Do investments in phosphorus recovery from dairy processing wastewater pay off?

While phosphorus fertilizers contribute to food security, part of the introduced phosphorus dissipates into water bodies leading to eutrophication. At the same time, conventional mineral phosphorus sources are increasingly scarce. Therefore, closing phosphorus cycles reduces pollution while decreasing trade dependence and increasing food security. A major part of the phosphorus loss occurs during food processing. In this article, we combine a systematic literature review with investment and efficiency analysis to investigate the financial feasibility of recovering phosphorus from dairy processing wastewater. This wastewater is particularly rich in phosphorus, but while recovery technologies are readily available, they are rarely adopted. We calculate the Net Present Value (NPV) of investing in phosphorus recycling technology for a representative European dairy processing company producing 100,000 tonnes of milk per year. We develop sensitivity scenarios and adjust the parameters accordingly. Applying struvite precipitation, the NPV can be positive in two scenarios. First, if the phosphorus price is high (1.51 million EUR) or second if phosphorus recovery is a substitute for mandatory waste disposal (1.48 million EUR). However, for a variety of methodological specifications, the NPV is negative, mainly because of high input costs for chemicals and energy. These trade-offs between off-setting pollution and reducing energy consumption imply, that policy makers and investors should consider the energy source for phosphorus recovery carefully.

Hydrothermal carbonization of milk/dairy processing sludge: Fate of plant nutrients.

Dairy processing sludge (DPS) is a byproduct generated in wastewater treatment plants located in dairy (milk) processing companies (waste activated sludge). DPS presents challenges in terms of its management (as biosolids) due to its high moisture content, prolonged storage required, uncontrolled nutrient loss and accumulation of certain substances in soil in the proximity of dairy companies. This study investigates the potential of hydrothermal carbonization (HTC) for recovery of nutrients in the form of solid hydrochar (biochar) produced from DPS originating from four different dairy processing companies. The HTC tests were carried out at 160 °C, 180 °C, 200 °C and 220 °C, and a residence time of 1h. The elemental properties of hydrochars (biochars), the content of primary and secondary nutrients, as well as contaminants were examined. The transformation of phosphorus in DPS during HTC was investigated. The fraction of plant available phosphorus was determined. The properties of hydrochar (biochar) were compared against the European Union Fertilizing Products Regulation. The findings of this study demonstrate that the content of nutrient in hydrochars (biochars) meet the requirements for organo-mineral fertilizer with nitrogen and phosphorus as the declared nutrients (13.9-26.7%). Further research on plant growth and field tests are needed to fully assess the agronomic potential of HTC hydrochar (biochar).

Greenhouse gas emissions and soil properties following amendment with manure-derived biochars: Influence of pyrolysis temperature and feedstock type.

Manure-derived biochars can offer a potential option for the stabilization of manure, while mitigating climate change through carbon sequestration and the attenuation of nitrous oxide emission. A laboratory incubation study was conducted to assess the effects of four different manure-derived biochars produced from different feedstocks (poultry litter and swine manure) at different temperatures (400 or 600 °C). A commonly available standard wood chip biochar, produced at a greater temperature (1000 °C), and non-amended treatments were used as references. Two different soils (sandy and silt-loam) were amended with 2% (w/w) biochar on a dry soil weight basis (corresponding to 20 Mg ha(-1)), with the soil moisture being adjusted to 75% saturation level. After a pre-incubation period (21 days), 170 kg N ha(-1) of NH4NO3 fertilizer was added. Measurements of CO2, N2O, CH4 emissions and soil N mineralisation were carried out on different days during the 85 days of incubation. The net C mineralization and N2O emissions from both soils amended with poultry litter biochar at 400 °C were significantly greater than the other biochar treatments. Nitrate availability was greater in both soils in which the manure-derived biochar was used instead of the standard biochar. All of the biochars increased the pH of the silt-loam, sub-acid soil, but failed to improve the cation exchange capacities (CEC) in either soil. Total C and N, P, K and Mg (except Ca) were significantly increased in the manure-derived biochar amended soils, compared to the Control, and were positively correlated to the biochar nutrient contents. This study indicates that the soil application of biochar engenders effects that can vary considerably according to the biochar properties, as determined on the basis of the feedstock types and process conditions. Low-temperature biochar production from manure represents a possible way of producing a soil amendment that can stabilize C while supplying a significant quantity of nutrients.

