Recovery of Cerium Salts from Sewage Sludge Resulting from the Coagulation of Brewery Wastewater with Recycled Cerium Coagulant.

Due to the high cost and limited sources of cerium coagulants, it is extremely important to take measures to recycle this raw material. This paper presents the new possibility of recovering cerium(III) chloride, cerium(III) sulphate, cerium(IV) sulphate, and potentially phosphate from sewage sludge (101.5 g/kg Ce and 22.2 g/kg total P) through a brewery wastewater treatment process using recycled CeCl3 as a coagulant. In order to recover the Ce and P, the sludge was subjected to extraction using an HCl solution. Optimal process conditions were determined by means of central composite design and response surface methodology (CCD/RSM) for three input parameters (HCl mass, reaction time, and extractant volume). Under optimal conditions (0.35 g HCl per 1 g of sludge, 40 min reaction time, extractant volume of 25 mL per 1 g of sludge), the highest efficiency obtained was 99.6% and 97.5% for Ce and P, respectively. Cerium(III) oxalate as Ce2(C2O4)3∙10H2O was precipitated from the obtained solution using H2C2O4 (99.97%) and decomposed into CeO2 (at 350 °C), which was afterwards subjected to a reaction with HCl (30%, m/m) and H2O2 (30%, m/m), which led to the crystallisation of CeCl3∙7H2O with a purity of 98.6% and a yield of 97.0%. The obtained CeO2 was also subjected to a reaction with H2SO4 (96%, m/m) and H2O2 (30%, m/m), which produced Ce2(SO4)3 with a yield of 97.4%. The CeO2 was also subjected to a reaction with only H2SO4 (96%, m/m), which produced Ce(SO4)2 with a yield of 98.3%. The filtrate obtained after filtering the Ce2(C2O4)3∙10H2O contained 570 mg/L of P, which enabled its use as a source of phosphorus compounds. The presented processes of Ce and potentially P recovery from sewage sludge originating from brewery wastewater contribute to the idea of a circular economy.

Removal of phosphate from brewery wastewater by cerium(III) chloride originating from spent polishing agent: Recovery and optimization studies.

This paper presents the possibility of using hydrated cerium(III) chloride (CeCl3∙7H2O) recovered from a spent polishing agent containing cerium(IV) dioxide (CeO2) to remove phosphate and other impurities from brewery wastewater (phosphate 43.0 mg/L, total P 19.8 mg/L, pH 7.5, COD(Cr) 827 mg O2/L, TSS 630 mg/L, TOC 130 mg/L, total N 46 mg/L, turbidity 390 NTU, colour 170 mg Pt/L. CCD (Central Composite Design) and RSM (Response Surface Methodology) were applied to optimise the brewery wastewater treatment process. The removal efficiency (mainly of PO43-) was the highest under optimal conditions (pH 7.0-8.5, Ce3+:PO43- molar ratio of 1.5-2.0). Applying recovered CeCl3 under optimal conditions yielded a treated effluent in which the concentration of PO43- decreased by 99.86 %, total P by 99.56 %, COD(Cr) by 81.86 %, TSS by 96.67 %, TOC by 60.38 %, total N by 19.24 %, turbidity by 98.18 %, and colour by 70.59 %. The Ce3+ ion concentration in the treated effluent was 0.058 mg/L. These findings suggest that CeCl3‧7H2O recovered from the spent polishing agent may constitute an optional reagent for phosphate removal from brewery wastewater. The sludge from wastewater treatment can be recycled for Ce and P recovery. The recovered cerium can be reused for wastewater treatment, creating a cyclic cerium cycle in the process, and the recovered phosphorus can be used, for example, for fertilization purposes. The optimised cerium recovery and application is in accordance with the ideas of circular economy.

Ash from Poultry Manure Incineration as a Substitute for Phosphorus Fertiliser.

The goal of the tests was to separate a phosphate concentrate from ash and to assess its fertiliser use efficiency in anthropogenic land. Ash obtained from poultry manure incineration is an interesting fertiliser, as it contains both of the necessary nutrients, i.e., phosphorus and potassium. The ash selected for the tests contained 15.73 wt% P2O5, and 6.75 wt% K2O. CaO also constituted the main component (44.79 wt%). Phosphorus in crystalline form was present as hydroxyapatite and carbonate apatite. The first stage, applied in order to separate a phosphate concentrate from ash, involved a number of physicochemical methods: (i) a method based on grain wettability differences; (ii) a method based on grain density differences; and (iii) methods based on size distribution differences. Wet sieving made it possible to separate a fraction with a P2O5 content of 24.56 wt%. The second stage, applied to assess fertiliser use efficiency, involved cassette tests as well as pot and field cultivation using as fertiliser, the obtained product as well as raw ash and commercial ones. Therefore, the conducted research allowed for the development of a methodology for the management of ash from the incineration of a poultry manure and their use as a substitute for phosphorus fertiliser. The tested material was applied in various doses. Using the obtained phosphate concentrate at a dose of 95 g/m3 resulted in a comparable yield as in the case of the commercial fertiliser at a dose recommended by the producer (75 g/m3). Unprocessed ash had to be used in larger amounts, i.e., 165 g/m3, to have a comparable yield as a commercial fertiliser.

