US20050224411A1 - Method of cleaning membranes - Google Patents
Method of cleaning membranes Download PDFInfo
- Publication number
- US20050224411A1 US20050224411A1 US11/145,773 US14577305A US2005224411A1 US 20050224411 A1 US20050224411 A1 US 20050224411A1 US 14577305 A US14577305 A US 14577305A US 2005224411 A1 US2005224411 A1 US 2005224411A1
- Authority
- US
- United States
- Prior art keywords
- membrane
- reducing agent
- solvent
- cleaning
- sulfite
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Abandoned
Links
- 239000012528 membrane Substances 0.000 title claims abstract description 130
- 238000004140 cleaning Methods 0.000 title claims abstract description 53
- 238000000034 method Methods 0.000 title claims abstract description 41
- LSNNMFCWUKXFEE-UHFFFAOYSA-N Sulfurous acid Chemical compound OS(O)=O LSNNMFCWUKXFEE-UHFFFAOYSA-N 0.000 claims abstract description 57
- 239000000203 mixture Substances 0.000 claims abstract description 51
- 239000003638 chemical reducing agent Substances 0.000 claims abstract description 48
- 239000002904 solvent Substances 0.000 claims abstract description 37
- HRZFUMHJMZEROT-UHFFFAOYSA-L sodium disulfite Chemical compound [Na+].[Na+].[O-]S(=O)S([O-])(=O)=O HRZFUMHJMZEROT-UHFFFAOYSA-L 0.000 claims description 28
- JVBXVOWTABLYPX-UHFFFAOYSA-L sodium dithionite Chemical compound [Na+].[Na+].[O-]S(=O)S([O-])=O JVBXVOWTABLYPX-UHFFFAOYSA-L 0.000 claims description 28
- 229940001584 sodium metabisulfite Drugs 0.000 claims description 28
- 235000010262 sodium metabisulphite Nutrition 0.000 claims description 28
- 239000000356 contaminant Substances 0.000 claims description 24
- 239000002033 PVDF binder Substances 0.000 claims description 12
- 239000003795 chemical substances by application Substances 0.000 claims description 12
- 239000012510 hollow fiber Substances 0.000 claims description 11
- 229920002981 polyvinylidene fluoride Polymers 0.000 claims description 11
- 238000010790 dilution Methods 0.000 claims description 9
- 239000012895 dilution Substances 0.000 claims description 9
- GEHJYWRUCIMESM-UHFFFAOYSA-L sodium sulfite Chemical compound [Na+].[Na+].[O-]S([O-])=O GEHJYWRUCIMESM-UHFFFAOYSA-L 0.000 claims description 8
- 229910000000 metal hydroxide Inorganic materials 0.000 claims description 7
- 229910044991 metal oxide Inorganic materials 0.000 claims description 7
- 150000004706 metal oxides Chemical class 0.000 claims description 7
- 230000002708 enhancing effect Effects 0.000 claims description 6
- 150000004692 metal hydroxides Chemical class 0.000 claims description 6
- 229920000642 polymer Polymers 0.000 claims description 5
- 235000010265 sodium sulphite Nutrition 0.000 claims description 4
- HEZHYQDYRPUXNJ-UHFFFAOYSA-L potassium dithionite Chemical compound [K+].[K+].[O-]S(=O)S([O-])=O HEZHYQDYRPUXNJ-UHFFFAOYSA-L 0.000 claims description 3
- RWPGFSMJFRPDDP-UHFFFAOYSA-L potassium metabisulfite Chemical compound [K+].[K+].[O-]S(=O)S([O-])(=O)=O RWPGFSMJFRPDDP-UHFFFAOYSA-L 0.000 claims description 3
- 229940043349 potassium metabisulfite Drugs 0.000 claims description 3
- 235000010263 potassium metabisulphite Nutrition 0.000 claims description 3
- BHZRJJOHZFYXTO-UHFFFAOYSA-L potassium sulfite Chemical compound [K+].[K+].[O-]S([O-])=O BHZRJJOHZFYXTO-UHFFFAOYSA-L 0.000 claims description 3
- 235000019252 potassium sulphite Nutrition 0.000 claims description 3
- 238000001471 micro-filtration Methods 0.000 abstract description 9
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 38
- KRKNYBCHXYNGOX-UHFFFAOYSA-N citric acid Chemical compound OC(=O)CC(O)(C(O)=O)CC(O)=O KRKNYBCHXYNGOX-UHFFFAOYSA-N 0.000 description 36
- 238000001914 filtration Methods 0.000 description 21
- XEEYBQQBJWHFJM-UHFFFAOYSA-N iron Substances [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 description 18
- 239000000243 solution Substances 0.000 description 17
- 238000011084 recovery Methods 0.000 description 13
- 239000012459 cleaning agent Substances 0.000 description 12
- 230000035699 permeability Effects 0.000 description 12
- 239000007788 liquid Substances 0.000 description 11
- 239000000460 chlorine Substances 0.000 description 10
- 239000002245 particle Substances 0.000 description 9
- 239000011148 porous material Substances 0.000 description 9
- 239000008394 flocculating agent Substances 0.000 description 7
- 229910052742 iron Inorganic materials 0.000 description 7
- 238000000108 ultra-filtration Methods 0.000 description 7
- 238000011001 backwashing Methods 0.000 description 6
- 239000000835 fiber Substances 0.000 description 6
- 239000012530 fluid Substances 0.000 description 6
- 239000000463 material Substances 0.000 description 6
- 230000007423 decrease Effects 0.000 description 5
- 238000002474 experimental method Methods 0.000 description 5
- 230000004907 flux Effects 0.000 description 5
- 238000005259 measurement Methods 0.000 description 5
- -1 polypropylene Polymers 0.000 description 5
- 230000009467 reduction Effects 0.000 description 5
- ZAMOUSCENKQFHK-UHFFFAOYSA-N Chlorine atom Chemical compound [Cl] ZAMOUSCENKQFHK-UHFFFAOYSA-N 0.000 description 4
- 239000004743 Polypropylene Substances 0.000 description 4
- 229910052801 chlorine Inorganic materials 0.000 description 4
- 238000012733 comparative method Methods 0.000 description 4
- 238000007796 conventional method Methods 0.000 description 4
- 150000007522 mineralic acids Chemical class 0.000 description 4
- 238000012986 modification Methods 0.000 description 4
- 230000004048 modification Effects 0.000 description 4
- 229920001155 polypropylene Polymers 0.000 description 4
- 238000005273 aeration Methods 0.000 description 3
- 230000008901 benefit Effects 0.000 description 3
- 150000007524 organic acids Chemical class 0.000 description 3
- 238000000926 separation method Methods 0.000 description 3
- QJZYHAIUNVAGQP-UHFFFAOYSA-N 3-nitrobicyclo[2.2.1]hept-5-ene-2,3-dicarboxylic acid Chemical compound C1C2C=CC1C(C(=O)O)C2(C(O)=O)[N+]([O-])=O QJZYHAIUNVAGQP-UHFFFAOYSA-N 0.000 description 2
- CIWBSHSKHKDKBQ-JLAZNSOCSA-N Ascorbic acid Chemical compound OC[C@H](O)[C@H]1OC(=O)C(O)=C1O CIWBSHSKHKDKBQ-JLAZNSOCSA-N 0.000 description 2
- 241000894006 Bacteria Species 0.000 description 2
- 229910021578 Iron(III) chloride Inorganic materials 0.000 description 2
- 229910019093 NaOCl Inorganic materials 0.000 description 2
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 description 2
- 230000015556 catabolic process Effects 0.000 description 2
- 239000000084 colloidal system Substances 0.000 description 2
- 238000006731 degradation reaction Methods 0.000 description 2
- WBZKQQHYRPRKNJ-UHFFFAOYSA-L disulfite Chemical compound [O-]S(=O)S([O-])(=O)=O WBZKQQHYRPRKNJ-UHFFFAOYSA-L 0.000 description 2
- 239000000706 filtrate Substances 0.000 description 2
- 239000002529 flux (metallurgy) Substances 0.000 description 2
- 239000004021 humic acid Substances 0.000 description 2
- RBTARNINKXHZNM-UHFFFAOYSA-K iron trichloride Chemical compound Cl[Fe](Cl)Cl RBTARNINKXHZNM-UHFFFAOYSA-K 0.000 description 2
- 239000013618 particulate matter Substances 0.000 description 2
- 229920002239 polyacrylonitrile Polymers 0.000 description 2
- 239000002244 precipitate Substances 0.000 description 2
- 230000008569 process Effects 0.000 description 2
- 238000001223 reverse osmosis Methods 0.000 description 2
- SUKJFIGYRHOWBL-UHFFFAOYSA-N sodium hypochlorite Chemical compound [Na+].Cl[O-] SUKJFIGYRHOWBL-UHFFFAOYSA-N 0.000 description 2
- 239000007858 starting material Substances 0.000 description 2
