CN111879888A - Method for detecting fluoride ions in hydrochloric acid - Google Patents
Method for detecting fluoride ions in hydrochloric acid Download PDFInfo
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- CN111879888A CN111879888A CN202010769181.XA CN202010769181A CN111879888A CN 111879888 A CN111879888 A CN 111879888A CN 202010769181 A CN202010769181 A CN 202010769181A CN 111879888 A CN111879888 A CN 111879888A
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- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 title claims abstract description 62
- 238000000034 method Methods 0.000 title claims abstract description 45
- -1 fluoride ions Chemical class 0.000 title claims abstract description 42
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 58
- 150000002500 ions Chemical class 0.000 claims abstract description 54
- KRHYYFGTRYWZRS-UHFFFAOYSA-M Fluoride anion Chemical compound [F-] KRHYYFGTRYWZRS-UHFFFAOYSA-M 0.000 claims abstract description 45
- 239000012086 standard solution Substances 0.000 claims abstract description 27
- 229910052731 fluorine Inorganic materials 0.000 claims abstract description 16
- 239000011737 fluorine Substances 0.000 claims abstract description 16
- 239000002253 acid Substances 0.000 claims abstract description 15
- 239000003957 anion exchange resin Substances 0.000 claims abstract description 15
- 239000000835 fiber Substances 0.000 claims abstract description 12
- 239000012528 membrane Substances 0.000 claims abstract description 12
- 238000010812 external standard method Methods 0.000 claims abstract description 7
- 238000005086 pumping Methods 0.000 claims abstract description 5
- PUZPDOWCWNUUKD-UHFFFAOYSA-M sodium fluoride Chemical compound [F-].[Na+] PUZPDOWCWNUUKD-UHFFFAOYSA-M 0.000 claims description 62
- 239000011775 sodium fluoride Substances 0.000 claims description 31
- 235000013024 sodium fluoride Nutrition 0.000 claims description 31
- 239000012470 diluted sample Substances 0.000 claims description 19
- 239000000243 solution Substances 0.000 claims description 17
- 239000000523 sample Substances 0.000 claims description 15
- 229920000915 polyvinyl chloride Polymers 0.000 claims description 11
- 239000004800 polyvinyl chloride Substances 0.000 claims description 11
- 238000005303 weighing Methods 0.000 claims description 11
- 238000004255 ion exchange chromatography Methods 0.000 claims description 10
- 239000004698 Polyethylene Substances 0.000 claims description 6
- 238000001816 cooling Methods 0.000 claims description 6
- 238000007865 diluting Methods 0.000 claims description 6
- 229920000573 polyethylene Polymers 0.000 claims description 6
- BVKZGUZCCUSVTD-UHFFFAOYSA-M Bicarbonate Chemical compound OC([O-])=O BVKZGUZCCUSVTD-UHFFFAOYSA-M 0.000 claims description 3
- BVKZGUZCCUSVTD-UHFFFAOYSA-L Carbonate Chemical compound [O-]C([O-])=O BVKZGUZCCUSVTD-UHFFFAOYSA-L 0.000 claims description 3
- 229910052784 alkaline earth metal Inorganic materials 0.000 claims description 3
- 150000001342 alkaline earth metals Chemical class 0.000 claims description 3
- 239000012670 alkaline solution Substances 0.000 claims description 3
- 238000001035 drying Methods 0.000 claims description 3
- XLYOFNOQVPJJNP-UHFFFAOYSA-M hydroxide Chemical group [OH-] XLYOFNOQVPJJNP-UHFFFAOYSA-M 0.000 claims description 3
- 238000005349 anion exchange Methods 0.000 abstract 1
- 230000000052 comparative effect Effects 0.000 description 11
- 238000001514 detection method Methods 0.000 description 10
- 238000010790 dilution Methods 0.000 description 7
- 239000012895 dilution Substances 0.000 description 7
- 238000005259 measurement Methods 0.000 description 7
- UIIMBOGNXHQVGW-UHFFFAOYSA-M Sodium bicarbonate Chemical compound [Na+].OC([O-])=O UIIMBOGNXHQVGW-UHFFFAOYSA-M 0.000 description 6
- KJFMBFZCATUALV-UHFFFAOYSA-N phenolphthalein Chemical compound C1=CC(O)=CC=C1C1(C=2C=CC(O)=CC=2)C2=CC=CC=C2C(=O)O1 KJFMBFZCATUALV-UHFFFAOYSA-N 0.000 description 6
- 238000011084 recovery Methods 0.000 description 6
- VEXZGXHMUGYJMC-UHFFFAOYSA-M Chloride anion Chemical compound [Cl-] VEXZGXHMUGYJMC-UHFFFAOYSA-M 0.000 description 5
- 238000000926 separation method Methods 0.000 description 5
- 238000004458 analytical method Methods 0.000 description 4
