CN112240917A - Ion chromatograph - Google Patents
Ion chromatograph Download PDFInfo
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- CN112240917A CN112240917A CN202010916690.0A CN202010916690A CN112240917A CN 112240917 A CN112240917 A CN 112240917A CN 202010916690 A CN202010916690 A CN 202010916690A CN 112240917 A CN112240917 A CN 112240917A
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- cationic
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- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 82
- 150000002500 ions Chemical class 0.000 claims abstract description 57
- VEXZGXHMUGYJMC-UHFFFAOYSA-M Chloride anion Chemical compound [Cl-] VEXZGXHMUGYJMC-UHFFFAOYSA-M 0.000 claims abstract description 35
- 238000000746 purification Methods 0.000 claims abstract description 26
- 238000004255 ion exchange chromatography Methods 0.000 claims abstract description 6
- 238000004458 analytical method Methods 0.000 claims abstract description 4
- 239000011347 resin Substances 0.000 claims description 242
- 229920005989 resin Polymers 0.000 claims description 240
- 125000002091 cationic group Chemical group 0.000 claims description 166
- 239000000523 sample Substances 0.000 claims description 118
- SQGYOTSLMSWVJD-UHFFFAOYSA-N silver(1+) nitrate Chemical compound [Ag+].[O-]N(=O)=O SQGYOTSLMSWVJD-UHFFFAOYSA-N 0.000 claims description 84
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 80
- 239000000243 solution Substances 0.000 claims description 74
- 150000001768 cations Chemical class 0.000 claims description 65
- 239000007788 liquid Substances 0.000 claims description 65
- 238000002347 injection Methods 0.000 claims description 58
- 239000007924 injection Substances 0.000 claims description 58
- 239000012498 ultrapure water Substances 0.000 claims description 53
- 229910001961 silver nitrate Inorganic materials 0.000 claims description 42
- 238000005406 washing Methods 0.000 claims description 36
- 238000002156 mixing Methods 0.000 claims description 33
- 238000002360 preparation method Methods 0.000 claims description 33
- 238000004140 cleaning Methods 0.000 claims description 27
- 238000001816 cooling Methods 0.000 claims description 25
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 claims description 22
- 239000002699 waste material Substances 0.000 claims description 20
- WDIHJSXYQDMJHN-UHFFFAOYSA-L barium chloride Chemical compound [Cl-].[Cl-].[Ba+2] WDIHJSXYQDMJHN-UHFFFAOYSA-L 0.000 claims description 16
- 229910001626 barium chloride Inorganic materials 0.000 claims description 16
- 239000012521 purified sample Substances 0.000 claims description 16
- 239000003153 chemical reaction reagent Substances 0.000 claims description 15
- 238000002791 soaking Methods 0.000 claims description 15
- 238000003756 stirring Methods 0.000 claims description 15
- 238000001291 vacuum drying Methods 0.000 claims description 15
- 238000005303 weighing Methods 0.000 claims description 15
- 239000008367 deionised water Substances 0.000 claims description 13
- 229910021641 deionized water Inorganic materials 0.000 claims description 13
- 238000000926 separation method Methods 0.000 claims description 13
- 238000001035 drying Methods 0.000 claims description 10
- 230000003213 activating effect Effects 0.000 claims description 9
- 238000007789 sealing Methods 0.000 claims description 9
- 238000011049 filling Methods 0.000 claims description 7
- 238000000034 method Methods 0.000 claims description 7
- 238000002835 absorbance Methods 0.000 claims description 5
- 238000004587 chromatography analysis Methods 0.000 claims description 5
- 238000004321 preservation Methods 0.000 claims description 5
- 229910002651 NO3 Inorganic materials 0.000 claims description 4
- 239000002253 acid Substances 0.000 claims description 4
- 238000005342 ion exchange Methods 0.000 claims description 4
- -1 nitrate ions Chemical class 0.000 claims description 4
- 238000011068 loading method Methods 0.000 claims description 3
- 125000004435 hydrogen atom Chemical group [H]* 0.000 claims 1
- VLTRZXGMWDSKGL-UHFFFAOYSA-N perchloric acid Chemical compound OCl(=O)(=O)=O VLTRZXGMWDSKGL-UHFFFAOYSA-N 0.000 abstract description 31
- VLTRZXGMWDSKGL-UHFFFAOYSA-M perchlorate Inorganic materials [O-]Cl(=O)(=O)=O VLTRZXGMWDSKGL-UHFFFAOYSA-M 0.000 abstract description 28
- 238000012360 testing method Methods 0.000 abstract description 22
- 238000001514 detection method Methods 0.000 abstract description 16
- BVKZGUZCCUSVTD-UHFFFAOYSA-M Bicarbonate Chemical compound OC([O-])=O BVKZGUZCCUSVTD-UHFFFAOYSA-M 0.000 abstract description 15
- BVKZGUZCCUSVTD-UHFFFAOYSA-L Carbonate Chemical compound [O-]C([O-])=O BVKZGUZCCUSVTD-UHFFFAOYSA-L 0.000 abstract description 15
- QAOWNCQODCNURD-UHFFFAOYSA-L Sulfate Chemical compound [O-]S([O-])(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-L 0.000 abstract description 15
- 229910021645 metal ion Inorganic materials 0.000 abstract description 12
- 230000002411 adverse Effects 0.000 abstract description 7
- 239000002352 surface water Substances 0.000 abstract description 7
- 239000003651 drinking water Substances 0.000 abstract description 6
- 235000020188 drinking water Nutrition 0.000 abstract description 6
- 230000000694 effects Effects 0.000 abstract description 5
- 238000005516 engineering process Methods 0.000 abstract description 5
- 239000002351 wastewater Substances 0.000 abstract description 5
- 238000012113 quantitative test Methods 0.000 abstract description 2
- 241001089723 Metaphycus omega Species 0.000 description 9
- CURLTUGMZLYLDI-UHFFFAOYSA-N Carbon dioxide Chemical compound O=C=O CURLTUGMZLYLDI-UHFFFAOYSA-N 0.000 description 4
- TZCXTZWJZNENPQ-UHFFFAOYSA-L barium sulfate Chemical compound [Ba+2].[O-]S([O-])(=O)=O TZCXTZWJZNENPQ-UHFFFAOYSA-L 0.000 description 4
- 239000002244 precipitate Substances 0.000 description 4
- OYPRJOBELJOOCE-UHFFFAOYSA-N Calcium Chemical compound [Ca] OYPRJOBELJOOCE-UHFFFAOYSA-N 0.000 description 3
- 239000011575 calcium Substances 0.000 description 3
- 230000000052 comparative effect Effects 0.000 description 3
- 239000012535 impurity Substances 0.000 description 3
- YPJKMVATUPSWOH-UHFFFAOYSA-N nitrooxidanyl Chemical compound [O][N+]([O-])=O YPJKMVATUPSWOH-UHFFFAOYSA-N 0.000 description 3
- 238000012545 processing Methods 0.000 description 3
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 2
- JLVVSXFLKOJNIY-UHFFFAOYSA-N Magnesium ion Chemical compound [Mg+2] JLVVSXFLKOJNIY-UHFFFAOYSA-N 0.000 description 2
- KWYUFKZDYYNOTN-UHFFFAOYSA-M Potassium hydroxide Chemical compound [OH-].[K+] KWYUFKZDYYNOTN-UHFFFAOYSA-M 0.000 description 2
- 229910021607 Silver chloride Inorganic materials 0.000 description 2
- CDBYLPFSWZWCQE-UHFFFAOYSA-L Sodium Carbonate Chemical compound [Na+].[Na+].[O-]C([O-])=O CDBYLPFSWZWCQE-UHFFFAOYSA-L 0.000 description 2
- FAPWRFPIFSIZLT-UHFFFAOYSA-M Sodium chloride Chemical compound [Na+].[Cl-] FAPWRFPIFSIZLT-UHFFFAOYSA-M 0.000 description 2
- 229910052791 calcium Inorganic materials 0.000 description 2
- 239000001569 carbon dioxide Substances 0.000 description 2
- 229910002092 carbon dioxide Inorganic materials 0.000 description 2
- 230000008021 deposition Effects 0.000 description 2
- AXZAYXJCENRGIM-UHFFFAOYSA-J dipotassium;tetrabromoplatinum(2-) Chemical compound [K+].[K+].[Br-].[Br-].[Br-].[Br-].[Pt+2] AXZAYXJCENRGIM-UHFFFAOYSA-J 0.000 description 2
- 238000007599 discharging Methods 0.000 description 2