- 239000002699 waste material Substances 0.000 description 2
- LSNNMFCWUKXFEE-UHFFFAOYSA-M Bisulfite Chemical compound OS([O-])=O LSNNMFCWUKXFEE-UHFFFAOYSA-M 0.000 description 1
- KZBUYRJDOAKODT-UHFFFAOYSA-N Chlorine Chemical compound ClCl KZBUYRJDOAKODT-UHFFFAOYSA-N 0.000 description 1
- KCXVZYZYPLLWCC-UHFFFAOYSA-N EDTA Chemical compound OC(=O)CN(CC(O)=O)CCN(CC(O)=O)CC(O)=O KCXVZYZYPLLWCC-UHFFFAOYSA-N 0.000 description 1
- DGAQECJNVWCQMB-PUAWFVPOSA-M Ilexoside XXIX Chemical compound C[C@@H]1CC[C@@]2(CC[C@@]3(C(=CC[C@H]4[C@]3(CC[C@@H]5[C@@]4(CC[C@@H](C5(C)C)OS(=O)(=O)[O-])C)C)[C@@H]2[C@]1(C)O)C)C(=O)O[C@H]6[C@@H]([C@H]([C@@H]([C@H](O6)CO)O)O)O.[Na+] DGAQECJNVWCQMB-PUAWFVPOSA-M 0.000 description 1
- GRYLNZFGIOXLOG-UHFFFAOYSA-N Nitric acid Chemical compound O[N+]([O-])=O GRYLNZFGIOXLOG-UHFFFAOYSA-N 0.000 description 1
- 239000004698 Polyethylene Substances 0.000 description 1
- ZLMJMSJWJFRBEC-UHFFFAOYSA-N Potassium Chemical compound [K] ZLMJMSJWJFRBEC-UHFFFAOYSA-N 0.000 description 1
- DWAQJAXMDSEUJJ-UHFFFAOYSA-M Sodium bisulfite Chemical compound [Na+].OS([O-])=O DWAQJAXMDSEUJJ-UHFFFAOYSA-M 0.000 description 1
- 241000700605 Viruses Species 0.000 description 1
- 239000002253 acid Substances 0.000 description 1
- 230000009471 action Effects 0.000 description 1
- 239000000654 additive Substances 0.000 description 1
- 230000000996 additive effect Effects 0.000 description 1
- 229910052783 alkali metal Inorganic materials 0.000 description 1
- 150000001340 alkali metals Chemical class 0.000 description 1
- 229910052784 alkaline earth metal Inorganic materials 0.000 description 1
- 150000001342 alkaline earth metals Chemical class 0.000 description 1
- 230000004075 alteration Effects 0.000 description 1
- 230000003373 anti-fouling effect Effects 0.000 description 1
- 235000010323 ascorbic acid Nutrition 0.000 description 1
- 229960005070 ascorbic acid Drugs 0.000 description 1
- 239000011668 ascorbic acid Substances 0.000 description 1
- 239000002585 base Substances 0.000 description 1
- 230000000903 blocking effect Effects 0.000 description 1
- 229920002301 cellulose acetate Polymers 0.000 description 1
- 230000008859 change Effects 0.000 description 1
- 239000002738 chelating agent Substances 0.000 description 1
- 238000004891 communication Methods 0.000 description 1
- 230000000052 comparative effect Effects 0.000 description 1
- 150000001875 compounds Chemical class 0.000 description 1
- 239000012141 concentrate Substances 0.000 description 1
- 238000010612 desalination reaction Methods 0.000 description 1
- 238000000502 dialysis Methods 0.000 description 1
- 238000004090 dissolution Methods 0.000 description 1
- GRWZHXKQBITJKP-UHFFFAOYSA-L dithionite(2-) Chemical compound [O-]S(=O)S([O-])=O GRWZHXKQBITJKP-UHFFFAOYSA-L 0.000 description 1
- 239000004744 fabric Substances 0.000 description 1
- 238000009472 formulation Methods 0.000 description 1
- 229940093915 gynecological organic acid Drugs 0.000 description 1
- 150000004679 hydroxides Chemical class 0.000 description 1
- 239000012535 impurity Substances 0.000 description 1
- 238000011065 in-situ storage Methods 0.000 description 1
- 150000007529 inorganic bases Chemical class 0.000 description 1
- 238000011835 investigation Methods 0.000 description 1
- NQXWGWZJXJUMQB-UHFFFAOYSA-K iron trichloride hexahydrate Chemical compound O.O.O.O.O.O.[Cl-].Cl[Fe+]Cl NQXWGWZJXJUMQB-UHFFFAOYSA-K 0.000 description 1
- JEIPFZHSYJVQDO-UHFFFAOYSA-N iron(III) oxide Inorganic materials O=[Fe]O[Fe]=O JEIPFZHSYJVQDO-UHFFFAOYSA-N 0.000 description 1
- 230000002427 irreversible effect Effects 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- 238000009285 membrane fouling Methods 0.000 description 1
- 229910017604 nitric acid Inorganic materials 0.000 description 1
- 235000005985 organic acids Nutrition 0.000 description 1
- 150000002894 organic compounds Chemical class 0.000 description 1
- 239000007800 oxidant agent Substances 0.000 description 1
- 238000000614 phase inversion technique Methods 0.000 description 1
- 229920002492 poly(sulfone) Polymers 0.000 description 1
- 229920000573 polyethylene Polymers 0.000 description 1
- 230000036619 pore blockages Effects 0.000 description 1
- 229910052700 potassium Inorganic materials 0.000 description 1
- 239000011591 potassium Substances 0.000 description 1
- 238000004382 potting Methods 0.000 description 1
- 238000000746 purification Methods 0.000 description 1
- 230000004044 response Effects 0.000 description 1
- 150000003839 salts Chemical class 0.000 description 1
- 229910052708 sodium Inorganic materials 0.000 description 1
- 239000011734 sodium Substances 0.000 description 1
- 235000010267 sodium hydrogen sulphite Nutrition 0.000 description 1
- 239000007787 solid Substances 0.000 description 1
- 239000011343 solid material Substances 0.000 description 1
- 238000005063 solubilization Methods 0.000 description 1
- 230000007928 solubilization Effects 0.000 description 1
- 238000010561 standard procedure Methods 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 239000000725 suspension Substances 0.000 description 1
- 230000002195 synergetic effect Effects 0.000 description 1
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
- B01D61/00—Processes of separation using semi-permeable membranes, e.g. dialysis, osmosis or ultrafiltration; Apparatus, accessories or auxiliary operations specially adapted therefor
- B01D61/14—Ultrafiltration; Microfiltration
- B01D61/145—Ultrafiltration
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D61/00—Processes of separation using semi-permeable membranes, e.g. dialysis, osmosis or ultrafiltration; Apparatus, accessories or auxiliary operations specially adapted therefor
- B01D61/14—Ultrafiltration; Microfiltration
- B01D61/147—Microfiltration
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D61/00—Processes of separation using semi-permeable membranes, e.g. dialysis, osmosis or ultrafiltration; Apparatus, accessories or auxiliary operations specially adapted therefor
- B01D61/14—Ultrafiltration; Microfiltration
- B01D61/16—Feed pretreatment
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D71/00—Semi-permeable membranes for separation processes or apparatus characterised by the material; Manufacturing processes specially adapted therefor
- B01D71/06—Organic material
- B01D71/30—Polyalkenyl halides
- B01D71/32—Polyalkenyl halides containing fluorine atoms
- B01D71/34—Polyvinylidene fluoride
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D2311/00—Details relating to membrane separation process operations and control
- B01D2311/04—Specific process operations in the feed stream; Feed pretreatment
-
- 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
- B01D2321/04—Backflushing
-
- 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
-
- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F1/00—Treatment of water, waste water, or sewage
- C02F1/44—Treatment of water, waste water, or sewage by dialysis, osmosis or reverse osmosis
- C02F1/444—Treatment of water, waste water, or sewage by dialysis, osmosis or reverse osmosis by ultrafiltration or microfiltration
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02A—TECHNOLOGIES FOR ADAPTATION TO CLIMATE CHANGE
- Y02A20/00—Water conservation; Efficient water supply; Efficient water use
- Y02A20/124—Water desalination
- Y02A20/131—Reverse-osmosis
Definitions
- the present invention relates a method for cleaning polymeric microfiltration membranes and membrane units, and to compositions useful in such methods.
