Membrane fouling is a process whereby a solution or a particle is deposited on a membrane surface or in membrane pores in a processes such as in a membrane bioreactor, [1] reverse osmosis, [2] forward osmosis, [3] membrane distillation, [4] ultrafiltration, microfiltration, or nanofiltration [5] so that the membrane's performance is degraded. It is a major obstacle to the widespread use of this technology. Membrane fouling can cause severe flux decline and affect the quality of the water produced. Severe fouling may require intense chemical cleaning or membrane replacement. This increases the operating costs of a treatment plant. There are various types of foulants: colloidal (clays, flocs), biological (bacteria, fungi), organic (oils, polyelectrolytes, humics) and scaling (mineral precipitates). [6]
Fouling can be divided into reversible and irreversible fouling based on the attachment strength of particles to the membrane surface. Reversible fouling can be removed by a strong shear force or backwashing. Formation of a strong matrix of fouling layer with the solute during a continuous filtration process will result in reversible fouling being transformed into an irreversible fouling layer. Irreversible fouling is the strong attachment of particles which cannot be removed by physical cleaning. [7]
Factors that affect membrane fouling:
Recent fundamental studies indicate that membrane fouling is influenced by numerous factors such as system hydrodynamics, operating conditions, [8] membrane properties, and material properties (solute). At low pressure, low feed concentration, and high feed velocity, concentration polarisation effects are minimal and flux is almost proportional to trans-membrane pressure difference. However, in the high pressure range, flux becomes almost independent of applied pressure. [9] Deviation from linear flux-pressure relation is due to concentration polarization. At low feed flow rate or with high feed concentration, the limiting flux situation is observed even at relatively low pressures.
Flux, [3] transmembrane pressure (TMP), Permeability, and Resistance are the best indicators of membrane fouling. Under constant flux operation, TMP increases to compensate for the fouling. On the other hand, under constant pressure operation, flux declines due to membrane fouling. In some technologies such as membrane distillation, fouling reduces membrane rejection, and thus permeate quality (e.g. as measured by electrical conductivity) is a primary measurement for fouling. [8]
Even though membrane fouling is an inevitable phenomenon during membrane filtration, it can be minimised by strategies such as cleaning, appropriate membrane selection and choice of operating conditions.
Membranes can be cleaned physically, biologically or chemically. Physical cleaning includes gas scour, sponges, water jets or backflushing using permeate [10] or pressurized air. [11] Biological cleaning uses biocides to remove all viable microorganisms, whereas chemical cleaning involves the use of acids and bases to remove foulants and impurities.
Additionally, researchers have investigated the impact different coatings have on resistance to wear. A 2018 study from the Global Aqua Innovation Center in Japan reported improved surface roughness properties of PA membranes by coating them with multi-walled carbon nanotubes. [12]
Another strategy to minimise membrane fouling is the use of the appropriate membrane for a specific operation. The nature of the feed water must first be known; then a membrane that is less prone to fouling with that solution is chosen. For aqueous filtration, a hydrophilic membrane is preferred. [13] For membrane distillation, a hydrophobic membrane is preferred. [14]
Operating conditions during membrane filtration are also vital, as they may affect fouling conditions during filtration. For instance, crossflow filtration is often preferred to dead end filtration, because turbulence generated during the filtration entails a thinner deposit layer and therefore minimises fouling (e.g. tubular pinch effect). In some applications such as in many MBR applications, air scour is used to promote turbulence at the membrane surface.
Membrane performance can suffer from fouling-induced mechanical degradation. This may result in unwanted pressure and flux gradients, both of the solute and the solvent. The mechanism of membrane failure may be the direct consequence of fouling by means of physical alterations to the membrane, or by indirect means, in which the foulant removal processes yield membrane damage.
It is important to note that the majority of membranes used commercially are polymers such as polyvinylidene fluoride (PVDF), polyacrylonitrile (PAN), polyethersulfone (PES) and polyamide (PA), which are materials which offer desirable properties (elasticity and strength) to withstand constant osmotic pressures. [15] The accumulation of foulants, however, degrades these properties through physical alterations to the membrane structure.