- 239000002384 drinking water standard Substances 0.000 description 2
- 239000003344 environmental pollutant Substances 0.000 description 2
- 239000007789 gas Substances 0.000 description 2
- 239000003673 groundwater Substances 0.000 description 2
- 238000004519 manufacturing process Methods 0.000 description 2
- 231100000719 pollutant Toxicity 0.000 description 2
- 229910001487 potassium perchlorate Inorganic materials 0.000 description 2
- HKZLPVFGJNLROG-UHFFFAOYSA-M silver monochloride Chemical compound [Cl-].[Ag+] HKZLPVFGJNLROG-UHFFFAOYSA-M 0.000 description 2
- 238000006467 substitution reaction Methods 0.000 description 2
- FYYHWMGAXLPEAU-UHFFFAOYSA-N Magnesium Chemical compound [Mg] FYYHWMGAXLPEAU-UHFFFAOYSA-N 0.000 description 1
- PMZURENOXWZQFD-UHFFFAOYSA-L Sodium Sulfate Chemical compound [Na+].[Na+].[O-]S([O-])(=O)=O PMZURENOXWZQFD-UHFFFAOYSA-L 0.000 description 1
- AUYYCJSJGJYCDS-LBPRGKRZSA-N Thyrolar Chemical class IC1=CC(C[C@H](N)C(O)=O)=CC(I)=C1OC1=CC=C(O)C(I)=C1 AUYYCJSJGJYCDS-LBPRGKRZSA-N 0.000 description 1
- 238000010306 acid treatment Methods 0.000 description 1
- 239000000654 additive Substances 0.000 description 1
- 229910001424 calcium ion Inorganic materials 0.000 description 1
- 238000011161 development Methods 0.000 description 1
- 230000005611 electricity Effects 0.000 description 1
- 239000003337 fertilizer Substances 0.000 description 1
- 239000000945 filler Substances 0.000 description 1
- 230000037406 food intake Effects 0.000 description 1
- 230000002401 inhibitory effect Effects 0.000 description 1
- 239000003621 irrigation water Substances 0.000 description 1
- 239000010985 leather Substances 0.000 description 1
- 239000010687 lubricating oil Substances 0.000 description 1
- 229910052749 magnesium Inorganic materials 0.000 description 1
- 239000011777 magnesium Substances 0.000 description 1
- 229910001425 magnesium ion Inorganic materials 0.000 description 1
- 230000004060 metabolic process Effects 0.000 description 1
- 238000013508 migration Methods 0.000 description 1
- 230000005012 migration Effects 0.000 description 1
- 229910052757 nitrogen Inorganic materials 0.000 description 1
- 238000012856 packing Methods 0.000 description 1
- 239000003973 paint Substances 0.000 description 1
- 239000003380 propellant Substances 0.000 description 1
- 238000011002 quantification Methods 0.000 description 1
- 239000002994 raw material Substances 0.000 description 1
- 230000000717 retained effect Effects 0.000 description 1
- 238000005070 sampling Methods 0.000 description 1
- 230000028327 secretion Effects 0.000 description 1
- 229910000029 sodium carbonate Inorganic materials 0.000 description 1
- 239000011780 sodium chloride Substances 0.000 description 1
- 229910052938 sodium sulfate Inorganic materials 0.000 description 1
- 235000011152 sodium sulphate Nutrition 0.000 description 1
- 239000002689 soil Substances 0.000 description 1
- 239000007787 solid Substances 0.000 description 1
- 210000001685 thyroid gland Anatomy 0.000 description 1
- 239000005495 thyroid hormone Substances 0.000 description 1
- 229940036555 thyroid hormone Drugs 0.000 description 1
Images
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
- G01N30/02—Column chromatography
-
- 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
- G01N30/02—Column chromatography
- G01N30/04—Preparation or injection of sample to be analysed
- G01N30/16—Injection
- G01N30/20—Injection using a sampling valve
-
- 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
Landscapes
- Physics & Mathematics (AREA)
- Health & Medical Sciences (AREA)
- Life Sciences & Earth Sciences (AREA)
- Chemical & Material Sciences (AREA)
- Analytical Chemistry (AREA)
- Biochemistry (AREA)
- General Health & Medical Sciences (AREA)
- General Physics & Mathematics (AREA)
- Immunology (AREA)
- Pathology (AREA)
- Investigating Or Analyzing Non-Biological Materials By The Use Of Chemical Means (AREA)
Abstract
The invention provides an ion chromatograph, which solves the technical problems that when the existing perchlorate testing technology in water (surface water, waste water, drinking water and the like) is applied, the testing water sample contains carbonate, bicarbonate, sulfate, chloride and metal ions, the testing result and a testing instrument are adversely affected, the quantitative testing of perchlorate in water is inconvenient, and the long-period stable operation of the instrument is inconvenient. The system comprises a sample introduction system, a sample purification system, an ion chromatography analysis system and an ion chromatograph control system; the sample introduction system comprises a sample introduction valve, a first sample introduction pipe for water sample circulation, a first pipeline for mobile phase circulation and a first pump arranged on the first pipeline. The invention avoids the adverse effect on the detection result and the detection instrument due to the fact that the test water sample contains carbonate, bicarbonate, sulfate, chloride and metal ions, facilitates the quantitative test of perchlorate in water, and can ensure the long-period stable operation of the instrument.
Description
Technical Field
The invention relates to detection equipment for perchlorate in water, in particular to an ion chromatograph.
Background
Perchlorate is a common and potentially harmful pollutant that can disrupt thyroid function, both naturally occurring and artificially synthesized. The naturally occurring perchlorate is often used as a fertilizer raw material, and the artificially synthesized perchlorate is widely applied to the fields of leather processing, rubber manufacturing, paint production, lubricating oil additives and the like and is a main component of solid rocket propellants. The use and improper treatment of highly water-soluble perchlorate salts leads to migration to ground water, surface water, contaminated soil, drinking water and irrigation water.
In recent years, perchlorate has been detected in a large amount of ground water and surface water, and has attracted high attention from the world population. Perchlorate is listed in the list of post-supplementation pollutants of drinking water standards in the united states because it causes insufficient secretion of thyroid hormone after ingestion into humans, thereby inhibiting normal metabolism and growth and development of humans. The Chinese drinking water standard is about to be listed.
At present, the perchloric acid in water has no corresponding national, industrial and regional water detection standard in China. The international standard is only ISO standard, the standard operation process is complex, the instrument cost is high, the application and popularization are limited, and the detection result is adversely affected by the carbonate, bicarbonate, sulfate, chloride and metal ions contained in the reclaimed water sample.
The applicant has found that the prior art has at least the following technical problems:
when the existing perchlorate testing technology in water (surface water, waste water, drinking water and the like) is applied, the testing water sample contains carbonate, bicarbonate, sulfate, chloride and metal ions, so that the testing result and a testing instrument are adversely affected, and the quantitative testing of perchlorate in water and the long-period stable operation of the instrument are inconvenient.
