Produced water treatment by nanofiltration and reverse osmosis membranes

Produced water, water that is co-produced during oil and gas manufacturing, represents the largest source of oily wastewaters. Given high oil and gas prices, oil and gas production from non-conventional sources such as tar sands, oil shale and coal bed methane will continue to expand resulting in large quantities of impaired produced water. Treatment of this produced water could improve the economic viability of these oil and gas fields and lead to a new source of water for beneficial use.Two nanofiltration and one low-pressure reverse osmosis membrane have been tested using three produced waters from Colorado, USA. The membranes were analyzed before and after produced water filtration using field emission scanning electron microscopy (FESEM), attenuated total reflection Fourier transform infrared (ATR-FTIR) spectroscopy and X-ray photoelectron spectroscopy (XPS). In addition, membrane–water contact angles have been measured. XPS data indicate adsorption of organic and inorganic species during filtration. FESEM and ATR-FTIR data support theses findings. Water contact angles indicate the effect of membrane hydrophilicity on fouling. Our results highlight the value of using multiple surface characterization methods with different depths of penetration in order to determine membrane fouling. Depending on the quality of the produced water and the water quality requirements for the beneficial uses being considered, nanofiltration may be a viable process for produced water treatment.     

Influence of membrane fouling by (pretreated) surface water on rejection of pharmaceutically active compounds (PhACs) by nanofiltration membranes

The effects of surface water pretreatment on membrane fouling and the influence of these different fouling types on the rejection of 21 neutral, positively and negatively charged pharmaceuticals were investigated for two nanofiltration membranes. Untreated surface water was compared with surface water, pretreated with a fluidized anionic ion exchange and surface water, pretreated with ultrafiltration. Fouling the nanofiltration membranes with anionic ion exchange resin effluent, resulted in the deposition of a mainly colloidal fouling layer, with a rough morphology. Fouling the nanofiltration membranes with ultrafiltration permeate, resulted in the deposition of a smooth fouling layer, containing mainly natural organic matter. The fouling layer on the nanofiltration membranes, caused by the filtration of untreated surface water, was a combination of both colloids and natural organic matter.Rejection of pharmaceuticals varied the most for the membranes, fouled with the anionic ion exchange effluent, and variations in rejection were caused by a combination of cake-enhanced concentration polarisation and electrostatic (charge) effects. For the membranes, fouled with the other two water types, variations in rejection were smaller and were caused by a combination of steric and electrostatic effects.Changes in membrane surface hydrophobicity due to fouling, changed the extent of partitioning and thus the rejection of hydrophobic, as well as hydrophilic pharmaceuticals.     

Colloidal interactions and fouling of NF and RO membranes: a review

Colloids are fine particles whose characteristic size falls within the rough size range of 1-1000 nm. In pressure-driven membrane systems, these fine particles have a strong tendency to foul the membranes, causing a significant loss in water permeability and often a deteriorated product water quality. There have been a large number of systematic studies on colloidal fouling of reverse osmosis (RO) and nanofiltration (NF) membranes in the last three decades, and the understanding of colloidal fouling has been significantly advanced. The current paper reviews the mechanisms and factors controlling colloidal fouling of both RO and NF membranes. Major colloidal foulants (including both rigid inorganic colloids and organic macromolecules) and their properties are summarized. The deposition of such colloidal particles on an RO or NF membrane forms a cake layer, which can adversely affect the membrane flux due to 1) the cake layer hydraulic resistance and/or 2) the cake-enhanced osmotic pressure. The effects of feedwater compositions, membrane properties, and hydrodynamic conditions are discussed in detail for inorganic colloids, natural organic matter, polysaccharides, and proteins. In general, these effects can be readily explained by considering the mass transfer near the membrane surface and the colloid-membrane (or colloid-colloid) interaction. The critical flux and limiting flux concepts, originally developed for colloidal fouling of porous membranes, are also applicable to RO and NF membranes. For small colloids (diameter?100 nm), the limiting flux can result from two different mechanisms: 1) the diffusion-solubility (gel formation) controlled mechanism and 2) the surface interaction controlled mechanism. The former mechanism probably dominates for concentrated solutions, while the latter mechanism may be more important for dilute solutions. Future research needs on RO and NF colloidal fouling are also identified in the current paper.     

