treatment and energy storage. The combination of the two activation methods resulted in a synergistic effect, leading to the production of carbon material of higher quality. Additionally, the diversified pore sizes will enable the sorption of various pollutants in the aquatic environment and air pollutants, where gas particles are much smaller.

Conversion of waste biomass to designed and tailored activated chars with valuable properties for adsorption and electrochemical applications.

Waste biomass, a renewable energy source, is inexpensive material that has great potential in sorption and electrochemical application. The selected waste materials (corncobs, coconut shells, walnuts, and pistachio husks) allow to close the production cycle and enable material recycling, which are important aspects in the hierarchy of waste management. The proposed methodology for production and activation of biochars can be used industrially due to highly porous structure, developed surface area, and sorption ability of the obtained activated carbons (AC). A significant increase (from 4 up to more than 10 times) in specific surface area (SSA) is observed for all samples after the CO2 activation process (0.5 h at 800 °C) up to 725 m2 g-1 for corncobs, 534.9 m2 g-1 for pistachio husks, 523 m2 g-1 for coconut shells, and 393 m2 g-1 for walnut husks. The highest value of SSA is achieved for the AC derived from corncobs. This material is evaluated for use as an adsorbent, revealing 99% removal of Rhodamine B (dye/AC ratio of 0.0017) and 69% removal of chromium (dye/AC ratio of 0.0028). Based on the adsorption kinetics analysis, it is demonstrated that the Cr(VI) undergoes physical adsorption, while RhB undergoes chemisorption. In addition, corncob-derived AC exhibits superior electrochemical performance in 6 M KOH compared to the nonactivated biochar. A specific capacitance of 70 F g-1 at 5 A g-1 is achieved, along with outstanding rate capability (45 F g-1 at 50 A g-1) and cycling stability (94% at 10 A g-1 after 10,000 cycles). In contrast, the nonactivated sample shows only 34 F g-1 at 5 A g-1 and 13 F g-1 at 50 A g-1, with a stability of 91.4%.

Pyrolysis and Torrefaction-Thermal Treatment of Creosote-Impregnated Railroad Ties as a Method of Utilization.

A fundamental issue of waste management and the rail transport industry is the problem of utilizing used railroad ties. Wooden railroad ties are treated with a preservative, usually creosote. Due to their high toxicity, railroad ties are considered hazardous waste and must be utilized under various directives. It is proposed to utilize the troublesome waste by using the pyrolysis and torrefaction process. The research proves that the thermal method is effective for disposing of this type of waste. Torrefaction up to 250 °C gives high efficiency of impregnation removal, while pyrolysis up to 400 °C completely neutralizes waste. A series of experiments were conducted for various final pyrolysis temperatures to determine a minimum temperature for which the obtained solid products are free from creosote. Extraction with the use of the Soxhlet technique was performed for the raw materials and the obtained solid products-chars. The oil content for liquid fraction was also examined for each sample. As a result of the thermal treatment of the waste, fuel with combustion parameters better than wood was obtained. For a high final temperature of the process, the calorific value of char is close to that of hard coal.

The role of additives in improving the flammability and calorific value of leather shavings and the binding of chromium compounds in ash.

Leather processing companies are struggling with the problem of increasing costs of post-production waste disposal. Therefore, the issue of thermal waste disposal at the plant and the use of generated heat in the production process is becoming more and more popular. Leather waste on its own does not allow for autothermal combustion despite the sufficient higher heating value (HHV). Therefore the Authors proposed to improve the flammability of the fuel by adding a small amount of wood sawdust to leather waste and produce premixed pellets. Six such samples were incinerated in a laboratory-scale reactor, which enables the simultaneous measurement of characteristic temperatures, exhaust gas analysis and sample mass loss rate. Research has shown that even a small addition of sawdust enables a stable combustion process and does not cause the formation of sinters. In addition, studies of the ash showed that in the case of chromium-containing waste, a large part of it remained in the ash in the form of Cr2O3. Nevertheless, very fine ash causes the small fraction chromium to be carried with the flue gas stream, therefore controlled agglomeration of the ash structure would be advisable in the final installation. Emission analysis showed high and moderately high NOx and SO2 emissions, decreasing with the increase in the amount of sawdust addition in the sample. Research has shown that leather waste is not a burden, but can be an attractive and safe source of energy for the company, while improving waste management in a circular economy.

The Course and the Effects of Agricultural Biomass Pyrolysis in the Production of High-Calorific Biochar.