Disclosure of Invention
The invention aims to provide an ion chromatograph, which aims to solve the technical problems that when the existing perchlorate testing technology in water (surface water, waste water, drinking water and the like) is applied, the testing water sample contains carbonate, bicarbonate, sulfate, chloride and metal ions, so that the testing result and a testing instrument are adversely affected, the quantitative testing of perchlorate in water is inconvenient, and the instrument can not stably run for a long period. The technical effects that can be produced by the preferred technical scheme in the technical schemes provided by the invention are described in detail in the following.
In order to achieve the purpose, the invention provides the following technical scheme:
the invention provides an ion chromatograph, which comprises a sample introduction system, a sample purification system, an ion chromatographic analysis system and an ion chromatograph control system; wherein,
the sample introduction system comprises a sample introduction valve, a first sample introduction pipe for water sample circulation, a first pipeline for mobile phase circulation and a first pump arranged on the first pipeline; wherein, a first liquid inlet of a mobile phase I, a second liquid inlet of a water sample injection and a first liquid outlet of waste liquid are arranged on the sample injection valve; the pipeline is connected to the first liquid inlet; the sample inlet pipe is connected to the second liquid inlet; a sample quantitative ring is arranged on the sample injection valve;
the sample purification system comprises a purified sample injection valve, a sample injection pipe II connected between the sample injection valve and the purified sample injection valve, a purification mixing column arranged on the sample injection pipe II, a pre-column connected on the purified sample injection valve, a pipeline II used for circulating the mobile phase II and a pump II arranged on the pipeline II; wherein, the purified sample injection valve is provided with a liquid inlet III of a mobile phase II, a liquid inlet IV of a water sample injection purified by the purifying mixing column and a liquid outlet II of waste liquid; the second pipeline is connected to the third liquid inlet; one end of the sample inlet pipe II is connected to the liquid inlet port IV, and the other end of the sample inlet pipe II is connected to a sample liquid outlet of the sample injection valve;
the ion chromatographic analysis system comprises a separation column, an ion suppressor, a conductivity detector and a recorder which are connected in sequence;
the ion chromatograph control system is internally provided with an ion chromatograph workstation which is respectively electrically connected with the sample injection valve, the purified sample injection valve, the ion suppressor, the conductivity detector and the recorder.
Optionally or preferably, the sample injection valve and the purified sample injection valve are both liquid six-way valves.
Alternatively or preferably, the purification mixing column includes a column in which Ba is sequentially packed in the direction of the flow of the mobile phase2+Cationic resins, Ag+Cationic resins, H+-a cationic resin; the end part of the column body at the liquid inlet end of the mobile phase is provided with a column joint, and the end part of the column body at the liquid outlet end is provided with a filter disc.
Alternatively or preferably, said Ba2+Cationic resins, Ag+Cationic resins, H+The filling height of the cationic resin is respectively 180-220mm, 180-220mm and 180-220 mm.
Alternatively or preferably, said Ba2+Cationic resins, Ag+Cationic resins, H+The filling heights of the cationic resin are 200mm, 200mm and 200mm, respectively.
Alternatively or preferably, the post adapter is connected to the post body by a nut; the column body is provided with a sealing structure at the position where the filter disc is arranged; the inner diameter of the column body is 5-7 mm.
Alternatively or preferably, the preparation of the purification mixing column comprises the following steps:
(1)Ba2+preparation of cationic resins
Activating cationic resin with barium chloride solution to obtain Ba2+-a cationic resin;
(2)Ag+preparation of cationic resins
Activating the cationic resin with silver nitrate solution to obtain Ag+-a cationic resin;
(3)H+preparation of cationic resins
Activating the cation resin with acid solution to obtain H+Cationic resins；
(4) Loading
Connecting the column joint to the liquid inlet end of the mobile phase of the column body through a screw cap, and then connecting the Ba prepared in the step (1)2+Cationic resin, Ag prepared in step (2)+Cationic resin and H prepared in step (3)+-the cationic resin mounting and filling heights are sequentially filled into the column; and finally, mounting the filter sheet and the sealing structure on the column body.
Alternatively or preferably, in the step (1), the Ba2+-the preparation of the cationic resin comprises the following steps:
preparing a reagent:
high-purity water, 0.8-1.2mol/L barium chloride solution, silver nitrate solution with the weight percentage concentration of 0.8-1.2% and ethanol with the purity of more than or equal to 99.0%;
secondly, cleaning the cation resin with the high-purity water prepared in the step I, cleaning with the ethanol prepared in the step I, drying the cation resin at the temperature of 85-95 ℃ for 4.5-5.5h in vacuum, taking out the cation resin from the oven, and cooling;
weighing 30 g of the cation resin cooled in the step II, putting the cation resin into a dry beaker, adding 200mL of the barium chloride solution prepared in the step I, continuously and slowly stirring, soaking for 18-22 hours, and taking out the cation resin;
fourthly, washing the cation resin treated in the third step by deionized water until no chloride ions exist, and verifying whether no chloride ions exist by using a silver nitrate solution;
fifthly, cleaning the cationic resin treated in the step (iv) with the ethanol prepared in the step (i);
finally vacuum drying the cationic resin treated in the fifth step at 85-95 deg.c for 3.5-4.5 hr, and cooling to obtain Ba2+-cationic resins, preservation.
Alternatively or preferably, in the step (2), the Ag+-the preparation of the cationic resin comprises the following steps:
preparing a reagent:
high-purity water, 0.8-1.2mol/L silver nitrate solution and ethanol with the purity of more than or equal to 99.0 percent;
secondly, cleaning the cation resin with the high-purity water prepared in the step I, cleaning with the ethanol prepared in the step I, drying the cation resin at the temperature of 85-95 ℃ for 4.5-5.5h in vacuum, taking out the cation resin from the oven, and cooling;
weighing 30 g of the cooled cationic resin obtained in the step II, putting the weighed cationic resin into a dry beaker, adding 200mL of silver nitrate solution prepared in the step I, continuously and slowly stirring the solution in the shade, soaking the solution for 18-22 hours, and taking out the cationic resin;
fourthly, the cation resin processed by the third step is cleaned by the high-purity water prepared in the first step until no nitrate ions exist; when the absorbance between the high-purity water before washing and the water after washing is less than 0.003, the cation resin has no nitrate ions, which is verified by an ultraviolet spectrophotometer at the wavelength of 220 nm;
fifthly, cleaning the cationic resin treated in the step (iv) with the ethanol prepared in the step (i);
finally vacuum drying the cationic resin treated in the fifth step at 85-95 deg.c for 3.5-4.5 hr, cooling to obtain Ag+Cationic resins, protected from light.
Alternatively or preferably, in the step (3), the H+-the preparation of the cationic resin comprises the following steps:
preparing a reagent:
high-purity water, 1.8-2.2mol/L hydrochloric acid solution, silver nitrate solution with the weight percentage concentration of 0.8% -1.2% and ethanol with the purity of more than or equal to 99.0%;
secondly, cleaning the cationic resin by using the high-purity water prepared in the step I;
weighing 30 g of the cationic resin cleaned in the step II, putting the cationic resin into a clean beaker, adding 200mL of hydrochloric acid solution prepared in the step I, continuously and slowly stirring, soaking for 9-11h, and taking out the cationic resin;
fourthly, washing the cation resin treated in the third step by deionized water until no chloride ions exist, and verifying whether no chloride ions exist by using a silver nitrate solution;
fifthly, cleaning the cationic resin treated in the step (iv) with the ethanol prepared in the step (i);
finally vacuum drying the cationic resin treated in the fifth step at 85-95 deg.c for 3.5-4.5 hr, cooling to obtain H+Cationic resins, protected from light.
Alternatively or preferably, the pre-column and the separation column both adopt a type ion exchange column.
