Natural waste materials containing chitin as adsorbents for textile dyestuffs: batch and continuous studies

In this work three natural waste materials containing chitin were used as adsorbents for textile dyestuffs, namely the Anodonta (Anodonta cygnea) shell, the Sepia (Sepia officinalis) and the Squid (Loligo vulgaris) pens. The selected dyestuffs were the Cibacron green T3G-E (CI reactive green 12), and the Solophenyl green BLE 155% (CI direct green 26), both from CIBA, commonly used in cellulosic fibres dyeing, the most used fibres in the textile industry. Batch equilibrium studies showed that the materials’ adsorption capacities increase after a simple and inexpensive chemical treatment, which increases their porosity and chitin relative content. Kinetic studies suggested the existence of a high internal resistance in both systems. Fixed bed column experiments performed showed an improvement in adsorbents’ behaviour after chemical treatment. However, in the column experiments, the biodegradation was the main mechanism of dyestuff removal, allowing the materials’ bioregeneration. The adsorption was strongly reduced by the pore clogging effect of the biomass. The deproteinised Squid pen (grain size 0.500–1.41 mm) is the adsorbent with highest adsorption capacity (0.27 and 0.037 g/g, respectively, for the reactive and direct dyestuffs, at 20ºC), followed by the demineralised Sepia pen and Anodonta shell, behaving like pure chitin in all experiments, but showing inferior performances than the granular activated carbon tested in the column experiments.

Mix design process of polyester polymer mortars modified with recycled GFRP waste materials

In this study, the effect of incorporation of recycled glass fibre reinforced plastics (GFRP) waste materials, obtained by means of shredding and milling processes, on mechanical behaviour of polyester polymer mortars (PM) was assessed. For this purpose, different contents of GFRP recyclates, between 4% up to 12% in weight, were incorporated into polyester PM materials as sand aggregates and filler replacements. The effect of the addition of a silane coupling agent to resin binder was also evaluated. Applied waste material was proceeding from the shredding of the leftovers resultant from the cutting and assembly processes of GFRP pultrusion profiles. Currently, these leftovers as well as non-conform products and scrap resulting from pultrusion manufacturing process are landfilled, with additional costs to producers and suppliers. Hence, besides the evident environmental benefits, a viable and feasible solution for these wastes would also conduct to significant economic advantages. Design of experiments and data treatment were accomplish by means of full factorial design approach and analysis of variance ANOVA. Experimental results were promising toward the recyclability of GFRP waste materials as partial replacement of aggregates and reinforcement for PM materials, with significant improvements on mechanical properties of resultant mortars with regards to waste-free formulations.

Mechanical behaviour analysis of polyester polymer mortars modified with recycled GFRP waste materials

In this study the effect of incorporation of recycled glass-fibre reinforced polymer (GFRP) waste materials, obtained by means of milling processes, on mechanical behaviour of polyester polymer mortars was assessed. For this purpose, different contents of recycled GFRP waste powder and fibres, with distinct size gradings, were incorporated into polyester based mortars as sand aggregates and filler replacements. Flexural and compressive loading capacities were evaluated and found better than unmodified polymer mortars. GFRP modified polyester based mortars also show a less brittle behaviour, with retention of some loading capacity after peak load. Obtained results highlight the high potential of recycled GFRP waste materials as efficient and sustainable reinforcement and admixture for polymer concrete and mortars composites, constituting an emergent waste management solution.

Recycled asphalt mixtures produced with high percentage of different waste materials

