CN102621241A - Ion chromatography detection device - Google Patents

Ion chromatography detection device Download PDF

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Publication number
CN102621241A
CN102621241A CN2012100754404A CN201210075440A CN102621241A CN 102621241 A CN102621241 A CN 102621241A CN 2012100754404 A CN2012100754404 A CN 2012100754404A CN 201210075440 A CN201210075440 A CN 201210075440A CN 102621241 A CN102621241 A CN 102621241A
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CN
China
Prior art keywords
leacheate
chromatography
conductivity detector
electric conductivity
film
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Pending
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CN2012100754404A
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Chinese (zh)
Inventor
章飞芳
杜青
杨丙成
梁鑫淼
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East China University of Science and Technology
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East China University of Science and Technology
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Application filed by East China University of Science and Technology filed Critical East China University of Science and Technology
Priority to CN2012100754404A priority Critical patent/CN102621241A/en
Publication of CN102621241A publication Critical patent/CN102621241A/en
Pending legal-status Critical Current

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Abstract

The invention relates to an ion chromatography detection device, which is mainly suitable for the field of ion chromatography and can be taken as an important selective device for increasing the detection sensitivity of an electric conductivity detector on line. In the structure of the ion chromatography detection device, a double-film leacheate generator is connected in series between an ion chromatography inhibitor and the electric conductivity detector. The basic principle is that: a constant voltage is applied to the double-film leacheate generator. The resistance of a system is reduced and current of the system is increased before and after a sample zone flowing out of the inhibitor enters the double-film leacheate generator, so that the double-film leacheate generator is used for generating an acid or alkali which corresponds to a current change on line in an electric way. An original sample zone and the acid or alkali are mixed, so that a multiplied electric conduction detection response signal is generated.

