DIGESTATE MANAGEMENT IN FLANDERS: NUTRIENT REMOVAL VERSUS NUTRIENT RECOVERY Viooltje Lebuf Flemish Coordination centre for Manure processing (VCM), address: Abdijbekestraat 9 – 8200, Bruges – Belgium - Tel: +32 (0) 50 - 40 72 03 - Fax: + 32 (0) 50 – 40 74 89 - e-mail: Viooltje.Lebuf@pomwvl.be Sara Van Elsacker Flemish Coordination centre for Manure processing (VCM), e-mail: sara.vanelsacker@vcmmestverwerking.be Frederik Accoe Flemish Coordination centre for Manure processing (VCM) Celine Vaneeckhaute Ghent University, Faculty of Bioscience Engineering, Laboratory of Applied Analytical and Physical Chemistry, Coupure Links 653, 9000 Ghent, Belgium, e-mail: celine.vaneeckhaute@ugent.be Erik Meers Ghent University, Faculty of Bioscience Engineering, Laboratory of Applied Analytical and Physical Chemistry Evi Michels Ghent University, Faculty of Bioscience Engineering, Laboratory of Applied Analytical and Physical Chemistry ABSTRACT Intensive livestock production combined with limited availability of land for manure disposal and fertilisation restrictions by the EU-legislation make Flanders (Belgium) a 100% Nitrate Vulnerable Zone. The Flemish Manure Decree has been implemented in order to take measures against nitrate and phosphate pollution in water, resulting from the produced nutrient excess. From the 39 anaerobic digestion plants operational in Flanders, most of the installations are codigestion plants that process an input mixture of animal manure, organic waste streams and energy crops. According to the Manure Decree however, digestate from co-digestion plants that take in manure also has the status of animal manure, and application on arable land is limited by the 170 kg N/ha/y restriction. For this reason, digestate from anaerobic digestion plants competes with manure for nutrient disposal on arable land, which forms a serious hinder for the biogas sector to develop in these regions. Hence, one of the biggest challenges for anaerobic digestion plants in a region like Flanders, is to find cost-effective and sustainable ways for digestate processing or disposal. In the framework of the ongoing Interreg NWE project ARBOR, VCM, Ghent University and Inagro investigate the options for nutrient recovery from digestate. This paper gives an overview, both of the currently applied techniques for digestate processing in Flanders, as well as the techniques that enable nutrient recovery from digestate. It also focuses on the physicochemical characteristics of the end-products, and the potential constraints for successful valorisation. KEY WORDS: Digestate processing, nutrient recovery. INTRODUCTION The region of Flanders (Belgium) has a high nutrient pressure because of intensive livestock production combined with limited availability of land for manure disposal, due to the defined fertilization restrictions. The Flemish Manure Decree has been implemented in order to take measures against nitrate and phosphate pollution in water, resulting from this nutrient excess. Since 2007, Flanders has been designated as a 100% Nitrate Vulnerable Zone according to the European Nitrates Directive, which implies a fertilization restriction of maximum 170 kg N/ha/y for animal manure in entire Flanders (except for some derogation zones). One of the policy measures implemented to cope with this high nutrient pressure is the obligation for farmers to process a percentage of their manure surplus on farm level. According to the Manure Decree, this processing obligation can be met by treating the manure in such a way that i) the manure products can be exported out of Flanders, ii) the nutrients are removed from the manure (e.g. by conversion of NH4 to N2-gas) or iii) the nutrients are converted into a mineral fertilizer. Export of untreated manure is an option for poultry or horse manure. Various techniques have been developed and implemented for manure processing, and currently about 20% of the net N manure production in Flanders is processed (VCM, 2012). Currently, there are 39 anaerobic digestion plants operational in Flanders, with a total input capacity of about 2.000.000 tons/year (Biogas-E, 2012). Most of these installations are co-digestion plants that process an input mixture of animal manure, organic waste streams and energy crops. According to the Manure Decree however, digestate from co-digestion plants that take in manure also has the status of animal manure, and thus application on arable land is limited by the 170 kg N/ha/y restriction. For this reason, digestate from anaerobic digestion plants competes with manure for nutrient disposal on arable land, which forms a serious hinder for the biogas sector to develop in these regions. Hence, one of the biggest challenges for anaerobic digestion plants in a region like Flanders, is to find costeffective and sustainable ways for digestate processing or disposal. Up to now, the technical approach for digestate processing in most of the co-digestion plants is similar to and adopted from the approach for manure