The use of sustainable solutions in construction is not just an option, but is increasingly becoming a need of the Society. Thus, nowadays the recycling of waste materials is a growing technology that needs to be continuously improved, namely by researching new solutions for waste valorisation and by increasing the amount of wastes reused. In the paving industry, the reuse of reclaimed asphalt (RA) is becoming common practice, but needs further research work. Thus, this study aims to increase the incorporation of RA and other waste materials in the production of recycled asphalt mixtures in order to improve their mechanical, environmental and economic performance. Recycled mixtures with 50% RA were analysed in this study, including: i) RA selection, preparation and characterization; ii) incorporation of other waste materials as binder additives or modifiers, like used motor oil (UMO) and waste high density polyethylene (HDPE); iii) production of different mixtures (without additives; with UMO; with UMO and HDPE) and comparison of their performance in order to assess the main advantages of each solution. With this study it was concluded that up to 7.5 % of UMO and 4.0 % of HDPE can be used in a new modified binder for asphalt mixtures with 50 % of RA, which have excellent properties concerning the rutting with WTS = 0.02 mm/103 cycles, the fatigue resistance with ε6 = 160.4, and water sensitivity with an ITSR of 81.9 %.

Utilization of waste materials to improve asphalt mixtures performance

This study aims to develop an innovative bitumen with large quantities of waste materials to improve asphalt mixtures performance. Different amounts of waste motor oil and waste HDPE were added to a new bitumen. The bitumen modified with 10% of waste motor oil and 5% of HDPE showed promising characteristics (high softening point temperatures and penetration slightly higher than the conventional bitumen). After the selection of the most promising modified bitumen, three asphalt mixtures were produced with different bitumens (namely conventional bitumen, commercial modified bitumen and the selected modified bitumen). Beyond that, this modified bitumen improved some mechanical characteristics of the asphalt mixture where it was used, in comparison to conventional and modified asphalt mixtures.

Effect of incorporating different waste materials in bitumen

The increasing environmental concern about waste materials and the necessity of improving the performance of asphalt mixtures prompted the study of incorporating different waste materials in conventional bitumen. The reuse of waste materials can present benefits at an environmental and economic level, and some wastes can be used to improve the pavement performance. Thus, the purpose of this study is to evaluate the incorporation of different waste materials in bitumen, namely waste motor oil and different polymers. In order to accomplish this goal, 10% of waste motor oil and 5% of polymers (high density polyethylene, crumb rubber and styrene-butadiene-styrene) were added to a conventional bitumen and the resulting modified bitumens were characterized through basic and rheological tests. From this work, it can be concluded that the incorporation of different waste materials improve some important properties of the conventional bitumen. Such improvements might indicate a good behaviour at medium/high temperatures and an increase of fatigue and rutting resistance. Therefore, these modified bitumens with waste materials can contribute to a sustainable development of road paving industry due to their performance and environmental advantages.

Utilization of steelmaking waste materials for production of calcium carbonate (CaCO3)

