Classifications

• • B—PERFORMING OPERATIONS; TRANSPORTING
  • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
  • B01D—SEPARATION
  • B01D65/00—Accessories or auxiliary operations, in general, for separation processes or apparatus using semi-permeable membranes
  • B01D65/02—Membrane cleaning or sterilisation ; Membrane regeneration
• • B—PERFORMING OPERATIONS; TRANSPORTING
  • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
  • B01D—SEPARATION
  • B01D2321/00—Details relating to membrane cleaning, regeneration, sterilization or to the prevention of fouling
  • B01D2321/16—Use of chemical agents
  • B01D2321/168—Use of other chemical agents

Definitions

• This invention relates to a cleaning system for substantially restoring transmembrane flux (hereafter "flux” for brevity), measured as liters of permeate per square meter of membrane surface per hour (L/m .hr or “LMH”), in fouled, porous/semipermeable microfiltration (MF) or ultrafiltration (UF) membranes in a membrane device (module) used to recover purified water from contamin ⁇ ated or "dirty" water in feedstream, without draining the feed (substrate), hence referred to as an "in situ cleaning” method.
• a MF or UF membrane is generally used to separate one liquid, usually water, from water containing various forms of undesirable matter, some in solution and some not.
• Such a membrane device which is to be periodically cleaned usually operates in "inside-out flow” in which the inner surfaces of the membranes are exposed to the feedstream of "dirty” water from which purified water is to be separated.
• this invention relates to hollow fiber membranes ("fibers” for brevity) which typically operate in “outside-in” flow.
• hollow fiber membranes we refer to membranes having an inside diameter (i.d) in the range from about 0.2 mm to 4.0 mm, with a wall thickness which corresponds to a particular diameter, the outside diameter (o.d.) usually being in the range from about 0.3 mm for the smallest fibers to about 6 mm for the largest.
• dirty water is used herein, in a generic sense to refer to any poor quality aqueous, or predominantly aqueous solution, suspension, dispersion or emulsion.
• Purified water is extracted from the dirty water with a desirably high flux despite the membrane being covered, in about 8 hr or less, with a "fouling film” deposited by "foulant(s)” in the substrate. This formation of the film is also referred to as concentration polarization which is unavoidable in practice.
• a foulant film formed in an aqueous medium rich in microorganisms (“biomass”) is termed a "biofilm", and the fouling phenomenon is referred to as "biofouling”.
• the cleaning method of this invention is particularly directed to cleaning fibers, rather than tubular membranes or spiral wound membranes. Fibers are used in a module, either in an array or in a bundle, deployed directly in a substrate without being enclosed; or, the array may be appropriately held within a shell.
• retentate liquid which is separated by, and flows through the microporous membrane into the lumens of the fibers
• permeate liquid which is separated by, and flows through the microporous membrane into the lumens of the fibers.
• Restoration of the flux is effected on the permeate side of the memb- rane, with a cleaning fluid, most preferably an aqueous cleaning fluid, under only enough pressure, below the bubblepoint of the fiber, which for reasons given below, is believed to provide diffusion-controlled permeation.
• a cleaning fluid most preferably an aqueous cleaning fluid, under only enough pressure, below the bubblepoint of the fiber, which for reasons given below, is believed to provide diffusion-controlled permeation.
• Other mechanisms may also play a part in cleaning.
• the membranes used herein are of a synthetic resinous material, rather than being ceramic, they are susceptible to swelling caused by interaction with the cleaning fluid.
• Diffusion-controlled flow occurs at low pressure through the walls of the membranes and out into the feed (hence referred to as "inside-out flow” of a “substantially pressureless” cleaning solution).
• the definition of "diffusion-con ⁇ trolled" permeation is that which occurs at a pressure below the "bubble-press- ure breakthrough" (or “bubble-point") for a membrane, and the permeating rate "J" is measured in gm-moles/sec/cm .
• This definition is adapted from a method for measuring the pore sizes of a membrane by diffusion of air through water which fills the pores of the membrane at the "bubble-pressure breakthrough" for a membrane.
• H -* solubility of the gas (N 2 ) in water at 20 °C
• the membrane device most preferably used for purifying non-sterile aqueous streams is a frameless array of fibers, immersed in an arbitrarily large body of water.
• a device is disclosed in U.S. Patent No. 5,248,424 to Cote et al.
• An alternative is to use a device of the "shell and tube” type in which the permeate is collected from the lumens of the fibers.
• a device of either type is referred to herein as a "module".
• a typical module is used to separate one liquid from another having clus ⁇ ters of molecules, or larger molecules than those of the liquid to be separated; or, to separate one liquid from another liquid containing a suspension or disper ⁇ sion of micron-size inorganic particles or organic particles.
