临阈浓度时纳滤膜软化过程中膜面动电现象研究

荷电纳滤(NF)膜在相似浓度范围的进水端主体溶液软化过程中,浓水端的膜面处易出现结垢污染,因此开展临阈浓度条件下膜表面动电现象研究是十分必要的。本文选定DK型NF膜和cK_2SO_4:cCaCl_2=1:1的双组分溶液为载体,以CaSO_4·0.5H_2O为典型代表的非碱性难溶垢为研究对象,通过自制的切向流动电位测试系统,分别考察临阈浓度条件下,进水端主体溶液中不同构晶离子浓度(0.5~18 mol·m~(-3))、操作压力(25~200 k Pa)和不同pH(3.0~10.0)对该NF膜流动电位、Zeta电位和膜表面电荷密度的影响效应。当操作压力恒定为180 k Pa且逐渐增加构晶离子浓度(0.5~18 mol·m~(-3))时,DK膜面流动电位和Zeta电位绝对值分别从87.37和59.13 mV下降至3.41和36.34 mV,均呈先急剧后缓慢下降的变化趋势。这可能是由于静电屏蔽和扩散层压缩共同作用的结果。而同时膜面电荷密度从13.94 mC·m~(-2)逐渐增加至34.86 mC·m~(-2)。研究表明,当NF浓水端膜面处开始出现结垢时,膜表面仍有中低强度的动电现象。     

氧化石墨烯-陶瓷复合纳滤膜的层层自组装制备及其性能

氧化石墨烯（GO）的片层边缘含有 COOH等含氧官能团,因而带负电荷,可以在带正电荷多孔基体上通过层层自组装实现快速沉积。以由3-氨丙基三乙氧基硅烷（APTES）修饰的多孔氧化铝管式陶瓷膜为基膜,令GO和聚乙烯亚胺（PEI）以溶液形态在其表面交替沉积实现自组装,继以环氧氯丙烷（ECH）交联之,制备新型氧化石墨烯-陶瓷复合纳滤膜。最佳制备工艺是,PEI浓度5 g·L^-1、pH=9,NaCl浓度0.3 mol·L^-1,GO浓度0.6 mg·ml^-1、pH 4.5,层数2层,ECH用量6.25 ml·L^-1,50℃条件下处理70 min。层数为1～4层的自组装膜在0.6 MPa操作压力下对2 g·L^-1的MgCl₂的截留率分别为90.16%、93.71%、97.54%、92.93%,其中1层自组装膜的渗透通量为21.92 L·m^-2·h^-1。氧化石墨烯-陶瓷复合纳滤膜对4种无机盐的截留率大小为MgCl₂ >MgSO₄ > NaCl >Na₂SO₄,符合典型正电荷纳滤膜的特征。     

基于电荷模型的荷电膜传递现象的研究进展

根据电荷模型（空间电荷和固定电荷模型）,将荷电膜传递现象分为膜的分离性能、电性质及传递参数3类.其中膜的分离性能用截留率和通量来表征;膜的电性质包括膜的电化学性质和膜的动电性质,膜的电化学性质用膜电位来表征,膜的动电性质用流动电位、Zeta电位和电滞效应等参数来表征;膜的传递参数则用反射系数、溶质透过系数、纯水透过系数、电导率、离子的迁移数及电渗系数6个系数来表征.概述了空间电荷和固定电荷模型描述电解质溶液在荷电膜中的传递现象的研究进展,介绍了两种模型在荷电膜中应用时的各自优势,展望了电荷模型在荷电膜体系中应用的发展方向.     

