WO2007123356A1 - Membrane composite de transport facilité d'oléfine comprenant un métal nanodimensionné et un liquide ionique - Google Patents

Membrane composite de transport facilité d'oléfine comprenant un métal nanodimensionné et un liquide ionique Download PDF

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Publication number
WO2007123356A1
WO2007123356A1 PCT/KR2007/001991 KR2007001991W WO2007123356A1 WO 2007123356 A1 WO2007123356 A1 WO 2007123356A1 KR 2007001991 W KR2007001991 W KR 2007001991W WO 2007123356 A1 WO2007123356 A1 WO 2007123356A1
Authority
WO
WIPO (PCT)
Prior art keywords
ionic liquid
bmim
composite membrane
nanoparticles
olefin
Prior art date
Application number
PCT/KR2007/001991
Other languages
English (en)
Inventor
Yong-Soo Kang
Sang-Wook Kang
Kook-Heon Char
Jong-Ho Kim
Original Assignee
Industry-University Cooperation Foundation Hanyang University
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 KR1020060037430A external-priority patent/KR100716470B1/ko
Priority claimed from KR1020070024412A external-priority patent/KR100872384B1/ko
Application filed by Industry-University Cooperation Foundation Hanyang University filed Critical Industry-University Cooperation Foundation Hanyang University
Priority to JP2009507584A priority Critical patent/JP2009535193A/ja
Publication of WO2007123356A1 publication Critical patent/WO2007123356A1/fr

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Classifications

    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01D—SEPARATION
    • B01D69/00—Semi-permeable membranes for separation processes or apparatus characterised by their form, structure or properties; Manufacturing processes specially adapted therefor
    • B01D69/14—Dynamic membranes
    • B01D69/141—Heterogeneous membranes, e.g. containing dispersed material; Mixed matrix membranes
    • B01D69/142—Heterogeneous membranes, e.g. containing dispersed material; Mixed matrix membranes with "carriers"
    • 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
    • B01D61/38—Liquid-membrane separation
    • 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
    • B01D71/66—Polymers having sulfur in the main chain, with or without nitrogen, oxygen or carbon only
    • B01D71/68—Polysulfones; Polyethersulfones
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C7/00—Purification; Separation; Use of additives
    • C07C7/144—Purification; Separation; Use of additives using membranes, e.g. selective permeation
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01D—SEPARATION
    • B01D2323/00—Details relating to membrane preparation
    • B01D2323/12—Specific ratios of components used