processing. This means that the goals are nutrient removal or treating the digestate in such a way that the products can be exported. However, we are now facing the challenge to evolve to more sustainable approaches which focus on nutrient recovery, rather than nutrient removal, both for manure and digestate processing. In the framework of the ongoing Interreg NWE project ARBOR, VCM, Ghent University and Inagro investigate the options for nutrient recovery from digestate. There is a diverse range of techniques that can be applied for digestate processing, but certainly not all of them can be considered as a nutrient recovery technique. There is no straightforward definition of a nutrient recovery technique. In this paper we consider techniques that (1) create an end-product with higher nutrient concentrations than the raw digestate or (2) separate the envisaged nutrients from organic compounds, with the aim to produce an end-product that is fit for use in the chemical or fertiliser industry or as a mineral fertiliser replacement, as a nutrient recovery technique. This makes it possible to re-use the present nutrients locally and close the nutrient cycle. In Figure 1 an overview of the existing digestate treatment options is given. The techniques that are delineated as a nutrient recovery technique are indicated in grey. Figure 1: Schematic overview of digestate processing techniques (grey boxes indicate nutrient recovery techniques). In general, mechanical separation is a first processing step. Separation results in a solid fraction containing the major share of the initial phosphorus (60-70%) and organic matter content (69-73%), next to a liquid fraction that contains almost all soluble nutrients (N, K) and salts. As the solid fraction offers the opportunity to transport a more concentrated amount of nutrients and organic matter, it is often transported to nutrient deficient regions. European legislation (ER 1069/2009), however, obliges that a pasteurization treatment of 1 hour at 70°C is executed before export. To realize this and to further reduce transport volumes, the solid fraction is often dried or composted before being exported. Nevertheless, it could be more preferable if phosphorus could be extracted from its organic matrix and be re-used as a secondary raw material for industrial processes, as the phosphorus extracted from phosphate rock is becoming scarce. The most commonly applied post-treatment technique in Flanders, for the liquid fraction of the digestate, is biological nitrification/denitrification process which converts ammonium to nitrogen gas. Currently, 5 of the 39 digestion plants in Flanders apply this technique for treatment of the liquid fraction. Notwithstanding, from an environmental point of view, the biological treatment poses a paradox: while nitrogen gas is removed from the digestate and released into the air, the fertilizer industry captures nitrogen gas to produce artificial N-fertilizers through the energy-consuming HaberBosch process. These issues have put many researchers to think how nutrients (N, P and K) could be recovered from digestate in a sustainable way. Available techniques for the recovery of nitrogen are pressurized membrane filtration, ammonia stripping and scrubbing or thorough separation using polymers (coagulants and flocculants). A promising technique for phosphorus recovery is struvite crystallization. NUTRIENT RECOVERY TECHNIQUES FOR LIQUID FRACTION Pressurized membrane filtration The input stream for membrane filtration is either the liquid fraction of the digestate or a pre-processed stream, such as the condensate of the evaporator. The input stream is forced through the membrane by varying pressures. Several types of membranes are used in manure/digestate processing: MF(microfiltration, pore-size > 0,1 µm, 0,1-3 bar), UF- (ultra-filtration, pore-size > nm, 2-10 bar) and ROmembranes (reversed osmosis, semi-permeable, 10-100 bar). In a MF-concentrate suspended solids are retained, while in a UF-concentrate also macromolecules are retained. Both filtration steps can be used as a pre-treatment for reversed osmosis, in order to prevent that either suspended solids or macromolecules block the RO-membrane. Another technique that can be used prior to RO is dissolved air flotation (DAF), a technique that consists of blowing small air bubbles through the liquid fraction, entraining suspended solids to the surface where they form a crust. This crust is then scraped off. When using DAF coagulants and flocculants are often added. The permeate of RO, which consists mainly of water and small ions, can be discharged, if necessary after a ‘polishing’ step, or re-used as process water. This technique is developed on full-scale, but is not implemented frequently yet. In Flanders 4 biogas plants use RO for digestate treatment. The produced mineral concentrates cannot be used as mineral fertilizer (yet) because current European legislation (NitDir en ER 2003/2003) doesn’t allow production of mineral fertilizers from