CN112557142A - Sample pretreatment method, halogen content detection method and application - Google Patents
Sample pretreatment method, halogen content detection method and application Download PDFInfo
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- CN112557142A CN112557142A CN202011548707.8A CN202011548707A CN112557142A CN 112557142 A CN112557142 A CN 112557142A CN 202011548707 A CN202011548707 A CN 202011548707A CN 112557142 A CN112557142 A CN 112557142A
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- 229910052736 halogen Inorganic materials 0.000 title claims abstract description 67
- 150000002367 halogens Chemical class 0.000 title claims abstract description 58
- 238000002203 pretreatment Methods 0.000 title claims abstract description 21
- 238000001514 detection method Methods 0.000 title abstract description 26
- -1 hypophosphite ions Chemical class 0.000 claims abstract description 50
- 238000000034 method Methods 0.000 claims abstract description 49
- XMBWDFGMSWQBCA-UHFFFAOYSA-N hydrogen iodide Chemical compound I XMBWDFGMSWQBCA-UHFFFAOYSA-N 0.000 claims abstract description 29
- 150000002500 ions Chemical class 0.000 claims abstract description 29
- 229910052731 fluorine Inorganic materials 0.000 claims abstract description 25
- 239000011737 fluorine Substances 0.000 claims abstract description 25
- 238000004255 ion exchange chromatography Methods 0.000 claims abstract description 25
- 238000001914 filtration Methods 0.000 claims abstract description 22
- 239000007864 aqueous solution Substances 0.000 claims abstract description 21
- 238000006115 defluorination reaction Methods 0.000 claims abstract description 17
- 239000002351 wastewater Substances 0.000 claims abstract description 14
- AXCZMVOFGPJBDE-UHFFFAOYSA-L calcium dihydroxide Chemical compound [OH-].[OH-].[Ca+2] AXCZMVOFGPJBDE-UHFFFAOYSA-L 0.000 claims abstract description 10
- 239000000920 calcium hydroxide Substances 0.000 claims abstract description 9
- 229910001861 calcium hydroxide Inorganic materials 0.000 claims abstract description 9
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 claims description 113
- 239000001301 oxygen Substances 0.000 claims description 113
- 229910052760 oxygen Inorganic materials 0.000 claims description 113
- 239000007788 liquid Substances 0.000 claims description 33
- 238000010521 absorption reaction Methods 0.000 claims description 32
- 239000000243 solution Substances 0.000 claims description 32
- NLKNQRATVPKPDG-UHFFFAOYSA-M potassium iodide Chemical compound [K+].[I-] NLKNQRATVPKPDG-UHFFFAOYSA-M 0.000 claims description 27
- 238000006243 chemical reaction Methods 0.000 claims description 26
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 22
- FVAUCKIRQBBSSJ-UHFFFAOYSA-M sodium iodide Chemical compound [Na+].[I-] FVAUCKIRQBBSSJ-UHFFFAOYSA-M 0.000 claims description 18
- ZAMOUSCENKQFHK-UHFFFAOYSA-N Chlorine atom Chemical compound [Cl] ZAMOUSCENKQFHK-UHFFFAOYSA-N 0.000 claims description 16
- 229910052801 chlorine Inorganic materials 0.000 claims description 16
- 239000000460 chlorine Substances 0.000 claims description 16
- 238000002485 combustion reaction Methods 0.000 claims description 16
- 239000002244 precipitate Substances 0.000 claims description 13
- 239000008367 deionised water Substances 0.000 claims description 12
- 229910021641 deionized water Inorganic materials 0.000 claims description 12
- 229910001502 inorganic halide Inorganic materials 0.000 claims description 12
- UIIMBOGNXHQVGW-UHFFFAOYSA-M Sodium bicarbonate Chemical compound [Na+].OC([O-])=O UIIMBOGNXHQVGW-UHFFFAOYSA-M 0.000 claims description 10
- CPELXLSAUQHCOX-UHFFFAOYSA-M Bromide Chemical compound [Br-] CPELXLSAUQHCOX-UHFFFAOYSA-M 0.000 claims description 9
- CDBYLPFSWZWCQE-UHFFFAOYSA-L Sodium Carbonate Chemical compound [Na+].[Na+].[O-]C([O-])=O CDBYLPFSWZWCQE-UHFFFAOYSA-L 0.000 claims description 9
- 238000001816 cooling Methods 0.000 claims description 9
- 238000011049 filling Methods 0.000 claims description 9
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 8
- 150000001875 compounds Chemical class 0.000 claims description 7
- 235000009518 sodium iodide Nutrition 0.000 claims description 6
- 238000007599 discharging Methods 0.000 claims description 5
- 239000007789 gas Substances 0.000 claims description 5
- 229910000030 sodium bicarbonate Inorganic materials 0.000 claims description 5
- 229910000029 sodium carbonate Inorganic materials 0.000 claims description 5
- 235000017557 sodium bicarbonate Nutrition 0.000 claims description 4
- 238000001471 micro-filtration Methods 0.000 claims description 3
- 239000000047 product Substances 0.000 claims description 3
- 238000005374 membrane filtration Methods 0.000 claims description 2
- 238000005245 sintering Methods 0.000 claims description 2
- PXGOKWXKJXAPGV-UHFFFAOYSA-N Fluorine Chemical compound FF PXGOKWXKJXAPGV-UHFFFAOYSA-N 0.000 claims 2
- KRHYYFGTRYWZRS-UHFFFAOYSA-M Fluoride anion Chemical compound [F-] KRHYYFGTRYWZRS-UHFFFAOYSA-M 0.000 abstract description 12
- YCKRFDGAMUMZLT-UHFFFAOYSA-N Fluorine atom Chemical compound [F] YCKRFDGAMUMZLT-UHFFFAOYSA-N 0.000 abstract description 12
- 239000000523 sample Substances 0.000 description 155
