WO2006066319A1 - Cleaning in membrane filtration systems - Google Patents

Cleaning in membrane filtration systems Download PDF

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Publication number
WO2006066319A1
WO2006066319A1 PCT/AU2005/001919 AU2005001919W WO2006066319A1 WO 2006066319 A1 WO2006066319 A1 WO 2006066319A1 AU 2005001919 W AU2005001919 W AU 2005001919W WO 2006066319 A1 WO2006066319 A1 WO 2006066319A1
Authority
WO
WIPO (PCT)
Prior art keywords
membrane
cleaning solution
wall
membranes
cleaning
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.)
Ceased
Application number
PCT/AU2005/001919
Other languages
English (en)
French (fr)
Inventor
Warren Thomas Johnson
Thomas William Beck
Rebecca Yeo
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
Siemens Water Technologies Holding Corp
US Filter Wastewater Group Inc
Original Assignee
US Filter Wastewater Group Inc
Siemens Water Technologies Corp
Priority date (The priority date 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 date listed.)
Filing date
Publication date
Priority claimed from AU2004907391A external-priority patent/AU2004907391A0/en
Priority to CA2591408A priority Critical patent/CA2591408C/en
Priority to AT05818584T priority patent/ATE549076T1/de
Priority to NZ555856A priority patent/NZ555856A/en
Priority to EP05818584A priority patent/EP1835985B1/en
Priority to JP2007547083A priority patent/JP4763718B2/ja
Application filed by US Filter Wastewater Group Inc, Siemens Water Technologies Corp filed Critical US Filter Wastewater Group Inc
Priority to AU2005318930A priority patent/AU2005318930B2/en
Priority to US11/722,411 priority patent/US8496828B2/en
Publication of WO2006066319A1 publication Critical patent/WO2006066319A1/en
Anticipated expiration legal-status Critical
Priority to US13/874,151 priority patent/US20130334136A1/en
Ceased legal-status Critical Current

Links

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
    • B01D63/00—Apparatus in general for separation processes using semi-permeable membranes
    • B01D63/02—Hollow fibre modules
    • 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
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01D—SEPARATION
    • B01D2315/00—Details relating to the membrane module operation
    • B01D2315/06—Submerged-type; Immersion type
    • 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
    • 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
    • B01D2321/162—Use of acids
    • 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
    • B01D2321/164—Use of bases
    • 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

