Aqueous leaching of cattle manure incineration ash to produce a phosphate enriched fertilizer

Ash produced from the combustion of livestock manure contains large amounts of phosphorus (P), which is an important resource as a fertilizer. Some studies have extracted and recovered P from incinerated biomass ash using inorganic acid or alkaline agents, which produce wastewater that requires treatment and is expensive due to the cost of chemicals. Livestock manure ash contains not only P, but also water soluble salts, which could be a negative influence on plant growth and shall be preferably removed from the recovered fertilizer. In this study, we removed salinity from cattle manure incineration ash by simple aqueous leaching, while retaining the P content. The optimal condition was a 20 min leaching time at a liquid/solid (L/S) ratio of 10 mL g-ash^?1. Under this condition, over 90 % of Cl and 20 % of Na in the original ash was removed, while over 99 % of the P was retained in the leached residue. The leached residue met the fertilizer standard in Japan in terms of citrate soluble fertilizer components and contained few heavy metals. X-ray analyses of the ash indicated that Cl was mainly present as KCl in the original ash, while P was mainly present as Ca compounds in the ash.     

Crystalline phase analysis and phosphorus availability after thermochemical treatment of sewage sludge ash with sodium and potassium sulfates for fertilizer production

Phosphorus rich sewage sludge ash is a promising source to produce phosphorus recycling fertilizer. However, the low plant availability of phosphorus in these ashes makes a treatment necessary. A thermochemical treatment (800–1000 °C) with alkali additives transforms poorly plant available phosphorus phases to highly plant available calcium alkali phosphates (Ca,Mg)(Na,K)PO₄. In this study, we investigate the use of K₂SO₄ as additive to produce a phosphorus potassium fertilizer in laboratory-scale experiments (crucible). Pure K₂SO₄ is not suitable as high reaction temperatures are required due to the high melting point of K₂SO₄. To overcome this barrier, we carried out series of experiments with mixtures of K₂SO₄ and Na₂SO₄ resulting in a lower economically feasible reaction temperature (900–1000 °C). In this way, the produced phosphorus potassium fertilizers (8.4 wt.% K, 7.6 wt.% P) was highly plant available for phosphorus indicated by complete extractable phosphorus in neutral ammonium citrate solution. The added potassium is, in contrast to sodium, preferably incorporated into silicates instead of phosphorus phases. Thus, the highly extractable phase (Ca,Mg)(Na,K)PO₄ in the thermochemical products contain less potassium than expected. This preferred incorporation is confirmed by a pilot-scale trial (rotary kiln) and thermodynamic calculation.

     

Pyrolysis characteristics and kinetics of chicken litter

Chicken litter generally consists of a mixture of bedding, manure, feathers and spilled food. Flock of birds litter (flock) is a litter consisting of hardwood shavings, feed, feathers and manure; and broiler litter (broiler) is a cake of chicken litter. A kinetic investigation of the pyrolysis of chicken litter (flock and broiler) was carried out using thermogravimetric analysis (TGA) at heating rates of 5 degrees C/min, 10 degrees C/min and 20 degrees C/min. Most of the materials decomposed between 270 degrees C and 590 degrees C at each heating rate. The region of decomposition of flock and broiler was slightly lower than that of the wood chips. Wood chips (bedding material) decomposed in two stages, while flock and broiler decomposed in three stages. Apparent activation energies increased from 99 to 484 kJ/mol for the three samples when the pyrolytic conversion increased from 5% to 95%.     

REVIEW OF THE USE OF SWINE MANURE IN CROP PRODUCTION: EFFECTS ON YIELD AND COMPOSITION AND ON SOIL AND WATER QUALITY

The world swine population produces about 1.7 billion tonnes of liquid manure annually. At an application rate of 20 tonnes per hectare, this could fertilize about 85 million hectares of land annually. Storage and disposal of this material presents a challenge to producers because of the potential for environmental pollution. However, because swine manure contains essential plant nutrients, use of swine manure as a soil amendment for crop production is a practical method to solve the disposal problem. The composition and effectiveness of swine manure as a source of plant nutrients depends on several factors including type of ration fed, housing system, method of manure collection, storage and handling. Research has shown that manure application increased soil N, P, K, Ca, Mg and Na. However, heavy or excessive application of manure increased leaching of NO₃-N, P and Mg. Swine manure is reported to be effective in increasing the yields of cereals, legumes, oilseeds, vegetables and pastures, and in increasing plant nutrient concentration, especially N, P and K. The efficient use of swine manure can be an agronomically and economically viable management practice for sustainable crop production in temperate regions such as the Canadian prairies where the swine industry is expanding rapidly.     