Based on the technical scheme, the embodiment of the invention can at least produce the following technical effects:
when a water sample enters the ion chromatograph for analysis, the water sample is carried into the purifying mixing column through the mobile phase and passes through Ba in the purifying mixing column2+Cationic resins, Ag+Cationic resins, H+Removal of metal ions (Ba) such as carbonate ion, bicarbonate ion, sulfate ion, chloride ion, calcium and magnesium by cation resin2+Ba in cationic resins2+Reacting with sulfate ion to generate barium sulfate precipitate, Ag+Ag in cationic resins+Reacting with chloride ion to generate silver chloride precipitate H+-H in cationic resins+Reacting with carbonate and bicarbonate to generate carbon dioxide gas for volatilization); and then the water sample enters a pre-column, a small amount of mechanical impurities and deposition are removed through the pre-column, perchlorate in the water sample is reserved in the pre-column, then the switching of a pre-column flow path is controlled through an ion chromatograph control system, a pre-column control valve is switched to enable the pre-column to be connected into a flow path of a mobile phase II, the perchlorate reserved in the water sample in the pre-column sequentially enters a separation column and an ion suppressor through the carrying of the mobile phase II, then the water sample enters a conductivity detector for detection and is recorded through a recorder, finally a workstation processes detection data, and the content of the perchlorate is calculated through a standard curve method. The ion chromatograph removes carbonate, bicarbonate, sulfate, chloride and metal ions in water after pre-treating a water sample and purifying a purifying mixing column, and avoids the situation that a testing water sample contains carbonate, bicarbonate, sulfate, chloride and metal ions when the existing perchlorate testing technology in water (surface water, wastewater, drinking water and the like) is appliedThe adverse effect on the detection result and the detection instrument is convenient for quantitatively testing the perchlorate in the water, and the long-period stable operation of the instrument can be ensured.
Drawings
In order to more clearly illustrate the embodiments of the present invention or the technical solutions in the prior art, the drawings used in the description of the embodiments or the prior art will be briefly described below, it is obvious that the drawings in the following description are only some embodiments of the present invention, and for those skilled in the art, other drawings can be obtained according to the drawings without creative efforts.
FIG. 1 is a schematic view of a connecting structure of examples 1 to 3 of the present invention;
FIG. 2 is a schematic view showing the structure of a purification mixing column in examples 1 to 3 of the present invention;
FIG. 3 is an enlarged schematic view of section A of FIG. 2;
FIG. 4 is an ion chromatogram of an application example of example 1 of the present invention;
FIG. 5 is an ion chromatogram of a comparative example of the present invention.
In the figure: 1. a cylinder; 2. ba2+-a cationic resin; 3. ag+-a cationic resin; 4. h+-a cationic resin; 5. a column joint; 6. a nut; 7. a filter disc; 8. a front seal ring; 9. a rear seal ring; 10. a ferrule female assembly; 11. a ferrule male component; 12. a sample injection valve; 13. purifying a sample injection valve; 14. a separation column; 15. an ion suppressor; 16. a first pipeline; 17. a first sample inlet pipe; 18. a waste liquid outlet pipe I; 19. A second pipeline; 20. a second sampling pipe; 21. purifying the mixed column; 22. pre-column; 23. a first pump; 24. a second pump; 25. a conductance detector; 26. a recorder; 27. a waste liquid outlet pipe II; 28. and a waste liquid outlet pipe III.
Detailed Description
In order to make the objects, technical solutions and advantages of the present invention more apparent, the technical solutions of the present invention will be described in detail below. It is to be understood that the described embodiments are merely exemplary of the invention, and not restrictive of the full scope of the invention. All other embodiments, which can be derived by a person skilled in the art from the examples given herein without any inventive step, are within the scope of the present invention.
As shown in fig. 1-5:
example 1:
the invention provides an ion chromatograph, which comprises a sample introduction system, a sample purification system, an ion chromatographic analysis system and an ion chromatograph control system; wherein,
the sample injection system comprises a sample injection valve 12, a first sample injection pipe 17 for water sample circulation, a first pipeline 16 for mobile phase circulation and a first pump 23 arranged on the first pipeline 16; wherein, the sample injection valve 12 is provided with a first liquid inlet of a mobile phase I, a second liquid inlet of a water sample injection and a first liquid outlet of waste liquid; the first pipeline 16 is connected to the first liquid inlet; the sample inlet pipe I17 is connected to the liquid inlet II; a sample quantitative ring is arranged on the sample injection valve 12; the first liquid outlet is connected with a first waste liquid outlet pipe 18;
the sample purification system comprises a purified sample injection valve 13, a sample injection pipe II 20 connected between the sample injection valve 12 and the purified sample injection valve 13, a purification mixing column 21 arranged on the sample injection pipe II 20, a pre-column 22 connected on the purified sample injection valve 13, a pipeline II 19 for circulating a mobile phase II and a pump II 24 arranged on the pipeline II 19; wherein, the purified sample injection valve 13 is provided with a liquid inlet III of a mobile phase II, a liquid inlet IV of a water sample injection purified by the purifying mixing column 21 and a liquid outlet II of waste liquid; the second pipeline 19 is connected to the third liquid inlet; one end of the second sample inlet pipe 20 is connected to the fourth liquid inlet, and the other end of the second sample inlet pipe 20 is connected to the sample liquid outlet of the sample inlet valve 12; the second liquid outlet is connected with a second waste liquid outlet pipe 27;
the ion chromatographic analysis system comprises a separation column 14, an ion suppressor 15, a conductivity detector 25 and a recorder 26 which are connected in sequence;
be equipped with the ion chromatography workstation in the ion chromatograph control system, the ion chromatography workstation is connected in use with sample injection valve 12, purification sample injection valve 13, ion suppressor 15, conductance detector 25 and record appearance 26 electricity respectively and carries out the appearance control of advancing of sample injection valve 12, purification sample injection valve 13 through the ion chromatography workstation to the opening and close of control pump one 23 and pump two 24 carries out data acquisition, data processing and time node's control simultaneously.
When a water sample enters the ion chromatograph for analysis, the water sample firstly enters the purifying mixing column 21 through the first carrying of the mobile phase and then passes through Ba in the purifying mixing column 212+Cationic resin 2, Ag+Cationic resins 3, H+Cation resin 4 for removing metal ions (Ba) such as carbonate ion, bicarbonate ion, sulfate ion, chloride ion, calcium and magnesium2+Ba in cationic resin 22+Reacting with sulfate ion to generate barium sulfate precipitate, Ag+Ag in cationic resin 3+Reacting with chloride ion to generate silver chloride precipitate H+H in cationic resin 4+Reacting with carbonate and bicarbonate to generate carbon dioxide gas for volatilization); then the water sample enters the pre-column 22, a small amount of mechanical impurities and deposits are removed, perchlorate in the sample is retained in the pre-column 22, then the switching of a flow path of the pre-column 22 is controlled through an ion chromatograph control system, a control valve of the pre-column 22 is switched to enable the pre-column 22 to be connected into a flow path of a mobile phase II, the perchlorate remained in the water sample in the pre-column 22 sequentially enters the separation column 14 and the ion suppressor 15 through the carrying of the mobile phase II, then the water sample enters the conductivity detector 25 for detection and is recorded through the recorder 26, finally the workstation processes detection data, and the content of the perchlorate is calculated through a standard curve method. The ion chromatograph removes carbonate, bicarbonate, sulfate, chloride and metal ions in water after pre-treating a water sample and purifying a purifying mixing column 21, avoids adverse effects on detection results and detection instruments due to the carbonate, bicarbonate, sulfate, chloride and metal ions in a test water sample when the existing perchlorate test technology in water (surface water, wastewater, drinking water and the like) is applied, is convenient for quantitatively testing perchlorate in water, and can ensure the quantitative test of the perchlorate in the waterThe long-period stable operation.
As an alternative embodiment, the sample injection valve 12 and the purified sample injection valve 13 are both liquid six-way valves.