  • the present invention relates to the backwashing of hollow permeable membranes used in membrane filtration systems and, in particular, to an improved method of backwashing and cleaning the hollow permeable membranes.
  • cleaning solutions are often flowed through the membranes and their permeable walls to clean foulants from the membranes. Applying the cleaning solution under pressure assists the removal of foulants from the surface.
  • the typical known cleaning procedure for membranes involves cleaning the membranes in-situ. This procedure adds a set concentration of chemical, commonly 2% citric acid followed by 200 - 1000 ppm sodium hypochlorite, to the membrane in a solution of filtrate. This usually occurs at the start of the two hour cleaning period, after which the cleaning solution is filtered through the membrane and left to soak.
  • chemical commonly 2% citric acid followed by 200 - 1000 ppm sodium hypochlorite
  • the present invention provides a method of cleaning permeable, hollow membranes in an arrangement of the type wherein a pressure differential is applied across the walls of the permeable, hollow membranes immersed in a liquid suspension, said liquid suspension being applied to the outer surface of the porous hollow membranes to induce and sustain filtration through the membrane walls wherein:
  • the method of cleaning comprising the steps of; i) removing, at least partially, liquid from the filtrate side of the membrane; ii) removing, at least partially, liquid from the outer side of the membrane; iii) applying a cleaning solution to the outer side of the membrane; iv) applying a pressure differential across said membrane wall to cause flow of said cleaning solution through said wall from the outer side of the membrane into the membrane lumen to at least partially fill said lumen with cleaning solution; v) isolating the outer side of the membrane; vi) applying a pressurized gas to the filtrate side of the membrane wall to cause flow of the cleaning solution back to the outer side through the membrane wall; vii) accumulating the increased pressure developed on the outer side of the membrane as a result of said flow of cleaning solution; viii) releasing the pressure applied by said pressurised gas to said filtrate side of the membrane wall to cause flow of said cleaning solution through said membrane from the outer side to the filtrate side under the effect of
  • the cleaning solution is a chemical cleaning solution.
  • gas usually air, is applied such that the membrane lumen is substantially drained of cleaning solution.
  • the pressure is
  • step vii) in a gas space provided on the outer side of the membrane wall or alternatively in a bladder arrangement.
  • the differential pressure of step iv) may be provided by applying gas pressure to the outer side of the membrane wall or by applying a vacuum to the filtrate side.
  • the present invention provides a method of cleaning permeable, hollow membranes in an arrangement of the type wherein a pressure differential is applied across the walls of the permeable, hollow membranes immersed in a liquid suspension, said liquid suspension being applied to the outer surface of the porous hollow membranes to induce and sustain filtration through the membrane walls wherein: (a) some of the liquid suspension passes through the walls of the membranes to be drawn off as clarified liquid or permeate from the hollow membrane lumens, and (b) at least some of the solids are retained on or in the hollow membranes or otherwise as suspended solids within the liquid surrounding the membranes, the method of cleaning comprising the steps of; i) applying a cleaning solution to one side of the membrane wall; ii) applying a pressure differential across said membrane wall to cause flow of said cleaning solution through said wall from said one side of the membrane wall to the other side of the membrane wall; iii) applying a reverse pressure differential across said membrane
  • the present invention provides a method of cleaning permeable, hollow membranes in an arrangement of the type wherein a pressure differential is applied across the walls of the permeable, hollow membranes immersed in a liquid suspension, said liquid suspension being applied to the outer surface of the porous hollow membranes to induce and sustain filtration through the membrane walls wherein:
  • the method of cleaning comprising the steps of; i) removing, at least partially, liquid from the filtrate side of the membrane; ii) removing, at least partially, liquid from the outer side of the membrane; iii) applying a cleaning solution to the outer side of the membrane; iv) applying a pressure differential across said membrane wall to cause flow of said cleaning solution through said wall from the outer side of the membrane into the membrane lumen to at least partially fill said lumen with cleaning solution; v) applying a pressure differential across said membrane wall to cause flow of said cleaning solution through said wall from the lumen side of the membrane back to the outer side of the
  • the pressure differential in step v) is produced by applying a pressurized gas to the filtrate side of the membrane wall to cause flow of the cleaning solution back to the outer side through the membrane wall.
  • the cleaning process can be repeated in cycles such that the cleaning solution is alternately moved from one side of the membrane to the other through the membrane wall.
  • the process can be applied to membranes submerged in an open vessel as well as pressurized membrane filtration systems.
  • a method of controlling a chemical clean of a membrane comprising: measuring pH and/or membrane resistance of a membrane for at least a portion of said clean; and ceasing said chemical clean when pH and/or membrane resistance attains
  • a method of controlling a chemical clean of a membrane comprising: measuring pH and/or membrane resistance of a membrane for at least a portion of said clean; measuring elapsed time of the clean; calculating a rate of change of pH with respect to time (dpH/dt) and/or a rate of change of membrane resistance (dR/dt) with respect to time; and ceasing said chemical clean when dpH/dt and/or dR/dt attains a predetermined value.
