剩余污泥水解酸化液磷去除的影响因素研究

城市污水厂剩余污泥水解酸化后可产生高浓度挥发性有机酸(VFAs),其中的乙酸和丙酸是增强生物除磷(EBPR)工艺的有利基质.但水解酸化液中含有大量的磷,如不进行处理就作为碳源回用到污水处理工艺中,势必增加除磷负荷.利用鸟粪石沉淀法可以去除污水中的磷.对城市污水厂剩余污泥水解酸化液形成鸟粪石的影响因素进行了试验研究.结果表明,在最佳工艺条件下,正磷和总磷的去除率分别可达92.5%和83.8%.     

Co-conditioning of the anaerobic digested sludge of a municipal wastewater treatment plant with alum sludge: benefit of phosphorus reduction in reject water.

In this study, alum sludge was introduced to co-conditioning and dewatering with an anaerobic digested sludge from a municipal wastewater treatment plant, to examine the role of the alum sludge in improving the dewaterbility of the mixed sludge and also in immobilizing phosphorus in the reject water. Experiments have demonstrated that the optimal mix ratio for the two sludges is 2:1 (anaerobic digested sludge:alum sludge: volume basis), and this can bring approximately 99% phosphorus reduction in the reject water through the adsorption of phosphorus by alum in the sludge. The phosphorus loading in wastewater treatment plants is itself derived from the recycling of reject water during the wastewater treatment process. Consequently, this co-conditioning and dewatering strategy can achieve a significant reduction in phosphorus loading in wastewater treatment plants. In addition, the use of the alum sludge has been shown to beneficially enhance the dewaterability of the resultant mixed sludge, by decreasing both the specific resistance to filtration and the capillary suction time. This is attributed to the alum sludge acting in charge neutralization and/or as adsorbent for phosphate in the aqueous phase of the sludge. Experiments have also demonstrated that the optimal polymer (Superfloc C2260, Cytec, Botlek, Netherlands) dose for the anaerobic digested sludge was 120 mg/L, while the optimal dose for the mixed sludge (mix ratio 2:1) was 15 mg/L, highlighting a huge savings in polymer addition. Therefore, from the technical perspective, the co-conditioning and dewatering strategy can be viewed as a "win-win" situation. However, for its full-scale application, integrated cost-effective analysis of process capabilities, sludge transport, increased cake disposal, additional administration, polymer saving, and so on, should be factored in.     

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.     

Coagulant recovery from water treatment plant sludge and reuse in post-treatment of UASB reactor effluent treating municipal wastewater

In the present study, feasibility of recovering the coagulant from water treatment plant sludge with sulphuric acid and reusing it in post-treatment of upflow anaerobic sludge blanket (UASB) reactor effluent treating municipal wastewater were studied. The optimum conditions for coagulant recovery from water treatment plant sludge were investigated using response surface methodology (RSM). Sludge obtained from plants that use polyaluminium chloride (PACl) and alum coagulant was utilised for the study. Effect of three variables, pH, solid content and mixing time was studied using a Box–Behnken statistical experimental design. RSM model was developed based on the experimental aluminium recovery, and the response plots were developed. Results of the study showed significant effects of all the three variables and their interactions in the recovery process. The optimum aluminium recovery of 73.26 and 62.73 % from PACl sludge and alum sludge, respectively, was obtained at pH of 2.0, solid content of 0.5 % and mixing time of 30 min. The recovered coagulant solution had elevated concentrations of certain metals and chemical oxygen demand (COD) which raised concern about its reuse potential in water treatment. Hence, the coagulant recovered from PACl sludge was reused as coagulant for post-treatment of UASB reactor effluent treating municipal wastewater. The recovered coagulant gave 71 % COD, 80 % turbidity, 89 % phosphate, 77 % suspended solids and 99.5 % total coliform removal at 25 mg Al/L. Fresh PACl also gave similar performance but at higher dose of 40 mg Al/L. The results suggest that coagulant can be recovered from water treatment plant sludge and can be used to treat UASB reactor effluent treating municipal wastewater which can reduce the consumption of fresh coagulant in wastewater treatment.     