A critical flux to avoid biofouling of spiral wound nanofiltration and reverse osmosis membranes: Fact or fiction?

The relation between biofouling and membrane flux in spiral wound nanofiltration and reverse osmosis membranes in drinking water stations with extensive pretreatment such as ultrafiltration has been studied. The flux – water volume flowing through the membrane per unit area and time – is not influencing the development of membrane biofouling. Irrespective whether a flux was applied or not, the feed spacer channel pressure drop and biofilm concentration increased in reverse osmosis and nanofiltration membranes in a monitor, test rigs, a pilot scale and a full-scale installation. Identical behavior with respect to biofouling and feed channel pressure drop development was observed in membrane elements in the same position in a nanofiltration installation operated with and without flux. Calculation of the ratio of diffusive and convective flux showed that the diffusive flux is considerably larger than the convective flux, supporting the observations that the convective flux due to permeate production is playing an insignificant role in biofouling. Since fouling occurred irrespective of the actual flux, the critical flux concept stating that “below a critical flux no fouling occurs” is not a suitable approach to control biofouling of spiral wound reverse osmosis and nanofiltration membranes.     

Production of process water using integrated membrane processes

Application of ultrafiltration, nanofiltration, reverse osmosis, membrane distillation, and integrated membrane processes for the preparation of process water from natural water or industrial effluents was investigated. A two-stage reverse osmosis plant enabled almost complete removal of solutes from the feed water. High-purity water was prepared using the membrane distillation. However, during this process a rapid membrane fouling and permeate flux decline was observed when the tap water was used as a feed. The precipitation of deposit in the modules was limited by the separation of sparingly soluble salts from the feed water in the nanofiltration. The combined reverse osmosis—membrane distillation process prevented the formation of salt deposits on the membranes employed for the membrane distillation. Ultrafiltration was found to be very effective removing trace amounts of oil from the feed water. Then the ultrafiltration permeate was used for feeding of the remaining membrane modules resulting in the total removal of oil residue contamination. The ultrafiltration allowed producing process water directly from the industrial effluents containing petroleum derivatives. Presented at the 33rd International Conference of the Slovak Society of Chemical Engineering, Tatranské Matliare, 22–26 May 2006.     

Pore blocking mechanisms during early stages of membrane fouling by colloids

A method based on a simple linear regression fitting was proposed and used to determine the type, the chronological sequence, and the relative importance of individual fouling mechanisms in experiments on the dead-end filtration of colloidal suspensions with membranes ranging from loose ultrafiltration (UF) to nanofiltration (NF) to non-porous reverse osmosis (RO). For all membranes, flux decline was consistent with one or more pore blocking mechanisms during the earlier stages and with the cake filtration mechanism during the later stages of filtration. For ultrafiltration membranes, pore blocking was identified as the largest contributor to the observed flux decline. The chronological sequence of blocking mechanisms was interpreted to depend on the size distribution and surface density of membrane pores. For salt-rejecting membranes, the flux decline during the earlier stages of filtration was attributed to either intermediate blocking of relatively more permeable areas of the membrane skin, or to the cake filtration in its early transient stages, or a combination of these two mechanisms. The findings emphasize the practical importance of the clear identification of, and differentiation between mechanisms of pore blocking and cake formation as determining the potential for the irreversible fouling of membranes and the efficiency of membrane cleaning.     

The effect of pH on the separation of manure nutrients with reverse osmosis membranes

This paper reports on the effect of pH on the retention of dry matter (DM), total ammonia-nitrogen (TAN), potassium, phosphorus and volatile fatty acids (VFAs) during the filtration of pretreated swine manure by three highly selective reverse osmosis (RO) membranes. The manure was pretreated using various combinations of biological and physical technologies, namely anaerobic digestion (AD), vacuum filtration through diatomaceous earth (DE), nanofiltration (NF), and a first stage RO filtration. The objective was to establish the level of acidification required to optimize permeate quality while minimizing chemical addition.     