季铵盐接枝提高玻璃纤维膜表面Zeta电位

以玻璃纤维膜为基体,通过等离子处理,再进行化学接枝有机硅季铵盐,制备出荷正电玻璃纤维膜。采用扫描电子显微镜(SEM)、全衰减反射-傅里叶红外光谱图(ATR-FTIR)、X射线光电子能谱分析(XPS)、热重分析(TGA)等对改性玻璃纤维膜的结构与性能进行表征。采用Zeta电位法考察电解质溶液的种类、浓度、pH对改性玻璃纤维膜表面Zeta电位的影响。结果表明:季铵盐在玻璃纤维膜上的接枝量为2.47%;电解质种类对膜表面Zeta电位值影响较大,电解质浓度对Zeta电位测试稳定性影响较大;Zeta电位随pH的升高而下降,在pH值为7.0的0.001 mol/L的KCl溶液条件下,改性玻璃纤维膜表面Zeta电位提高到27.35 mV。     

进水水质对纳滤膜苦咸水软化的分离性能

针对黄淮地区苦咸水,构建了小试级别的纳滤膜法软化系统,并开展了包括pH、总溶解固体含盐量（TDS）和总有机碳（TOC）等进水水质对DL、DK型纳滤膜的软化分离实验。结果表明,pH为3~10、TDS为1317~5926 mg·L^-1和TOC为2.72~12.24 mg·L^-1的进水条件下,DL和DK纳滤膜比通量随pH的增加分别呈先上升后下降和缓慢下降的趋势,随进水TDS和TOC的增加呈整体下降趋势,而纳滤膜对硬度离子（Mg²⁺和Ca²⁺）的截留率均呈明显的上升趋势。DL膜运行至267 h时,膜比通量下降幅度超过10%,进行化学清洗,酸洗后膜比通量恢复率达到85.05%,酸洗加碱洗后该值高达97.2%,结合扫描电子显微镜和原子力显微镜表征结果,可知化学清洗对膜面污染有较好的去除效果。     

锌催化电还原脱氯合成2,3,5,6-四氯吡啶:反应机理和工艺优化

采用循环伏安法和恒电位电解法,探讨了含有ZnCl₂的乙睛水混合溶液中五氯吡啶(PCP)在不锈钢阴极表面电还原脱氯生成2,3,5,6-四氯吡啶(2,3,5,6-TCP)的反应机理;采用恒电流电解法对该电还原脱氯过程的各种工艺条件进行了优化。结果表明:该体系中PCP电还原脱氯生成2,3,5,6-TCP主要遵循以Zn/Zn²⁺为氧化还原媒介的间接电还原机理;优化工艺条件下(阴极液含0.025mol·L^-1HCl+15%(体积分数)水+0.2mol·L^-1苯磺酸钠+0.16mol·L^-1ZnCl₂的乙腈溶液;电流密度为1.25A·dm^-2),0.08mol·L^-1PCP能高选择性地脱氯生成2,3,5,6-TCP,2,3,5,6-TCP的收率和电解电流效率分别可达88.7%和59.1%。     

富氧空位Co3O4纳米线的制备及其电解水性能研究

在室温下利用NaBH₄溶液还原Co₃O₄纳米线获得富含氧空位（V_O）的三维自支撑纳米线阵列用作全水解电催化剂，其中NaBH₄处理10 min的Co₃O₄/NF在碱性介质中对析氧反应（OER）和析氢反应（HER）表现出很高的活性，在10 mA·cm^-2电流密度下分别仅需240和132 mV的过电位。V_O-Co₃O₄/NF同时作为阴极和阳极电催化剂时，在10 mA·cm^-2下电解水槽电压仅为1.63 V，其耐久性可达60 h以上。该工作为富含氧空位结构的过渡金属氧化物双功能电催化剂的制备提供了新的方法和思路。     

液相还原法制备纳米镍粉

采用液相还原法在搅拌反应器内进行了纳米镍粉的制备研究。系统考察了反应物浓度、反应物配比（N₂H₄：NiSO₄）、引发剂浓度、氢氧化钠浓度、反应温度、搅拌速度等操作条件对镍粉物性的影响规律,获得了较优操作条件：NiSO₄为0.8 mol·L^-1,反应物配比为6：1,NaBH₄浓度为0.01 mol·L^-1,NaOH浓度为1 mol·L^-1,反应温度80℃,搅拌速度为2400 r·min^-1,在较优条件下制备出常温下稳定性良好、平均粒径107 nm的面心立方结构的纳米镍粉。     