- 239000012535 impurity Substances 0.000 description 4
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 3
- 235000017557 sodium bicarbonate Nutrition 0.000 description 3
- 229910000030 sodium bicarbonate Inorganic materials 0.000 description 3
- UQSXHKLRYXJYBZ-UHFFFAOYSA-N Iron oxide Chemical compound [Fe]=O UQSXHKLRYXJYBZ-UHFFFAOYSA-N 0.000 description 2
- FAPWRFPIFSIZLT-UHFFFAOYSA-M Sodium chloride Chemical compound [Na+].[Cl-] FAPWRFPIFSIZLT-UHFFFAOYSA-M 0.000 description 2
- 238000003321 atomic absorption spectrophotometry Methods 0.000 description 2
- 239000007853 buffer solution Substances 0.000 description 2
- 238000004737 colorimetric analysis Methods 0.000 description 2
- 230000000694 effects Effects 0.000 description 2
- 238000004817 gas chromatography Methods 0.000 description 2
- 230000014759 maintenance of location Effects 0.000 description 2
- 238000004519 manufacturing process Methods 0.000 description 2
- 238000012986 modification Methods 0.000 description 2
- 230000004048 modification Effects 0.000 description 2
- 239000000126 substance Substances 0.000 description 2
- BHPQYMZQTOCNFJ-UHFFFAOYSA-N Calcium cation Chemical compound [Ca+2] BHPQYMZQTOCNFJ-UHFFFAOYSA-N 0.000 description 1
- UXVMQQNJUSDDNG-UHFFFAOYSA-L Calcium chloride Chemical compound [Cl-].[Cl-].[Ca+2] UXVMQQNJUSDDNG-UHFFFAOYSA-L 0.000 description 1
- KRHYYFGTRYWZRS-UHFFFAOYSA-N Fluorane Chemical compound F KRHYYFGTRYWZRS-UHFFFAOYSA-N 0.000 description 1
- YCKRFDGAMUMZLT-UHFFFAOYSA-N Fluorine atom Chemical compound [F] YCKRFDGAMUMZLT-UHFFFAOYSA-N 0.000 description 1
- FOIXSVOLVBLSDH-UHFFFAOYSA-N Silver ion Chemical compound [Ag+] FOIXSVOLVBLSDH-UHFFFAOYSA-N 0.000 description 1
- 230000002378 acidificating effect Effects 0.000 description 1
- 150000001450 anions Chemical class 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 239000012496 blank sample Substances 0.000 description 1
- 239000001110 calcium chloride Substances 0.000 description 1
- 229910001628 calcium chloride Inorganic materials 0.000 description 1
- 229910001424 calcium ion Inorganic materials 0.000 description 1
- 150000001768 cations Chemical class 0.000 description 1
- 238000004040 coloring Methods 0.000 description 1
- 238000002845 discoloration Methods 0.000 description 1
- 238000004821 distillation Methods 0.000 description 1
- 238000005558 fluorometry Methods 0.000 description 1
- 239000007789 gas Substances 0.000 description 1
- 239000001257 hydrogen Substances 0.000 description 1
- 229910052739 hydrogen Inorganic materials 0.000 description 1
- 229910000040 hydrogen fluoride Inorganic materials 0.000 description 1
- 125000002887 hydroxy group Chemical group [H]O* 0.000 description 1
- 238000002347 injection Methods 0.000 description 1
- 239000007924 injection Substances 0.000 description 1
- 230000010354 integration Effects 0.000 description 1
- XEEYBQQBJWHFJM-UHFFFAOYSA-N iron Substances [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 description 1
- 229910052742 iron Inorganic materials 0.000 description 1
- RBTARNINKXHZNM-UHFFFAOYSA-K iron trichloride Chemical compound Cl[Fe](Cl)Cl RBTARNINKXHZNM-UHFFFAOYSA-K 0.000 description 1
- 229910052751 metal Inorganic materials 0.000 description 1
- 239000002184 metal Substances 0.000 description 1
- 229910021645 metal ion Inorganic materials 0.000 description 1
- 230000007935 neutral effect Effects 0.000 description 1
- 238000005375 photometry Methods 0.000 description 1
- 238000002360 preparation method Methods 0.000 description 1
- 238000002203 pretreatment Methods 0.000 description 1
- 239000002994 raw material Substances 0.000 description 1
- 238000005070 sampling Methods 0.000 description 1
- 238000010187 selection method Methods 0.000 description 1
- 239000011780 sodium chloride Substances 0.000 description 1
- 229910001415 sodium ion Inorganic materials 0.000 description 1
- 238000006467 substitution reaction Methods 0.000 description 1
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- 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
- G01N30/02—Column chromatography
- G01N30/04—Preparation or injection of sample to be analysed
-
- 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
- G01N30/06—Preparation
-
- 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
- G01N30/06—Preparation