- Synthetic membranes are used for a variety of applications including desalination, gas separation, filtration, and dialysis.
- the properties of the membranes vary depending on the morphology of the membrane, i.e. properties such as symmetry, pore shape, and pore size, and the polymeric material used to form the membrane.
- MF and UF processes are carried out under differential pressure and are distinguished by the size of the particle or molecule that the membrane is capable of retaining or passing.
- MF can remove very fine colloidal particles in the micrometer and sub micrometer range. As a general rule, it can filter particles down to 0.1 ⁇ m, whereas ultrafiltration can retain particles as small as 0.01 ⁇ m and smaller.
- Reverse osmosis operates on an even smaller scale.
- the pore size of the membrane decreases and the pressure required to carry out the separation accordingly increases.
- a large surface area is generally needed when a large filtrate flow is required.
- One known technique to make a filtration apparatus more compact is to form a membrane in the shape of a hollow porous fiber. Modules of such fibers can be made with an extremely large surface area per unit volume. Microporous synthetic membranes are particularly suitable for use in hollow fibers and are typically produced by phase inversion techniques.
- Microporous phase inversion membranes are particularly well suited to the application of removal of colloidal suspensions, viruses, and bacteria.
- the hollow fiber membrane contains the largest membrane area per unit volume.
- UF and MF membranes are used in separating particles and colloidal matter from liquids.
- water containing solutes and precipitates is passed through a bank of semipermeable tubular membranes housed in a module, often at elevated pressures.
- the filtered water is drawn off and collected, leaving a residue of solid material in the membrane pores or on the unfiltered side of the membrane.
- the pores of the membrane be kept relatively free of contaminants. As the amount of pore blockage increases, the filtration efficiency of the module decreases and the amount of pressure required to maintain a viable throughput of liquid increases. As pressure increases, the likelihood of membrane rupture becomes more significant.
- flocculating agents are to cause dispersed colloids to coagulate and form ‘flocs’.
- Flocs have the advantage of entrapping smaller colloidal particles, thereby making filtration more efficient. They may also aid in the removal of dissolved particles. Under the influence of a flocculating agent, dissolved and suspended particles coagulate and precipitate from the water, thereby removing color, and turbidity.
- the filtrate containing the flocculating agents, colloids, bacteria and other particulate matter is passed through the filtration unit under pressure, expelling filtered water and leaving the floc trapped within the unit, and more particularly on the waste side of the membrane and in the pores of the membrane. Flocs are particularly problematical in causing membrane blockage, and membrane performance gradually diminishes with use until it becomes necessary to clean the membranes.
- Residual material accumulating in and on the membrane is often removed by ‘backwashing’, that is, running the current of water counter to its normal direction of flow to dislodge the contaminants from the membrane. Gas backwashing of the membrane is also possible.
- Backwashing generally involves increasing the pressure on both sides of the hollow fibers within a module a relatively high value before suddenly releasing that pressure on the unfiltered side of the membrane walls to cause a sudden pressure differential across the walls, which causes a backwash action.
- the membranes may be de-fouled by more conventional cleaning regimes such as solution treatment with one or more of (and usually in a sequential manner) citric acid, oxidizing agents, in particular chlorine, and chelating agents such as EDTA.
- solution treatment with one or more of (and usually in a sequential manner) citric acid, oxidizing agents, in particular chlorine, and chelating agents such as EDTA.
- Citric acid is usually regarded as a satisfactory cleaning agent, however, even it does not provide ideal levels of cleaning, and the membrane performance diminishes even following regular use/cleaning cycles. Moreover, the cleaning process usually involves a number of steps, and one or more of the steps may need to be conducted for long periods of time. Temperature control is also usually required.
- Inorganic acids and bases are the mainstay of conventional cleaning agents. As well as suffering from the drawbacks mentioned above, these agents present their own problems because they may chemically attack the membranes and/or module components. Combinations of an aqueous inorganic acid, generally nitric acid, and a reducing agent, e.g., ascorbic acid, have also been used. However, none of the above regimes sufficiently de-foul membranes, particularly PVDF membranes, of the floc. Hence, there exists the need to improve the cleaning regime while at the same time avoiding the use of potentially severe cleaning agents.
- a method of cleaning a membrane contaminated with a contaminant including the step of contacting the contaminant with a composition including at least one soluble sulfite reducing agent and a compatible solvent.
- sulfite as used herein is used in its broadest general sense and includes, without limitation, sulfite, bisulfite, metabisulfite, hydrosulfite, and the like.
- the membrane is of a hollow fiber configuration, although alternatively it may be a flat sheet membrane or other membrane configuration.
- the membrane is formed from PVDF (polyvinylidene fluoride) polymer, although the methods of the preferred embodiments are applicable to polysulfone, polyethylene, polypropylene, polyacrylonitrile (PAN), fluorinated membranes, cellulose acetate membranes and the like and mixtures of the above, as well as all commonly used membrane polymers.
- PVDF polyvinylidene fluoride
- the soluble sulfite reducing agent is sodium metabisulfite, sodium hydrosulfite, sodium sulfite or mixtures thereof. Most preferably, a mixture of sodium metabisulfite and sodium hydrosulfite is used.
- the solvent is preferably water. However any suitable solvent that is compatible with the materials comprising the membrane and is a suitable solvent for the sulfite may also be employed.
- the sodium metabisulfite and sodium hydrosulfite are present in an amount of 20 wt. % to 65 wt. % each, when used alone or in combination. This combination may be used neat or further diluted when in use, for example, to around 0.5 wt. %. Dilutions of about 2 wt. % are particularly preferred. However, any suitable dilution may be employed.
- the contaminant is believed to be removed by solubilization resulting from a reduction to a lower valence state of at least a part of the contaminant.
- the method reduces the cleaning time relative to known cleaning methods and is carried out at low or ambient temperatures.
- a method of cleaning a membrane contaminated with a contaminant including the step of contacting the contaminant with a composition including a sulfite reducing agent and a solvent, wherein the sulfite reducing agent is soluble in the solvent, and wherein the solvent is compatible with the membrane.
- the contaminant includes a metal oxide or a metal hydroxide.
- the contaminant includes ferric floc.
- the contaminant includes an organic compound.
- the solvent includes water.
- the sulfite reducing agent includes sodium metabisulfite, sodium hydrosulfite, sodium sulfite, potassium metabisulfite, potassium hydrosulfite, potassium sulfite, or mixtures thereof.
- method further includes the step of reducing a valence state of an atom of the contaminant to a lower valence state, whereby the contaminant is solublized and removed from the membrane.
- the composition further includes an enhancing agent.
- the enhancing agent includes inorganic acids, organic acids, or mixtures thereof.
- the enhancing agent includes citric acid.
- the solvent includes water and the sulfite reducing agent includes sodium metabisulfite, sodium hydrosulfite, or mixtures thereof.
- the sulfite reducing agent includes from about 0.1 wt. % to about 5 wt. % of a component including sodium metabisulfite, sodium hydrosulfite, or mixtures thereof.
- the sulfite reducing agent includes from about 0.5 wt. % to about 2 wt. % of a component including sodium metabisulfite, sodium hydrosulfite, or mixtures thereof.
- the composition includes from about 0.5 wt. % to about 1.5 wt. % sodium metabisulfite and from about 0.5 wt. % to about 1.5 wt. % sodium hydrosulfite.
- the membrane includes a hollow fiber microfiltration membrane or a hollow fiber ultrafiltration membrane.
- the membrane includes a flat microfiltration membrane or a flat ultrafiltration membrane.
- the membrane includes a polyvinylidene fluoride polymer.
- a composition for cleaning a membrane contaminated with a contaminant including a sulfite reducing agent and a solvent, wherein the sulfite reducing agent is soluble in the solvent, and wherein the solvent is compatible with the membrane.
- the contaminant includes a metal oxide or a metal hydroxide.
- the contaminant is ferric floc.
- the sulfite reducing agent includes sodium metabisulfite, sodium hydrosulfite, sodium sulfite, potassium metabisulfite, potassium hydrosulfite, potassium sulfite, or mixtures thereof.
- the sulfite reducing agent includes sodium metabisulfite and sodium hydrosulfite.
- the composition further includes an enhancing agent.
- the enhancing agent includes an inorganic acid or an organic acid.
