Struvite precipitation by the dissolved CO2 degasification technique: impact of the airflow rate and pH

In the present work, struvite precipitation was provoked by the dissolved CO(2) degasification technique where precipitation occurred following the degassing of the CO(2) by atmospheric air. The impact of the airflow rate and initial solution pH on struvite precipitation were assessed. For initial solution pH<6.5, no precipitation was observed. For initial solution pH>6.5, the phosphorus removal through struvite precipitation could be improved by increasing the airflow rate up to 25 L min(-1), or by increasing the initial pH for higher airflow rates. Compared to traditional techniques of struvite precipitation such as stirring and aeration, the dissolved CO(2) degasification technique is promising since a high amount of phosphorus (approximately 78%) could be removed at relatively short experiment time.     

鸟粪石结晶法回收垃圾渗滤液氨氮研究

采用MgSO₄·7H₂O和Na₂HPO₄·12H₂O使NH₃-N生成MgNH₄PO₄·6H₂O（鸟粪石）结晶沉淀法回收渗滤液中NH₃-N。考察了pH值、反应时间、药剂配比对NH₃-N去除率的影响。结果表明,鸟粪石结晶回收NH₃-N反应的适宜pH值为9～9.5之间,过高的pH会破坏鸟粪石晶体结构,导致固定氨从MgNH₄PO₄中游离出来,不利于氨氮的去除。在pH值为9.5、反应时间为25 min、Mg²⁺∶NH⁺₄∶PO^3-₄=1.5∶1∶1.5的最佳条件下,渗滤液中NH₃-N浓度由初始3 500 mg/L,经结晶沉淀后降低至175 mg/L,去除率达95%。鸟粪石结晶沉淀过程中几乎不吸收重金属,同时回收了氨氮,其沉淀产物鸟粪石是一种优良的缓释肥原料。     

酸性条件下剩余污泥中Ca2＋和Mg2＋溶出对磷回收的影响

为了在酸性条件下实现剩余污泥中磷的高效回收,对pH=3时剩余污泥水解酸化过程中氨氮、正磷酸盐和钙镁离子的溶出现象以及磷回收进行了研究分析。结果表明：当pH=3时,所溶出的氨氮、镁离子和钙离子与磷酸盐的摩尔比均大于1,能满足采用鸟粪石沉淀法或者羟磷灰石沉淀法回收磷的要求;但所溶出的钙镁离子的摩尔比大于1,会对鸟粪石沉淀法回收磷的顺利进行有较大影响;有无外加镁剂对磷回收率影响不大。采用改型后的镁型强酸性阳离子交换树脂进行离子交换可以得到较高纯度的鸟粪石沉淀产品,通过XRD检测其纯度为95％以上。     

Overcoming challenges to struvite recovery from anaerobically digested dairy manure

Recovering struvite from dairy manure has consistently posed problems for researchers. This study separated solids from anaerobically digested dairy manure using a filtration system. Filtrate was rich in free magnesium (160 to 423 mg/L), ammonium (320 to 1800 mg N/L) and orthophosphate (93 to 332 mg P/L). High concentrations of free calcium (128 to 361 mg/L) and alkalinity (3309 to 6567 mg/L as CaCO3), however, may hinder struvite precipitation. Batch precipitation tests were conducted to identify and overcome factors that interfere with struvite formation. Precipitation tests at pH 9 identified calcium and ionic strength as most probable interferences. Calcium addition did not significantly change phosphorus removal efficiency, but decreased struvite purity because of formation of calcium phosphates when Ca:P activity ratio was greater than 0.5 to 1. Batch tests demonstrated effective calcium removal from anaerobically digested dairy manure through precipitation of calcium carbonate at pH 9 to 10 while retaining magnesium and orthophosphate, lessening hindrance to struvite formation.     

Coagulation and precipitation as post-treatment of anaerobically treated primary municipal wastewater.

