Combined supported liquid membrane/strip dispersion process...

Organic compounds -- part of the class 532-570 series – Organic compounds – Heterocyclic carbon compounds containing a hetero ring...

Reexamination Certificate

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C562S445000, C562S580000, C562S584000, C562S600000, C562S606000, C562S608000

Reexamination Certificate

active

06433163

ABSTRACT:

FIELD OF THE INVENTION
The present invention relates to the removal and recovery of penicillin and organic acids from feed solutions, such as process streams and waste waters, using supported liquid membrane technology.
BACKGROUND OF THE INVENTION
Liquid membranes combine extraction and stripping into one step, rather than the two separate steps required in conventional processes such as solvent extractions. A one-step liquid membrane process provides the maximum driving force for the separation of a targeted species, leading to the best clean-up and recovery of the species (W. S. Winston Ho and Kamalesh K. Sirkar, eds.,
Membrane Handbook
, Chapman & Hall, New York, 1992).
There are two types of liquid membranes: (1) supported liquid membranes (SLMs) and (2) emulsion liquid membranes (ELMs). In SLMs, the liquid membrane phase is the organic liquid imbedded in pores of a microporous support, e.g., microporous polypropylene hollow fibers (W. S. Winston Ho and Kamalesh K. Sirkar, eds.,
Membrane Handbook
, Chapman & Hall, New York, 1992). When the organic liquid contacts the microporous support, it readily wets the pores of the support, and the SLM is formed.
For the extraction of a target species from a feed solution, the organic-based SLM is placed between two aqueous solutions—the feed solution and the strip solution where the SLM acts as a semi-permeable membrane for the transport of the target species from the feed solution to the strip solution. The organic liquid in the SLM is immiscible in the aqueous feed and strip streams and contains an extractant, a diluent, and sometimes a modifier. The diluent is generally an inert organic solvent.
The use of SLMs to remove penicillin and organic acids from aqueous feed solutions has attracted considerable attention in the scientific and industrial community. The extraction of penicillin G from aqueous feed solutions has been investigated (C. J. Lee, H. J. Yeh, W. Y. Yang, and C. R. Kan, “Preparation of penicillin G from Phenylacetic Acid in a Supported Liquid Membrane System”,
Biotechnol. Bioeng
., 43, 309-313 (1994); R. S. Juang and Y. S. Lin, “Investigation on Interfacial Reaction Kinetics of Penicillin G and Amberlite LA-2 from Membrane Flux Measurements”,
J. Membrane Sci
., 141, 19-30 (1998)).
The extraction of organic acids, including phenylalanine, acrylic acid, lactic acid, proprionic acid, citric acid, and acetic acid, from aqueous solutions with SLMs has been studied (L. K. Ju and A. Verma, “Characteristics of Lactic Acid Transport in Supported Liquid Membranes”,
Sep. Sci. Technol
., 29, 2299-2315 (1994); J. T. Rockman, E. Kehat, and R. Lavie, “Mathematical Model for Thermally Enhanced Facilitated Transport”,
Ind. Eng. Chem. Res
., 34, 2455-2463 (1995); F. Ozadali, B. A. Glatz, and C. E. Glatz, “Fed-batch Fermentation with and without On-line Extraction for Propionic and Acetic Acid Production by Propionibacterium Acidipropionici”,
Applied Microb. Biotechnol
., 44 710-716 (1996); R. S. Juang and L. J. Chen, “Analysis of the Transport Rates of Citric Acid through a Supported Liquid Membrane Containing Tri-n-octylamine”,
Ind. Eng. Chem. Res
., 35, 1673-1679 (1996); R. S. Juang, S. H. Lee, and R. C. Shiau, “Mass-transfer Modeling of Permeation of Lactic Acid across Amine-mediated Supported Liquid Membranes”,
J. Membrane Sci
., 137, 231-239 (1997); R. S. Juang, S. H. Lee, and R. H. Huang, “Modeling of Amine-facilitated Liquid Membrane Transport of Binary Organic Acids,
Sep. Sci. Technol
., 33, 2379-2395 (1998)).
One disadvantage of SLMs is their instability due mainly to loss of the membrane liquid (organic solvent, extractant, and/or modifier) into the aqueous phases on each side of the membrane (A. J. B. Kemperman, D. Bargeman, Th. Van Den Boomgaard, H. Strathmann, “Stability of Supported Liquid Membranes: State of the Art”,
Sep. Sci. Technol
