耐氯纳滤/反渗透复合膜的研究进展

聚酰胺纳滤/反渗透复合膜的耐氯性能较差,严重影响膜的使用寿命,增加了膜系统运行成本。就此,很多学者从多方面展开了耐氯复合膜的研究工作。本文对近年来国内外耐氯纳滤/反渗透复合膜的研究进行综述,阐述了聚酰胺的氯化降解机理,归纳介绍了新的膜制备工艺、新型膜材料的研究、传统单体的改性、膜表面的接枝和涂覆等提高纳滤/反渗透复合膜耐氯性的方法。在分析各类方法优劣的基础上,对聚酰胺膜的耐氯改性工作进行介绍和分析,并对聚酰胺反渗透膜复合膜耐氯改性所面临的问题及前景进行了展望。     

抗油污染α-纤维素中空纤维超滤膜油-水分离性能的研究

以α-纤维素为原料,一水合N-甲基吗琳-N-氧化物(NMMO.H2O)为溶剂,聚乙二醇(PEG400)为添加剂,去离子水为内外凝胶浴,采用浸入相转化法制备用于油水分离的中空纤维非对称超滤膜,并采用纯水通量表征了膜的性能.用纤维素中空纤维超滤膜进行油水分离实验,油水乳液的截留率可达到99%以上,渗透液含油量小于10 mg/L,达到国家环境保护排放要求.考察了物理清洗、物理清洗加0.1 mol/L HCL清洗、物理清洗加0.1 mol/L NaOH清洗3种清洗方法对油水污染后膜的清洗效果.其中,物理清洗加0.1 mol/LNaOH清洗的清洗方法的通量恢复率达到99%.与其它种类的膜相比,α-纤维素中空纤维膜的油水通量衰减率仅为9.5%,表现出优异的抗油污染性能.     

中孔分子筛负载的钴基催化剂F-T合成反应研究

以中孔分子筛HMS-2为载体,浸渍法制香钴质量分数为15.00%的钴基催化剂,F-T合成反应研究表明：载体焙烧时间对F-T合成反应性能影响不大;Co/HMS-2催化剂的F-T合成反应在运行141.00h达到483.00K后,在H2/CO摩尔比为2.00,压力2.00MPa,空速500.00h^-1反应条件下,CO转化率达到88.00%,烃选择性保持在98.00%左右,烃分布中C5^+含量可达85.00%左右,进一步运转了384.00h,CO转化率仅下降了9.00%,而烃选择性和烃分布几乎不变,说明Co/HMS-2催化剂F-T合成反应性能和稳定性优异。载体中孔结构在473.00K催化剂开始F-T合成反应24.00h后已经塌陷,随后催化剂结构趋于稳定。     

(CeO_2-ZrO_2-Al_2O_3)-(La_2O_3-Al_2O_3)复合氧化物负载的Pd密偶催化剂:载体焙烧温度的影响

采用同时共沉淀法制备了(CeO2-ZrO2-Al2O3)-(La2O3-Al2O3)新型复合氧化物(CZA-LA),考察了焙烧温度对CZA-LA负载的Pd密偶催化剂的影响,并采用N2吸附-脱附法和X射线衍射对其进行了表征.结果表明,随着焙烧温度的升高,尽管CZA-LA样品的比表面积降低,但即使在1000°C焙烧5h后,其比表面积仍能保持在122m2/g左右;另外,CZA-LA样品的孔体积降低幅度不大,当在700℃及更高温度下焙烧后基本上保持稳定.以不同温度焙烧5h后的样品为载体,采用等体积浸渍法制备了一系列整体式Pd/CZA-LA密偶催化剂(Pd含量2.0g/L).催化剂对消除模拟汽油车尾气中C3H8活性测试结果表明,各新鲜催化剂的活性相差不大,均具有较低的起燃温度T50和完全转化温度T90.当催化剂经老化处理后,以1000°C焙烧的载体负载的Pd催化剂活性最高,T50和T90分别为310和341℃,ΔT仅为31℃,仅比新鲜催化剂的高7℃.可见,该催化剂表现出优异的催化活性和抗老化性能,可以满足欧Ⅳ及更高标准的用于汽油车尾气净化的密偶催化剂的性能要求.     

