胶州湾海水纳滤软化的研究

采用超滤-纳滤膜集成膜技术,进行了胶州湾海水纳滤软化现场试验,筛选了纳滤膜,考察了料液流量、操作压力对纳滤膜元件运行效果的影响,评价了纳滤作为海水淡化预处理对海水中主要离子的截留效果,并进行了短期试验。结果表明超滤-纳滤膜集成技术可为淡化系统提供优质的软化水,为胶州湾地区膜法海水淡化奠定了基础。     

Boron in seawater and methods for its separation — A review

The seawater reverse osmosis (SWRO) membrane desalination process is a relevant and reliable technology for desalination of seawater. However, some serious limitations had recently been discovered during field practice, among them the boron problem seems to have a critical meaning. According to the WHO regulations, the boron concentration should be reduced to less than 0.5 mg/L for drinking water. It was also reported that, this limit is rarely reached for conventional reverse osmosis desalination plants equipped with commercially available membranes. This paper reviews the extensive published literature on separation methods of boron removal from seawater.     

Novel chitosan-piperazine composite nanofiltration membranes for the desalination of brackish water and seawater

A novel chitosan (CS)-piperazine (PIP) composite nanofiltration (NF) membrane with satisfied characteristics for brackish water and seawater desalination was successfully developed. PIP was mixed with CS during the interfacial polymerization (IP) process to enhance the NF membrane permeate flux. The resultant NF membranes were characterized by X-ray photoelectron spectroscopy (XPS), scanning electron microscope (SEM), atomic force microscope (AFM), contact angle. Effects of CS concentration, trimesoyl chloride (TMC) concentration, reaction time and the mixing ratio of CS/PIP on NF membrane performance were investigated thoroughly. When PIP in the aqueous phase monomers reached to 25% (w/w), the PWF (60.6 L·m^?2·h^?1) was synergistically improved by nearly 2 times without a significant reduction of Na₂SO₄ rejection (89.1%). Moreover, the NF membranes possessed excellent performance for the desalination of brackish water and seawater, which showed high potential to be applied in the desalination process for water treatment.     

Removal of boron from seawater by selective ion exchange resins

Reverse osmosis (RO) desalination process is an efficient and reliable membrane technology for the production of drinking water from seawater. However, some serious limitations had recently been discovered during the field practice. Boron problem is one of them. According to the WHO regulations, the boron concentration should be lower than 0.5 mg/L in drinking water. It is still difficult to reduce boron level to 0.5 mg/L or lower with the conventional reverse osmosis desalination plants equipped with commercially available RO membranes. Therefore, more efficient separation technologies are needed for boron removal.In this study, the performance of the boron-selective ion exchange resins containing N-methyl glucamine groups, as Diaion CRB 02 and Dowex XUS 43594.00, have been tested for boron removal from model seawater. The kinetic performances of these resins were compared. The kinetic data obtained were evaluated using Lagergren pseudo-first-order and second-order models. Also, the process kinetics were predicted by using diffusion models. In addition, column-mode tests have been carried out for boron removal from model seawater.     

高回收率反渗透海水淡化工艺

目前反渗透海水淡化的回收率小于40％。本文研究开发死端超滤预处理技术和反渗透一纳滤联合脱盐相结合的膜集成海水淡化新工艺,与传统工艺比较,具有装置体积小,产水回收率高等优点。文章介绍了采用新工艺的海水淡化装置样机的试制情况及现场运行结果。沿岸海水为料液,操作压力1为5．1MPa条件下,操作压力2为2.0MPa条件下,装置脱盐率99．21％,产水量3971.3L/h,产水回收率55％。海水淡化装置对海水中Ca^2 、Mg^2 、Na^ 、HCO3^-、Cl^-、SO4^2-、TDS,总碱度,总硬度的脱除率分别为99％,99．6％,99．21％,95％,99．35％,98．48％,99.21％,95％,99．42％。     

芬顿-絮凝联合处理高浓度有机物海水的试验研究

为了使盐场晒盐池海水能用于海水淡化,针对有机物浓度较高的盐池海水进行了芬顿-絮凝联合预处理试验。选取聚丙烯酰胺(PAM)作为絮凝剂,考察Fe SO4·7H2O和H2O2用量、芬顿反应条件和絮凝剂用量等参数对CODMn和浊度去除效果的影响。结果表明,在氧化阶段p H值为4,Fe SO4·7H2O投加量为125 mg/L,H2O2投加量为50 mg/L,反应时间为60 min,PAM投加量为1 mg/L,海水CODMn和浊度去除率分别为59.6%和96.2%,均较单独采用传统絮凝技术有较大提高。     

