溶液条件对磷酸钙沉淀法回收磷的影响

磷酸钙沉淀法是从富磷废水中回收磷的主要工艺.为优化工艺,利用批次沉淀实验、热力学模拟计算和X-射线衍射法研究了溶液pH值、初始Ca/P物质的量比、碳酸根和腐殖质浓度对磷酸钙沉淀的影响.结果表明,初始Ca/P物质的量比为1.67,磷酸根浓度为0.35 mmol/L、0.70 mmol/L、1.4 mmol/L时,能够实现快速反应的最小pH值分别为9.5、9.0和8.0.最终沉淀产物以热力学上最稳定的羟磷灰石形态存在.pH=8.0时,碳酸根和腐殖质会抑制磷酸钙沉淀反应; 但pH>9.0时,它们对反应的影响甚小.提高溶液pH值和Ca/P物质的量比均可降低干扰,有效提高沉淀反应效率.调控溶液pH值和Ca/P物质的量比是利用磷酸钙沉淀工艺从废水中回收磷的关键.     

3-甲基-3-丁烯基-1-醇与硫酸/过氧化氢混合溶液的吸收反应研究

应用配置有湿式流动反应管的真空紫外激光单光子电离飞行时间质谱研究了3-甲基-3-丁烯基-1-醇气体在硫酸/过氧化氢混合溶液表面的吸收反应,实验中首次测得了反应的摄取系数,并根据气相产物信息推测了其反应机制.3-甲基-3-丁烯基-1-醇与硫酸/过氧化氢混合溶液的吸收反应速率很快,在ω（H2SO4）为40%～60%范围,摄取系数为2.52×10-4～1.05×10-2.在反应过程的气相收集物中检测出3种气相产物：乙醛、丙酮和3-甲基-3,4-环氧-1-丁醇,由此推测了3-甲基-3-丁烯基-1-醇与H2 SO4/H2 O2混合溶液的非均相反应机制.3-甲基-3,4-环氧-1-丁醇可以经过多步转化形成多羟基化合物,同时生成的醛酮化合物在酸性溶液中可进一步反应,这些对大气二次有机气溶胶的形成起着重要作用.因此,3-甲基-3-丁烯基-1-醇的非均相催化氧化过程可能对二次有机气溶胶的形成有重要贡献.     

磷酸酯抗燃油劣化机理及脱水净化技术研究

磷酸酯抗燃油是一种新的人工合成有机脂类液体,由于它具有优异的抗燃、润滑、耐磨性能,逐步取代传统的矿物基润滑油成为新的趋势。为了保证核电等高参数火力发电机组的安全经济运行,针对磷酸酯抗燃油的挥发性、抗燃性、润滑性等基本理化特性,从合成液的温度、酸值和所含水分等影响因素分析了磷酸酯抗燃油的劣化机理。文章分析了现有磷酸酯抗燃油脱水技术的真空分离和重力沉降脱水净化方法的不足,在此基础上提出了反沉降脱水净化的方法,使合成液与水分的分层更加顺利。文章还对油中固体杂质所受作用力进行了力学分析。目前,国内已有研究将该技术用于核电机组等工程案例,实现了对劣化磷酸酯抗燃油的资源化回用和污染的有效治理。     

鸟粪石结晶法回收氨氮影响因素的研究

为了预处理化工厂的高氨氮废水,采用向废水中投加Na2HPO.412H2O和MgCl.26H2O生成磷酸铵镁(鸟粪石)的方法,以去除其中的高浓度氨氮同时获得缓释肥鸟粪石。试验以模拟氨氮废水为研究对象,研究了鸟粪石结晶法回收氨氮的影响因素:反应时间、氨氮初始浓度、pH值、磷酸盐与镁盐投加量对高氨氮废水的去除效果,然后进行不同影响因素的试验,确定了氨氮去除的最佳工艺条件。研究结果表明,鸟粪石结晶法回收氨氮的最佳工艺条件为:反应时间10 min,pH值为9,NH4-N:PO4-P:Mg摩尔比为1:1.05:1.15,NH4-N、PO4-P与Mg的去除率分别为91.52%、99.58%与90.52%;残余浓度分别为90.87、4.96与174.1 mg/L,加入的磷几乎全部回收,无二次污染。预处理的废水进入污水处理厂进一步深度处理。     

Species-dependent effects of the phenolic herbicide ioxynil with potential thyroid hormone disrupting activity: modulation of its cellular uptake and activity by interaction with serum thyroid hormone-binding proteins

Ioxynil, a phenolic herbicide, is known to exert thyroid hormone (TH) disrupting activity by interfering with TH-binding to plasma proteins and a step of the cellular TH-signaling pathway in restricted animal species. However, comparative studies are still lacking on the TH disruption.We investigated the interaction of [¹²⁵I]ioxynil with serum proteins from rainbow trout, bullfrog, chicken, pig, rat, and mouse, using native polyacrylamide gel electrophoresis. Candidate ioxynil-binding proteins, which included lipoproteins, albumin and transthyretin (TTR), differed among the vertebrates tested. Rainbow trout and bullfrog tadpole serum had the lowest binding activity for ioxynil, whereas the eutherian serum had the highest binding activity. The cellular uptake of, and response to, ioxynil were suppressed by rat serum greater than by tadpole serum. The cellular uptake of [¹²⁵I]ioxynil competed strongly with phenols with a single ring, but not with THs. Our results suggested that ioxynil interferes with TH homeostasis in plasma and with a step of cellular TH-signaling pathway other than TH-uptake system, in a species-specific manner.     

