污泥灰中磷的湿化学法回收技术研究进展

从污泥灰中磷的提取、磷与重金属的分离和磷产品的制备3方面综述了国内外湿化学法回收污泥灰中磷的研究进展,重点分析了磷提取过程中的各种影响因素,并对今后污泥灰中磷的湿化学法回收技术的研究方向进行了展望。指出:利用萃取的方法将提取液中的无机强酸萃取出来并回收重复利用,可大幅降低酸的消耗量;在回收磷的同时可研究回收不同种类金属的方法,尤其是价值较大的重金属,以进一步提高污泥灰资源的回收价值。     

Phosphorus recovery from sewage sludge ash through an electrodialytic process

The electrodialytic separation process (ED) was applied to sewage sludge ash (SSA) aiming at phosphorus (P) recovery. As the SSA may have high heavy metals contents, their removal was also assessed. Two SSA were sampled, one immediately after incineration (SA) and the other from an open deposit (SB). Both samples were ED treated as stirred suspensions in sulphuric acid for 3, 7 and 14 days. After 14 days, phosphorus was mainly mobilized towards the anode end (approx. 60% in the SA and 70% in the SB), whereas heavy metals mainly electromigrated towards the cathode end. The anolyte presented a composition of 98% of P, mainly as orthophosphate, and 2% of heavy metals. The highest heavy metal removal was achieved for Cu (ca. 80%) and the lowest for Pb and Fe (between 4% and 6%). The ED showed to be a viable method for phosphorus recovery from SSA, as it promotes the separation of P from the heavy metals.     

Thermochemical treatment of sewage sludge ashes for phosphorus recovery

Phosphorus (P) is an essential element for all living organisms and cannot be replaced. Municipal sewage sludge is a carrier of phosphorus, but also contains organic pollutants and heavy metals. A two-step thermal treatment is suggested, including mono-incineration of sewage sludge and subsequent thermochemical treatment of the ashes. Organic pollutants are completely destroyed by mono-incineration. The resulting sewage sludge ashes contain P, but also heavy metals. P in the ashes exhibits low bioavailability, a disadvantage in farming. Therefore, in a second thermochemical step, P is transferred into mineral phases available for plants, and heavy metals are removed as well. The thermochemical treatment was investigated in a laboratory-scale rotary furnace by treating seven different sewage sludge ashes under systematic variation of operational parameters. Heavy metal removal and the increase of the P-bioavailability were the focus of the investigation. The present experimental study shows that these objectives have been achieved with the proposed process. The P-bioavailability was significantly increased due to the formation of new mineral phases such as chlorapatite, farringtonite and stanfieldite during thermochemical treatment.     

RecoPhos: Full-scale fertilizer production from sewage sludge ash

The substitution potential of sewage sludge for German primary phosphate imports has been estimated as 40%. Yet, a marketable option for the full scale recovery has been lacking. This study focuses on a full-scale process for the manufacture of a P-fertilizer from sewage sludge ash (SSA) adapted from the production of Triple Superphosphate. Given (i) conformity of the input with phosphate ores mined from sedimentary deposits, (ii) comparability of the product with a commercially available P-fertilizer regarding contaminant levels, P-fractionation and yield effects, and (iii) compliance of the output with the German Fertilizer Ordinance the RecoPhos P 38 fertilizer was discharged from the waste legislation regime. The fertilizer is currently being produced at a rate of 1000 tonnes per month and sold at a competitive price.     