The thermal pyrolysis of agriculture biomass has been studied in a fixed-bed reactor, where the pyrolysis was conducted at a steady temperature of 800 °C. This work analyses the pyrolysis products of six agricultural wastes: pistachio husks, walnut husks, sunflower hulls, buckwheat husks, corncobs and coconut shells. The conducted research compared examples of large waste biomass streams from different parts of the world as a potential source of renewable energy. Additionally, the kinetics of the reaction with the activation energy were analyzed and calculated for all raw materials in pyrolysis process. Biochars are characterised by higher combustion heat in comparison to the raw material samples. The average value of the heat of combustion increased due to pyrolysis process from 10 MJ/kg, with minimal value of 2.7 MJ/kg (corncob) and maximum of 13.0 MJ/kg for coconut, which is also characterised by the maximal absolute combustion heating value (32.3 MJ/kg). The increase in calorific values varied from 15% to 172% (with 54% reference for wood chips), which indicates that charring is an effective method for increasing the energy concentration. The obtained biochar were compared with wood chips, which are widely used solid fuel of organic origin. The studied biomass-derived fuels are characterised by lower ash contribution than wood. An analogous observation was made for the obtained biochars, whose ash contribution was lower than for the chips in terms of both unit-mass and unit-combustion-heat. The main advantage of this method is the production of solid fuel from biomass, which increases the calorific value and bulk density of biochar in comparison to raw material.

Pyrolysis of Pruning Residues from Various Types of Orchards and Pretreatment for Energetic Use of Biochar.

The routine pruning and cutting of fruit trees provides a considerable amount of biowaste each year. This lignocellulosic biomass, mainly in the form of branches, trunks, rootstocks, and leaves, is a potential high-quality fuel, yet often is treated as waste. The results of a feasibility study on biochar production by pyrolysis of residues from orchard pruning were presented. Three types of biomass waste were selected as raw materials and were obtained from the most common fruit trees in Poland: apple (AP), pear (PR), and plum (PL) tree prunings. Two heating rates and three final pyrolysis temperatures were applied. For the slow (SP) and fast pyrolysis (FP) processes, the heating rates were 15 °C/min and 100 °C/min, respectively. The samples were heated from 25 °C up to 400, 500, and 600 °C. Chemical analyses of the raw materials were conducted, and the pyrolysis product yields were determined. A significant rise of higher heating value (HHV) was observed for the solid pyrolysis products, from approximately 23.45 MJ/kg for raw materials up to approximately 29.52 MJ/kg for pyrolysis products at 400 °C, and 30.53 MJ/kg for pyrolysis products at 600 °C. Higher carbon content was observed for materials obtained by fast pyrolysis conducted at higher temperatures.

Microstructure-Property Relationship of Polyurethane Foams Modified with Baltic Sea Biomass: Microcomputed Tomography vs. Scanning Electron Microscopy.

In this paper, novel rigid polyurethane foams modified with Baltic Sea biomass were compared with traditional petro-based polyurethane foam as reference sample. A special attention was focused on complex studies of microstructure, which was visualized and measured in 3D with high-resolution microcomputed tomography (microCT) and, as commonly applied for this purpose, scanning electron microscopy (SEM). The impact of pore volume, area, shape and orientation on appearance density and thermal insulation properties of polyurethane foams was determined. The results presented in the paper confirm that microcomputed tomography is a useful tool for relatively quick estimation of polyurethane foams' microstructure, what is crucial especially in the case of thermal insulation materials.

Chestnut-Derived Activated Carbon as a Prospective Material for Energy Storage.

In this work, we present the preparation and characterization of biomass-derived activated carbon (AC) in view of its application as electrode material for electrochemical capacitors. Porous carbons are prepared by pyrolysis of chestnut seeds and subsequent activation of the obtained biochar. We investigate here two activation methods, namely, physical by CO2 and chemical using KOH. Morphology, structure and specific surface area (SSA) of synthesized activated carbons are investigated by Brunauer-Emmett-Teller (BET) technique and scanning electron microscopy (SEM). Electrochemical studies show a clear dependence between the activation method (influencing porosity and SSA of AC) and electric capacitance values as well as rate capability of investigated electrodes. It is shown that well-developed porosity and high surface area, achieved by the chemical activation process, result in outstanding electrochemical performance of the chestnut-derived porous carbons.

Waste Rubber Pyrolysis: Product Yields and Limonene Concentration.