Pyrolysis, a recovery solution to reduce landfilling of residual organic waste generated from mixed municipal waste.

Despite policies to restrict the mixing of organic waste with other general waste and improve its separation at source, municipal solid waste still contains a high proportion of organic waste. The residual organic waste is generated as a by-product of the mechanical treatment of municipal solid waste (MSW) and is mainly disposed in landfills after composting. Its reuse and recovery status varies across European countries. Most countries restrict the use of biostabilised residual waste (BSRW) to landfill cover, whereas others have regulated it as marketable compost. Crucially, BSRW is set to lose its "recycled" status under the revised European Union waste framework, with probably tighter restrictions and increased costs imposed for the landfilling of organic waste. Our research aimed to investigate pyrolysis as an alternative technology to treat the 10-40 mm fraction of BSRW (representing 50% of BSRW generated). Pyrolysis at 700 °C was carried out and feedstock and pyrolysis products were characterized. Mass and energy balances showed that pyrolysis produced hot vapour/gas whose combustion may render the pyrolysis process energetically sustainable. Biochar comprises 30-50% of BRSW mass after removal of glass, metal and stones. Our results indicate that pyrolysis has the potential to create options for contributing to reduce the landfilling of BSRW; however, the presence of residual impurities may limit biochar applications.

Effect of sawdust addition on composting of separated raw and anaerobically digested pig manure.

Manures need the addition of carbon-rich bulking agents to conserve N during composting, which increases the cost of the composting process. The recommended proportion of manure/sawdust, based on a carbon (C):nitrogen (N) ratio, is approximately 3:2. Two composting experiments were conducted to determine the impact of varying the proportion of sawdust to either separated raw, or separated anaerobically digested pig manures. To determine stability and maturity of the final compost, oxygen uptake rate (OUR) and germination index (GI) tests were conducted. For both experiments, three treatments were employed: manure-only (Treatment A), manure/sawdust mixed 4:1, fresh weight (Treatment B), and manure/sawdust mixed 3:2, fresh weight (Treatment C). The mixtures were composted in tumblers for 56 days with regular turning. The composting material was tested over the study duration for temperature, pH, water content, organic matter, C:N ratio and bulk density. For both Treatments B and C, the GI indicated low levels of phytotoxicity, and OUR values were lower than the recommended Irish threshold of 13 mmol O(2) kg OM(-1) h(-1), indicating that a high quality compost was produced. The proportion of sawdust to separated manure used can be reduced to make a cost saving, while still producing a stable end-product: 60% less sawdust is required to compost at a manure-to-sawdust ratio of 4:1 compared to the previously recommended ratio of 3:2.

ANN-Kriging hybrid model for predicting carbon and inorganic phosphorus recovery in hydrothermal carbonization.

Modeling of hydrothermal carbonization (HTC) of poultry litter to high-value materials was conducted in order to understand the process and predict the influence of process parameters on product properties. Reaction temperature and time were considered as inputs, whereas carbon and inorganic phosphorous recovery were considered as responses in the model. Artificial neural network (ANN) model was used in order to correlate the process parameters to the outputs. The model was trained and validated using the data collected from HTC experiments carried out at temperatures between 150 ≤ T ≤ 300 °C, and residence time between 30 ≤ t ≤ 480 min. In order to improve the predictability of ANN, more theoretical data points were generated using Kriging approach based on the available measured data. Kriging interpolation improved the ANN model dramatically in training and validation phases, where the carbon recovery model fitting was improved by 0.94% and 9.2% in training and validation respectively, and the inorganic phosphorous (IP) recovery model fitting was improved by a staggering 16.4% and 19.6% in training and validation respectively. This improvement is also reflecting on the derived profiles of carbon and IP recovery in terms of the process parameters. The validated model was then used to understand the effect of process parameters on the response. It was revealed that temperature has more significant effect on the carbon and phosphorous recovery, while the effect of reaction time is more important at low reaction temperatures. The derived profiles shows a monotonic increase in IP recovery and a monotonic decrease in Carbon recovery at higher temperatures and time, this is due to multiple mechanism occurring simultaneously in the HTC reactor at various temperatures and times.