Limitations for heavy metal release during thermo-chemical treatment of sewage sludge ash

Phosphate recycling from sewage sludge can be achieved by heavy metal removal from sewage sludge ash (SSA) producing a fertilizer product: mixing SSA with chloride and treating this mixture (eventually after granulation) in a rotary kiln at 1000 ± 100 °C leads to the formation of volatile heavy metal compounds that evaporate and to P-phases with high bio-availability. Due to economical and ecological reasons, it is necessary to reduce the energy consumption of this technology. Generally, fluidized bed reactors are characterized by high heat and mass transfer and thus promise the saving of energy. Therefore, a rotary reactor and a fluidized bed reactor (both laboratory-scale and operated in batch mode) are used for the treatment of granulates containing SSA and CaCl₂. Treatment temperature, residence time and - in case of the fluidized bed reactor - superficial velocity are varied between 800 and 900 °C, 10 and 30 min and 3.4 and 4.6 m s⁻¹. Cd and Pb can be removed well (>95 %) in all experiments. Cu removal ranges from 25% to 84%, for Zn 75-90% are realized. The amount of heavy metals removed increases with increasing temperature and residence time which is most pronounced for Cu.In the pellet, three major reactions occur: formation of HCl and Cl₂ from CaCl₂; diffusion and reaction of these gases with heavy metal compounds; side reactions from heavy metal compounds with matrix material. Although, heat and mass transfer are higher in the fluidized bed reactor, Pb and Zn removal is slightly better in the rotary reactor. This is due the accelerated migration of formed HCl and Cl₂ out of the pellets into the reactor atmosphere. Cu is apparently limited by the diffusion of its chloride thus the removal is higher in the fluidized bed unit.     

Potential benefits and risks of land application of sewage sludge

Sewage sludge, also referred as biosolids, is a byproduct of sewage treatment processes. Land application of sewage sludge is one of the important disposal alternatives. Characteristics of sewage sludge depend upon the quality of sewage and type of treatment processes followed. Being rich in organic and inorganic plant nutrients, sewage sludge may substitute for fertilizer, but availability of potential toxic metals often restricts its uses. Sludge amendment to the soil modifies its physico-chemical and biological properties. Crop yield in adequately sludge-amended soil is generally more than that of well-fertilized controls. Bioavailability of metals increases in sludge amended soil at excessive rates of application for many years. Plants differ in their abilities to absorb sludge-derived metals from the soil. The purpose of this paper is to review the available information on various aspects of sewage sludge application on soil fertility and consequent effects on plant production to explore the possibility of exploiting this byproduct for agronomy and horticulture.     

Waste paper and clinoptilolite as a bulking material with dewatered anaerobically stabilized primary sewage sludge (DASPSS) for compost production

Environmental problems associated with sewage sludge disposal have prompted strict legislative actions over the past few years. At the same time, the upgrading and expansion of wastewater treatment plants have greatly increased the volume of sludge generated. The major limitation of land application of sewage sludge compost is the potential for high heavy metal content in relation to the metal content of the original sludge. Composting of sewage sludge with natural zeolite (clinoptilolite) can enhance its quality and suitability for agricultural use. However, the dewatered anaerobically stabilized primary sewage sludge (DASPSS) contained a low concentration of humic substances (almost 2%), and the addition of the waste paper was necessary in order to produce a good soil conditioner with high concentrations of humics. The final results showed that the compost produced from DASPSS and 40-50% w/w of waste paper was a good soil fertilizer. Finally, in order to estimate the metal leachability of the final compost product, the generalized acid neutralization Capacity (GANC) procedure was used, and it was found that by increasing the leachate pH, the heavy metal concentration decreased. The application of the sequential chemical extraction indicated that metals were bound to the residual fraction characterized as a stabilize fractions.     