  • a method of controlling the chemical cleaning of a filtration system comprising the
  • a method of controlling a chemical clean of a membrane comprising: increasing the amount of chemical cleaning agent present during the clean; measuring membrane resistance of a membrane for at least a portion of said clean; ceasing the increase in chemical cleaning agent when membrane resistance attains a predetermined value.
  • the amount of cleaning agent is increased incrementally.
  • the predetermined value approximates a steady-state value of membrane resistance.
  • the membranes are microfiltration or ultrafiltration type membranes.
  • Figure 1a shows a simplified sectional side elevation of a membrane module with a lower portion of the module immersed in a chemical cleaning solution and suction applied to the membrane lumens;
  • Figure 1b shows an enlarged sectional view of the membranes in the indicated region of Figure 1a;
  • Figure 1c shows an enlarged sectional view of the membranes in the indicated region of Figure 1a;
  • Figure 2a shows a simplified sectional side elevation of a membrane module of Figure 1 with a lower portion of the module immersed in a chemical cleaning solution and pressurized gas applied to the membrane lumens;
  • Figure 2b shows an enlarged sectional view of the membranes in the indicated region of Figure 2a;
  • Figure 3a shows a simplified sectional side elevation of a membrane module of Figure 1 with a lower portion of the module immersed in a chemical cleaning solution and suction applied to the membrane lumens;
  • Figure 3b shows an enlarged sectional view of the membranes in the indicated region of Figure 3a;
  • Figure 3c shows an enlarged sectional view of the membranes in the indicated region of Figure 3a
  • Figure 4a shows a simplified sectional side elevation of another embodiment of a membrane module with a lower portion of the module immersed in a chemical cleaning solution and suction applied to the membrane lumens;
  • Figure 4b shows an enlarged sectional view of the membranes in the indicated region of Figure 4a
  • Figure 4c shows an enlarged sectional view of the membranes in the indicated region of Figure 4a;
  • Figure 5a shows a simplified sectional side elevation of the membrane module of Figure 4 with a lower portion of the module immersed in a chemical cleaning solution and pressurized gas applied to the membrane lumens;
  • Figure 5b shows an enlarged sectional view of the membranes in the indicated region of Figure 5a;
  • Figure 6a shows a simplified sectional side elevation of another embodiment of a membrane module with a lower portion of the module immersed in a chemical cleaning solution and suction applied to the membrane lumens;
  • Figure 6b shows an enlarged sectional view of the membranes in the indicated region of Figure 6a;
  • Figure 6c shows an enlarged sectional view of the membranes in the indicated region of Figure 6a;
  • Figure 7a shows a simplified sectional side elevation of the membrane module of Figure 6 with a lower portion of the module immersed in a chemical cleaning solution and pressurized gas applied to the membrane lumens;
  • Figure 7b shows an enlarged sectional view of the membranes in the indicated region of Figure 7a;
  • Figure 8a shows a simplified sectional side elevation of an embodiment of a membrane module in an open vessel with a lower portion of the module immersed in a chemical cleaning solution and suction applied to the membrane lumens;
  • Figure 8b shows an enlarged sectional view of the membranes in the indicated region of Figure 8a;
  • Figure 8c shows an enlarged sectional view of the membranes in the indicated region of Figure 8a
  • Figure 9a shows a simplified sectional side elevation of a membrane module of the embodiment of Figure 8 with a lower portion of the module immersed in a chemical cleaning solution and pressurized gas applied to the membrane lumens;
  • Figure 9b shows an enlarged sectional view of the membranes in the indicated region of Figure 9a;
  • FIG 10 shows a graph of transmembrane pressure (TMP) measured over time for a membrane module of the type illustrated in Figures 8 and 9 undergoing a chemical clean using the method according to the invention
  • Figure 11 shows a graph of membrane resistance measured over time for two types of chemical cleaning process with incremental increases in the volume of chemical cleaning agent added during the cleaning process
  • Figure 12 shows a graph of membrane resistance measured over time with incremental increases in the volume of chemical cleaning agent added during the cleaning process.
  • a membrane module 5 having a plurality of hollow fibre membranes 6.
  • the fibre membranes 6 have their lumens 7 closed at the lower end in a lower pot 8 and open at the upper end through upper pot 9.
  • the module 5 is contained in a vessel 10 having a controllable valve 11 for opening/closing the vessel 10 to atmosphere.
  • Upper pot 8 is connected to a filtrate collection chamber 12 having a port 13.
  • a differential pressure is then applied across the membrane walls 15, in this embodiment by applying a vacuum to port 13, so that the cleaning solution 14 is drawn through the membrane walls 15 (as shown in Figure 1b) and up the membrane lumen 7 until it is, at least partially, filled with cleaning solution.
  • valve 11 is then closed to isolate the vessel 10 while pressurized gas is applied through port 13 to the cleaning solution filling the membrane lumen 7 and displaced through the membrane wall 15 until the lumen 7 is substantially drained of cleaning solution.
  • the transfer of cleaning solution 14 through the membrane wall 15 to the outer side of the membrane 6 results in the pressure within the vessel to increase as the gas space 16 within the vessel 10 is compressed.
  • FIGs 4a to 7b illustrate embodiments of the invention where a bladder arrangement may be used instead of the gas space 16 to accumulate pressure.