The accumulation of foulants can lead to the formation of cracks, surface roughening, and changes in pore size distribution. [15] These physical changes are the result of impacts of hard material with a soft polymer membrane, weakening its structural integrity. Degradation of the mechanical structure makes the membranes more susceptible to mechanical damage, potentially reducing its overall lifespan. A 2006 study observed this degradation by uniaxially straining hollow fibers that were both clean and fouled. The researchers reported the relative embrittlement of the fouled fibers. [16]
Beyond direct physical damage, fouling can also induce indirect effects on membrane mechanical properties due to the strategies used to combat it. Backwashing subjects not only the particulates, but the membrane to strong shear forces. Greater fouling frequency therefore exposes the membrane to cyclic loading which can lead to fatigue failure. This is a process whereby existing imperfections in the membrane (such as microcracks) can grow and propagate due to the complex stress state dynamics. These impacts are not unknown; A 2007 study simulated aging via cyclic backwash pulses, and reported similar embrittlement due to the effects. [17]
Additionally, repeated chemical treatment of fouling subjects membranes to excessive amounts of chlorine or other treatment chemicals which can cause degradation. [18] This chemical degradation can lead to delamination of the membrane components, ultimately leading to failure.
Desalination is a process that takes away mineral components from saline water. More generally, desalination is the removal of salts and minerals from a target substance, as in soil desalination, which is an issue for agriculture. Saltwater is desalinated to produce water suitable for human consumption or irrigation. The by-product of the desalination process is brine. Desalination is used on many seagoing ships and submarines. Most of the modern interest in desalination is focused on cost-effective provision of fresh water for human use. Along with recycled wastewater, it is one of the few rainfall-independent water resources.
Semipermeable membrane is a type of biological or synthetic, polymeric membrane that allows certain molecules or ions to pass through it by osmosis. The rate of passage depends on the pressure, concentration, and temperature of the molecules or solutes on either side, as well as the permeability of the membrane to each solute. Depending on the membrane and the solute, permeability may depend on solute size, solubility, properties, or chemistry. How the membrane is constructed to be selective in its permeability will determine the rate and the permeability. Many natural and synthetic materials which are rather thick are also semipermeable. One example of this is the thin film on the inside of an egg.
Ultrafiltration (UF) is a variety of membrane filtration in which forces such as pressure or concentration gradients lead to a separation through a semipermeable membrane. Suspended solids and solutes of high molecular weight are retained in the so-called retentate, while water and low molecular weight solutes pass through the membrane in the permeate (filtrate). This separation process is used in industry and research for purifying and concentrating macromolecular (103–106 Da) solutions, especially protein solutions.
Forward osmosis (FO) is an osmotic process that, like reverse osmosis (RO), uses a semi-permeable membrane to effect separation of water from dissolved solutes. The driving force for this separation is an osmotic pressure gradient, such that a "draw" solution of high concentration, is used to induce a net flow of water through the membrane into the draw solution, thus effectively separating the feed water from its solutes. In contrast, the reverse osmosis process uses hydraulic pressure as the driving force for separation, which serves to counteract the osmotic pressure gradient that would otherwise favor water flux from the permeate to the feed. Hence significantly more energy is required for reverse osmosis compared to forward osmosis.
Solar desalination is a desalination technique powered by solar energy. The two common methods are direct (thermal) and indirect (photovoltaic).
Osmotic power, salinity gradient power or blue energy is the energy available from the difference in the salt concentration between seawater and river water. Two practical methods for this are reverse electrodialysis (RED) and pressure retarded osmosis (PRO). Both processes rely on osmosis with membranes. The key waste product is brackish water. This byproduct is the result of natural forces that are being harnessed: the flow of fresh water into seas that are made up of salt water.
Thin-film composite membranes are semipermeable membranes manufactured to provide selectivity with high permeability. Most TFC's are used in water purification or water desalination systems. They also have use in chemical applications such as gas separations, dehumidification, batteries and fuel cells. A TFC membrane can be considered a molecular sieve constructed in the form of a film from two or more layered materials. The additional layers provide structural strength and a low-defect surface to support a selective layer that is thin enough to be selective but not so thick that it causes low permeability.
In chemical engineering, biochemical engineering and protein purification, crossflow filtration is a type of filtration. Crossflow filtration is different from dead-end filtration in which the feed is passed through a membrane or bed, the solids being trapped in the filter and the filtrate being released at the other end. Cross-flow filtration gets its name because the majority of the feed flow travels tangentially across the surface of the filter, rather than into the filter. The principal advantage of this is that the filter cake is substantially washed away during the filtration process, increasing the length of time that a filter unit can be operational. It can be a continuous process, unlike batch-wise dead-end filtration.