- 238000012360 testing method Methods 0.000 description 22
- VEXZGXHMUGYJMC-UHFFFAOYSA-M Chloride anion Chemical compound [Cl-] VEXZGXHMUGYJMC-UHFFFAOYSA-M 0.000 description 12
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 description 12
- ACVYVLVWPXVTIT-UHFFFAOYSA-M phosphinate Chemical compound [O-][PH2]=O ACVYVLVWPXVTIT-UHFFFAOYSA-M 0.000 description 10
- 238000011084 recovery Methods 0.000 description 8
- 238000002156 mixing Methods 0.000 description 6
- 229910052759 nickel Inorganic materials 0.000 description 6
- GDTBXPJZTBHREO-UHFFFAOYSA-N bromine Substances BrBr GDTBXPJZTBHREO-UHFFFAOYSA-N 0.000 description 5
- 229910052794 bromium Inorganic materials 0.000 description 5
- WUKWITHWXAAZEY-UHFFFAOYSA-L calcium difluoride Chemical compound [F-].[F-].[Ca+2] WUKWITHWXAAZEY-UHFFFAOYSA-L 0.000 description 5
- 229910001634 calcium fluoride Inorganic materials 0.000 description 5
- 238000011088 calibration curve Methods 0.000 description 5
- 150000004820 halides Chemical class 0.000 description 5
- 238000002386 leaching Methods 0.000 description 5
- 238000004458 analytical method Methods 0.000 description 4
- 239000012086 standard solution Substances 0.000 description 4
- 229920000742 Cotton Polymers 0.000 description 3
- 230000000740 bleeding effect Effects 0.000 description 3
- 230000000052 comparative effect Effects 0.000 description 3
- 238000007865 diluting Methods 0.000 description 3
- 238000006213 oxygenation reaction Methods 0.000 description 3
- 238000002360 preparation method Methods 0.000 description 3
- 238000000197 pyrolysis Methods 0.000 description 3
- 238000004445 quantitative analysis Methods 0.000 description 3
- 239000002352 surface water Substances 0.000 description 3
- 239000002912 waste gas Substances 0.000 description 3
- WKBOTKDWSSQWDR-UHFFFAOYSA-N Bromine atom Chemical compound [Br] WKBOTKDWSSQWDR-UHFFFAOYSA-N 0.000 description 2
- BHPQYMZQTOCNFJ-UHFFFAOYSA-N Calcium cation Chemical compound [Ca+2] BHPQYMZQTOCNFJ-UHFFFAOYSA-N 0.000 description 2
- 239000003513 alkali Substances 0.000 description 2
- 230000009286 beneficial effect Effects 0.000 description 2
- 230000015572 biosynthetic process Effects 0.000 description 2
- 229910001424 calcium ion Inorganic materials 0.000 description 2
- 239000003153 chemical reaction reagent Substances 0.000 description 2
- 239000012528 membrane Substances 0.000 description 2
- 230000004048 modification Effects 0.000 description 2
- 238000012986 modification Methods 0.000 description 2
- 150000002894 organic compounds Chemical class 0.000 description 2
- 238000007500 overflow downdraw method Methods 0.000 description 2
- 239000012488 sample solution Substances 0.000 description 2
- 239000011734 sodium Substances 0.000 description 2
- PUZPDOWCWNUUKD-UHFFFAOYSA-M sodium fluoride Chemical compound [F-].[Na+] PUZPDOWCWNUUKD-UHFFFAOYSA-M 0.000 description 2
- 238000005303 weighing Methods 0.000 description 2
- KWSLGOVYXMQPPX-UHFFFAOYSA-N 5-[3-(trifluoromethyl)phenyl]-2h-tetrazole Chemical compound FC(F)(F)C1=CC=CC(C2=NNN=N2)=C1 KWSLGOVYXMQPPX-UHFFFAOYSA-N 0.000 description 1
- 229910021607 Silver chloride Inorganic materials 0.000 description 1
- 238000000184 acid digestion Methods 0.000 description 1
- 229910001382 calcium hypophosphite Inorganic materials 0.000 description 1
- 229940064002 calcium hypophosphite Drugs 0.000 description 1
- 150000001768 cations Chemical class 0.000 description 1
- 239000003795 chemical substances by application Substances 0.000 description 1
- 238000004140 cleaning Methods 0.000 description 1
- 239000003480 eluent Substances 0.000 description 1
- 238000010828 elution Methods 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 238000009616 inductively coupled plasma Methods 0.000 description 1
- 239000010842 industrial wastewater Substances 0.000 description 1
- 230000010354 integration Effects 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- 238000005259 measurement Methods 0.000 description 1
- 150000007522 mineralic acids Chemical class 0.000 description 1
- 239000012188 paraffin wax Substances 0.000 description 1
- 238000004451 qualitative analysis Methods 0.000 description 1
- 150000003839 salts Chemical class 0.000 description 1
- HKZLPVFGJNLROG-UHFFFAOYSA-M silver monochloride Chemical compound [Cl-].[Ag+] HKZLPVFGJNLROG-UHFFFAOYSA-M 0.000 description 1
- 239000011775 sodium fluoride Substances 0.000 description 1
- 235000013024 sodium fluoride Nutrition 0.000 description 1
- 229910001379 sodium hypophosphite Inorganic materials 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- CNALVHVMBXLLIY-IUCAKERBSA-N tert-butyl n-[(3s,5s)-5-methylpiperidin-3-yl]carbamate Chemical compound C[C@@H]1CNC[C@@H](NC(=O)OC(C)(C)C)C1 CNALVHVMBXLLIY-IUCAKERBSA-N 0.000 description 1
- 238000009736 wetting Methods 0.000 description 1
Images
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- G—PHYSICS
- G01—MEASURING; TESTING
- G01N—INVESTIGATING OR ANALYSING MATERIALS BY DETERMINING THEIR CHEMICAL OR PHYSICAL PROPERTIES
- G01N1/00—Sampling; Preparing specimens for investigation
- G01N1/28—Preparing specimens for investigation including physical details of (bio-)chemical methods covered elsewhere, e.g. G01N33/50, C12Q
