WO1999044054A1 - Continuous electrolytically regenerated packed bed suppressor for ion chromatography - Google Patents
Continuous electrolytically regenerated packed bed suppressor for ion chromatography Download PDFInfo
- Publication number
- WO1999044054A1 WO1999044054A1 PCT/US1999/003427 US9903427W WO9944054A1 WO 1999044054 A1 WO1999044054 A1 WO 1999044054A1 US 9903427 W US9903427 W US 9903427W WO 9944054 A1 WO9944054 A1 WO 9944054A1
- Authority
- WO
- WIPO (PCT)
- Prior art keywords
- suppressor
- bed
- barrier
- chamber
- cathode
- Prior art date
Links
Classifications
-
- G—PHYSICS
- G01—MEASURING; TESTING
- G01N—INVESTIGATING OR ANALYSING MATERIALS BY DETERMINING THEIR CHEMICAL OR PHYSICAL PROPERTIES
- G01N30/00—Investigating or analysing materials by separation into components using adsorption, absorption or similar phenomena or using ion-exchange, e.g. chromatography or field flow fractionation
- G01N30/96—Investigating or analysing materials by separation into components using adsorption, absorption or similar phenomena or using ion-exchange, e.g. chromatography or field flow fractionation using ion-exchange
-
- G—PHYSICS
- G01—MEASURING; TESTING
- G01N—INVESTIGATING OR ANALYSING MATERIALS BY DETERMINING THEIR CHEMICAL OR PHYSICAL PROPERTIES
- G01N30/00—Investigating or analysing materials by separation into components using adsorption, absorption or similar phenomena or using ion-exchange, e.g. chromatography or field flow fractionation
- G01N30/96—Investigating or analysing materials by separation into components using adsorption, absorption or similar phenomena or using ion-exchange, e.g. chromatography or field flow fractionation using ion-exchange
- G01N2030/965—Investigating or analysing materials by separation into components using adsorption, absorption or similar phenomena or using ion-exchange, e.g. chromatography or field flow fractionation using ion-exchange suppressor columns
Definitions
- Hydronium ions generated at the anode displace the sodium ions which associate with the hydroxide ions for passage to waste, in this instance through the conductivity cell.
- This process electrochemically regenerates the suppressor, and after the electrical potential is turned off, the device can be used as a conventional PBS.
- a second ion exchange resin bed is used with suitable valving to pass liquid streams through the system.
- a second sample in an eluent stream is chromatographically separated, typically on a chromatographic column using an eluent.
- the eluent and separated second sample flow through a second packed bed suppressor including ion exchange resin to convert the electrolyte to weakly ionized form.
- the separated sample ionic species in the suppressor effluent are detected in the detector.
- the effluent then flows -4-
- the suppressor is normally used in combination with (g) a flow-through separator bed of ion exchange resin having exchangeable ions of opposite charge to the exchangeable ions of said suppressor bed, said separator bed having a sample inlet port and an outlet port, said separator bed outlet port being in fluid communication with said suppressor bed inlet port, and with a detector disposed in the path of said recycle conduit to detect sample flowing through said conduit.
- the present invention relates to ion chromatography using continuous electrochemical regeneration of a packed bed suppressor.
- the gases created by the electrolysis of the aqueous liquid stream, hydrogen and oxygen, are separated from the eluent flow by the ion exchange connector so that detection is not adversely affected by the gas production.
- the resin or the electrode is directly embedded in the resin. At least one of the electrodes is separated from the eluent flow path by the ion exchange connector, but still in electrical contact or communication with the resin. Also, the barrier is in electrical communication with both the suppressor bed resin and both electrodes.
- This configuration permits eluent counter-ions to be removed from the eluent stream and replaced with either hydroxide or hydronium to form water or other weakly conducting aqueous streams.
- the suppressor contains cation exchange resin which is continually regenerated to the hydronium ion form by formation of hydronium ions at the anode, which migrate toward the cathode, displacing sodium ions from the ion exchange sites.
- ion exchange beds other than packed resin beds can be used in column 24, such as a porous continuous structure with sufficient porosity to permit flow of an aqueous stream at a sufficient rate for use in chromatography without undue pressure drop and with sufficient ion exchange capacity to form a conducting bridge of cations or anions between the electrodes.