臭氧氧化深度处理印染废水改造工程实例

采用"前物化-水解酸化-好氧"组合工艺处理高浓度印染废水,新增臭氧氧化工艺进行深度处理,进一步提高废水处理效率。经调试运行结果表明,新增工艺使系统出水COD_(Cr)从100mg/L降至70 mg/L,SS从50 mg/L降至28 mg/L,色度从100倍降至36倍,排放水质达到《纺织染整工业水污染物排放标准》GB 4287-2012的排放标准。通过实际运行表明该系统深度处理的出水水质稳定性好,处理效率高。     

高回收率膜法苦咸水淡化工艺的应用研究进展

膜法苦咸水淡化过程中,符合环境保护要求的浓排水处理方法成本高昂,所以只有当回收率达到较高值时,在实际运行中才具有经济可行性。目前,在不加剧膜污染的条件下进一步提高苦咸水淡化系统回收率的方法已成为该领域研究热点。本文详细综述了高回收率膜法苦咸水淡化工艺的应用研究进展,包括基于反渗透、纳滤、正渗透、膜蒸馏、电渗析和电容去离子化淡化工艺过程,以及这些过程面临的热点问题,并对此提出了建议。     

不同基团修饰聚苯乙烯微塑料对大型溞的影响及其在肠道中的积累

选择3种结构不同的绿色荧光聚苯乙烯微塑料(聚苯乙烯微球(PS)、表面键合羧基聚苯乙烯微球(PS-COOH)和表面键合氨基聚苯乙烯微球(PS-NH₂))为研究目标,探讨其对淡水模式生物大型溞的影响及其在肠道中的积累情况。急性毒性实验结果表明,PS,PS-COOH和PS-NH2的72 h半数致死浓度(LC50)分别为12.29,41.36和24.89 mg/L。显微荧光成像结果表明,3种微塑料主要在大型溞的肠道积累,其中低浓度暴露组(50μg/L)在72 h微塑料生物积累达到最大,高浓度组(500μg/L)在24～48 h微塑料生物积累达到最大。将暴露的大型溞转移至不含微塑料的纯培养液中,1 h即可观察到微塑料通过肠道开始排出体外,低浓度组的微塑料在12 h后基本排出,高浓度组的微塑料在36 h基本排出。     

制备方法对 Ni-Al2O3催化剂在 CO2-CH4重整反应中 催化性能的影响

为提高镍基催化剂的干法重整活性,采用溶液燃烧法、等体积浸渍法、胶体磨循环浸渍法和水热-沉积法制备了SCM、IMP、T310和HTP四种催化剂,在800 ℃考察了其在CO₂-CH₄重整反应中的催化性能,并结合ICP-AES、N₂吸附-脱附、XRD、H₂-TPR和TEM等表征手段对催化剂进行分析。结果表明,水热-沉积法和胶体磨循环浸渍法制备的催化剂比表面积较大,分别为190.83和182.21 m²/g,可为反应提供较多的接触面积,进而提高催化剂的初始活性(HTP试样CH₄和CO₂初始转化率相对较高,分别达85.15%和90.84%);而溶液燃烧法和等体积浸渍法制备的催化剂具有较多的NiAl₂O₄尖晶石,其还原峰面积占总还原峰面积90%以上,还原后可获得更多晶粒粒径更小的稳定活性组分Ni(SCM和IMP试样稳定性更好,反应50 h后活性超过HTP和T310试样,100 h后CH₄转化率方降至50%以下)。因此,决定催化剂稳定活性的更重要的因素应该是活性组分Ni晶粒粒径的大小及其抗烧结能力的强弱。     

同时测定海水中K+、Na+、Ca2+、Cl-的流动注射离子选择电极分析

建立了一种用于海水中K+、Na+、Ca2+、Cl-同时快速、自动测定的流动注射离子选择电极自动方法(FI-ISE-M),优化了方法的最佳条件:总离子强度调节液(TISAB)的组成为0.3 mmol/L K+、6.0 mmol/L Na+、1.4 mmol/L Ca2+、21.0 mmol/L Cl-及pH8.0的80 mmol/L的tris-H3BO3缓冲溶液,其流量为1.25mL/min;每次测定的样品用量仅为160μL,载流流量为1.42 mL/min,混合盘管长度为30cm(I.D.0.5 mm)。本方法的分析速度为100样/h,相对标准偏差为2.0%(n=11),标准添加回收率为94.9%～104.3%,测定范围分别为1.0～8.0 mmol/L K+、50～290 mmol/L Na+、3.2～16.0 mmol/L Ca2+、70～430 mmol/LCl-。本方法已应用于反渗透海水淡化系统的水质检测。     

