Phosphorus recovery from municipal solid waste digestate aiming at its valorization as a fertilizer

1.º Encontro de doutorandos e pós-doutorados do CERNAS, realizado na Escola Superior Agrária do Politécnico de Coimbra (ESAC-IPC), a 8 julho 2022.O fósforo (P) é um nutriente essencial para o desenvolvimento das plantas e a produção de alimento. É um dos principais constituintes dos fertilizantes e até ao momento ainda não foi encontrado nenhum outro elemento que o possa substituir. O P é obtido principalmente da rocha fosfatada, que é um recurso não renovável. Isto suscita uma questão fundamental sobre como garantir um fornecimento contínuo de P para a produção de fertilizantes fosfatados necessários para produzir alimento para a humanidade, no futuro. Portanto, é de extrema importância promover a circularidade do P por meio da sua reciclagem e da recuperação a partir de fluxos de resíduos. O presente trabalho foi desenvolvido no âmbito de uma tese de doutoramento em que, pela primeira vez, foi explorada a extração de P do digestato de RU utilizando o processo electrodialítico (ED) combinado com a precipitação de estruvite. Este trabalho foi realizado em três etapas: i) extração de P do digestato utilizando o processo electrodialítco; ii) síntese de um biofertilizante – a estruvite secundária, utilizando o processo de precipitação química e, iii) avaliação agronómica da estruvite secundária produzida. Os resultados mostraram que cerca de 90% do P que está presente no digestato de RU pode efetivamente ser extraído através do processo ED e convertido em estruvite secundária. Esta estruvite secundária apresentou uma elevada qualidade, mesmo quando durante a sua precipitação foram utilizados materiais alternativos em vez de materiais sintéticos. Neste trabalho verificou-se também que a utilização desta estruvite secundária como biofertilizante é semelhante à de um fertilizante sintético comercial. Este biofertilizante livre de contaminantes, produzido à escala de laboratório, amplia assim as possibilidades para a reciclagem do P em larga escala e para a implementação de estratégias eficientes para fechar o ciclo do nutriente P, contribuindo assim para uma gestão mais sustentável dos recursos.Phosphorus (P) is a vital nutrient for plant development and food production. It is a key fertilizer constituent and no feasible substitute has been found yet. P is mainly obtained from phosphate rock, which is a non-renewable resource. This raises the critical issue of ensuring a continuous supply of P-fertilizers to feed mankind in the future. Therefore, it is of utmost importance to promote the circularity of P by recycling and recovering P from waste streams. The presente research was developed during a PhD thesis, in which the extraction of P from MSW digestate using the electrodialytic (ED) process combined with struvite formation was explored for the first time. This work was carried out in three stages: i) extraction of P from the digestate using the electrodialytic process; ii) synthesis of a biofertilizer – secondary struvite, using chemical precipitation process and, iii) agronomic evaluation of the produced secondary struvite. The research findings show that up to 90% of P present in MSW digestate could be extracted using ED and converted to secondary struvite. This secondary struvite produced in this work using P recovered from MSW digestate proved to be of high quality, even when alternative materials were used instead of synthetic ones during its precipitation. Also, it was verified that Its action as an effective P biofertilizer is similar to that of a commercial synthetic fertilizer. This contaminant-free biofertilizer, produced at lab scale, widens the possibilities for the large scale recycling of P and for the implementation of efficient strategies to close P-nutrient cycling, thus contributing to a more sustainable resource management.info:eu-repo/semantics/publishedVersio

Glasses and glass-ceramics of the system CaO-MgO-Al2O3-SiO2 obtained from natural sedimentary raw materials

Common and low-cost natural sedimentary raw materials such as ball clay, dolomite, quartz sand and diatomite were used as the main constituents for the production of glasses and glass-ceramics of the system CaO-MgO-Al2O3-SiO2. The crystallization of the glassy batch was promoted by the addition of a nucleation agent (TiO2). The crystallization sequence was examined by DTA, XRD, SEM, and thermal expansion analyses. Wollastonite and diopside are the main phases detected and the amount and grain size/shape of crystals were found to be strongly dependent on titania additions and on the annealing conditions. The characterization of relevant functional parameters of glass and glass-ceramic samples revealed interesting results

In situ degradation of YSZ and YSZ + Al2O3 electrolytes of sensors used in glass melting furnaces