-
- G—PHYSICS
- G01—MEASURING; TESTING
- G01N—INVESTIGATING OR ANALYSING MATERIALS BY DETERMINING THEIR CHEMICAL OR PHYSICAL PROPERTIES
- G01N1/00—Sampling; Preparing specimens for investigation
- G01N1/28—Preparing specimens for investigation including physical details of (bio-)chemical methods covered elsewhere, e.g. G01N33/50, C12Q
- G01N1/34—Purifying; Cleaning
-
- G—PHYSICS
- G01—MEASURING; TESTING
- G01N—INVESTIGATING OR ANALYSING MATERIALS BY DETERMINING THEIR CHEMICAL OR PHYSICAL PROPERTIES
- G01N1/00—Sampling; Preparing specimens for investigation
- G01N1/28—Preparing specimens for investigation including physical details of (bio-)chemical methods covered elsewhere, e.g. G01N33/50, C12Q
- G01N1/44—Sample treatment involving radiation, e.g. heat
-
- 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
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- Life Sciences & Earth Sciences (AREA)
- Health & Medical Sciences (AREA)
- General Health & Medical Sciences (AREA)
- Chemical & Material Sciences (AREA)
- Analytical Chemistry (AREA)
- Biochemistry (AREA)
- Physics & Mathematics (AREA)
- General Physics & Mathematics (AREA)
- Immunology (AREA)
- Pathology (AREA)
- Engineering & Computer Science (AREA)
- Biomedical Technology (AREA)
- Molecular Biology (AREA)
- Investigating Or Analyzing Non-Biological Materials By The Use Of Chemical Means (AREA)
Abstract
The invention discloses a sample pretreatment method, a halogen content detection method and application, and relates to the technical field of analytical chemistry. The sample pretreatment method comprises the following steps: reacting a sample to be detected with a first iodide aqueous solution to obtain an intermediate sample; and (3) reacting the intermediate sample with a calcium hydroxide aqueous solution, and filtering to obtain a defluorination sample. The detection method of the halogen content comprises the following steps: pretreating a sample by adopting the pretreatment method; and respectively detecting the ion content in the intermediate sample and the defluorination sample by adopting an ion chromatography, and subtracting the ion content of the peak appearing between 2-4 min in the defluorination sample from the ion content of the peak appearing between 2-4 min in the intermediate sample to obtain the fluorine content in the sample to be detected. The detection method can avoid inaccurate fluorine ion detection data caused by the fact that the peak emergence time and the peak shape of hypophosphite ions and fluorine ions are close when ion content is detected by adopting an ion chromatography; therefore, the method has accurate detection result and can be applied to the detection of the halogen content in the wastewater.
Description
Technical Field
The invention relates to the technical field of chemical analysis, in particular to a sample pretreatment method, a halogen content detection method and application.
Background
The industrial wastewater usually contains inorganic salts of halogen (free halogen) and organic compounds of halogen (combined halogen), so that the halogen (fluorine, chlorine and bromine) in different states in the wastewater can be accurately, qualitatively and quantitatively analyzed, and the method is particularly important for parameter adjustment of a production line and wastewater discharge. The pretreatment of the sample is the key of the analysis of the wastewater sample, the accuracy of the test result is greatly affected, and the recovery rate of the halogen is low, so that the conventional inorganic acid digestion is not suitable for the accurate quantitative analysis of the halogen. The prior pretreatment technology aiming at halogen samples mainly comprises a pyrolysis method, an alkali fusion method and an oxygen bomb method. The pyrolysis method causes the sample to generate heat to explain and release halogen through high temperature, and the sample is tested by IC (ion chromatography) or ICP-MS (inductively coupled plasma mass spectrometer) after being absorbed by the alkaline trapping liquid. The pyrolysis method has not high enough recovery rate of halogen, and the sample treatment and device cleaning are time-consuming, which is not beneficial to batch test. In the alkali fusion method, more cations are introduced due to the use of a fusing agent, and the subsequent treatment of a sample is troublesome. The conventional oxygen bomb method is that a sample is oxidized in a calorimetric bomb containing high-pressure oxygen by combustion, so that compounds containing fluorine, chlorine and bromine are respectively converted into fluoride, chloride and bromide, and then are mixed with an absorption liquid (Na)2CO3/NaHCO3) And (4) absorbing. However, this method can analyze only soluble halides, and insoluble halides cannot be absorbed by the eluent, thereby causing inaccurate measurement in the next quantitative analysis test by ion chromatography. Even though the problems of the prior art are overcome, the inventor finds that the accuracy of the test result of the halogen in the wastewater still needs to be improved.