., 31, 2733 (1996); T. M. Dreher and G. W Stevens, “Instability Mechanisms of Supported Liquid Membranes”,
Sep. Sci. Technol
., 3, 835-853 (1998); J. F. Dozol, J. Casas, and A. Sastre, “Stability of Flat Sheet Supported Liquid Membranes in the Transport of Radionuclides from Reprocessing Concentrate Solutions”,
J. Membrane Sci
., 82, 237-246 (1993)). The prior art has attempted to solve this problem through the combined use of SLM with a module containing two sets of hollow fibers, i.e., the hollow-fiber contained liquid membrane (W. S. Winston Ho and Kamalesh K. Sirkar, eds.,
Membrane Handbook
, Chapman & Hall, New York, 1992). In this configuration with two sets of microporous hollow-fiber membranes, one carries the aqueous feed solution, and the other carries the aqueous strip solution. The organic phase is contained between the two sets of hollow fibers by maintaining the aqueous phases at a higher pressure than the organic phase. The use of the hollow-fiber contained liquid membrane increases membrane stability, because the liquid membrane can be continuously replenished. However, this configuration is not advantageous because it requires mixing two sets of fibers to achieve a low contained liquid membrane thickness.
In ELMs, an emulsion acts as a liquid membrane for the separation of the target species from a feed solution. An ELM is created by forming a stable emulsion, such as a water-in-oil emulsion, between two immiscible phases, followed by dispersion of the emulsion into a third, continuous phase by agitation for extraction. The membrane phase is the oil phase that separates the encapsulated, internal aqueous droplets in the emulsion from the external, continuous phase (W. S. Winston Ho and Kamalesh K. Sirkar, eds.,
Membrane Handbook
, Chapman & Hall, New York, 1992). The species-extracting agent is contained in the membrane phase, and the stripping agent is contained in the internal aqueous droplets. Emulsions formed from these two phases are generally stabilized by use of a surfactant. The external, continuous phase is the feed solution containing the target species. The target species is extracted from the aqueous feed solution into the membrane phase and then stripped into the aqueous droplets in the emulsion. The target species can then be recovered from the internal aqueous phase by breaking the emulsion, typically via electrostatic coalescence, followed by electroplating or precipitation.
The use of ELMs to remove penicillin and organic acids from aqueous feed solutions has long been pursued in the scientific and industrial community. The use of ELMs for the extraction of Penicillin G from aqueous feed solutions has been described (T. Scheper, Z. Likidis, K. Makryaleas, Ch. Nowattny, and K. Schugerl, “Three Different Examples of Enzymatic Bioconversion in Liquid Membrane Reactors”,
Enzyme Microb. Technol
., 2, 625-631 (1987); K. H. Lee, S. C. Lee, and W. K. Lee, “Penicillin G Extraction from Model Media Using an Emulsion Liquid Membrane: A Theoretical Model of Product Decomposition”,
J. Chem. Technol. Biotechnol
., 59, 365-370 (1994); K. H. Lee, S. C. Lee, and W. K. Lee, “Penicillin G Extraction from Model Media Using an Emulsion Liquid Membrane: Determination of Optimum Extraction Conditions,
J. Chem. Technol. Biotechnol
., 59, 371-376 (1994); Y. S. Mok, S. C. Lee, and W. K. Lee, “Synergistic Effect of Surfactant on Transport Rate of Organic Acid in Liquid Emulsion Membranes”,
Sep. Sci. Technol
., 30, 399-417 (1995); S. C. Lee, K. H. Lee, G. H. Hyun, and W. K. Lee, “Continuous Extraction of Penicillin G by an Emulsion Liquid Membrane in a Countercurrent Extraction Column”,
J. Membrane Sci
., 124, 43-51 (1997); S. C. Lee, J. H. Chang, B. S. Ahn, and W. K. Lee, “Mathematical Modeling of Penicillin G Extraction in an Emulsion Liquid Membrane System Containing only a Surfactant in the Membrane Phase”,
J. Membrane Sci
., 149, 39-49 (1998); S. C. Lee, “Effect of Volume Ratio of Internal Aqueous Phase to Organic Membrane Phase (W/O Ratio) of Water-in-Oil Emulsion on Penicillin G Extraction by Emulsion Liquid Membrane”,
J. Membrane Sci
., 163, 193-201 (1999)).
The extraction of organic acids, including phenylalanine, acrylic acid, lactic acid, proprioni

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