This work reports on the degradation of pure YSZ and YSZ +10 wt% alumina composite electrolytes by exposure to the atmosphere of a heat recovery chamber of an industrial glass furnace, at a temperature around 1300 °C. Microstructural observations and impedance spectroscopy measurements were used to evaluate the corrosion effects. YSZ samples directly placed in the sidewalls and intimately exposed to the dusts and volatiles in the atmosphere show strong corrosion effects after short periods. These samples present large amounts of a glassy phase in the intergranular region, containing the same elements as the common batch with inclusion of volatile species from the fuel. At the same time, the average composition of YSZ grains remains almost unchanged. Effects on the electrical properties are obviously stronger in the intergranular response, as confirmed by changes in the typical relaxation frequency. The protection of samples and/or their careful placement in the furnace strongly inhibit the corrosion process. The effectiveness of alumina addition to the YSZ electrolyte in increasing its corrosion resistance was only tested in protected samples, where the corrosion is less severe. For this reason, the expected benefits of this incorporation were found almost irrelevant

Innovative application for bauxite residue: red mud-based inorganic polymer spheres as pH regulators

In this study, and for the first time, red mud (RM)-based geopolymer spheres were synthesised, with varying porosity and RM content, and then their use as pH regulators was evaluated. The aluminosilicate sources of these inorganic polymers were 100% waste-based, consisting of a mixture of RM and fly ash wastes. Geopolymer spheres containing up to 60 wt.% RM were successfully produced, while higher RM contents distorted the specimens' spherical shape. Results showed that alkalis leaching from the spheres over time can be controlled by their porosity, while the RM content induces only minor changes to leaching. The RM-based spheres leached up to 0.0237 mol/dm3g of OH- ions from their structure, this being among the highest values ever reported for geopolymers. This allowed a continuous and prolonged pH buffer capacity with narrow pH decay over the 28 days (2.4 pH units), suggesting the use of the RM-based spheres as pH buffering materials in wastewater treatment and anaerobic digestion systems.publishe

Role of the mixing conditions and composition of galvanic sludges on the inertization process in clay-based ceramics

Hydroxide-metal sludges from electroplating industry are a potential source of environmental contamination due to their high content of heavy metals. The incorporation of these residues in a ceramic matrix can be a promising way to suppress the harmful effect of metals normally present in those sludges. This work reports the role of the mixing time between the waste and ceramic materials and of the calcination step on the fixing level of several metal-containing species (Al, Zn, Ni, Fe, Ca, Cu, Cr) after sequential leaching in different media (aqueous, acetate and citrate). A strong and/or long mixing process will promote the deagglomeration of the coarser agglomerates and then will increase the reactivity of remaining grains towards the ceramic material during the calcination. As a consequence, inertization is improved for fired samples. With non-calcined samples leaching increases as a result of increasing dispersability/availability of species

Effect of experimental variables on the inertization of galvanic sluges in clay-based ceramics

The incorporation of several industrial wastes in ceramic matrixes had been attempted as an effective low expense technique for the fixation of metallic species in usable products or simply to reduce the residue volume for further disposal. However, the dominant mechanism of the inertization process and the relevant influent parameters are still unknown, mostly due to the complexity of the systems. This work reports the effect of several processing parameters such as the mixing time, the calcination temperature and duration, the relative amount of sludge, and the physical aspect of the sample (powdered or pressed pellets) on the fixing level of relevant species (SiO2, SO4 2−, Zn, Ni, Ca, Cu, Cr) by leaching in different media (aqueous, acetate, and citrate). Statistical tools were used to define the relevance of each experimental variable on the inertization process of the used galvanic sludge. The relative amount of sludge in the mixture, the calcination temperature and the agglomeration state of the sample were found to be the most influent parameters of the inertization process. The incipient reaction between sludge and ceramic matrix components points out for the dominance of a macro- encapsulation mechanism

Physical and chemical characterisation of metal finishing industrial wastes

In EU countries approximately 150,000 ons/year of galvanic sludges are generated by 4000 industrial units from the orresponding wastewater treatment plants. These sludges are generally classified as hazardous (European Waste Catalogue as adopted in Council Decision 2000/532/CE and as amended by Decisions 2001/118/EC, 2001/119/EC and 2001/573/CE), basically due to the presence of heavy metals. This work attempts to better understand the physical and chemical characteristics of these sludges, by studying 39 samples collected in different Portuguese industries that should represent all kinds of similar wastes independent of their place of generation. Chemical composition and leaching characteristics are given, together with density, grain size distribution, and specific surface area values. Statistical analysis was used for grouping the wastes according to chemical parameters, which might be useful to predict potential reuse as raw materials for different applications