- the organic acid includes citric acid.
- the sulfite reducing agent includes from about 20 wt. % to about 60 wt. % sodium metabisulfite, wherein the sulfite reducing agent is capable of dilution to a working concentration of about 0.5 wt. % to about 2 wt. % of sulfite reducing agent in a solubilized form.
- the sulfite reducing agent includes from about 0.5 wt. % to about 2 wt. % sodium metabisulfite.
- the sulfite reducing agent includes from about 20 wt. % to about 65 wt. % sodium hydrosulfite, and wherein the sulfite reducing agent is capable of dilution to a working concentration of about 0.5 wt. % to about 2 wt. % soluble sulfite reducing agent present in solubilized form.
- the sulfite reducing agent includes from about 0.5 wt. % to about 2 wt. % sodium hydrosulfite.
- the composition includes from about 20 wt. % to about 65 wt. % sodium metabisulfite and from about 20 wt. % to about 65 wt. % sodium hydrosulfite, wherein the sodium metabisulfite and sodium hydrosulfite are capable of dilution to a working concentration of about 0.5 wt. % to about 2 wt. % sulfite reducing agent in solubilized form.
- the composition includes from about 0.5 wt. % to about 2 wt. % sodium metabisulfite and sodium hydrosulfite.
- a method for cleaning a membrane including the step of cleaning the membrane using a composition including a sulfite reducing agent and a solvent, wherein the sulfite reducing agent is soluble in the solvent, and wherein the solvent is compatible with the membrane.
- a membrane is provided wherein the membrane is capable of cleaning by a composition including a sulfite reducing agent and a solvent, wherein the sulfite reducing agent is soluble in the solvent, and wherein the solvent is compatible with the membrane.
- a membrane is provided, wherein the membrane is contaminated with a contaminant including a metal oxide or a metal hydroxide, and wherein the membrane is capable of cleaning by a composition including a sulfite reducing agent and a solvent, wherein the sulfite reducing agent is soluble in the solvent, and wherein the solvent is compatible with the membrane.
- the membrane includes a hollow fiber or a flat sheet.
- the membrane includes a polyvinylidene fluoride polymer.
- Ferric chloride is the preferred flocculating agent in water clean-up procedures.
- standard cleaning regimes have not been highly effective in cleaning PVDF membranes of the resultant Fe floc, leading to significant commercial costs associated with ultimate irreversible membrane fouling by metal oxides and/or hydroxides.
- the present inventors have found that the methods of the preferred embodiments are particularly suited for PVDF membranes.
- metabisulfite was used as a cleaning agent on PVDF membranes, there was successful removal of metal oxides and metal hydroxides.
- This material may be used neat, although it is possible to use it diluted in an amount such that the dilution is as low as 0.5 wt. %, although dilutions of around 2 wt. % have been found advantageous.
- standardized solutions may be prepared from the starting materials. While the exact concentration will be selected depending on the time limits set for the membrane cleaning and on cost considerations, it has been found particularly useful to use solutions of around 2 wt. %/volume total sulfite content based on the starting materials, i.e. 2 g sodium metabisulfite per 100 ml of water, or 1 g sodium bisulfite and 1 g of sodium hydrosulfite per 100 ml of water, and the like.
- ferric floc applications can be run at the higher flux and the fouled membranes can be quickly and efficiently cleaned.
- the ability to use such high fluxes can translate into a significant commercial advantage.
- CIP cleaning-in-place
- one form of CIP cleaning involves isolating the module to be cleaned by means of taps and pipes and the like from fluid communication with the remainder of the system.
- the water or liquid normally filtered is then replaced with a cleaning fluid.
- the cleaning fluid is then allowed to run through the membrane module to carry out the cleaning.
- the cleaning fluid may be recycled through the module, or allowed to pass through the module just once before being run off to waste, depending upon the particular requirements of the system and the amount of contaminants being removed.
- the CIP procedure can take place at ambient temperatures or at controlled temperatures outside the normal range of filtration temperatures, e.g. at higher temperatures to increase dissolution of solids, or at lower temperatures to allow for a greater concentration of dissolved gaseous agents e.g., especially chlorine gas, in the fluid.
- the CIP can be carried out for varying lengths of time and at pressures outside the normal range of those used for filtration.
- the filtration agent is flushed to remove traces of the cleaning agent before being returned to service by being reconnected to the normal fluid flow.
- CIP can be carried out manually or by means of fully automated systems which activate in response to pressure differentials or after predetermined module operating times.
- the examples given below relate to modules prepared from banks of hollow fiber PVDF membranes.
- the membrane modules are as described in U.S. Pat. No. 6,159,373, the contents of which are incorporated herein by reference.
- the module includes a shell within which is positioned a bundle containing from about 2800 to about 30,000 hollow fibers with a diameter of 500 ⁇ m to 650 ⁇ m and a lumen diameter of 250 ⁇ m to 310 ⁇ m, with a pore size of 0.2 ⁇ m, but these sizes may be varied as required.
- membrane and module configurations different from the one described above may also be employed with the methods of preferred embodiments, as will be appreciated by one skilled in the art.
- a potting compound holds the ends of the fibers in place without blocking the lumens and closes off each end of the module.
- the liquid feed is pumped into the module, between the shell and the outside of the hollow fibers. Some of the feed liquid passes into the lumen of the fibers, being filtered as it does so. The clean liquid then concentrates in the inside of the lumen, and flows, or is drawn off and taken outside the module, as a clarified liquid.
- the cleaning agent is introduced in place of the untreated liquid stream.
- the flow can be introduced counter to that normally used.
- Membranes in a raw water filtration module were cleaned using a 2 wt. % solution of citric acid in water at 35° C., which was recirculated for 60 minutes. Three repeats of a 300 second aeration followed by a 300 second soak were conducted. Then, a solution of 300 ppm Cl in water at 20° C. was recirculated for 60 minutes, followed by a 30 minute soak. The total duration of the CIP was 3 hours.
- Table 1 provides measurements of transmembrane pressure (TMP), resistance (R), and flow (in gallons per minute per module) both before and after the CIP. TABLE 1 BEFORE CIP AFTER CIP TMP Flow TMP Flow (psi) R (gpm/mod) (psi) R (gpm/mod) 8.1 4.27 4.4 3.5 2.21 4.9
- Membranes in a clarified water filtration module were cleaned 400 ppm solution of Cl in water at 20° C., which was recirculated for 60 minutes, followed by a 30 minute soak. Then the membranes were washed with a 2.7 wt. % citric acid solution in water at 35° C., which was recirculated for 60 minutes. Three repeats of a 300 second aeration followed by a 300 second soak were conducted. Then, an overnight soak was conducted. The total duration of the CIP was 13 hours. Table 2 provides measurements of transmembrane pressure, resistance, and flow both before and after the CIP. TABLE 2 BEFORE CIP AFTER CIP TMP Flow TMP Flow (psi) R (gpm/mod) (psi) R (gpm/mod) 11 7.48 4.9 5.9 3.56 4.9
- Membranes in a clarified water filtration module were cleaned using a 1000 ppm solution of Cl in water at 20° C., which was recirculated for 60 minutes, followed by a 30 minute soak. Then the membranes were washed with a 4 wt. % citric acid solution in water at 35° C., which was recirculated for 60 minutes. Three repeats of a 300 second aeration followed by a 300 second soak were conducted. Then, an overnight soak in a 1000 ppm Cl solution in water was conducted. The total duration of the CIP was 13 hours. Table 3 provides measurements of transmembrane pressure, resistance, and flow both before and after the CIP. TABLE 3 BEFORE CIP AFTER CIP TMP Flow TMP Flow (psi) R (gpm/mod) (psi) R (gpm/mod) 10.9 10.61 3.6 5.4 3.34 3.6
- Membranes in a raw water filtration module were cleaned using a solution of 300 ppm Cl in water at 20° C., followed by an overnight soak. Then, the membranes were cleaned with a 2 wt. % citric acid solution in water at 40° C. for two hours. The total duration of the CIP was 13 hours.
- Table 4 provides measurements of transmembrane pressure (TMP), resistance (R), and flow (in gallons per minute per module) both before and after the CIP. TABLE 4 BEFORE CIP AFTER CIP TMP Flow TMP Flow (psi) R (gpm/mod) (psi) R (gpm/mod) 5.58 4.08 3.85 3.5 2.63 3.75
- Sulfite agents such as sodium metabisulfite and SUPER IRON OUT® can also be used in conjunction with other conventional methods, for example, in conjunction with sulfuric acid for cleaning membranes (including polypropylene membranes). In low concentrations, it is believed sodium metabisulfite may act as a sacrificial agent, protecting the membrane from degradation by other cleaning agents.