- One form of structure is a porous matrix or a sponge-like material formed of sulfonated, cross-linked polystyrene with a porosity of about 10 to 15% permitting a flow rate of about 0.1 to 3 ml/min. without excessive pressure drop.
- barrier 40 separates bed 26 from electrode 42 in the interior of a hollow housing defining electrode chamber 44 preventing any significant liquid flow but permitting transport of ions only of the same charge as the charge of exchangeable ions on resin bed 26.
- barrier 40 is suitably in the form of a cation exchange membrane or plug separating electrode chamber
- Electrode 42 can extend across all or part of the aqueous liquid flow path through electrode chamber 42 to provided intimate contact with the flowing aqueous stream.
- Anion exchange resin in bed 18 is of a suitable conventional low capacity form used for ion chromatography as illustrated in U.S. Patent Nos. 3,897,213, 3,920,397, 3,925,019 and 3,926,559.
- bed 18 has typically a total capacity of about 0.01 to 0.1 milhequivalents.
- the anion exchange capacity of the separator is low in comparison to that of the suppressor.
- the water is electrolyzed and hydronium ions are generated at anode 36 -22-
- the suppressed effluent liquid containing the separated anions leaves bed 26 through port 27 and conduit 30 and passes to conductivity cell 34 in which the conductivity of the separated anions is detected.
- the flux of hydronium "upwards" in the resin phase toward bed inlet section 26a is equivalent to or greater than the flux of cation hydroxide "downwards" in the mobile phase toward bed outlet section 26b. Since the balance prevails at different current levels, the position of the hydronium/cation boundary line X-X remains fixed. Thus, the system operates as a continuous suppressor of cation hydroxide.
- Figure 2 Another embodiment of the invention is illustrated in Figure 2. Like the embodiment in Figure 1 , the Figure 2 embodiment may be used with a conventional packed ion exchange resin bed separator column. The principal difference between the embodiments of Figs. 1 and 2 is that in the latter one, there are two external electrode chambers rather than one so that the analyte ions are prevented from contacting any electrodes.
- Figure 2 schematically illustrates only that portion of the system downstream from the separation column.
- the effluent from the separator column flows in conduit 60 through suppressor 62 which includes a housing (suitably of cylindrical cross-section) including a body 64 defining a central bore, screw threaded top and bottom caps 66 and 68, and top and bottom flow-through bed supports 70 and 72, respectively, at opposite ends of the bore.
- Suppressor 62 contains a high-capacity ion exchange resin bed 68 of the type described above.
- Electrode chamber 70 contains electrode 72 separated from bed 68 by barrier 74, all of the same type described above.
- Figure 2 includes an electrode chamber 76 containing a second electrode 78 separated by barrier 80 from bed 68.
- Electrode 78 in electrode chamber 76 replaces electrode 36 in Figure 1 which was in direct contact with the resin bed of the suppressor.
- the electrodes are connected to a DC power supply, not shown, and are suitably formed of platinum.
- Beds supports 70 and 72 are first positioned and then caps 66 and 68 are screwed into a secure position.
- the end caps include screw-threaded ports for connecting to the -26-
- the electrochemically generated hydronium flux must be greater than or equal to the incoming sodium hydroxide flux. This assures that every mole of hydroxide is neutralized by a mole of hydronium and that the sodium is displaced by hydronium through the ion exchange connector, to the cathode compartment which is swept to waste.
- the current is 110-160% of the eluent flux.
- Suppressor 22 was packed with 20 ⁇ fully sulfonated polystyrene/8%) divinylbenzene which was packed in the sodium form and then converted to the hydronium form with sulfuric acid.
- a cation exchange membrane AMI-7000 (217 in Figure 2) from Membrane International, NJ was used as barrier 40 in electrode chamber 44.
- platinum form was placed at the outlet of suppressor 22 which also acts as a flow-through bed support to retain the resin.
- a conductivity detector and cell, 32, 34 was used to monitor the effluent from the suppressor.
- Backpressure was applied to the cell using 15 cm of 0.076 mm id PEEK tubing as restrictor 170. Data was collected using Dionex AI450 Chromatography software.
