Influence of some additives to aluminium species distribution in aluminium coagulants

Aluminium ions hydrolyse and polymerise into different species in water. Main aluminium species in aluminium coagulant solutions are monomeric Al species (Al1) and polymeric Al species Al13O4(OH)24(7+) (Al13). The aluminium species distribution in coagulant solutions can be influenced by many parameters. This paper studies influences of concentrations of total aluminium species (Al(t)) and other species--OH-, polysilicic acid and ferric species, which were added in aluminium coagulant solutions, on the aluminium species distribution through 27Al nuclear magnetic resonance (NMR) analysis. Results show that only Al1 and no Al13 exist in coagulant solutions at higher Al(t) concentrations (over 1 mol l(-1)), while both species exist at lower Al(t) concentrations (0.1 mol l(-1)). The increase of OH/Al value (molar ratio) increases the concentration of Al13 in coagulant solutions, while the addition of polysilicic acid and ferric species decreases the concentration of Al13.     

新型絮凝剂含硼聚硅铝铁的制备和性能研究

向聚硅酸中引入Al³⁺、Fe³⁺、B,制得稳定性更好的高效絮凝剂含硼聚硅铝铁（PFASB）。通过实验得到其最佳配比为：n_(B)/n_(Si)=0.16、n_(Fe)/n_(Al)=0.5 、n_(Al+Fe)/n_(Si)=1。对造纸废水和焦化废水进行混凝实验表明,PFASB的除浊、除COD的能力均优于聚合铝、聚合铝铁和聚硅铝铁,而且矾花产生迅速,矾花粗大密实,是一种性能优异的新型高分子絮凝剂。实验还考察了絮凝剂的形貌和结构,结果表明B、铝及其水解产物、铁及其水解产物和聚硅酸等多种组分之间有相互作用,形成了尺度更大的聚集单元。PFASB的这种特殊结构是其具有良好稳定性和混凝性能的根本原因。     

聚合硅酸钛铝复合絮凝剂的结构及性能

为了克服有机絮凝剂的二次投加及有毒性的缺点,以硅酸钠、硫酸钛、硫酸铝为原料,制备了聚合硅酸钛铝(PTAS)无机高分子复合絮凝剂处理模拟江水。结果表明,在n(Ti+Al)∶n(Si)=1∶3,n(Ti)∶n(Al)=1∶5,模拟江水pH值为5～9.3,絮凝剂投加量为0.3 mmol/L(以金属离子计)时,PTAS对模拟江水的混凝效果最好,除浊率达到92.5%以上。此外,通过X-射线衍射说明聚硅酸与硫酸铝、硫酸钛不是单纯的原料复合;红外吸收光谱显示钛、铝离子及其水解聚合产物可与共存的聚硅酸生成Si—O—Al键和Ti—O—Si键;激光粒度分析表明PTAS在聚合过程中粒度并没有明显变化,但均比聚硅酸粒径大。     

优化混凝处理低温低浊黄河水及对余铝的控制

考察了4种混凝剂,高效聚合氯化铝（HPAC）,聚合氯化铝（PACl）,硫酸铝（Al2（SO4）3）,混合PACl和氯化铁（FeCl3）,对低温低浊黄河原水的混凝效果与沉后水残留铝含量的关系。结果表明,当采用Al2（SO4）3或PACl做混凝剂时,在取得较好浊度去除的投药量下,水中余铝浓度会超过国家标准（0．2131g／L）。而采用HPAC或FeCl3和PACl复配药剂,在取得与Al2（SO4）3或PACl类似的浊度去除效果的同时,也能较好地控制水中的余铝含量。当HPAC投加量为21mg／L时,沉后水浊度降至1．3NTU,残留铝含量为0．147mg／L。复配投加PACl 15mg／L和FeCl3 12mg／L后,沉后水浊度为1．18NTU,残留铝含量为0．074mg／L。PACl和氯化铁的复配比例需要精确的调控,否则容易导致出水余铁余铝含量增加。而HPAC投加量小于21mtg／L时出水余铝浓度均低于国家标准。因此,在这4种混凝剂中,就混凝效果及余铝控制而言,HPAC更适合充当低温低浊水源水的混凝处理药剂。     

Optimum conditions for Al13 polymer formation in PACl preparation by electrolysis process

