用煤矸石合成4A沸石分子筛处理氨氮废水

以煤矸石为原料,采用碱熔-水热法合成4A沸石分子筛。由于煤矸石中铝、硅主要以高岭土形式存在,其活化过程是合成4A沸石分子筛关键环节。为提高4A沸石分子筛钙离子的交换能力,增加对模拟废水氨氮的去除率,实验考察了碳酸钠与煤矸石质量比、活化温度、活化时间、晶化温度和晶化时间对4A沸石分子筛钙离子交换能力的影响,同时也考察了模拟废水的pH、4A沸石分子筛加入量及吸附时间对氨氮去除率的影响。结果表明,最佳工艺条件为,碳酸钠与煤矸石质量比为0.9、活化温度为800℃、活化时间1.5 h、晶化温度90℃和晶化时间3 h。合成4A沸石分子筛的钙离子交换能力为310 mg/g,在pH为6的100 mL模拟氨氮废水中加入6 g 4A沸石分子筛吸附40 min后,废水中氨氮的去除率达到86%。通过最佳工艺条件合成4A沸石分子筛,在处理氨氮废水方面具有一定的应用前景。     

诱导结晶法同时去除铜、锌离子

考察投药量、水力负荷、停留时间等因素,对诱导结晶反应器去除Cu2+、Zn2+效果的影响,确定最佳运行参数为：水力负荷40 m3·（m2·h）-1,结晶药剂投药量2：1,停留时间90 min。在最佳运行参数下,结晶反应器处理含铜20 mg·L-1,含锌10 mg·L-1、pH为5.5~6.0的混合重金属废水。反应器连续运行40 d,出水中铜离子和锌离子平均浓度分别为1.31 mg·L-1和4.57 mg·L-1,铜离子和锌离子平均去除率分别是93.4%和51.3%。诱晶载体粒径由0.568 mm长至0.617 mm,平均生长速度为0.001 23 mm·d-1。研究表明,该诱导结晶工艺可以用作同时去除废水中的Cu2+、Zn2+。     

不同诱导条件对结晶产物形貌特征的影响

在流化床反应器中,以含铜废水为处理对象,重点考察了诱导条件改变对结晶系统运行效率及结晶产物形貌特征的影响。结果表明,进水200 mg/L,进药比([Cu2+]/[CO32-])1:1.2,pH为10.2的条件下,铜离子去除率可接近100%,诱导晶种表面平滑,诱导颗粒生长成致密杆状晶体结构,以碳酸盐为沉淀剂的诱导结晶系统依赖于体系的pH,高pH体系下发生的共结晶现象是影响系统运行的主要原因;随着进药摩尔比的增加,结晶产物由短杆状向球状转化,晶体机械强度显著降低大量破碎,影响出水水质;进药比1:1.2,pH为11的条件下,含铜废水浓度为500 mg/L时,系统去除率可达95%以上,微晶产率低于5%。     

新型真空膜渗透结晶工艺初探

真空膜渗透结晶工艺(vacuum membrane percrystallization, VMPC)是一种新型膜结晶工艺,可同步实现溶质的结晶及其与溶剂的分离回收。以NaCl溶液为目标物系,对VMPC过程的原理进行了分析,初步考察了进料液温度、浓度和操作压力对该工艺产能的影响。结果表明：VMPC过程是膜渗透和真空压差闪蒸结晶的协同作用的过程,随进料液温度的升高,结晶盐通量和水通量均增大;随进料液浓度的升高,结晶盐通量增大,水通量降低;而操作压力对工艺产能影响较小,但对生成晶体的形貌影响显著;当进料液温度为34 ℃,进料质量分数为25%,操作压力为0.5 kPa时,可获得高达8.04 kg·(m²·h)⁻¹的盐通量和30 L·(m²·h)⁻¹的水通量,远高于现有太阳能驱动膜结晶技术的产能。针对现有膜滤浓缩液类高浓盐水结晶工艺流程复杂、能耗高、效率和产能低的问题,VMPC工艺为新型高效处置技术的开发及应用提供了可行的解决方案。     

Crystallization behavior of predominantly syndiotactic poly(β-hydroxybutyrate)