Gasification of poultry litter in a lab-scale bubbling fluidised bed reactor: Impact of process parameters on gasifier performance and special focus on tar evolution.

Poultry litter (PL) gasification was experimentally investigated using a lab-scale bubbling fluidised bed reactor. Characterisation of the gasification process was performed in terms of yields and compositions of both gas and tar, lower calorific value (LCV) of the product gas, cold gas efficiency (CGE) and carbon conversion efficiency (CCE). Experiments were carried out at different temperatures (700-750 °C) and equivalence ratios (ERs). The effect of gasifier temperature at a constant ER of 0.21 shows that an increase in temperature improved the gasification process performance whilst the total tar content decreased, implying that higher temperature enhances the conversion of biomass to product gas. The total gas yield increased from 0.93 to 1.24 N2-free m3/kgfeedstock-daf, LCV increased from 3.38 MJ/m3 to 4.2 MJ/m3, while the tar content was reduced by 24% (5.6-4.25 gtar/kgfeedstock-daf). The detailed analyses of tar compositions reveal that styrene and xylenes were the most abundant compounds in the secondary tar group. Moreover, naphthalene and 1, 2-methyl naphthalene were the dominant compounds found in tertiary polycyclic aromatic hydrocarbons (PAH) and alkyl tertiary groups, respectively. Furthermore, at the highest tested temperature of 750 °C and ER of 0.25, bed agglomeration took place causing the shutdown of the gasifier. The defluidisation of the bed occurred due to the high ash content of PL comprising of low melting temperature alkali compounds. The results obtained from this study showed the performance and potential challenges associated with gasifying PL in a fluidised bed reactor for the combined heat and power production at farm level.

Tar yield and composition from poultry litter gasification in a fluidised bed reactor: effects of equivalence ratio, temperature and limestone addition.

Air gasification of poultry litter was experimentally investigated in a laboratory scale bubbling fluidised bed gasifier. Gasification tests were conducted at atmospheric pressure using silica sand as the bed material. This paper examines the effect of the equivalence ratio (ER) in the range of 0.18-0.41, temperature between 700 and 800 °C, and the addition of limestone blended with the poultry litter on the yield and composition of tar. An off-line solid phase adsorption method was employed in order to quantify tar compounds heavier than styrene, whereas lighter species such as benzene and toluene were measured by means of on-line micro gas chromatography. Total tar yields were in the range from 15.7 to 30.7 gtotal tar kgpoultry litter (dry and ash free basis) -1. These values are considered low with respect to the feedstocks with a higher organic fraction. It also needs to be noted that the yields of benzene and toluene were measured by on-line micro gas chromatography, a technique which inherently delivers higher tar values compared to commonly employed off-line techniques. By varying the ER, poultry litter blended with limestone showed a reduction in total tar yield whereas poultry litter on its own showed an increasing tar yield over the ER range tested. In the presence of limestone, polycyclic aromatic hydrocarbons (PAHs), heterocyclic compounds, toluene and benzene showed a tendency to reduce over the ER range tested. Since the ER also plays a crucial role in tar reduction, the reduction in tar cannot be unambiguously attributed to calcined limestone/lime (CaCO3/CaO). Increasing the temperature was shown to be effective for reducing the total tar yield but the amounts of polycyclic aromatic hydrocarbons increased. However, no definitive correlation could be established between limestone/lime catalytic activity for tar reduction and elevated gasification temperature, because there was no possibility to study their effects separately. The chemical composition of the tar arising from poultry litter is distinctive compared with conventional lignocellulosic fuels linked to the fact that poultry litter has a higher nitrogen content (≈6.5% w/w (dry and ash free basis)). Nitrogen-containing hydrocarbons such as pyridine, 2-methylpyridine, 2-methyl-1H-pyrrole and benzonitrile were identified in significant amounts. This study has demonstrated that poultry litter gasified in a bubbling fluidised bed yielded a product gas with relatively low tar content while its composition reflects the chemical nature of the feedstock.