Tires, conveyor belts, floor mats, and shoe soles form a main-stream of rubber waste. The amount of these used materials continuously increases due to development of the rubber market. Therefore, pro-ecological utilization (i.e., energy recycling instead of burning) and recovering valuable and recyclable materials becomes an urgent necessity. In this regard, this work was devoted to the chemical recycling of selected used rubber products, and it especially explores the possibility of limonene production. Different types of waste rubber were characterized and pyrolyzed at microgram and laboratory scales, and the results were compared. Additionally, the pyrolysis of tires, the most significant stream of rubber waste, was also conducted in a semi-technical scale reactor. The effectiveness of limonene formation in the liquid fractions obtained from different types of waste rubber was compared.

Pre-Treatment of Furniture Waste for Smokeless Charcoal Production.

The aim of this study was to assess the possibility of using furniture waste for smokeless fuel production using the pyrolysis process. Four types of wood-based wastes were used in the pyrolysis process: pine sawdust (PS), chipboard (CB), medium-density fiberboard (MDF), and oriented strand board (OSB). Additionally, the slow and fast types of pyrolysis were compared, where the heating rates were 15 °C/min and 100 °C/min, respectively. Chemical analyses of the raw materials and the pyrolysis product yields are presented. A significant calorific value rise was observed for the solid pyrolysis products (from approximately 17.5 MJ/kg for raw materials up to approximately 29 MJ/kg for slow pyrolysis products and 31 MJ/kg for fast pyrolysis products). A higher carbon content of char was observed in raw materials (from approximately 48% for raw materials up to approximately 75% for slow pyrolysis products and approximately 82% for fast pyrolysis products) than after the pyrolysis process. This work presents the possibility of utilizing waste furniture material that is mostly composed of wood, but is not commonly used as a substrate for conversion into low-emission fuel. The results prove that the proposed solution produced char characterized by the appropriate properties to be classified as smokeless coal.

Activated Carbon Produced by Pyrolysis of Waste Wood and Straw for Potential Wastewater Adsorption.

Pyrolysis of straw pellets and wood strips was performed in a fixed bed reactor. The chars, solid products of thermal degradation, were used as potential materials for activated carbon production. Chemical and physical activation processes were used to compare properties of the products. The chemical activation agent KOH was chosen and the physical activation was conducted with steam and carbon dioxide as oxidising gases. The effect of the activation process on the surface area, pore volume, structure and composition of the biochar was examined. The samples with the highest surface area (1349.6 and 1194.4 m2/g for straw and wood activated carbons, respectively) were obtained when the chemical activation with KOH solution was applied. The sample with the highest surface area was used as an adsorbent for model wastewater contamination removal.

Waste Tyres Pyrolysis for Obtaining Limonene.

This review deals with the technologies of limonene production from waste tyre pyrolysis. Thermal decomposition is attractive for tackling the waste tyre disposal problem, as it enables both: energy to be recovered and limonene to be obtained. This material management recycling of tyres is environmentally more beneficial than the burning of all valuable products, including limonene. Given this recoverability of materials from waste tyres, a comprehensive evaluation was carried out to show the main effect of process conditions (heating rate, temperature, pressure, carrier gas flow rate, and type of volatile residence and process times) for different pyrolytic methods and types of apparatus on the yield of limonene. All the results cited are given in the context of the pyrolysis method and the type of reactor, as well as the experimental conditions in order to avoid contradictions between different researchers. It is shown that secondary and side reactions are very sensitive to interaction with the above-mentioned variables. The yields of all pyrolytic products are also given, as background for limonene, the main product reported in this study.

Post-Pyrolytic Carbon as a Phase Change Materials (PCMs) Carrier for Application in Building Materials.

This article covers new application for char as a carrier of phase-change materials (PCM) that could be used as an additive to building materials. Being composed of bio-char and PCM, the granulate successfully competes with more expensive commercial materials of this type, such as Micronal® PCM. As a PCM carrier, char that was obtained from the pyrolysis of chestnut fruit (Aesculus hippocastanum) with different absorbances of the model phase-change material, Rubitherm RT22, was tested. DSC analysis elucidated several thermal properties (such as enthalpy, phase transition temperature, and temperature peak) of those mixtures and the results were compared with a commercial equivalent, Micronal DS 5040 X. Comparative research, approximating realistic conditions, were also performed by cooling and heating samples in a form of coatings that were made from chars with different content of RT22. These results indicated that the use of char as a PCM carrier was not only possible, but also beneficial from a thermodynamic point of view and it could serve as an alternative to commercial products. In this case, adsorption RT22 into char allowed for temperature stabilization comparable to Micronal DS 5040 X with ease of use as well as the economic advantages of being very low cost to produce due to microencapsulation. Other advantage of the proposed solution is related with the application of char obtained from waste biomass pyrolysis as a PCM carrier, and using this product in building construction to improve thermal comfort and increase energy efficiency.