An examination of the exothermic nature of fluidized bed combustion (FBC) residues

Circulating fluidized bed combustion (CFBC) ashes from nine operational periods at the 183 MWe CFBC boiler at Point Aconi were examined for exothermic behaviour. Bed ashes and fly ashes were investigated using a Parr 1455 solution calorimeter. Limited tests were also carried out with additional samples from Point Aconi and from the 160 MWe TVA Bubbling Fluidized Bed Combustion boiler to evaluate the effects of particle size and aging on exothermic behaviour. For the Point Aconi ashes, heat release from the bed ash ranged from 11 to 52 J/g, and the maximum heat release rates ranged from 0.06 to 0.17 J/g/s. For the fly ash heat release varied from 114 to 187 J/g and the maximum heat release rates ranged from 0.8 to 1.9 J/g/s. In the fly ash samples, 50% or more of available CaO was converted to Ca(OH)₂, while for the bed ash a third or less of the CaO was converted to Ca(OH)₂. The exothermicity of the bed ash is directly proportional to the CaO content of the ash. However, this is not true for the fly ash. The exothermic behaviour of fresh FBC ash appeared to be greatly reduced by exposure in air over a 48-h period. Another conclusion of this work is that particle size effects the exothermic behaviour.     

Mercury leaching characteristics of waste treatment residues generated from various sources in Korea

In this study, mercury (Hg) leaching characteristics of the waste treatment residues (fly ash, bottom ash, sludge, and phosphor powder) generated from various sources (municipal, industrial, medical waste incinerators, sewage sludge incinerator, oil refinery, coal-fired power plant, steel manufacturing plant, fluorescent lamp recycler, and cement kiln) in Korea were investigated. First, both Hg content analysis and toxicity characteristic leaching procedure (TCLP) testing was conducted for 31 collected residue samples. The Hg content analysis showed that fly ash from waste incinerators contained more Hg than the other residue samples. However, the TCLP values of fly ash samples with similar Hg content varied widely based on the residue type. Fly ash samples with low and high Hg leaching ratios (R_L) were further analyzed to identify the major factors that influence the Hg leaching potential. Buffering capacity of the low-R_L fly ash was higher than that of the high-R_L fly ash. The Hg speciation results suggest that the low-R_L fly ashes consisted primarily of low-solubility Hg compounds (Hg₂Cl₂, Hg⁰ or HgS), whereas the high-R_L fly ashes contain more than 20% high-solubility Hg compounds (HgCl₂ or HgSO₄).     

Utilization of blended fluidized bed combustion (FBC) ash and pulverized coal combustion (PCC) fly ash in geopolymer

In this paper, synthesis of geopolymer from fluidized bed combustion (FBC) ash and pulverized coal combustion (PCC) fly ash was studied in order to effectively utilize both ashes. FBC-fly ash and bottom ash were inter-ground to three different finenesses. The ashes were mixed with as-received PCC-fly ash in various proportions and used as source material for synthesis of geopolymer. Sodium silicate (Na₂SiO₃) and 10 M sodium hydroxide (NaOH) solutions at mass ratio of Na₂SiO₃/NaOH of 1.5 and curing temperature of 65 °C for 48 h were used for making geopolymer. X-ray diffraction (XRD), scanning electron microscopy (SEM), degree of reaction, and thermal gravimetric analysis (TGA) were performed on the geopolymer pastes. Compressive strength was also tested on geopolymer mortars. The results show that high strength geopolymer mortars of 35.0–44.0 MPa can be produced using mixture of ground FBC ash and as-received PCC-fly ash. Fine FBC ash is more reactive and results in higher degree of reaction and higher strength geopolymer as compared to the use of coarser FBC ash. Grinding increases reactivity of ash by means of increasing surface area and the amount of reactive phase of the ash. In addition, the packing effect due to fine particles also contributed to increase in strength of geopolymers.     