- G01N30/14—Preparation by elimination of some components
-
- 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
- G01N30/86—Signal analysis
- G01N30/8624—Detection of slopes or peaks; baseline correction
- G01N30/8631—Peaks
- G01N30/8634—Peak quality criteria
-
- 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
- G01N2030/042—Standards
- G01N2030/047—Standards external
-
- 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
- G01N30/06—Preparation
- G01N30/14—Preparation by elimination of some components
- G01N2030/146—Preparation by elimination of some components using membranes
Abstract
A method for detecting fluoride ions in hydrochloric acid comprises the following steps: preparing fluorine ion standard solution; making a standard curve by an external standard method; connecting a sample diluted in a 1ml standard injector with a strong acid type anion exchange resin chromatographic pretreatment column, then connecting with a 0.45um water system mixed fiber microporous filter membrane, injecting the sample diluted in the injector into an ion chromatogram, quantifying according to the peak area of the ion chromatogram, and obtaining the concentration c of the fluorine ions from a standard curve1(ii) a Pumping the diluted water by using a 1ml standard syringe, and then carrying out chromatographic pretreatment on the diluted water in the 1ml standard syringe and a strong acid type anion exchange resinConnecting with column, connecting with 0.45um water system mixed fiber microporous filter membrane, injecting diluted water in injector into ion chromatogram, quantifying according to ion chromatogram peak area, and obtaining fluorine ion concentration c from standard curve0(ii) a According to the formula, the fluorine ion content X is (c)1‑c0) 100 x 100/m gives the fluoride ion content in the hydrochloric acid.
Description
Technical Field
The invention relates to the technical field of chemical industry, in particular to a method for detecting fluoride ions in hydrochloric acid.
Background
Examples of the method for measuring fluorine ions include colorimetry, fluorometry, atomic absorption spectrophotometry, gas chromatography, ion selective electrode method, ion chromatography and the like. The concentration range of fluorine measured by a colorimetric method, a fluorescence photometry method and an atomic absorption spectrophotometry method is narrow, the alkalinity, impurities, the coloring or the turbidity of a water sample and the like of water can interfere the analysis result, direct measurement cannot be realized, pre-distillation is needed, and the analysis process is complex. Gas chromatography is suitable for the determination of hydrogen fluoride in gas phase, and is not suitable for the detection of fluorine ions in water. The most commonly used methods are ion selective electrode method and ion chromatography.
The ion selective electrode method is used for measuring the fluoride ion standard in water as follows: MT/T360-94, GB 7484-87, ISO 10359-1. The standards are all the determination of the fluorine ions in the water, the determination of the fluorine ions in the hydrochloric acid has no relevant standard, and the detection of the fluorine ions in the hydrochloric acid by the standards has the characteristics of poor repeatability, low accuracy and the like. GB/T35925 and 2018 are the determination of water-soluble chemical variety impurity fluorine ions, and adopt ion chromatography, wherein the determination relates to the fluorine ions in hydrochloric acid. The hydrochloric acid in the standard is high-grade pure hydrochloric acid and has high requirements on chromatographic columns, and industrial hydrochloric acid in actual production has the phenomenon that a fluorine ion peak is covered when the method is used for measurement, so that integration cannot be performed. Therefore, after a sample is diluted, impurity ions are removed through the chromatographic pretreatment column, the influence of other ions on the separation and determination of fluorine ions is avoided, the mobile phase is adjusted, and the influence of a water negative peak is reduced, so that the method is wider in application range, higher in accuracy and better in repeatability.