• Such particles include bacteria both dead and alive, or, a colloidal suspension of submicron size solids, or an emulsion, from which the aqueous component is to be separated.
• the membranes may have pores ranging in size from as large as 5 ⁇ m (micrometers or microns) or as small as 50 A, and are commonly termed "semipermeable" membranes.
• Membranes with circumferential walls having relatively large pores are used in MF.
• the pores in a MF membrane range from about 300 A to 20,000 A in nominal diameter; and those in a UF membrane, from about 50 A to about 1,000 A (0.1 ⁇ m).
• the fouling film is a thin continuous layer which develops on the surface of the membrane within the first 0.25 - 3 hr, generally no more than about 8, after the membrane is placed in operating service. Presence of the film is in ⁇ ferred from concentration of foulant in the substrate feed. Such concentration may be measured as the cell count in the water phase, or the concentration of metal salts, and is judged in terms of how much performance (flux) has dropped below target.
• the target flux is normally the initial stable flux obtained in the
• a biofilm typically comprises cells, both dead and alive, cell debris and extracellular polymer substances (EPS), with the EPS accounting for a substantial portion of the biofilm's dry mass.
• EPS extracellular polymer substances
• Wet biofilm may contain up to 95% or more of water.
• the surprisingly effective method disclosed herein for cleaning membranes uses a cleaning fluid which is most preferably a liquid biocidal oxid ⁇ izing liquid, and it contacts the lumens of the fibers at low, negligibly small fluid velocity, if any, and typically at less than 1 meter/sec through the lumens, the fibers are under only enough internal pressure to cause gentle permeation of the cleaning fluid through the membrane and fouling film.
• the cleaning system of this invention does not require a conventional holding tank such as used in a prior art clean-in-place system.
• the biocidal liquid in our system may be dispensed from a container the fluid volume of which is only slightly greater than that of the sum of the lumens of all the fibers to be cleaned simultaneous ⁇ ly, or the sum of the bores of all the tubes, or all the spiral passages. The solution is recirculated when it returns to the container.
• a further unexpected advantage is that there is no need to counteract or recover the cleaning fluid which diffuses into the feed since that amount is too small to be objectionable, typically less than 10 ppm in a reservoir of substrate, and is biooxidized at that low concentration, negating biocide build-up.
• a first method relies on cleaning a fouled outer surface from the outside; the second relies on cleaning the fouled outer surface from the inside.
• the outer surface may be that of a fiber, or a tube, or a roll; the method of this invention is mainly applicable to fibers.
• the fouled surfaces are scoured, sometimes after a soaking period in a cleaning solution made up of specific chemicals. Scouring is effected by a suspension of finely divided solids which have essentially no affinity for the membrane, the solids having a diameter larger than the largest pores in the membrane so as not to be trapped therein, the scouring action being controlled by the rate at which the suspension is flowed over the membrane surfaces.
• An alternative first method uses a chemical cleaning solution to remove the solid or semi-solid matter which is deposited on the membrane's outer surface. Such a cleaning solution is aptly formulated to dissolve or chemically react with the organic or inorganic matter deposited on the membrane.
• a drained module may be soaked in the solution, or the solution may be recycled through the shell-side of the module until the fouling matter is chemically de ⁇ graded and dislodged. It will be understood that in outside-in flow, the permeate side of the membrane (the lumens of fibers) does not get fouled because essen ⁇ tially no solids pass through a membrane.
• the feed must be shut off, and the module is preferably taken out of service and drained, before the chosen cleaning fluid in the appropriate concentration, is introduced in lieu of the feed.
• the cleaning solution is recycled over the surfaces of the membrane until they are cleaned, then discarded to drain. If a bioreactor is available, the cleaning solution is collected and gradually bled into the bio- reactor where the chemicals and fouling solids are biodegraded.
• This method comprises introducing a gas into the fibers under sufficient pressure to pass through the walls of the fibers, in a direction opposite to that in which the feed is being filtered, so as to dislodge solids retained on the walls of the fibers.
• This method is the subject of U.S. Patents Nos. 4,767,539 and 4,921,610 to Ford, and related patents assigned to Memtec Limited.
• gas is introduced into the lumens of the fiber as the back-wash medium, optionally after “back-flushing” ("back-washing” and “rinsing” are two other terms used interchangeably in the art with back-flushing) with permeate.
• the gas pressure in the lumens swells fouled fibers to enlarge their pores making it easier to free the particles lodged in the pores, and to carry them away in the expansion of the back-wash gas.
• a Memcor microfiltration system (Memtec).
• the hydraulic forces act over a much longer period of time than do the forces of a pressurized gas, and the time during which they act provides enough time for the hydraulic fluid to find a path of less resistance than that of the path blocked by fouling solids.