面向烟气NOx净化与回收的新型吸附工艺

合理高效的吸附工艺是决定吸附法净化和回收烟气中NO_x工业可行性的关键工艺环节。提出一种通过外部补充气体实现固定床循环体空间内多次循环解吸NO_x的新型吸附工艺（GVTSA）。基于该工艺,采用Na-ZSM-5分子筛作为吸附剂,以某钢厂烧结机脱硫后烟气为原料（组分）进行了NO_x吸附回收实验研究。结果表明,GVTSA工艺相较传统吸附工艺（TSA工艺、VSA工艺）可获取更高的NO_x回收量,在优选条件下（220℃,-50 kPa）,NO_x回收率达到90%,解吸气中NO₂浓度由原料气的36 mg·m^-3提升到2%以上,NO_x循环吸附量可达0.10 mmol·g^-1,16次吸脱附循环稳定。研究结果可为烟气NO_x治理与资源化工业应用提供参考。     

氧化石墨烯掺杂反渗透混合基质膜制备及性能

由于芳香族聚酰胺反渗透膜在抗污染性以及耐氯性方面存在不足,限制了其在海水淡化等方面的应用。采用往油相中添加氧化石墨烯（GO）的二次界面聚合法改性了商业反渗透膜,评价了GO掺杂反渗透混合基质膜的分离性能和耐氯性能,并用接触角仪、Zeta电位仪、扫描电镜和原子力显微镜等仪器表征了膜的亲水性能、荷电性能以及膜表面形貌。结果表明,GO的添加提高了膜的分离性能、耐氯性能和亲水性能;当GO添加量为30 mg·L^-1时,膜的通量为（77.7±0.9） L·m^-2·h^-1,膜的截留率为97.6%±0.5%,相比商业膜分别提高了38.4%和4.5%。当氯化强度低于4800 mg·L^-1·h时,膜的水通量和盐截留率变化不明显。     

超声作用对NaCl和MgSO4溶液在纳滤膜内传质的影响

将超声波用于强化电解质溶液在纳滤膜内的传质过程,研究超声作用下NaCl和MgSO₄溶液在聚酰胺纳滤膜内的传质机理,考察超声作用对膜通量、截留率和跨膜电位随跨膜压差变化规律的影响。实验结果表明,与无超声作用相比,施加在膜表面的超声作用增大了膜通量,降低了截留率,提高了跨膜电位。     

Gas separation using sol-gel derived microporous zirconia membranes with high hydrothermal stability☆

A microporous zirconia membrane with hydrogen permeance about 5 × 10?8 mol·m?2·s?1·Pa?1, H2/CO2 permselectivity of ca. 14, and excellent hydrothermal stability under steam pressure of 100 kPa was fabricated via polymeric sol–gel process. The effect of calcination temperature on single gas permeance of sol–gel derived zirconia membranes was investigated. Zirconia membranes calcined at 350 °C and 400 °C showed similar single gas permeance, with permselectivities of hydrogen towards other gases, such as oxygen, nitrogen, methane, and sulfur hexafluoride, around Knudsen values. A much lower CO2 permeance (3.7 × 10?9 mol·m?2·s?1·Pa?1) was observed due to the interaction between CO2 molecules and pore wall of membrane. Higher calcination tem-perature, 500 °C, led to the formation of mesoporous structure and, hence, the membrane lost its molecular siev-ing property towards hydrogen and carbon dioxide. The stability of zirconia membrane in the presence of hot steam was also investigated. Exposed to 100 kPa steam for 400 h, the membrane performance kept unchanged in comparison with freshly prepared one, with hydrogen and carbon dioxide permeances of 4.7 × 10?8 and~3 × 10?9 mol·m?2·s?1·Pa?1, respectively. Both H2 and CO2 permeances of the zirconia membrane de-creased with exposure time to 100 kPa steam. With a total exposure time of 1250 h, the membrane presented hydrogen permeance of 2.4 × 10?8 mol·m?2·s?1·Pa?1 and H2/CO2 permselectivity of 28, indicating that the membrane retains its microporous structure.     