Description

The chromatography of ions pick-up unit
Technical field
The present invention relates to chromatography of ions detection technique field, particularly a kind of chromatography of ions pick-up unit.
Background technology
Chromatography of ions is a branch of liquid chromatography, is mainly used in the compartment analysis of ionic state compound.Wherein chromatography of ions is an one preferred technique of analyzing inorganic anion at present.In inorganic metal cation is analyzed, because can realizing a plurality of ions, this technology analyzes simultaneously, therefore have certain advantage apart from spectrum with respect to traditional atomic absorption or plasma.In present numerous detecting patterns, electric conductivity detector is used the most general in ion chromatography system, and the introducing that this mainly has benefited from the rejector technology has realized to the inhibition of high background conductance leacheate and to measuring the raising of component sensitivity.It is pointed out that with respect to other high-sensitivity detection patterns the sensitivity of electric conductivity detector is still not enough, can't satisfy the requirement of analyzing for trace detection.
The electric conductivity detector detection signal is proportional to the conductivity of all ions in the solution and the summation of its concentration product.Because the conductivity difference of different ions is very big, such as H in the kation +And Na +Limiting molar conductivity be respectively 350 and 50 Sm2/mol, and OH in the negative ion -And Cl -Limiting molar conductivity be respectively 199 and 76 Sm2/mol, can find out H in kation +Limiting molar conductivity maximum, and OH in the negative ion -Limiting molar conductivity is maximum.Therefore for the HCl and NaCl solution of same concentration, the two response signal on electric conductivity detector differs about 3.4 times; The NaOH and the response signal of NaCl solution on electric conductivity detector of concentration differ about 1.9 times equally, equally.Based on this contrast, can infer if the sample area band is mixed with hydroxide ion and can significantly improves detection sensitivity when the sample area band is mixed with hydrogen ion or analyzes kation when detecting negative ion.
Referring to accompanying drawing 1; According to the conventional order of connection; The critical piece of chromatography of ions is followed successively by high-pressure pump 1, leacheate generator 2, injector 3, chromatographic column 4, rejector 5 and electric conductivity detector 6, and chromatographic work station 7 rejectors 5 are one of main core components of modern chromatography of ions.Its ultimate principle is known, and its major function can be summarized and significantly improves signal to noise ratio (S/N ratio).It is the important apolegamy parts of present novel ion chromatography system that electricity causes the leacheate generator, and its function is to utilize the electrolysis of electrodialysis principle by the needed leacheate of the online generation chromatography of ions of the pure water of upper reaches high pressure pump drive, gets into sampling valve then.Existing configuration electricity causes the ion chromatograph of leacheate generator, and its position all is between high-pressure pump and sampling valve.Wherein the leacheate generator is monofilm type structure, and the power supply that is applied during work all is constant current supplies.
Therefore, the output signal of chromatography of ions pick-up unit of the prior art is not strong, and detection sensitivity is low.
Summary of the invention
To the objective of the invention is in order solving the problems of the technologies described above, a kind of chromatography of ions pick-up unit to be provided, in the hope of realizing promoting the sensitivity that chromatography of ions detects.
The technical scheme that the present invention takes is:
A kind of chromatography of ions pick-up unit; Comprise the leacheate input end, injector, chromatographic column, rejector and the electric conductivity detector that connect successively; It is characterized in that, the two film leacheate generators of series connection between said rejector and said electric conductivity detector, said pair of film leacheate generator comprises an anionic membrane and a cationic membrane; Apply direct supply at said anionic membrane and said cationic membrane both sides, said direct supply is a stiff.
Further, said anionic membrane and cationic membrane are ion-exchange flat sheet membrane or ion-exchange microballoon or ion-exchange integral disc.
Further, said rejector is that packed column rejector or flat sheet membrane Chemical Inhibition device or flat sheet membrane electricity cause rejector.
Further, said electric conductivity detector is contact-type electric conductivity detector or contactless conductivity detector.
Further, said leacheate input end is through a high-pressure pump input leacheate.
Further, said leacheate input end comprises high-pressure pump, leacheate generator, and said high-pressure pump is carried pure water to said leacheate generator, said leacheate generator input leacheate.
Further, said leacheate generator is monofilm type structure or two membranous type structure.
Further, said leacheate is NaOH or pyrovinic acid.
The invention has the beneficial effects as follows:
Utilize the original parts of chromatography of ions pick-up unit to reconfigure that the back realizes, can online raising detection sensitivity and help realizing robotization.
Description of drawings
Accompanying drawing 1 is the synoptic diagram of prior art intermediate ion chromatographic detection apparatus;
Accompanying drawing 2 is synoptic diagram of chromatography of ions pick-up unit of the present invention;
Accompanying drawing 3 is inner structure synoptic diagram of bimodulus leacheate generator.
Label in the accompanying drawing is respectively:
1. high-pressure pump; 2. leacheate generator;
3. injector; 4. chromatographic column;
5. rejector; 6. electric conductivity detector;
7. chromatographic work station; 8. two film leacheate generators;
9. cationic membrane; 10. anionic membrane;
11. leacheate passage; 12. constant-voltage DC source;
13. regenerated liquid passage; 14. regenerated liquid passage.
Embodiment
Elaborate below in conjunction with the embodiment of accompanying drawing to chromatography of ions pick-up unit of the present invention.
Referring to accompanying drawing 2,3, the two film leacheate generators 8 of series connection between rejector 5 and electric conductivity detector 6, and use the power supply of dc constant voltage source as two membranous type leacheate generators.Rejector 5 is chosen as packed column rejector or flat sheet membrane Chemical Inhibition device or flat sheet membrane electricity and causes rejector.Electric conductivity detector 6 is chosen as contact-type electric conductivity detector or contactless conductivity detector.Two membranous type leacheate generators 8 can be selected for use like disclosed pair of film leacheate generator among the american documentation literature US7632404B2; Its ultimate principle is to utilize the sample that flows out from rejector 5 after getting into two film leacheate generators 8; Two film leacheate generators under the constant voltage source effect because system resistance reduces the increase cause system power; And online electricity causes generation and this electric current changes corresponding acid or alkali leacheate, and mixes back entering electric conductivity detector with primary sample district band and realize electric the significantly improving of detection response signal of leading.High-pressure pump of the prior art, leacheate generator can be used on leacheate input end of the present invention; The optional monofilm of leacheate generator or two film; Do not influence effect of the present invention, also can directly be pressed into NaOH at the leacheate input end, can both real the object of the invention.
