Silica removal in industrial effluents with high silica content and low hardness

High silica content of de-inked paper mill effluents is limiting their regeneration and reuse after membrane treatments such as reverse osmosis (RO). Silica removal during softening processes is a common treatment; however, the effluent from the paper mill studied has a low hardness content, which makes the addition of magnesium compounds necessary to increase silica removal. Two soluble magnesium compounds (MgCl₂?6H₂O and MgSO₄?7H₂O) were tested at five dosages (250–1,500 mg/L) and different initial pH values. High removal rates (80–90 %) were obtained with both products at the highest pH tested (11.5). With these removal efficiencies, it is possible to work at high RO recoveries (75–85 %) without silica scaling. Although pH regulation significantly increased the conductivity of the waters (at pH 11.5 from 2.1 to 3.7–4.0 mS/cm), this could be partially solved by using Ca(OH)₂ instead of NaOH as pH regulator (final conductivity around 3.0 mS/cm). Maximum chemical oxygen demand (COD) removal obtained with caustic soda was lower than with lime (15 vs. 30 %). Additionally, the combined use of a polyaluminum coagulant during the softening process was studied; the coagulant, however, did not significantly improve silica removal, obtaining a maximum increase of only 10 %.     

Interactions between chloride and sulfate or silica removals using an advanced lime-aluminum softening process.

An advanced softening process called the ultra-high lime with aluminum process (UHLA) was initiated in this research. The UHLA process has the ability to remove sulfate, silica, and chloride from waters such as recycled cooling water and desalination brines. Furthermore, it can remove other scale-forming materials, such as calcium, magnesium, carbonate, and phosphate. The purpose of this paper is to study the interactions among chloride, sulfate, and silica in the UHLA process. Results of equilibrium experiments indicated that sulfate is preferentially removed over chloride. Final chloride concentration increased with increasing initial sulfate concentration. However, initial chloride concentration was found to have negligible effect on final sulfate concentration. Silica was found to have only a small effect on chloride removal.     

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.     

Accelerated seeded precipitation pre-treatment of municipal wastewater to reduce scaling

Membrane based treatment processes are very effective in removing salt from wastewater, but are hindered by calcium scale deposit formation. This study investigates the feasibility of removing calcium from treated sewage wastewater using accelerated seeded precipitation. The rate of calcium removal was measured during bench scale batch mode seeded precipitation experiments at pH 9.5 using various quantities of calcium carbonate as seed material. The results indicate that accelerated seeded precipitation may be a feasible option for the decrease of calcium in reverse osmosis concentrate streams during the desalination of treated sewage wastewater for irrigation purposes, promising decreased incidence of scaling and the option to control the sodium adsorption ratio and nutritional properties of the desalted water. It was found that accelerated seeded precipitation of calcium from treated sewage wastewater was largely ineffective if carried out without pre-treatment of the wastewater. Evidence was presented that suggests that phosphate may be a major interfering substance for the seeded precipitation of calcium from this type of wastewater. A pH adjustment to 9.5 followed by a 1-h equilibration period was found to be an effective pre-treatment for the removal of interferences. Calcium carbonate seed addition at 10 g l⁻¹ to wastewater that had been pre-treated in this way was found to result in calcium precipitation from supersaturated level at 60 mg l⁻¹ to saturated level at 5 mg l⁻¹. Approximately 90% reduction of the calcium level occurred 5 min after seed addition. A further 10% reduction was achieved 30 min after seed addition.     

Fouling mechanisms in a laboratory-scale UV disinfection system.