  • the operation is similar to that shown in Figure 3a to 3c, however, in this embodiment when the lumen side of the membranes is vented to atmosphere through valve 17, the bladder 16 delivers pressure to the feed side of the vessel 10 forcing the cleaning solution 14 through the membrane wall 15 and along the membrane lumen 7 as best shown in Figures 4b and 4c.
  • pressurising of the lumen/filtrate side is shown.
  • Pressurised gas is applied to the lumen/filtrate side of the membranes 6 by feeding pressurised gas through line 18 and valve 17 to port 13.
  • the pressurised gas causes the cleaning solution within the lumen 7 to flow through the membrane wall 15 to the outer side of the membrane resulting in the pressure within the vessel 10 increasing and being transferred to the bladder 16 connected to the vessel 10 through line 19 and valve 11.
  • Figures 6a to 6c show a similar arrangement to Figures 4a to 4c but in this embodiment the gas pressure is applied to the vessel 10 from an external source, rather than the bladder 16, through line 19 and valve 11. Bladder 16 is used to accumulate pressure on the lumen side of the membranes 6 as shown
  • FIG. 8 and 9 an embodiment of the cleaning process according to the invention is illustrated where the vessel 10 is open to atmosphere.
  • flow of cleaning solution through the membrane wall 15 is provided by alternately applying suction/vacuum or pressure to the lumen side of the membranes 6.
  • the membrane module 5 is again immersed at least partially in chemical cleaning solution 14 and suction is applied to the open ends of the fibre membrane lumens 7.
  • the cleaning solution 14 is drawn through the membrane wall 15 and into the fibre membrane lumen 7.
  • the cleaning solution 14 is then drawn up through the lumen 7 until it is completely filled as shown in Figure 8c.
  • pressurized gas is then applied to the cleaning solution 14 filling the membrane lumen 7 and the cleaning solution is displaced through the membrane wall 15 as previously described.
  • the process illustrated in the embodiments can be repeated in cycles such that cleaning solution is alternatively moved from one side of the membrane wall 15 to the other.
  • This flow of cleaning solution to and from the membrane lumens 7 and well as along their length results in an effective chemical clean of the membrane module 5.
  • Figure 10 shows the results of applying the cleaning regime according to the invention to a membrane module of the type where the vessel 10 is open to atmosphere.
  • the cleaning process was performed as follows:
  • the membrane vessel was filled with filtrate via backfilling from the lumen side to the shell side, with simultaneous chlorine dosing into the filtrate line.
  • the vessel filtrate level was about 30%, with a target volume of cleaning solution (NaOCI) of 30 mL. 2.
  • the filtrate was then recirculated briefly through the system in order to ensure a well-mixed cleaning solution.
  • the lumens were then drained of liquid by 100 kPa air being applied to the filtrate line. This allowed the cleaning solution to diffuse through the pores and down the fibre length, which raised the filtrate vessel level. This step may be ended when the liquid level stops rising.
  • the lumens were then filled with the cleaning solution by using vacuum air applied to the lumen side of the membranes. During this step the level in the filtrate tank dropped as the liquid was pulled into the fibre lumens. This step may be ended when the liquid level stops falling.
  • the data graphed in Figure 10 shows a period when the cleaning regime was performed once every 24 filtration hours for 4 days in succession, with the module operating at 1.7m3/hr with a 30 minute backwash interval.
  • Chlorine in the form of sodium hypochlorite (NaOCI) was used, the average free chlorine concentration during the clean being 100 ppm.
  • Feed water turbidity was between 60 - 90 NTU throughout.
  • TMP transmembrane pressure
  • the resistance value can be monitored during filtrate recirculation.
  • the chemical cleaning solution is recirculated at the start of the clean only, followed by up to 48 hours of soaking of the membranes.
  • the chemical cleaning solution is recirculated for several minutes (for example - 3 minutes) every 15 - 30 minutes during the soak/aeration steps, allowing the membrane resistance to be measured periodically throughout the cleaning process.
  • FIG. 11 shows a graph of resistance value variation of the duration of the cleaning process for two different cleaning regimes using citric (CIP1) and chlorine (CIP2) cleaning agents.
  • the volume of chemical agent begins around 100ml as shown at A resulted in a significant drop in membrane resistance.
  • the amount of chemical agent was further increased as shown at B and C resulting in further decreases in membrane resistance.
  • the membrane resistance change reached substantially a steady state as shown at D and further increases (E) in chemical agent had minimal effect.
  • the volume of chemical agent added can be ceased without adversely affecting the cleaning process and recovery in transmembrane flow. It will be appreciated that using the above measurements it is possible to determine a resistance profile during the cleaning process for a particular membrane arrangement or configuration. The resistance profile can then be used to predict the end of cleaning process time, half-life and reduce chemical use in simultaneous cleans of similar systems. The resistance profile may be further used to determine whether chemicals are required to be added during the cleaning process with the type and amount of chemical being dependent on feed and foulant quality.
  • Typical cleaning solutions which may be used include acids, caustic solutions and oxidizing solutions (e.g. chlorine).
  • Th ⁇ invention may be embodied in a similar apparatus to that described in the aforementioned International Application No. WO93/02779 appropriately modified to operate in accordance with the inventive method.