Disclosure of Invention
The invention aims to solve the technical problem of providing a method for detecting fluoride ions in hydrochloric acid. Compared with the traditional ion electrode selection method, the method is less affected by external factors, and has the advantages of more accurate result, high recovery rate, good repeatability and easy operation. Compared with the national standard, the method has better applicability to industrial hydrochloric acid.
In order to achieve the purpose, the invention adopts the technical scheme that:
a method for detecting fluoride ions in hydrochloric acid comprises the following steps:
taking 0.5-1.5 g of high-grade pure sodium fluoride, drying the high-grade pure sodium fluoride in an oven at 110 ℃ for 2 hours, and slowly cooling the high-grade pure sodium fluoride in a dryer to room temperature; 0.2210g of sodium fluoride treated by a dryer is weighed, water is added for dissolving, the solution is transferred into a polyethylene 100ml volumetric flask, and the volume is constant, so that 1000mg/L of fluoride ion standard solution is prepared;
diluting a fluorine ion standard solution, preparing 0-200 mg/L diluted fluorine ion standard solution, and making a standard curve by an external standard method, wherein the ion concentration is used as a horizontal coordinate, and the peak area is used as a vertical coordinate;
adding water into a 100ml polyvinyl chloride volumetric flask, peeling, adding 2-3 g of a sample, weighing and recording as m, and fixing the volume to 100 ml; extracting a diluted sample by using a 1ml standard injector, connecting the diluted sample in the 1ml standard injector with a strong acid type anion exchange resin chromatographic pretreatment column, then connecting with a 0.45um water system mixed fiber microporous filter membrane, injecting the diluted sample in the injector into an ion chromatograph, wherein the concentration of a mobile phase in the ion chromatograph is 1-100 mmol, the flow rate is 0.1-5 ml/min, and finally obtaining the concentration c of fluorine ions from a standard curve after quantifying according to the peak area of the ion chromatograph1；
Adding water into a 100ml polyvinyl chloride volumetric flask, peeling, adding 2-3 g of water, weighing and recording as m, and fixing the volume to 100 ml; pumping diluted water by using a 1ml standard injector, connecting the diluted water in the 1ml standard injector with a strong acid type anion exchange resin chromatographic pretreatment column, then connecting with a 0.45um water system mixed fiber microporous filter membrane, and injecting the diluted water in the injector into an ion chromatograph, wherein the concentration of a mobile phase in the ion chromatograph is 1-100 mmol, the flow rate is 0.1-5 ml/min, and the concentration is determined according to the separationAfter the peak area of the sub-chromatogram is quantified, the fluoride ion concentration c is obtained from the standard curve0(ii) a Finally, according to the formula, the content of fluorinion X is (c)1-c0) 100 x 100/m gives the fluoride ion content in the hydrochloric acid.
Further preferably, the dilution ratio of the sodium fluoride standard solution in the step (2) is 10-1000.
Further preferably, the pretreatment column is a strongly acidic anion exchange resin pretreatment column including Ag type and Ba type.
Further preferably, the mobile phase is a hydroxide, carbonate or bicarbonate solution of an alkaline earth metal.
Further preferably, the mobile phase in the ion chromatography is 10mmol/L alkaline solution with a flow rate of 1 ml/min.
The invention has the following beneficial effects:
1. the invention adopts ion chromatography to analyze the fluoride ions, avoids the influence of other metal ions complexed with the fluoride ions on the detection of the fluoride ions, and eliminates the influence of pH on the potential, so that the result is more accurate, the recovery rate is high, the repeatability is good, and the operation is easy.
2. The invention introduces the chromatographic pretreatment column, can effectively remove other anions which are difficult to separate in the chromatogram, enlarges the detection range of the method and ensures that the method is more suitable for the detection of industrial hydrochloric acid.