Anaerobic digestion of chicken feather with swine manure or slaughterhouse sludge for biogas production

Biogas production from anaerobic digestion of chicken feathers with swine manure or slaughterhouse sludge was assessed in two separate experiments. Ground feathers without any pre-treatment were added to 42-L digesters inoculated with swine manure or slaughterhouse sludge, representing 37% and 23% of total solids, respectively and incubated at 25 °C in batch mode. Compared to the control without feather addition, total CH₄ production increased by 130% (P < 0.001) and 110% (P = 0.09) in the swine manure and the slaughterhouse sludge digesters, respectively. Mixed liquor NH₄N concentration increased (P < 0.001) from 4.8 and 3.1 g/L at the beginning of the digestion to 6.9 and 3.5 g/L at the end of digestion in the swine manure and the slaughterhouse sludge digesters, respectively. The fraction of proteolytic microorganisms increased (P < 0.001) during the digestion from 12.5% to 14.5% and 11.3% to 13.0% in the swine manure and the slaughterhouse sludge digesters with feather addition, respectively, but decreased in the controls. These results are reflective of feather digestion. Feather addition did not affect CH₄ yields of the swine manure digesters (P = 0.082) and the slaughterhouse sludge digesters (P = 0.21), indicating that feathers can be digested together with swine manure or slaughterhouse sludge without negatively affecting the digestion of swine manure and slaughterhouse sludge.     

Stabilization of sewage sludge in the presence of nanoscale zero-valent iron (nZVI): abatement of odor and improvement of biogas production

The potential benefits of nanoscale zero-valent iron (nZVI) on sludge stabilization, either the abatement of odor or the improvement of biogas production, were investigated in this study. Two commercial-grade microscale iron powders were also utilized for comparison. Adding 0.10 wt% of nZVI in sludge during anaerobic incubation significantly reduced the concentration of H₂S in biogas by 98.0 % (96.2–98.9 %), probably attributed by reactions between sulfides and the neo-formed hydrous Fe(II)/Fe(III) oxides layer at the surface of ZVI nanoparticles. Meanwhile, the percentage of P in bioavailable fractions decreased from 76.8 to 52.5 %, possibly due to the formation of vivianite [Fe₃(PO₄)₂]. Furthermore, 0.10 wt% of nZVI in anaerobic digestion for 17 days enhanced the concentration of CH₄ in biogas by 5.1–13.2 % and improved the production of biogas and methane by 30.4 and 40.4 %, respectively. The amendment of iron nanoparticles during anaerobic digestion can not only effectively reduce H₂S in biogas, but also potentially boost methane production significantly.     

Preparation of zeolitic material with simultaneous removal of NH4 + and PO4 3− from paper sludge ash via acid leaching

This study investigates the preparation of zeolitic material with removal of both NH₄ ⁺ and PO₄ ^3? from paper sludge ash (PSA) via acid leaching. PSA typically has a low Si and high Ca content, owing to the presence of calcite fillers. Acid leaching with 3 M HCl was used firstly to reduce the Ca content of the PSA, whereafter a zeolite-P (Na-P) product with high cation exchange capacity (CEC) was synthesized through reaction with 2.5 M NaOH solution at 80 °C. Ca-P zeolitic products were prepared by Ca-treatment with the leachant that had been in contact with the PSA. The product with high CEC capacity including Na-P could be synthesized from the acid-leached ash, and the high Ca content in the ash could be reduced by extraction of the Ca into the leachant via the acid leaching. The Ca-P zeolitic product could be prepared by Ca-treatment with the solution obtained from neutralization of the leachant with NaOH. This product was capable of removing NH₄ ⁺ and PO₄ ^3? from aqueous solution, simultaneously.     