Pyrolysis of wastewater sludge and composted organic fines from municipal solid waste: laboratory reactor characterisation and product distribution.

Sludge from municipal wastewater treatment plants and organic fines from mechanical sorting of municipal solid waste (MSW) are two common widespread waste streams that are becoming increasingly difficult to utilise. Changing perceptions of risk in food production has limited the appeal of sludge use on agricultural land, and outlets via landfilling are diminishing rapidly. These factors have led to interest in thermal conversion technologies whose aim is to recover energy and nutrients from waste while reducing health and environmental risks associated with material re-use. Pyrolysis yields three output products: solid char, liquid oils and gas. Their relative distribution depends on process parameters which can be somewhat optimised depending on the end use of product. The potential of pyrolysis for the conversion of wastewater sludge (SS) and organic fines of MSW (OF) to a combustion gas and a carbon-rich char has been investigated. Pyrolysis of SS and OF was done using a laboratory fixed-bed reactor. Herein, the physical characterisation of the reactor is described, and results on pyrolysis yields are presented. Feedstock and chars have been characterised using standard laboratory methods, and the composition of pyrolysis gases was analysed using micro gas chromatography. Product distribution (char/liquid/gas) from the pyrolysis of sewage sludge and composted MSW fines at 700°C for 10 min were 45/26/29 and 53/14/33%, respectively. The combustible fractions of pyrolysis gases range from 36 to 54% for SS feedstock and 62 to 72% from OF. The corresponding lower heating value range of sampled gases were 11.8-19.1 and 18.2-21.0 MJ m-3, respectively.

Hydrothermal carbonisation of poultry litter: Effects of initial pH on yields and chemical properties of hydrochars.

In this study, hydrothermal carbonisation (HTC) of poultry litter (PL) was carried out to evaluate the impact of initial pH using acetic acid (CH3COOH) or sulfuric acid (H2SO4) on the yields and properties of hydrochar (HC). The PL samples were treated by HTC at various initial pH and at 250°C for 2h. The HCs produced were characterized by ultimate, proximate and fibre analyses as well as heating value and surface area measurements. The results indicated that undertaking HTC in the presence of acids (CH3COOH, H2SO4) significantly affects the yields and properties of HC. The C content and HHV of the HC increased with decreasing initial pH. In the presence of H2SO4, the hydrochar yield (HY) increased while the ash content was significantly reduced. The lowest ash content and the highest HY were measured in the HC produced from the suspension with an initial pH of 2 using H2SO4.

Factors Influencing the Performance of Pd/C Catalysts in the Green Production of Hydrogen from Formic Acid.

Formic acid derived from biomass is known to be used for hydrogen production over Pd catalysts. The effects of preparation variables, structure of the carbon support, surface functional composition on the state of Pd, and catalytic properties of the samples in the vapor-phase decomposition of formic acid were studied. In all catalysts derived from Pd acetate, metal particles visible by conventional TEM had similar sizes, but the adsorption capacity towards CO responded strongly to N-doping of the carbon surface. Moreover, a decrease in the CO/Pd values was accompanied by a significant increase in the reaction rate. Taking account of X-ray photoelectron spectroscopy (XPS) and atomic resolution high-angle annular dark-field scanning transmission electron microscopy (HAADF/STEM) data, the trends observed were assigned to a larger fraction of single electron-deficient Pd atoms in the N-doped samples, which do not adsorb CO but interact with formic acid to produce hydrogen. This was confirmed by extended DFT studies. The obtained results are valuable for the development of Pd catalysts on carbon supports for different processes.