3. The invention improves the mobile phase, thereby not only effectively relieving the interference of hydrogen ions on the detection, but also avoiding the influence of the fluctuation of pH on the separation effect.
Drawings
FIG. 1 is an ion chromatogram of the present invention.
FIG. 2 is an ion chromatogram of comparative example 1.
Detailed Description
The present invention is further illustrated by the following examples, which are not intended to limit the invention to these embodiments. It will be appreciated by those skilled in the art that the present invention encompasses all alternatives, modifications and equivalents as may be included within the scope of the claims.
In the present invention, the raw materials and equipment used are commercially available or commonly used in the art, unless otherwise specified. The methods in the following examples are conventional in the art unless otherwise specified.
A method for detecting fluoride ions in hydrochloric acid comprises the following steps:
taking 0.5-1.5 g of high-grade pure sodium fluoride, drying the high-grade pure sodium fluoride in an oven at 110 ℃ for 2 hours, and slowly cooling the high-grade pure sodium fluoride in a dryer to room temperature; 0.2210g of sodium fluoride treated by a dryer is weighed, water is added for dissolving, the solution is transferred into a polyethylene 100ml volumetric flask, and the volume is constant, so that 1000mg/L of fluoride ion standard solution is prepared;
diluting a fluorine ion standard solution, preparing 0-200 mg/L diluted fluorine ion standard solution, and making a standard curve by an external standard method, wherein the ion concentration is used as a horizontal coordinate, and the peak area is used as a vertical coordinate;
adding water into a 100ml polyvinyl chloride volumetric flask, peeling, adding 2-3 g of a sample, weighing and recording as m, and fixing the volume to 100 ml; extracting a diluted sample by using a 1ml standard injector, connecting the diluted sample in the 1ml standard injector with a strong acid type anion exchange resin chromatographic pretreatment column, then connecting with a 0.45um water system mixed fiber microporous filter membrane, injecting the diluted sample in the injector into an ion chromatograph, wherein the concentration of a mobile phase in the ion chromatograph is 1-100 mmol, the flow rate is 0.1-5 ml/min, and finally obtaining the concentration c of fluorine ions from a standard curve after quantifying according to the peak area of the ion chromatograph1；
Adding water into a 100ml polyvinyl chloride volumetric flask, peeling, adding 2-3 g of water, weighing and recording as m, and fixing the volume to 100 ml; pumping diluted water by using a 1ml standard injector, connecting the diluted water in the 1ml standard injector with a strong acid type anion exchange resin chromatographic pretreatment column, then connecting with a 0.45um water system mixed fiber microporous filter membrane, and then injecting the diluted water in the injector into an ion chromatograph, wherein the concentration of a mobile phase in the ion chromatograph is 1-100 mmol, the flow rate is 0.1-5 ml/min, quantifying according to the peak area of the ion chromatograph, and obtaining the concentration c of fluorine ions from a standard curve0(ii) a Finally, according to the formula, fluorinatingA sub-content of X ═ c1-c0) 100 x 100/m gives the fluoride ion content in the hydrochloric acid.
Further, the dilution multiple of the sodium fluoride standard solution in the step (2) is 10-1000 times.
Preferably, the preparation concentration of the fluoride ion standard solution is 0-50 mg/L, and a standard curve is prepared by an external standard method.
Furthermore, the sample is diluted before sample injection, and the dilution multiple is generally 20-100 times.
Further, the pretreatment column is a strong acid anion exchange resin pretreatment column, and comprises an Ag type and a Ba type.
Further, the mobile phase is hydroxide, carbonate or bicarbonate solution of alkaline earth metal.
Further, the mobile phase in the ion chromatography is 10mmol/L alkaline solution, and the flow rate is 1 ml/min.
The following are methods of the present invention for specifically analyzing fluoride ions, and methods of comparing the methods of the present invention and the prior art.
Example 1
Taking about 1g of superior pure sodium fluoride, placing the superior pure sodium fluoride in an oven to be dried for 2 hours at the temperature of 110 ℃, and then slowly cooling the superior pure sodium fluoride in a dryer to the room temperature; 0.2210g of sodium fluoride treated by a dryer is weighed, water is added for dissolving, the solution is transferred into a polyethylene 100ml volumetric flask, and the volume is constant, so that 1000mg/L of fluoride ion standard solution is prepared;
and (2) taking a fluorine ion standard solution for dilution, specifically, preparing 0mg/L, 2.5mg/L, 5mg/L, 10mg/L, 20mg/L and 50mg/L diluted fluorine ion standard solutions with the dilution times of the sodium fluoride standard solution being 10-1000 times, and drawing a standard curve by adopting an external standard method and taking the ion concentration as a horizontal coordinate and the peak area as a vertical coordinate.