REVEGETATION OF WASTE FLY ASH LAGOONS II. SEEDLING TRANSPLANTS AND PLANT NUTRITION

As an alternative or in addition to direct seeding, container-grown transplants provide a means of economically and rapidly revegetating waste fly ash lagoons through the expeditious establishment of vegetation islands. Survival and growth ofEnchylaena tomentosaandNitraria billardiereitransplants were largely dependent on the size of the root volume at transplanting. Growth response of both species in fly ash increased significantly as transplant container size increased from 110 ml to 800 ml. Fly ash incorporated into the potting mix during the containerised stage of growth generally reduced plant growth and survival following eventual transplantation. Gradual hardening ofEnchylaena tomentosaseedlings to increasing concentrations of fly ash in the potting mix (25 to 50 to 75% fly ash), however, improved immediate survival following transplantation, into pure ash. Nitrogen deficiency in Port Augusta fly ash was a major nutritional limitation to growth of these two species. Growth and dry matter production responded optimally to application of N fertiliser (NH₄NO₃) at 100–150 kg N ha⁻¹. Although bicarbonate-extractable P levels in fly ash were high (over 250 mg kg⁻¹), a response ofEnchylaena tomentosato supplementary P application [Ca(H₂PO₄)₂.H₂O] at 100–200 kg P ha⁻¹was observed.N. billardiereidid not respond to supplementary P, and it was suggested that fly ash P may be selectively available to plants on a species dependent basis. No growth responses to K application (KCl) at rates of up to 400 kg K ha⁻¹were found.     

Glass–ceramic from mixtures of bottom ash and fly ash

Along with the gradually increasing yield of the residues, appropriate management and treatment of the residues have become an urgent environmental protection problem. This work investigated the preparation of a glass–ceramic from a mixture of bottom ash and fly ash by petrurgic method. The nucleation and crystallization kinetics of the new glass–ceramic can be obtained by melting the mixture of 80% bottom ash and 20% fly ash at 950 °C, which was then cooled in the furnace for 1 h. Major minerals forming in the glass–ceramics mainly are gehlenite (Ca₂Al₂SiO₇) & akermanite (Ca₂MgSiO₇) and wollastonite (CaSiO₃). In addition, regarding chemical/mechanical properties, the chemical resistance showing durability, and the leaching concentration of heavy metals confirmed the possibility of engineering and construction applications of the most superior glass–ceramic product. Finally, petrurgic method of a mixture of bottom ash and fly ash at 950 °C represents a simple, inexpensive, and energy saving method compared with the conventional heat treatment.     

Bio fuel ash in a road construction: impact on soil solution chemistry

Limited natural resources and landfill space, as well as increasing amounts of ash produced from incineration of bio fuel and municipal solid waste, have created a demand for useful applications of ash, of which road construction is one application. Along national road 90, situated about 20 km west of Sollefteå in the middle of Sweden, an experiment road was constructed with a 40 cm bio fuel ash layer. The environmental impact of the ash layer was evaluated from soil solutions obtained by centrifugation of soil samples taken on four occasions during 2001–2003. Soil samples were taken in the ash layer, below the ash layer at two depths in the road and in the ditch. In the soil solutions, pH, conductivity, dissolved organic carbon (DOC) and the total concentration of cations (metals) and anions were determined. Two years after the application of the ash layers in the test road, the concentrations in the ash layer of K, SO₄, Zn, and Hg had increased significantly while the concentration of Se, Mo and Cd had decreased significantly. Below the ash layer in the road an initial increase of pH was observed and the concentrations of K, SO₄, Se, Mo and Cd increased significantly, while the concentrations of Cu and Hg decreased significantly in the road and also in the ditch. Cd was the element showing a potential risk of contamination of the groundwater. The concentrations of Ca in the ash layer indicated an ongoing hardening, which is important for the leaching rate and the strength of the road construction.     