As an alternative embodiment, the purifying mixing column 21 includes a column 1, and Ba is sequentially filled in the column 1 in the flowing direction of the mobile phase (the direction of arrow a in fig. 2 is the flowing direction of the mobile phase)2+ Cationic resin 2, Ag+Cationic resins 3, H+-a cationic resin 4; the column body 1 is provided with a column joint 5 at the end part of the liquid inlet end of the flowing phase, and the end part of the liquid outlet end of the column body 1 is provided with a filter disc 7. Filled Ba2+Cationic resin 2, Ag+Cationic resins 3, H+The cationic resin 4 is used to remove sulfate ions, chloride ions and carbonate ions, bicarbonate ions, respectively, from the water sample.
As an alternative embodiment, said Ba2+Cationic resin 2, Ag+Cationic resins 3, H+The packing height of the cation 4 resin is respectively 180-220mm, 180-220mm and 180-220 mm.
As an alternative embodiment, said Ba2+Cationic resin 2, Ag+Cationic resins 3, H+The filling heights of the cationic resin 4 are 200mm, 200mm and 200mm, respectively.
As an alternative embodiment, the post adapter 5 is connected to the column 1 by means of a screw cap 6.
As an alternative embodiment, the column body 1 is provided with a sealing structure at the position where the filter disc 7 is arranged; the sealing structure comprises a concave ferrule component 10 sleeved at the mobile phase liquid outlet end of the cylinder 1, a convex ferrule component 11 matched with the concave ferrule component 10, and a front sealing ring 8 and a rear sealing ring 9 sleeved outside the convex ferrule component 11.
As an alternative embodiment, the cylinder 1 has an internal diameter of 5-7 mm.
As an alternative embodiment, the preparation of the purification mixing column 21 comprises the following steps:
(1)Ba2+preparation of cationic resin 2
Activating cationic resin with barium chloride solution to obtain Ba2+-a cationic resin 2;
(2)Ag+preparation of cationic resin 3
Activating the cationic resin with silver nitrate solution to obtain Ag+-a cationic resin 3;
(3)H+preparation of cationic resins 4
Activating the cation resin with acid solution to obtain H+-a cationic resin 4;
(4) loading
Connecting a column connector 5 to the inlet end of the mobile phase of the column body 1 through a screw cap 6, and then connecting the Ba prepared in the step (1)2+ Cationic resin 2, Ag prepared in step (2)+ Cationic resin 3 and H prepared in step (3)+The cationic resin 4 is installed and filled in height sequentially into the column body 1; finally, the filter sheet 7 and the sealing structure are mounted on the column body 1.
In the present embodiment, in the step (1), the Ba2+The preparation of the cationic resin 2 comprises the following steps:
preparing a reagent:
high purity water (conductivity: 18.25 M.OMEGA.);
1.0mol/L barium chloride solution: preparing high-grade pure barium chloride and high-purity water;
1% by weight of silver nitrate solution: preparing high-grade pure silver nitrate and high-purity water;
ethanol with the purity of more than or equal to 99.0 percent;
secondly, washing the 100-mesh cationic resin with the high-purity water prepared in the step I, washing twice with the ethanol prepared in the step I, drying in vacuum at 90 ℃ for 5 hours, taking out the resin from the oven, and cooling;
weighing 30 g of the cation resin cooled in the step II, putting the cation resin into a 500mL dry beaker, adding 200mL barium chloride solution prepared in the step I, continuously and slowly stirring, soaking for 20 hours, and taking out the cation resin;
fourthly, washing the cation resin treated in the third step by deionized water until no chloride ions exist, and verifying whether no chloride ions exist by using a silver nitrate solution;
fifthly, cleaning the cationic resin treated in the step (iv) for 2 times by using the ethanol prepared in the step (i);
finally vacuum drying the cationic resin treated in the fifth step at 90 deg.c for 4 hr, and cooling to obtain Ba2 +-cationic resin 2, preservation.
In this embodiment, in the step (2), the Ag is+The preparation of the cationic resin 3 comprises the following steps:
preparing a reagent:
high purity water (conductivity: 18.25 M.OMEGA.);
1.0mol/L silver nitrate solution: preparing by adopting top-grade pure silver nitrate and high-purity water;
ethanol with the purity of more than or equal to 99.0 percent;
secondly, washing the 100-mesh cationic resin with the high-purity water prepared in the step I, washing twice with the ethanol prepared in the step I, drying in vacuum at 90 ℃ for 5 hours, taking out the resin from the oven, and cooling;
weighing 30 g of the cation resin cooled in the step II, putting the cation resin into a 500mL dry beaker, adding 200mL of silver nitrate solution, continuously and slowly stirring the solution in the shade, and taking out the cation resin after soaking the cation resin for 20 hours;
fourthly, washing the cation resin processed in the third step by deionized water until no nitrate radical exists, and verifying the cation resin at the wavelength of 220nm by an ultraviolet spectrophotometer, wherein the absorbance between high-purity water before washing and washing water is less than 0.003;
fifthly, cleaning the cationic resin treated in the step (iv) for 2 times by using the ethanol prepared in the step (i);
finally vacuum drying the cationic resin treated in the fifth step at 90 deg.c for 4 hr, cooling to obtain Ag+Cationic resin 3, stored protected from light.
In this embodiment, in the step (3), the H+The preparation of the cationic resin 4 comprises the following steps:
preparing a reagent:
high purity water (conductivity: 18.25 M.OMEGA.);
2.0mol/L hydrochloric acid solution: preparing by adopting high-purity water;
1% silver nitrate solution by weight: preparing by adopting top-grade pure silver nitrate and high-purity water;
ethanol with the purity of more than or equal to 99.0 percent;
secondly, cleaning the 100-mesh cationic resin with the high-purity water prepared in the step I;
weighing 30 g of the cationic resin cleaned in the step II, putting the cationic resin into a 500mL clean beaker, adding 200mL of the hydrochloric acid solution prepared in the step I, continuously and slowly stirring, soaking for 10 hours, and taking out the cationic resin;
fourthly, washing the cation resin treated in the third step by deionized water until no chloride ions exist, and verifying whether no chloride ions exist by using a silver nitrate solution;
fifthly, cleaning the cationic resin treated in the step (iv) for 2 times by using the ethanol prepared in the step (i);
finally vacuum drying the cationic resin treated in the fifth step at 90 deg.c for 4 hr, cooling to obtain H+Cationic resin 4, protected from light.
As an optional embodiment, a third waste liquid outlet is arranged on the conductivity detector 25, and a third waste liquid outlet pipe 28 is connected to the third waste liquid outlet.
As an alternative embodiment, the pre-column 22 is an a-type ion exchange column (4 mm. times.50 mm).
As an alternative embodiment, the separation column 14 is an a-type ion exchange column (phi 4 mm. times.300 mm).
And (3) treating waste liquid:
containing Ba2+Treating the waste liquid with sodium sulfate solution, discharging after being qualified; containing Ag+The waste liquid is discharged after being treated by sodium chloride solution; and the waste acid liquor is discharged after being treated by sodium carbonate solution.
For the treatment of spent cationic resin in the clean-up mixing column 21:
for failed Ba in purifying mixing column 212+-cationsResin 2, Ag+Cationic resins 3, H+The cationic resin 4 filler can be cleaned and qualified by acid treatment and can be reused after being activated.