And (3) adding water into a 100ml polyvinyl chloride volumetric flask, peeling, adding 2-3 g of a sample, weighing and recording as m, and fixing the volume to 100 ml. The diluted sample is extracted by a 1ml standard syringe, then the diluted sample in the 1ml standard syringe is connected with a strong acid type anion exchange resin chromatographic pretreatment column, and then is connected with a 0.45um water system mixed fiber microporous filter membrane, and then the diluted sample in the syringe is injected into an ion chromatograph, so that the heavy mobile phase of the ion chromatograph is a 10mmol/L sodium bicarbonate solution with the flow rate of 1ml/min as shown in figure 1.
Comparative example 1
Adding a small amount of water into a 100ml polyvinyl chloride volumetric flask, peeling, adding 2-3 g of a sample, weighing and recording as m, and fixing the volume to 100 ml. Extracting the diluted sample by using a 1ml standard injector, connecting the diluted sample in the 1ml standard injector with a strong acid type anion exchange resin chromatographic pretreatment column, and injecting the diluted sample in the injector into an ion chromatogram, wherein the chromatogram is shown in figure 2; the ion chromatography heavy mobile phase is 10mmol/L sodium bicarbonate solution, and the flow rate is 1 ml/min.
Specifically, as shown in fig. 2, the retention time of the fluorine ion in the ion chromatogram is about 4min, the retention time of the chloride ion in the ion chromatogram is about 5min, the inverse peak of the water is about 3min, and the inverse peak is relatively close to the inverse peak, and the content of the chloride ion in the industrial hydrochloric acid is much greater than that of the fluorine ion, so that the coverage phenomenon of the chloride ion peak on the fluorine ion peak is often occurred in the actual detection, which results in that the peak area of the fluorine ion cannot be displayed, and the negative peak of the water is relatively close to each other, which results in that the integral of the fluorine ion is greatly influenced by the negative peak of the water if the separation cannot be better, so that the analysis result has relatively large deviation. And the injector is connected with the strong acid type anion exchange resin silver ion chromatographic pretreatment column and then connected with the 0.45um water system mixed fiber microporous filter membrane, and after the sample in the injector is injected into the ion chromatograph, the chlorine ion peak is greatly reduced, the negative peak of water is also reduced, the fluorine ion peak is sharp, better separation and identification can be obtained, and the analysis result is more accurate.
Example 2
Taking about 1g of superior pure sodium fluoride, placing the superior pure sodium fluoride in an oven to be dried for 2 hours at the temperature of 110 ℃, and then slowly cooling the superior pure sodium fluoride in a dryer to the room temperature; 0.2210g of sodium fluoride treated by a dryer is weighed, water is added for dissolving, the solution is transferred into a polyethylene 100ml volumetric flask, and the volume is constant, so that 1000mg/L of fluoride ion standard solution is prepared;
and (2) taking a fluorine ion standard solution for dilution, specifically, preparing 0mg/L, 2.5mg/L, 5mg/L, 10mg/L, 20mg/L and 50mg/L diluted fluorine ion standard solutions with the dilution times of the sodium fluoride standard solution being 10-1000 times, and drawing a standard curve by adopting an external standard method and taking the ion concentration as a horizontal coordinate and the peak area as a vertical coordinate.