animal manure. In the Netherlands a large research project is ongoing since 2008 on the RO-concentrate of 8 different manure/digestate processing installations. This project received an exceptional permission of the European Commission to use the mineral concentrates as a mineral fertilizer (for the duration of the project) to investigate the agronomic, economic and environmental effects of the production and use of mineral concentrates as mineral fertilizer replacement (Velthof, 2011). The average composition varies between installations. This can be partially explained by differences of the input type of slurry. The pretreatment probably has an effect on the composition of the concentrate as well. The installations using a combination of a centrifuge and ultra-filtration and the ones using a combination of a sieve belt press and flotation tend to have higher nutrient contents in their concentrate than the ones using a screw press and flotation (Velthof, 2011). Ammonia stripping and scrubbing Ammonia is stripped by blowing air or steam through the liquid fraction in a packed tower. The stripgas, which is charged with ammonia and volatile organic matter, is then put in contact with a strong acid solution (H2SO4), which produces ammonium sulphate (see acid air washers further in the paper). Ammonia stripping is developed on a full-scale but is not yet frequently used for digestate and manure treatment. In the ongoing Flemish MIP-project Nutricycle, testing of ammonia stripping from digestate on a pilot scale is implemented. The results of the test will give information on the influence of pH change during the process and how scaling can be avoided. The goal of the project is to find the most suitable type of ammonia stripping for digestate treatment, and how process parameters can be optimized. A combination of the ammonia stripping technique and struvite precipitation (see phosphorus precipitation further in the paper) was studied by Quan et al. (2010). Both processes were taking place simultaneously in a water sparged aerocyclone reactor (WSA). The Dutch company Dorset developed another type of ammonia stripping system for manure and digestate without air recirculation or ventilation. The system consists of rotating disks that are partly submerged in either the liquid manure or the receiving sulphuric acid solution. The rotating disks are close to each other so the ammonia coming from the gas phase is absorbed at the other disc with the sulphuric acid (Dorset GM). Phosphorus precipitation Several ions can be added to a solution containing soluble phosphate (orthophosphate) to induce a precipitation reaction forming phosphate salts. Addition of calcium to a phosphate solution will result in the formation of calcium phosphate. By adding magnesium or potassium and adjusting pH to 9-11, MgNH4PO4 (MAP or struvite), KMgPO4 (Potassium Magnesium Phosphate) or K2NH4PO4 (potassium struvite) precipitates. Struvite is considered to be a slow-release fertilizer. Researchers at the Fraunhofer Institute for Interfacial Engineering and Biotechnology in Germany have patented an electrochemical process to precipitate struvite without the addition of salts or bases. The mobile pilot plant consists of an installation with a magnesium anode and a metallic cathode. The electrolytic process splits the water molecules into negatively charged hydroxyl ions at the cathode. At the anode an oxidation takes place: the magnesium ions migrate through the water and react with the phosphate and ammonium in the solution to form struvite. Struvite is mostly formed by adding MgO but adding MgCl2 is also a possibility. Main advantage of MgCl2 is that its production requires less energy than that of MgO. Main disadvantages are a slower and less complete reaction as well as the presence of chloride ions in the remaining solution. This implies that this solution can only be valorised as a fertiliser for crops that are tolerant for chloride ions, e.g. grass (Sanders, 2010). Besides from the addition of Mg or K, Ca(OH) 2 can also be added. Because of pH and temperature increase ammonia is stripped out of the solution and should be scrubbed with an acid air washer. Quan et al. (2010) examined the coupling of CaNH4PO4.4H2O precipitation and ammonia stripping in a water sparged aerocyclone reactor on lab scale. The amount of P that is bound to the organic fraction can be released by using an initial hydrolysis step (Schoumans et al., 2010) or by using an acidification step combined with solid/liquid separation. Current use of struvite precipitation is mostly limited to treatment of industrial and municipal wastewater. There is one full-scale system operating on calf manure in the Netherlands. A pilot plant is installed at research centre De Marke (NL) by Fermtech Systems bv for the treatment of cattle slurry digestate. The liquid fraction of the digestate goes to a crystallisation reactor where struvite is formed and a NK-effluent remains which can be used as a fertiliser on the dairy