Referring to accompanying drawing 3, two film leacheate generators 8 comprise cationic membrane 9 and anionic membrane 10, and cationic membrane 9 is chosen as ion-exchange flat sheet membrane or ion-exchange microballoon or ion-exchange integral disc with anionic membrane 10.Form leacheate passage 11 between cationic membrane 9 and the anionic membrane 10, can cross constant-voltage DC source 12 in cationic membrane 9 and anionic membrane 10 both sides and apply a constant voltage DC voltage.Two film leacheate generator 8 both sides regenerated liquids are certain density HNO 3Or the KOH WS; Depend on employed ion exchange material; Its concentration is generally 30-2000 mM, and its constant DC voltage that applies is generally 2-30 V, and wherein the regenerated liquid passage 13 of cationic membrane 9 is the anodic site; And the regenerated liquid passage 14 of anionic membrane 10 is the cathodic area, and center-aisle is a leacheate passage 11.
When ion chromatography yin, yang ion, leacheate commonly used is respectively NaOH (NaOH) and pyrovinic acid (CH 3SO 3H).These two kinds of leacheates are pure water through the inhibition product behind the rejector.Because pure water only has extremely faint ionization, thus the pure water conductive capability very a little less than, that is to say that pure water resistance is very big.The present invention is connected on two film leacheate generators 8 between rejector 5 and the electric conductivity detector 6, uses the NaOH leacheate as example its principle of operation to be described with analysis of anions: a constant voltage is applied on two film leacheate generators 8.The both sides regenerated liquid passage 13,14 of two film leacheate generators 8 is HNO 3The WS.When becoming pure water after rejector suppresses, the NaOH leacheate gets into electric conductivity detector 6 through two film leacheate generators.Because pure water resistance is very high, the constant voltage that is applied on two film leacheate generators 8 only can produce very little system power.Because electricity causes the eluent concentration of leacheate generator 8 generations and is proportional to system power, therefore the HNO of trace is only arranged 3Enter into electric conductivity detector 6.At this moment, electric conductivity detector is that background conductance can be expressed as G 1=G H2O+ G SHNO3(note: G SHNO3The micro-HNO that expression is produced under background current by leacheate generator 8 3The background conductance value); Behind sample introduction, sample area band (being assumed to be NaCl here) becomes HCl after rejector 5 suppresses.The conductive capability of HCl is much larger than pure water (that is to say that its resistance is much smaller than pure water); Therefore after HCl district band gets into two film leacheate generators 8 from rejector 5; Because the HCl district band conductive capability very strong with respect to pure water; Under constant voltage, will on two film leacheate generators 8, produce a very big current impulse, therefore two film leacheate generators 8 will be in the leacheate passage moment produce and the corresponding HNO of this strength of current 3Leacheate, and after HCl district band mixes, get into electric conductivity detector.At this moment, the electric conductivity value of electric conductivity detector output can be expressed as Gt=G HCl+ G HHNO3(note: G HHNO3The HNO that expression is produced under pulse current by the leacheate generator 3The background conductance value).Electric conductivity detector 6 output signals are changed to Δ G=G before and after the sample introduction HCl+ (G HHNO3-G SHNO3).The big gap of background current has caused the bigger increase of electric conductivity detector output signal before and after the sample introduction, that is to say because HNO 3Generation can significantly promote detection sensitivity, this programme is fit to inhibition type ion chromatography system very much.
Further specify testing process of the present invention through two embodiment below.
One, analysis of anions:
The both sides regenerated liquid of two film leacheate generators 8 is certain density HNO 3The WS.With NaOH leacheate, sample NaCl is the example explanation: the NaOH leacheate generates pure water and gets into electric conductivity detector 6 through the leacheate passage 11 of two film leacheate generators 8 after rejector 5 suppresses.Because pure water resistance is very high, the constant voltage that is applied on two film leacheate generators 8 only produces very little system power, therefore only has the HNO3 of denier to be caused to produce by electricity and enters into electric conductivity detector 6; Behind sample introduction, sample area band (is example with NaCl) becomes HCl behind rejector.HCl resistance is much smaller than pure water, therefore behind HCl district band entering pair film leacheate generators 8, under constant voltage, will produce a very big current impulse, will be in the leacheate passage moment produce and the corresponding HNO of this current impulse 3Leacheate, and after HCl district band mixes, get into electric conductivity detector 6, thus can significantly promote the sensitivity that electricity is led detection.
Two, analyze kation:
Two film leacheate generator 8 both sides regenerated liquids are the certain density KOH WS.With CH 3SO 3H leacheate, sample NaCl are example explanation: CH 3SO 3The H leacheate generates pure water and gets into electric conductivity detector 6 through the leacheate passage 11 of two film leacheate generators 8 after rejector 6 suppresses.Because pure water resistance is very high, the constant voltage that is applied on two film leacheate generators 8 only produces very little system power, therefore only has the KOH of denier to be caused to produce by electricity and enters into electric conductivity detector 6; Behind sample introduction, sample area band (is example with NaCl) becomes NaOH behind rejector.NaOH resistance is much smaller than pure water; Therefore, NaOH district band under constant voltage, will produce a very big current impulse after getting into two film leacheate generators 8; Will be in the leacheate passage moment produce and the corresponding KOH leacheate of this current impulse; And after NaOH district band mixes, get into electric conductivity detector 6, thereby can significantly promote the sensitivity that electricity is led detection.
The above only is a preferred implementation of the present invention; Should be pointed out that for those skilled in the art, under the prerequisite that does not break away from the principle of the invention; Can also make some improvement and retouching, these improvement and retouching also should be regarded as protection scope of the present invention.

