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WO1999006817A1 - Procede de controle qualite de membranes - Google Patents

Procede de controle qualite de membranes Download PDF

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Publication number
WO1999006817A1
WO1999006817A1 PCT/EP1998/004565 EP9804565W WO9906817A1 WO 1999006817 A1 WO1999006817 A1 WO 1999006817A1 EP 9804565 W EP9804565 W EP 9804565W WO 9906817 A1 WO9906817 A1 WO 9906817A1
Authority
WO
WIPO (PCT)
Prior art keywords
membrane
membranes
test solution
retention
quality
Prior art date
Application number
PCT/EP1998/004565
Other languages
German (de)
English (en)
Inventor
Thomas Tyborski
Ralf Krack
Original Assignee
Henkel-Ecolab Gmbh & Co. Ohg
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
Application filed by Henkel-Ecolab Gmbh & Co. Ohg filed Critical Henkel-Ecolab Gmbh & Co. Ohg
Priority to AU87322/98A priority Critical patent/AU8732298A/en
Priority to EP98938695A priority patent/EP1000339A1/fr
Publication of WO1999006817A1 publication Critical patent/WO1999006817A1/fr

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
    • B01D65/10—Testing of membranes or membrane apparatus; Detecting or repairing leaks
    • 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
    • B01D65/10—Testing of membranes or membrane apparatus; Detecting or repairing leaks
    • B01D65/109—Testing of membrane fouling or clogging, e.g. amount or affinity
    • G—PHYSICS
    • G01—MEASURING; TESTING
    • G01N—INVESTIGATING OR ANALYSING MATERIALS BY DETERMINING THEIR CHEMICAL OR PHYSICAL PROPERTIES
    • G01N15/00—Investigating characteristics of particles; Investigating permeability, pore-volume or surface-area of porous materials
    • G01N15/08—Investigating permeability, pore-volume, or surface area of porous materials
    • G01N15/082—Investigating permeability by forcing a fluid through a sample
    • G01N15/0826—Investigating permeability by forcing a fluid through a sample and measuring fluid flow rate, i.e. permeation rate or pressure change
    • G—PHYSICS
    • G01—MEASURING; TESTING
    • G01N—INVESTIGATING OR ANALYSING MATERIALS BY DETERMINING THEIR CHEMICAL OR PHYSICAL PROPERTIES
    • G01N15/00—Investigating characteristics of particles; Investigating permeability, pore-volume or surface-area of porous materials
    • G01N15/08—Investigating permeability, pore-volume, or surface area of porous materials
    • G01N2015/086—Investigating permeability, pore-volume, or surface area of porous materials of films, membranes or pellicules