In-depth investigation of the long-term strength and leaching behaviour of inorganic polymer mortars containing green liquor dregs

Green liquor dregs are the most challenging waste stream coming from the pulp and paper industry. Despite tremendous efforts, there are not currently any viable recycling alternatives for this massively produced waste (2 Mt/year), which inevitably ends up in landfills. Urgent actions must be undertaken to tackle this. In this work, a substantial amount of dregs was incorporated into eco-friendly, waste-based inorganic polymer (geopolymer) mortars as fine filler. Then, and for the first time, the long-term strength performance (up to 270 days) and heavy metals leaching behaviour of the dregs-containing mortars was evaluated. The effect of the mixture composition and dregs incorporation content on the fresh- and hardened-state properties of the mortars was also studied. Dregs were found to increase the initial and final setting time of the slurries, thus extending the open time before their in-situ application. The use of dregs as fine filler effectively enhances the compressive strength of the mortars, and decreases their water absorption levels. These eco-friendly building materials showed excellent long-term performance, as their strength continuously increases up to the 270th day (after mixture), and no signs of efflorescence formation were detected. Moreover, the heavy metals leaching levels of the mortars were well below the contamination limits in soil, which demonstrates the feasibility of this recycling methodology.publishe

Leaching behaviour of a galvanic sludge in sulphuric acid and ammoniacal media

Leaching studies of a sludge produced by the physico-chemical treatment of astewaters generated by a Ni/Cr plating plant were carried out in both sulphuric acid and ammoniacal media aiming to decide which of them would be the best treatment for this kind of waste material. The dissolution behaviour of some metals (Cu, Ni, Cr and Zn) was studied in order to assure the best metal recovery conditions in subsequent processes by the use of some separation methods such as solvent extraction and precipitation techniques. Therefore, the study here presented deals with the first chemical stage of an integrated treatment process. For the sulphuric acid leaching, maximal conversions obtained were 88.6% Cu, 98.0% Ni and 99.2% Zn for the following experimental conditions: a 100 g L−1 acid concentration, a 5:1 liquid-to-solid ratio (L/S), a particle size less than 1 mm, a digestion time of 1 h, a stirring speed of 700 rpm (all at room temperature and under atmospheric pressure). As expected, no selectivity was achieved for the sulphuric acid leaching, despite this option yielding much higher metal ion dissolution when compared with that reached by ammoniacal leaching. The use of this latter medium allowed the extraction of Cu and Ni without Cr species, but rates of conversion were only about 70% for Cu and 50% for Ni, much lower than those obtained for sulphuric acid leaching

Synthesis of red mud derived M-type barium hexaferrites with tuneable coercivity

Hexagonal ferrites can be employed in a multitude of applications, the most common hexaferrites are the M ferrites such as BaFe12O19 (barium hexaferrite, BaM). It is known that if Fe3+ is substituted with a combination of Ti4+/Co2+ the coercivity of BaM can be reduced to produce soft M ferrites with easily switchable magnetisation. They can be utilised as powders, films or bulk ceramics, and can be manufactured from a wide variety of synthesis methods. The production of hexaferrites usually requires commercial raw materials, but if an industrial waste can be utilised, this will help to ease waste disposal and storage costs, valorise a waste material and encourage circular economy. In this study, bauxite residue (red mud) from the production of alumina was used to synthesise M-type hexaferrites, using a simple ceramic process. BaCO3, or BaCO3+Co3O4, were added to the red mud, blended and heated at 1000 °C to produce the M-type hexaferrites. Without cobalt addition up to 81.1 wt% M ferrite was produced, and with Co addition up to 74.3 wt% M ferrite was formed. Without cobalt, the M ferrite phase closely resembled BaFe9Al3O19, and was a hard ferrite with a magnetisation of 12–19 A m2/kg for the whole powder (up to 23.6 A m2/kg for the M ferrite phase) and a coercivity of ~290 kA/m. When cobalt was added, secondary titanate phases vanished, and Ti4+/Co2+ partially substituted very soft M ferrite was formed with a low coercivity of ~16 kA/m but a higher magnetisation of 24.5 A m2/kg for the whole powder (up to 34.9 A m2/kg for the M ferrite phase). Therefore, not only can good quality magnetic materials be easily produced from this common waste material, but its magnetic properties can be tuned by varying the 2 + ions added during the process.publishe