This paper introduces a new and effective method for preparation of PACl-electrolysis process. A series of PACl with high content of Al13 polymer was successfully prepared by electrolysis process. The amount of Al13 polymer formed in electrolysis process was found to be highly influenced by current density (di), the distance between the electrodes, electrolysis time and the stirring rate of the electrolyte. For the AlT (total aluminum concentration) of 2.0 M PACl obtained by electrolysis process, the optimal di and distance between the electrodes were 1.1 Adm(-2) and 10 mm respectively. The optimum circulating rate was 5.5 l h(-1). Because of the inhomogeneous pH between the surface of cathode and the bulk solution, the electrolysis process has the advantage to form more Al(OH)4- as precursor of Al13 polymer. At the optimum condition, Al13 polymer accounted for above 70% of AlT (PACl of AlT=2.0 M and B=2.0), which was much higher than that of PACl prepared by other method.     

The application of novel coagulant reagent (polyaluminium silicate chloride) for the post-treatment of landfill leachates

Relatively "old" (stabilized) landfill leachates are a special category of wastewaters, which are difficult to treat further, mainly due to their bio-refractory organic content (humic substances). In this study, coagulation-flocculation was examined as post-treatment method for the biologically pre-treated stabilized leachates. The purpose was to examine the coagulation performance of alternative coagulant agents, i.e. the composite coagulant polyaluminium silicate chloride. Composite coagulants with different Al to Si molar ratio and different preparation methods were tested. Their efficiency was evaluated by monitoring from turbidity and phosphate content, other parameters strongly correlated with the presence of organic matter, such as UV absorbance at 254nm, COD and colour. The results suggest that the silica-based coagulants exhibit better coagulation performance, than the relevant conventional coagulant (alum) or simple pre-polymerized coagulants (PACl). Polyaluminium silicate chloride has greater tolerance against pH variation than alum or PACl, whereas this novel coagulant works better at pH values between 7 and 9. Coagulation-flocculation has proved to be an efficient post-treatment method for the biologically pre-treated leachates, promoting the removal of the refractory humic substances, while the treatment efficiency of coagulation can be improved by the application of the new coagulant agent.     

绿色絮凝剂PAS的性能及混凝机理探讨

通过向聚硅酸中加入一种高价亲生物环保的金属离子Ti⁴⁺,制备了一种适合处理长江水的绿色絮凝剂PAS,并且通过实验确定了其处理长江水的最佳处理条件：酸性聚硅酸与Ti金属盐溶液复合,n_Ti/n_Si=0.3;投加量为10 mg/L（以Ti⁴⁺计）,pH=6～8,UV254的去除率＞61.7％,浊度去除率＞99％。PAS的混凝效果明显优于聚合铝和聚硅铝,而且矾花形成迅速,絮体密实、沉降快、出水更加清澈,无残留铝。Ti也是亲生物金属,健康环保。因此,PAS是绿色环保友好型絮凝剂,可作为饮用水专用絮凝剂。观察所形成絮体的形貌以及观测红外光谱图均发现,絮凝剂对胶体颗粒污染物有较好的架桥网捕与络合反应作用。     

两种不同形态的铝盐混凝剂的吸附电中和特征

通过吸附历时过程,饱和吸附量,吸附过程Ｎａ＾＋离子交换释放,絮凝前后高岭土微粒的ζ电位测定等实验考察ＡｌＣｌ３（ＡＣ）和聚合铝两种不同形态的铝盐对高岭土悬浮水样的吸附电中和特征,并探讨了其作用机理。     

聚硅酸锌铝的制备及其性能研究

以硅酸钠、硫酸锌、硫酸铝为原料,通过共聚法制备了无机高分子絮凝剂聚硅酸锌铝（PSZAS）,研究了Na₂SiO₃的摩尔浓度、活化时间、Al/Si、Zn/Si 配比及絮凝剂的投加量对絮凝效果的影响,用X-射线衍射（XRD）和电子扫描电镜（SEM）对该絮凝剂的结构及形貌进行了表征。结果表明：当硅酸钠的浓度为0.4 mol/L,硅酸活化时间为2 h,Si∶Al∶Zn=1∶1∶1.5,絮凝剂投加量为20 mL/L废水时,絮凝剂的电中和能力和吸附架桥能力最强,絮凝剂对含H-酸染料模拟废水的絮凝效果最好。     