The fouling of quartz sleeves surrounding UV disinfection lamps is a perennial problem affecting both drinking water and wastewater applications. The mechanisms of fouling are not fully understood, but factors promoting fouling are believed to include heat, high hardness and/or high iron concentrations, and hydrodynamic forces. The role of UV radiation itself is unclear. The goal of this paper is to attempt to isolate the fouling mechanisms and to provide key information about those induced by UV radiation, using a unique laboratory-scale continuous-flow UV reactor. Its design allowed for irradiated and nonirradiated zones and control of both temperature and UV intensity at the fouling surface. Synthetic wastewater samples were tested with two levels of calcium, iron, phosphorus, and biochemical oxygen demand (as beef broth), and constant levels of magnesium and nitrogen to assess the effects of the four key variables. Average UV fluence before fouling exceeded 35 mJ/cm2, based on collimated beam tests. Foulant accumulation was monitored by UV intensity measurements and by mass and composition of foulant collected after an average of 56 hours of continuous operation. Tests showed that relative UV intensity dropped by as much as 100% when iron was present. Detailed results were assessed and yielded support for the following three UV-induced fouling mechanisms: (a) precipitation of ferric hydroxide [Fe(OH)3], (b) release of calcium from calcium-organics complexes followed by precipitation of iron-organics complexes, and (c) calcium carbonate precipitation. Other fouling mechanisms, such as sedimentation of preformed particles and sorption of calcium onto preformed colloids of Fe(OH)3, occurred outside the zone of UV radiation. Hence, these could be confused with concurrent UV-induced mechanisms in full-scale reactors. Iron and/or calcium undoubtedly created the most favorable conditions for fouling to occur; in the absence of both, fouling would be unlikely. The rates of fouling were enhanced when organics were also present; however, when phosphorus was present, fouling in the UV section was reduced. Indeed, UV may be viewed as inhibiting the fouling caused by phosphate complexes.     

pH对钢铁废水再生过程中CMF系统的影响

通过中试实验研究了钢铁废水再生过程中pH变化对微滤系统性能的影响。结果表明,进水pH的升高增加了微滤膜对UV254、Ca2+和总铁的去除,同时引起了有机物以及无机沉淀物在膜面的吸附。铁锰无机沉淀物在膜面的吸附和对膜孔的堵塞是引起膜污染的主要因素。降低pH有助于控制无机沉淀在膜面和膜孔内的形成,抑制膜污染的形成。     

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.     

印染生化尾水反渗透深度处理工艺膜污染成因分析简

为阐明印染生化尾水反渗透膜处理时膜污染的成因,使用小试装置进行40 h膜污染实验,研究膜污染速率、污染程度以及可逆性,同时应用扫描电子显微镜-EDS能谱仪、傅里叶变换红外光谱仪、电感耦合等离子发射光谱仪、总有机碳测定仪等仪器对进水水质、膜表面污染物的形态和组成等进行表征。结果表明,膜表面主要是碳酸钙无机污染和钙与有机物络合污染,无机污染占主导,且可逆性差,有机污染物主要含有—OH和—CC官能团;单一去除废水中有机物污染物（TOC去除率达88%）对膜污染缓解不明显,但钙离子的去除可显著缓解膜污染,膜通量可增加72.6%;同时去除有机物和钙离子,膜通量可增加80.4%。     

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。     

印染生化尾水反渗透深度处理工艺膜污染成因分析

为阐明印染生化尾水反渗透膜处理时膜污染的成因,使用小试装置进行40h膜污染实验,研究膜污染速率、污染程度以及可逆性,同时应用扫描电子显微镜一EDS能谱仪、傅里叶变换红外光谱仪、电感耦合等离子发射光谱仪、总有机碳测定仪等仪器对进水水质、膜表面污染物的形态和组成等进行表征。结果表明,膜表面主要是碳酸钙无机污染和钙与有机物络合污染,无机污染占主导,且可逆性差,有机污染物主要含有--OH和～c-c官能团;单一去除废水中有机物污染物（TOC去除率达88％）对膜污染缓解不明显,但钙离子的去除可显著缓解膜污染,膜通量可增加72．6％;同时去除有机物和钙离子,膜通量可增加80．4％。     

铁炭微电解-MAP沉淀法联合预处理垃圾渗滤液

采用铁炭微电解-磷酸氨镁(MAP)沉淀法对垃圾渗滤液进行预处理,实验结果表明,铁炭比为5∶1,pH值为3,反应时间为3 h时,铁炭微电解的COD的去除率为47.5%;在投加药剂n(Mg2+)∶n(PO43-)∶n(NH4+)为1.4∶1∶1,pH值为9,反应时间为1 h的条件下,垃圾渗滤液氨氮去除率达到79.7%。     

Waste green sands as reactive media for the removal of zinc from water

Waste green sands are industrial byproducts of the gray iron foundry industry. These green sands are composed of fine silica sand, clay binder, organic carbon, and residual iron particles. Because of their potential sorptive and reactive properties, tests were performed to determine the feasibility of using green sands as a low cost reactive medium in permeable reactive barriers (PRBs). Serial batch kinetic tests and conventional batch sorption tests were conducted to determine the removal characteristics for zinc in aqueous solutions. Removal characteristics for zinc in the presence of green sands are comparable to those of Peerless iron, a common reactive medium used in PRBs. High removal capacities for zinc of green sands are attributed to clay, organic carbon, and residual iron particles, which are known sorptive media for heavy metals. Furthermore, high pH values in the presence of clay and residual iron particles enhanced sorption and precipitation of zinc.     