Definitions

  • the present invention relates to a composite membrane enabling the separation of olefin from paraffin, which have similar molecular weights, and more particularly to a composite membrane, comprising ionic liquid and metal nanoparticles.
  • the present invention relates to a composite membrane, comprising ionic liquids
  • ILs metal nanoparticles
  • metal nanoparticles polarized by the anions of the ionic liquids act as carriers for facilitated transport carriers, to enable the separation of olefin from paraffin.
  • polymer membranes for use in such facilitated transport separation include technologies relating to supported or immobilized liquid membranes made by loading, as carriers, silver salts such as AgBF or AgCF SO .
  • silver salts such as AgBF or AgCF SO .
  • the ionic liquid consists of organic cations and anions.
  • the cations of the ionic liquids include dialkylimidazolium, alkylpyridinium, quaternary ammonium and quaternary phosphonium, and the anions thereof NO , BF , CF SO , PF 6 " , AlCl 4 " , Al 2Cl 7 “ , AcO " , TfO " (trifluoromethanesulfonate), Tf 2 N "
  • the ionic liquids are also used as catalysts for heterogeneous catalytic reactions, catalysts substituting for hazardous materials such as HF, cell electrolytes, and mediators of gas-gas separation or liquid-liquid separation.
  • the present inventors paid attention to the activity of metal nanoparticles and the function of ionic liquids as separation mediators, thereby completing the present invention.
  • the present invention provides a facilitated olefin transport composite membrane, comprising metal nanoparticles and ionic liquid.
  • the metal nanoparticles are selected from the group consisting of silver nanoparticles, gold nanoparticles and copper nanoparticles.
  • the facilitated olefin transport composite membrane preferably further comprises a porous support.
  • the porous support is preferably a poly sulf one porous support.
  • the metal nanoparticles are preferably contained in an amount of 0.05-1 part by weight based on one part by weight of the ionic liquid.
  • the metal nanoparticles preferably have a particle size of less than 100 nm.
  • the ionic liquid is preferably one selected from the group consisting of BMIM + BF
  • the technical characteristic of the present invention resides in that the metal nanoparticles are cationized (polarized) by the ionic liquid and thus act as carriers for facilitated transport.
  • the kind of metal nanoparticles and the kind of ionic liquids there are no limitations on the kind of metal nanoparticles and the kind of ionic liquids, because various ionic liquids are applied for various metal nanoparticles, so that partial cationization of the metal nanoparticles is achieved according to the same mechanism.
  • FIG. 1 is an illustrative view showing the mechanism by which the surface of a metal nanoparticle is partially cationized by BMIM + BF as an ionic liquid.
  • the anion BF of BMIM + BF approaches the surface of a metal nanoparticle to partially cationize the metal nanoparticle, such that the metal nanoparticle will act as an olefin carrier capable of reversibly reacting with the ⁇ -bond of olefin.
  • FIGS. 2 and 3 show the partial cationization mechanisms of metal nanoparticles in the cases of using BMIM + CF SO and BMIM + NO , respectively, as ionic liquids.
  • the partial cationization of metal nanoparticles is possible using all conventional ionic liquids, and hence, the present invention does not impose any particular limitation on the kind of ionic liquid or metal nanoparticle. Examples below are given to promote a better understanding of the present invention, and the scope of the present invention is not limited to the ionic liquids and metal nanoparticles used in these examples.
  • the present invention provides a composite membrane, comprising metal nanoparticles and a liquid, which allows the facilitated transport of olefin by the metal nanoparticles.
  • the composite membrane according to the present invention uses a facilitated transport mechanism and allows the easy separation of materials, which are difficult to separate, due to the similar molecular weights and physical properties thereof, for example, olefin/paraffin mixtures such as a propane/propylene mixture.
  • olefin/paraffin mixtures such as a propane/propylene mixture.
  • FIG. 1 is an illustrative view showing the interaction between ionic liquid BMIM +
  • FIG. 2 is an illustrative view showing the interaction between ionic liquid BMIM +
  • FIG. 3 is an illustrative view showing the interaction between ionic liquid BMIM +
  • FIG. 4 is a graphic diagram showing the pure gas permeances of propane and propylene through the composite membranes of Examples 1 to 6, measured in Test Example 1.
  • FIG. 5 shows Raman spectra for composite membranes of Comparative Example and Examples 2, 4 and 6, measured in Test Example 3.
  • FIG. 6 shows deconvoluted Raman spectra for the composite membranes of
  • FIG. 7 is a graphic diagram showing the pure gas permeances of propane and propylene through the composite membranes of Examples 7 to 12, measured in Test Example 4.
  • FIG. 8 is a graphic diagram showing the pure gas permeances of propane and propylene through the composite membranes of Examples 15 to 20, measured in Test
  • Silver nanoparticles (70-nm size and 99.5% pure) were purchased from Aldrich
  • a support to be coated with a mixture of the ionic liquid and the silver nanoparticles a microporous polysulfone support (Sanhan Industry Co., Ltd., Korea) was used, and the polymer mixture solution was coated on the support using an RK control coater (Model 101, Control Coater RK Print-Coat Instruments, Ltd., UK).