Example 2:
the present embodiment 2 is different from embodiment 1 in that:
in this embodiment, in the preparation of the purifying mixing column 21, in the step (1), the Ba is present2+The preparation of the cationic resin 2 comprises the following steps:
preparing a reagent:
high purity water (conductivity: 18.25 M.OMEGA.);
0.8mol/L barium chloride solution: preparing high-grade pure barium chloride and high-purity water;
1.2% silver nitrate solution by weight: preparing by adopting top-grade pure silver nitrate and high-purity water;
ethanol with the purity of more than or equal to 99.0 percent;
secondly, washing the cationic resin with 100 meshes by using the high-purity water prepared in the step I, washing twice by using the ethanol prepared in the step I, drying for 5.5 hours in vacuum at 85 ℃, taking out the resin from the oven and cooling;
weighing 30 g of the cation resin cooled in the step II, putting the cation resin into a 500mL dry beaker, adding 200mL barium chloride solution prepared in the step I, continuously and slowly stirring, soaking for 22 hours, and taking out the cation resin;
fourthly, washing the cation resin treated in the third step by deionized water until no chloride ions exist, and verifying whether no chloride ions exist by using a silver nitrate solution;
fifthly, cleaning the cationic resin treated in the step (iv) for 2 times by using the ethanol prepared in the step (i);
finally vacuum drying the cationic resin treated in the fifth step at 85 deg.c for 4.5 hr and cooling to obtain Ba2+-cationic resin 2, preservation.
In this embodiment, in the preparation of the purifying mixing column 21, in the step (2), the Ag+The preparation of the cationic resin 3 comprises the following steps:
preparing a reagent:
high purity water (conductivity: 18.25 M.OMEGA.);
1.2mol/L silver nitrate solution: preparing by adopting top-grade pure silver nitrate and high-purity water;
ethanol with the purity of more than or equal to 99.0 percent;
secondly, washing the cationic resin with 100 meshes by using the high-purity water prepared in the step I, washing twice by using the ethanol prepared in the step I, drying for 4.5 hours in vacuum at 95 ℃, taking out the resin from the oven and cooling;
weighing 30 g of the cation resin cooled in the step II, putting the cation resin into a 500mL dry beaker, adding 200mL of silver nitrate solution, continuously and slowly stirring the solution in the shade, and taking out the cation resin after soaking the cation resin for 18 hours;
fourthly, washing the cation resin processed in the third step by deionized water until no nitrate radical exists, and verifying the cation resin at the wavelength of 220nm by an ultraviolet spectrophotometer, wherein the absorbance between high-purity water before washing and washing water is less than 0.003;
fifthly, cleaning the cationic resin treated in the step (iv) for 2 times by using the ethanol prepared in the step (i);
finally vacuum drying the cationic resin treated in the fifth step at 95 deg.c for 3.5 hr and cooling to obtain Ag+Cationic resin 3, stored protected from light.
In this embodiment, in the preparation of the purification mixing column 21, in the step (3), the H+The preparation of the cationic resin 4 comprises the following steps:
preparing a reagent:
high purity water (conductivity: 18.25 M.OMEGA.);
2.2mol/L hydrochloric acid solution: preparing by adopting high-purity water;
1% silver nitrate solution by weight: preparing by adopting top-grade pure silver nitrate and high-purity water;
ethanol with the purity of more than or equal to 99.0 percent;
secondly, cleaning the 100-mesh cationic resin with the high-purity water prepared in the step I;
weighing 30 g of the cationic resin cleaned in the step II, putting the cationic resin into a 500mL clean beaker, adding 200mL of the hydrochloric acid solution prepared in the step I, continuously and slowly stirring, soaking for 9 hours, and taking out the cationic resin;
fourthly, washing the cation resin treated in the third step by deionized water until no chloride ions exist, and verifying whether no chloride ions exist by using a silver nitrate solution;
fifthly, cleaning the cationic resin treated in the step (iv) for 2 times by using the ethanol prepared in the step (i);
finally vacuum drying the cationic resin treated in the fifth step at 95 deg.c for 3.5 hr, cooling to obtain H+Cationic resin 4, protected from light.
The rest is the same as example 1.
Example 3:
the present embodiment 3 is different from embodiment 1 in that:
in this embodiment, in the preparation of the purifying mixing column 21, in the step (1), the Ba is present2+The preparation of the cationic resin 2 comprises the following steps:
preparing a reagent:
high purity water (conductivity: 18.25 M.OMEGA.);
1.2mol/L barium chloride solution: preparing high-grade pure barium chloride and high-purity water;
1.2% silver nitrate solution by weight: preparing by adopting top-grade pure silver nitrate and high-purity water;
ethanol with the purity of more than or equal to 99.0 percent;
secondly, washing the 80-mesh cationic resin with the high-purity water prepared in the step I, washing twice with the ethanol prepared in the step I, drying in vacuum at 95 ℃ for 4.5 hours, taking out the resin from the oven, and cooling;
weighing 30 g of the cation resin cooled in the step II, putting the cation resin into a 500mL dry beaker, adding 200mL barium chloride solution prepared in the step I, continuously and slowly stirring, soaking for 18 hours, and taking out the cation resin;
fourthly, washing the cation resin treated in the third step by deionized water until no chloride ions exist, and verifying whether no chloride ions exist by using a silver nitrate solution;
fifthly, cleaning the cationic resin treated in the step (iv) for 2 times by using the ethanol prepared in the step (i);
finally vacuum drying the cationic resin treated in the fifth step at 95 deg.c for 3.5 hr and cooling to obtain Ba2+-cationic resin 2, preservation.
In this embodiment, in the preparation of the purifying mixing column 21, in the step (2), the Ag+The preparation of the cationic resin 3 comprises the following steps:
preparing a reagent:
high purity water (conductivity: 18.25 M.OMEGA.);
0.8mol/L silver nitrate solution: preparing by adopting top-grade pure silver nitrate and high-purity water;
ethanol with the purity of more than or equal to 99.0 percent;
secondly, washing the 80-mesh cationic resin with the high-purity water prepared in the step I, washing twice with the ethanol prepared in the step I, drying in vacuum at 85 ℃ for 3.5 hours, taking out the resin from the oven, and cooling;
weighing 30 g of the cation resin cooled in the step II, putting the cation resin into a 500mL dry beaker, adding 200mL of silver nitrate solution, continuously and slowly stirring the solution in the shade, soaking the solution for 22 hours, and taking out the cation resin;
fourthly, washing the cation resin processed in the third step by deionized water until no nitrate radical exists, and verifying the cation resin at the wavelength of 220nm by an ultraviolet spectrophotometer, wherein the absorbance between high-purity water before washing and washing water is less than 0.003;
fifthly, cleaning the cationic resin treated in the step (iv) for 2 times by using the ethanol prepared in the step (i);
finally vacuum drying the cationic resin treated in the fifth step at 85 deg.c for 4.5 hr and cooling to obtain Ag+Cationic resin 3, stored protected from light.
In this embodiment, in the preparation of the purification mixing column 21, in the step (3), the H+The preparation of the cationic resin 4 comprises the following steps:
preparing a reagent:
high purity water (conductivity: 18.25 M.OMEGA.);
1.8mol/L hydrochloric acid solution: preparing by adopting high-purity water;
1% silver nitrate solution by weight: preparing by adopting top-grade pure silver nitrate and high-purity water;
ethanol with the purity of more than or equal to 99.0 percent;
secondly, washing the 80-mesh cationic resin with the high-purity water prepared in the step I;
weighing 30 g of the cationic resin cleaned in the step II, putting the cationic resin into a 500mL clean beaker, adding 200mL of the hydrochloric acid solution prepared in the step I, continuously and slowly stirring, soaking for 11 hours, and taking out the cationic resin;
fourthly, washing the cation resin treated in the third step by deionized water until no chloride ions exist, and verifying whether no chloride ions exist by using a silver nitrate solution;
fifthly, cleaning the cationic resin treated in the step (iv) for 2 times by using the ethanol prepared in the step (i);
finally vacuum drying the cationic resin treated in the fifth step at 85 deg.c for 4.5 hr, cooling to obtain H+Cationic resin 4, protected from light.
The rest is the same as example 1.