Fabrication of anti-fouling polyamide nanofiltration membrane by incorporating streptomycin as a novel co-monomer

Polyamide (PA) thin-film composite (TFC) nanofiltration (NF) membrane has extremely broad application prospects in separation of monovalent/divalent inorganic salts mixed solution. However, membrane fouling is the main obstacle to the application of PA, TFC and NF membrane. Streptomycin (SM) is a hydrophilic antibiotic containing a large number of hydroxyl and amino groups. In this work, the NF membrane was prepared via interfacial polymerization (IP) between trimesoyl chloride (TMC) in the organicphaseand SM/piperazine (PIP) mixture in theaqueousphase. The NF membrane structure and performance were characterized in detail. The results showed that SM successfully participated in the IP. The negative charge and hydrophilicity of membrane surface were improved. The prepared membrane exhibited good anti-adhesion and anti-bacterial performance. Additionally, when the SM concentration was 2%, the prepared membrane exhibited the optimal permselectivity. The water permeance was 89.4 L·m^-2·h^-1·MPa^-1. The rejection of NaCl and Na₂SO₄ were 17.17% and 97.84%, respectively. The NaCl/Na₂SO₄ separation factor of the SM2-PIP/TMC membrane in 1000 mg·L^-1 NaCl and 1000 mg·L^-1 Na₂SO₄ mixed solution was 40, which was 3.3 times that of PIP/TMC membrane. It indicated that SM2-PIP/TMC demonstrated excellent monovalent/divalent salts separation performance. This work provided an easy and effective approach to preparing anti-fouling NF membrane while possessing superior monovalent/divalent salts separation performance.     

Negatively charged organic–inorganic hybrid silica nanofiltration membranes for lithium extraction

Effective extraction of lithium from high Mg~(2+)/Li+ratio brine lakes is of great challenge. In this work, organic–inorganic hybrid silica nanofiltration(NF) membranes were prepared by dip-coating a 1,2-bis(triethoxysilyl)ethane(BTESE)-derived separation layer on tubular TiO_2 support, for efficient separation of LiC l and MgCl_2 salt solutions. We found that the membrane calcinated at 400 °C(M1–400) could exhibit a narrow pore size distribution(0.63–1.66 nm) owing to the dehydroxylation and the thermal degradation of the organic bridge groups. All as-prepared membranes exhibited higher rejections to LiCl than to MgCl_2, which was attributed to the negative charge of the membrane surfaces. The rejection for LiCl and MgCl_2 followed the order: LiCl N MgCl_2, revealing that Donnan exclusion effect dominated the salt rejection mechanism. In addition, the triplecoated membrane calcined at 400 °C(M3–400) exhibited a permeability of about 9.5 L·m~(-2)·h~(-1)·bar~(-1) for LiCl or MgCl_2 solutions, with rejections of 74.7% and 20.3% to LiCl and MgCl_2,respectively, under the transmembrane pressure at 6 bar. Compared with the previously reported performance of NF membranes for Mg~(2+)/Li+separation, the overall performance of M3–400 is highly competitive. Therefore, this work may provide new insight into designing robust silica-based ceramic NF membranes with negative charge for efficient lithium extraction from salt lakes.     