  • Examples 7 to 12 Use of BMIM + NO as ionic liquid [40]
  • Silver nanoparticles 70-nm size and 99.5% pure) were purchased from Aldrich Chemical Co., Inc. and BMIM + NO (l-butyl-3-methylimidazolium nitrate) was purchased from C-TRI Co., Ltd., Korea. The purchased materials were used in experiments without any further treatment.
  • the preparation of composite membranes, comprising silver nanoparticles and BMIM + NO was performed in the same manner as in Example 1.
  • Composite membranes of Examples 7 to 12 were prepared by changing the weight ratio of the ionic liquid BMIM + NO to the silver nanoparticles within the range from 1:0.1 to 1:1, as shown in Table 2 below.
  • Example 13 Composite membrane comprising copper nanoparticles and BMIM + BF " as ionic liquid
  • Copper nanoparticles (70-nm average particle size) were purchased from Aldrich Chemical Co., Inc., and BMIM + BF ⁇ (l-butyl-3-methylimidazolium tetrafluoroborate) was purchased from C-TRI Co., Ltd., Korea. The purchased materials were used in experiments without any further treatment.
  • Example 14 Composite membrane comprising gold nanoparticles and BMIM + BF as ionic liquid
  • a composite membrane was prepared in the same manner as in Example 13, except that gold nanoparticles (50-130-nm average particle size) purchased from Aldrich Chemical Co., Inc., and the weight ratio of BMIM + BF to gold nanoparticles was 1: 0.1.
  • BMIM + Tf (l-butyl-3-methylimidazolium triflate, also referred to as BMIM + Tf) as an ionic liquid.
  • the remaining process conditions and the content ratio of silver nanoparticles were the same as in Examples 1 to 6. That is, the prepared composite membranes were comprised of silver nanoparticles at ratios of 0.1, 0.25, 0.5, 0.7, 0.8 and 1.0 parts by weight based on one part by weight of BMIM + CF SO .
  • a membrane was prepared by coating only BMIM + BF " on a polysulfone support.
  • Test Example 1 Test of total permeance and selectivity of Comparative Example and Example 4
  • Table 3 shows the results of Test Example 1. As can be seen in Table 3, the membrane of Comparative Example, comprising only BMIM + BF " , showed a
  • Example 4 propylene selectivity of only 0.9 and a total permeance of 0.5 GPU, suggesting that it would not be used as a membrane for the separation of propylene from propane.
  • the composite membrane of Example 4 according to the present invention had a propylene selectivity of 17 and a total permeance of 2.7, and thus showed the characteristics of a typical facilitated transport membrane, showing increased selectivity and total permeance. That is, it could be seen that the improvement in the performance of the facilitated olefin transport composite membrane of Example 4 according to the present invention was because the silver nanoparticles were partially cationized by the ionic liquid to make the facilitated transport of olefin possible.
  • Test Example 2 unlike Test Example 2, the pure gas permeance of each of propylene and propane gases through the membranes of Examples 1 to 6 was measured. The measurement results are shown in FIG. 4. As can be seen in the graphs of FIG. 4, the permeance of propane was almost constant, but the permeance of propylene gas abruptly increased with an increase in the content of silver nanoparticles, and then decreased. Examples 1 to 6 showed the permeance of propylene, which was much higher than the permeance of propane gas, suggesting that the facilitated transport of olefin through the membranes of Examples 1 to 6 occurred.
  • FIG. 5 shows Raman spectra for the composite membranes of Examples 2, 4 and 6 in the stretching band region of BMIM + BF ⁇ .
  • the wavenumbers of free ions, ion pairs and higher ion aggregates are 765 cm “ , 770 cm “ and 774 cm “ , respectively.
  • the fraction of free ions increased until a weight ratio of silver nanoparticles to ionic liquid of 0.7: 1 (Example 4), but the peak decreased at a wavenumber of 774 cm corresponding to BF ion aggregates.
  • FIG. 6 shows deconvoluted Raman spectra for composite membranes of
  • Test Example 5 Measurement of total permeance and selectivity for Comparative
  • the present inventors propose that the silver nanoparticles be used in an amount of 0.05-1.0 parts by weight based on one part by weight of the ionic liquid.
  • the weight ratio of silver nanoparticles to ionic liquid is determined within the specified range depending on the kind of ionic liquid.
  • the present invention provides a facilitated transport composite membrane, comprising ionic liquid and metal nanoparticles, which enables the separation of olefin from paraffin through the facilitated transport of olefin.
  • a facilitated transport composite membrane comprising ionic liquid and metal nanoparticles, which enables the separation of olefin from paraffin through the facilitated transport of olefin.
  • Such fa- cilitated transport of olefin is possible because the metal nanoparticles are polarized by the ionic liquid.
  • the present invention can be used in a process for the separation of olefin and paraffin, which were difficult to separate in the prior art because their molecular weights are similar.
  • the separation of olefin and paraffin like the separation of propylene and propane, having very similar molecular weights, can be achieved through the facilitated transport mechanism according to the present invention. Accordingly, the present invention can be used in various separation processes.