- Example 2 In order to demonstrate the dynamic suppression capacity of the device described in Example 1, a gradient separation of anions was performed. In this example, the maximum eluent concentration is 30 mM NaOH. The chromatogram shown in Figure 4 was obtained under the following conditions:
- Example 3 This example illustrates the use of an continuous electrolytically regenerated packed bed suppressor of the type illustrated in Figure 2. This example is given for the suppression of sulfuric acid which is used as an eluent for cation separations.
- a conventional chromatographic system (Dionex Corp., Sunnyvale, CA) was used consisting of a gradient pump 10, with injection valve 14 connected to an ion exchange separator column 18.
- a Dionex cation separator, IonPac CS12A was used.
- a continuous electrolytically regenerated packed bed suppressor, 62 as shown in
- the suppressor includes central flow channel that is 4x70 mm column.
- the suppressor was packed with -30-
- a flow-through sponge-like cation exchange bed is formed to act as a suppressor for anion analysis.
- the porogen can be a finely divided solid which can be easily removed by dissolution in acid or base (e.g., calcium carbonate or silica), or it can be a solvent which is rejected by the polymer as it forms and is subsequently displaced by another solvent or water.
- Suitable liquid porogens include an alcohol, e.g., used in the manner described in Analytical Chemistry, Vol. 68, No. 2, pp. 315-321, January 15, 1996.
Abstract
Description
Claims
Priority Applications (4)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
EP99936120A EP1057013A1 (en) | 1998-02-26 | 1999-02-17 | Continuous electrolytically regenerated packed bed suppressor for ion chromatography |
AU32988/99A AU754051B2 (en) | 1998-02-26 | 1999-02-17 | Continuous electrolytically regenerated packed bed suppressor for ion chromatography |
CA002319813A CA2319813C (en) | 1998-02-26 | 1999-02-17 | Continuous electrolytically regenerated packed bed suppressor for ion chromatography |
JP2000533752A JP3488202B2 (en) | 1998-02-26 | 1999-02-17 | Packed bed suppressor for ion chromatography with continuous electrolysis regeneration |
Applications Claiming Priority (2)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
US09/031,221 | 1998-02-26 | ||
US09/031,221 US6325976B1 (en) | 1998-02-26 | 1998-02-26 | Continuous electrolytically regenerated packed bed suppressor for ion chromatography |
Publications (1)
Publication Number | Publication Date |
---|---|
WO1999044054A1 true WO1999044054A1 (en) | 1999-09-02 |
Family
ID=21858253
Family Applications (1)
Application Number | Title | Priority Date | Filing Date |
---|---|---|---|
PCT/US1999/003427 WO1999044054A1 (en) | 1998-02-26 | 1999-02-17 | Continuous electrolytically regenerated packed bed suppressor for ion chromatography |
Country Status (7)
Country | Link |
---|---|
US (3) | US6325976B1 (en) |
EP (1) | EP1057013A1 (en) |
JP (1) | JP3488202B2 (en) |
KR (1) | KR100423660B1 (en) |
AU (1) | AU754051B2 (en) |
CA (1) | CA2319813C (en) |
WO (1) | WO1999044054A1 (en) |
Cited By (12)
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EP1074837A1 (en) * | 1999-08-02 | 2001-02-07 | Alltech Associates, Inc. | Suppressor for continuous electrochemically suppressed ion chromatography and method |
EP1092977A1 (en) * | 1999-10-13 | 2001-04-18 | Alltech Associates, Inc. | Ion chromatography apparatus and method for removing gas prior to sample detection |
WO2002004940A1 (en) * | 2000-07-07 | 2002-01-17 | Dionex Corporation | Electrolytic suppressor and separate eluent generator combination |
WO2002018930A1 (en) * | 2000-08-25 | 2002-03-07 | Dionex Corporation | Continuous electrolytically regenerated packed suppressor for ion chromatography |
US6425284B1 (en) | 2000-03-08 | 2002-07-30 | Dionex Corporation | Method and apparatus for gas-assisted suppressed chromatography |
US6436719B1 (en) | 2000-03-08 | 2002-08-20 | Dionex Corporation | Displacement chemical regeneration method and apparatus |