Separate and Concentrate Lactic Acid Using Combination of Nanofiltration and Reverse Osmosis Membranes

The processes of lactic acid production include two key stages, which are (a) fermentation and (b) product recovery. In this study, free cell of Bifidobacterium longum was used to produce lactic acid from cheese whey. The produced lactic acid was then separated and purified from the fermentation broth using combination of nanofiltration and reverse osmosis membranes. Nanofiltration membrane with a molecular weight cutoff of 100–400 Da was used to separate lactic acid from lactose and cells in the cheese whey fermentation broth in the first step. The obtained permeate from the above nanofiltration is mainly composed of lactic acid and water, which was then concentrated with a reverse osmosis membrane in the second step. Among the tested nanofiltration membranes, HL membrane from GE Osmonics has the highest lactose retention (97 ± 1%). In the reverse osmosis process, the ADF membrane could retain 100% of lactic acid to obtain permeate with water only. The effect of membrane and pressure on permeate flux and retention of lactose/lactic acid was also reported in this paper.     

Influence of membrane surface properties on initial rate of colloidal fouling of reverse osmosis and nanofiltration membranes

Recent studies have shown that membrane surface morphology and structure influence permeability, rejection, and colloidal fouling behavior of reverse osmosis (RO) and nanofiltration (NF) membranes. This investigation attempts to identify the most influential membrane properties governing colloidal fouling rate of RO/NF membranes. Four aromatic polyamide thin-film composite membranes were characterized for physical surface morphology, surface chemical properties, surface zeta potential, and specific surface chemical structure. Membrane fouling data obtained in a laboratory-scale crossflow filtration unit were correlated to the measured membrane surface properties. Results show that colloidal fouling of RO and NF membranes is nearly perfectly correlated with membrane surface roughness, regardless of physical and chemical operating conditions. It is further demonstrated that atomic force microscope (AFM) images of fouled membranes yield valuable insights into the mechanisms governing colloidal fouling. At the initial stages of fouling, AFM images clearly show that more particles are deposited on rough membranes than on smooth membranes. Particles preferentially accumulate in the “valleys” of rough membranes, resulting in “valley clogging” which causes more severe flux decline than in smooth membranes.     

Relation between membrane characteristics and performance in nanofiltration

The performance of commercial membranes during nanofiltration of aqueous solutions containing dissolved uncharged or charged organic components, was studied on the basis of membrane characteristics by means of multiple linear regression.

The membrane characteristics studied were surface hydrophobicity, surface roughness, surface charge, molecular weight cut-off (MWCO), permeability and porosity of the top layer (expressed as the volume fraction of small and large pores, determined by Positron Annihilation Lifetime Spectroscopy). Filtration and adsorption experiments were performed in the presence of various components, which differ in molecular mass, hydrophobicity and (in the case of charged organic components) in charge.

It was concluded that in order to minimize fouling, the membrane should have a low volume fraction of small pores in the top layer. When the organic components are charged, a membrane with a large surface charge and a high hydrophilicity is also favourable. Not only the membrane, but also the feed characteristics have an influence on fouling: the best results during nanofiltration of dissolved uncharged or charged components were obtained with hydrophilic or negatively charged components, respectively. Dissolved organic components were the best retained by membranes with a low MWCO. In addition, uncharged organic components should be hydrophilic and small to obtain a high retention and minimal flux decline, while the interplay between membrane and component charge is crucial during filtration of dissolved charged organic components.     

Fouling of reverse osmosis and nanofiltration membranes by humic acid—Effects of solution composition and hydrodynamic conditions

Fouling of reverse osmosis (RO) and nanofiltration (NF) membranes by humic acid, a recalcitrant natural organic matter (NOM), was systematically investigated. The membrane flux performance depended on both hydrodynamic conditions (flux and cross-flow velocity) and solution composition (humic acid concentration, pH, ionic strength, and calcium concentration), and was largely independent of virgin membrane properties. While increasing humic acid concentration and ionic strength, and lowering cross-flow velocity affected flux performance moderately, severe flux reduction occurred at high initial flux, low pH, and high calcium concentration. At a calcium concentration of 1 mM, all the membranes exhibited an identical stable flux, independent of their respective intrinsic membrane permeabilities. The effect of solution composition was more significant at higher fluxes. Improved salt rejection was observed as a result of humic acid fouling, which was likely due to Donnan exclusion by humic material close to membrane surfaces. Greater rejection improvement was observed for membranes with rougher surfaces.     