Performance evaluation of intermediate cover soil barrier for removal of heavy metals in landfill leachate

This pilot-scale study evaluated the use of intermediate cover soil barriers for removing heavy metals in leachate generated from test cells for co-disposed fly ash from municipal solid waste incinerators, ash melting plants, and shredder residue. Cover soil barriers were mixtures of Andisol (volcanic ash soil), waste iron powder, (grinder dust waste from iron foundries), and slag fragments. The cover soil barriers were installed in the test cells' bottom layer. Sorption/desorption is an important process in cover soil bottom barrier for removal of heavy metals in landfill leachate. Salt concentrations such as those of Na, K, and Ca in leachate were extremely high (often greater than 30 gL(-1)) because of high salt content in fly ash from ash melting plants. Concentrations of all heavy metals (nickel, manganese, copper, zinc, lead, and cadmium) in test cell leachates with a cover soil barrier were lower than those of the test cell without a cover soil barrier and were mostly below the discharge limit, probably because of dilution caused by the amount of leachate and heavy metal removal by the cover soil barrier. The cover soil barriers' heavy metal removal efficiency was calculated. About 50% of copper, nickel, and manganese were removed. About 20% of the zinc and boron were removed, but lead and cadmium were removed only slightly. Based on results of calculation of the Langelier saturation index and analyses of core samples, the reactivity of the cover soil barrier apparently decreases because of calcium carbonate precipitation on the cover soil barriers' surfaces.     

Phosphate recovery from greenhouse wastewater

A study was conducted to investigate the suitability of phosphate recovery from greenhouse wastewaters by using precipitation/crystallization process. More than 90% of the phosphate could be removed from the greenhouse wastewater. Various calcium phosphate salts were obtained in the process; hydroxyapatite [Ca5(PO4)3OH] could be the main product from the precipitates. Phosphate removal was affected by the presence of magnesium ion in wastewaters. An increase of magnesium concentrations in wastewaters decreased phosphate removal rates. The chemical contents of precipitates in terms of calcium, magnesium and phosphate were affected by calcium to magnesium molar ratio. Higher calcium contents were obtained at wastewaters with high calcium to magnesium molar ratio. An addition of magnesium did not affect the potassium contents in the precipitates. K-struvite, MgKPO4 x 6H2O, was not the major product in the precipitate, even with addition of a large quantity of magnesium.     

Iron oxide-loaded slag for arsenic removal from aqueous system

An effective adsorbent for arsenic removal from aqueous system was synthesized by loading iron(III) oxide on municipal solid waste incinerator melted slag. The loading was accomplished via chemical processes and thermal coating technique. The key point of the technique was the simultaneous generation of amorphous FeOOH sol and silica sol in-situ and eventually led to the formation of Fe-Si surface complexes which combined the iron oxide with the melted slag tightly. The surface morphology of the iron oxide-loaded slag was examined and the loading mechanisms were discussed in detail. The adsorbent was effective for both arsenate and arsenite removal and its removal capabilities for As(V) and As(III) were 2.5 and 3 times of those of FeOOH, respectively. Both affinity adsorption and chemical reactions contributed to arsenic removal. The effects of solution pH, contact time, arsenic concentration and adsorbent dosage on arsenic removal were examined and the optimum removal conditions were established. Furthermore, leaching of hazardous elements such as Cr(VI), As, Se, Cd and Pb from the adsorbent at a pH range of 2.5-12.5 was below the regulation values. Accordingly, it is believed that the iron oxide-loaded slag developed in this study is environmentally acceptable and industrially applicable for wastewater treatment.     

Phosphate Recovery from Greenhouse Wastewater

A study was conducted to investigate the suitability of phosphate recovery from greenhouse wastewaters by using precipitation/crystallization process. More than 90% of the phosphate could be removed from the greenhouse wastewater. Various calcium phosphate salts were obtained in the process; hydroxyapatite [Ca₅(PO₄)₃OH] could be the main product from the precipitates. Phosphate removal was affected by the presence of magnesium ion in wastewaters. An increase of magnesium concentrations in wastewaters decreased phosphate removal rates. The chemical contents of precipitates in terms of calcium, magnesium and phosphate were affected by calcium to magnesium molar ratio. Higher calcium contents were obtained at wastewaters with high calcium to magnesium molar ratio. An addition of magnesium did not affect the potassium contents in the precipitates. K‐struvite, MgKPO₄·6H₂O, was not the major product in the precipitate, even with addition of a large quantity of magnesium.     