The steel industry produces, besides steel, also solid mineral by-products or slags, while it emits large quantities of carbon dioxide (CO2). Slags consist of various silicates and oxides which are formed in chemical reactions between the iron ore and the fluxing agents during the high temperature processing at the steel plant. Currently, these materials are recycled in the ironmaking processes, used as aggregates in construction, or landfilled as waste. The utilization rate of the steel slags can be increased by selectively extracting components from the mineral matrix. As an example, aqueous solutions of ammonium salts such as ammonium acetate, chloride and nitrate extract calcium quite selectively already at ambient temperature and pressure conditions. After the residual solids have been separated from the solution, calcium carbonate can be precipitated by feeding a CO2 flow through the solution. Precipitated calcium carbonate (PCC) is used in different applications as a filler material. Its largest consumer is the papermaking industry, which utilizes PCC because it enhances the optical properties of paper at a relatively low cost. Traditionally, PCC is manufactured from limestone, which is first calcined to calcium oxide, then slaked with water to calcium hydroxide and finally carbonated to PCC. This process emits large amounts of CO2, mainly because of the energy-intensive calcination step. This thesis presents research work on the scale-up of the above-mentioned ammonium salt based calcium extraction and carbonation method, named Slag2PCC. Extending the scope of the earlier studies, it is now shown that the parameters which mainly affect the calcium utilization efficiency are the solid-to-liquid ratio of steel slag and the ammonium salt solvent solution during extraction, the mean diameter of the slag particles, and the slag composition, especially the fractions of total calcium, silicon, vanadium and iron as well as the fraction of free calcium oxide. Regarding extraction kinetics, slag particle size, solid-to-liquid ratio and molar concentration of the solvent solution have the largest effect on the reaction rate. Solvent solution concentrations above 1 mol/L NH4Cl cause leaching of other elements besides calcium. Some of these such as iron and manganese result in solution coloring, which can be disadvantageous for the quality of the PCC product. Based on chemical composition analysis of the produced PCC samples, however, the product quality is mainly similar as in commercial products. Increasing the novelty of the work, other important parameters related to assessment of the PCC quality, such as particle size distribution and crystal morphology are studied as well. As in traditional PCC precipitation process, the ratio of calcium and carbonate ions controls the particle shape; a higher value for [Ca2+]/[CO32-] prefers precipitation of calcite polymorph, while vaterite forms when carbon species are present in excess. The third main polymorph, aragonite, is only formed at elevated temperatures, above 40-50 °C. In general, longer precipitation times cause transformation of vaterite to calcite or aragonite, but also result in particle agglomeration. The chemical equilibrium of ammonium and calcium ions and dissolved ammonia controlling the solution pH affects the particle sizes, too. Initial pH of 12-13 during the carbonation favors nonagglomerated particles with a diameter of 1 μm and smaller, while pH values of 9-10 generate more agglomerates of 10-20 μm. As a part of the research work, these findings are implemented in demonstrationscale experimental process setups. For the first time, the Slag2PCC technology is tested in scale of ~70 liters instead of laboratory scale only. Additionally, design of a setup of several hundreds of liters is discussed. For these purposes various process units such as inclined settlers and filters for solids separation, pumps and stirrers for material transfer and mixing as well as gas feeding equipment are dimensioned and developed. Overall emissions reduction of the current industrial processes and good product quality as the main targets, based on the performed partial life cycle assessment (LCA), it is most beneficial to utilize low concentration ammonium salt solutions for the Slag2PCC process. In this manner the post-treatment of the products does not require extensive use of washing and drying equipment, otherwise increasing the CO2 emissions of the process. The low solvent concentration Slag2PCC process causes negative CO2 emissions; thus, it can be seen as a carbon capture and utilization (CCU) method, which actually reduces the anthropogenic CO2 emissions compared to the alternative of not using the technology. Even if the amount of steel slag is too small for any substantial mitigation of global warming, the process can have both financial and environmental significance for individual steel manufacturers as a means to reduce the amounts of emitted CO2 and landfilled steel slag. Alternatively, it is possible to introduce the carbon dioxide directly into the mixture of steel slag and ammonium salt solution. The process would generate a 60-75% pure calcium carbonate mixture, the remaining 25-40% consisting of the residual steel slag. This calcium-rich material could be re-used in ironmaking as a fluxing agent instead of natural limestone. Even though this process option would require less process equipment compared to the Slag2PCC process, it still needs further studies regarding the practical usefulness of the products. Nevertheless, compared to several other CO2 emission reduction methods studied around the world, the within this thesis developed and studied processes have the advantage of existing markets for the produced materials, thus giving also a financial incentive for applying the technology in practice.

Organic contaminant content and physico-chemical characteristics of waste materials recycled in agriculture

A range of wastes representative of materials currently applied, or with future potential to be applied, to agricultural land in the UK as fertilisers and soil improvers or used as animal bedding in livestock production, were investigated. In addition to full physico-chemical characterization, the materials were analysed for a suite of priority organic contaminants. In general, contaminants were present at relatively low concentrations. For example, polychlorinated dibenzo-p-dioxins/dibenzofurans and polychlorinated biphenyls in biosolids and compost-like-outputs (CLOs) were, in most cases, between 5-50 times lower than proposed and implemented European limit values for biosolids or composts applied to agricultural land. However, the technical basis for these limits may need to be re-evaluated. Polybrominated, and mixed halogenated, dibenzo-p-dioxins/dibenzofurans are not currently considered in risk assessments of dioxins and dioxin-like chemicals, but were detected in the biosolids and compost-like-outputs and their potential contribution to the overall toxic equivalency will be assessed. Other, ‘emerging’ contaminants such as perfluoralkyl compounds (PFCs) and organophosphate flame retardants were detected in several of the waste materials, and their potential significance is discussed. The study is part of a wider research programme that will provide evidence to improve confidence in the use of waste-derived materials in agriculture and establish guidelines to protect the food chain where necessary.