Phosphorus recovery from fosfomycin pharmaceutical wastewater by wet air oxidation and phosphate crystallization

Fosfomycin pharmaceutical wastewater contains highly concentrated and refractory antibiotic organic phosphorus (OP) compounds. Wet air oxidation (WAO)-phosphate crystallization process was developed and applied to fosfomycin pharmaceutical wastewater pretreatment and phosphorus recovery. Firstly, WAO was used to transform concentrated and refractory OP substances into inorganic phosphate (IP). At 200 °C, 1.0 MPa and pH 11.2, 99% total OP (TOP) was transformed into IP and 58% COD was reduced. Subsequently, the WAO effluent was subjected to phosphate crystallization process for phosphorus recovery. At Ca/P molar ratio 2.0:1.0 or Mg/N/P molar ratio 1.1:1.0:1.0, 99.9% phosphate removal and recovery were obtained and the recovered products were proven to be hydroxyapatite and struvite, respectively. After WAO-phosphate crystallization, the BOD/COD ratio of the wastewater increased from 0 to more than 0.5, which was suitable for biological treatment. The WAO-phosphate crystallization process was proven to be an effective method for phosphorus recovery and for fosfomycin pharmaceutical wastewater pretreatment.     

造纸白泥和粉煤灰的添加对污泥消化液中氮磷回收的影响

污泥厌氧消化液中含有丰富的氮磷，若直接排放到环境中，将会对附近水体造成严重污染。由于消化液中Mg^2＋和Ca^2＋的含量很低，严重影响了氮磷的回收效果。把造纸白泥和粉煤灰引入到污泥厌氧消化液氮磷的回收当中，可以明显地提升消化液pH和提高PO4^3-P和NH3-N回收率。实验结果表明：当造纸白泥添加量为4g／（L·h）时，曝气12h后，pH可达10．19，此时PO4^3-P和NH3-N回收率分别达到64％和45％；而当粉煤灰添加量为4g／（L·h）时，曝气12h后，pH达到9．63，PO4^3-P和NH3-N回收率分别为46％和41％。但仅用曝气方式处理，12h后，pH值仅为8．52，PO4^3-P和NH3-N回收率分别只有20％和18％。实验结果还表明，水力停留时间（HRT）越大，pH上升速度越快，幅度越大，氮磷的回收效果就越好。     

Combined anaerobic/aerobic digestion: effect of aerobic retention time on nitrogen and solids removal

A combined anaerobic/aerobic sludge digestion system was studied to determine the effect of aerobic solids retention time (SRT) on its solids and nitrogen removal efficiencies. After the anaerobic digester reached steady state, effluent from the anaerobic digester was fed to aerobic digesters that were operated at 2- to 5-day SRTs. The anaerobic system was fed with a mixture of primary and secondary sludge from a local municipal wastewater treatment plant. Both systems were fed once per a day. The aerobic reactor was continuously aerated with ambient air, maintaining dissolved oxygen level at 1.1 +/- 0.3 mg/L. At a 4-day or longer SRT, more than 11% additional volatile solids and 90% or greater ammonia were removed in the aerobic digester, while 32.8 mg-N/L or more nitrite/nitrate also was measured. Most total Kjeldahl nitrogen removal was via ammonia removal, while little organic nitrogen was removed in the aerobic digester.     

工艺条件对磷回收过程中鸟粪石沉淀颗粒粒径的影响

在鸟粪石沉淀法回收废水中磷的过程中,鸟粪石颗粒的大小将直接影响其沉淀的速率,进而影响鸟粪石的沉淀效果和磷的回收率。本文采用激光粒度分析仪测定鸟粪石的平均粒径,详细考察在小型连续搅拌反应-沉淀磷回收装置中不同的工艺条件下鸟粪石颗粒粒径的变化规律,并结合Stokes公式计算鸟粪石颗粒在废水出口处的沉降速率,为沉淀池的设计提供参考依据。结果表明:鸟粪石的平均粒径在12～25μm之间,沉降速率在5.46×10-5～2.37×10-4m/s之间。随着反应室水力停留时间的延长,鸟粪石颗粒的粒径逐渐增大,当停留时间超过18 min时,颗粒的粒径基本不变;随着沉淀室水力停留时间的延长,鸟粪石颗粒的平均粒径缓慢增大,当停留时间超过70 min后颗粒粒径的变化不大;鸟粪石颗粒的平均粒径在一定程度上受废水中磷初始浓度变化的影响,在磷初始浓度为62～128 mg/L时颗粒的粒径变化不大,当磷浓度为496 mg/L时粒径有较大增加,此时鸟粪石颗粒的沉降速率也大幅度增加;鸟粪石颗粒的平均粒径受pH值的影响不大;随氮磷摩尔比的增大,鸟粪石颗粒的平均粒径略有增加;随镁磷摩尔比的增大,鸟粪石颗粒的平均粒径逐渐减小,沉降速率则有明显的下降。     

