CN104237426A - On-line pretreatment ion chromatogram column switching system and method used for detecting conventional anions and organic acids in biodiesel samples - Google Patents
On-line pretreatment ion chromatogram column switching system and method used for detecting conventional anions and organic acids in biodiesel samples Download PDFInfo
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- CN104237426A CN104237426A CN201410428751.3A CN201410428751A CN104237426A CN 104237426 A CN104237426 A CN 104237426A CN 201410428751 A CN201410428751 A CN 201410428751A CN 104237426 A CN104237426 A CN 104237426A
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Abstract
The invention discloses an on-line pretreatment ion chromatogram column switching system used for detecting conventional anions and organic acids in biodiesel samples and a detection method thereof. The on-line pretreatment ion chromatogram column switching system comprises a quaternary gradient pump, an anion capturing column, a pretreatment column, a six-way valve, a ten-way valve, a sample feeder, a quantifying ring, a leacheate generator, a liquid conveying pump, an enriching column, a protection column, an analysis column, a suppressor, an electrical conductivity detector and a waste liquid cylinder, wherein the ten-way valve is used as the six-way valve; the ten-way valve is connected with the pretreatment column, the anion capturing column, the sample feeder, the quantifying ring and the waste liquid cylinder. The anion capturing column used in the ion chromatogram column switching system can be regenerated by high-concentration leacheate; trace anions pumped by the quaternary gradient pump can be removed; the accuracy of the detection result is ensured; the application range is wide.
Description
Technical field
The present invention relates to a kind of chromatography of ions Vavle switching system of online pre-treatment, specifically, be a kind of conventional anion and organic acid method in chromatography of ions on-line checkingi biodiesel, can realize 7 kinds of conventional anion in biodiesel and 2 kinds of organic acid on-line checkingi.
Technical background
Biodiesel, refer to oil crops as soybean, rape, cotton, palm etc., the hydrophyte such as Wild oil plant and engineering microalgae grease and animal fat, food garbage wet goods are the reproducibility diesel fuel of the replaced petrifaction diesel that feedstock oil is made by ester exchange process.Biodiesel, as the substitute metirials of diesel oil of high-quality, belongs to environmentally friendly green fuel.In the GB of current China, the physical and chemical quality indexes of biodiesel comprises biodiesel density, acid number, sulfur content, moisture etc.Existing detection method is fixed total body detecting method for each index, needs each to measure.Operate more loaded down with trivial details.And due to the polytrope of biodiesel raw material and production technology, and this province composition is more complicated, there is larger difference in its physicochemical property of different biodiesel of originating.This experiment establishes the chromatography of ions and measures conventional anion and organic acid method in biodiesel respectively, can be used to the quality judging biodiesel, also can be used as a physical and chemical quality indexes of biodiesel.
Chromatography of ions is present analysis ionic substance effective method the most, and it achieves great success in Anionic recognition, and maximum contribution is exactly to conventional 7 kinds of negative ion (F
-, Cl
-, NO
2-, Br
-, NO
3-, PO
4 3-, SO
4 2-) and part organic acid detection (CHO
2 -, CH
3cO
2 -) detection.But when containing a large amount of water-soluble organic substrate in sample, direct injected can damage ion chromatographic column, reduces its serviceable life.Based on this, the application of chromatography of ions just receives certain restriction.The present invention increases online preprocessing system and enriching column establishes a set of chromatography of ions Vavle switching system, the water-soluble organic substrate existed in removing Bio-diesel Samples, achieve the online pre-treatment to sample, Sync enrichment post enrichment 7 kinds of conventional anion and organic acid, reach testing goal.
Summary of the invention
The present invention establish a kind of can the chromatography of ions Vavle switching system of pre-treatment Bio-diesel Samples online, protect ion chromatographic column, avoid loaded down with trivial details time-consuming sample pre-treatments step, decrease manpower consumption.In Vavle switching process, the regeneration on the one hand to pre-treatment post NG1, and the balance of preprocessing system; Ion chromatography conventional anion and organic acid on the one hand, reaches efficient time and utilizes.The present invention is achieved through the following technical solutions:
The invention discloses a kind of for conventional anion in detection of complex sample and organic acid ion chromatographic column switched system, comprise quaternary gradient pump, negative ion catches post, pre-treatment post, six-way valve, ten-way valve, injector, quantitative loop, leacheate generator, infusion pump, enriching column, guard column, analytical column, rejector, electric conductivity detector, waste liquid bottle.Ten-way valve uses as six-way valve, ten-way valve connects pre-treatment post, negative ion catches post, injector, quantitative loop, waste liquid bottle.Six-way valve connects leacheate generator, enriching column, pre-treatment post, waste liquid bottle, guard column, linking parsing post, rejector, electric conductivity detector, leacheate generator and waste liquid bottle successively after guard column.