Phosphorus leaching from soils amended with thermally gasified piggery waste ash

In regions with intensive livestock farming, thermal treatment for local energy extraction from the manure and export of the P rich ash as a fertilizer has gained interest. One of the main risks associated with P fertilizers is eutrophication of water bodies. In this study P and K mobility in ash from anaerobically digested, thermally gasified (GA) and incinerated (IA) piggery waste has been tested using water loads ranging from 0.1 to 200 ml g^?1. Leaching of P from soil columns amended with GA was investigated for one P application rate (205 kg P ha^?1 corresponding to 91 mg P kg^?1 soil dry matter) as a function of precipitation rate (9.5 and 2.5 mm h^?1), soil type (Jyndevad agricultural soil and sand), amount of time elapsed between ash amendment and onset of precipitation (0 and 5 weeks) and compared to leaching from soils amended with a commercial fertilizer (Na₂HPO₄). Water soluble P in GA and IA constituted 0.04% and 0.8% of total ash P. Ash amended soil released much less P (0.35% of total P applied in sand) than Na₂HPO₄ (97% and 12% of total P applied in Jyndevad and sand, respectively).     

Effect of unburned carbon on lead, zinc, and copper recovery from molten fly ash by chloride-induced volatilization

The present work focuses on investigation of the effective recovery of heavy metals from molten fly ash by applying chloride-induced volatilization. In particular, the effect of unburned carbon on the chloride-induced volatilization of lead, zinc, and copper from model and real molten fly ashes was investigated in the temperature range 873–1173 K under a N₂ atmosphere. As a result, almost 100% of lead and a significant proportion of zinc were volatilized from the real molten fly ash samples at 1173 K. In contrast, for the model fly ash, volatilization ratios of lead and zinc at 1173 K were only 85% and 25%, respectively. Further, the results of X-ray diffraction analysis suggested that PbO in molten fly ash was converted either to Pb₂OCl₂ or Pb by respective chlorination and reduction reactions. Meanwhile ZnO and CuO in the molten fly ash were reduced to Zn and Cu by reaction with unburned carbon. Subsequently, Pb, Zn, and Pb₂OCl₂ were volatilized, but Cu remained in the solid residue. Finally, the volatilization ratio of zinc increased with the addition of carbon, and more than 98% of zinc was volatilized at 1173 K from a fly ash with a carbon content of 20%.     

PHYSICO-CHEMICAL CHARACTERIZATION AND LEACHING OF DESULPHURIZATION COAL FLY ASH

Fly ash produced by coal combustion using two types of desulphurization process were studied: a conventional pulverized coal boiler equipped with lime injection (PCL ash), and a circulating fluidized bed combustion boiler with limestone injection (CFBC ash). The ashes were characterized completely: granulometry, morphology, mineralogy, chemical composition and behaviour to water contact. Both PCL ash and CFBC ash present similar features: fine granulometry, presence of anhydrite phase and sulphate content. However, PCL ash also shows lots of spherical particles, unlike CFBC ash, and a much higher lime content, due to the lower desulphurization rate in PC boilers. Unlike CFBC ash, most of the trace elements in PCL ash show an inverse concentration–particle size dependence. Leachates obtained from both samples are rich in soluble salts [CaSO₄and Ca(OH)₂] and arsenic and selenium are prevented from solubilizing by high lime content. In wetted PCL ash, the formation of ettringite crystals stabilizes calcium and sulphate ions. Simultaneously, arsenate, selenate and chromate anions are trapped in the crystal. CFBC ash does not really harden because the lime content is too low. However, the leached selenium concentration is cut down in wetted CFBC ash samples.     

Characterization and phosphate stabilization of dusts from the vitrification of MSW combustion residues