In view of this, the invention is particularly proposed.
Disclosure of Invention
The invention aims to provide a sample pretreatment method, a halogen content detection method and application.
The invention is realized by the following steps:
in a first aspect, an embodiment of the present invention provides a sample pretreatment method, including:
reacting a sample to be detected with a first iodide aqueous solution to enable fluorine, chlorine and bromide ions in insoluble inorganic halides to be dissociated to obtain an intermediate sample;
and (3) reacting the intermediate sample with a calcium hydroxide aqueous solution, and filtering to obtain a defluorination sample.
In an optional embodiment, after the reaction between the sample to be detected and the first iodide aqueous solution is finished, filtering to remove the precipitate;
in an alternative embodiment, the filtration means is microfiltration.
In an alternative embodiment, the first aqueous iodide solution is selected from at least one of a sodium iodide solution and a potassium iodide solution.
In a second aspect, an embodiment of the present invention provides a method for detecting a halogen content, including:
the sample pretreatment method provided by the embodiment of the invention is adopted to pretreat the sample to be detected;
respectively detecting the ion content in the intermediate sample and the defluorination sample by adopting an ion chromatography;
and subtracting the measured ion content of the peak appearing between 2-4 min in the defluorination sample from the measured ion content of the peak appearing between 2-4 min in the intermediate sample to obtain the free state fluorine content in the sample to be measured.
In an alternative embodiment, the method further comprises:
converting organic halogen-containing compounds in a sample to be detected into inorganic halides by adopting an oxygen bomb method through combustion to obtain a partial conversion sample, and reacting the partial conversion sample with a second iodide aqueous solution, filtering and removing precipitates to obtain a conversion sample;
detecting the ion content in the converted sample by adopting an ion chromatography;
and subtracting the corresponding halogen ion content in the intermediate sample from the measured halogen ion content in the conversion sample to obtain the bound halogen content in the sample to be measured.
In an alternative embodiment, the second aqueous iodide solution is selected from at least one of a sodium iodide solution and a potassium iodide solution.
In an alternative embodiment, the combustion conversion of the organic halogen-containing compound in the sample to be tested into the inorganic halide by the oxygen bomb method is:
placing a sample to be detected in a crucible of an oxygen bomb device, and installing an ignition wire;
adding absorption liquid into the oxygen bomb cup in a manner of rinsing the inner wall of the oxygen bomb cup to completely wet the inner wall of the oxygen bomb cup;
filling oxygen into the oxygen bomb cup;
closing the circuit of the ignition lead to burn the sample to be tested;
after the sintering is finished, the oxygen bomb device is cooled, and the absorption liquid fully absorbs combustion products to obtain a partial conversion sample.
In an alternative embodiment, ethanol is used as a combustion improver when the sample to be tested is combusted by an oxygen bomb method.
In an optional embodiment, when the sample to be detected is combusted by adopting an oxygen bomb method, at least one of deionized water, a sodium carbonate solution and a sodium bicarbonate solution is used as an absorption liquid;
in an optional embodiment, the concentration of the sodium carbonate solution is 50-200 mg/l;
in an alternative embodiment, the concentration of the sodium bicarbonate solution is 40-200 mg/l.
In an alternative embodiment, the charging of oxygen into the oxygen bomb cup is:
and (3) filling oxygen into the oxygen bomb cup, enabling the air pressure in the oxygen bomb cup to be 2.8-3.2 MPa, keeping for 15-20 s, then discharging the air in the oxygen bomb cup, repeating for three times, displaying the pressure of the oxygen pressure gauge to be 2.8-3.2 MPa, and stopping for 15-20 s to enable the oxygen to be used as combustion-supporting gas.
The method for detecting the halogen content provided by the embodiment of the invention is applied to the detection of the halogen content in the wastewater.
The invention has the following beneficial effects:
the sample pretreatment method enables insoluble fluoride, chloride and bromide in a sample to react with iodide to generate iodide precipitate, so that fluorine, chlorine and bromide ions in original insoluble inorganic halide are dissociated, the recovery rate of free halogen is greatly improved, the subsequent ion chromatograph is convenient to test, and the accuracy of detecting the content of the free halogen in the halide is improved; the intermediate sample is then reacted with calcium hydroxide to precipitate out the fluoride ions in the sample. The method avoids inaccurate fluorine ion detection data caused by the fact that the peak-out time and the peak shape of hypophosphite ions and fluorine ions are close to each other when ion chromatography is adopted to detect the ion content.
The detection method comprises the sample pretreatment method provided by the invention, so that the detection method can more accurately detect the contents of fluorine, chlorine and bromine ions in the sample compared with the existing detection method. The detection method provided by the invention can be applied to the detection of the content of halogen in the wastewater.
Drawings
In order to more clearly illustrate the technical solutions of the embodiments of the present invention, the drawings needed to be used in the embodiments will be briefly described below, it should be understood that the following drawings only illustrate some embodiments of the present invention and therefore should not be considered as limiting the scope, and for those skilled in the art, other related drawings can be obtained according to the drawings without inventive efforts.
FIG. 1 is a graph showing the peak formation of fluorine ions in a sample by ion chromatography;
FIG. 2 is a graph showing the peak formation of hypophosphite when a sample is detected by ion chromatography.
Detailed Description
In order to make the objects, technical solutions and advantages of the embodiments of the present invention clearer, the technical solutions in the embodiments of the present invention will be clearly and completely described below. The examples, in which specific conditions are not specified, were conducted under conventional conditions or conditions recommended by the manufacturer. The reagents or instruments used are not indicated by the manufacturer, and are all conventional products available commercially.