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  • Chemical & Material Sciences (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Organic Chemistry (AREA)
  • Engineering & Computer Science (AREA)
  • Water Supply & Treatment (AREA)
  • Dispersion Chemistry (AREA)
  • Analytical Chemistry (AREA)
  • Oil, Petroleum & Natural Gas (AREA)
  • Separation Using Semi-Permeable Membranes (AREA)

Abstract

L'invention concerne une membrane composite, qui comprend des nanoparticules de métal et un liquide ionique, les nanoparticules de métal étant partiellement cationisées (polarisées) par les anions du liquide ionique pour agir comme véhicules facilitant le transport d'oléfine. Ainsi, la membrane composite facilite le transport d'oléfine lors de la séparation d'un gaz mixte d'oléfine et de paraffine.
PCT/KR2007/001991 2006-04-26 2007-04-24 Membrane composite de transport facilité d'oléfine comprenant un métal nanodimensionné et un liquide ionique WO2007123356A1 (fr)

Priority Applications (1)

Application Number Priority Date Filing Date Title
JP2009507584A JP2009535193A (ja) 2006-04-26 2007-04-24 金属ナノ粒子およびイオン性液体含有オレフィン促進輸送複合分離膜

Applications Claiming Priority (4)

Application Number Priority Date Filing Date Title
KR10-2006-0037430 2006-04-26
KR1020060037430A KR100716470B1 (ko) 2006-04-26 2006-04-26 은나노입자 및 이온성액체를 포함하여 이루어지는 올레핀촉진수송 복합분리막
KR10-2007-0024412 2007-03-13
KR1020070024412A KR100872384B1 (ko) 2007-03-13 2007-03-13 구리나노입자 또는 금나노입자와 이온성액체를 포함하여 이루어지는 올레핀 촉진수송 복합분리막

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WO2007123356A1 true WO2007123356A1 (fr) 2007-11-01

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Cited By (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO2009017425A1 (fr) * 2007-07-27 2009-02-05 Industrial Research Limited Utilisation de liquides ioniques pour l'extraction ou le fractionnement de lipides
KR100968123B1 (ko) * 2008-07-09 2010-07-06 한양대학교 산학협력단 산화은 나노입자 또는 산화구리 나노입자와 이온성액체를포함하여 이루어지는 올레핀 촉진수송 복합분리막
US20140102884A1 (en) * 2007-02-07 2014-04-17 Esionic Es, Inc. Liquid Composite Compositions Using Non-Volatile Liquids And Nanoparticles And Uses Thereof
US9397366B2 (en) 2011-07-11 2016-07-19 Cornell University Ionic-liquid nanoscale ionic material (IL-NIM) compositions, methods and applications

Families Citing this family (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP6806778B2 (ja) * 2016-08-31 2021-01-06 旭化成株式会社 気体分離膜

Citations (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US4154770A (en) * 1978-06-28 1979-05-15 Standard Oil Company (Indiana) Isoparaffin-olefin alkylation utilizing a membrane to separate olefins from a feed stream
DE19929482A1 (de) * 1999-06-28 2001-03-01 Univ Stuttgart Polymermembran zur Anreicherung von Olefinen aus Olefin/Paraffin-Mischungen
US20040154980A1 (en) * 2001-07-16 2004-08-12 Korea Institute Of Science And Technology Method for producing silver salt-containing facilitated transport membrane for olefin separation having improved stability
US20050150383A1 (en) * 2004-01-08 2005-07-14 Korea Institute Of Science And Technology Facilitated transport membranes for an alkene Hydrocarbon separation

Patent Citations (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US4154770A (en) * 1978-06-28 1979-05-15 Standard Oil Company (Indiana) Isoparaffin-olefin alkylation utilizing a membrane to separate olefins from a feed stream
DE19929482A1 (de) * 1999-06-28 2001-03-01 Univ Stuttgart Polymermembran zur Anreicherung von Olefinen aus Olefin/Paraffin-Mischungen
US20040154980A1 (en) * 2001-07-16 2004-08-12 Korea Institute Of Science And Technology Method for producing silver salt-containing facilitated transport membrane for olefin separation having improved stability
US20050150383A1 (en) * 2004-01-08 2005-07-14 Korea Institute Of Science And Technology Facilitated transport membranes for an alkene Hydrocarbon separation

Cited By (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US20140102884A1 (en) * 2007-02-07 2014-04-17 Esionic Es, Inc. Liquid Composite Compositions Using Non-Volatile Liquids And Nanoparticles And Uses Thereof
US9403190B2 (en) * 2007-02-07 2016-08-02 Esionic Corp. Liquid composite compositions using non-volatile liquids and nanoparticles and uses thereof
WO2009017425A1 (fr) * 2007-07-27 2009-02-05 Industrial Research Limited Utilisation de liquides ioniques pour l'extraction ou le fractionnement de lipides
KR100968123B1 (ko) * 2008-07-09 2010-07-06 한양대학교 산학협력단 산화은 나노입자 또는 산화구리 나노입자와 이온성액체를포함하여 이루어지는 올레핀 촉진수송 복합분리막
US9397366B2 (en) 2011-07-11 2016-07-19 Cornell University Ionic-liquid nanoscale ionic material (IL-NIM) compositions, methods and applications

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