From coffee industry waste materials to skin-friendly products with improved skin fat levels

Spent coffee grounds (SCG), which are the residue obtained from the treatment of coffee with hot water or steam, can be used for industrial applications, due to the high content in lipids. The cosmetic products might be a suitable application for these types of residues because the barrier properties of the stratum corneum (SC) are largely dependent on the intactness of the lipid lamellae that surrounds the corneocytes. The purpose of this work was to assess the feasibility of using the lipid fraction of SCG extracted with supercritical carbon dioxide in the development of new cosmetic formulations with improved skin lipids (sebum) and hydration. The use of spent coffee lipid extract in cosmetic industry seems to be a suitable approach to recycle the wastes from coffee industry. Emulsion containing 10% of the lipid fraction of SCG (SpentCofOil cream) presented promising characteristics in the improvement of sebum skin levels with a good acceptance by consumers when compared to an emulsion containing 10% w/w of green coffee oil (GreenCofOil cream) and a placebo without coffee oil (NoCofOil cream). Practical applications: In this work, the authors develop and characterize a cream containing 10% of the lipid fraction of SCG extracted with supercritical carbon dioxide with improved skin lipids (sebum) and hydration. © 2013 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

Rice husk derived waste materials as partial cement replacement in lightweight concrete

In this study rice husk ash (RHA) and broiler bed ash from rice husk (BBA), two agricultural waste materials, have been assessed for use as partial cement replacement materials for application in lightweight concrete. Physical and chemical characteristics of RHA and BBA were first analyzed. Three similar types of lightweight concrete were produced, a control type in which the binder was just CEMI cement (CTL) and two other types with 10% cement replacement with, respectively, RHA and BBA. All types of similar lightweight concrete were prepared to present the same workability by adjusting the amount of superplasticizer. Properties of concrete investigated were compressive and flexural strength at different ages, absorption by capillarity, resistivity and resistance to chloride ion penetration (CTH method) and accelerated carbonation. Test results obtained for 10% cement replacement level in lightweight concrete indicate that although the addition of BBA conducted to lower performance in terms of the degradation indicative tests, RHA led to the enhancement of mechanical properties, especially early strength and also fast ageing related results, further contributing to sustainable construction with energy saver lightweight concrete.

Rice husk derived waste materials as partial cement replacement in lightweight concrete

In this study rice husk ash (RHA) and broiler bed ash from rice husk (BBA), two agricultural waste materials, have been assessed for use as partial cement replacement materials for application in lightweight concrete. Physical and chemical characteristics of RHA and BBA were first analyzed. Three similar types of lightweight concrete were produced, a control type in which the binder was just CEMI cement (CTL) and two other types with 10% cement replacement with, respectively, RHA and BBA. All types of similar lightweight concrete were prepared to present the same workability by adjusting the amount of superplasticizer. Properties of concrete investigated were compressive and flexural strength at different ages, absorption by capillarity, resistivity and resistance to chloride ion penetration (CTH method) and accelerated carbonation. Test results obtained for 10% cement replacement level in lightweight concrete indicate that although the addition of BBA conducted to lower performance in terms of the degradation indicative tests, RHA led to the enhancement of mechanical properties, especially early strength and also fast ageing related results, further contributing to sustainable construction with energy saver lightweight concrete.

Rhizopus arrhizus - a producer for simultaneous saccharification and fermentation of starch waste materials to L(+)-lactic acid

Rhizopus arrhizus, strain DAR 36017, produced L(+)-lactic acid in a simultaneous saccharification and fermentation process using starch waste effluents. Lactic acid at 19.5 - 44.3 g l(-1) with a yield of 0.85 - 0.96 g g(-1) was produced in 40 h using 20 - 60 g starch l(-1). Supplementation of nitrogen source may be unnecessary if potato or corn starch waste effluent was used as a production medium.