Claims (8)

1. chromatography of ions pick-up unit; Comprise the leacheate input end, injector, chromatographic column, rejector and the electric conductivity detector that connect successively; It is characterized in that: the two film leacheate generators of series connection between said rejector and said electric conductivity detector; Said pair of film leacheate generator comprises an anionic membrane and a cationic membrane, applies direct supply at said anionic membrane and said cationic membrane both sides, and said direct supply is a stiff.
2. chromatography of ions pick-up unit according to claim 1 is characterized in that: said anionic membrane and cationic membrane are ion-exchange flat sheet membrane or ion-exchange microballoon or ion-exchange integral disc.
3. chromatography of ions pick-up unit according to claim 1 is characterized in that: said rejector is that packed column rejector or flat sheet membrane Chemical Inhibition device or flat sheet membrane electricity cause rejector.
4. chromatography of ions pick-up unit according to claim 1 is characterized in that: said electric conductivity detector is contact-type electric conductivity detector or contactless conductivity detector.
5. chromatography of ions pick-up unit according to claim 1 is characterized in that: said leacheate input end is through a high-pressure pump input leacheate.
6. chromatography of ions pick-up unit according to claim 1 is characterized in that: said leacheate input end comprises high-pressure pump, leacheate generator, and said high-pressure pump is carried pure water to said leacheate generator, said leacheate generator input leacheate.
7. chromatography of ions pick-up unit according to claim 6 is characterized in that: said leacheate generator is monofilm type structure or two membranous type structure.
8. according to each described chromatography of ions pick-up unit in the claim 1 to 7, it is characterized in that: said leacheate is NaOH or pyrovinic acid.
CN2012100754404A 2012-03-21 2012-03-21 Ion chromatography detection device Pending CN102621241A (en)

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Citations (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
EP0180321A2 (en) * 1984-10-04 1986-05-07 Dionex Corporation Modified membrane suppressor and method of use
US5045204A (en) * 1990-02-13 1991-09-03 Dionex Corporation Method and apparatus for generating a high purity chromatography eluent
US6225129B1 (en) * 1998-02-02 2001-05-01 Dionex Corporation Large capacity acid or base generation apparatus and method of use
CN101377477A (en) * 2008-10-09 2009-03-04 北京市东西电子技术研究所 Automatic generating apparatus of ion chromatogram eluate
CN101971020A (en) * 2008-02-28 2011-02-09 迪奥尼克斯公司 Ion detector and system

Patent Citations (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
EP0180321A2 (en) * 1984-10-04 1986-05-07 Dionex Corporation Modified membrane suppressor and method of use
US5045204A (en) * 1990-02-13 1991-09-03 Dionex Corporation Method and apparatus for generating a high purity chromatography eluent
US6225129B1 (en) * 1998-02-02 2001-05-01 Dionex Corporation Large capacity acid or base generation apparatus and method of use
CN101971020A (en) * 2008-02-28 2011-02-09 迪奥尼克斯公司 Ion detector and system
CN101377477A (en) * 2008-10-09 2009-03-04 北京市东西电子技术研究所 Automatic generating apparatus of ion chromatogram eluate

Non-Patent Citations (4)

* Cited by examiner, † Cited by third party
Title
《ANALYTICAL CHEMISTRY 》 20071207 Yang, Bingcheng; Takeuchi, Masaki; Dasgupta, Purnendu K. On-line gas-free electrodialytic eluent generator for capillary ion chromatography 40-47 第80卷, 第1期 *
《JOURNAL OF CHROMATOGRAPHY A》 20090115 Yang, Bingcheng; Zhang, Feifang; Liang, Xinmiao A multifunctional dual membrane electrodialytic eluent generator for capillary ion chromatography 第1216卷, 第12期 *
YANG, BINGCHENG; TAKEUCHI, MASAKI; DASGUPTA, PURNENDU K.: "On-line gas-free electrodialytic eluent generator for capillary ion chromatography", 《ANALYTICAL CHEMISTRY 》, vol. 80, no. 1, 7 December 2007 (2007-12-07), pages 40 - 47 *
YANG, BINGCHENG; ZHANG, FEIFANG; LIANG, XINMIAO: "A multifunctional dual membrane electrodialytic eluent generator for capillary ion chromatography", 《JOURNAL OF CHROMATOGRAPHY A》, vol. 1216, no. 12, 15 January 2009 (2009-01-15) *

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Application publication date: 20120801