The inventor conducts a great deal of creative work to find that in an ion chromatography test, the peak emergence time and the peak shape of hypophosphite and fluoride ions are very close, when a sample contains both fluoride ions and hypophosphite ions, software cannot distinguish, and the sum of the contents of the two ions is quantified. If the tested sample contains hypophosphite, the method is easy to cause serious interference to the qualitative and quantitative analysis of the fluorine ions. Therefore, the inventor proposes the technical scheme of the application to improve the accuracy of halogen test in wastewater aiming at the test sample of wastewater possibly containing hypophosphite.
The embodiment of the invention provides a sample pretreatment method, which comprises the following steps:
reacting a sample to be detected with a first iodide aqueous solution to enable fluorine, chlorine and bromide ions in insoluble inorganic halides to be dissociated to obtain an intermediate sample;
and (3) reacting the intermediate sample with a calcium hydroxide aqueous solution, and filtering to obtain a defluorination sample.
Insoluble fluoride, chloride and bromide in a sample react with iodide to generate iodide precipitate, so that fluorine, chlorine and bromide ions in original insoluble inorganic halide are dissociated, the recovery rate of free halogen is greatly improved, a subsequent ion chromatograph is convenient to test, and the accuracy of detecting the content of the free halogen in the halide is improved; the intermediate sample is then reacted with calcium hydroxide to precipitate out the fluoride ions in the sample. Because the peak emergence time and the peak shape of the hypophosphite ions and the fluorine ions are very close, the fluorine ions are precipitated first, and the subsequent ion content detection by adopting the ion chromatography can avoid the confusion of the hypophosphite ions and the fluorine ions. Testing the sum of the content of the fluorine ions and the content of the hypophosphite ions in the intermediate sample to be C1 by adopting an ion chromatography, and testing the content of the hypophosphite ions in the defluorination sample to be C2 by adopting the ion chromatography; then C1-C2 are the true fluoride ion content in the sample.
Therefore, the method for pretreating the sample provided by the invention can ensure that the test result is more accurate by adopting the ion chromatography to test the content of the fluorine ions in the sample after the sample to be tested is treated by adopting the sample pretreatment method provided by the invention.
Preferably, the sample to be tested is filtered to remove the precipitate after the reaction with the first aqueous iodide solution is completed.
Preferably, the filtration mode is microfiltration membrane filtration.
Preferably, the first aqueous iodide solution is selected from at least one of a sodium iodide solution and a potassium iodide solution.
The embodiment of the invention provides a method for detecting halogen content, which comprises the following steps:
the sample is pretreated by adopting the sample pretreatment method provided by the embodiment of the invention;
respectively detecting the ion content in the intermediate sample and the defluorination sample by adopting an ion chromatography;
and subtracting the measured ion content which appears in the middle sample within 2-4 min from the measured ion content which appears in the defluorination sample within 2-4 min to obtain the fluorine content in the sample to be measured.
The peak emergence time of hypophosphite ions and fluoride ions is about 3min, and the peak shapes of the hypophosphite ions and the fluoride ions are very similar, so that the total amount of the hypophosphite ions and the fluoride ions is detected by an intermediate sample through ion chromatography. The detection method comprises the sample pretreatment method provided by the embodiment of the invention, so that the content of halogen ions, particularly fluorine ions in the sample can be more accurately tested by the detection method provided by the invention.
Preferably, in order to be able to test the content of bound (e.g. halogen-containing organic compound) halide ions in the sample. The method for detecting the halogen content provided by the embodiment of the invention further comprises the following steps:
converting organic halogen-containing compounds in a sample to be detected into inorganic halides by adopting an oxygen bomb method through combustion to obtain a partial conversion sample, and reacting the partial conversion sample with a second iodide aqueous solution, filtering and removing precipitates to obtain a conversion sample;
detecting the ion content in the converted sample by adopting an ion chromatography;
and subtracting the corresponding halogen ion content in the intermediate sample from the measured halogen ion content in the conversion sample to obtain the bound halogen content in the sample to be measured.
The halogen contained in the sample is completely dissociated into the conversion sample as far as possible by the method, and taking chloride ions as an example, the content of the chloride ions in the conversion sample is detected to be C3 by adopting ion chromatography, the content of the chloride ions in the intermediate sample is detected to be C4 by adopting ion chromatography, and the content of the chloride ions in a binding state is detected to be C3-C4.
Preferably, the second aqueous iodide solution is selected from at least one of a sodium iodide solution and a potassium iodide solution.
The detection method specifically comprises the following steps:
s1, sample pretreatment:
taking 0.1-1 g (accurate to 0.0001g) of sample into a 50ml volumetric flask, and then adding 10-20 ml of iodide aqueous solution into the volumetric flask, wherein the concentration of soluble iodide is 10-50 mmol/l. And fully and uniformly mixing the sample and the iodide aqueous solution, standing for reaction for 5-10min, filtering by using a microporous filter membrane, transferring into a 50ml volumetric flask, and metering the volume to 50ml by using a proper amount of deionized water to obtain an intermediate sample.
Putting 10g of the intermediate sample into a 50ml volumetric flask, adding 10ml of calcium hydroxide aqueous solution (the concentration is 20mmol/L), fully shaking to enable fluoride ions in the sample to react with calcium ions to generate insoluble calcium fluoride precipitate, filtering the insoluble calcium fluoride precipitate, and retaining hypophosphite. And (4) adding a proper amount of deionized water to the volume of 50ml to obtain a defluorinated sample.