Heterogeneous reaction of NO2 on the surface of montmorillonite particles

The studies on heterogeneous reactions over montmorillonite, which is a typical 2:1 layered aluminosilicate, will benefit to the understanding of heterogeneous reactions on clay minerals. Montmorillonite can be classified as sodium montmorillonite or calcium montmorillonite depending on the cation presented between the different layers. Using diffuse reflectance infrared Fourier transform spectroscopy (DRIFTS), the heterogeneous reaction mechanism of NO₂ on the surface of montmorillonite was firstly investigated. Results showed that the reaction of NO₂ on the surface of sodium and calcium montmorillonite fit a first-order kinetics, and the reaction duration of calcium montmorillonite was longer than that of sodium montmorillonite under the dry condition. For either sodium or calcium montmorillonite, the uptake coefficient decreased as humidity increased.     

Zeolite (Na) modified by nano-Fe particles adsorbing phosphate in rainwater runoff

Zeolite (Na) modified by self-synthesized nano-Fe particles was used as infiltration media to adsorb phosphate in rainwater runoff. The adsorption capacities increased up to 75 times that of natural zeolite at a saturated equilibrium phosphate concentration of 0.42 mg/L. The correlation of capacity and material-specific surface area indicated that specific surface area was not the key factor contributing to the capacity improvement. SEM and XRD analysis showed that chemical reaction between Fe and P to form new products like cacoxenite is the main reason for the increased capacity, and that the method of adding metal ions or particles to improve the adsorption capacity for phosphate is feasible.     

基于钴的磷酸盐离子选择性电极研究

文章以金属钴为基体,在其表面形成对磷酸二氢盐有良好电化学响应的氧化钴敏感膜,成功的制备了磷酸盐离子选择性电极。详细讨论了不同活化时间和不同活化溶液对磷酸盐检测的线性响应范围、响应斜率及检测限的影响。实验结果表明:该基于钴的磷酸盐离子选择性电极在0.025 mol/L邻苯二甲酸氢钾的底液中,对磷酸二氢盐在10-4~10-1mol/L浓度范围内呈线性响应,其响应斜率为-48.27 mV/dec,检测限为2.27×10-5mol/L,相关系数R2为0.99。该电极具有良好的稳定性和重现性。已成功用于实际自来水样中磷酸二氢盐的检测,结果满意。     

FNA对好氧吸磷的长期抑制及污泥吸磷方式转化

本研究采用交替厌氧/好氧(An/O)SBR反应器,在21~23℃的条件下启动系统并长期投加亚硝酸盐,考察游离亚硝酸(FNA)对系统好氧吸磷性能的长期抑制作用及驯化后污泥吸磷方式的转化.结果表明,投加FNA后,污泥的释磷和吸磷能力不仅未受到抑制,比释磷速率和比吸磷速率反而高于投加前.FNA浓度(以HNO2-N计)低于0.53×10-3mg·L-1时,系统除磷率均大于96.9%;当FNA浓度提高至0.99×10-3、1.46×10-3、1.94×10-3mg·L-1时,系统除磷率均会大幅下降,分别经过50、12、30 d的运行,除磷率恢复至64.42%、67.33%、44.14%,说明抑制作用导致的除磷性能恶化可以恢复且长期驯化作用能缩短恢复过程.值得注意的是,在低于1.46×10-3mg·L-1范围内,随着FNA投加量的提高,好氧段亚硝酸盐的损失量不断增大.研究还发现,经FNA长期抑制的好氧除磷系统内污泥吸磷方式发生转变,硝酸盐型和亚硝酸盐型缺氧吸磷能力分别为驯化前的3.35倍和3.86倍,说明长期投加FNA有利于富集以NO-2为电子受体的反硝化聚磷菌;而且,长期驯化有利于系统内污泥的沉降.     

厌氧环境雌黄溶解产物形态的XAS研究

雌黄是砷的环境地球化学过程中的重要的次生矿物.雌黄的溶解性研究对于研究砷在水环境中的形态转化和环境归趋具有重要意义.环境中p H和硫化程度对于雌黄中的砷的形态变化及其稳定性有重要影响.通过室内模拟实验,结合同步辐射X射线近边吸收光谱(XANES)和扩展X射线吸收光谱(EXAFS)表征手段研究了近中性厌氧条件下,有硫和无硫体系中雌黄溶解产物中稳定存在的砷形态.结果表明,在p H中性条件下,雌黄在两种体系中均形成硫代砷和亚砷酸盐的混合物,有硫体系中硫代砷是以全硫代为主,而无硫体系中硫代亚砷酸盐是部分硫代为主.线性拟合分析确定在有硫体系中硫代亚砷酸盐形态占总砷形态的88.2%,亚砷酸盐形态占总砷形态的11.8%,而在无硫体系中,硫代三价砷形态占总砷形态的43.7%,亚砷酸盐形态占总砷形态的56.3%.可见亚砷酸盐的形成与砷硫比有关,提高硫砷比可以提高亚砷酸盐中硫取代的比例以及全硫代亚砷酸盐的形成.