聚合铝水解形态对混凝效果及絮体特性的影响

采用微量滴定法制备不同碱化度的聚合铝,并测定其铝形态分布,通过其对腐殖酸-高岭土水样进行烧杯实验,依据絮体的Zeta电位、浊度、UV254及絮体强度因子及恢复因子等参数,以综合评价聚合铝水解形态的混凝机理及其絮体特性。结果表明：聚合铝投加前后铝形态分布存在很大差异,碱化度越低影响越明显,碱化度为0.5的聚合铝中Ala含量由原来的69.57%变为4%左右,而其Alc由9.36%变为50%左右;预制铝的中聚体和高聚体形态在混凝过程中相对比较稳定,而低聚合度的Ala变化显著;Alb电中和能力强,对溶解性有机物去除效果好,其絮体成长速度慢但絮体强度高;Alc具有较强的吸附架桥能力,能促进浊度的去除;预制Alc的吸附架桥能力强于水解生成的Alc,但其絮体恢复性能差。     

Silica reduces the toxicity of aluminium to a tropical freshwater fish (Mogurnda mogurnda)

The toxicity of aluminium (Al) to fish in acidic waters has been well documented. It was therefore expected that Al toxicity would be significant in fish communities in Gadjarrigamarndah (Gadji) Creek, a seasonally flowing stream in tropical northern Australia. This creek receives acidic groundwater containing elevated concentrations of Al from earlier land irrigation of treated mine tailings water from the former Nabarlek uranium mine. It was hypothesised that Al toxicity was reduced by high levels of silica (Si) in the water, and the subsequent formation of Al-silicate complexes. This prompted a laboratory assessment of the toxicity of Gadji Creek water to sac-fry of the native fish, Mogurnda mogurnda, followed by more detailed investigation of the toxicity of Al and the influence of Si in reducing Al toxicity. No mortality of M. mogurnda sac-fry was observed in two toxicity tests using Gadji Creek water collected in August 1997 and September 1998. The majority of Al (80-95%) was calculated to be complexed with humic substances and sulfate, with < 1% being complexed with silicate. Assessment of the influence of silica on the acute toxicity of Al in the absence of natural organic complexants (i.e. in reconstituted freshwater, pH 5) revealed that Si reduced Al toxicity. As the molar ratio of Si:Al was increased, the percent survival of M. mogurnda sac-fry increased until there was no significant (P > 0.05) difference from the controls. However, speciation modelling again predicted that little (< 3%) Al complexed with silicate, with the speciation and bioavailability of Al remaining constant as the molar ratio of Si:Al increased. Therefore, the original hypothesis that Al-silicate complexes in solution reduced the toxicity of Al to M. mogurnda could not be supported. This potential mechanism, and an alternative hypothesis, that Si competes with Al for binding sites at the fish gill surface, requires further investigation.     

Evaluation of Al30 polynuclear species in polyaluminum solutions as coagulant for water treatment

Polyaluminum coagulant with a content of 76.8% of Al30 (PACAl30) was prepared. Its coagulation behaviors were compared with high Al13 content polyaluminum coagulant (PACAl13) and AlCl3. The species stability was studied using Al-Ferron method and 27Al NMR. The coagulation performances were investigated by studying the rate of flocs development, the turbidity removal efficiency and charge neutralization capacity under fixed pH conditions and uncontrolled pH conditions. The effect of pH on coagulation was also studied. The results show that PACAl30 are stable for using as coagulant. PACAl30 causes less pH depression than PACAl13. The charge neutralization capacity of PACAl30 is slightly lower than that of PACAl13 at pH6.8 and higher at pH 6.5. PACAl30 achieves the most effective turbidity removal in these three coagulants. And it acts effectively within a much broader dosage range and a wider pH range when compared with PACAl13. PACAl30 achieves the highest turbidity removal due to its strong flocs formation capacity. The results verify that Al30 is another highly active coagulation/flocculation species for turbidity removal.     

