水质对UV/H2O2降解17α-乙炔基雌二醇（EE2）的影响

采用UV/H₂O₂间歇式光氧化反应器,研究了溶液pH值、腐殖酸及水中常见阴离子HCO₃^-、NO₃^-、CO₃^2-、Cl^-和SO₄^2-对UV/H₂O₂工艺降解17α-乙炔基雌二醇(EE2)的影响.结果表明,UV/H₂O₂工艺可以有效地去除水中的EE2,光降解过程符合一级反应动力学模型.双氧水投加量为5 mg/L时,在14W低压汞灯照射下,EE2在自来水和蒸馏水中的光降解一级反应速率常数为0.063 0min^-1和0.132 4min^-1.溶液中的腐殖酸和阴离子HCO₃^-、NO₃^-、Cl^-、SO₄^2-对EE2的光降解反应有抑制作用,4种阴离子浓度为5 mmol/L时,抑制作用依次为HCO₃^->SO₄^2->Cl^->NO₃^-,HCO₃^-可使光降解速率常数降低到50%.自来水中的光降解速率常数低于蒸馏水中的光降解速率常数是水中多种离子影响的结果.     

化学沉淀分离-置换法提纯Al13的工艺研究

采用AlCl₃溶液和Na₂CO₃粉末在不同温度下制备了不同浓度的聚合氯化铝(PACl). 以选定的中等浓度、高Al₁₃含量的PACl为原液,研究了Al₁₃与硫酸盐沉淀反应过程中SO₄/Al摩尔比、反应体系起始总铝浓度的影响以及Al₁₃硫酸盐与Ba(NO₃)₂置换反应过程中的Ba/SO₄摩尔比、超声、温度等因素的影响. 实验结果表明,在制备温度为50℃条件下,浓度在0.4～0.6　mol/L范围的PACl含有较高的Al₁₃. 沉淀分离反应的最佳SO₄/Al摩尔比为0.6∶1;生成的 Al₁₃硫酸盐沉淀物为正四面体状晶体. 在Al₁₃硫酸盐与Ba(NO₃)₂溶液置换反应过程中,Ba/SO₄的最佳摩尔比为1∶1,反应温度及超声作用对置换反应的影响较小;提高Ba(NO₃)₂的起始浓度可以得到相应较高浓度的纯化Al₁₃溶液. 所得Al₁₃纯度的统计平均值为92.1％.     

紫外/亚硫酸盐高级还原工艺加速降解水中难降解含碘造影剂

紫外/亚硫酸盐（UV/SO₃^2-）是一种基于紫外活化SO₃^2-离子依靠生成还原性自由基——水合电子降解目标污染物的高级还原工艺.本文研究了UV/SO₃^2-加速降解含碘造影剂泛影酸钠（DTZ）的效能、机制与影响因素以及UV/SO₃^2-降解DTZ的路径.结果表明,UV/SO₃^2-降解DTZ符合一级动力学模型,降解速率快于单独UV和紫外/过氧化氢工艺,且降解速率随SO₃^2-浓度的增加而升高.弱碱性或碱性水质可强化UV/SO₃^2-降解效率,背景有机物对降解DTZ有一定抑制作用.DTZ降解机制包括直接光解和还原性自由基攻击,其中自由基攻击占主要部分.DTZ在UV/SO₃^2-的降解路径包括取代、脱羧基羟基化和酰胺键断裂等.     

溴代甲烷在SO42-/TiO2上的光催化降解

采用溶胶-凝胶法制备了SO₄^2-/TiO₂催化剂,运用XRD、BET比表面测定,FTIR等技术对催化剂进行了表征,并在微型常压连续反应装置上进行CH₃Br光催化反应性能考察.结果表明,SO₄^2-引入TiO₂体系使得催化剂的结构和光催化性能得到显著改善.SO₄^2-负载量为9%,烧结温度为450℃时,SO₄^2-/TiO₂催化剂的光催化活性最高;SO₄^2-/TiO₂催化剂对反应物料中的水汽有很好的耐受性;当反应温度低于85℃时,提高反应温度,有利于改善对CH₃Br的光催化反应活性,表观活化能约为19.6kJ·mol^-1,反应温度在85℃～105℃区间时,CH3Br的光催化降解表观活化能为0.     