Vitrification as an alternative to landfilling of tannery sewage sludge

Due to high content of heavy metals such as chromium, tannery sewage sludge is a material which is difficult to be biologically treated as it is in the case of organic waste. Consequently, a common practice in managing tannery sewage sludge is landfilling. This poses a potential threat to both soil and water environments and it additionally generates costs of construction of landfills that meet specific environment protection requirements. Vitrification of this kind of sewage sludge with the addition of mineral wastes can represent an alternative to landfilling.The aim of this study was to investigate the possibility of obtaining an environmentally safe product by means of vitrification of tannery sewage sludge from a flotation wastewater treatment process and chemical precipitation in order to address the upcoming issue of dealing with sewage sludge from the tannery industry which will be prohibited to be landfilled in Poland after 2016. The focus was set on determining mixtures of tannery sewage sludge with additives which would result in the lowest possible heavy metal leaching levels and highest hardness rating of the products obtained from their vitrification.The plasma vitrification process was carried out for mixtures with various amounts of additives depending on the type of sewage sludge used. Only the materials of waste character were used as additives.One finding of the study was an optimum content of mineral additives in vitrified mixture of 30% v/v waste molding sands with 20% v/v carbonate flotation waste from the zinc and lead industry for the formulations with flotation sewage sludge, and 45% v/v and 5% v/v, respectively, for precipitation sewage sludge. These combinations allowed for obtaining products with negligible heavy metal leaching levels and hardness similar to commercial glass, which suggests they could be potentially used as construction aggregate substitutes. Incineration of sewage sludge before the vitrification process lead to increased hardness of the vitrificates and reduced leaching of some heavy metals.     

Monitoring the stabilization of municipal solid waste incineration fly ash by phosphation: mineralogical and balance approach

The application of a micro-characterization protocol coupled with a balance approach has allowed the relevant monitoring of a phosphation process for fly ash produced by municipal solid waste incineration. The three main steps of this process consist in removing the salts (chlorides, sulfates) by dissolution at basic pH, phosphation of the residue to trap metals, and its calcination to destroy dioxin-like compounds. The chemical and mineralogical balances compiled on the samples after each step of the process validate these main objectives and highlight the wide phosphorus distribution throughout the sample during the phosphation process, as well as the formation of apatite-type crystallized phosphates. During calcination, the increase in the proportion of crystallized phosphates apatite and whitlockite is largely attributable to the presence of an available calcium source, corresponding to the calcite formed during washing. The metals Pb and Zn, initially distributed in the silicate and carbonate phases, are broadly redistributed in the phosphate neoformations after carbonate dissolution, thus guaranteeing a more permanent stabilization.     

Changes in soil chemical and microbiological properties during 4 years of application of various organic residues

A 4-year field trial was established in eastern Sweden to evaluate the effects of organic waste on soil chemical and microbiological variables. A simple crop rotation with barley and oats was treated with either compost from household waste, biogas residue from household waste, anaerobically treated sewage sludge, pig manure, cow manure or mineral fertilizer. All fertilizers were amended in rates corresponding to 100kgNha(-1)year(-1). The effects of the different types of organic waste were evaluated by subjecting soil samples, taken each autumn 4 weeks after harvest, to an extensive set of soil chemical (pH, Org-C, Tot-N, Tot-P, Tot-S, P-AL, P-Olsen, K-AL, and some metals) and microbiological (B-resp, SIR, microSIR active and dormant microorganisms, PDA, microPDA, PAO, Alk-P and N-min) analyses. Results show that compost increased pH, and that compost as well as sewage sludge increased plant available phosphorus; however, the chemical analysis showed few clear trends over the 4 years and few clear relations to plant yield or soil quality. Biogas residues increased substrate induced respiration (SIR) and, compared to the untreated control amendment of biogas residues as well as compost, led to a higher proportion of active microorganisms. In addition, biogas residues increased potential ammonia oxidation rate (PAO), nitrogen mineralization capacity (N-min) as well as the specific growth rate constant of denitrifiers (microPDA). Despite rather large concentrations of heavy metals in some of the waste products, no negative effects could be seen on either chemical or microbiological soil properties. Changes in soil microbial properties appeared to occur more rapidly than most chemical properties. This suggests that soil microbial processes can function as more sensitive indicators of short-term changes in soil properties due to amendment of organic wastes.     

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.     

Evaluation of bangkok sewage sludge for possible agricultural use.