纳米聚硅酸铝锌絮凝剂的制备及表征简

在SiO₂含量为3%,pH为3,活化时间为85 min,（Al+Zn ）/Si摩尔比为1.5,Al/Zn摩尔比为2,表面活性剂硬脂酸钠加入量为0.1%,超声频率为40 Hz,超声时间为60 min的最佳制备条件下制备出液体PSAZS絮凝剂,用超声法制成纳米级Nano-PSAZS,用环境扫描电子显微镜（ESEM）和智能型傅里叶变换红外光谱（FT-IR）等仪器进行分析。结果表明,硅有助于絮凝剂分子链的延伸,有助于生成更大分子的聚合物;铝盐和锌盐的加入到聚硅酸中,并不是简单的混合,而是发生了缩聚和配位反应,有助于生成链网状结构,能更好地发挥吸附架桥和网捕卷扫作用。同时Nano-PSAZS陈化时间为24 h时的结构有利于絮凝效果的发挥。     

Synthesis of high-purity Na-A and Na-X zeolite from coal fly ash

Coal fly ash (CFA) was used as a raw material for the synthesis of zeolite molecular sieve. The synthesis began with the pretreatment of CFA to remove impurities (e.g., Fe₂O₃, CaO, etc.) under various acid types (HCl, H₂SO₄, and HNO₃) and acid/CFA ratios (5–25 mL_acid/g_CFA). High product purity (up to 97%) was achieved with HCl (20%wt), and acid/CFA ratio of 20 mL_HCl/g_CFA. The treated CFA was then converted to zeolite by the fusion reaction under various Si/Al molar ratios (0.54–1.84). Zeolite type A was synthesized when the Si/Al molar ratios were lower than 1, whereas sodium aluminum silicate hydrate was formed when the Si/Al molar ratio were higher than 1. The highest water adsorption performance of the zeolite product, i.e., the outlet ethanol concentration of 99.9%wt and the specific adsorption capacity of 2.31 × 10^?2 g_water/g_zeolite, was observed with the Si/Al molar ratio of 0.82. The zeolite was tested for its water adsorption capacity repeatedly 10 times without deactivation.

Implications: This work evaluated the technical feasibility in the conversion of CFA to zeolite, which would help reduce the quantity of waste needed to be landfilled. This adds value to the unwanted material by converting it into something that can be further used. The synthesized products were shown to be quite stable as water adsorbent for the dehydration of ethanol solution.     

Effect of Al(III) speciation on coagulation of highly turbid water

In Taiwan, the turbidity of raw water for fresh water treatments can sometimes reach as high as 40 000 NTU due to intensive rainfall, especially in typhoon seasons. In response, water works often apply large quantities of coagulants such as polyaluminium chloride (PACl). In this study, simulated and natural highly turbid water was coagulated with two PACls, a commercial product (PACl-1) and a laboratory product (PACl-E). The Al species distributions of PACl-1 and PACl-E under various pH conditions were determined, and the corresponding coagulation efficiency was evaluated. The PACl-E has a wider range of operational pH, while the efficiency of PACl-1 peaks at around neutral pH. For simulated water up to 5000 NTU, the PACl-E was superior to PACl-1 at low dosage and in the pH range studied. Similar results were discovered with natural water, except that when the turbidity was extremely high, the coagulation efficiency of PACl-E decreased significantly due to the presence of large amounts of organic matter. The coagulation of PACl-E was closely related to the content of polycationic aluminium (Al₁₃) while that of PACl-1 was dictated by the amount of Al_c. The sludge from PACl-E coagulation had better dewaterability when the optimum dosage was applied. The experimental results suggest that for natural water up to 5000 NTU, PACl containing high Al₁₃ species is recommended for coagulation. In cases when the water contains high organic matter, efficient coagulation depends upon enmeshment by amorphous aluminium hydroxide.     

PATS的制备表征及其处理低浊水效能与残留铝控制

以水玻璃、硫酸铝和硫酸钛为原料,采用共聚法制备了聚硅酸硫酸铝钛（PATS）混凝剂。考察了混凝剂处理模拟低浊水的效能和出水残留铝含量,并且运用FTIR、XRD和SEM对混凝剂的结构形貌进行了表征。研究发现,当Al/Ti摩尔比为10：1,（Al+Ti）/Si摩尔比为1：2,水体pH为7~9,水体温度为10℃时,合成的PATS混凝剂对模拟低浊水的混凝性能最好,残留铝含量较低,当该混凝剂投量为0.10 mmol·L-1（以金属离子计）时,余浊和残留铝含量分别可达到0.36 NTU和0.022 mg·L-1。结果表明, PATS中存在铝、钛及其水解产物与硅发生相互作用生成的Al-O-Si键和Ti-O-Si键。PATS不是几种原料的简单混合,而是一种无定形共聚物。与聚合氯化铝、聚硅酸硫酸铝相比,PATS具有更好的混凝效果和更低的残留铝含量。     