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  • Chemical & Material Sciences (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Life Sciences & Earth Sciences (AREA)
  • Hydrology & Water Resources (AREA)
  • Engineering & Computer Science (AREA)
  • Environmental & Geological Engineering (AREA)
  • Water Supply & Treatment (AREA)
  • Organic Chemistry (AREA)
  • Separation Using Semi-Permeable Membranes (AREA)
  • Toys (AREA)
PCT/AU2005/001919 2004-12-24 2005-12-19 Cleaning in membrane filtration systems Ceased WO2006066319A1 (en)

Priority Applications (8)

Application Number Priority Date Filing Date Title
US11/722,411 US8496828B2 (en) 2004-12-24 2005-12-19 Cleaning in membrane filtration systems
AT05818584T ATE549076T1 (de) 2004-12-24 2005-12-19 Reinigung in membranfiltrationssystemen
NZ555856A NZ555856A (en) 2004-12-24 2005-12-19 Cleaning in membrane filtration systems
EP05818584A EP1835985B1 (en) 2004-12-24 2005-12-19 Cleaning in membrane filtration systems
JP2007547083A JP4763718B2 (ja) 2004-12-24 2005-12-19 膜濾過システムの洗浄
CA2591408A CA2591408C (en) 2004-12-24 2005-12-19 Cleaning in membrane filtration systems
AU2005318930A AU2005318930B2 (en) 2004-12-24 2005-12-19 Cleaning in membrane filtration systems
US13/874,151 US20130334136A1 (en) 2004-12-24 2013-04-30 Cleaning in membrane filtration systems

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
AU2004907391A AU2004907391A0 (en) 2004-12-24 Cleaning in membrane filtration systems
AU2004907391 2004-12-24

Related Child Applications (1)

Application Number Title Priority Date Filing Date
US13/874,151 Division US20130334136A1 (en) 2004-12-24 2013-04-30 Cleaning in membrane filtration systems

Publications (1)

Publication Number Publication Date
WO2006066319A1 true WO2006066319A1 (en) 2006-06-29

Family

ID=36601255

Family Applications (1)

Application Number Title Priority Date Filing Date
PCT/AU2005/001919 Ceased WO2006066319A1 (en) 2004-12-24 2005-12-19 Cleaning in membrane filtration systems

Country Status (10)

Country Link
US (2) US8496828B2 (enExample)
EP (2) EP1835985B1 (enExample)
JP (2) JP4763718B2 (enExample)
CN (2) CN100548451C (enExample)
AT (1) ATE549076T1 (enExample)
AU (1) AU2005318930B2 (enExample)
CA (1) CA2591408C (enExample)
NZ (2) NZ583228A (enExample)
SG (2) SG150505A1 (enExample)
WO (1) WO2006066319A1 (enExample)

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WO2010121628A1 (de) * 2009-03-31 2010-10-28 Inge Watertechnologies Ag Rückspülbares filtrationsmodul sowie filtrationsanlage zur reinigung von partikelbehafteten flüssigkeiten
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