Application example:
the detection of perchlorate in a water sample using the ion chromatograph of example 1 above, comprising the following steps:
drawing a standard curve:
the standard sequence is shown in the following table 1, the sample volume is 5ml, and the correlation coefficient R is more than or equal to 0.999
TABLE 1 Standard sequences
| Sequence numbering | 1 | 2 | 3 | 4 | 5 | 6 | 7 | 8 |
| Concentration (in ClO)4Meter, ug/L) | 1 | 1.5 | 2 | 2.5 | 3 | 4 | 5 | 6 |
(1) Pretreating a water sample
A1, adjusting the pH value of the water sample to 3.5 by 1mol/L hydrochloric acid solution;
a2, aerating the water sample for 10min by high-purity nitrogen (with the purity of 9.999%);
(2) analyzing the pretreated water sample by an ion chromatograph
B1, enabling the water sample pretreated in the step (1) to enter a sample injection valve 12 through a first sample injection pipe 17, wherein the sample injection amount of the water sample is 5ml, and enabling a first mobile phase to enter the sample injection valve 12 through a first pipeline 16; the mobile phase I carries the water sample pretreated in the step (1) to enter a purifying mixing column 21 for purification through a second pipeline 19By purifying the mixed column 21 from Ba2+Cationic resin 2, Ag+Cationic resins 3, H+The cation resin 4 removes metal ions such as carbonate ions, bicarbonate ions, sulfate ions, chloride ions, calcium and magnesium ions and the like; the first mobile phase adopts high-purity water; the flow rate of the mobile phase I is 1.2 ml/L; the column temperature of the purification mixing column 21 during purification treatment is normal temperature;
b2, enabling the water sample subjected to purification treatment by the purification mixing column 21 in the step B1 to enter a purification sample injection valve 13 through a sample injection pipe II 20, enabling the water sample to enter a pre-column 22, and keeping perchlorate in the water sample in the pre-column 22 except for removing a small amount of mechanical impurities and deposition through the treatment of the pre-column 22;
b3, controlling the switching of the flow path of the pre-column 22 through an ion chromatograph control system, switching a control valve of the pre-column 22 to enable the pre-column 22 to be connected into the flow path of the mobile phase II, and enabling the perchlorate in the water sample remained in the pre-column 22 to sequentially enter the separation column 14 and the ion suppressor 15 through the carrying of the mobile phase II; the second mobile phase adopts 35mmol/L potassium hydroxide solution; the flow rate of the second mobile phase is 1.2 ml/L; the column temperature of the separation column 14 during treatment is 30 ℃;
b4, finally, detecting the sample by the conductivity detector 25 and recording the sample by the recorder 26, processing the detected data by the ion chromatography workstation, drawing a standard curve, and calculating the content of the sample by a standard curve method; and discharging the detected waste liquid from the waste liquid outlet pipe III. The standard sequence is shown in the table 1 above, the ion chromatogram is shown in fig. 4, and the B position in fig. 4 is the chromatographic peak of potassium perchlorate in the water sample.
Comparative example:
the detection steps are different from the application example: the water sample is not subjected to the pretreatment in the step (1) and the treatment of the purification mixing column 21 in the step (2) B1, and directly enters the pre-column 22 for treatment and then enters the separation column 14 for treatment; finally, detecting through a conductivity detector 25 of an ion chromatograph to obtain a detection result, wherein an ion chromatogram is shown in fig. 5, and a chromatographic peak of potassium perchlorate in the water sample is shown in a position B in the fig. 5; the mobile phase adopts 35mmol/L potassium hydroxide solution; the flow rate of the mobile phase is 1.2 ml/L; the column temperature at the time of treatment in the separation column 14 was 30 ℃.
As can be seen from fig. 4 and 5, in the comparative example, the water sample which has not been subjected to the pretreatment of step (1) and the treatment of the purification mixing column 21 of step (2) B1 is directly analyzed, and the perchlorate chromatographic peak is on the tailing peak of other ion peaks, which is not convenient for quantification; in the application example of the invention, the interference of other ions is completely eliminated by the ion chromatographic peak of the water sample which is pretreated in the step (1) and treated by the purifying mixing column 21 in the step (2) B1, and a foundation is laid for accurate determination of the amount.
The above description is only for the specific embodiments of the present invention, but the scope of the present invention is not limited thereto, and any person skilled in the art can easily conceive of the changes or substitutions within the technical scope of the present invention, and all the changes or substitutions should be covered within the scope of the present invention.
Claims (10)
1. An ion chromatograph, characterized by: comprises a sample introduction system, a sample purification system, an ion chromatography analysis system and an ion chromatograph control system; wherein,
the sample introduction system comprises a sample introduction valve, a first sample introduction pipe for water sample circulation, a first pipeline for mobile phase circulation and a first pump arranged on the first pipeline; wherein, a first liquid inlet of a mobile phase I, a second liquid inlet of a water sample injection and a first liquid outlet of waste liquid are arranged on the sample injection valve; the pipeline is connected to the first liquid inlet; the sample inlet pipe is connected to the second liquid inlet; a sample quantitative ring is arranged on the sample injection valve;
the sample purification system comprises a purified sample injection valve, a sample injection pipe II connected between the sample injection valve and the purified sample injection valve, a purification mixing column arranged on the sample injection pipe II, a pre-column connected on the purified sample injection valve, a pipeline II used for circulating the mobile phase II and a pump II arranged on the pipeline II; wherein, the purified sample injection valve is provided with a liquid inlet III of a mobile phase II, a liquid inlet IV of a water sample injection purified by the purifying mixing column and a liquid outlet II of waste liquid; the second pipeline is connected to the third liquid inlet; one end of the sample inlet pipe II is connected to the liquid inlet port IV, and the other end of the sample inlet pipe II is connected to a sample liquid outlet of the sample injection valve;
the ion chromatographic analysis system comprises a separation column, an ion suppressor, a conductivity detector and a recorder which are connected in sequence;
the ion chromatograph control system is internally provided with an ion chromatograph workstation which is respectively electrically connected with the sample injection valve, the purified sample injection valve, the ion suppressor, the conductivity detector and the recorder.
2. The ion chromatograph of claim 1, wherein: the purifying mixing column comprises a column body in which Ba is sequentially packed in the direction of the flow of the mobile phase2+Cationic resins, Ag+Cationic resins, H+-a cationic resin; the end part of the column body at the liquid inlet end of the mobile phase is provided with a column joint, and the end part of the column body at the liquid outlet end is provided with a filter disc.
3. The ion chromatograph of claim 2, wherein: said Ba2+Cationic resins, Ag+Cationic resins, H+The filling height of the cationic resin is respectively 180-220mm, 180-220mm and 180-220 mm.
4. The ion chromatograph of claim 3, wherein: said Ba2+Cationic resins, Ag+Cationic resins, H+The filling heights of the cationic resin are 200mm, 200mm and 200mm, respectively.
5. The ion chromatograph of claim 4, wherein: the column joint is connected with the column body through a nut; the column body is provided with a sealing structure at the position where the filter disc is arranged; the inner diameter of the column body is 5-7 mm.
6. The ion chromatograph of any of claims 1-5, wherein: the preparation of the purifying mixing column comprises the following steps:
（1）Ba2+preparation of cationic resins
Activating cationic resin with barium chloride solution to obtain Ba2+-a cationic resin;
（2）Ag+preparation of cationic resins
Activating the cationic resin with silver nitrate solution to obtain Ag+-a cationic resin;
（3）H+preparation of cationic resins
Activating the cation resin with acid solution to obtain H+-a cationic resin;
(4) loading
Connecting the column joint to the liquid inlet end of the mobile phase of the column body through a screw cap, and then connecting the Ba prepared in the step (1)2+Cationic resin, Ag prepared in step (2)+Cationic resin and H prepared in step (3)+-the cationic resin mounting and filling heights are sequentially filled into the column; and finally, mounting the filter sheet and the sealing structure on the column body.