响应面分析法优化造纸污泥吸附剂除磷工艺

以造纸厂废水污泥为原料,采用微波加热法制备造纸污泥吸附剂。利用制备的造纸污泥吸附剂对模拟含磷废水进行了吸附研究,探讨了吸附时间、投加量、pH值、转速和温度等因素对除磷效果的影响,并采用响应面设计法优化吸附工艺条件。结果表明,获得了最佳除磷工艺条件为吸附时间97 min,投加量6.9 g/L,pH=6,转速200 r/min,温度30℃,在此条件下磷的去除率可达99%以上。因此,造纸污泥吸附剂对磷的吸附效果良好,具有重要的实际应用价值。     

Comparison of mechanical pretreatment methods for the enhancement of anaerobic digestion of pulp and paper waste activated sludge

The conventional anaerobic digestion process, requiring long solids retention times (SRTs) to digest solids, is currently viewed as impractical for the pulp and paper industry because of high capital costs associated with the construction of new digesters. Recent developments in sludge solubilization technology could be promising in reducing digester size, which also allows for the potential use of decommissioned tanks, both of which can reduce the capital cost. Three pretreatment technologies for use with anaerobic digestion were tested on laboratory-scale to investigate their feasibility. The SRTs in all three digesters systematically decreased from 20 to 3 days. The reference digester was fed waste activated sludge (WAS) to serve as the control at the same SRTs. The other digesters were fed WAS that had been preconditioned using mechanical shearing, sonication, or high-pressure homogenization technology. Anaerobic digestion with high-pressure homogenization produced as much methane at 3-day mean SRT as that from the reference digester operated at 20-day SRT. Therefore, a new digester can theoretically be 85% smaller than a conventional digester. An added benefit of WAS to methane conversion is the recovery of nutrients nitrogen and phosphorus.     

利用白云石回收污泥厌氧消化液中的磷

为经济有效地从污泥厌氧消化液中回收磷,构建了以白云石提供钙镁源的磷回收方法,探讨了磷回收的工艺条件与效果。通过盐酸酸化厌氧消化液以降低其碳酸盐含量,同时利用白云石溶于冷稀盐酸的特性使其钙镁缓慢释放到酸化的厌氧消化液中形成第一步磷回收体系,考察体系酸化pH、白云石与厌氧消化液的固液比以及反应pH对白云石的钙镁释放和磷回收效果的影响;第一步磷回收后的上清液为第二步厌氧消化液磷回收提供钙镁源,研究投加钙磷摩尔比对磷回收效果的影响。实验结果表明,当固液比为5.0时,在酸化pH为4.0～4.5且酸化溶出时间为10 h以及反应pH为9.0的条件下,第一步磷回收产物以磷酸钙盐沉淀为主,厌氧消化液磷回收率及回收产物含磷率（以P2O5计）分别达到99.43%和38.49%;第一步磷回收后的上清液按一定的钙磷摩尔比投加到酸化后的厌氧消化液中进行第二步磷回收,当投加钙磷摩尔比为0.20时,在反应pH为9.0的条件下,回收产物同时含有磷酸钙盐和磷酸铵镁,厌氧消化液中氮、磷回收率分别达到13.19%和90.90%,回收产物氮、磷含量（以P2O5计）分别为0.26%和39.58%;经XRD、XRF、ICP及SEM等分析表征,2步磷回收的产物以磷酸钙盐和磷酸铵镁为主要成分,杂质少。研究表明,利用白云石为钙镁源,通过分别构建不同的磷回收体系可以分步从污泥厌氧消化液中经济有效地回收磷,且磷回收率和回收产物含磷率高。     