The main objective of this study was to investigate the feasibility of coagulation as a post-treatment method of anaerobically treated primary municipal wastewater. Both mesophilic and ambient (20 degrees C) temperature conditions were investigated in a laboratory-scale upflow anaerobic sludge bed (UASB) reactor. In addition, optimization of the coagulant, both in terms of type and dose, was performed. Finally, phosphorus removal by means of aluminum and iron coagulation and phosphorus and ammonia nitrogen removal by means of struvite precipitation were studied. Anaerobic treatment of primary effluent at low hydraulic retention times (less than 15 hours) resulted in mean chemical oxygen demand (COD) removals ranging from 50 to 70%, while, based on the filtered treated effluent, the mean removals increased to 65 to 80%. Alum coagulation of the UASB effluent gave suspended solids removals ranging from approximately 35 to 65%. Turbidity removal reached up to 80%. Remaining COD values after coagulation and settling were below 100 mg/L, while remaining total organic carbon (TOC) levels were below 50 mg/L. Filterable COD levels were generally below 60 mg/L, while filterable TOC levels were below 40 mg/L. All coagulants tested, including prepolymerized aluminum and iron coagulants, demonstrated similar efficiency compared with alum for the removal of suspended solids, COD, and TOC. Regarding struvite precipitation, optimal conditions for phosphorus and nitrogen removal were pH 10 and molar ratio of magnesium: ammonia-nitrogen: phosphate-phosphorus close to the stoichiometric ratio (1:1:1). During struvite precipitation, removal of suspended solids reached 40%, while turbidity removal reached values up to 80%. The removal of COD was approximately 30 to 35%; yet, when removal of organic matter was based on the treated filterable COD, the removal increased to approximately 65%. In addition, nitrogen was removed by approximately 70%, while phosphorus removal ranged between approximately 30 and 45% on the basis of the initial phosphorus concentration. Finally, size fractionation of the organic matter (COD) showed that the various treatment methods were capable of removing different fractions of the organic matter.     

The Effects of Magnesium and Ammonium Additions on Phosphate Recovery from Greenhouse Wastewater

Phosphorus recovery from greenhouse wastewater, using precipitation-crystallization, was conducted under three levels of calcium concentration, 304 mg/L (7.6 mmol/L), 384 mg/L (9.6 mmol/L), and 480 mg/L (12 mmol/L), and also with additions of ammonium and magnesium into the wastewater. Jar test results confirmed high phosphate removal, with more than 90% of the removal achieved with a pH as low as 7.7. Under the low calcium concentration, ammonium addition affected the chemical reactions at pH lower than 8.0, where struvite was produced; when the pH was raised to 8.8, other calcium compounds dominated the precipitation. Under the medium calcium concentration, ammonium and magnesium addition helped struvite precipitation in the low pH range. Hydroxyapatite (HAP) was the main product. Under the high calcium concentration, ammonium addition showed no effects on the precipitation.     

The effects of magnesium and ammonium additions on phosphate recovery from greenhouse wastewater

Phosphorus recovery from greenhouse wastewater, using precipitation-crystallization, was conducted under three levels of calcium concentration, 304 mg/L (7.6 mmol/L), 384 mg/L (9.6 mmol/L), and 480 mg/L (12 mmol/L), and also with additions of ammonium and magnesium into the wastewater. Jar test results confirmed high phosphate removal, with more than 90% of the removal achieved with a pH as low as 7.7. Under the low calcium concentration, ammonium addition affected the chemical reactions at pH lower than 8.0, where struvite was produced; when the pH was raised to 8.8, other calcium compounds dominated the precipitation. Under the medium calcium concentration, ammonium and magnesium addition helped struvite precipitation in the low pH range. Hydroxyapatite (HAP) was the main product. Under the high calcium concentration, ammonium addition showed no effects on the precipitation.     