As improving further, pre-treatment post of the present invention, utilizes the functional group of filling surface to retain water soluble organic substance, to conventional anion ion and organic acid without reserve, reaches the effect of water soluble organic substance in removing biodiesel.
As improving further, enriching column of the present invention is guard column, utilizes the negative ion that surperficial quaternary ammonium group enrichment is to be detected, reaches the effect of enrichment.
Present invention also offers a kind of can the method for the chromatography of ions Vavle switching of pre-treatment Bio-diesel Samples online, comprise regeneration four steps of the chromatographic resolution analysis pre-treatment simultaneously post of ion after the collection of baseline, the online pre-treatment of sample, desired anion and organic acid enrichment, enrichment, concrete steps are as follows:
(1), the drafting of baseline: leacheate is continuously delivered to above-mentioned ion chromatographic column switched system, makes system reach equilibrium state, and conductance signal is detected by electric conductivity detector and got off to draw out corresponding figure line by computer record;
(2), the pre-treatment of sample: the water that sample is pumped by quaternary gradient pump is brought into the water-soluble organic substrate in NG1 pre-treatment post removing Bio-diesel Samples, and conventional anion and organic acid are not then retained by NG1 post, in enriching column.
(3), desired anion and organic acid enrichment: then, the water pumped by quaternary gradient pump is brought in enriching column for the conventional anion do not retained by pre-treatment post NG1 and organic acid.
(4), the regeneration of the chromatographic resolution analysis pre-treatment simultaneously post of ion after enrichment: infusion pump conveying leacheate, to enriching column, will treat that measured ion is delivered to guard column, separating column, rejector, electric conductivity detector successively; The acetonitrile that quaternary gradient pump pumps simultaneously rinses NG1 pre-treatment post, to pre-treatment column regeneration, then watering balance system, for sample introduction is prepared next time.
Beneficial effect of the present invention is as follows:
1, in the chromatography of ions Vavle switching system that the present invention sets up, used negative ion catches post, can regenerate with the leacheate of high concentration, can remove the trace anion pumped by quaternary gradient pump, the accuracy of guarantee testing result;
2, applied range.The present invention, except being applicable to conventional anion and organic acid on-line checkingi in Bio-diesel Samples, equally also can be used for detecting after other contains the online pre-treatment of organic substrate sample;
3, the pre-treatment post described in the present invention can utilize the functional group of filling surface to retain water soluble organic substance, to conventional anion ion and organic acid without reserve, reaches the effect of water soluble organic substance in removing biodiesel.
4, the enriching column of the present invention negative ion that utilizes surperficial quaternary ammonium group enrichment to be detected, reaches the effect of enrichment.
Accompanying drawing explanation
Fig. 1 is the sample online pre-treatment Vavle switching system that the present invention sets up;
In figure, 1-infusion pump, 2-enriching column, 3-guard column, 4-analytical column, 5-rejector, 6-electric conductivity detector, 7-waste liquid bottle, 8-quaternary gradient pump, 9-negative ion catches post, 10-NG1 pre-treatment post, 11-injector, 12-quantitative loop, 13-ten-way valve, 14-six-way valve;
Fig. 2 is seven kinds of negative ion (5mg/LF
-, 5mg/LCl
-, 5mg/LNO
2-, 5mg/LBr
-, 5mg/LNO3,10mg/LSO
4 2-, 10mg/LPO
4 3) and two kinds of organic acid (20mg/LCHO
2 -, 10mg/LCH
3cO
2 -) the chromatogram of mixed standard solution;
Fig. 3 is the chromatogram of Bio-diesel Samples.