S2, converting organic halogen-containing compounds in the sample to be detected into inorganic halides by combustion through an oxygen bomb method, specifically:
1. weighing 0.5g (to the nearest 0.0001g) of sample into a nickel bomb crucible, and adding 1.5ml of ethanol as a combustion improver for some samples which are not easy to burn.
2. Installing an ignition wire and a sample, opening an oxygen bomb upper cover, fixing a nickel crucible containing the sample, fixing two ends of the ignition wire on an electrode column, and binding a cotton thread with proper length on the ignition wire to enable the ignition wire to be in contact with the sample.
3. Adding an absorption liquid:
(1) preparation of absorption liquid: pure water can be added as an absorption liquid for a sample with low halogen content, and the leacheate used by the instrument can be added for a sample with high halogen content. Na in leaching2CO3NaHCO with concentration of 50-200 mg/l3The concentration is 40-200 mg/l, and the absorption liquid is prepared by fully and uniformly mixing.
(2) Addition of an absorption liquid: adding about 20ml of absorption liquid into the oxygen bomb cup in a manner of eluting the inner wall of the oxygen bomb, completely wetting the inner wall of the oxygen bomb cup, covering the oxygen bomb cup and screwing down;
4. oxygenation: connecting an oxygen guide pipe on an oxygen bomb cup cover, slowly filling oxygen, increasing the oxygen at intervals from zero to about 3MPa, stopping for 15-20 s, slowly discharging air in the oxygen bomb, and stopping for about 15s when an oxygen pressure gauge shows 3.0MPa after repeating for three times to serve as combustion-supporting gas during combustion; placing the oxygen bomb device in cold water for ignition: and connecting an ignition lead, closing a circuit to ignite the sample, and ending the process after the sample in the oxygen bomb burns and releases heat.
5. Cooling and shaking: the oxygen bomb was placed in a cold water bath to allow the water level to completely submerge the oxygen bomb unit. About 40min, the oxygen bomb device can be shaken properly in the cooling process, so that the measured ions are completely absorbed by the absorption liquid.
6. Air bleeding: and taking out the oxygen bomb to wipe the surface water of the oxygen bomb clean, slowly releasing oxygen in the oxygen bomb by using a release valve, and absorbing the released waste gas in the leacheate when necessary.
7. Filtering and fixing volume: eluting the oxygen bomb barrel, the sample cup and the oxygen bomb cover with a proper amount of deionized water for more than 3 times, mixing elution tail liquid with absorption liquid to obtain a partially converted sample, then standing and reacting the partially converted sample with 10-20 mL of iodide aqueous solution (the concentration of soluble iodide is 10-50 mmol/l) for 5-10min, filtering and transferring to a 100mL volumetric flask after the reaction is finished, and then diluting with deionized water to a constant volume to obtain the converted sample.
And S3, detecting the ion content in the intermediate sample, the defluorination sample and the conversion sample respectively by adopting ion chromatography. And (3) sample testing:
1. and (3) standard curve preparation: the calibration curve was prepared by diluting a standard solution of 100mg/l to prepare standard element solutions of different gradients of the element to be measured, and preparing standard solutions of 1mg/l, 2mg/l, 4mg/l, and 8mg/l, respectively. And (4) measuring the peak area reading of the absorption intensity of the target element, and establishing a calibration curve of the relation between the absorption intensity and the concentration of the target element by using a calibration curve method.
2. Test samples: under the corresponding sequence of the standard curve, the ion content in the reagent blank, the intermediate sample, the defluorination sample and the conversion sample are respectively tested, and the integration mode which is the same as that of the standard curve is adopted. If the concentration of the sample solution is beyond the concentration range of the calibration curve, the sample solution is diluted to be within the concentration range of the corresponding calibration curve and then tested again.
The method for detecting the halogen content provided by the embodiment of the invention can be applied to testing the halogen content in the wastewater.
The features and properties of the present invention are described in further detail below with reference to examples.
Example 1
1. Weighing: 0.5000g of the initial sample to be measured is weighed into a 50ml volumetric flask, and then 15ml of an aqueous potassium iodide solution having a concentration of 30mmol/l is added to the volumetric flask. And fully and uniformly mixing the sample and the potassium iodide aqueous solution, standing for reaction for 10min, filtering by using a microporous filter membrane, transferring into a 50ml volumetric flask, and metering the volume to 50ml by using a proper amount of deionized water to obtain an intermediate sample. Putting 10g of the intermediate sample into a 50ml volumetric flask, adding 10ml of calcium hydroxide aqueous solution (the concentration is 20mmol/L), fully shaking to enable fluoride ions in the sample to react with calcium ions to generate insoluble calcium fluoride precipitate, filtering the insoluble calcium fluoride precipitate, and retaining hypophosphite. And (4) adding a proper amount of deionized water to the volume of 50ml to obtain a defluorinated sample.
2. 0.5000g (accurate to 0.0001g) of initial sample to be measured is weighed into an oxygen bomb nickel crucible, and 1.5ml of ethanol is added as a combustion improver.
3. Mounting ignition wire and sample: opening an upper cover of the oxygen bomb, fixing a nickel crucible containing the sample, fixing two ends of an ignition wire on an electrode column, and selecting a cotton thread with a proper length to bind the ignition wire and enable the ignition wire to be in contact with the sample;
4. adding an absorption liquid:
(1) preparation of absorption liquid: preparing the leaching absorption liquid used by the instrument, wherein Na2CO3NaHCO at a concentration of 100mg/l3The concentration is 100mg/l, and the absorption liquid is prepared by fully and uniformly mixing.