Adsorption characteristics of Ni(II) on gamma-type alumina particles and its determination of overall adsorption rate by a differential bed reactor

The adsorption experiment of nickel ion [Ni(II)] on gamma-type alumina by a differential bed reactor in aqueous solutions was investigated to determine the adsorption characteristics and overall adsorption rate. The adsorbed amount increased rapidly with pH from pH 2 to 6 and kept constant over pH 6. The adsorbed amount of Ni(II) increased with temperature from 20 to 50 degrees C. Correlation coefficients (R2) of Langmuir and Freundlich adsorption isotherms were 0.9268 and 0.9489, respectively, and Freundlich isotherm was more suitable for adsorption on gamma-type alumina than Langmuir isotherm.The overall adsorption rate of Ni(II) on gamma-type alumina at pH 6 by a differential bed rector was determined as follows: r = 68.77Ce(1.61) - 17.60qe(0.36). Al(III) ions in solutions were away from the alumina surface during the adsorption of Ni(II) and Al(III) concentration increased with an increasing Ni(II) adsorbed amount on alumina.     

天然及CaCl2改性沸石对四环素的吸附

通过静态吸附实验研究了水中四环素在天然和CaCl2改性沸石上的吸附行为及机制。实验表明,天然沸石对四环素具有吸附能力,CaCl2改性可以提高沸石对四环素的吸附能力。天然和改性沸石对四环素的吸附符合拟二级动力学模型,颗粒内扩散不是吸附过程的主要控制步骤。Freundlich和Dubinin-Radushkevich(D-R)等温吸附模型可以较好地描述实验所用2种沸石对四环素的吸附行为,D-R等温方程拟合结果显示吸附过程包含离子交换作用。通过对天然和改性沸石吸附四环素前后溶液中主要阳离子浓度变化分析证实了该吸附过程包含离子交换作用。实验研究了pH值变化对沸石吸附四环素的影响,当pH=3～5时,天然和改性沸石对四环素的吸附量均随pH值的增加而急剧下降,而pH=5～10时,天然和改性沸石对四环素的吸附量变化均不明显,推测可能是离子交换作用和化学沉淀吸附作用所致。另外,实验还初步探索了溶液离子强度对沸石吸附四环素的影响情况,随着溶液中Na+和Ca2+离子强度的增加,吸附量先急剧降低随后趋向平稳,进一步说明了沸石对四环素的吸附过程不是由单一机制控制的。     

Effect of fly ash characteristics on the removal of Cu(II) from aqueous solution

Fly ash is a particulate substance containing metal oxides, carbon and other microelements. In this study, fly ashes with different quantities of carbon and minerals prepared by a thermal process in the laboratory were used as adsorbents to investigate the contribution of precipitation and adsorption to the removal of aqueous Cu(II). Experimental results showed that the specific surface area of fly ash increased linearly with the quantity of carbon. The specific surface areas of the carbon and mineral fraction were 60 m2/g and 0.68 m2/g, respectively. The specific adsorption capacities of carbon ranged from 2.2 to 2.8 mg Cu/g carbon, while those for mineral were only about 0.63 to approximately 0.81 mg Cu/g mineral. Consequently, the carbon fraction in fly ash was important in the removal of Cu(II) at pH 5. However, Cu(II) removal owing to precipitation increases with a decreasing carbon fraction and the contribution of copper precipitation was estimated to be approximately 23% to approximately 82% of total removal, depending on the carbon fraction of fly ash.     

Prospect of recovering phosphorus in magnesium slag-packed wetland filter

Phosphorus recovery from wastewater not only reduces the unbearable impacts of excessive nutrient discharge on environmental systems but also favor the reuse of phosphorus resource. Based on the mechanism as well as technical analysis for major phosphorus recovery techniques including struvite precipitation and wetland substrate adsorption, a novel magnesium slag-packed wetland filter and corresponding operational procedures are proposed, which aim to reduce the dependence of using magnesium-containing chemical reagent as magnesium sources for struvite precipitation, and improve the accumulation and recovery performance for struvite precipitation within porous wetland substrate. Results from preliminary experiments indicated that magnesium slag particles with approximately 2 mm in diameter can recover 43.20–72.39% phosphorus from 1–25 mol/L PO₄ ^3? solution, and the presence of 5–50 mol/L NH₄ ⁺ contributed to 11.71–29.11% enhancement of phosphorus recovery mainly due to struvite precipitation. The detected generation of struvite via XRD spectrum analysis partly demonstrated the potential of phosphorus recovery in magnesium slag-packed wetland filter. The proposed phosphorus recovery technology is free of secondary pollution and solid waste generation; phosphorus-saturated (mainly due to struvite precipitation and adsorption) magnesium slag particles can be potentially used as phosphorus fertilizer and thus partly solved the traditional shortages of disposing phosphorus-saturated substrate due to low phosphorus contents.     