Embodiment
Below by specific embodiment, in conjunction with Figure of description, technical scheme of the present invention is described in further detail:
The detection of Bio-diesel Samples
Fig. 1 is the schematic diagram of the on-line sample preparation chromatography of ions Vavle switching system that the present invention sets up, and this system comprises infusion pump 1, enriching column 2; guard column 3, analytical column 4, rejector 5; electric conductivity detector 6, waste liquid bottle 7, quaternary gradient pump 8; negative ion catches post 9; pre-treatment post 10, injector 11, quantitative loop 12; ten-way valve 13, six-way valve 14.Wherein ten-way valve 13 connects NG1 pre-treatment post 10, negative ion catches post 9, injector 11, quantitative loop 12, waste liquid bottle 7.Six-way valve 14 connects infusion pump 1, enriching column 2, pre-treatment post 10, waste liquid bottle 7, guard column 3, linking parsing post 4, rejector 5, electric conductivity detector 6, leacheate generator 1 and waste liquid bottle 7 successively after described guard column.By Bio-diesel Samples sample introduction to ten-way valve 13, sample is brought into pre-treatment post 10 and is removed water-soluble organic substrate by quaternary gradient pump 8, and conventional anion and organic acid are collected enriching column.Switch ten-way valve 13, the acetonitrile that quaternary gradient pump 8 pumps rinses NG1 pre-treatment post 10, regenerates pre-treatment post 10.Switch six-way valve 14, sample delivery to guard column 3, analytical column 4, rejector 5, electric conductivity detector 6, is finally drained into waste liquid bottle 7 by leacheate generator 1.
Concrete steps are as follows:
The configuration of standard solution: the original 1000mg/L (F in laboratory
-, Cl
-, NO
2-, Br
-, NO
3-, PO
4 3-, SO
4 2-, CHO
2 -, CH
3cO
2 -) standard reserving solution, at 4 DEG C preserve, standard reserving solution is diluted to desired concn by the used time.
Leacheate condition: adopt the gradient elution of KOH leacheate generator, 0-9minKOH concentration is 2mmol/L, 9-18minKOH concentration be 14mmol/L, 18-23minKOH concentration be 30mmol/L, 23-27minKOH concentration is 2mmol/L.
The pre-treatment of sample: by the standard solution sample introduction containing 9 kinds of negative ion to quantitative loop 12, switch ten-way valve 13, infusion pump quaternary gradient pump 8 carries water to be brought into by the sample in quantitative loop 12 in NG1 pre-treatment post 10, water-soluble base in removing Bio-diesel Samples, prevents disturbed specimen from measuring and pollutes chromatographic column.
The enrichment of desired anion: switch six-way valve 14, the conventional anion do not retained by NG1 pre-treatment post 10 and organic acid, the water pumped along with quaternary gradient pump 8 is brought into enrichment in enriching column.
The regeneration of the stratographic analysis pre-treatment simultaneously pillar of ion after enrichment: infusion pump 1 carries leacheate to enriching column 2, will treat that measured ion is delivered to guard column 3, analytical column 4, rejector 5, electric conductivity detector 6 successively in enriching column 2; The acetonitrile that quaternary gradient pump 8 pumps simultaneously rinses NG1 pre-treatment post 10, regenerates pre-treatment post 10, then by the water balance system that quaternary gradient pump 8 pumps, for sample introduction is prepared next time.Fig. 2 is seven kinds of negative ion (5mg/LF-, 5mg/LCl-, 5mg/LNO2-, 5mg/LBr-, 5mg/LNO3,10mg/LSO42-, 10mg/LPO43) and the chromatogram of mixed standard solution of two kinds of organic acids (20mg/LCHO2-, 10mg/LCH3CO2-); Show that the method can detect 9 kinds of negative ion simultaneously.
By Bio-diesel Samples sample introduction in quantitative loop 12, repeat above step.Fig. 3 is the chromatogram of Bio-diesel Samples, and show that the method can to the fluorine in biodiesel, acetic acid, formic acid, chlorine, bromine, sulfate radical 6 kinds of ions measure simultaneously.
Finally, it is also to be noted that enumerate above be only specific embodiments of the invention son.Obviously, the invention is not restricted to above examples of implementation, many distortion can also be had.All distortion that those of ordinary skill in the art can directly derive from content disclosed by the invention or associate, all should think protection scope of the present invention.
Claims (4)
1. the ion chromatographic column switched system that after eliminating for the online body of complex sample, conventional anion and organic acid detect, it is characterized in that, described system comprises infusion pump (1), enriching column (2), guard column (3), analytical column (4), rejector (5), electric conductivity detector (6), waste liquid bottle (7), quaternary gradient pump (8), negative ion catches post (9), pre-treatment post (10), ten-way valve (13) and six-way valve (14), described ten-way valve (13) uses as six-way valve, described ten-way valve (13) connects negative ion and catches post (9), pre-treatment post (10), syringe (11), quantitative loop (12), waste liquid bottle (7), six-way valve (14) connects enriching column (2), pre-treatment post (10), infusion pump (1), waste liquid bottle (7), guard column (3), linking parsing post (4) successively after described guard column (3), rejector (5), electric conductivity detector (6) and waste liquid bottle (7).