实际污水与模拟污水活性污泥系统的特性差异

实验中经常采用人工配置的模拟生活污水,为了研究其与实际生活污水活性污泥系统的特性差异,采用2个序批式间歇反应器(SBR)进行平行实验(厌氧、好氧方式运行),系统地考察了在进水主要组分和运行参数相同的情况下,不同原水对活性污泥系统脱氮、除磷、比好氧速率、污泥絮体形态和出水水质等方面的影响。结果表明,模拟污水系统的硝化活性强于实际污水系统,两者的平均硝化速率分别为7.43 mg NH4+-N/(L.h)和5.55 mg NH4+-N/(L.h)。在前置厌氧段,模拟污水系统的释磷量比实际污水系统高出36.45%。两者在后续好氧阶段都能够充分吸磷。模拟污水系统的平均比好氧速率(SOUR)高达64.54 mg O2/(g MLSS.h),而实际污水系统的则只有32.81 mg O2/(g MLSS.h)。模拟污水系统的污泥絮体疏松,粒径小,形状不规则,沉降性差,沉后出水平均悬浮物浓度(SS)为20 mg/L;而实际污水系统的污泥絮体则密实、粒径大,沉降性好,沉后水十分清澈,SS几乎检测不出。     

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。     

Fate of sex hormones in two pilot-scale municipal wastewater treatment plants: conventional treatment

The fate of seven sex hormones (estrone (E1), estradiol (E2), estriol (E3), ethinylestradiol (EE2), testosterone, androstenedione, and progesterone) was determined in two pilot-scale wastewater treatment plants operated under conventional loading conditions. The levels of hormones in both the liquid and the solid matrixes of the plants were determined. Each of the two 20-l/h pilot-scale plants consisted of a primary clarifier followed by a three-stage aeration tank and a final clarifier. The primary sludge and the waste activated sludge (WAS) were digested anaerobically in one pilot plant and aerobically in the other. The pilot plants were fed a complex synthetic wastewater spiked with the hormones. Levels of testosterone, androstenedione and progesterone were close to method detection limit (MDL) concentrations in the final and digester effluents (both liquid and solid phases) and were considered as completely removed. Average mass flux removals from the liquid streams (plant influent minus secondary clarifier effluent) for the natural estrogens were 82% for E1, 99% for E2, and 89% for (E1+E2). An average overall removal of only 42% was achieved for EE2. These values reflect removals averaged for the two pilot plants.     

Microwave treatment and struvite recovery potential of dairy manure

Microwave digestion of liquid dairy manure was tested for the release of nutrients, such as orthophosphates, ammonia-nitrogen, magnesium, calcium and potassium, both with and without the aid of an oxidizing agent (hydrogen peroxide). The orthophosphate to total phosphorus ratio of the manure increased from 21% to greater than 80% with 5 minutes of microwave treatment. More than 36% of total chemical oxygen demand (t-COD) of the manure was reduced when microwave digestion was assisted with peroxide addition. In addition, the volatile fatty acids (VFAs) distribution shifted to simpler chain acids (acetic acid in particular) with an increase in operating temperature. In the second part of the study, digested manure with increased soluble phosphate was tested for the recovery of struvite (magnesium ammonium phosphate) at different pH. It was found that up to 90% of orthophosphate can be removed from the solution. Overall, it was concluded that the oxidizing agent-assisted microwave digestion process can be used upstream of anaerobic digestion, following which the anaerobically digested manure can be used for struvite recovery. Thus, this microwave digestion process presents the potential for enhanced efficiencies in both manure digestion and struvite recovery.     

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.     

Microwave treatment and struvite recovery potential of dairy manure

Microwave digestion of liquid dairy manure was tested for the release of nutrients, such as orthophosphates, ammonia-nitrogen, magnesium, calcium and potassium, both with and without the aid of an oxidizing agent (hydrogen peroxide). The orthophosphate to total phosphorus ratio of the manure increased from 21% to greater than 80% with 5 minutes of microwave treatment. More than 36% of total chemical oxygen demand (t-COD) of the manure was reduced when microwave digestion was assisted with peroxide addition. In addition, the volatile fatty acids (VFAs) distribution shifted to simpler chain acids (acetic acid in particular) with an increase in operating temperature. In the second part of the study, digested manure with increased soluble phosphate was tested for the recovery of struvite (magnesium ammonium phosphate) at different pH. It was found that up to 90% of orthophosphate can be removed from the solution. Overall, it was concluded that the oxidizing agent-assisted microwave digestion process can be used upstream of anaerobic digestion, following which the anaerobically digested manure can be used for struvite recovery. Thus, this microwave digestion process presents the potential for enhanced efficiencies in both manure digestion and struvite recovery.     

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.     

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.