And (3) adding water into a 100ml polyvinyl chloride volumetric flask, peeling, adding 2-3 g of a sample, weighing and recording as m, and fixing the volume to 100 ml. Extracting the diluted sample by using a 1ml standard injector, connecting the diluted sample in the 1ml standard injector with a strong acid type anion exchange resin chromatographic pretreatment column, then connecting with a 0.45um water system mixed fiber microporous filter membrane, injecting the diluted sample in the injector into an ion chromatogram, so that as shown in figure 1, the heavy mobile phase of the ion chromatogram is a 10mmol/L sodium bicarbonate solution, the flow rate is 1ml/min, then quantifying according to the peak area in the ion chromatogram, and finding out the fluorine ion concentration c from a standard curve1。
Adding water into a 100ml polyvinyl chloride volumetric flask, peeling, adding 2-3 g of water, weighing and recording as m, and fixing the volume to 100 ml; pumping diluted water by using a 1ml standard injector, connecting the diluted water in the 1ml standard injector with a strong acid type anion exchange resin chromatographic pretreatment column, then connecting with a 0.45um water system mixed fiber microporous filter membrane, and then injecting the diluted water in the injector into an ion chromatograph, wherein the concentration of a mobile phase in the ion chromatograph is 1-100 mmol, the flow rate is 0.1-5 ml/min, quantifying according to the peak area of the ion chromatograph, and obtaining the concentration c of fluorine ions from a standard curve0(ii) a Finally, according to the formula, the content of fluorinion X is (c)1-c0) 100 x 100/m gives the fluoride ion content in the hydrochloric acid.
Comparative example 2
Taking about 1g of superior pure sodium fluoride, placing the superior pure sodium fluoride in an oven to be dried for 2 hours at the temperature of 110 ℃, and then slowly cooling the superior pure sodium fluoride in a dryer to the room temperature; 0.2210g of sodium fluoride treated by a dryer is weighed, water is added for dissolving, the solution is transferred into a polyethylene 100ml volumetric flask, and the volume is constant, so that 1000mg/L of fluoride ion standard solution is prepared;
and (2) diluting the fluorine ion standard solution, specifically, diluting the sodium fluoride standard solution by 10-1000 times, preparing 0mg/L, 2.5mg/L, 5mg/L, 10mg/L, 20mg/L and 50mg/L of the diluted fluorine ion standard solution respectively, taking 20ml of the standard solution, adding 20ml of a TISAB buffer solution, and drawing a standard curve by adopting an ion selective electrode method and taking logarithm of ion concentration as a horizontal coordinate and potential as a vertical coordinate.
And (3) adding water into a 100ml polyvinyl chloride volumetric flask, peeling, adding 2-3 g of a sample prepared in advance, weighing and recording the sample as m, adding two drops of phenolphthalein, titrating the solution to be reddish from colorless by using 1mol/L of sodium hydroxide, and fixing the volume to 100 ml. 20ml of the diluted sample was added to 20ml of the TISAB buffer solution, and the potential was measured by the ion selective electrode method. According to the potential value, the fluorine ion concentration c is calculated from a standard curve1The fluorine ion content X ═ c1*100/m。
Precision and accuracy comparisons were made for samples of different concentrations and the data obtained for example 2 versus comparative example 2 precision are given in the following table.
Example 3
The same steps as the detection steps in example 2, the same samples were added with sodium fluoride solutions equivalent to 10mg, 50mg, 200mg and 500mg respectively, the sample volume was adjusted to 1L, and the recovery rate of the added standard of the fluoride ions was determined.
Comparative example 3
The sample of example 3 was tested according to the method of comparative example 2 to determine the recovery of the fluoride ion spiked. The comparative data for normalized recovery of example 3 versus comparative example 3 are shown in table two below.
Watch two
In the actual production process, the rectifying tower, the pipeline and the valve are all made of ironware, and part of iron oxide or chloride inevitably enters water, so the industrial hydrochloric acid at least contains iron ions, calcium ions, sodium ions and other related metal cations. In addition, before the ion selective electrode method is used for measurement, hydrochloric acid is required to be titrated to be neutral, and phenolphthalein is used for calibration, but the actual discoloration range of phenolphthalein is about 8-9, and the influence of hydroxyl on the actual measurement result is also considered in the measurement process.
100g of a fluoride ion 31% hydrochloric acid solution with a standard concentration of 10ppm is prepared, 11.6mg of ferric trichloride, 12.6mg of calcium chloride, 25.4mg of sodium chloride and a blank are added respectively. The anti-interference performance of the two methods is compared by adopting ion chromatography and ion selective electron method for determination.
Example 4
The fluorine ion content was measured in the same manner as in the detection procedure of example 2.