US6495371B2 (en) | 1998-02-26 | 2002-12-17 | Dionex Corporation | Continuous electrolytically regenerated packed bed suppressor for ion chromatography |
US6902937B2 (en) | 2001-07-13 | 2005-06-07 | Air Liquide America, L.P. | Method for the determination of low-concentration anions in the presence of an excess of another anion |
EP1868947A2 (en) * | 2005-04-14 | 2007-12-26 | John M. Riviello | Method of ion chromatography wherein a specialized electrodeionization apparatus is used |
WO2009097311A1 (en) * | 2008-01-28 | 2009-08-06 | Dionex Corporation | Electrolytic eluent recycle device, apparatus and method of use |
US7618535B2 (en) | 2001-03-01 | 2009-11-17 | Dionex Corporation | Suppressed chromatography and salt conversion system |
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US20050100477A1 (en) * | 2003-11-06 | 2005-05-12 | Alltech Associates, Inc. | Apparatus and method for removing gas prior to sample detection and/or analysis |
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US7473354B2 (en) * | 2005-09-16 | 2009-01-06 | Dionex Corporation | Recycled suppressor regenerants |
US7618826B2 (en) * | 2006-09-19 | 2009-11-17 | Dionex Corporation | Membrane suppressor with an outlet substantially non-retentive for ionic species |
US7632404B2 (en) * | 2007-11-15 | 2009-12-15 | Dionex Corporation | Barrier with a seated ion exchange bead and method |
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US9914651B2 (en) | 2013-05-08 | 2018-03-13 | Dionex Corporation | Current efficient electrolytic device and method |
US9400268B2 (en) | 2014-08-08 | 2016-07-26 | Dionex Corporation | Method for reducing suppressor noise |
US20160137530A1 (en) | 2014-11-13 | 2016-05-19 | Dionex Corporation | Ion exchange based volatile component removal device for ion chromatography |
US10175211B2 (en) | 2014-12-31 | 2019-01-08 | Dionex Corporation | Current-efficient suppressor and pretreatment device and method |
US11287403B2 (en) | 2016-01-07 | 2022-03-29 | Board Of Regents, The University Of Texas System | Ion chromatography system and methods utilizing a weak acid or weak base extraction device |
US10416137B2 (en) * | 2016-09-07 | 2019-09-17 | Board Of Regents, University Of Texas System | Electrodialytic capillary suppressor for suppressed conductometric ion chromatography |
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US11865531B2 (en) | 2018-02-28 | 2024-01-09 | Lilac Solutions, Inc. | Ion exchange reactor with particle traps for lithium extraction |
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JP2023529444A (en) | 2020-06-09 | 2023-07-10 | ライラック ソリューションズ,インク. | Lithium extraction in presence of scale material |
US20220107292A1 (en) * | 2020-10-06 | 2022-04-07 | Board Of Regents, The University Of Texas System | On-line suppressor |
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-
1999
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- 1999-02-17 AU AU32988/99A patent/AU754051B2/en not_active Expired
- 1999-02-17 KR KR10-2000-7009449A patent/KR100423660B1/en not_active IP Right Cessation
- 1999-02-17 JP JP2000533752A patent/JP3488202B2/en not_active Expired - Lifetime
- 1999-02-17 WO PCT/US1999/003427 patent/WO1999044054A1/en active IP Right Grant
- 1999-02-17 EP EP99936120A patent/EP1057013A1/en not_active Ceased
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2001
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Cited By (29)
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---|---|---|---|---|
US6610546B1 (en) | 1998-02-26 | 2003-08-26 | Dionex Corporation | Continuous electrolytically regenerated packed suppressor for ion chromatography |
US6508985B2 (en) | 1998-02-26 | 2003-01-21 | Dionex Corporation | Continuous electrolytically regenerated packed bed suppressor for ion chromatography |
US6495371B2 (en) | 1998-02-26 | 2002-12-17 | Dionex Corporation | Continuous electrolytically regenerated packed bed suppressor for ion chromatography |