重金属杂质对磷酸铵镁结晶法处理制药废水的影响

磷酸铵镁沉淀法处理废水时常受众多因素影响,其中重金属类杂质对该过程影响较大。实验研究了Mn²⁺、Cu²⁺杂质存在条件下,用该法去除制药废水中PO₄^3-、NH₄⁺污染物,同时,用XRD、XRF、SEM等手段研究了所得鸟粪石晶体特征。结果表明,pH为9.5时,Mn²⁺、Cu²⁺杂质存在条件下,PO₄^3-去除率分别为88%和85%,投加晶种有利于回收特定晶形鸟粪石,Cu²⁺对磷酸铵镁结晶过程的影响较Mn²⁺存在时显著。     

四环素在石墨上的吸附行为研究

考察了石墨和四环素的相关性质,并通过静态吸附实验探讨了四环素在石墨表面的吸附行为及其机理。结果表明,四环素在石墨表面的吸附量、四环素的K_(ow)值以及四环素(+,-,0)的形态分布在pH尺度上的变化趋势表现出较高的相似性。据此推断四环素主要通过疏水力作用吸附于石墨表面,该作用力最大值出现在pH=5～6之间,而其他pH条件下,该作用力会随吸附剂、吸附质间静电斥力的增强和四环素自身溶解度的增加而被削弱。     

Removal of toxic heavy metal ions from waste water by functionalized magnetic core–zeolitic shell nanocomposites as adsorbents

Functionalized magnetic core–zeolitic shell nanocomposites were prepared via hydrothermal and precipitation methods. The products were characterized by vibrating sample magnetometer, X-ray powder diffraction, Fourier transform infrared spectroscopy, nitrogen adsorption–desorption isotherms, and transmission electron microscopy analysis. The growth of mordenite nanocrystals on the outer surface of silica-coated magnetic nanoparticles at the presence of organic templates was well approved. The removal performance and the selectivity of mixed metal ions (Pb²⁺ and Cd²⁺) in aqueous solution were investigated via the sorption process. The batch method was employed to study the sorption kinetic, sorption isotherms, and pH effect. The removal mechanism of metal ions was done by chem–phys sorption and ion exchange processes through the zeolitic channels and pores. The experimental data were well fitted by the appropriate kinetic models. The sorption rate and sorption capacity of metal ions could be significantly improved by optimizing the parameter values.     

Characterization of primary precipitate composition formed during co-removal of Cr(VI) with Cu(II) in synthetic wastewater