(2) Addition of an absorption liquid: adding 20ml of absorption liquid into the oxygen bomb cup in a manner of eluting the inner wall of the oxygen bomb so as to completely wet the inner wall of the oxygen bomb cup, covering the oxygen bomb cup and screwing down the oxygen bomb cup;
5. oxygenation and ignition: connecting an oxygen guide pipe on an oxygen bomb cup cover, slowly filling oxygen, increasing the oxygen at intervals from zero to about 3MPa, stopping for 20s, slowly discharging air in the oxygen bomb, stopping for 15s when an oxygen pressure gauge shows 3.0MPa after repeating for three times, and filling combustion-supporting gas during combustion; placing the oxygen bomb device in cold water for ignition: connecting an ignition lead, closing a circuit to ignite the sample, and ending the process after the sample in the oxygen bomb burns and releases heat;
6. cooling and shaking: the oxygen bomb was placed in a cold water bath to allow the water level to completely submerge the oxygen bomb unit. Cooling for about 40min, and properly shaking the oxygen bomb device in the cooling process to ensure that the detected halogen ions are completely absorbed by the absorption liquid.
7. Air bleeding: taking out the oxygen bomb to wipe the surface water of the oxygen bomb clean, slowly releasing oxygen in the oxygen bomb by using an air release valve, and absorbing the released waste gas in leacheate when necessary;
8. filtering and fixing volume: leaching the oxygen bomb barrel, the sample cup and the oxygen bomb cover with a proper amount of deionized water for more than 3 times, mixing leaching tail liquid with absorption liquid to obtain a partially converted sample, standing and reacting the partially converted sample with 15mL (the concentration of potassium iodide is 30mmol/l) of iodide aqueous solution for 10min, filtering and transferring to a 100mL volumetric flask after the reaction is finished, and then diluting with deionized water to a constant volume to obtain the converted sample.
And respectively detecting the ion content in the intermediate sample, the defluorination sample and the conversion sample by adopting an ion chromatography.
Comparative example 1:
1. 0.5000g (to the nearest 0.0001g) of the sample was weighed into an oxygen bomb nickel crucible.
2. Mounting ignition wire and sample: opening an upper cover of the oxygen bomb, fixing a nickel crucible containing the sample, fixing two ends of an ignition wire on an electrode column, and selecting a cotton thread with a proper length to bind the ignition wire and enable the ignition wire to be in contact with the sample;
3. adding an absorption liquid: adding the absorption liquid prepared in the example 1, adding 20ml of the absorption liquid into the oxygen bomb cup in a manner of rinsing the inner wall of the oxygen bomb so as to completely wet the inner wall of the oxygen bomb cup, covering the oxygen bomb cup and screwing down;
4. oxygenation and ignition: connecting an oxygen guide pipe on an oxygen bomb cup cover, slowly filling oxygen, increasing the oxygen at intervals from zero to about 3MPa, stopping for 20s, slowly discharging air in the oxygen bomb, stopping for 15s when an oxygen pressure gauge shows 3.0MPa after repeating for three times, and filling combustion-supporting gas during combustion; placing the oxygen bomb device in cold water for ignition: connecting an ignition lead, closing a circuit to ignite the sample, and ending the process after the sample in the oxygen bomb burns and releases heat;
5. cooling and shaking: the oxygen bomb was placed in a cold water bath to allow the water level to completely submerge the oxygen bomb unit. Cooling for about 40min, and properly shaking the oxygen bomb device in the cooling process to ensure that the detected halogen ions are completely absorbed by the absorption liquid;
6. air bleeding: taking out the oxygen bomb to wipe the surface water of the oxygen bomb clean, slowly releasing oxygen in the oxygen bomb by using an air release valve, and absorbing the released waste gas in leacheate when necessary;
7. filtering and fixing volume: and filtering the absorption liquid, transferring the absorption liquid into a 100mL volumetric flask, leaching the oxygen bomb barrel, the sample cup and the oxygen bomb cover for more than 3 times by using a proper amount of deionized water, transferring the absorption liquid into the volumetric flask, and then performing constant volume by using the deionized water to obtain a comparison sample.
Experimental example 1
According to the detection method provided by the embodiment of the invention and the comparative example, the wastewater is taken as an object, the content of the chloride ions in each sample is detected, and the recovery rate of the free halogen and the combined halogen in the wastewater is calculated by taking the chloride ions as an example. The analysis was carried out using a standard solution of silver chloride containing 1.0mg/L of free chlorine and chlorinated paraffin containing 1.0mg/L of bound chlorine. Data are recorded in tables 1 and 2.
TABLE 1 chloride ion content test results
TABLE 2 chloride ion recovery test results
The results in tables 1 and 2 show that the content of free chlorine and the content of total chlorine can be respectively obtained by testing the content of free chlorine and the content of total chlorine in two steps after the sample to be tested is respectively treated by the soluble iodide aqueous solution. The recovery rate of the scheme of the invention is obviously higher than that of the conventional oxygen bomb method, the deviation of the parallel sample is smaller, and the loss of halogen in the sample in the pretreatment process is smaller, so that the accuracy and the feasibility of the sample pretreatment method of the scheme are high.
Experimental example 2
According to the steps provided in the examples and comparative examples, sodium fluoride containing fluoride ion 1.0mg/L and sodium hypophosphite standard solution containing hypophosphite 1.0mg/L are used for analysis.