Forward Osmosis Membranes for Water Reclamation

This review addressed the fundamental principles, advantages and challenges of forward osmosis (FO) membrane processes. FO is receiving more and more research attractions because it can concurrently produce clean water with low energy input and generate hydraulic energy (pressure retarded osmosis). FO typically requires zero or low hydraulic driving pressure, therefore the fouling potential of the FO membranes is much lower than conventional pressure-driven membrane processes. However, concentration polarization (CP), especially the internal CP significantly reduces the effective osmotic pressure across the FO membrane, the major driving force for the filtration process. As a result, innovative FO membrane materials like electrospun nanofibers have been explored to make low tortuosity, high porosity, and thin FO membranes with a high rejection rate of solutes and low or zero diffusion of the draw solute. The orientation of the FO membrane with active layer-facing-feed solution has less fouling than active layer-facing-draw solution. In addition, to further decrease the fouling potential, a hydrophilic and more negatively charged membrane is preferred when filtration of natural organic matter (NOM) or alginate in the absence of multivalent cations.     

Impact of gel layer formation on colloid retention in membrane filtration processes

Colloidal particles in the feed streams of membrane filtration processes control membrane fouling rate in many instances. In this study, the non-gelling colloidal Na-alginate and the gelling colloidal Ca-alginate are employed to investigate the significance of gel layer formation in membrane filtration processes in terms of contribution to membrane fouling and supplementary impurity removal. The results show that contribution of colloidal particles to membrane fouling depends on the gelling propensity of the colloids and the operational mode (constant pressure or constant flux) implemented. A small dose of either Na-alginate or Ca-alginate was found to greatly increase membrane fouling rate during constant pressure filtration. Both the resistance to removal by application of shear and the lower susceptibility of the concentration polarization layer to shear resulted in more severe fouling during constant flux filtration in the presence of Ca-alginate assemblages than in the presence of Na-alginate. Apparent channel sizes of the Ca-alginate gel layer were calculated from the material properties of the fouling layer. Incomplete catalase retention highlighted the likely heterogeneity in size of liquid transport pathways. Adsorption also contributed to the trapping of colloidal particles according to the retention behaviour of BSA by the Ca-alginate gel layer. Gel layer formation propensity should be seriously considered for the operation of membrane filtration processes. Two simple methods based on (i) a permeability recovery experiment and (ii) comparison of dead-end filtration behaviour with and without shear application are proposed for evaluation of the gelling propensity of colloidal dispersions.     

苦咸水反渗透淡化中膜面结垢预测及防垢进展

苦咸水反渗透（BWRO）中的防垢过程,首先取决于给水水质,而根据水质条件和垢在膜面的形成机理采取相应的防垢措施是非常重要的。 显然,有效地管控膜面无机结垢及抑制膜面污染需要开展无机结垢趋势的预测、防垢措施和非破坏性无机垢监控等方面的技术研究。 一系列传统和新兴的分析技术,包括摩尔比率法、直接目测法和光谱法等已应用于BWRO过程中膜面防垢研究。 本文详细综述了该过程中无机结垢趋势的预测、防垢方法和非破坏性无机垢监控技术等方面的研究进展。 此外,针对目前的研究方向提出了建议。     

纳滤膜盐水溶液软化过程中膜面动态结垢机理研究进展

膜面结垢是纳滤(NF)膜盐水溶液软化过程中遇到的最主要问题之一。尽管已有大量的研究者对NF膜面结垢趋势预测和膜面污染物形貌的先进科学表征进行了深入广泛的研究,但对NF膜面动态结垢机制和过程还没有系统的报道。本文详细描述了包括膜阻力、浓差极化阻力、滤饼层阻力和膜孔堵塞阻力在内的NF膜结垢阻力理论模型;综述了包括膜面浓差极化、构晶离子成核和膜面结晶沉淀的NF膜面动态结垢过程的研究进展,重点阐述了表面结晶和主体结晶两种NF膜面结晶生长机制的研究概况,并展望了NF膜面结垢机理的研究前景。     