冬季PM2.5中无机水溶性离子与大气相对湿度的相关性

依托河北省灰霾污染防治重点实验室,对2019年11月26日—12月31日石家庄市大气PM_2.5中的NO₃^-和SO₄^2-进行连续在线观测,研究NO₃^-和SO₄^2-与环境空气相对湿度的相关性,解析冬季发生PM_2.5重污染天气的RH阈值.观测期间,RH为10%~60%时,NO₃^-的浓度与RH呈显著正相关,为PM_2.5中浓度最高的无机水溶性离子.RH超过70%后,NO₃^-与RH呈负相关,NO₃^-浓度和NOR开始下降.SO₄^2-浓度与RH在整个湿度区间均呈正相关.RH低于50%时,SO₂向SO₄^2-的转化以气相反应为主.RH高于50%以后,颗粒物达到潮解点,SO₂的主要反应转入液相,转化速率加快,SO₂液相反应贡献逐渐增加至64.6%.RH超过70%后,SO₄^2-成为PM_2.5中浓度最高的无机水溶性离子.RH超过PM_2.5潮解点以后,NO₃^-和SO₄^2-大量合成,推高PM_2.5环境浓度,易于形成重污染天气.     

钠盐对高负荷餐厨垃圾和剩余污泥中温厌氧混合发酵过程的抑制作用

针对高负荷餐厨垃圾和剩余污泥混合发酵系统在实际应用过程中存在的盐度抑制问题,通过批次试验探究了不同钠盐（CH₃COONa、NaCl和Na₂SO₄）对中温混合发酵体系的影响,考察了添加不同浓度钠盐时混合发酵体系的甲烷累积产量、有机物去除率、挥发性脂肪酸（VFAs）累积量及水解、酸化、乙酸化和产甲烷速率的抑制作用.结果表明,随着CH₃COONa浓度的增加,相应的甲烷产量逐渐增加,但在高浓度时理论甲烷产量降低,当Na⁺浓度为8 g·L^-1时,对产甲烷抑制率为21%.此外,NaCl和Na₂SO₄对甲烷累积产量具有抑制作用,相同Na⁺浓度下,Na₂SO₄对混合发酵体系甲烷产量的抑制作用更大;当SO₄^2-浓度为8.3 g·L^-1时,相应甲烷抑制率为23%.相反,Cl^-浓度为3.1~6.2 g·L^-1时,对混合发酵过程中甲烷抑制率为4.6%~7.7%;但随着Cl^-浓度增至9.3~12.3 g·L^-1时,甲烷产量提升了14.5%~37.6%.分析认为,NaCl对混合发酵过程有机物去除率的抑制作用主要是Na⁺的影响,而Na₂SO₄的抑制作用主要来源于SO₄^2-和Na⁺的协同作用.NaCl和Na₂SO₄对水解速率和产甲烷速率的抑制作用较大,而对酸化速率和乙酸化速率抑制作用较小.     

COD/SO42-值对硫酸盐还原率的影响

研究利用 UASB反应器考察了 COD和硫酸盐浓度的比值对硫酸盐还原的影响 ,同时分析了硫酸盐还原菌和产甲烷菌对COD的竞争情况 .发现在 HRT为 3.8h,SO₄^2- 负荷为 6～7kg·( m³· d)^-1,SO₄^2- 浓度为 1000mg·L^-1 条件下 :1在 COD不足时 ,SRB与 MPB在竞争中占微弱优势 ;对于产甲烷活性比较好的厌氧污泥要经过较长的时间 ,SRB才能确立优势菌种的地位 .2 COD/ SO₄^2- 比值决定了 SO₄^2- 的去除率 .比值等于2时 ,SO₄^2- 的还原率在 95%以上 ;当比值为 1.5时 ,SO₄^2- 还原率为 75% ;当比值为 1时 ,SO₄^2-的还原率为 60 % .     