Menachem Elimelech is the Sterling Professor of Chemical and Environmental Engineering at Yale University. Elimelech is the only professor from an engineering department at Yale to be awarded the Sterling professorship since its establishment in 1920. Elimelech moved from the University of California, Los Angeles (UCLA) to Yale University in 1998 and founded Yale's Environmental Engineering program.
Nanofiltration is a membrane filtration process that uses nanometer sized pores through which particles smaller than about 1–10 nanometers pass through the membrane. Nanofiltration membranes have pore sizes of about 1–10 nanometers, smaller than those used in microfiltration and ultrafiltration, but a slightly bigger than those in reverse osmosis. Membranes used are predominantly polymer thin films. It is used to soften, disinfect, and remove impurities from water, and to purify or separate chemicals such as pharmaceuticals.
Membrane bioreactors are combinations of membrane processes like microfiltration or ultrafiltration with a biological wastewater treatment process, the activated sludge process. These technologies are now widely used for municipal and industrial wastewater treatment. The two basic membrane bioreactor configurations are the submerged membrane bioreactor and the side stream membrane bioreactor. In the submerged configuration, the membrane is located inside the biological reactor and submerged in the wastewater, while in a side stream membrane bioreactor, the membrane is located outside the reactor as an additional step after biological treatment.
Reverse osmosis (RO) is a water purification process that uses a semi-permeable membrane to separate water molecules from other substances. RO applies pressure to overcome osmotic pressure that favors even distributions. RO can remove dissolved or suspended chemical species as well as biological substances, and is used in industrial processes and the production of potable water. RO retains the solute on the pressurized side of the membrane and the purified solvent passes to the other side. It relies on the relative sizes of the various molecules to decide what passes through. "Selective" membranes reject large molecules, while accepting smaller molecules.
Pressure retarded osmosis (PRO) is a technique to separate a solvent from a solution that is more concentrated and also pressurized. A semipermeable membrane allows the solvent to pass to the concentrated solution side by osmosis. The technique can be used to generate power from the salinity gradient energy resulting from the difference in the salt concentration between sea and river water.
A membrane is a selective barrier; it allows some things to pass through but stops others. Such things may be molecules, ions, or other small particles. Membranes can be generally classified into synthetic membranes and biological membranes. Biological membranes include cell membranes ; nuclear membranes, which cover a cell nucleus; and tissue membranes, such as mucosae and serosae. Synthetic membranes are made by humans for use in laboratories and industry.
Membrane distillation (MD) is a thermally driven separation process in which separation is driven by phase change. A hydrophobic membrane presents a barrier for the liquid phase, allowing the vapour phase to pass through the membrane's pores. The driving force of the process is a partial vapour pressure difference commonly triggered by a temperature difference.
Water shortages have become an increasingly pressing concern recently and with recent predictions of a high probability of the current drought turning into a megadrought occurring in the western United States, technologies involving water treatment and processing need to improve. Carbon nanotubes (CNT) have been the subject of extensive studies because they demonstrate a range of unique properties that existing technologies lack. For example, carbon nanotube membranes can demonstrate higher water flux with lower energy than current membranes. These membranes can also filter out particles that are too small for conventional systems which can lead to better water purification techniques and less waste. The largest obstacle facing CNT is processing as it is difficult to produce them in the large quantities that most of these technologies will require.
Phase inversion or phase separation is a chemical phenomenon exploited in the fabrication of artificial membranes. It is performed by removing the solvent from a liquid-polymer solution, leaving a porous, solid membrane.
The liquid entry pressure (LEP) of a hydrophobic membrane is the pressure that must be applied to a dry membrane so that the liquid penetrates inside the membrane. LEP with the application in membrane distillation or pervaporation can be calculated as a first parameter to indicate how wettable a membrane is toward different liquid solutions.
John Henry Lienhard V is the Abdul Latif Jameel Professor of Water and Mechanical Engineering at the Massachusetts Institute of Technology. His research focuses on desalination, heat transfer, and thermodynamics. He has also written several engineering textbooks.
Membrane scaling is when one or more sparingly soluble salts precipitate and form a dense layer on the membrane surface in reverse osmosis (RO) applications. Figures 1 and 2 show scanning electron microscopy (SEM) images of the RO membrane surface without and with scaling, respectively. Membrane scaling, like other types of membrane fouling, increases energy costs due to higher operating pressure, and reduces permeate water production. Furthermore, scaling may damage and shorten the lifetime of membranes due to frequent membrane cleanings and therefore it is a major operational challenge in RO applications.