Artificial neural network based modelling approach for municipal solid waste gasification in a fluidized bed reactor.

In this paper, multi-layer feed forward neural networks are used to predict the lower heating value of gas (LHV), lower heating value of gasification products including tars and entrained char (LHVp) and syngas yield during gasification of municipal solid waste (MSW) during gasification in a fluidized bed reactor. These artificial neural networks (ANNs) with different architectures are trained using the Levenberg-Marquardt (LM) back-propagation algorithm and a cross validation is also performed to ensure that the results generalise to other unseen datasets. A rigorous study is carried out on optimally choosing the number of hidden layers, number of neurons in the hidden layer and activation function in a network using multiple Monte Carlo runs. Nine input and three output parameters are used to train and test various neural network architectures in both multiple output and single output prediction paradigms using the available experimental datasets. The model selection procedure is carried out to ascertain the best network architecture in terms of predictive accuracy. The simulation results show that the ANN based methodology is a viable alternative which can be used to predict the performance of a fluidized bed gasifier.

Hydrothermal carbonisation of poultry litter: Effects of treatment temperature and residence time on yields and chemical properties of hydrochars.

In this study, hydrochars were prepared by hydrothermal carbonisation (HTC) of poultry litter (PL) at temperatures between 150-300°C with residence times of 30, 120 and 480min. The effects of treatment temperature and residence time on the yield and composition of hydrochar were investigated. Both treatment temperature and residence time effects were observed however, the effect of residence time was lower. The results indicated that the HHV was improved by up to 25.17% and the overall ash in hydrochar was significantly lower compared to PL, however this coincided with a lower hydrochar yield.

Effects of Soluble Lignin on the Formic Acid-Catalyzed Formation of Furfural: A Case Study for the Upgrading of Hemicellulose.

A comprehensive study is presented on the conversion of hemicellulose sugars in liquors obtained from the fractionation of Miscanthus, spruce bark, sawdust, and hemp by using formic acid. Experimental tests with varying temperature (130-170 °C), formic acid concentration (10-80 wt%), carbohydrate concentrations, and lignin separation were carried out, and experimental data were compared with predictions obtained by reaction kinetics developed in a previous study. The conversions of xylose and arabinose into furfural were inherently affected by the presence of polymeric soluble lignin, decreasing the maximum furfural yields observed experimentally by up to 24%. These results were also confirmed in synthetic mixtures of pentoses with Miscanthus and commercial alkali lignin. This observation was attributed to side reactions involving intermediate stable sugar species reacting with solubilized lignin during the conversion of xylose into furfural.

Multi-gene genetic programming based predictive models for municipal solid waste gasification in a fluidized bed gasifier.

A multi-gene genetic programming technique is proposed as a new method to predict syngas yield production and the lower heating value for municipal solid waste gasification in a fluidized bed gasifier. The study shows that the predicted outputs of the municipal solid waste gasification process are in good agreement with the experimental dataset and also generalise well to validation (untrained) data. Published experimental datasets are used for model training and validation purposes. The results show the effectiveness of the genetic programming technique for solving complex nonlinear regression problems. The multi-gene genetic programming are also compared with a single-gene genetic programming model to show the relative merits and demerits of the technique. This study demonstrates that the genetic programming based data-driven modelling strategy can be a good candidate for developing models for other types of fuels as well.

Conversion of hemicellulose sugars catalyzed by formic acid: kinetics of the dehydration of D-xylose, L-arabinose, and D-glucose.