- the best post-clean fouling rates were also investigated.
- the poorest post-clean fouling rate was found using the conventional chlorine clean.
- the best post clean fouling was found using 2 wt. % citric acid and 2 wt. % SMBS, with the 1.5 wt. % SMBS/0.5 wt. % SHS and 0.5 wt. % SMBS/1.5 wt. % SHS mixtures also performing very well.
- the citric acid gave the lowest permeability recovery.
- Three cleans, 1.5% SMBS+0.5 wt. % SHS, 1 wt. % SMBS+1 wt. % SHS, and 2 wt. % SHS gave the best permeability recoveries.
- the permeability recoveries for the sulfite cleaning agents show that for two specific combinations, 1.5 wt. % SMBS/0.5 wt. % SHS and 1 wt. % SMBS/1 wt. % SHS, the permeability recovery (of 221% and 236%, respectively) was greater than the permeability recovery for either the SMBS or SHS alone, indicating a synergistic relationship between the two.
- the other cleaning combinations are likewise not simply additive, indicating that in combination, the two sulfite cleaning agents may act co-operatively.
- the sulfite cleaning method of the preferred embodiments provided in all cases a good TMP recovery, good permeability recovery and a low rate of post clean fouling.
- the all round performance was not matched by conventional cleaning methodologies.
- sulfite cleaning required less time to achieve CIP (cleaning in place) de-fouling of membranes than conventional (chlorine) membrane cleans.
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Abstract
The present invention relates a method for cleaning polymeric microfiltration membranes and membrane units, and to compositions useful in such methods. The compositions include at least one soluble sulfite reducing agent and a compatible solvent.
Description
- This application claims the benefit of U.S. Provisional Application No. 60/333,828, filed Nov. 16, 2001.
- The present invention relates a method for cleaning polymeric microfiltration membranes and membrane units, and to compositions useful in such methods.
- Synthetic membranes are used for a variety of applications including desalination, gas separation, filtration, and dialysis. The properties of the membranes vary depending on the morphology of the membrane, i.e. properties such as symmetry, pore shape, and pore size, and the polymeric material used to form the membrane.
- Different membranes can be used for specific separation processes, including microfiltration (MF), ultrafiltration (UF), and reverse osmosis. MF and UF processes are carried out under differential pressure and are distinguished by the size of the particle or molecule that the membrane is capable of retaining or passing. MF can remove very fine colloidal particles in the micrometer and sub micrometer range. As a general rule, it can filter particles down to 0.1 μm, whereas ultrafiltration can retain particles as small as 0.01 μm and smaller. Reverse osmosis operates on an even smaller scale.
- As the size of the particles to be separated decreases, the pore size of the membrane decreases and the pressure required to carry out the separation accordingly increases.
- A large surface area is generally needed when a large filtrate flow is required. One known technique to make a filtration apparatus more compact is to form a membrane in the shape of a hollow porous fiber. Modules of such fibers can be made with an extremely large surface area per unit volume. Microporous synthetic membranes are particularly suitable for use in hollow fibers and are typically produced by phase inversion techniques.
- Microporous phase inversion membranes are particularly well suited to the application of removal of colloidal suspensions, viruses, and bacteria. Of all types of membranes, the hollow fiber membrane contains the largest membrane area per unit volume.
- UF and MF membranes are used in separating particles and colloidal matter from liquids. In a typical scenario, water containing solutes and precipitates is passed through a bank of semipermeable tubular membranes housed in a module, often at elevated pressures. The filtered water is drawn off and collected, leaving a residue of solid material in the membrane pores or on the unfiltered side of the membrane.
- It is preferred that the pores of the membrane be kept relatively free of contaminants. As the amount of pore blockage increases, the filtration efficiency of the module decreases and the amount of pressure required to maintain a viable throughput of liquid increases. As pressure increases, the likelihood of membrane rupture becomes more significant.
- Under some circumstances, it may be desirable to treat water containing impurities with a flocculating agent prior to filtration. The purpose of flocculating agents is to cause dispersed colloids to coagulate and form ‘flocs’. Flocs have the advantage of entrapping smaller colloidal particles, thereby making filtration more efficient. They may also aid in the removal of dissolved particles. Under the influence of a flocculating agent, dissolved and suspended particles coagulate and precipitate from the water, thereby removing color, and turbidity.
- Thus, in practice, the filtrate containing the flocculating agents, colloids, bacteria and other particulate matter is passed through the filtration unit under pressure, expelling filtered water and leaving the floc trapped within the unit, and more particularly on the waste side of the membrane and in the pores of the membrane. Flocs are particularly problematical in causing membrane blockage, and membrane performance gradually diminishes with use until it becomes necessary to clean the membranes.
- One of the most commonly employed flocculating agents in the water purification field is ferric chloride, and the resultant floc is known as Fe floc. Build-up of Fe floc leads to iron fouling and eventually results in membrane performance degradation that diminishes the lifetime of these high cost membrane units. Two of the most widely used membrane compositions, polypropylene (PP) and polyvinylidene fluoride (PVDF), foul irreversibly with Fe floc and can become useless.
- Residual material accumulating in and on the membrane is often removed by ‘backwashing’, that is, running the current of water counter to its normal direction of flow to dislodge the contaminants from the membrane. Gas backwashing of the membrane is also possible.
- Backwashing generally involves increasing the pressure on both sides of the hollow fibers within a module a relatively high value before suddenly releasing that pressure on the unfiltered side of the membrane walls to cause a sudden pressure differential across the walls, which causes a backwash action. However, it is difficult to achieve complete removal of particulate matter, especially when flocculants have been used.
- In addition to backwashing, the membranes may be de-fouled by more conventional cleaning regimes such as solution treatment with one or more of (and usually in a sequential manner) citric acid, oxidizing agents, in particular chlorine, and chelating agents such as EDTA.
- Citric acid is usually regarded as a satisfactory cleaning agent, however, even it does not provide ideal levels of cleaning, and the membrane performance diminishes even following regular use/cleaning cycles. Moreover, the cleaning process usually involves a number of steps, and one or more of the steps may need to be conducted for long periods of time. Temperature control is also usually required.
- Inorganic acids and bases are the mainstay of conventional cleaning agents. As well as suffering from the drawbacks mentioned above, these agents present their own problems because they may chemically attack the membranes and/or module components. Combinations of an aqueous inorganic acid, generally nitric acid, and a reducing agent, e.g., ascorbic acid, have also been used. However, none of the above regimes sufficiently de-foul membranes, particularly PVDF membranes, of the floc. Hence, there exists the need to improve the cleaning regime while at the same time avoiding the use of potentially severe cleaning agents.
- It is desirable to overcome or ameliorate at least one of the disadvantages of the prior art methods of de-fouling membranes, to provide a useful alternative to conventional methods of de-fouling membranes, or to provide suitable compositions for use in cleaning or de-fouling membranes.
- In a preferred embodiment, there is provided a method of cleaning a membrane contaminated with a contaminant including the step of contacting the contaminant with a composition including at least one soluble sulfite reducing agent and a compatible solvent. The term sulfite as used herein is used in its broadest general sense and includes, without limitation, sulfite, bisulfite, metabisulfite, hydrosulfite, and the like.
- Preferably the membrane is of a hollow fiber configuration, although alternatively it may be a flat sheet membrane or other membrane configuration. In highly preferred embodiments, the membrane is formed from PVDF (polyvinylidene fluoride) polymer, although the methods of the preferred embodiments are applicable to polysulfone, polyethylene, polypropylene, polyacrylonitrile (PAN), fluorinated membranes, cellulose acetate membranes and the like and mixtures of the above, as well as all commonly used membrane polymers.
- Preferably, the soluble sulfite reducing agent is sodium metabisulfite, sodium hydrosulfite, sodium sulfite or mixtures thereof. Most preferably, a mixture of sodium metabisulfite and sodium hydrosulfite is used. Those skilled in the art will appreciate that, for instance, besides sodium, other soluble salts such as potassium or other alkali metals or alkaline earth metals may be used. The solvent is preferably water. However any suitable solvent that is compatible with the materials comprising the membrane and is a suitable solvent for the sulfite may also be employed.
- It is also preferred that the sodium metabisulfite and sodium hydrosulfite are present in an amount of 20 wt. % to 65 wt. % each, when used alone or in combination. This combination may be used neat or further diluted when in use, for example, to around 0.5 wt. %. Dilutions of about 2 wt. % are particularly preferred. However, any suitable dilution may be employed.