7. The ion chromatograph of claim 6, wherein: in the step (1), the Ba2+-the preparation of the cationic resin comprises the following steps:
preparing a reagent:
high-purity water, 0.8-1.2mol/L barium chloride solution, silver nitrate solution with the weight percentage concentration of 0.8-1.2% and ethanol with the purity of more than or equal to 99.0%;
secondly, cleaning the cation resin with the high-purity water prepared in the step I, cleaning with the ethanol prepared in the step I, drying the cation resin at the temperature of 85-95 ℃ for 4.5-5.5h in vacuum, taking out the cation resin from the oven, and cooling;
weighing 30 g of the cation resin cooled in the step II, putting the cation resin into a dry beaker, adding 200mL of the barium chloride solution prepared in the step I, continuously and slowly stirring, soaking for 18-22 hours, and taking out the cation resin;
fourthly, washing the cation resin treated in the third step by deionized water until no chloride ions exist, and verifying whether no chloride ions exist by using a silver nitrate solution;
fifthly, cleaning the cationic resin treated in the step (iv) with the ethanol prepared in the step (i);
finally vacuum drying the cationic resin treated in the fifth step at 85-95 deg.c for 3.5-4.5 hr, and cooling to obtain Ba2+-cationic resins, preservation.
8. The ion chromatograph of claim 7, wherein: in the step (2), the Ag+-the preparation of the cationic resin comprises the following steps:
preparing a reagent:
high-purity water, 0.8-1.2mol/L silver nitrate solution and ethanol with the purity of more than or equal to 99.0 percent;
secondly, cleaning the cation resin with the high-purity water prepared in the step I, cleaning with the ethanol prepared in the step I, drying the cation resin at the temperature of 85-95 ℃ for 4.5-5.5h in vacuum, taking out the cation resin from the oven, and cooling;
weighing 30 g of the cooled cationic resin obtained in the step II, putting the weighed cationic resin into a dry beaker, adding 200mL of silver nitrate solution prepared in the step I, continuously and slowly stirring the solution in the shade, soaking the solution for 18-22 hours, and taking out the cationic resin;
fourthly, the cation resin processed by the third step is cleaned by the high-purity water prepared in the first step until no nitrate ions exist; when the absorbance between the high-purity water before washing and the water after washing is less than 0.003, the cation resin has no nitrate ions, which is verified by an ultraviolet spectrophotometer at the wavelength of 220 nm;
fifthly, cleaning the cationic resin treated in the step (iv) with the ethanol prepared in the step (i);
finally vacuum drying the cationic resin treated in the fifth step at 85-95 deg.c for 3.5-4.5 hr, cooling to obtain Ag+Cationic resins, protected from light.
9. The ion chromatograph of claim 8, wherein: in the step (3), the hydrogen atom+Preparation package of-cationic resinsThe method comprises the following steps:
preparing a reagent:
high-purity water, 1.8-2.2mol/L hydrochloric acid solution, silver nitrate solution with the weight percentage concentration of 0.8% -1.2% and ethanol with the purity of more than or equal to 99.0%;
secondly, cleaning the cationic resin by using the high-purity water prepared in the step I;
weighing 30 g of the cationic resin cleaned in the step II, putting the cationic resin into a clean beaker, adding 200mL of hydrochloric acid solution prepared in the step I, continuously and slowly stirring, soaking for 9-11h, and taking out the cationic resin;
fourthly, washing the cation resin treated in the third step by deionized water until no chloride ions exist, and verifying whether no chloride ions exist by using a silver nitrate solution;
fifthly, cleaning the cationic resin treated in the step (iv) with the ethanol prepared in the step (i);
finally vacuum drying the cationic resin treated in the fifth step at 85-95 deg.c for 3.5-4.5 hr, cooling to obtain H+Cationic resins, protected from light.
10. The ion chromatograph of any of claims 1-9, wherein: the pre-column and the separation column both adopt a type ion exchange columns.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202010916690.0A CN112240917A (en) | 2020-09-03 | 2020-09-03 | Ion chromatograph |
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Citations (10)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2005315771A (en) * | 2004-04-30 | 2005-11-10 | National Institute Of Advanced Industrial & Technology | Highly sensitive separation measuring method for silicate ion, and instrument therefor |
| WO2008024500A2 (en) * | 2006-08-25 | 2008-02-28 | Analytica Of Branford, Inc. | Sample component trapping, release, and separation with membrane assemblies interfaced to electrospray mass spectrometry |
| JP2009216399A (en) * | 2008-03-07 | 2009-09-24 | Sumitomo Metal Mining Co Ltd | High precision analytical method for cations by ion chromatograph method |
| US20120141789A1 (en) * | 2007-02-21 | 2012-06-07 | Waters Investments Limited | Porous inorganic/organic hybrid particles having high organic content and enhanced pore geometry for chromatographic separations |
| US20150051383A1 (en) * | 2012-05-09 | 2015-02-19 | Dalhousie University | Filtration and Extraction Assembly |
| CN104535564A (en) * | 2014-12-26 | 2015-04-22 | 四川大学 | Concentration pillar filling, concentration pillar and application of concentration pillar in analysis of trace metal elements |
| CN106053686A (en) * | 2016-07-08 | 2016-10-26 | 中国石油化工股份有限公司 | Sample preprocessing device provided with ion chromatograph and used for detecting anions and use method |
| CN106645502A (en) * | 2017-02-27 | 2017-05-10 | 天津出入境检验检疫局动植物与食品检测中心 | Ion chromatograph based on multi-valve switching and for offline and online analysis and detection method of ion chromatograph |
| CN206656989U (en) * | 2017-02-27 | 2017-11-21 | 天津出入境检验检疫局动植物与食品检测中心 | A kind of binary channels based on more Vavle switchings is offline and the ion chromatograph of on-line analysis |
| CN213240035U (en) * | 2020-09-03 | 2021-05-18 | 四川佳士特环境检测有限公司 | Ion chromatograph |
-
2020
- 2020-09-03 CN CN202010916690.0A patent/CN112240917A/en active Pending
Patent Citations (10)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2005315771A (en) * | 2004-04-30 | 2005-11-10 | National Institute Of Advanced Industrial & Technology | Highly sensitive separation measuring method for silicate ion, and instrument therefor |
| WO2008024500A2 (en) * | 2006-08-25 | 2008-02-28 | Analytica Of Branford, Inc. | Sample component trapping, release, and separation with membrane assemblies interfaced to electrospray mass spectrometry |
| US20120141789A1 (en) * | 2007-02-21 | 2012-06-07 | Waters Investments Limited | Porous inorganic/organic hybrid particles having high organic content and enhanced pore geometry for chromatographic separations |
| JP2009216399A (en) * | 2008-03-07 | 2009-09-24 | Sumitomo Metal Mining Co Ltd | High precision analytical method for cations by ion chromatograph method |
| US20150051383A1 (en) * | 2012-05-09 | 2015-02-19 | Dalhousie University | Filtration and Extraction Assembly |
| CN104535564A (en) * | 2014-12-26 | 2015-04-22 | 四川大学 | Concentration pillar filling, concentration pillar and application of concentration pillar in analysis of trace metal elements |
| CN106053686A (en) * | 2016-07-08 | 2016-10-26 | 中国石油化工股份有限公司 | Sample preprocessing device provided with ion chromatograph and used for detecting anions and use method |
| CN106645502A (en) * | 2017-02-27 | 2017-05-10 | 天津出入境检验检疫局动植物与食品检测中心 | Ion chromatograph based on multi-valve switching and for offline and online analysis and detection method of ion chromatograph |
| CN206656989U (en) * | 2017-02-27 | 2017-11-21 | 天津出入境检验检疫局动植物与食品检测中心 | A kind of binary channels based on more Vavle switchings is offline and the ion chromatograph of on-line analysis |
| CN213240035U (en) * | 2020-09-03 | 2021-05-18 | 四川佳士特环境检测有限公司 | Ion chromatograph |
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