The pre-treatment of lignocellulosic biomass produces a liquid stream of hemicellulose-based sugars, which can be further converted to high-value chemicals. Formosolv pulping and the Milox process use formic acid as the fractionating agent, which can be used as the catalyst for the valorisation of hemicellulose sugars to platform chemicals. The objective of this study was to investigate the reaction kinetics of major components in the hemicelluloses fraction of biomass, that is, D-xylose, L-arabinose and D-glucose. The kinetics experiments for each sugar were performed at temperatures between 130 and 170 °C in various formic acid concentrations (10-64 wt %). The implications of these kinetic models on the selectivity of each sugar to the desired products are discussed. The models were used to predict the reaction kinetics of solutions that resemble the liquid stream obtained from the fractionation process of biomass using formic acid.

Synthesis and characterization of sulfated TiO2 nanorods and ZrO2/TiO2 nanocomposites for the esterification of biobased organic acid.

TiO(2) nanorods and ZrO(2)-modified TiO(2) nanocomposites have been prepared by hydrothermal synthesis and the deposition-precipitation method. Their sulfated products were tested as solid superacid catalysts for the esterification of levulinic acid which was used as a model bio-oil molecule. SEM and TEM characterization showed that TiO(2) nanorods with diameters ranging from 20 to 200 nm and with lengths of up to 5 µm were synthesized by a hydrothermal method at 180 °C. ZrO(2) nanoparticles with the diameters ranging from 10 to 20 nm were evenly deposited on TiO(2) nanorods. IR and XPS results suggested that sulfated ZrO(2)/TiO(2) nanocomposite has higher content of sulfate groups on the surface with a S/(Zr+Ti) ratio of 13.6% than sulfated TiO(2) nanorods with a S/Ti ratio of 4.9%. The HPLC results showed that sulfated ZrO(2)/TiO(2) nanocomposite have enhanced catalytic activity for esterification reaction between levulinic acid and ethanol compared to sulfated TiO(2) nanorods. The conversion of levulinic acid to ethyl levulinate can reach to 90.4% at the reaction temperature of 105 °C after 180 min.

An integrated process for the production of platform chemicals and diesel miscible fuels by acid-catalyzed hydrolysis and downstream upgrading of the acid hydrolysis residues with thermal and catalytic pyrolysis.

This study evaluates an integrated process for the production of platform chemicals and diesel miscible biofuels. An energy crop (Miscanthus) was treated hydrothermally to produce levulinic acid (LA). Temperatures ranging between 150 and 200 °C, sulfuric acid concentrations 1-5 wt.% and treatment times 1-12 h were applied to give different combined severity factors. Temperatures of 175 and 200 °C and acid concentration of 5 wt.% were found to be necessary to achieve good yield (17 wt.%) and selectivities of LA while treatment time did not have an effect. The acid hydrolysis residues were characterized for their elemental, cellulose, hemicellulose and lignin contents, and then tested in a small-scale pyrolyzer using silica sand and a commercial ZSM-5 catalyst. Milder pretreatment yielded more oil (43 wt.%) and oil O(2) (37%) while harsher pretreatment and catalysis led to more coke production (up to 58 wt.%), less oil (12 wt.%) and less oil O(2) (18 wt.%).

Characterization of compost produced from separated pig manure and a variety of bulking agents at low initial C/N ratios.

The aim of this study was to investigate the composting of separated pig manure solids with or without a variety of bulking agents at a low initial C/N ratio (12.5-23.3). Compost stability was investigated using an oxygen uptake rate (OUR) test and compost maturity was investigated using a germination index test. All treatments showed typical patterns of compost temperature. Temperatures above 60°C were achieved by Day 2, followed by a thermophilic phase (50-60°C), which lasted for 1 to 2 weeks followed by a cooling phase. The stability of one of treatments which did not contain any bulking agent - OUR of 25 mmol O(2) kg(-1) OM hour(-1) - was negatively affected by its initial high water content (69%). The addition of a bulking agent and initial water content below 60% were necessary to compost the separated solid fraction of pig manure at a low initial C/N ratio.