US6444475B1 (en) | 1999-08-02 | 2002-09-03 | Alltech Associates, Inc. | Ion chromatography apparatus and method for removing gas prior to sample detection |
EP1074837A1 (en) * | 1999-08-02 | 2001-02-07 | Alltech Associates, Inc. | Suppressor for continuous electrochemically suppressed ion chromatography and method |
US6468804B1 (en) | 1999-08-02 | 2002-10-22 | Alltech Associates, Inc. | Suppressor for continuous electrochemically suppressed ion chromatography and method |
AU773509B2 (en) * | 1999-10-13 | 2004-05-27 | Alltech Associates, Inc. | Ion chromatography apparatus and method for removing gas prior to sample detection |
EP1092977A1 (en) * | 1999-10-13 | 2001-04-18 | Alltech Associates, Inc. | Ion chromatography apparatus and method for removing gas prior to sample detection |
US6436719B1 (en) | 2000-03-08 | 2002-08-20 | Dionex Corporation | Displacement chemical regeneration method and apparatus |
US6425284B1 (en) | 2000-03-08 | 2002-07-30 | Dionex Corporation | Method and apparatus for gas-assisted suppressed chromatography |
JP4845316B2 (en) * | 2000-03-08 | 2011-12-28 | ダイオネックス コーポレイション | Substitution chemical regeneration method and apparatus |
JP2003526782A (en) * | 2000-03-08 | 2003-09-09 | ダイオネックス コーポレイション | Displacement chemical regeneration method and apparatus |
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WO2002004940A1 (en) * | 2000-07-07 | 2002-01-17 | Dionex Corporation | Electrolytic suppressor and separate eluent generator combination |
AU2001271848B2 (en) * | 2000-07-07 | 2004-09-09 | Dionex Corporation | Electrolytic suppressor and separate eluent generator combination |
AU2001285169B2 (en) * | 2000-08-25 | 2007-06-07 | Dionex Corporation | Continuous electrolytically regenerated packed suppressor for ion chromatography |
JP2004507761A (en) * | 2000-08-25 | 2004-03-11 | ダイオネックス コーポレイション | Continuous electrolytic regeneration filling suppressor for ion chromatography |
JP4795621B2 (en) * | 2000-08-25 | 2011-10-19 | ダイオネックス コーポレイション | Continuous electrolytic regenerative packing suppressor for ion chromatography |
WO2002018930A1 (en) * | 2000-08-25 | 2002-03-07 | Dionex Corporation | Continuous electrolytically regenerated packed suppressor for ion chromatography |
US7618535B2 (en) | 2001-03-01 | 2009-11-17 | Dionex Corporation | Suppressed chromatography and salt conversion system |
US6902937B2 (en) | 2001-07-13 | 2005-06-07 | Air Liquide America, L.P. | Method for the determination of low-concentration anions in the presence of an excess of another anion |
EP1868947A2 (en) * | 2005-04-14 | 2007-12-26 | John M. Riviello | Method of ion chromatography wherein a specialized electrodeionization apparatus is used |
EP1868947A4 (en) * | 2005-04-14 | 2010-05-05 | John M Riviello | Method of ion chromatography wherein a specialized electrodeionization apparatus is used |
WO2009097311A1 (en) * | 2008-01-28 | 2009-08-06 | Dionex Corporation | Electrolytic eluent recycle device, apparatus and method of use |
US8597571B2 (en) | 2008-01-28 | 2013-12-03 | Dionex Corporation | Electrolytic eluent recycle device, apparatus and method of use |
US9664655B2 (en) | 2008-01-28 | 2017-05-30 | Dionex Corporation | Electrolytic eluent recycle device, apparatus and method of use |
US9964510B2 (en) | 2013-09-16 | 2018-05-08 | Dionex Corporation | Electrolytic four-channel device and method |
US10241070B2 (en) | 2013-09-16 | 2019-03-26 | Dionex Corporation | Electrolytic four-channel device and method |
Also Published As
Publication number | Publication date |
---|---|
EP1057013A1 (en) | 2000-12-06 |
US6495371B2 (en) | 2002-12-17 |
AU754051B2 (en) | 2002-10-31 |
JP3488202B2 (en) | 2004-01-19 |
AU3298899A (en) | 1999-09-15 |
CA2319813C (en) | 2005-05-03 |
JP2002509238A (en) | 2002-03-26 |
KR20010041336A (en) | 2001-05-15 |
CA2319813A1 (en) | 1999-09-02 |
US6325976B1 (en) | 2001-12-04 |
US6508985B2 (en) | 2003-01-21 |
US20010026774A1 (en) | 2001-10-04 |
US20010026773A1 (en) | 2001-10-04 |
KR100423660B1 (en) | 2004-03-18 |
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