The removal of phosphorus during wastewater treatment: a review

Phosphorus removal from wastewater can be achieved either through chemical removal, advanced biological treatment or a combination of both. The chemical removal of phosphorus involves the addition of calcium, iron and aluminium salts to achieve phosphorus precipitation by various mechanisms which are discussed. In addition, the effects of operating conditions, especially wastewater characteristics; sludge production in terms of quality and quantity; optimisation of chemical use and re-use; points of chemical addition combined with biological treatment; alternative chemical/physical treatments and examples of full-scale applications are also reviewed. Biological phosphorus removal is dependent upon the uptake of phosphorus in excess of normal bacterial metabolic requirements and is proposed as an alternative to chemical treatment. Early developments and the postulated removal mechanisms are reviewed; these include either natural chemical precipitation, enhanced biological removal, or a combination of both. The nature of excess biological phosphorus removal in activated sludge wastewater treatment plants is evaluated, considering various operating parameters, bacteriology and process designs.     

Acid generation upon thermal concentration of natural water: The critical water content and the effects of ionic composition

Thermal evaporation of a variety of simulated pore waters from the region of Yucca Mountain, Nevada, produced acidic liquids and gases during the final stages of evaporation. Several simulated pore waters were prepared and then thermally distilled in order to collect and analyze fractions of the evolved vapor. In some cases, distillates collected towards the end of the distillation were highly acidic; in other cases the pH of the distillate remained comparatively unchanged during the course of the distillation. The results suggest that the pH values of the later fractions are determined by the initial composition of the water. Acid production stems from the hydrolysis of magnesium ions, especially at near dryness. Near the end of the distillation, magnesium nitrate and magnesium chloride begin to lose water of hydration, greatly accelerating their thermal decomposition to form acid. Acid formation is promoted further when precipitated calcium carbonate is removed. Specifically, calcium chloride-rich pore waters containing moderate (10–20 ppm) levels of magnesium and nitrate and low levels of bicarbonate produced mixtures of nitric and hydrochloric acid, resulting in a precipitous drop in pH to values of 1 or lower after about 95% of the original volume was distilled. Waters with either low or moderate magnesium content coupled with high levels of bicarbonate produced slightly basic fractions (pH 7–9). If calcium was present in excess of bicarbonate, waters containing moderate levels of magnesium produced acid even in the presence of bicarbonate, due to the precipitation of calcium carbonate. Other salts such as halite and anhydrite promote the segregation of acidic vapors from residual basic solids. The concomitant release of wet acid gas has implications for the integrity of the alloys under consideration for containers at the Yucca Mountain nuclear waste repository. Condensed acid gases at very low pH, especially mixtures of nitric and hydrochloric acid, are capable of corroding even alloys, such as nickel-based Alloy 22, which are considered to be corrosion-resistant under milder conditions.     

Interactions between chloride and sulfate or silica removals from wastewater using an advanced lime-aluminum softening process: equilibrium modeling.

Interactions among chloride, sulfate, and silica removals from recycled industrial wastewater using an ultra-high lime with aluminum process (UHLA) were studied. An equilibrium model that is able to accurately predict the chemical behavior and interactions between chloride and sulfate or silica with UHLA at various initial conditions and chemical reagents was developed. X-ray diffraction (XRD) analysis was conducted to identify the precipitated solids formed in the UHLA process. Model predictions indicated that simultaneous removal of sulfate and chloride can be best described by the formation of a solid solution containing calcium chloroaluminate, calcium sulfoaluminate (ettringite), calcium monosulfate, tricalcium hydroxyaluminate, and tetracalcium hydroxyaluminate. However, simultaneous removal of silica and chloride can be best described by precipitation of calcium silicate and calcium aluminosilicate in addition to a solid solution containing calcium chloroaluminate, tricalcium hydroxyaluminate, and tetracalcium hydroxyaluminate. The XRD results indicated the presence of the same solids assumed by the equilibrium model.