Improving the Properties of Degraded Soils from Industrial Areas by Using Livestock Waste with Calcium Peroxide as a Green Oxidizer.

Over the past years, the treatment and use of livestock waste has posed a significant problem in environmental engineering. This paper outlines a new approach to application of calcium peroxide (CaO2) as a green oxidizer and microbiocidal agent in the treatment of poultry manure. It also presents the application of pretreated waste in improvement of degraded soils in industrial areas. The CCD (Central Composite Design) and RSM (Response Surface Methodology) were employed for optimizing the process parameters (CaO2 concentration 1.6-8.4 wt %, temperature 5.2-38.8 °C and contact time 7-209 h). The analysis of variance (ANOVA) was used to analyze the experimental results, which indicated good fit of the approximated to the experimental data (R2 = 0.8901, R2adj = 0.8168). The amendment of CaO2 in optimal conditions (8 wt % of CaO2, temperature 22 °C and contact time 108 h) caused a decrease in bacteria Escherichia coli (E. coli) in poultry manure from 8.7 log10 CFU/g to the acceptable level of 3 log10 CFU/g. The application of pretreated livestock waste on degraded soils and the studies on germination and growth of grass seed mixture (Lollum perenne-Naki, Lollum perenne-Grilla, Poa pratensis-Oxford, Festuca rubbra-Relevant, Festuca rubbra-Adio and Festuca trachypylla-Fornito) showed that a dose of 0.08 g of CaO2 per 1 gram of poultry manure induced higher yield of grass plants. The calculated indicators for growth of roots (GFR) and shoots (GFS) in soils treated with poultry manure were 10-20% lower compared to soils with amended CaO2. The evidence from this study suggests that CaO2 could be used as an environmentally friendly oxidizer and microbiocidal agent for livestock waste.

Solid Peroxy Compounds as Additives to Organic Waste for Reclamation of Post-Industrial Contaminated Soils.

Solid peroxy compounds have been increasingly applied for the removal of organic pollution from contaminated groundwater and soil due to their ability to release oxygen and hydrogen peroxide. The influence of two solid peroxy compounds (sodium percarbonate, 2Na2CO3·3H2O2 and calcium peroxide, CaO2) with poultry manure (PM) added to contaminated soil on the growth of the tested plants (Sinapis alba, Lepidium sativum L. and Sorghum bicolor L. Moench) and the quality of soil water leachates was investigated. A series of experiments involving the addition of CaO2 and 2Na2CO3·3H2O2 at the dose of 0.075 g/g PM improved the growth of tested plants. The conducted study indicated that the use of peroxy compounds not only removed pathogens from livestock waste, but also improved the quality of plant growth. The calculated factors for the growth of roots (GFR) and growth of shoots (GFS) in soils treated with a mixture of peroxy compounds and PM were higher than in soils treated only with PM. The physicochemical analysis of soil water leachates indicated that solid peroxy compounds may be a promising alternative compared to the currently used hygienizing agent such as calcium hydroxide (Ca(OH)2). Solid peroxy compounds increased the bioavailability of components necessary for proper seed germination and plant growth (N, P, K, Ca, Mg and S). In most of the studied cases, the obtained plant shoot and root growth rates were higher for soil mixtures containing organic waste deactivated by biocidal compounds, compared to soils that contained only poultry manure.

Poultry litter ash characterisation and recovery.

This paper reports a complete characterisation of poultry litter ash and its potential use as a heavy metal stabiliser. We propose a novel approach, in which the ashes deriving from municipal solid waste incineration (MSWI) are combined with poultry litter ash, rather than with coal combustion flue gas desulfurisation (FGD) residues. Heavy metals stabilisation was demonstrated by comparing the elemental concentrations in the leaching solutions of the starting raw and stabilised materials: leachable Pb and Zn showed a reduced solubility. The characterisation was conducted by total reflection X-ray fluorescence (TXRF), X-ray diffraction (XRD), micro-Raman spectroscopy and scanning electron microscopy combined with energy-dispersive X-ray spectrometry (SEM-EDX). The results showed that the poultry litter ash was Ca-, P-, K- and S-rich (>29 g/kg). It contained amorphous materials (i.e. fly ash economiser (FAECO) 73% and fly ash cyclone (FACYC) 61%) and soluble phases (e.g. arkanite and sylvite; up to 13% FAECO and 28% FACYC), as well as resilient crystalline (up to 2% of FAECO and FACYC) and amorphous phases (e.g. hydroxyapatite). After two months, the Pb and Zn concentrations in the leachate solutions were below the limit set by the European regulations for waste disposal (<0.2 mg/L and 1.5 mg/L, respectively). We propose a mechanism for the heavy metals stabilisation based on the carbonation process and high amounts of P, Ca and reactive amorphous phases. In conclusion, it is demonstrated that poultry litter ash can be an effective secondary source of heavy metals, allowing their immobilisation through P- and Ca-based reactive amorphous phases.