北京大气气溶胶部分无机组分及相关气体的浓度变化

利用SJAC-MOBIC在2000-05～2000-09的3个采样时段测量了北京大气中的气溶胶SO₄^2-、NO₃^-、NO₂^-、Cl^-及相关气体组分,得出了这些污染组分的逐时变化.结果表明气溶胶Cl^-、NO₂^-、NO₃^-及气体HCl、HNO₂和HNO₃有明显的变化规律,SO₂和气溶胶SO₄^2-的变化取决于SO₂的排放,SO₄^2-的峰值一般比SO₂的峰值晚2h左右.     

UV/TiO_2光催化还原Cr(Ⅵ)过程中吸附作用的影响及其消除

研究了水体中Cr(Ⅵ)离子在UV/TiO₂体系中光催化还原过程.结果表明,Cr(Ⅵ)离子UV/TiO₂光催化还原过程符合Langmuir-Hinshelwood动力学规律.不存在有机物时,TiO₂吸附作用是该反应的前提.pH=1.5～2.5时吸附性能较好,而且pH=1.5～10的初始反应速率同pH值有线性关系.在TiO₂表面的竞争吸附能力按PO₄^3->SO₄^2->Cl^->NO₃^-依次减弱.甲酸、甲醛有机物的协同作用可提高Cr(Ⅵ)离子的光催化还原速率和效率,并消除由暗态吸附对反应所起的作用,磷酸根离子极强的竞争吸附能力,使有机物的协同作用减弱.     

土霉素结晶母液酸化水解过程的研究

土霉素结晶母液是一类含高浓度有机物和氮的废水,反硝化电子供体相对不足,且含有多种生物抑制性物质.为了提高废水的可生化性、增加可利用反硝化电子供体的数量,利用厌氧污泥床对土霉素结晶母液进行了水解处理,并对反应的pH、COD、NH₄⁺、和SO₄^2--浓度等进行了考察.水解过程对COD的去除功能不强,在HRT1.5h～6.0h的条件下,COD去除率也仅从10%提高到16%.由于有机氮氨化和硫酸盐还原作用,酸化后废水的pH值增加.当HRT超过2h以后,SO₄^2-基本上都被还原成S^2-采用经过水解的废水进行批量实验,结果证明硝化速率和反硝化速率分别比未水解时提高90.9%和45.2%.     

Interaction of PACls with sulfate

IntroductionPolyaluminumchloride (PACl)asamainkindofinorganicpolymerflocculantsisanewhighereffectivewaterandwastewatertreatmentreagent.Basedonthetraditionallow molecularaluminum ,ithasbeendevelopedworldwidesincethe 196 0s(Tang,1994 ;1990 ;1987) .PAClistheintermediateproductofthehydrolysis polymerization ageingprocessofAl(III)undersuitableconditions.Atpresent,itisgenerallyknownthattherearemanypossiblespeciesexistintheAl(III)solution ,suchasmonomers,oligomers,Al13 [AlO4Al12 (OH) 2 4(H2 …     

Interaction of PACIs with sulfate

This article discusses the influential factors on Al13 separation considering the interaction of sulfate with various polyaluminum chloride (PACI). The experimental results showed that the basicity (B = [OH]/[Al]), the concentration of PACI and Al/SO4 ratio exhibited significant roles in the PACI-sulfate reaction. It indicated that different species in various PACI underwent different reaction pathway with sulfate. The Alc, colloidal species,formed precipitation quickly with sulfate, while Alb, oligomers and polymers, underwent slow crystallization. And Ala,monomers, reacted with sulfate to form soluble complexes. The kinetic difference of reaction made it possible to realize the separation of Alb and further purification. The decrease of Ala resulted in the limit of ferron method wasalso mentioned.     

不同铝聚合形态对聚合铝混凝效果的影响

通过氯化铝(铝单体或初聚物形态Ala)、高Alb含量聚合铝(中等聚合形态Alb)、高Alc含量聚合铝(铝溶胶等高聚合形态Alc)和工业PACl(不同聚合度铝的混合形态Alabc)对某水厂沉后水实际水样进行烧杯混凝实验,依据絮体生长状况、浊度、UV254、颗粒数和过滤指数等参数综合评价不同铝形态的混凝作用效果,从而得出铝的最佳混凝形态.结果表明,高Alb含量聚合铝对浊度去除较好;而高Alc含量聚合铝对于颗粒物和UV254的去除效果较佳.     