- Preferably, and without wishing to be bound by any particular theory, the contaminant is believed to be removed by solubilization resulting from a reduction to a lower valence state of at least a part of the contaminant.
- Preferably, the method reduces the cleaning time relative to known cleaning methods and is carried out at low or ambient temperatures.
- Accordingly, in a first embodiment, a method of cleaning a membrane contaminated with a contaminant is provided, the method including the step of contacting the contaminant with a composition including a sulfite reducing agent and a solvent, wherein the sulfite reducing agent is soluble in the solvent, and wherein the solvent is compatible with the membrane.
- In an aspect of the first embodiment, the contaminant includes a metal oxide or a metal hydroxide.
- In an aspect of the first embodiment, the contaminant includes ferric floc.
- In an aspect of the first embodiment, the contaminant includes an organic compound.
- In an aspect of the first embodiment, the solvent includes water.
- In an aspect of the first embodiment, the sulfite reducing agent includes sodium metabisulfite, sodium hydrosulfite, sodium sulfite, potassium metabisulfite, potassium hydrosulfite, potassium sulfite, or mixtures thereof.
- In an aspect of the first embodiment, method further includes the step of reducing a valence state of an atom of the contaminant to a lower valence state, whereby the contaminant is solublized and removed from the membrane.
- In an aspect of the first embodiment, the composition further includes an enhancing agent.
- In an aspect of the first embodiment, the enhancing agent includes inorganic acids, organic acids, or mixtures thereof.
- In an aspect of the first embodiment, the enhancing agent includes citric acid.
- In an aspect of the first embodiment, the solvent includes water and the sulfite reducing agent includes sodium metabisulfite, sodium hydrosulfite, or mixtures thereof.
- In an aspect of the first embodiment, the sulfite reducing agent includes from about 0.1 wt. % to about 5 wt. % of a component including sodium metabisulfite, sodium hydrosulfite, or mixtures thereof.
- In an aspect of the first embodiment, the sulfite reducing agent includes from about 0.5 wt. % to about 2 wt. % of a component including sodium metabisulfite, sodium hydrosulfite, or mixtures thereof.
- In an aspect of the first embodiment, the composition includes from about 0.5 wt. % to about 1.5 wt. % sodium metabisulfite and from about 0.5 wt. % to about 1.5 wt. % sodium hydrosulfite.
- In an aspect of the first embodiment, the membrane includes a hollow fiber microfiltration membrane or a hollow fiber ultrafiltration membrane.
- In an aspect of the first embodiment, the membrane includes a flat microfiltration membrane or a flat ultrafiltration membrane.
- In an aspect of the first embodiment, the membrane includes a polyvinylidene fluoride polymer.
- In a second embodiment, a composition for cleaning a membrane contaminated with a contaminant is provided, the composition including a sulfite reducing agent and a solvent, wherein the sulfite reducing agent is soluble in the solvent, and wherein the solvent is compatible with the membrane.
- In an aspect of the second embodiment, the contaminant includes a metal oxide or a metal hydroxide.
- In an aspect of the second embodiment, the contaminant is ferric floc.
- In an aspect of the second embodiment, the sulfite reducing agent includes sodium metabisulfite, sodium hydrosulfite, sodium sulfite, potassium metabisulfite, potassium hydrosulfite, potassium sulfite, or mixtures thereof.
- In an aspect of the second embodiment, the sulfite reducing agent includes sodium metabisulfite and sodium hydrosulfite.
- In an aspect of the second embodiment, the composition further includes an enhancing agent.
- In an aspect of the second embodiment, the enhancing agent includes an inorganic acid or an organic acid.
- In an aspect of the second embodiment, the organic acid includes citric acid.
- In an aspect of the second embodiment, the sulfite reducing agent includes from about 20 wt. % to about 60 wt. % sodium metabisulfite, wherein the sulfite reducing agent is capable of dilution to a working concentration of about 0.5 wt. % to about 2 wt. % of sulfite reducing agent in a solubilized form.
- In an aspect of the second embodiment, the sulfite reducing agent includes from about 0.5 wt. % to about 2 wt. % sodium metabisulfite.
- In an aspect of the second embodiment, the sulfite reducing agent includes from about 20 wt. % to about 65 wt. % sodium hydrosulfite, and wherein the sulfite reducing agent is capable of dilution to a working concentration of about 0.5 wt. % to about 2 wt. % soluble sulfite reducing agent present in solubilized form.
- In an aspect of the second embodiment, the sulfite reducing agent includes from about 0.5 wt. % to about 2 wt. % sodium hydrosulfite.
- In an aspect of the second embodiment, the composition includes from about 20 wt. % to about 65 wt. % sodium metabisulfite and from about 20 wt. % to about 65 wt. % sodium hydrosulfite, wherein the sodium metabisulfite and sodium hydrosulfite are capable of dilution to a working concentration of about 0.5 wt. % to about 2 wt. % sulfite reducing agent in solubilized form.
- In an aspect of the second embodiment, the composition includes from about 0.5 wt. % to about 2 wt. % sodium metabisulfite and sodium hydrosulfite.
- In a third embodiment, a method for cleaning a membrane is provided, the method including the step of cleaning the membrane using a composition including a sulfite reducing agent and a solvent, wherein the sulfite reducing agent is soluble in the solvent, and wherein the solvent is compatible with the membrane.
- In a fourth embodiment, a membrane is provided wherein the membrane is capable of cleaning by a composition including a sulfite reducing agent and a solvent, wherein the sulfite reducing agent is soluble in the solvent, and wherein the solvent is compatible with the membrane.
- In a fifth embodiment, a membrane is provided, wherein the membrane is contaminated with a contaminant including a metal oxide or a metal hydroxide, and wherein the membrane is capable of cleaning by a composition including a sulfite reducing agent and a solvent, wherein the sulfite reducing agent is soluble in the solvent, and wherein the solvent is compatible with the membrane.
- In an aspect of the fifth embodiment, the membrane includes a hollow fiber or a flat sheet.
- In an aspect of the fifth embodiment, the membrane includes a polyvinylidene fluoride polymer.
- The following description and examples illustrate a preferred embodiment of the present invention in detail. Those of skill in the art will recognize that there are numerous variations and modifications of this invention that are encompassed by its scope. Accordingly, the description of a preferred embodiment should not be deemed to limit the scope of the present invention.
- Ferric chloride is the preferred flocculating agent in water clean-up procedures. However, standard cleaning regimes have not been highly effective in cleaning PVDF membranes of the resultant Fe floc, leading to significant commercial costs associated with ultimate irreversible membrane fouling by metal oxides and/or hydroxides.
- Surprisingly, the present inventors have found that the methods of the preferred embodiments are particularly suited for PVDF membranes. When metabisulfite was used as a cleaning agent on PVDF membranes, there was successful removal of metal oxides and metal hydroxides.
- More surprisingly, when sodium hydrosulfite and sodium metabisulfite were used in combination as cleaning agents for PVDF membranes, significant antifouling properties were observed.
- One commercial blend of sodium hydrosulfite (20-65 wt. %) and sodium metabisulfite (20-65 wt. %) was found to be particularly useful. This mixture, marketed as SUPER IRON OUT®, has been commercially available since the 1950's, although it has not been used for cleaning membranes. SUPER IRON OUT® has been marketed to household consumers as an all-purpose rust and stain remover, water softener, a cleaning agent for toilets, sinks tubs, dishwashers, white clothing, and fabrics as well as exterior surfaces, i.e. as a general household reductant.
- This material may be used neat, although it is possible to use it diluted in an amount such that the dilution is as low as 0.5 wt. %, although dilutions of around 2 wt. % have been found advantageous.
- Alternatively, standardized solutions may be prepared from the starting materials. While the exact concentration will be selected depending on the time limits set for the membrane cleaning and on cost considerations, it has been found particularly useful to use solutions of around 2 wt. %/volume total sulfite content based on the starting materials, i.e. 2 g sodium metabisulfite per 100 ml of water, or 1 g sodium bisulfite and 1 g of sodium hydrosulfite per 100 ml of water, and the like.
- The commercial importance of this new application is that it allows ferric floc applications to be run at 20 to 30% higher water flux than has previously been thought possible. Using such high fluxes is normally to be avoided because of the extreme fouling that takes place under such conditions, and the resultant difficulty in cleaning badly fouled membranes, wherein the floc is forced hard into the pores and cannot be readily physically removed by backwashing, or by chemical cleaners.