• the hydraulic back-flushing system is also referred to as "dead-end" washing because the discharge of the manifold carrying fluid from of the bores of the fibers is blocked to allow the build-up of necessary hydraulic pressure above 240 kPa.
• the cleaning solution is held for a period of time under press ⁇ ure, then drained through the discharge into a spent cleaning-solution tank.
• This prior art back-flushing method is only effective when the cleaning solution is relatively non-toxic because a large portion of the cleaning agent escapes through pores which are not plugged, or only partially plugged, and also through pores after they are cleaned and before the hydraulic pressure is remov ⁇ ed. Since, after cleaning fibers in raw or "dirty" water, by back-flushing with toxic cleaning solution, clean water is withdrawn into the fibers as permeate, the toxic cleaning solution re-enters the fibers with the permeate. Even if the amount of cleaning agent re-entering with permeate is insignificantly small, a far greater amount of cleaning agent is used than is necessary to effect desirable cleaning.
• the fibers are withdrawing water from a medium containing live biomass, particularly a biomass which desirably helps purify the water
• the discharge of a relatively large amount of toxic cleaning solution into the biomass kills so many cells that it takes an abnormally long period to return the biomass to its desired cell concentration, if it can be returned at all.
• back-flushing a membrane's outer surfaces with biocidal solu ⁇ tion, then back-flushing inner surfaces with permeate is generally limited to processes in which the operating transmembrane pressure is relatively low, in the range from 1 - 3 bar, at which low pressure the solids are not forced into the - 14 - pores of the membrane.
• the flux is relatively low, in the range from 5 to 20 LMH, the fluid velocity of cleaning fluid to clean from the outside is too low. If cleaned with high velocity fluid the cleaning liquid enters the lumens, making this an unrealistic alternative.
• the cleaning systems which can be operat ⁇ ed effectively without draining the feed, include those using pressurized back- flushing with a biocidal solution, such as in the Japanese system JP 4-265127 A, and those using pressurized back-flushing with a gas, such as in the Ford '539 or '610 gas-distension systems. It is not practical to back-flush fibers with permeate because the cleaning effect of permeate is solely due to hydraulic pressure and is therefore relatively ineffective.
• the pressure drop through the lumen is so high that a length of fiber only 1 meter, requires fiber-bursting pressure at the inlet to generate a pressure below the bubble-point, at some point downstream of the inlet.
• the pressure does not exceed that which can be tolerated by the fibers, tubes or rolls, and they are back-flushed with permeate at such pressure, permeate is lost to the feed.
• the fibers are to be cleaned from the outside, the feed is shut off and drained, as is the permeate, the fibers are soaked in clean ⁇ ing solution, washed and rinsed, on their outside surfaces, then finish-rinsed with fresh permeate before the membranes are returned to service.
• the feed is always on the outside.
• the i.d. of a fiber is at least 20 m and may be as large as about 3 mm, typically being in the range from about 0.1 mm to 2 mm.
• the larger the o.d. the less desirable the ratio of surface area per unit volume of fiber, but the lower the pressure drop for a back-flushing cleaning fluid.
• the wall thickness of a fiber is at least 5 ⁇ m and may be as much as 1.2 mm, typically being in the range from about 15% to about 60% of the o.d. of the fiber, most preferably from 0.5 mm to 1.2 mm.
• the average pore cross sectional diameter in a fiber may vary widely, being in the range from about 5 A to 10,000 A.
• the preferred pore diameter for ultrafiltration of components in a substrate feedstream being in the range from about 5 A to 1,000 A; and for microfiltration, in the range from 1,000 A to 10,000 A.
• a module containing fibers may be viewed as being analogous to a liquid-liquid shell-and-tube heat exchanger.
• a first liquid is recycled through the tubes either to heat (or cool) a second liquid in the shell side, and the tube side gets frequently fouled.
• a cleaning solution which can provide substantially the same heating (or cooling) function as the first liquid.
• the clean ⁇ ing solution is run into a cleaning solution holding tank and the first liquid is substituted.
• the logical approach would be to pressurize the fibers with the cleaning solution from within, to reap the benefits of both (a) a higher flux for the cleaning solu ⁇ tion, and (b) enlargement of the pores such as is obtained with the gas pressur- ization process.
• the obvious way to pressurize the fibers is to "dead-end" them, that is, to block the discharge of the cleaning solution from the outflow end of the lumens so as to force the cleaning solution out of the pores under high pressure greater than the bubble point of the membranes.
• any cleaning solution applied to the outer surface of a tube or fiber from the outside is typically done under sufficient pressure to force the solution from outside the membrane through the biofilm on it and its pores.