A new methodology for removal of boron from water by coal and fly ash

High levels of boron concentrations in water present a serious problem for domestic and agriculture utilizations.The recent EU drinking water directive defines an upper limit of 1 mgB/l. In addition, most crops are sensitive to boron levels >0.75 mg/1 in irrigation water. The boron problem is magnified by the partial (∼60%) removal of boron in reverse osmosis (RO) desalination due to the poor ionization of boric acid and the accumulation of boron in domestic sewage effluents. Moreover, high levels of boron are found in regional groundwater in some Mediterranean countries, which requires special treatment in order to meet the EU drinking water regulations. Previous attempts to remove boron employed boron-specific ion-exchange resin and several cycles of RO desalination under high pH conditions. Here, we present an alternative methodology for boron removal by using coal and fly ash as adsorbents. We conducted various column and batch experiments that explored the efficiency of boron removal from seawater and desalinated seawater using several types of coal and fly ash materials under controlled conditions (pH, liquid/solid ratio, time of reaction, pre-treatment, regeneration). We examined the effect of these factors on the boron removal capacity and the overall chemical composition of the residual seawater. The results show that the selected coal and fly ash materials are very effective in removing boron such that the rejection ratio of boron can reach 95% of the initial boron content under certain optimal conditions (e.g., pH = 9, L/S = , reaction time > 6 h). Our experiments demonstrated that use of glycerin enables regeneration of boron uptake into coal, but the boron uptake capacity of fly ash reduces after several cycles of treatment-reaction. The boron removal is associated with Mg depletion and Ca enrichment in the residual seawater and conversely with relative Mg enrichment and Ca depletion in the residual fly ash We propose that the reaction of Ca-rich fly ash with Mg-rich seawater causes co-precipitation of magnesium hydroxide in which boron is co-precipitated. The new methodology might provide an alternative technique for boron removal in areas where coal and fly ash are abundant.     

Boron removal from saline water: A comprehensive review

Boron is an essential micronutrient for plants and animals as well as a useful component for numerous industries. It is necessary to produce low boron containing water from RO desalination plants for both human consumption and for agriculture. For plants, a small amount of boron is necessary for their growth and development, but boron becomes toxic if the amount is slightly greater than required. Desalinated seawater from RO plants often contains high boron content and, when used for irrigation, has been proven to be damaging to crops including blackberry, lemon, and grapefruit. Apart from the toxic effects of boron on plants, boron should be removed from RO desalination plants to comply with the current guideline value, 0.5 mg/L, for potable water issued by the World Health Organisation (WHO). Currently there is no simple method to remove boron from saline water. The use of multi-pass reverse osmosis membrane (RO) with pH modification and the use of ion exchange using boron selective resins (BSRs) have both been considered as effective methods for the removal of boron. A hybrid process, Adsorption Membrane Filtration (AMF), has received attention as an emerging technology for boron removal with a high efficiency and low operating costs. The purpose of this review is to give an overview on boron in general and to discuss its toxicity. The problems of boron in the MENA (Middle East and North Africa) region are discussed as well as technologies, current and future, for the removal of boron from seawater. The focus is placed on current RO and ion exchange methodologies using BSRs as well as the future for the AMF method. The fundamentals of each process, the effects of experimental parameters, and findings are discussed.     

风电-海水淡化联合系统中脱硼技术方案选择

该文针对风电海水淡化联合系统的主要特点及特殊要求,通过对国内外海水脱硼技术的研究分析,结合实际工程经验,提出了适合该系统不同制水规模的脱硼方案,为风电-海水淡化联合系统的推广应用提供有益参考。     

Performance of Nanofiltration Membranes in the Treatment of Synthetic and Real Seawater

Abstract

Nanofiltration membranes (NF) are being employed in pretreatment unit operations in both thermal and membrane seawater desalination processes and as partial demineralization to seawater. In order to predict NF membrane performance, a systematic study on the filtration performance of selected commercial NF membranes against seawater is presented in this paper. Two commercial nanofiltration membranes (NF90 and NF270) have been investigated in details to study their performance in filtering the salt mixture, synthetic and real seawater in a cross‐flow NF membrane process at a pressure range from 4 to 9 bars. The Spiegler‐Kedem model was used to fit the experimental data of rejection with the permeate flux in order to determine the fitting parameters of the reflection coefficient (σ) and the solute permeability (P_s). The results showed that the rejection increases with pressure for NF90 and slightly increases with pressure for NF270. Also, the NF90 membrane has shown to be able to reject both monovalent and divalent of all investigated mixtures and seawater with very reasonable values but at a relatively low flux. Moreover, it reduced the salinity of investigated seawater from 38 to 25.5 g/L using one stage of the NF membrane at 9 bars. This makes NF90 more suitable for the application in the pretreatment of desalination processes. On the other hand, NF270 can reject monovalent ions at relatively low values and divalent ions at reasonable values. It has also reduced the seawater salinity to 33.6 g/L, but at a very high permeate flux. The SKM model fitted the experimental data of divalent ions in salt mixture and seawater.     