用反渗透法浓缩一磷酸腺苷洗脱液的研究

从离子交换树脂洗脱出来的一磷酸腺苷(AMP)稀溶液可以用反渗透法浓缩。一次浓缩除去3/4水时,浓缩收率在99％以上,如用多次浓缩,将浓度为0.3mg/ml的AMP洗脱液浓缩至33.0mg/ml(浓缩100倍,即达到其结晶沉淀浓度)时,浓缩收率达98％。浓缩产品质量符合要求。在累积300多小时的运行试验中,AMP洗脱液妇膜的污染不大,膜的透水量下降不严重。此外,还考察了AMP溶液浓度、pH值、以及操作压力对膜性能的影响。     

Optimum design of reverse osmosis system under different feed concentration and product specification

The design of various multistage RO systems under different feed concentration and product specification is presented in this work. An optimization method using the process synthesis approach to design an RO system has been developed. First, a simplified superstructure that contains all the feasible design in present desalination process has been presented. It offers extensive flexibility towards optimizing various types of RO system and thus may be used for the selection of the optimal structural and operating schemes. A pressure vessel model that takes into account the pressure drop and concentration changes in the membrane channel has also been given to simulate multi-element performance in the pressure vessel. Then the cost equation relating the capital and operating cost to the design variables, as well as the structural variables of the designed system have been introduced in the objective function. Finally the optimum design problem can be formulated as a mixed-integer nonlinear programming (MINLP) problem, which minimizes the total annualized cost. The solution to the problem includes optimal arrangement of the RO modules, pumps, energy recovery devices, the optimal operating conditions, and the optimal selection of types and number of membrane elements. The effectiveness of this design methodology has been demonstrated by solving several seawater desalination cases. Some of the trends of the optimum RO system design have been presented.     

The Resting Oxidized State of Small Laccase Analyzed with Paramagnetic NMR Spectroscopy

The enzyme laccase catalyzes the reduction of dioxygen to water at the trinuclear copper center (TNC). The TNC comprises a type-3 (T3) and a type-2 (T2) copper site. The paramagnetic NMR spectrum of the small laccase from Streptomyces coelicolor (SLAC) without the substrate shows a mixture of two catalytic states, the resting oxidized (RO) state and the native intermediate (NI) state. An analysis of the resonances of the RO state is reported. In this state, hydrogen resonances only of the T3 copper ligands can be found, in the region of 12–22 ppm. Signals from all six histidine ligands are found and can be attributed to Hδ1, Hβ or backbone amide H^N nuclei. Two sequence-specific assignments are proposed on the basis of a second-coordination shell variant that also lacks the copper ion at the T1 site, SLAC−T1D/Q291E. This double mutant is found to be exclusively in the RO state, revealing a subtle balance between the RO and the NI states.     

羟丙基醋酸纤维素反渗透膜

研究了羟丙基醋酸纤维素反渗透膜的制膜工艺和膜性能。实验表明,以甘油—正丙醇或磷酸为添加剂,蒸发时间30—60s,预热处理温度70℃,时间3—5min,可得到在2MPa操作压力下,氯化钠脱除率95—98％,水通量1.0～2.1ml/cm~2·h的反渗透膜。羟丙基醋酸纤维素膜具有一定的耐热性,其使用温度上限比醋酸纤维素膜至少提高了10℃以上。羟丙基醋酸纤维素的溶解性能与醋酸纤维素相似。X射线衍射和热重分析显示羟丙基醋酸纤维素具有与醋酸纤维素相似的聚集态结构。     

5,9,14,18,23,27,32,36-八烷氧基2,3-萘酞菁镍(Ⅱ)的结构与光谱性质关系的研究

测定了一组八烷氧基萘酞菁镍（Ⅱ）配合物Ni（Ⅱ）（RO）8NPC（R＝C4H9，C8H17，C12H25，NPC＝C48H16N8）在5种有机溶剂（Py、DMSO、DMF、CH2Cl2、C6H12）中的电子吸收光谱和荧光光谱，研究了这些配合物的结构与光谱的关系。结果表明该系列RO取代萘酞菁镍（Ⅱ）配合物的Q带吸收光谱比无取代的红移75nm左右，荧光光谱屯相应红移50～80nm，而溶剂对其影响不大。     

Osmotic backwash mechanism of reverse osmosis membranes

A new osmotic backwash (BW) model for reverse osmosis (RO) membranes was developed for conditions of no applied pressures across the membrane. This analytical model has one adjustable parameter representing the coefficient of a linearized convection term in the general convection–diffusion equation. An experimental RO/BW system was used for 12 data sets to verify the proposed BW model and illustrate its predictability. Results show deviations of the model from the data within a range of 5–15%. The described dilution mechanism of the feed concentration polarization (CP) layer is based on RO originated concentrated layer detachment from the membrane surface followed by its gradual dilution.The understanding gained in this research may be applied to automatic RO/BW cleaning cycles. A dominant RO parameter of the BW process is the RO initial driving force—the concentration difference across the membrane. Other RO process parameters – applied pressure and feed flow rate – have lesser effects. Both theoretical and experimental methods provide quantitative relationships between RO and BW variables that enable an understanding and control of the BW process.     