• a relatively high pressure is applied, higher than is otherwise necessary, and such pressure has the effect of compacting the gel layer and foulants on the memb ⁇ rane wall, thus exacerbating the cleaning problem.
• the low pressure may be substantially constant, or it may be deliberately varied within a period of less than 5 sec, preferably less than 1 sec.
• the pressure exerted by the cleaning fluid may vary from a minimum of about 100 kPa (1 bar, at least 0.1 psig, preferably 0.5 psig) for a "loose" MF (5 / ⁇ m) to a maximum of 100 psig for a "tight" UF (5 ⁇ A), within less than 1 sec, which pulsing affords diffusion-controlled permeation.
• the pulsed maximum pressure which provides diffusion-controlled flow depends upon the pore size and distribution of the membrane but is generally no higher than about 300 kPa.
• Such flow discharges a predetermined amount of cleaning fluid into the feed and effectively removes the fouling film sufficiently to restore the transmembrane flux to within 20% of its initial stable flux over a period of 24 hr.
• the amount of cleaning fluid discharged into the feed is so small with each cleaning cycle that, even after an arbitrarily large number of cycles greater than 1000, continued withdrawal of permeate from the feed contaminated with cleaning fluid, does not deleteriously affect the permeate quality.
• diffusion through the wall of the membrane under diffusion-controlled flow occurs in a surprisingly short time, which provides for a short cleaning period; and a short cleaning period is a critical factor in the commercial attractiveness of a membrane separation.
• the clean-in-place process of this invention does not dead-end the fibers to be cleaned, and it does not use high pressure; nor does the instant process physically dislodge fouled particles from pores in which they may be trapped with mechanical force or hydraulic force, but by chemical attack which affects the chemical bond between the fouling compound and the wall of the memb- rane.
• the process capitalizes on the superior effectiveness of chemically removing a "foulant" (fouling material) whether organic or inorganic, in contrast with mechanically doing so by reliance on enough mechanical or hyd ⁇ raulic pressure to obtain measurable, or evident membrane wall distension known to loosen the mechanical bond of the foulant to the membrane's wall.
• an aqueous cleaning fluid comprising a biocidal oxidative electrolyte in aqueous solution, having an active, preferably oxidizing anion and an associated, preferably active cation, is found to migrate through partially blocked pores in a membrane and chemically attack organic and inorganic foul ⁇ ing matter on the surface of the membrane until the fouling matter is removed from the pores.
• the oxidizing anion may be contributed by an aqueous organic acid, particularly mono and polycarboxylic acids such as citric or oxalic acid and inorganic acids such as phosphoric acid.
• the cleaning fluid may be a gas which can diffuse through the pores of the membrane and chemically react with the foulant to remove it.
• Such gases may be biocidal, or oxidative, or both, and include sulfur dioxide, chlorine, fluorine, ethylene oxide and the like. It is therefore a general object of this invention to provide a method for restoring the flux of a surface of a microfiltration or ultrafiltration semiperme ⁇ able membrane after the surface is contacted with a non-sterile aqueous subs ⁇ trate such as dirty water containing inorganic material which can be deposited on the surface, or beneficial bacteria, from which substrate purified water is to be withdrawn. When the substrate includes the bacteria, the purified water is to be withdrawn without vitiating the benefits of the bacteria population.
• a non-sterile aqueous subs ⁇ trate such as dirty water containing inorganic material which can be deposited on the surface, or beneficial bacteria
• the dirty water Whether the dirty water contains undesirable inorganic salts, particularly water-soluble halides, oxides and sulfides of the transition elements of Groups VI, VII and VIII of the Periodic Table, or organic matter, the dirty water being non-sterile usually contains enough bacteria to produce an initial biofilm on the surface of the membrane, which initial biofilm, with time, gets progressively denser or thicker, or both. Operation with the initial biofilm is unavoidable, but the membrane's initial stable transmembrane flux soon decreases as a function of time by at least 20%.
• the method of restoring the flux comprises, contacting the surface with a cleaning fluid at a pressure no higher than its bubble pressure breakthrough, but enough to diffuse through said pores and said film, over a period sufficient to remove enough fouling film to provide a restored flux equal to at least 70% of said initial stable flux; discontinuing contacting the surface of said membrane with the cleaning fluid; and, re-establishing flow of purified water through the membrane.
• the pressure is no greater than the bubble-point but sufficient to diffuse through the pores and the biofilm, but insufficient to kill numerically more than 20% of living bacteria in the biomass so as to maintain the viability of the bacteria population in the bioreactor; withdrawing the electrolyte from within lumens of the fibers; and, reestablishing normal operation.
• this is done without blocking the flow of the biocidal solution, but if desired, the flow of the solution may be blocked so long as the pressure on the solution does not exceed the bubble- point of the fibers, and the solution may be held in the lumens for long enough to remove most of the biofilm.