Preparation of high concentration polyaluminum chloride by chemical synthesis-membrane distillation method with self-made hollow fiber membrane

A method of direct contact membrane distillation (DCMD) with a self-made hollow polyvinylidene fluoride membrane was applied to prepare high concentration polyaluminum chloride (PACl) with high Al_b content based on chemical synthesis. The permeate flux and Al species distribution were investigated. The experimental results showed that the permeate flux decreased from 14 to 6 kg/(m²·hr) at the end of the DCMD process, which can be mainly attributed to the formation of NaCl deposits on the membrane surface. The Al_b content decreased slightly, only from 86.3% to 84.4%, when the DCMD experiment finished, correspondingly the Al_c content increased slightly from 7.2% to 8.5%, and the Al_a content remained at 7% during the whole DCMD process. A PACl with Al_b content of 84% at total aluminum concentration 2.2 mol/L was successfully prepared by the chemical synthesis-DCMD method.     

铝系混凝剂优势形态分析及其混凝特性

聚合氯化铝（PACl）是常用的水处理混凝剂,在应用过程中通常表现出比传统铝盐更为优异的效果.研究表明,这种优异性能主要得益于其特殊的组成,特别是高分子聚合物Al₁₃和Al₃₀独特的物化特性.Al₁₃和Al₃₀是铝离子水解过程中的中间产物,在地球科学和环境化学等领域有着重要的研究价值.于水处理而言,二者的结构和分子特性是研究者关注的重点,大量研究基于此展开,很多重要的发现为实际应用奠定了基础.基于对PACl及其组成性质的研究,本文对PACl的混凝特性及其优势形态分子的分析进行了综合阐述.     

Disinfection byproduct precursor removal by enhanced coagulation and their distribution in chemical fractions

Raw water from the Songhua River was treated by four types of coagulants, ferric chloride(FeCl3), aluminum sulfate(Al2(SO4)3),polyaluminum chloride(PACl) and composite polyaluminum(HPAC), in order to remove dissolved organic matter(DOM). Considering the disinfection byproduct(DBP) precursor treatability, DOM was divided into five chemical fractions based on resin adsorption.Trihalomethane formation potential(THMFP) and haloacetic acid formation potential(HAAFP) were measured for each fraction. The results showed that hydrophobic acids(HoA), hydrophilic matter(HiM) and hydrophobic neutral(HoN) were the dominant fractions.Although both HoN and HoA were the main THM precursors, the contribution for THMFP changed after coagulation. Additionally,HoA and HiM were the main HAA precursors, while the contribution of HoN to HAAFP significantly increased after coagulation.HoM was more easily removed than HiM, no matter which coagulant was used, especially under enhanced coagulation conditions.DOC removal was highest for enhanced coagulation using FeCl3 while DBPFP was lowest using PACl. This could indicate that not all DOC fractions contained the precursors of DBPs. Reduction of THMFP and HAAFP by PACl under enhanced coagulation could reach51% and 59% respectively.     

聚合铝混凝过程研究:不同形态硅酸的影响作用

研究了不同形态硅酸对聚合铝混凝过程的影响作用 .实验结果表明经预制形成的具有不同形态分布组成的硅酸与聚合铝 ,在投加后相互间发生了十分复杂的物理化学作用 ,并受溶液pH值的影响 ,从而最终决定了混凝效果 .反应过程中所生成的形态产物及其物化特征 ,很大程度上取决于聚合铝碱化度以及所投加的Si Al比 .其中碱化度越高 ,最终产物所带电荷越高 .而不同硅酸所起影响作用分别取决于聚合程度 ,在与聚合铝反应过程中表现出一定的规律性 .单体硅酸与单体铝迅速发生较强的络合作用 ,抑制了多聚水解铝阳离子的形成 .聚合硅酸则倾向于与聚合铝形态相互作用形成一定的胶状化合物 ,从而在溶液中稳定存在 .对于胶体硅酸 ,在聚合铝作用下迅速凝聚形成更大的聚集体 ,在颗粒物间架桥形成粗大的絮体 .所得结果对混凝机理的解释与复合混凝剂的发展提供了一定的参考作用     