Bangkok (Thailand) covers more than 1500 km2 and has 10 million inhabitants. The disposal of wastewater is creating huge problems of pollution. The estimated amount of sewage sludge was estimated to be around 108 tonnes dry matter (DM) per day in 2005. In order to find a lasting way of disposal for this sewage sludge, the suitability of the sludge produced from three waste-water treatment plants for use as fertilizing material was investigated. Monthly samplings and analysis of sewage sludge from each plant showed that the composition of sludge varied according to the area of collection and period of sampling, and there was no link to rainfall cycle. Plant nutrient content was high (i.e. total N from 19 to 38 g kg(-1) DM) whereas organic matter content was low. The concentrations of heavy metals varied between sludge samples, and were sometimes higher than the E.U. or U.S. regulations for sewage sludge use in agriculture. Faecal coliforms were present in the sludge from one of the plants, indicating a possible contamination by night soil. In order to decrease this potentially pathogenic population the sewage sludge should be heated by composting. As the C/N ratio of sewage sludge was low (around 6) some organic by-products with high carbon content could be added as structural material to enhance the composting.     

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.

     

Comparative fertilizer properties of digestates from mesophilic and thermophilic anaerobic digestion of dairy manure: focusing on plant growth promoting bacteria (PGPB) and environmental risk

The fertilizer properties of anaerobic digestate depend on the feedstock and operating conditions of digestion. In this study, the comparative fertilizer properties of mesophilic and thermophilic digestates from dairy manure were evaluated for plant nutrient contents, and special attention was paid to plant growth promoting bacteria (PGPB). Two digestates contained similar plant nutrient contents, while the thermophilic digestate contained higher contents of NH₄⁺–N. The quantity of Bacillus and Pseudomonas in the mesophilic digestate was significantly higher than in the thermophilic digestate. Furthermore, Bacillus showed siderophore production and antifungal activity (43.5–75.3%), and Pseudomonas showed siderophore and phytohormone production (4.2–75.2 µg ml^?1). One phosphate solubilizing isolate was also detected in the mesophilic digestate. These results indicated that two digestates showed different fertilizer properties with respect to nutrient contents and PGPB, and digestates had the potential to increase the availability of phosphorus and iron in the soil, both to provide phytohormones to plant roots and protect plants from fungal phytopathogens. The contents of indicator bacteria and heavy metals were analyzed to determine their environmental risk, and the results showed a high reduction in indicator bacteria and lower levels of heavy metals than in other feedstocks.     

Influence of combustion temperature on the performance of sewage sludge ash as a supplementary cementitious material

The potential for using sewage sludge ash (SSA) as a supplementary cementitious material (SCM) has been investigated. Controlled combustion of sewage sludge collected in Croatia from two wastewater treatment plants produced SSA with different characteristics. These were used to substitute for cement in mortar samples. The chemical composition and physical properties of SSA depend on wastewater composition, the sludge treatment process and the combustion temperature. These factors influence the suitability of SSA to be used as a SCM. For three different combustion temperatures (800, 900 and 1000 °C), it was concluded that properties of fresh mortar were not affected while in the hardened state, the most favorable combustion temperature is 900 °C regarding mechanical properties. Regardless of combustion temperature, for all types of SSA used in mortars as cement replacement (up to 30%), the average decrease in both compressive and flexural strength values was less than 8% for every 10% of added SSA. The results presented indicate that using up to 20% replacement of cement by SSA produces mortars that meet the specific technical requirements analyzed in this work.     

Agronomic characterisation of different types of sewage sludge: Policy implications

Spain is one of the main municipal sewage sludge producers of Europe. This paper aims to agronomically characterise different types of sewage sludge stabilised by different methods (anaerobically digested, composted, and pelletised) and deliver policy recommendations from the results of this characterisation. Anaerobic sewage sludge quality is found to be better in plants with a lower volume of water processing. Composted sludge shows the best quality from a heavy metal point of view, but its low available nitrogen content increases the input of heavy metals when spread, as compared to digested or pelletised sludge. Pelletised sludge has higher heavy metal content than anaerobically digested sludge. Despite the good quality of the sludges, future regulations, especially with regard to Cd levels, will limit the use of this waste in agriculture.     