• Figure 1 is a bar graph depicting the results of a factorial analysis showing the average main effects and interaction of variables: time during which the cleaning fluid was in contact with the membrane, or "duration" (D), the con- centration of the cleaning fluid (C), and the pressure of the cleaning fluid (P).
• Figure 2 is a perspective view schematically illustrating a membrane device disclosed in the '424 patent, comprising a frameless array of a skein of fibers, unsupported during operation of the device, with each set of the opposed ends of the fibers potted in one of two spaced apart headers, each atop and in open fluid communication with a permeate collection pan, and a permeate with- drawal conduit.
• unsupported is meant “not supported during operation of the membrane device, except by the substrate”.
• Figure 3 diagrammatically illustrates the cleaning of a cartridge of wafers comprising arrays of hollow fiber MF membranes, the cartridge being housed in a shell through which feed is flowed in outside-in flow.
• Figure 4 is a graph in which the variation of flux is plotted as a function of time, comparing the results obtained by back-flushing the lumens of poly- sulfone fibers with (i) permeate, (ii) deionized water, and (iii) a dilute solution of sodium hypochlorite (NaOCl) at concentrations which provided 150 ppm or 300 ppm "active" oxidizing anion all back-washed for the same amount of time, 30 min at a maximum continuous pressure of 245 kPa (30 psig).
• NaOCl sodium hypochlorite
• Figure 5 is a graph in which the variation of flux is plotted as a function of time, showing the results obtained by back-flushing for only 15 min per 24 hr of operation, the lumens of polyfluorovinylpyrrolidone fibers used to filter domestic wastewater having a high BOD5 of 1,800 mg/L after the fibers are fouled sufficiently to halve their initial transmembrane flux of about 78 LMH.
• Figure 6 is a graph in which the variation of flux is plotted as a function of time, showing the results obtained by back-flushing for only 15 min per 24 hr of operation, the lumens of polyfluorovinylpyrrolidone fibers used to filter groundwater containing a high level 0.4 ppm of iron and manganese (2.1 ppm) after the fibers are fouled sufficiently to decrease their initial transmembrane flux by about 15%.
• Figure 7 schematically illustrates a single bank of 3 modules, in a large tank (not shown) of non-sterile ground water, each of which modules is similar in construction to the one with the frameless array shown in Fig 2; and, the simplicity of the piping scheme to clean the bank in place, without having to drain the feed tank.
• Figure 8 diagrammatically illustrates the use in a single large body of bacterially contaminated water, such as a lake (not shown) of 4 banks, each having 3 modules, each of which banks is similar in configuration to the one shown in Fig 7; and the simplicity of the piping scheme to clean all 4 banks in place, concurrently, without having to drain the feed tank.
• Fig 1 there is shown a bar graph in which the results of a factorial analysis of data derived from in situ cleaning of polysulfone membranes were plotted. As is evident from the contribution of each variable to flux, plot ⁇ ted along the vertical axis, the duration of contact with the cleaning fluid is the variable with the most dominant effect. The next most dominant variable is con ⁇ centration, followed by pressure which has the least effect. Since duration and pressure are the most influential variables, and these variables define the type o flow, we believe this flow to be diffusion-controlled flow.
• the in situ cleaning process may be used in any membrane filtration system using hollow fiber membranes.
• the process is most particularly directed to water purification membranes such as are used in wastewater containing domestic sewage, chemicals, oily water, and pulp and paper byproducts; and, in surface water purification where the feed is brackish water or polluted lake water.
• the fouling film is to be removed sufficiently to restore the flux to desirable level relative to the initial stable flux.
• the in situ cleaning process is most preferred in particular situations where it is practical deliberately to kill no more than 20%, preferably ⁇ 10% (cell count, CFU/ml) of the bacterial population in the interest of maintaining the beneficial effects of that population.
• this invention relies on cleaning from the permeate side, that is, through the lumens of the fibers. In this manner, cleaning solution permeates through pores in the membrane and first reaches foulants embedded in those pores while the cleaning fluid is at its highest concentration, then permeates to the surface. The fluid thus has maximum effect on the foulant in the pore and in the fouling film.
• gaseous cleaning fluids such as chlorine, sulfur dioxide, ethylene oxide and the like are highly effective.
• a biocidal solution When a biocidal solution is used, it must first permeate the macroporous wall of the membrane in which essentially no bacteria are lodged (they cannot come through the skin and intermediate transport layers of a membrane) and attack bacteria, dead and alive, randomly lodged in the biofilm to provide a random network of pores through as much of the biofilm as is left. In general, there always is some biofilm left because the time over which diffusion takes place is insufficient to remove all the biofilm even if all the bacteria are killed in the biofilm.