MembrFactory: A Force Field and composition Double Independent Universal Tool for Constructing Polyamide Reverse Osmosis Membranes

The topmost polyamide (PA) layer of the thin-film-composite reverse osmosis (RO) membrane is the most important part in the membrane-based RO technology. With the aid of molecular dynamics simulations, many PA layer-related features in the RO process can be revealed. With many novel types of PA RO membranes out of trimesoyl chloride/m-phenylenediamine monomers developed in the laboratory, a convenient model building tool for these PA layer systems is urgently needed to conduct the theoretical analysis. Here, we develop a new universal toolkit for constructing PA RO membranes, named as MembrFactory, which combines flexibility of force fields and membrane compositions. A key characteristic of our approach is the use of monomers as the starting state, and the final membrane model was obtained automatically by stepwise reaction between the functional groups on the monomers. The reliability of MembrFactory has been validated by constructing several common PA RO membranes. © 2019 Wiley Periodicals, Inc.     

Synthesis and Coordination Properties of Multifunctional Carbamoylmethyl Phosphonates

Abstract

Bifunctional carbamoylmethylphosphonates are useful extractants for lanthanide and actinide ions and the structural mechanics involved in extraction processes have been under study in our laboratory. We have recently prepared several new multifunctional ligands of the general types (RO)₂P(O)CH[C(O)NR₂][CH₂C(O)NR₂], [(RO)₂P(O)]₂CHCH₂C(O)NR₂ and [(RO)₂P(O)CHC(O)NEt₂]₂CH_2. The syntheses and characterization data for the new extractants will be described. The coordination chemistry of these ligands with lanthanide and actinide ions has been studied and crystal structure determinations for selected complexes will be shown. Lastly, liquid-liquid extraction distribution measurements for several ligands with lanthanide ions will be presented.     

Flexible Waste Management to Increase the Effectiveness of Minor Actinide P&T Technology

Partitioning and transmutation (P&T) technologies have been developed for minor actinides (MA) to reduce the high level waste (HLW) volume and long-term radiotoxicity. Although the MA P&T can reduce the potential radiotoxicity effectively by 1-3 orders of magnitude, the actual operation of P&T requires several tens of years for developing elemental technologies of nuclide separation, MA containing fuel fabrication, transmutation and their practical systematization. The high level liquid waste (HLLW) containing MA is presently vitrified immediately after spent fuel reprocessing, stored about 50 years at surface facility and will be disposed of at deep geological repository. Vitrified HLW form works as an excellent artificial barrier against nuclides release during storage and disposal. On the other hand, it is difficult to recover MA from the form. So the present waste management scheme has an issue of MA P&T technology application until its deployment, which will produce much amount of vitrified HLW including long-lived MA without P&T application. Thus the authors proposed the flexible waste management method to increase the effectiveness of the MA P&T. The system adopts the HLLW calcination instead of the vitrification to produce granule for its dry storage of about 50 years until the MA P&T technology will be applicable. The granule should be easily dissolved by the nitric acid solution to apply the typical aqueous MA partitioning technologies to be developed. This paper reports the purpose of the study, the feasibility evaluation results for the calcined granule storage and the evaluation results for the environmental burden reduction effect.     

微波场中T型分子筛的合成及晶化研究

研究了微波场中T型分子筛的结晶过程。考察了微波加热体系中合成参数如合成时间、溶胶组成、反应压力和模板剂用量对分子筛晶化的影响。微波加热的主要优点是减少合成时间,无模板剂的溶胶在普通加热条件下的晶化时间需要120 h,而在微波场中则仅需要20～25 h。另一方面,由于微波的快速加热特性促进了稳定相钙十字沸石的生成,从而减小了次稳定相T型分子筛的结晶区间。在未添加模板剂条件时,100 ℃下微波水热合成T型分子筛的结晶区间为：20≤n_SiO2/n_Al2O3≤22和0.31≤ n_M2O/n_SiO2≤0.33(其中M₂O=Na₂O+K₂O, n_Na/n_K=3和n_M2O/n_SiO2=11.70)。在普通加热和微波加热合成体系中,添加模板剂均能扩大结晶区间,同时还可以进一步减少合成时间。