BACKGROUND, AIMS AND SCOPE: Hexavalent chromium [Cr(VI)] cannot react with either carbonate or hydroxide to form chromium precipitates. However, by using a precipitation technology to treat plating wastewater containing Cr(VI), Cu(II), Ni(II) and Zn(II), approximately 78% of Cr(VI) (initial 60 mg/L) was co-removed with the precipitation of Cu(II), Ni(II) and Zn(II) (each 150 mg/L) by dosing with Na2CO3 (Sun 2003). Direct precipitation by forming Cu(II)-Cr(VI) precipitates followed by adsorption of Cr(VI) onto freshly formed Cu-precipitates was subsequently found to be the main mechanism(s) involved in Cr(VI) co-removal with Cu(II) precipitation by dosing Na2CO3 stepwise to various pH values (Sun et al. 2003). This study was. carried out to further characterize the formation of primary precipitates during the early stages of copper precipitation and simultaneous removal of Cr(VI) with Cu(II). METHODS: Test metal-solutions were prepared with industrial grade chemicals: CuCl2 x 2H2O, Na2SO4 and K2Cr2207. NaCO3 was added drop-wise to synthetic metal-solution to progressively increase pH. For each pH increment, removal of soluble metals was detected by atomic absorption spectrophotometer (AAS) and surface morphology of precipitates was analyzed by scanning electron microscope (SEM). To further characterize the formation of primary precipitates, a series of MINEQL+ thermodynamic calculations/analyses and equilibrium calculations/ analyses were conducted. RESULTS AND DISCUSSION: MINEQL+ thermodynamic calculation indicated that, for a system containing 150 mg/L Cu(II) and 60 mg/L Cr(VI) with gradual Na2CO3 dosing, if any precipitates can be formed at pH 5.0 or lower, it should be in the form of CuCrO4. Comparison tests using systems containing the same equivalent of Cu(II) plus Cr(VI) and Cu(II) plus SO4(2-) showed that the precipitation occurred at a pH of around 5.0 in the Cu(II)-Cr(VI) system and around 6.0 in the Cu(II)-SO4(2-) system. The discrepancy of the precipitation was indeed caused by the formation of Cu-Cr precipitates. The initiation of copper removal at pH around 5.0 for the Cu-Cr co-removal test was not attributable to the formation of Cu-CO3 precipitates, instead, it was most likely through the formation of insoluble Cu-Cr precipitates, such as CuCrO4 and CuCrO4 x 2Cu(OH)2. Experimental tests, equilibrium calculations, MINEQL+ thermodynamic calculations and surface morphologies for systems using higher concentrations of Cu(II) and Cr(VI) further verified the most probable composition of primary precipitates is copper-chromate. CONCLUSION: In the Cu-Cr co-removal test with Na2O3 dosing to increase pH and induce metal precipitation, copper-chromate precipitates are the primary precipitates produced and contribute to the initial simultaneous removal of copper and chromium.     

Degradation of tetracycline at a boron-doped diamond anode: influence of initial pH,applied current intensity and electrolyte

The anodic oxidation of tetracycline was performed in an up-flow reactor, operating in batch mode with recirculation, using as anode a boron-doped diamond electrode. The influence on the degradation rate of solution initial pH (2 to 12), applied current intensity (25 to 300 A m^?2) and type of electrolyte (sodium sulphate or sodium chloride) were investigated. For the assays run at equal current density, with sodium sulphate as electrolyte, the solution’s initial pH of 2 presented the highest absorbance and chemical oxygen demand removals. Regarding the influence of current density, for equal charge passed, the organic load removal rate decreased with the increase in applied current. When sodium sulphate was used as an electrolyte, high-performance liquid chromatography (HPLC) results have shown an almost complete removal of tetracycline after a 2-h assay. HPLC results have also shown the presence of oxamic acid as one of the intermediates of tetracycline anodic oxidation. The complete removal of tetracycline was much faster in the presence of chloride ions that promoted the complete degradation of this antibiotic in 30 min. However, in the presence of chloride ions, the tetracycline mineralization is slower, as observed by the lower organic carbon removal rate when compared to that of the tetracycline degradation in the presence of sulphate.     

负载TiO2的活性炭纤维改性电极电吸附除氟

采用溶胶-凝胶法制备TiO2凝胶,将TiO2凝胶涂覆在活性炭纤维表面并进行热处理制备改性电极(TiO2/ACF),利用扫描电子显微镜(SEM)、X射线衍射光谱仪(XRD)、比表面和孔隙度分析仪对负载前后电极的表面特性进行表征,并探讨了其对NaF溶液的电吸附效果。结果表明,电极负载TiO2后表面变得粗糙,比表面积和总孔体积减小,而介孔体积和平均孔径增大。此外,表面的TiO2同时以金红石和锐钛矿的晶型存在。电吸附实验结果显示,加电可以提高吸附容量,而且电压、pH和初始氟离子浓度均对电吸附容量产生影响:电压增大,吸附容量增加,当施加电压为2 V时,电吸附容量为1.03 mg/g,比开路电位时提高40%;pH可以通过影响氟离子在溶液中的存在形态和TiO2/ACF电极表面的羟基基团对电吸附容量产生影响;初始氟离子浓度升高,电极吸附容量增大,但是去除率降低。在处理初始氟离子浓度为4 mg/L的NaF溶液时,在2 V电压、中性pH和12 h的吸附时间下,改性ACF为电极的吸附量为1.32 mg/g。     