• biocidal solution which is incapable of diffusing through the biofilm easily will require too long a soak period and/or too long a recirculation period. Therefore the choice of biocidal solution is typically an oxidative electrolyte, and the concentration in which it is to be used, must be related to the transmembrane flux of that solution through the membrane to be cleaned and to the foulant(s) to be removed.
• oxidative electrolyte we refer to one which at least has an active anion, and preferably also an active associated cation and include such materials as the organic peroxides and hydrogen per ⁇ oxide.
• Preferred biocidal solutions and the foulants for which they are generally particularly effective are listed side-by-side in Table herebelow:
• solution is used since it is most conven- ient to use an aqueous biocidal solution of known concentration.
• non- aqueous liquid oxidant may be used if the amount diffusing through the memb ⁇ ranes can be controlled.
• fuming nitric acid, chloracetic acid, or non-aqueous HC1 may be injected into permeate held in the piping and lumens, but it is difficult to inject just the right amount.
• non-aqueous cleaning fluids are difficult to meter accurately in the minuscule amounts required.
• the cleaning fluid chosen is preferably inert relative to the synthetic resinous material of the membrane though it may swell in contact with the cleaning fluid; for example, polypropylene fibers tend to be hydrolyzed with NaOCl solution, but are inert with respect to aqueous H 2 ⁇ 2 (hydrogen per ⁇ oxide); and, polysulfone fibers tend to swell in contact with NaOCl solution but are otherwise inert to the solution.
• polypropylene fibers tend to be hydrolyzed with NaOCl solution, but are inert with respect to aqueous H 2 ⁇ 2 (hydrogen per ⁇ oxide); and, polysulfone fibers tend to swell in contact with NaOCl solution but are otherwise inert to the solution.
• H 2 ⁇ 2 hydrogen per ⁇ oxide
• polysulfone fibers tend to swell in contact with NaOCl solution but are otherwise inert to the solution.
• as little as 10 ppm of the cleaning fluid can be effective.
• a concentration no greater than 500 ppm of the active anion, e.g. OC1 " , or CI " is preferred, since higher concentrations up to 0.1% by weight of the active anion fails to provide significantly improved performance.
• the temperature of the biocidal solution as well as its concen ⁇ tration may be raised provided neither is deleterious to the membrane, and the increased concentration provides a justifiable effectiveness of "kill" without jeopardizing the vitality of the bacteria population.
• the fibers used in an array may be formed of any conventional organic membrane material. They are typically polymers which form an asymmetric membrane having a thin layer or "skin" on the outside or “shell side” of the fibers.
• Preferred materials for a base membrane which do not contain a repeat- ing unit derived from acrylonitrile are polysulfones, poly(styrenes), including styrene-containing copolymers such as butadiene-styrene and styrene-vinylben- zylhalide copolymers, polycarbonates, cellulosic polymers, polypropylene, poly(vinyl chloride), poly(ethylene terephthalate), poly(vinylidene fluoride), aromatic polyamides and the like disclosed in U.S. Patent No. 4,230,463 the disclosure of which is incorporated by reference thereto as if fully set forth herein.
• the fibers are chosen with a view to performing their desired function and are non-randomly oriented in each array, and in the module as described in the '424 patent, the disclosure of which is incorporated by reference thereto as if fully set forth herein.
• a frameless array such as is shown in Fig 2
• the direction of the flow of feed is immaterial as the direction in which the feed enters a lumen is generally transverse to the upstanding fibers.
• a module housing one or more cartridges of wafers such as are shown in the '593 patent to Pedersen et al
• the flow of feed through the module is over the fibers and orthogonal thereto. It is preferred to use banks of modules constructed as disclosed in the '424 patent, the disclosure as to the construction of which is incorporated by reference thereto as if fully set forth herein.
• Typical hollow fiber membranes which are particularly amenable to being cleaned in situ have an i.d. in the range from 0.5 mm to 2.5 mm and have an o.d. in the range from 0.7 mm to 3.5 mm.
• the average pore cross sectional diameter in a fiber may vary widely, being in the range from about 5 A to 2000 A.
• the preferred pore diameter for separation of components in a liquid feedstream is in the range from about 10 A to 200 A.
• the length of a fiber in a skein is essentially independent of the strength of the fiber, or its diameter, because the skein is buoyed, both by bubbles of oxygen-containing gas introduced if live aerobic bacteria ar present, and the substrate in which it is deployed.
• each fiber in the skein is preferably determined by the conditions under which the array is to operate.
• fibers of a skein range from 1 m to about 10 m long, depending upon dimensions of the body of substrate (depth and width) in which the array is deployed.