farm (van Zessen, 2012). Biomass production and harvest González-Fernández et al. (2011) inoculated four open ponds with microalgae-bacteria consortia to treat anaerobically digested pig slurry to observe nitrogen transformations in the ponds under realistic conditions of light and temperature. When digestate was fed to the ponds, nitrification followed by biomass uptake and denitrification were the main nitrogen transformations. In ACRRES (part of Wageningen UR) lab tests were performed where liquid fraction digestate (containing 5 g N/l) was added to growing media containing algae. A high concentration of the liquid fraction reduced the algal growth capacity significantly (R. Schipperus, pers.comm.). Besides algae, macrophytes have also been studied to recover nutrients from digestate. Xu and Shen (2011) studied the use of duckweed (Spirodella oligorrhiza) for nutrient recovery from anaerobically digested pig slurry. During the growing season, the duckweed was capable of removing 83.7% and 89.4% of total nitrogen and total phosphorus respectively in eight weeks at a harvest frequency of twice a week. The produced algae/macrophytes can serve as feedstock for chemical industry and biofuel industry or could be used as animal feed or spread out as a fertilizer on the fields. For bulk products the cost of producing algae is too high in comparison with other types of biomass (Muylaert and Sanders, 2010). Nor in Flanders nor in the Netherlands there are commercial scale ponds operational at the moment that treat digestate or manure. In ACRRES there is a pilot algae pond installed which is currently fed with artificial fertiliser. However, if future legislation allows the marketing of algae fed on digestate in feed industry, pilot scale experiments could be performed at that site. A first legislative bottleneck to be tackled will be the acceptance in the feed safety database of GMP+. For algae and duckweed there are no restrictions for use in feed, still if they are grown on a medium containing animal manure, the biomass will also be defined as animal manure, unless it can be marketed free of manure particles (A. Kroon and R. Schipperus, pers.comm.). Other techniques During the last couple of years there has been an increased interest in forward osmosis as opposed to reversed osmosis. In forward osmosis there is also a semi-permeable membrane, but no external pressure. The water flow is obtained by imposing an osmotic pressure by means of a draw solution such as NaCl. Forward osmosis can be an interesting technique for use in wastewater treatment, food processing and seawater desalination. More research is necessary to investigate if this technique could also be used for concentration of digestate sludge. During electrodialysis ammonia in the diluate solution is transferred by electromigration to an adjacent solution by an ion-exchange membrane under the driving force of an electrical potential. This means that the main ionic compounds in the liquid digestate (in the diluate cells) i.e. NH4+, K+ and HCO3- are transferred and concentrated. In the Netherlands a pilot plant was installed at Dairy Campus in Leeuwarden, where digestate is treated by means of electrodialysis. An ammonium concentrate (10%) is produced as well as a potassium concentrate (10%). These nutrients are captured in a gas scrubbers by means of CO2 as carbonates. The remaining nitrogen will be captured in an acid air washer. In 2013 extensive research will be performed on the fertilising value of the endproducts (van Zessen, 2012). Transmembranechemosorption (TMCS) is used in pig slurry treatment systems in the Netherlands, where the ammonia is stripped and removed using TMCS. Ammonia is brought in the gaseous phase by means of a pH increase. The ammonia diffuses through a hollow-fibre membrane with gas-filled pores and is captured at the other side of the membrane in a sulphuric acid solution (www.sustec.nl). NUTRIENT RECOVERY TECHNIQUES FOR SOLID FRACTION Phosphorous extraction Phosphorus extraction has been tested extensively for dried or dewatered sludge and ashes from sludge incineration. However, tests on dried fraction, ashes or biochar from digestate are absent in literature. Digestate is considered a waste stream that is eligible for recycling as soil conditioner, which makes it not eligible for conversion to energy by combustion according to Flemish waste legislation. On the other hand, animal manure, which is not subject to the waste legislation, can be combusted, taking into account the emission standards (Art. 4.5.2., VLAREMA, 2012). The goal of combustion could be to produce electricity from the released energy and to recover nutrients (mainly P) from the ashes. Also a strong reduction in volume is obtained and pathogens are killed. However, a thorough flue gas cleaning system is indispensible, which makes small-scale combustion up till now not viable. The remaining ashes after combusting digestate/manure contain up to 20-25% P2O5, next to K- , Al-, Mgand Si-compounds and