Definitions

  • membrane filtration For the selective separation of substances of different particle sizes from solutions, membrane filtration has developed into a widespread method in the past three decades due to its environmentally friendly and energy-saving procedure.
  • the membrane filters used in this process are thin, film-like and microporous separating layers that are permeable to certain molecular sizes, while they retain substances that exceed this size (or a certain molecular weight).
  • the filters have a foam-like network structure with cavities.
  • cellulose derivatives, polyamides, polyvinyl chloride, polysulfones and Teflon are used as the material for the approximately 50 to 250 ⁇ m thin membranes of the membrane filters.
  • inorganic membranes made of aluminum oxide, carbon fibers or zirconium oxide have also been used since the late 80s.
  • Technically relevant processes in which membranes are used include, for example, micro and ultrafiltration, reverse osmosis, electrodialysis and pervaporation. The first two methods, which are also the most technically relevant, differ in the size of the particles to be separated. While microfiltration is a process for separating colloidal or suspended particles with particle sizes between 0.1 and 10 ⁇ m, i.e.
  • ultrafiltration is a method for separating molecules (especially macromolecules) from solutions.
  • the particle sizes that are retained by ultrafiltration membranes are in the order of 0.001 to 0.1 ⁇ m, corresponding to molecular weights of 10 3 to 2D 10 6 daltons.
  • Such micro and ultrafiltration membrane systems are used on an industrial scale in a wide variety of areas, for example in whey processing (concentration of dairy proteins), beer filtration, water treatment (recovery of valuable substances, process wastewater treatment), in the pharmaceutical industry (separation problems, separation of pyrogens, Extraction of ultrapure water), in the concentration of juices and in medicine (hemodialysis on the "artificial kidney”).
  • the flow rate corresponds to the actual amount of liquid that penetrates through the membrane wall.
  • the cut off corresponds to the retention rate or separation limit in g / mol specified by the membrane manufacturer.
  • Gas or water flow through the membranes is measured to detect leaks or membrane damage. This method only provides very rough information that is difficult to evaluate.
  • Monodisperse macromolecules (colloidal particles of uniform size) are retained by the membrane to be checked. About retention membrane damage (leaks or blockages, e.g. due to the formation of deposits) should be recognized. The test conditions and results are not transferable to membranes of the same type. There is a risk that a non-removable monomolecular layer of these colloidal particles will form on the membrane surfaces. In addition, the test substances are very expensive and can only be detected with great analytical effort (GC-MS, HPLC, DC). Polyethylene glycol (PEG) fractions are retained by the membranes, and statements about the membrane damage can in turn be made via the retention capacity. The method using the PEG fractions is mainly used to determine comparison values for membranes from a manufacturer. As water-soluble linear macromolecules, the polyethylene glycols form strong bonds to the membrane surfaces and can therefore form fouling on the membranes, which result in reduced liquid throughput through the membrane. Detection of the test solution is also only possible with great analytical effort.
  • Dextran / vitamin B12, tryptophan fractions are also used as test solutions.
  • these substances have the disadvantage that the substances are very expensive and the measurement results continue to depend on the pore structure of a membrane.
  • the object of the invention was now to provide a simple, economical and universally usable method for quality control of membranes, which makes it possible to identify damage to or formation of deposits on membranes without permanently changing them.
  • the object of the invention is achieved by a method for quality inspection of membranes, in which the water output and retention rate of an aqueous test solution, the polyacrylic acid (s) and / or their salts and / or their derivatives are contained, before and after the treatment of the membrane with the determined solution to be filtered.
  • the test solution contains the polyacrylic acid (s) and / or their salts and / or their derivatives in amounts between 0.05 and 5, preferably between 0.1 and 2 and in particular between 0.2 and 1 wt. -%, based on the test solution.
  • the proof of the polyacrylates is simple, quick and inexpensive by simple conductivity measurements.
  • the measurement results can also be transferred to membranes from different manufacturers.
  • the method is very inexpensive due to the use of inexpensive substances and the simple detection of these substances.
  • Salts or derivatives are available in many different molecular weights, which enables the method according to the invention to be used widely.
  • test solutions do not cause any corrosion on the membranes examined and are therefore also suitable for sensitive membranes (for example cellulose acetate).
  • copolymers of acrylic acid with other monomers for example maleic acid
  • Polyacrylates are, for example, under the names Versicol ® E5, Versicol ® E7 and Versicol ® E9 (trademark of the ied Colloids), Narlex ® LD 30 and Narlex ® LD 34 (trademark of the national adhesives), Acrysol ® LMW-10, Acrysol ® LMW- 20, Acrysol ® LMW-45 and Acrysol ® Al-N (trademark of Rohm & Haas) as well as Sokalan ® PA-20, Sokalan ® PA-40, Sokalan ® PA-70 and Sokalan ® PA-110 (trademark of BASF) available in the stores.
  • Acrylic acid / maleic acid copolymers are sold under the names Sokalan ® CP5 and Sokalan ® CP7 (trademark of BASF).
  • Acrylic phosphinates are available as DKW ® (trademark of National Adhesives) and Belperse ® types (trademark of Ciba-Geigy).
  • DKW ® trademark of National Adhesives
  • Belperse ® types trademark of Ciba-Geigy
  • polysodium acrylates have proven to be preferred compounds.
  • the test solution preferably contains between 0.1 and 3% by weight of polysodium acrylate, in particular between 0.2 and 2% by weight, based in each case on the test solution.
  • the membrane to be checked is cleaned with a common membrane cleaning agent which is compatible with the membrane.
  • this cleaning serves to remove any ingredients such as conditioning agents, additives, stabilizers, easily adhering contaminants or preservatives.
  • the cleaning is carried out only with water, in order not to remove any deposits which may be recognized by the process according to the invention. Is such a deposit formation e.g. detected by means of the method according to the invention, the effectiveness of cleaning with commercially available cleaning agents can be checked by performing the method according to the invention a second time.
  • the water value of the membrane is determined, for example by allowing deionized water to flow through the membrane under a pressure of 4 bar for 15 minutes and then measuring the flow rate.
  • the retention characteristic of the membrane can then be determined by filtering the test solution over the membrane, for example for 5 hours, the test solution being circulated for economic reasons (circulation).
  • the water value can be determined again. While the water value can be measured directly as a liter flow rate per square meter of membrane area and hour, the rate of salt retention is determined indirectly via the conductivity of the test solution, based on the following mathematical relationship:
  • the difference between the initial value and the final value should not exceed 20% for the first
  • PA 1 polysodium acrylate solution (average molecular weight 20 086), solids content 35% by weight
  • PA 2 polysodium acrylate solution (average molecular weight 24,341)
  • HP 3043 Hydropalat ® 3043 (polysodium acrylate ex Henkel), average molecular weight 28,000 +/- 10%),
  • HP 3051 Hydropalat ® 3051 (polyammonium acrylate ex Henkel), average molecular weight 28,000 - 30,500),
  • Nopco 44 Solids content 39-41% by weight
  • Nopco 44 Nopcosperse ® 44 (polysodium acrylate ex Henkel-Nopco), average molecular weight 10,000 - 30,000),
  • HP 1706 Hydropalat ® 1706 (polysodium acrylate ex Henkel), average molecular weight 15,000 +/- 10%),