• a larger dia ⁇ meter membrane is desirable to minimize the pressure drop through the fiber.
• the number of fibers in an array is arbitrary, typically being in the range from about 1,000 to about 10,000, and the preferred surface area for a skein in commercial service is in the range from 10 m 2 to 100 m 2 .
• the materials for the headers are most preferably either thermosetting or thermoplastic synthetic resinous materials, optionally reinforced with glass fibers, boron or graphite fibers and the like.
• Thermoplastic materials are preferred for relatively low temperature service below 100 °C, these being chosen so as to be sufficiently compatible with the material of the fibers to produce a lasting, fluid- tight bond.
• Such thermoplastic materials may be crystalline, such as polyolefins, polyamides (nylon), polycarbonates and the like, semi-crystalline such as poly- etherether ketone (PEEK), or substantially amorphous, such as poly(vinyl chloride) (PVC), and the like.
• Thermosetting resins are preferred for higher temperature service, and for ease of use.
• each of the headers is not narrowly critical, the choice depending upon the materials of the header and the fiber, and the cost of using a method other than potting.
• a membrane device referred to generally by reference numeral 10, comprising an upstream header 11 and a downstream header 11', one being substantially identical to the other, upstream and downstream collection pans 15 and 15' to collect the permeate, and their respective permeate withdrawal conduits 17 and 17'.
• the purpose of the headers 11 and 11' is to pot fibers 12 in spaced apart relationship with each other in a potting resin such as an epoxy.
• the headers are conveniently formed as described in the '424 patent, but any other method may be used which serves the aforementioned purpose.
• the bases 13 and 13' of each header are snugly accommodated in collection pans 15 and 15' sized to the base 13 above a per ⁇ meate collection zone within the pan.
• Air is provided through a gas distribution means 19 to maintain beneficial bacteria present in the dirty water.
• Permeate withdrawn into the lumens of the fibers preferably under suction, collects in the pans and is discharged to a collection point as is described in the '424 patent, until the flow of permeate is about one-half of the flow at initial stable flux, at which time the flow of dirty water is shut off so that the lumens of the fibers remain filled with permeate, and the cleaning cycle is commenced.
• Conduits 21, 22 and 23 are provided as shown, connecting the lumens of fibers 12 in valved communication with the discharge of a pump 24 via a 3-way valve 25, which in one of its positions allows permeate to be withdrawn from the headers.
• Conduit 22 serves as a manifold for the collection pans 15, and an intermediate portion 22' of the conduit 22 is provided with a check valve 26 which allows biocidal solution held in cleaning tank 27 to be circulated through the lumens of fibers 12, and returned through conduit 23 to the tank 27.
• a check valve 28 is provided in conduit 23 to shut off flow of either permeate or biocidal solution to the cleaning tank.
• the 3-way valve 25 is positioned to flow biocidal solution to the upstream collection pan and enough solution is pumped from tank 27 to fill the upstream collection pan and the lumens of the fibers 12, then flow into the downstream collection pan from which it is returned to the tank 27.
• Check valve 23 is left open when cleaning solution is either circulated with pump 24 or pulsed when a pulse pump is substituted for pump 24. In those instances where it is desired to "dead end" the biocidal solution under only enough pressure to permit its diffusion-controlled flow out of the fibers, both the check valves 26 and 28 are closed.
• a module 40 having a shell 41 within which at least one cartridge 42 of wafers (only the rectangular-mesh protective screen 43 on the topmost wafer is visible) is disposed between upper and lower feed plates 44 and 44' (not visible in this view) which are longitudinally axially connected with diametrical baffles 45 and 45' which extend the length of the shell and fit in fluid-tight relationship with diagonally opposed ends 46 and 46' of the cartridge so that the permeate side of the shell is divided into two separate permeate withdrawal zones.
• the fibers in each wafer are in parallel spaced apart relationship and discharge permeate under suction conditions into both permeate withdrawal zones when dirty water is flowed axially through the center of the module as described in greater detail in the '593 patent.
• the feed is shut off and the cleaning cycle commenced.
• the feed does not need to be shut off since it does not interfere with the effectiveness of the cleaning cycle.
• the bubblepoint may change depending upon the exerted hydrostatic pressure.
• biocidal solution is circulated through conduits analogous to those used in the prior embodiment, except that a 3-way valve 29 is substituted for check valves 26 and 28 in Fig 2.
• the 3- way valves indicate that permeate is being withdrawn from the module 40 through permeate withdrawal conduits 17 and 17'.
• biocidal solution is circulated through their lumens until the flux is restored to at least 70% of the initial stable flux, and preferably to more than 80%.
• permeate withdrawal in normal operation is re-cornmenced.