Rejection of salt mixtures from high saline by nanofiltration membranes

Nanofiltration (NF) membranes have recently been employed as pretreatment unit operations in seawater desalination processes and as partial demineralization to seawater. The present paper investigates the performance of selected commercial NF membranes to reject salts of high concentrations at salinity levels representative of brackish and sea water. Two commercial nanofiltration membranes (NF90 and NF270) have been investigated in detail to study their performance in filtering aqueous solutions containing different salt mixtures in a cross-flow NF membrane process within the pressure range from 4 to 9 bar. Spiegler-Kedem model (SKM) was used to fit the experimental data of rejection with the permeate flux. The results showed that NF90 membrane was shown to have a distinct ability to reject both monovalent and divalent ions of all investigated mixtures with very reasonable values but with relatively low flux. This will make NF90 more suitable for the application in the pretreatment of desalination processes. On the other hand, NF270 can reject monovalent ions at relatively low values and divalent ions at reasonable values, but at very high permeate flux. The SKM model only fitted well the experimental data of divalent ions in salt mixture. Based on the evaluation of the overall performance of NF90 and NF270 membranes, their distinct ability to reject salts at high salinity from seawater is considered an advantage in the field of pretreatment of seawater feed to desalination units.     

阻垢剂对海水淡化膜蒸馏试验的影响

采用直接接触式膜蒸馏技术进行海水淡化试验研究。在海水温度为55℃,循环水温度为20℃的条件下,考察了不同阻垢剂用量对膜蒸馏海水淡化的影响、工艺连续运行过程中膜通量和产水电导率随时间的变化情况,确定了膜蒸馏过程稳定运行的最优浓缩倍率。结果表明,阻垢剂的加入可明显提高淡水的产水率,产水率可达到85%以上,减少了高盐度海水浓缩液的排放,膜通量稳定,产水水质好,其电导率不超过10μS/cm,膜蒸馏海水淡化具有一定的技术可行性和可操作性。     

海水淡化过程优化设计的研究进展

海水淡化是能源密集型工业,对淡化工艺、操作参数及设备结构等进行优化设计是降低淡化过程能耗的有效途径。本文分析了不同海水淡化方法的技术特点,详细介绍了海水淡化过程的优化设计方法及海水淡化技术集成的研究进展。     

固体颗粒对流化床多相蒸发海水淡化操作浓缩比及膜传热系数的影响

提高海水淡化操作浓缩比,不仅可以提高造水比,还可以有效降低淡化后浓海水再利用的后处理成本,故其是实现低成本零排放的关键之一。在一套循环流化床多相蒸发海水淡化实验装置上,分别采用汽-液两相及汽-液-固三相操作,考察固体颗粒对海水淡化操作浓缩比及膜传热系数的影响,并分析垢层的主要成分。实验表明：高温下CaSO4首先析出,是形成垢层的主要成分;采取汽-液两相操作,膜传热系数保持在1.75 kW·m-2·K-1左右,操作浓缩比可达到3.8左右;采取汽-液-固三相操作,固体颗粒强化传热和防除垢的作用显著,加入颗粒体积分数为4%时,在膜传热系数保持在2.3 kW·m-2·K-1左右不降低的情况下,海水淡化操作浓缩比达到5.8以上。     

硼酸、硼酸盐及其络合物在反渗透膜内扩散过程的分子模拟

利用分子模拟的方法建立了交联的反渗透膜模型,采用分子动力学模拟方法研究了水、氯化钠、硼酸、硼酸盐、山梨醇-硼酸盐络合物在反渗透膜和溶液中的扩散过程,以及其他几种硼酸盐与多羟基化合物（D-甘露醇、N-甲基D-葡糖胺和D-葡萄糖酸钠）的络合物在4种反渗透膜中的扩散过程。分析各粒子的均方位移曲线可得,各粒子在溶液中的扩散系数均大于在膜体系的扩散系数,水分子的扩散系数远大于各溶质分子和离子。与硼酸分子相比,硼酸盐离子与其体积相差不大,但受电荷效应的影响,其扩散系数小于硼酸分子一个数量级。与单络合物相比,双络合物由于分子体积增大,扩散系数更小。因此在反渗透络合强化脱硼过程中应保持过量的山梨醇添加量,以提高其双络合物浓度。在1,3,5-环己烷三甲酰氯/4-甲基间苯二胺（HT/MMPD）反渗透膜中,N-甲基D-葡糖胺-硼酸盐络合物的扩散系数是5种络合物中最低的,D-葡萄糖酸钠-硼酸盐络合物在含有间苯二胺（MPD）单体的膜类型中扩散系数较低,而D-甘露醇-硼酸盐络合物在含有MMPD单体的膜类型中扩散系数较低。由各粒子的轨迹图可知,各粒子在溶液中做较稀疏的无规则扩散运动,在膜内粒子由于受到聚酰胺膜结构的限制做较密集的扩散运动。     