- With the advent of the cleaning method of the preferred embodiments, the ferric floc applications can be run at the higher flux and the fouled membranes can be quickly and efficiently cleaned. The ability to use such high fluxes can translate into a significant commercial advantage.
- As more liquid is filtered, the amount of residue removed from that liquid increases in the pores and on the outside and needs to be cleaned.
- The methods of the preferred embodiments can be used in conjunction with backwashing methodology, or as a stand-alone cleaning method suitable for carrying out “cleaning-in-place” (CIP). CIP involves cleaning the membrane module without removal from its normal in situ place of operation.
- In general terms, one form of CIP cleaning involves isolating the module to be cleaned by means of taps and pipes and the like from fluid communication with the remainder of the system. The water or liquid normally filtered is then replaced with a cleaning fluid. The cleaning fluid is then allowed to run through the membrane module to carry out the cleaning. The cleaning fluid may be recycled through the module, or allowed to pass through the module just once before being run off to waste, depending upon the particular requirements of the system and the amount of contaminants being removed.
- The CIP procedure can take place at ambient temperatures or at controlled temperatures outside the normal range of filtration temperatures, e.g. at higher temperatures to increase dissolution of solids, or at lower temperatures to allow for a greater concentration of dissolved gaseous agents e.g., especially chlorine gas, in the fluid. The CIP can be carried out for varying lengths of time and at pressures outside the normal range of those used for filtration.
- Once the cleaning is completed, the filtration agent is flushed to remove traces of the cleaning agent before being returned to service by being reconnected to the normal fluid flow.
- CIP can be carried out manually or by means of fully automated systems which activate in response to pressure differentials or after predetermined module operating times.
- A preferred embodiment is described below, by way of example only.
- The examples given below relate to modules prepared from banks of hollow fiber PVDF membranes. The membrane modules are as described in U.S. Pat. No. 6,159,373, the contents of which are incorporated herein by reference. The module includes a shell within which is positioned a bundle containing from about 2800 to about 30,000 hollow fibers with a diameter of 500 μm to 650 μm and a lumen diameter of 250 μm to 310 μm, with a pore size of 0.2 μm, but these sizes may be varied as required. Moreover, membrane and module configurations different from the one described above may also be employed with the methods of preferred embodiments, as will be appreciated by one skilled in the art.
- At each end of the fiber bundle, a potting compound holds the ends of the fibers in place without blocking the lumens and closes off each end of the module. The liquid feed is pumped into the module, between the shell and the outside of the hollow fibers. Some of the feed liquid passes into the lumen of the fibers, being filtered as it does so. The clean liquid then concentrates in the inside of the lumen, and flows, or is drawn off and taken outside the module, as a clarified liquid.
- In the CIP method exemplified, the cleaning agent is introduced in place of the untreated liquid stream. However, those skilled in the art will realize that the flow can be introduced counter to that normally used.
- Membranes in a raw water filtration module were cleaned using a 2 wt. % solution of citric acid in water at 35° C., which was recirculated for 60 minutes. Three repeats of a 300 second aeration followed by a 300 second soak were conducted. Then, a solution of 300 ppm Cl in water at 20° C. was recirculated for 60 minutes, followed by a 30 minute soak. The total duration of the CIP was 3 hours. Table 1 provides measurements of transmembrane pressure (TMP), resistance (R), and flow (in gallons per minute per module) both before and after the CIP.
TABLE 1 BEFORE CIP AFTER CIP TMP Flow TMP Flow (psi) R (gpm/mod) (psi) R (gpm/mod) 8.1 4.27 4.4 3.5 2.21 4.9 - Membranes in a clarified water filtration module (containing flocculant) were cleaned 400 ppm solution of Cl in water at 20° C., which was recirculated for 60 minutes, followed by a 30 minute soak. Then the membranes were washed with a 2.7 wt. % citric acid solution in water at 35° C., which was recirculated for 60 minutes. Three repeats of a 300 second aeration followed by a 300 second soak were conducted. Then, an overnight soak was conducted. The total duration of the CIP was 13 hours. Table 2 provides measurements of transmembrane pressure, resistance, and flow both before and after the CIP.
TABLE 2 BEFORE CIP AFTER CIP TMP Flow TMP Flow (psi) R (gpm/mod) (psi) R (gpm/mod) 11 7.48 4.9 5.9 3.56 4.9 - Membranes in a clarified water filtration module (containing flocculant) were cleaned using a 1000 ppm solution of Cl in water at 20° C., which was recirculated for 60 minutes, followed by a 30 minute soak. Then the membranes were washed with a 4 wt. % citric acid solution in water at 35° C., which was recirculated for 60 minutes. Three repeats of a 300 second aeration followed by a 300 second soak were conducted. Then, an overnight soak in a 1000 ppm Cl solution in water was conducted. The total duration of the CIP was 13 hours. Table 3 provides measurements of transmembrane pressure, resistance, and flow both before and after the CIP.
TABLE 3 BEFORE CIP AFTER CIP TMP Flow TMP Flow (psi) R (gpm/mod) (psi) R (gpm/mod) 10.9 10.61 3.6 5.4 3.34 3.6 - Membranes in a raw water filtration module were cleaned using a solution of 300 ppm Cl in water at 20° C., followed by an overnight soak. Then, the membranes were cleaned with a 2 wt. % citric acid solution in water at 40° C. for two hours. The total duration of the CIP was 13 hours. Table 4 provides measurements of transmembrane pressure (TMP), resistance (R), and flow (in gallons per minute per module) both before and after the CIP.
TABLE 4 BEFORE CIP AFTER CIP TMP Flow TMP Flow (psi) R (gpm/mod) (psi) R (gpm/mod) 5.58 4.08 3.85 3.5 2.63 3.75 - Membranes in a clarified water filtration module (containing flocculant) were cleaned using a 2 wt. % solution of SUPER IRON OUT® in water at 20° C. for 30 minutes. Then the membranes were washed with a solution of 1000 ppm Cl in water at 20° C., which was recirculated for 60 minutes, followed by a 30 minute soak. The total duration of the CIP was 2 hours. Table 5 provides measurements of transmembrane pressure, resistance, and flow both before and after the CIP. The data demonstrate a substantial reduction in transmembrane pressure and resistance, and an increase in flow following the cleaning method.
TABLE 5 BEFORE CIP AFTER CIP TMP Flow TMP Flow (psi) R (gpm/mod) (psi) R (gpm/mod) 10.6 7.19 4.8 5 2.8 5.7 - It can be seen from all the above examples that cleaning the membranes, by both conventional methods and by the methods of the preferred embodiments, results in a reduction in transmembrane pressure, a decrease in resistance, and an increase in flow, all indicators that the membrane has been cleaned.
- The results with SUPER IRON OUT® are significantly better than the comparative conventional methods. It enables the highest restoration of flow and the most significant decrease in resistance on cleaning.
- It has also achieved these results at ambient temperatures, and with fewer steps, meaning that the amount of external apparatus required to carry out the CIP of the module is considerably reduced.
- Possibly most significantly, however, it achieved this high level of cleaning in 2 hours for clarified (flocculant-containing) water. To achieve close to this result using the standard methods required overnight CIP times, typically around 13 hours. This dramatic reduction in CIP time translates into a reduction in downtime of modules, as well as allowing higher liquid throughput by permitting effective clean up after running at high flux rates.
- Sulfite agents such as sodium metabisulfite and SUPER IRON OUT® can also be used in conjunction with other conventional methods, for example, in conjunction with sulfuric acid for cleaning membranes (including polypropylene membranes). In low concentrations, it is believed sodium metabisulfite may act as a sacrificial agent, protecting the membrane from degradation by other cleaning agents.
- Further investigations were carried out to better standardize the active amount of sulfite agent present (rather than relying on the broader ranges which may be found in proprietary formulations and to investigate the optimal cleaning compositions, as established by the differing criteria to determine membrane de-fouling.
- Two sets of experiments were carried out to determine the efficiency of sulfite cleaning compositions of precisely defined composition relative to citric acid and chlorine, and measured with reference to different criteria. In both sets of experiments, the membranes were fouled with a mixture of 100 ppm humic acid and 100 ppm FeCl3.6H2O, by filtering this mixture through the membranes.
- In the transmembrane pressure recovery and refouling experiments, the same equipment was used to filter the cleaning solution through the membranes. The TMP change versus time was recorded while filtering this humic acid/iron solution through the membrane before and after the clean. The results are shown in Table 6.