• the flow of dirty water need not be shut off. If shut off the dirty water remains in the casing outside the tube and in contact with the biofilm on the outer surface of the membrane 54.
• Fig 4 there is plotted the results of a pilot plant test in which the effect of various back-flushes, each having a duration of 30 min, and carried out sequentially, was evaluated.
• the integers in brackets identify the value of the flux after the array was back-flushed with the solution/water/- permeate identified, as follows: (1) 300 ppm CI as NaOCl solution at 170 kPa (10 psig); (2) RO water at 170 kPa; (3) RO water at 170 kPa, dead-ended; (4) permeate at 170 kPa; (5) 150 ppm CI as NaOCl solution; (6) 300 ppm CI as NaOCl solution at 150 kPa.
• the initial flux is about 44 LMH, but the initial stable flux after a soak period of 4 hr is 38 LMH under a permeate withdrawal suction of 25.4 cm of Hg. After 72 hr the flux decreases to about 12 LMH, and the permeate being withdrawn is drained to storage.
• the piping is configured to recycle a 300 ppm CI NaOCl solution through the lumens by positioning the 3-way valve 25, closing check valve 26 and opening check valve 28 (see Fig 3). On the scale illustrated, the 30 min period for back- flushing is not visible. Though restoration to the initial stable flux is not instantaneous (as evident from the inclination of the near-vertical line) after circulation of the biocidal solution is stopped, it is clear that the recovery is rapid.
• the pressure of 170 kPa was arrived at by trial and error for the part ⁇ icular fibers used, this pressure being sufficient to provide diffusion-controlled flow, the rate of which was not noticeably changed between 150 - 170 kPa. At 190 kPa the rate of flow was noticeably increased indicating flow under pressure due to developed hydraulic forces.
• the biocidal solution was made from a commercially available Javex bleach solution containing 5.25% NaOCl, and 300 ppm was made up according to the following calculations: NaOCl — > Na + + OC1 "
• FIG 5 there is plotted the results of a pilot plant test in which a frameless array analogous to that shown in Fig 2, of 1400 MF fibers each 2 meters long, having an o.d. of 2 mm, an i.d. of 1.5 mm, and pores having a nominal diameter of about 0.15 ⁇ m, the majority of which are smaller than 0.15 ⁇ m, the smallest being about 0.08 ⁇ m and the largest 0.35 ⁇ m.
• the array is fully immersed in a tank into which domestic wastewater is fed.
• the initial stable flux after a soak period of 4 hr is 78 LMH.
• FIG 6 there is plotted the results of a pilot plant test for recovering purified water from groundwater flowing into a tank in which a frameless array analogous to that shown in Fig 2, is immersed. As permeate is withdrawn, the groundwater is concentrated into an aqueous substrate. A portion of this substrate is purged either continuously or periodically, to maintain a desired concentration of contaminants in the substrate.
• the array used 110 MF fluoropolymer fibers each 2 meters long, having an o.d. of 2 mm, an i.d. of 1.5 mm, and pores having a nominal diameter of about 0.15 ⁇ m, the majority of which are smaller than 0.15 ⁇ m, the smallest being about 0.08 ⁇ m and the largest 0.35 ⁇ m.
• the array is fully immersed in a tank into which the groundwater contaminated with iron and manganese salts, is fed.
• the initial stable flux after a soak period of 4 hr is 90 LMH.
• Fig 7 is schematically illustrated the use of 3 modules of frameless arrays of fibers freely swaying in skeins above headers which are manifolded for withdrawal of permeate from the lumens, in the medium of a reservoir in which beneficial aerobic bacteria are nourished. Conduits for supplying air under the skeins are not shown. As indicated, the cleaning cycles of each module may be undertaken separately, or they may be cleaned together. In each case, the flow of cleaning solution is not blocked through the skeins of fibers.
• FIG 8 is schematically illustrated another, larger use than that described in Fig 7.
• 4 banks of 3 modules each are manifolded for withdrawal of permeate from the lumens.
• the cleaning cycles of each bank may be undertaken separately, or they may be cleaned together. In each case, the flow of cleaning solution is not blocked through the skeins of fibers.

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• 1993
  • 1993-12-20 US US08/170,053 patent/US5403479A/en not_active Expired - Fee Related
• 1994
  • 1994-12-19 WO PCT/CA1994/000691 patent/WO1995017241A1/en not_active Ceased
  • 1994-12-19 DE DE69412647T patent/DE69412647T2/de not_active Expired - Fee Related
  • 1994-12-19 EP EP95903730A patent/EP0738180B1/en not_active Expired - Lifetime
  • 1994-12-19 AU AU12697/95A patent/AU1269795A/en not_active Abandoned
• 1995
  • 1995-01-25 TW TW084100631A patent/TW259726B/zh active

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