Synchronous removal of CuO nanoparticles and Cu2+ by polyaluminum chloride-Enteromorpha polysaccharides: Effect of Al species and pH

Copper oxide nanomaterials have been extensively applied and can have serious impacts when discharged into the aquatic environment, especially when complexed with humic acid (HA) to form composite contaminants. As an innovative recycled coagulant aid, Enteromorpha polysaccharides (Ep) were associated with polyaluminum chloride (PACl) (denoted as PACl-Ep) to simultaneously remove CuO nanoparticles, Cu²⁺ and HA in this study. The influence of different Al species coagulants (AlCl₃, PACl_b and PACl_c) and water pH on coagulation performance, floc properties and reaction mechanisms was investigated in detail. Results showed that in the three PACl-Ep systems, PACl_b-Ep gave the highest removal efficiencies for turbidity and Cu²⁺, and the best UV₂₅₄ removal effect was reached by using PACl_c-Ep. Higher contents of Al_b and Al_c contributed to great coagulation performance because of their stronger bridging and sweeping effects. For all the Al species coagulants, alkalescent conditions were more conducive to removing Cu and HA compared to acidic conditions. Additionally, smaller and more agminated flocs with great recovery ability were formed by PACl_b-Ep and PACl_c-Ep systems (bridging and enmeshment effects cooperated with the chelated reticular structure formed by the Ep and Al species). Similarly, due to the increased hydrolysis and hydroxide precipitates, flocs formed under the condition of alkalescence were smaller, denser and stronger compared with weakly acidic conditions.     

Deposition behavior of residual aluminum in drinking water distribution system: Effect of aluminum speciation

Finished drinking water usually contains some residual aluminum.The deposition of residual aluminum in distribution systems and potential release back to the drinking water could significantly influence the water quality at consumer taps.A preliminary analysis of aluminum content in cast iron pipe corrosion scales and loose deposits demonstrated that aluminum deposition on distribution pipe surfaces could be excessive for water treated by aluminum coagulants including polyaluminum chloride（PACl）.In this work,the deposition features of different aluminum species in PACl were investigated by simulated coil-pipe test,batch reactor test and quartz crystal microbalance with dissipation monitoring.The deposition amount of non-polymeric aluminum species was the least,and its deposition layer was soft and hydrated,which indicated the possible formation of amorphous Al（OH）₃.Al₁₃ had the highest deposition tendency,and the deposition layer was rigid and much less hydrated,which indicated that the deposited aluminum might possess regular structure and self-aggregation of Al₁₃could be the main deposition mechanism.While for Al₃₀,its deposition was relatively slower and deposited aluminum amount was relatively less compared with Al₁₃.However,the total deposited mass of Al₃₀ was much higher than that of Al₁₃,which was attributed to the deposition of particulate aluminum matters with much higher hydration state.Compared with stationary condition,stirring could significantly enhance the deposition process,while the effect of pH on deposition was relatively weak in the near neutral range of 6.7 to 8.7.     

Preparation of high concentration polyaluminum chloride with high content of Alb or Alc

A novel membrane distillation concentration method was used to prepare high concentration polyaluminum chloride (PACl) with high content of Al_b or Al_c. 2.52 mol/L PACl₁ with 88% Al_b and 2.38 mol/L PACl₂ with 61% Al_c were successfully prepared. Three coagulants, AlCl₃, PACl₁ and PACl₂ were investigated on their hydrolysis behavior and speciation under different conditions. The effects of pH and dilution ratio on Al species distribution were investigated by ferron assay. Experimental result showed that pH had a significant effect on Al species distribution for the three coagulants. Dilution ratio had little effects on Al_b and Al_c distribution in whole dilution process except the beginning for PACl₁ and PACl₂. The results indicated that transformation of Al depends largely on their original composition. AlCl₃ was the most unstable coagulant among these three coagulants during hydrolysis process. PACl₁ and PACl₂ with significant amounts of highly charged and stable polynuclear aluminum hydrolysis products were less affected by the hydrolysis conditions and could maintain high speciation stability under various conditions.