TABLE 6 Fouling Final TMP Initial TMP TMP rate before clean after clean recovery post-clean Clean (kPa) (kPa) (kPa) (kPa/min) 2 wt. % Citric acid 38 18 20 0.07 200 ppm NaOCl 46 21 25 0.6 2 wt. % SHS 60 21 39 0.15 2 wt. % SMBS 36 20 16 0.08 1.5 wt. % SMBS + 31 17 14 0.1 0.5 wt. % SHS 0.5 wt. % SMBS + 39 20 19 0.1 1.5 wt. % SHS 1 wt. % SMBS + 36 20 16 0.3 1 wt. % SHS
SMBS = sodium metabisulfite
SHS = sodium hydrosulfite
- The results in the experiment show that the TMP recoveries were similar for all the cleaning methodologies used except for 2 wt. % sodium hydrosulfite which gave a significantly higher recovery than the other cleaning agents.
- The best post-clean fouling rates were also investigated. The poorest post-clean fouling rate was found using the conventional chlorine clean. The best post clean fouling was found using 2 wt. % citric acid and 2 wt. % SMBS, with the 1.5 wt. % SMBS/0.5 wt. % SHS and 0.5 wt. % SMBS/1.5 wt. % SHS mixtures also performing very well.
- In the second set of experiments, the dirty membranes were placed in jars of the cleaning solution and allowed to soak. The permeability of the fibers was measured before and after the clean. The results are shown in Table 7.
TABLE 7 Permeability Permeability Permeability % before clean after clean recovery Permeability Clean (L/m2 · hour) (L/m2 · hour) (L/m2 · hour) recovery 2 wt. % Citric 589 795 206 135 acid 200 ppm 277 576 299 207 NaOCl 2 wt. % SHS 383 795 412 208 2 wt. % SMBS 454 714 260 157 1.5 wt. % 350 774 424 221 SMBS + 0.5 wt. % SHS 0.5 wt. % 591 835 244 141 SMBS + 1.5 wt. % SHS 1 wt. % 378 824 446 236 SMBS + 1 wt. % SHS
SMBS = sodium metabisulfite
SHS = sodium hydrosulfite
- The citric acid gave the lowest permeability recovery. Three cleans, 1.5% SMBS+0.5 wt. % SHS, 1 wt. % SMBS+1 wt. % SHS, and 2 wt. % SHS gave the best permeability recoveries. The permeability recoveries for the sulfite cleaning agents show that for two specific combinations, 1.5 wt. % SMBS/0.5 wt. % SHS and 1 wt. % SMBS/1 wt. % SHS, the permeability recovery (of 221% and 236%, respectively) was greater than the permeability recovery for either the SMBS or SHS alone, indicating a synergistic relationship between the two. On the basis of the individual mixture components, a 1 wt. %: 1 wt. % SMBS/SHS mixture would be expected to restore about 183% (based on 208%/2+157%/2) of the permeability, yet the actual value was 236%.
- The other cleaning combinations are likewise not simply additive, indicating that in combination, the two sulfite cleaning agents may act co-operatively.
- Thus, it can be seen that the sulfite cleaning method of the preferred embodiments provided in all cases a good TMP recovery, good permeability recovery and a low rate of post clean fouling. The all round performance was not matched by conventional cleaning methodologies. Further, sulfite cleaning required less time to achieve CIP (cleaning in place) de-fouling of membranes than conventional (chlorine) membrane cleans.
- The above description discloses several methods and materials of the present invention. This invention is susceptible to modifications in the methods and materials, as well as alterations in the fabrication methods and equipment. Such modifications will become apparent to those skilled in the art from a consideration of this disclosure or practice of the invention disclosed herein. Consequently, it is not intended that this invention be limited to the specific embodiments disclosed herein, but that it cover all modifications and alternatives coming within the true scope and spirit of the invention as embodied in the attached claims. All patents, applications, and other references cited herein are hereby incorporated by reference in their entirety.
Claims (19)
1. A method of cleaning a membrane contaminated with a contaminant, the method comprising the step of:
contacting the contaminant with a composition comprising a sulfite reducing agent and a solvent, wherein the sulfite reducing agent is soluble in the solvent, and wherein the solvent is compatible with the membrane and wherein the contaminant comprises a metal oxide or a metal hydroxide.
2. (canceled)
3. The method according to claim 1 , wherein the contaminant comprises ferric floc.
4-17. (canceled)
18. A composition for cleaning a membrane contaminated with a contaminant, the composition comprising a sulfite reducing agent and a solvent, wherein the sulfite reducing agent is soluble in the solvent, and wherein the solvent is compatible with the membrane and wherein the sulfite reducing agent is selected from the group consisting of sodium metabisulfite, sodium hydrosulfite, sodium sulfite, potassium metabisulfite, potassium hydrosulfite, potassium sulfite, and mixtures thereof.
19-21. (canceled)
22. The composition according to claim 18 , wherein the sulfite reducing agent comprises sodium metabisulfite and sodium hydrosulfite.
23. The composition according to claim 18 , further comprising an enhancing agent.
24-26. (canceled)
27. The composition according to claim 18 , wherein the sulfite reducing agent comprises from about 0.5 wt. % to about 2 wt. % sodium metabisulfite.
28. The composition according to claim 18 , wherein the sulfite reducing agent comprises from about 20 wt. % to about 65 wt. % sodium hydrosulfite, and wherein the sulfite reducing agent is capable of dilution to a working concentration of about 0.5. wt. % to about 2 wt. % soluble sulfite reducing agent present in solubilized form.
29. The composition according to claim 18 , wherein the sulfite reducing agent comprises from about 0.5 wt. % to about 2 wt. % sodium hydrosulfite.
30. The composition according to claim 18 , comprising from about 20 wt. % to about 65 wt. % sodium metabisulfite and from about 20 wt. % to about 65 wt. % sodium hydrosulfite, wherein the sodium metabisulfite and sodium hydrosulfite are capable of dilution to a working concentration of about 0.5 wt. % to about 2 wt. % sulfite reducing agent in solubilized form.
31. The composition according to claim 18 , comprising from about 0.5 wt. % to about 2 wt. % sodium metabisulfite and sodium hydrosulfite.
32. A method for cleaning a membrane, the method comprising the step of:
cleaning the membrane using a composition comprising a sulfite reducing agent and a solvent, wherein the sulfite reducing agent is soluble in the solvent, and wherein the solvent is compatible with the membrane.
33. A membrane, wherein the membrane is capable of cleaning by a composition comprising a sulfite reducing agent and a solvent, wherein the sulfite reducing agent is soluble in the solvent, and wherein the solvent is compatible with the membrane.
34. A membrane, wherein the membrane is contaminated with a contaminant comprising a metal oxide or a metal hydroxide, and wherein the membrane is capable of cleaning by a composition comprising a sulfite reducing agent and a solvent, wherein the sulfite reducing agent is soluble in the solvent, and wherein the solvent is compatible with the membrane.
35. The membrane of claim 32 , wherein the membrane comprises a hollow fiber or a flat sheet.
36. The membrane according to claim 35 , wherein the membrane comprises a polyvinylidene fluoride polymer.
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US11/145,773 US20050224411A1 (en) | 2001-11-16 | 2005-06-06 | Method of cleaning membranes |
US12/130,664 US20080237125A1 (en) | 2001-11-16 | 2008-05-30 | Method of cleaning membranes |
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US33382801P | 2001-11-16 | 2001-11-16 | |
US10/298,471 US6955762B2 (en) | 2001-11-16 | 2002-11-15 | Method of cleaning membranes |
US11/145,773 US20050224411A1 (en) | 2001-11-16 | 2005-06-06 | Method of cleaning membranes |
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US11/145,773 Abandoned US20050224411A1 (en) | 2001-11-16 | 2005-06-06 | Method of cleaning membranes |
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Cited By (1)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
US11117099B2 (en) | 2016-04-19 | 2021-09-14 | Gwinnett County Board of Commissioners | Method of cleaning microfiltration and ultrafiltration membranes |
Also Published As
Publication number | Publication date |
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DE60213184T2 (en) | 2007-06-28 |
EP1312408A2 (en) | 2003-05-21 |
EP1312408A3 (en) | 2003-08-06 |
US6955762B2 (en) | 2005-10-18 |
ATE333318T1 (en) | 2006-08-15 |
US20050218073A1 (en) | 2005-10-06 |
US20040000520A1 (en) | 2004-01-01 |
DE60213184D1 (en) | 2006-08-31 |
US20080237125A1 (en) | 2008-10-02 |
EP1312408B1 (en) | 2006-07-19 |
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