possibly also some heavy metals such as Cu, Zn and Cd. Several companies have designed different processes to extract phosphorus from the combustion ashes (Schoumans et al., 2010). These techniques can be subdivided into thermochemical and wet-chemical techniques. Pyrolysis exposes the digestate to a temperature of 150-900°C in the absence of oxygen. Organic matter fractionates into syngas, bio-oil and biochar (Lemmens et al., 2006). Preliminary pyrolysis tests on digestate revealed that oil yield and quality (very viscous) were suboptimal (K. Smets, pers. comm.). Experiments with pyrolysis of manure cakes have been conducted. The fraction of nutrients recovered in biochar is larger than in ashes and the plant-availability of the nutrients tends to be higher, especially for phosphorus (Schoumans et al., 2010). Techniques for phosphorus extraction from sewage sludge or sludge incineration ash are existing on full scale or demonstration scale. However, techniques to recover phosphorus from digestate ashes/biochars are less frequently mentioned. NUTRIENT RECOVERY TECHNIQUES FOR GASEOUS STREAMS Acid air washer Thermal drying, composting and evaporation result in emissions of dust particles, water vapour, ammonia and odour compounds. Air treatment is obligatory before emission to the environment. Often an acid air washer is used, which captures the NH3 in sulphuric acid by means of a packed tower where sulphuric acid is sprayed with nozzles over the packing material and treatment air is blown into the tower in counterstream. Ammonium sulphate is produced and the wash water is recycled until it is saturated and the removal efficiency of ammonia cannot be guaranteed anymore. At that point the ammonium sulphate solution should be removed and fresh sulphuric acid added. The reject solution is variable in N-content and pH, due to the variable efficiency of acid air washers. The supplier of the acid air washer defines a certain flow of reject wash water that guarantees a minimal ammonia reduction of 70%. The (NH4)2SO4 solution contains between 30-70 kg N/ton. The pH is often acid, unless an alkaline step is incorporated. The pH varies between 3-7 (M. Heijmans, pers.comm.; N. Van Hemelrijck, pers.comm.). This technique is developed on full-scale. It is frequently used in manure processing and digestate processing activities, as well as for pig stables. In Flanders and The Netherlands ammoniumsulphate is accepted as mineral fertilizer. However, the low pH, high variability of N-content, small volume production at farm scale are the main bottlenecks for valorization of ammoniumsulphate as a mineral fertilizer. CONCLUSIONS In nutrient rich zones it has become inevitable for anaerobic digestion plants to invest in a digestate processing technique as only a small fraction of the digestate can be spread out on land. Because of increased attention for nutrient recycling and the possible depletion of phosphorus, digestate should be considered a valuable source of nutrients and treated accordingly. Defining nutrient recovery techniques is not as straightforward as it seems. This paper proposes following definition: techniques that create an end-product in which nutrients are present in a higher concentration than before processing or those that separate the envisaged nutrients from organic compounds, with the aim to produce an end-product that is fit for use in chemical or fertilizer industry or as a mineral fertilizer replacement. Out of the discussed nutrient recovery techniques, only acid air washers, membrane filtration plants and ammonia stripping plants are operative at full scale at anaerobic digestion plants. Nonetheless, they may need further technical fine-tuning, especially towards energy saving and decreasing the addition of chemicals. A breakthrough in full-scale plants is to be expected for phosphorus precipitation. In the long run also electrodialysis, forward osmosis, TMCS and biomass production could become part of commonly used digestate processing techniques. The extraction of phosphorus from ashes or biochars seems less promising, because it is questionable if combustion/pyrolysis of digestate is a sustainable treatment option and if this should be encouraged. However, extraction techniques could also be applied on the (dried) solid fraction of digestate. For all techniques described it is essential to put attention on fertilizing value of the end-products or marketing value towards industrial end-users. To be economically profitable, the price allocated to the recovered nutrients should be in accordance to the market price of N, P and K in mineral fertilizers. Obtaining the regulatory status of “mineral fertilizer” is thus considered to be very important to achieve successful marketing of these products for agricultural use. REFERENCES 1. BIOGAS-E VZW, Progress report 2012- Anaerobic digestion in Flanders, Kortrijk, Belgium, 2012. 2. DORSET GM, brochure: Dorset LGL Ammonia Stripper, 2012. 3. 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