2. according to claim 1 for detecting wherein conventional anion and organic acid ion chromatographic column switched system after the online pre-treatment of Bio-diesel Samples, it is characterized in that, described pre-treatment post (10) is for removing the water soluble organic substance of low pole.
3. the ion chromatographic column switched system detected for the online pre-treatment conventional anion of Bio-diesel Samples and organic acid according to claim 1, it is characterized in that, be filled with polymer beads in described enriching column (2) post, the negative ion utilizing surperficial quaternary ammonium group enrichment to be detected is in order to enrichment.
4. the detection method for detecting wherein conventional anion and organic acid ion chromatographic column switched system after the online pre-treatment of Bio-diesel Samples according to claim 1 or 2 or 3, it is characterized in that, described method comprises regeneration four steps of the stratographic analysis pre-treatment simultaneously pillar of ion after the collection of baseline, sample pre-treatments, desired anion and organic acid enrichment, enrichment, and concrete steps are as follows:
1), the drafting of baseline: leacheate is continuously delivered to above-mentioned ion chromatographic column switched system by infusion pump (1), make system reach equilibrium state, conductance signal is detected by electric conductivity detector (6) and is got off to draw out corresponding figure line by computer record;
2), the pre-treatment of sample: the water that sample is pumped by quaternary gradient pump (8) enters into the water-soluble organic substrate of NG1 pre-treatment post (10) removing sample, conventional anion and organic acid are not then retained by NG1 post, flow in enriching column (2);
3), desired anion and organic acid enrichment: the conventional anion do not retained by NG1 pre-treatment post (10) and organic acid, the water pumped along with quaternary gradient pump (8) is brought into enrichment in enriching column (2);
4), ion enters chromatographic column and carries out analysis pre-treatment simultaneously column regeneration after enrichment: infusion pump (1) conveying leacheate, to enriching column (2), will treat that measured ion is delivered to guard column (3), analytical column (4), rejector (5), electric conductivity detector (6) successively; The acetonitrile that quaternary gradient pump pumps simultaneously rinses NG1 pre-treatment post (10), to pre-treatment post (10) regeneration, then the water balance system using quaternary gradient pump (8) to pump, for sample introduction is prepared next time.
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|---|---|---|---|
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Cited By (5)
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| CN105424865A (en) * | 2015-12-10 | 2016-03-23 | 苏州国环环境检测有限公司 | Illegal cooking oil detection method |
| CN105929033A (en) * | 2016-04-12 | 2016-09-07 | 海南大学 | System and method for measuring trace lactic acid ion in lobaplatin by using column switching-ion chromatography method |
| CN107655992A (en) * | 2017-09-25 | 2018-02-02 | 佛山市顺德区孚延盛润滑油有限公司 | A kind of method with the low acid number of ion chromatography refrigerator oil |
| CN111610278A (en) * | 2020-06-16 | 2020-09-01 | 浙江浙能技术研究院有限公司 | Method and device for switching and measuring sulfur trioxide in isopropanol solution by ion chromatography valve |
| CN114324635A (en) * | 2021-12-20 | 2022-04-12 | 杭州医学院 | Method for measuring bromate in drinking water by using ion chromatography online matrix elimination system |
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Cited By (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN105424865A (en) * | 2015-12-10 | 2016-03-23 | 苏州国环环境检测有限公司 | Illegal cooking oil detection method |
| CN105929033A (en) * | 2016-04-12 | 2016-09-07 | 海南大学 | System and method for measuring trace lactic acid ion in lobaplatin by using column switching-ion chromatography method |
| CN107655992A (en) * | 2017-09-25 | 2018-02-02 | 佛山市顺德区孚延盛润滑油有限公司 | A kind of method with the low acid number of ion chromatography refrigerator oil |
| CN111610278A (en) * | 2020-06-16 | 2020-09-01 | 浙江浙能技术研究院有限公司 | Method and device for switching and measuring sulfur trioxide in isopropanol solution by ion chromatography valve |
| CN114324635A (en) * | 2021-12-20 | 2022-04-12 | 杭州医学院 | Method for measuring bromate in drinking water by using ion chromatography online matrix elimination system |
| CN114324635B (en) * | 2021-12-20 | 2024-04-16 | 杭州医学院 | Method for measuring bromate in drinking water by utilizing ion chromatography on-line matrix elimination system |
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Application publication date: 20141224 |