Comparative example 4
Based on the pH meter, the pH value is measured to be about 5.5 after sampling. And (3) measuring the content of the fluorine ions by adopting an ion selective electrode method. The blank samples were separately titrated to pH 8.5 and 4.5 and the fluoride ion content was determined. The comparative anti-interference measurement results of the fluoride ion detection of example 4 and comparative example 4 are shown in table three.
Watch III
From the above results, it is known that the measurement of fluoride ions in industrial hydrochloric acid cannot be completed according to the method of GB/T35925-2018 because of the effect of other impurity ions in industrial hydrochloric acid on the separation of fluoride ions, and the method can be further improved by using the pretreatment method mentioned in this patent. Compared with the existing ion selective electrode method, the method is superior to the ion selective electrode method in the aspects of interference resistance, precision and standard addition recovery rate.
The above-mentioned embodiments are only used for illustrating the technical solutions of the present invention, and not for limiting the same; although the present invention has been described in detail with reference to the foregoing embodiments, it will be understood by those skilled in the art that various changes in form and details may be made therein without departing from the spirit and scope of the invention; and such modifications or substitutions do not depart from the spirit and scope of the corresponding technical solutions of the embodiments of the present invention.
Claims (5)
1. A method for detecting fluoride ions in hydrochloric acid is characterized in that: the method comprises the following steps:
taking 0.5-1.5 g of high-grade pure sodium fluoride, drying the high-grade pure sodium fluoride in an oven at 110 ℃ for 2 hours, and slowly cooling the high-grade pure sodium fluoride in a dryer to room temperature; 0.2210g of sodium fluoride treated by a dryer is weighed, water is added for dissolving, the solution is transferred into a polyethylene 100ml volumetric flask, and the volume is constant, so that 1000mg/L of fluoride ion standard solution is prepared;
diluting a fluorine ion standard solution, preparing 0-200 mg/L diluted fluorine ion standard solution, and making a standard curve by an external standard method, wherein the ion concentration is used as a horizontal coordinate, and the peak area is used as a vertical coordinate;
adding water into a 100ml polyvinyl chloride volumetric flask, peeling, adding 2-3 g of a sample, weighing and recording as m, and fixing the volume to 100 ml; extracting a diluted sample by using a 1ml standard injector, connecting the diluted sample in the 1ml standard injector with a strong acid type anion exchange resin chromatographic pretreatment column, then connecting with a 0.45um water system mixed fiber microporous filter membrane, injecting the diluted sample in the injector into an ion chromatograph, wherein the concentration of a mobile phase in the ion chromatograph is 1-100 mmol, the flow rate is 0.1-5 ml/min, and finally obtaining the concentration c of fluorine ions from a standard curve after quantifying according to the peak area of the ion chromatograph1；
Adding water into a 100ml polyvinyl chloride volumetric flask, peeling, adding 2-3 g of water, weighing and recording as m, and fixing the volume to 100 ml; pumping the diluted water by using a 1ml standard injector, then connecting the diluted water in the 1ml standard injector with a strong acid type anion exchange resin chromatographic pretreatment column, then connecting with a 0.45um aqueous mixed fiber microporous filter membrane, and then injecting the diluted water in the injector into an ion chromatograph, wherein the flow in the ion chromatographThe phase concentration is 1-100 mmol, the flow rate is 0.1-5 ml/min, and the fluorine ion concentration c is obtained from a standard curve after the peak area of ion chromatography is quantified0(ii) a Finally, according to the formula, the content of fluorinion X is (c)1-c0) 100 x 100/m gives the fluoride ion content in the hydrochloric acid.
2. The method for detecting fluoride ions in hydrochloric acid as claimed in claim 1, wherein: and (3) diluting the sodium fluoride standard solution in the step (2) by 10-1000 times.
3. The method for detecting fluoride ions in hydrochloric acid as claimed in claim 1, wherein: the pretreatment column is a strong acid anion exchange resin pretreatment column and comprises an Ag type and a Ba type.
4. The method for detecting fluoride ions in hydrochloric acid as claimed in claim 1, wherein: the mobile phase is hydroxide, carbonate and bicarbonate solution of alkaline earth metal.
5. The method for detecting fluoride ions in hydrochloric acid as claimed in claim 1, wherein: the mobile phase in the ion chromatography is 10mmol/L alkaline solution, and the flow rate is 1 ml/min.
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