Biomimetic Approaches for Membrane Technologies

Membrane technology is the dominant process in water treatment. However, the operation cost of membranes cannot be decreased unless the amount of fouling, the “Achilles heel” of membranes, and energy consumed are cut. The high energy requirements in commercial nanofiltration, reverse osmosis and forward osmosis technologies lead researchers to develop new membrane designs having high flux values with high salt rejection values. The purpose of this review is to present the inadequacies of the membrane processes by considering studies related to fouling and energy minimization. In this respect, lipid bilayers, block copolymers, aquaporin Z proteins and aligned carbon nanotubes can be the base to build biomimetic membranes. Such studies are summarized due to their remarkable properties in fouling control. Furthermore, the review describes the membrane design strategies and points the limitations hindering commercialization. Additionally, it is hoped that this review will trigger further needed studies.     

Humic acid fouling during microfiltration

A major factor limiting the use of microfiltration for surface water treatment is membrane fouling by natural organic matter. The extent and mechanisms of humic acid fouling during microfiltration have been examined using stirred cell filtration experiments and scanning electron microscopy. The extent of fouling was strongly dependent on both the source and preparation of the humic acid solutions. The large flux decline observed during constant pressure microfiltration was caused by the formation of a humic acid deposit located on the upper surface of the membrane. Prefiltration of the humic acid solutions dramatically reduced the rate of fouling through the removal of large humic acid aggregates. The initial fouling in this system was determined almost entirely by the convective deposition of these large particles/aggregates on the membrane surface. This initial deposit accelerated the subsequent rate of humic acid fouling, possibly serving as a nucleation site for deposition of macromolecular humic acids.     

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。     

Reverse osmosis as a concentration technique for soluble organic phosphorus in fresh water

The chemical nature and availability of soluble organic phosphorus for algal growth is largely unknown. A commercially available reverse osmosis water purification system was adapted for concentrating the soluble organic phosphorus fraction form 100-l volumes of drainage water collected from tile drains underlying an intensively managed grassland area in the Lough Neagh catchment. After membrane filtration the drainage water was recirculated through the reverse osmosis module while the permeate was removed from the system. During a single passage across the reverse osmosis membrane, 20% of the sample was discarded as pure water while the remaining 80% of the sample was pumped back to the reverse osmosis cartridge. Recirculation was continued, with the addition of an intermediate sodium ion-exchange step to prevent the precipitation of insoluble (largely calcium and magnesium) salts, until the volume was reduced to 2.5 l. The recovery of soluble organic phosphorus based on the original sample concentration was almost 93%. A further tenfold increase in concentration was achieved without salt precipitation or loss of soluble organic phosphorus by vacuum-assisted rotary evaporation. The mild, efficient concentration process developed a soluble organic phosphorus concentrate suitable for chemical fractionation and algal availability studies.     

Periodic air/water cleaning for control of biofouling in spiral wound membrane elements

The main problem during the operation of nanofiltration or reverse osmosis membrane plants is fouling of feed spacers in membrane elements due to biofouling and particulate fouling. In order to control biofouling and particulate fouling in membrane elements, both daily air/water cleaning (AWC) and daily copper sulphate dosing (CSD) were investigated and compared to a reference without daily cleaning. A pilot study was carried out for 110 days with three parallel spiral wound membrane elements; AWC, CSD and the reference which were fed by tap water enriched with a biodegradable compound (100 μg acetate-C/L). The CSD element, which combined daily copper sulphate dosing and sporadically air/water cleaning, performed best with an increase in pressure drop of 18% and a biomass concentration of 8000 pg ATP/cm² within 110 days. This was followed by the AWC element with a pressure increase of 37% and biomass concentration of 20,000 pg ATP/cm² within 110 days. The reference element showed a pressure increase of 120% within 21 days. The presented approach is considered very successful in controlling particulate fouling and biofouling, especially when air/water cleaning is combined with copper sulphate dosing.