天然沸石同步去除水中氨氮和磷酸盐

通过静态吸附实验考察了浙江缙云产天然沸石对溶液中氨氮和磷酸盐的同步去除能力及机制,结果表明,天然沸石对溶液中氨氮的吸附过程较好地满足拟二级动力学模型、Langmuir和Dubinin-Radushkevich等温吸附模型。天然沸石对磷酸盐的去除能力随溶液中初始氨氮浓度的增加而增加。当溶液pH由7.0增加到9.0时,天然沸石对氨氮的吸附能力随之增加,而当pH由9.0增加到10时,天然沸石对氨氮的吸附能力则下降。当溶液pH低于7.5时,天然沸石对溶液中的磷酸盐无去除能力,当溶液pH位于7.5～9.0时,天然沸石对磷酸盐的去除能力随pH的增加急剧增加,当溶液pH大于9.0时,天然沸石对磷酸盐的去除能力随pH的增加则呈下降趋势。天然沸石对溶液中氨氮和磷酸盐的同步去除过程是自发进行、吸热及熵增加的过程。天然沸石对溶液中氨氮的吸附机制为离子交换,对磷酸盐的去除机制则为化学沉淀作用。     

高比表面积活性炭的制备及对Cr(Ⅵ)吸附的研究

以椰树壳为原料,运用水蒸汽和二氧化碳复合物理活化法在4 h内制备了2 162.84 m2/g的高比表面积活性炭,其孔径分布范围为1.1~2.5 nm。应用此吸附剂考察了溶液pH、吸附剂用量、接触时间和初始浓度对Cr(VI)离子吸附效果的影响,并讨论了固定吸附床中不同溶液流量对Cr(VI)去除效果的影响。结果表明:在温度为298 K、溶液pH为1.96、吸附剂用量为0.10 g、铬离子初始浓度为100 mg/L与接触时间为70 min的条件下,活性炭对铬离子具有较高的吸附容量,去除率高达99.32%;铬离子在吸附床中的穿透曲线具有陡峭的传质锋面,但随着铬离子溶液流量的增大脱除果率降低。     

Removal mechanisms and kinetics of trace tetracycline by two types of activated sludge treating freshwater sewage and saline sewage

Understanding the removal mechanisms and kinetics of trace tetracycline by activated sludge is critical to both evaluation of tetracycline elimination in sewage treatment plants and risk assessment/management of tetracycline released to soil environment due to the application of biosolids as fertilizer. Adsorption is found to be the primary removal mechanism while biodegradation, volatilization, and hydrolysis can be ignored in this study. Adsorption kinetics was well described by pseudo-second-order model. Faster adsorption rate (k ₂?=?2.04?×?10^?2?g?min^?1?μg^?1) and greater adsorption capacity (q _e?=?38.8 μg?g^?1) were found in activated sludge treating freshwater sewage. Different adsorption rate and adsorption capacity resulted from chemical properties of sewage matrix rather than activated sludge surface characteristics. The decrease of tetracycline adsorption in saline sewage was mainly due to Mg²⁺ which significantly reduced adsorption distribution coefficient (K _d) from 12,990?±?260 to 4,690?±?180 L?kg^?1. Species-specific adsorption distribution coefficients followed the order of $ K_{\mathrm{d}}^{{ + 00}} \gg K_{\mathrm{d}}^{{ + - 0}} > K_{\mathrm{d}}^{{ + - - }} $ . Contribution of zwitterionic tetracycline to the overall adsorption was >90 % in the actual pH range in aeration tank. Adsorption of tetracycline in a wide range of temperature (10 to 35 °C) followed the Freundlich adsorption isotherm well.