高通量聚醚砜纳滤膜的制备及对染料浓缩脱盐

以聚醚砜（PES）为膜材料,以嵌段式聚醚 Pluronic F127为添加剂,利用特制刮膜设备通过相转化法制备出高通量PES/Pluronic F127复合纳滤膜,并将其用于染料的浓缩脱盐。研究了添加剂含量、溶剂蒸发温度和蒸发时间对膜结构和膜性能的影响,考察了不同操作压力和操作温度下膜对染料的分离性能。扫描电镜 （SEM）、接触角、孔隙率数据和蛋白吸附测试结果表明,Pluronic F127改善了膜孔结构,提高了孔隙率,并且显著提高了膜的抗污染性能。纯水通量、截留率以及膜表面孔径表征结果表明,当Pluronic F127含量为3%、溶剂蒸发温度为90℃、 蒸发时间为18 s时,膜的分离性能最佳。在0.6 MPa下该膜对低分子量染料的截留率可达99.9%,且通量达到110.2 L·m^-2·h^-1,对NaCl的截留率仅为5.5%。在12 h的染料浓缩脱盐中,膜对染料的通量维持在较高水平且截留率始终保持在99%左右,具有良好的稳定性和抗污染性。     

Treatment of a textile effluent: application of a combination method involving adsorption and nanofiltration

A combination of adsorption and nanofiltration (NF) was adopted for the treatment of a textile dyehouse effluent containing a mixture of two reactive dyes. The effluent stream was first treated in a batch adsorption process with sawdust as an adsorbent to reduce the dye concentration of the effluent by about 83% for Dye 1 and 93% for Dye 2. The effluent from the adsorption unit was passed through an NF unit for the removal of the remaining small amount of dyes and to recover the associated chemicals (mainly salt) in the effluent stream. The dyes remaining after this step were less than 1 ppm. The percentage removal of COD was greater than 99%, and the salt recovery was on the order of 90%. Equilibrium studies were carried out with synthetic solutions of the dyes (both single component as well as two-component systems) at room temperature. The adsorption rates were studied in detail using varying amounts of the adsorbent. NF of the effluent was performed in a cross-flow system using a 400 molecular weight cut-off membrane. A detailed study was carried out to observe the effect of the process parameters, namely applied pressure and bulk velocity on the process outputs such as dye rejection, COD removal, permeate flux and salt recovery. Finally, direct NF of the effluent (with the original high concentration) was undertaken, and the performance of the process was compared with the combination method. The permeate flux for the proposed combined method was found to be about twice that for the direct NF method. The dye rejection improved significantly compared to adsorption.     

氧化还原脱除海水中的Cu2+离子

阐述了去除海水中的重金属离子对提高海水淡化装置中铝合金材料耐腐蚀性能的作用。采用填充在离子交换塔中的5052铝合金环作为还原剂,研究了海水流速、海水温度以及海水中铜离子的初始浓度对脱除海水中Cu2+效果的影响,并对试验前后的铝合金还原剂的表面进行了表征。结果表明,铜离子的脱除率可达88%。流速的降低与温度的上升,使铜离子的脱除率升高;铜离子浓度增大,铜离子的脱除率降低。     

投加粉末活性炭对超滤膜去除海水中有机物的影响

超滤膜的有机污染问题是膜法海水预处理技术在海水淡化工程应用面临的重要挑战,粉末活性炭吸附是目前常用的膜前预处理手段之一。本文对比分析了直接超滤和投加粉末活性炭后对海水中有机物的截留能力,利用三维荧光光谱分析了投加粉末活性炭对超滤膜截留有机物的影响机制,并考察了海水超滤过程中通量变化及膜污染情况。研究结果表明,投加粉末活性炭能够强化超滤膜对海水浊度和有机物的去除,当粉末活性炭投量为200mg/L时,整个系统对海水中DOC去除率从直接超滤时的55.1%提高到77.6%。利用粉末活性炭的吸附作用及其在超滤膜表面形成的疏松滤饼层能够显著提高超滤系统对海水中腐植酸类有机物的去除能力。与直接超滤相比,粉末活性炭-超滤系统对改善膜通量的作用有限,但粉末活性炭形成的滤饼层能够避免超滤膜与有机物直接接触,可显著减缓超滤膜的不可逆污染。     

Span 60合成工艺改进与应用

加入醚化催化剂A,采用先醚化后酯化的工艺,合成结构合理、性能优良的Span60。讨论原料质量、原料配比、催化剂浓度、反应温度、反应时间等因素对合成反应的影响,并确定了最佳反应条件。较为理想的醇酸比为1︰1.45;催化剂浓度为0.6%;醚化温度为150℃;反应温度为200℃;反应时间3h。