TABLE 3 fluoride ion content test results
The results in table 3 show that when the sample contains both fluoride and hypophosphite, the peak-off times for both ions are consistent, as shown in fig. 1 and 2. Because the software cannot distinguish, what is quantified is the sum of the contents of the two ions, and hypophosphite is easily classified as fluoride ion. When calcium hydroxide solution is introduced to separate calcium fluoride from calcium hypophosphite by filtration, the contents of hypophosphite and fluoride ions can be distinguished, namely the content of fluoride ions and hypophosphite ions measured by the intermediate sample is C1, the content of hypophosphite ions measured by the defluorination sample is C2, and the contents of fluoride ions corresponding to C1-C2.
In conclusion, the sample pretreatment method provided by the invention enables insoluble fluoride, chloride and bromide in the sample to react with iodide to generate iodide precipitate, so that fluorine, chlorine and bromine ions in original insoluble inorganic halide are dissociated, the recovery rate of free halogen is greatly improved, a subsequent ion chromatograph is convenient to test, and the accuracy of detecting the content of free halogen in the halide is improved; the intermediate sample is then reacted with calcium hydroxide to precipitate out the fluoride ions in the sample. The method avoids inaccurate fluorine ion detection data caused by the fact that the peak-out time and the peak shape of hypophosphite ions and fluorine ions are close to each other when ion chromatography is adopted to detect the ion content.
The method for detecting the content of the halogen provided by the invention comprises the sample pretreatment method provided by the invention, so that the method can more accurately detect the content of fluorine, chlorine and bromine ions in the sample compared with the conventional detection method. The detection method provided by the invention can be applied to the detection of the content of halogen in the wastewater.
The above description is only a preferred embodiment of the present invention and is not intended to limit the present invention, and various modifications and changes may be made by those skilled in the art. Any modification, equivalent replacement, or improvement made within the spirit and principle of the present invention should be included in the protection scope of the present invention.
Claims (10)
1. A sample pretreatment method is characterized by comprising:
reacting a sample to be detected with a first iodide aqueous solution to enable fluorine, chlorine and bromide ions in insoluble inorganic halides to be dissociated to obtain an intermediate sample;
and (3) reacting the intermediate sample with a calcium hydroxide aqueous solution, and filtering to obtain a defluorination sample.
2. The sample pretreatment method according to claim 1, wherein the sample to be tested is filtered to remove precipitates after the reaction with the first iodide aqueous solution is completed;
preferably, the filtration mode is microfiltration membrane filtration.
3. The method for pretreating a sample according to claim 1, wherein the first aqueous iodide solution is at least one selected from a sodium iodide solution and a potassium iodide solution.
4. A method for detecting halogen content is characterized by comprising the following steps:
pretreating a sample to be tested by adopting the sample pretreatment method as claimed in any one of claims 1 to 3;
detecting the ion content in the intermediate sample and the defluorination sample respectively by adopting ion chromatography;
and subtracting the measured ion content of the peak appearing between 2-4 min in the defluorination sample from the measured ion content of the peak appearing between 2-4 min in the intermediate sample to obtain the content of the free fluorine in the sample to be measured.
5. The method for detecting halogen content according to claim 4, further comprising:
converting organic halogen-containing compounds in a sample to be detected into inorganic halides by adopting an oxygen bomb method through combustion to obtain a partial conversion sample, and reacting the partial conversion sample with a second iodide aqueous solution to remove precipitates through filtration to obtain a conversion sample;
detecting the ion content in the converted sample by adopting ion chromatography;
subtracting the corresponding halogen ion content in the intermediate sample from the measured halogen ion content in the conversion sample to obtain the bound halogen content in the sample to be measured;
preferably, the second aqueous iodide solution is selected from at least one of a sodium iodide solution and a potassium iodide solution.
6. The method for detecting halogen content according to claim 5, wherein the step of converting organic halogen-containing compounds in the sample to be detected into inorganic halides by combustion using an oxygen bomb method comprises:
placing a sample to be detected in a crucible of an oxygen bomb device, and installing an ignition wire;
adding absorption liquid into the oxygen bomb cup in a manner of rinsing the inner wall of the oxygen bomb cup to completely wet the inner wall of the oxygen bomb cup;
filling oxygen into the oxygen bomb cup;
closing a circuit of an ignition lead to burn the sample to be tested;
and after the sintering process is finished, cooling the oxygen bomb device, and fully absorbing combustion products by the absorption liquid to obtain the partially converted sample.
7. The method for detecting halogen content according to claim 6, wherein ethanol is used as a combustion improver when the sample to be detected is combusted by an oxygen bomb method.
8. The method for detecting halogen content according to claim 6, wherein at least one of deionized water, a sodium carbonate solution and a sodium bicarbonate solution is used as an absorption liquid when the sample to be detected is combusted by an oxygen bomb method;
preferably, the concentration of the sodium carbonate solution is 50-200 mg/l;
preferably, the concentration of the sodium bicarbonate solution is 40-200 mg/l.
9. The method for detecting halogen content according to claim 6, wherein the charging of oxygen into the oxygen bomb cup is:
and filling oxygen into the oxygen bomb cup, enabling the air pressure in the oxygen bomb cup to be 2.8-3.2 MPa, keeping for 15-20 s, then discharging the air in the oxygen bomb cup, repeating for three times, displaying the pressure of the oxygen pressure gauge to be 2.8-3.2 MPa, and stopping for 15-20 s to enable the oxygen to be used as combustion-supporting gas.
10. Use of the method according to any one of claims 4 to 9 for detecting halogen content in wastewater.
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