Bioleaching of zinc and aluminium from industrial waste sludges by means of Thiobacillus ferrooxidans

Biological solubilisation of heavy metals contained in two different kinds of industrial wastes was performed in batches employing a strain of Thiobacillus ferroxidans. The wastes tested were: a dust coming from the iron-manganese alloy production in an electric furnace (sludge 1) and a sludge coming from a process treatment plant of aluminium anodic oxidation (sludge 2). The experimental results pointed out the ability of the used strain to maintain the environment, that initially has a pH about 8, at strongly acid conditions (pH 2.5-3.5), producing sulphuric acid that is the chemical agent responsible for the metals solubilisation. At wastes initial concentration of 1%, the percentage of solubilised metals was 76 and 78% for the wastes 1 and 2, respectively, but the lag phase was considerably longer for sludge 2 than for sludge 1, indicating a different affinity of microorganisms for the solid phase. Increasing the initial slurry concentration, the percentage of removed metal reached 72-73% for the sludge 1, while in case of sludge 2, the total amount of solubilized metal progressively decreased. Two kinetic models are proposed to describe the trends of metals solubilization curves.     

Heavy metals fractionation before, during and after composting of sewage sludge with natural zeolite

The main limiting factor, in order to use compost in agriculture, is the total concentration of heavy metals. Natural zeolites, such as clinoptilolite, have the ability to take up and remove those metals by utilizing ion exchange. However, it is important to know about the fractionation of the heavy metals during the thermophilic phase and the maturation phase. The purpose of this work was to determine the changes in the fraction of heavy metals in sewage sludge compost in which clinoptilolite is used as a bulking agent to remove metals. The final result indicates that a significant (p < 0.05) percentage of the metals, which is not removed by the zeolite, is associated with the residual fraction which is considered as an inert form.     

Characteristic of heavy metals in biochar derived from sewage sludge

This study investigates the characteristic of heavy metals (Pb, Zn, Cu, Cd, Cr, Ni and As) in biochar derived from sewage sludge at different pyrolysis temperatures (300, 400, 500, 600 and 700 °C). The heavy metal concentrations, chemical speciation distribution, leaching toxicity, and bio-available contents were investigated using ICP-OES after microwave digestion, a sequential extraction procedure recommended by the Community Bureau of Reference (BCR), an improved nitric acid–sulphuric acid method, and diethylenetriamine pentaacetic acid (DTPA) extraction method, respectively. The results showed that a great percentage of the heavy metals remained in biochar, the concentrations of heavy metals in biochar (except Cd in B7) were higher than that in sludge, and the enrichment of the heavy metals in biochar enhanced with the pyrolysis temperature. Although the effect of pyrolysis temperature on the chemical speciation distribution, the leaching toxicity and the bio-available contents of heavy metals in biochar was inconsistent, the potential risk of biochar on soil and groundwater contamination was lower than sewage sludge.     

Sludge earthworm composting technology by Eisenia fetida

Prior to vermicompost application to the soils, there is a need to determine the heavy metal concentrations in the final vermicomposts. Acute toxicity on Eisenia fetida for copper (Cu) and cadmium (Cd) were conducted by artificial soils tests. The dosage of interest is typically the median lethal concentration (LC₅₀) that will kill 50 % of the population of organisms within the test period. The dry artificial soil is pre-moistened 1 or 2 days before the test by adding deionized water to obtain approximately half of the required final water content of 40–60 % of the maximum water holding capacity. The 14-day LC₅₀ values (95 % confidence interval) for Cu and Cd were 530 (450–624) and 1118 (988–1265) mg kg^?1, respectively. The vermicomposting was designed to evaluate the effects of earthworm activity on heavy metals in sewage sludge. Compared with the sludge before vermicomposting by Eisenia fetida, the results are as follows: (1) water content, the pH value and organic matter content decreased, (2) total nitrogen content increased, total phosphorus content and total potassium content decreased, (3) available nitrogen concentration, available phosphorus content increased, and (4) the total content of five metals (Cu, Ni, Cd, Pb and Zn) decreased, and the bioaccumulation factor shows that vermicomposting can efficiently remove heavy metals. Therefore, it can be concluded that the soil use of sludge of the Wastewater Treatment Plant in Huaibei is feasible.