The use of soluble PO₄³⁻ as a heavy metal chemical stabilization agent was evaluated for a dust generated from melting or vitrification of municipal solid waste combustion residues. Vitrification dusts contain high concentrations of volatile elements such as Cl, Na, K, S, Pb, and Zn. These elements are present in the dusts largely as simple salts (e.g. PbCl₂, ZnSO₄) which are highly leachable. At an experimental dose of 0.4 moles of soluble PO₄³⁻ per kg of residue, the pH-dependent leaching (pH 5,7,9) showed that the treatment was able to reduce equilibrium concentrations by factors of 3 to 100 for many metals; particularly Cd, Cu, Pb and Zn. Bulk and surface spectroscopies showed that the insoluble reaction products are tertiary metal phosphate [e.g. Zn₃(PO₄)₂] and apatite [e.g. Pb₅(PO₄)₃Cl] family minerals. Geochemical thermodynamic equilibrium modeling showed that apatite family and tertiary metal phosphate phases act as controlling solids for the equilibrium concentrations of Ca²⁺, Zn²⁺, Pb²⁺, Cu²⁺, and Cd²⁺ in the leachates during pH-dependent leaching. Both end members and ideal solid solutions were seen to be controlling solids. Soluble phosphate effectively converted soluble metal salts into insoluble metal phosphate phases despite the relatively low doses and dry mixing conditions that were used. Soluble phosphate is an effective stabilization agent for divalent heavy metals in melting dusts where leachable metals are present in high concentrations.     

The application and evaluation research of coffee residue ash into mortar

Coffee residue is usually regarded as a kind of agriculture waste; as its quantity increases the treatment of coffee residue will become an environmental problem. This research is innovative in that it derives the possibility of recycle application using coffee residue ash for cement replacement. In this research, coffee residue is burned in an electronic oven to three kinds of coffee residue ash at 500, 600 and 700 °C, and then appropriate apparatus is used to check the chemical and physical properties of these three types of coffee residue ash. After a general comparison, this study selected 500 and 600 °C coffee residue ashes with 2, 3, 5, 10 and 15 % cement replacements to make 5 cm³ cube mortar specimen to test different curing ages’ compressive strength. Through measurement and experiment, this research found that the compressive strength decreased by adding 500 or 600 °C coffee residue ash into the mortar. By considering waste reduction and practice application, this research derives that using the 600 °C coffee residue ash with 10 % replacement is better than others application, such using result also can get valuable efficiencies of financial and CO₂ reduction.     

Wet extraction of heavy metals and chloride from MSWI and straw combustion fly ashes

Fly ash residues from combustion often do not meet the criteria neither for reuse as construction materials nor landfilling as non-hazardous waste, mainly because of the high concentration of heavy metals and chlorides. This work aimed to technically evaluate an innovative wet treatment process for the extraction of chloride (Cl^?), cadmium (Cd), copper (Cu), lead (Pb) and zinc (Zn) from fly ashes from a municipal solid waste incineration (MSWI) plant and from a straw combustion (SC) facility. Factors investigated were liquid/solid (L/S) ratio, full carbonation (CO₂ treatment), influence of pH and leaching time, using a two-level full factorial design. The most significant factor for all responses was low pH, followed by L/S ratio. Multiple linear regression models describing the variation in extraction data had R² values ranging from 58% to 98%. An optimization of the element extraction models was performed and a set of treatment conditions is suggested.     

Assessing the environmental impact of ashes used in a landfill cover construction

Large amounts of construction materials will be needed in Europe in anticipation for capping landfills that will be closed due to the tightening up of landfill legislation. This study was conducted to assess the potential environmental impacts of using refuse derived fuel (RDF) and municipal solid waste incineration (MSWI) ashes as substitutes for natural materials in landfill cover designs. The leaching of substances from a full-scale landfill cover test area built with different fly and bottom ashes was evaluated based on laboratory tests and field monitoring. The water that drained off above the liner (drainage) and the water that percolated through the liner into the landfill (leachate) were contaminated with Cl^?, nitrogen and several trace elements (e.g., As, Cu, Mo, Ni and Se). The drainage from layers containing ash will probably require pre-treatment before discharge. The leachate quality from the ash cover is expected to have a minor influence on overall landfill leachate quality because the amounts generated from the ash covers were low, <3–30 l (m² yr)^?1. Geochemical modelling indicated that precipitation of clay minerals and other secondary compounds in the ash liner was possible within 3 years after construction, which could contribute to the retention of trace elements in the liner in the long term. Hence, from an environmental view point, the placement of ashes in layers above the liner is more critical than within the liner.