Predominantly syndiotactic poly(-hydroxybutyrate), syn-PHB, of variable syndioregularity (syndyad fractions 0.59, 0.62, 0.64, and 0.71) and molecular weight was prepared by the dibutyltin dimethoxide catalyzed ring opening of racemic-butyrolactone (BL). The crystallization behavior of the syn-PHB polymers was investigated by DSC and X-ray diffraction analyses. DSC of films after melting and annealing showed at least one, and often two distinct melting transitions occuring over a broad (often 40°C) temperature range. These results indicate that syn-PHB chain segments of variable syndioregularity form crystalline regions with very different thermodynamic stabilities. Maximum degrees of crystallinity for melt annealed 0.64- and 0.71-syn-PHB was observed at an annealing temperature (T _c ) of 30°C. AtT _c values at 45°C and higher, crystallization of relatively lower syndioregular chain segments was apparently excluded to variable degrees dependent onT _c and sample syndiotactic dyad content. After crystallization of syn-PHB samples at elevated temperatures, ambient temperature annealing resulted in an observed lower temperature melting transition at 50°C. This result showed little to no dependence on syn-PHB syndio-regularity andT _c . Both solution precipitated 0.62-syn-PHB and 0.71-syn-PHB have WAXS patterns with poorly resolved crystalline reflections superimposed on amorphous haloes indicating low levels of crystallinity (17% and 25%, respectively) and poorly formed crystals. Isothermal crystallization monitored by DSC showed that the syn- and natural origin PHB showed fastest crystallization rates at temperatures between 50°C and 70°C and 60°C and 90°C, respectively. From the dependence of the higher melting transition onT _c it was determined that the equilibrium melting temperatures for 0.62-syn-PHB (M _n =83,700 g/mol) and a 0.64-syn-PHB (M _n =11,900 g/mol) were 157 and 154°C, respectively. An Avrami analysis of syn-PHB yielded results similar to that found for natural origin PHB indicating that crystal growth occurs by a two-dimensional mechanism.Guest Editor: Dr. Graham Swift, Rohm & Haas.     

Nitrogen and phosphorus removal for swine wastewater by ammonium crystallization and intermittent aeration process

Abstract

A process on crystallized precipitation of ammonium by adding magnesium salt and phosphate was carried out to improve C/N ratio in swine wastewater. After completion of crystallized precipitation of ammonium, an intermittent aeration process with aeration and non‐aeration periods alternated at interval of 1:1 hr day^‐1 is used for the improved swine wastewater (T‐N/BOD=0.14: BOD=8200 mg/liter and T‐N=1166 mg/liter). The results obtained from the experiment show that the removal ratios of T‐N and NH₄‐N are 91% and 99%, respectively. T‐P is not removed, while the removal ratio of PO₄‐P is 60% as 3% of CaCl₂ liquid is added. The results also indicate that dilution with water is effective to improve the removal of phosphorus even if raw swine wastewater contains high concentrations of T‐N, T‐P, BOD, and TOC.     

晶析辅助化学沉淀法处理高含磷废水

在常温条件下,将价格低廉的氯化镁、碳酸氢铵加入到高浓度含磷废水中,不仅有较高的除磷率,且可兼得缓效复合肥MgNH4PO4·6H2O。为了使一次处理液能达标排放,以MgNH4PO4·6H2O作为晶种,采用晶析辅助化学沉淀法进一步除磷。在一次处理液放置时间为2.7h、水力停留时间维持0.1h左右的条件下,处理后的废水可达到Ⅱ类水排放标准(磷质量浓度不超过2.0mg/L)。     

悬浮结晶法冷冻处理喹乙醇生产废液

采用悬浮结晶法处理喹乙醇生产废液,考察了成冰率(冰晶融化后的体积占原水总体积的百分比)对废液COD、氨氮、TN和电导率去除效果的影响。在一级冷冻成冰率45%的条件下,经过三级冷冻处理后,三级出水的COD、氨氮、TN和电导率的去除率分别为99.4%、98.7%、98.5%和98.2%,一级浓缩液的COD、氨氮和TN的浓缩比分别为1.6、1.5和1.5;在一级冷冻成冰率80%的条件下,每一级出水的各项指标的去除率均有所下降,三级出水的COD、氨氮、TN和电导率的去除率分别为98.6%、98.3%、97.1%和95.9%,但一级浓缩液的浓缩比明显提高,COD、氨氮和TN的浓缩比分别为2.7、2.2和2.4。成冰率为80%时一级浓缩液的热值为7 449 J/g,在焚烧过程中可以依靠自身热量维持燃烧,不需要添加辅助燃料,减少焚烧处理的成本。     

晶析辅助化学沉淀法的研究

在用化学沉淀法处理高浓度氨氮废水的基础上,引入晶析辅助化学沉淀法的思路,即将晶种投加到反应器中,然后从氨氮去除率、生成晶体的粒型、粒径三个方面分析不同晶种对生成晶体的影响,并对生成的磷酸铵镁晶体进行X光衍射分析。得出结论：投加晶种有利于提高氨氮的去除率,但不会明显提高生成晶体的粒径。     

鸟粪石结晶法回收垃圾渗滤液氨氮研究

采用MgSO₄·7H₂O和Na₂HPO₄·12H₂O使NH₃-N生成MgNH₄PO₄·6H₂O（鸟粪石）结晶沉淀法回收渗滤液中NH₃-N。考察了pH值、反应时间、药剂配比对NH₃-N去除率的影响。结果表明,鸟粪石结晶回收NH₃-N反应的适宜pH值为9～9.5之间,过高的pH会破坏鸟粪石晶体结构,导致固定氨从MgNH₄PO₄中游离出来,不利于氨氮的去除。在pH值为9.5、反应时间为25 min、Mg²⁺∶NH⁺₄∶PO^3-₄=1.5∶1∶1.5的最佳条件下,渗滤液中NH₃-N浓度由初始3 500 mg/L,经结晶沉淀后降低至175 mg/L,去除率达95%。鸟粪石结晶沉淀过程中几乎不吸收重金属,同时回收了氨氮,其沉淀产物鸟粪石是一种优良的缓释肥原料。