铝污泥灰改性混凝土水化及耐硫酸腐蚀特性

为探究铝污泥灰改性混凝土水化特性,对煅烧后铝污泥灰按照不同掺量(0%、10%、20%、30%)制备试样并进行XRD、TG、SEM测试,结合耐硫酸腐蚀实验分析其抗腐蚀特性。结果表明：铝污泥灰掺量为10%~20%时,可以提高混凝土的抗折抗压强度,抗硫酸侵蚀性能在掺量为20%时最优。这是由于铝污泥灰的火山灰效应产生水化硅酸钙凝胶 (C-S-H) 充填毛细孔隙所致,微集料效应还可细化混凝土孔隙,提高混凝土微观结构致密化水平;另一方面,铝污泥灰的掺入,降低体系的Ca/Si比,提高Al/Si比,减少了水化产物Ca(OH)₂含量,促进C-A-H等耐酸侵蚀物相的生成,从而降低了侵蚀介质的侵入与腐蚀速度。本研究可为混凝土改性及耐蚀混凝土研发提供参考。     

混凝法去除城市生活污水中抗性基因

采用聚合氯化铝(PACl)和聚合硫酸铁(PFS)混凝处理城市生活污水(格栅出水和二级出水),考察混凝剂投加量、pH值对污水中抗生素抗性基因(ARGs)的去除率影响。结果表明,随着PACl和PFS投加量的增加,污水中目标基因的去除率先升高后降低;在pH 3~10的范围内,PACl对目标基因的去除效果随pH值的增加而降低,PFS对目标基因的去除随着pH值的增加先升高后降低。对于格栅出水,PACl和PFS的最佳投加量为400 mg/L,基因的去除率分别达到2.33~2.97 log和0.98~2.11 log,对于二级出水,PACl和PFS的最佳投加量分别为200 mg/L和150 mg/L,基因的去除率分别为1.85~2.64 log、1.81~2.46 log;混凝去除最优pH条件分别为pH=3(投加PACl)及pH=5~6(投加PFS)。PACl的处理效果优于PFS。     

利用粉煤灰硫酸浸取液制备十二水硫酸铝铵

粉煤灰提取氧化铝是粉煤灰高值化利用的重要方向.通过在粉煤灰酸浸液中加入硫酸铵形成常温下可结晶的十二水硫酸铝铵晶体(NH4Al(SO4)2·12H2O),从而实现铝盐的高效分离.考察了结晶温度、NH4+/Al3+摩尔比,初始Al3+浓度等因素对铝回收及NH4Al(SO4)2·12H2O结晶的影响;利用电感耦合等离子光谱仪(ICP)和X射线衍射仪(XRD)对晶体中的杂质含量及晶体组成进行了分析.结果表明,随着结晶温度的升高,铝回收率显著下降,但晶体纯度升高;铝回收率和晶体纯度均随着NH4+/Al3+摩尔比的增加而增加;较高的初始Al3+浓度可促进铝的回收和晶体纯度的提高.对十二水硫酸铝铵的结晶过程进行优化,结果表明,在结晶温度为15℃;NH4+/Al3+摩尔比为1.0~1.5;初始Al3+浓度为0.88 mol/L时,铝的回收率可达74%,十二水硫酸铝铵纯度在90%以上.     

聚合氯化铝混凝强化新生态铁锰复合氧化物吸附去除水中的磷

采用氧化-共沉淀法制备出新生态铁锰复合氧化物(FMBO),研究了单独投加FMBO和聚合氯化铝(PACl)强化FMBO吸附除磷效能及吸附磷后的颗粒物特性。结果表明,单独投加FMBO后形成的颗粒物表面带负电荷,颗粒物聚集和沉淀性能较差。PACl的投加降低了颗粒物的表面电荷,促进了颗粒物的聚集,平均粒径明显增加,改善了颗粒物的沉淀性能;通过SEM-EDAX发现,投加PACl形成的复合颗粒物表面更为粗糙,Al元素在复合颗粒物表面相对富集。PACl的投加强化了FMBO的吸附除磷效果,在实验原水条件下FMBO和PACl最佳投量分别为12和30 mg/L,此时TDP去除率高达95.6%。并且出水中Fe、Mn、Al浓度均远低于《地表水环境质量标准》中规定的限值。PACl强化新生态FMBO易于实现原位投加,在水体和水处理除磷工艺中具有较好的应用潜力。