Ti/Zr复合纳滤膜的制备及其性能

通过聚合溶胶路线制备出稳定的Ti/Zr(摩尔比=1:1)复合溶胶。采用浸浆法,在平均孔径为5～6 nm的片状a-Al₂O₃/g-Al₂O₃载体上制备出完整无缺陷的Ti/Zr复合纳滤膜。详细考察了焙烧温度对Ti/Zr粉体的影响,并考察了Ti/Zr复合纳滤膜的性能。结果表明:在较高烧成温度下(500℃),Ti/Zr粉体依然呈无定形态且保持微孔结构。在400℃烧成温度下制备出孔径为1.49 nm的Ti/Zr复合纳滤膜,该膜的截留分子量(MWCO)为880,纯水通量为4.3 L·m^-2·h^-1·MPa^-1。在pH=6,压力0.8 MPa的条件下,该膜对0.005 mol·L^-1的MgCl₂、CaCl₂的截留率分别为85%和78%。     

纳米聚苯胺改性聚哌嗪酰胺纳滤膜的制备

以导电态纳米聚苯胺(PANI)为添加剂, 哌嗪和均苯三甲酰氯(TMC)为反应单体, 通过界面聚合反应在聚砜超滤膜上形成复合层制备纳滤膜。采用扫描电子显微镜(SEM)和原子力显微镜(AFM)等对复合膜的性能和结构分别进行了测试和表征。SEM照片证实PANI含量低时, 可以在复合膜上分布得比较均匀;AFM图像看出膜表面粗糙度的增加;膜性能的测试结果证实了添加PANI的复合膜水通量得到了提高, 同时脱盐率也有变化。最优实验条件下, 膜对Na₂SO₄、MgSO₄、MgCl₂和NaCl的截留率分别为99.4%、98.5%、85.4%和59.2%。试验结果表明, 加入PANI能够提高膜的水通量, 并提升了膜的脱盐性能。     

Novel polyethyleneimine/TMC-based nanofiltration membrane prepared on a polydopamine coated substrate

Most commercial NF membranes are negatively charged at the pH range of a typical feed solution. In order to enhance the removal of cations (such as Mg²⁺ or Ca²⁺), we utilized polyethyleneimine (PEI) and trimesoyl chloride (TMC) to perform interfacial polymerization reaction on a polydopamine coated hydrolyzed polyacrylonitrile substrate to obtain a positively charged nanofiltration membrane. Effects of polydopamine coating time, PEI concentration, TMC reaction time and concentration on the membrane physicochemical properties and separation performance were systematically investigated using scanning electron microscopy, streaming potential and water contact angle measurements. The optimal NF membrane showed high rejection for divalent ions (93.6±2.6% for MgSO₄, 92.4±1.3% for MgCl₂, and 90.4±2.1% for Na₂SO₄), accompanied with NaCl rejection of 27.8±2.5% with a permeation flux of 17.2±2.8 L·m⁻²·h⁻¹ at an applied pressure of 8 bar (salt concentrations were all 1000 mg·L⁻¹). The synthesized membranes showed promising potentials for the applications of water softening.     

Feasibility analysis of SO2 absorption using a hydrophilic ceramic membrane contactor

Hydrophilic ceramic membranes would be potential candidates for membrane gas absorption if they could be applied to appropriate separation processes. This study highlights a novel concept for the practical implementation of SO₂ absorption in hydrophilic ceramic membrane that exhibits outstanding thermal and mechanical stabilities. With this aim, we investigated experimentally the performance of SO₂ absorption into aqueous sodium hydroxide (NaOH) solution in a hydrophilic alumina (Al₂O₃) membrane contactor in terms of SO₂ removal efficiency and SO₂ mass transfer flux, and compared the performance with that in a hydrophobic one. A series of experiments were performed at various conditions over a NaOH concentration range of 0-1.0 mol·L^-1, a liquid flow rate range of 30-180 ml·min^-1, a gas flow rate range of 120-1000 ml·min^-1, an inlet SO₂ concentration range of 400-2000 μl·L^-1, and a temperature range of 10-35℃. It was found that the hydrophilic membrane was more competitive when using a NaOH concentration higher than 0.2 mol·L^-1. Furthermore, it can be inferred that the hydrophilic α-Al₂O₃ membrane exhibited exceptional long-term stability under 480 h continuous operation.