Landscapes

  • Chemical & Material Sciences (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Physics & Mathematics (AREA)
  • Fluid Mechanics (AREA)
  • Dispersion Chemistry (AREA)
  • Health & Medical Sciences (AREA)
  • Life Sciences & Earth Sciences (AREA)
  • Analytical Chemistry (AREA)
  • Biochemistry (AREA)
  • General Health & Medical Sciences (AREA)
  • General Physics & Mathematics (AREA)
  • Immunology (AREA)
  • Pathology (AREA)
  • Separation Using Semi-Permeable Membranes (AREA)

Abstract

L'invention concerne un procédé de contrôle qualité de membranes, selon lequel une solution test aqueuse contenant de l'acide polyacrylique/des acides polyacryliques et/ou leurs sels et/ou leurs dérivés, est filtrée par la membrane avant et après le traitement de la membrane avec la solution à filtrer. On détermine ainsi le débit d'eau et la teneur résiduaire.
PCT/EP1998/004565 1997-07-30 1998-07-21 Procede de controle qualite de membranes WO1999006817A1 (fr)

Priority Applications (2)

Application Number Priority Date Filing Date Title
AU87322/98A AU8732298A (en) 1997-07-30 1998-07-21 Method for testing the quality of membranes
EP98938695A EP1000339A1 (fr) 1997-07-30 1998-07-21 Procede de controle qualite de membranes

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
DE19732775A DE19732775A1 (de) 1997-07-30 1997-07-30 Verfahren zur Qualitätsüberprüfung von Membranen
DE19732775.3 1997-07-30

Publications (1)

Publication Number Publication Date
WO1999006817A1 true WO1999006817A1 (fr) 1999-02-11

Family

ID=7837349

Family Applications (1)

Application Number Title Priority Date Filing Date
PCT/EP1998/004565 WO1999006817A1 (fr) 1997-07-30 1998-07-21 Procede de controle qualite de membranes

Country Status (4)

Country Link
EP (1) EP1000339A1 (fr)
AU (1) AU8732298A (fr)
DE (1) DE19732775A1 (fr)
WO (1) WO1999006817A1 (fr)

Cited By (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US7000437B2 (en) 2001-01-18 2006-02-21 Shell Oil Company System and method for economically viable and environmentally friendly central processing of home laundry

Citations (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US4339433A (en) * 1981-01-09 1982-07-13 Baxter Travenol Laboratories, Inc. Additives for peritoneal dialysis solutions
US4713975A (en) * 1986-05-30 1987-12-22 The Dow Chemical Company Dense star polymers for calibrating/characterizing sub-micron apertures

Patent Citations (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US4339433A (en) * 1981-01-09 1982-07-13 Baxter Travenol Laboratories, Inc. Additives for peritoneal dialysis solutions
US4713975A (en) * 1986-05-30 1987-12-22 The Dow Chemical Company Dense star polymers for calibrating/characterizing sub-micron apertures
EP0566165A1 (fr) * 1986-05-30 1993-10-20 The Dow Chemical Company Polymères et étoile denses pour le calibrage/caractérisation d'ouvertures submicroniennes

Cited By (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US7000437B2 (en) 2001-01-18 2006-02-21 Shell Oil Company System and method for economically viable and environmentally friendly central processing of home laundry

Also Published As

Publication number Publication date
DE19732775A1 (de) 1999-02-04
AU8732298A (en) 1999-02-22
EP1000339A1 (fr) 2000-05-17

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