CN110133067A - The measuring method of fluorine in a kind of calcirm-fluoride - Google Patents
The measuring method of fluorine in a kind of calcirm-fluoride Download PDFInfo
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Abstract
The invention discloses a kind of measuring methods of fluorine in calcirm-fluoride, the specific steps are as follows: in Muffle furnace, calcirm-fluoride is decomposed in silver crucible under the action of potassium hydroxide；Slag in crucible is leached with hot water, diluted hydrochloric acid dissolution to it is limpid, be filtered, washed and constant volume；Dividing takes sample solution at 25 DEG C using saturated calomel electrode as reference electrode, the fluorine in solution is measured with fluoride ion selective electrode, so as to find out the content of fluorine in calcirm-fluoride sample.This method advantage is: analysis is simple and efficient, as a result accurately and reliably.
Description
Technical field
The present invention relates to a kind of analysis test method, in particular to the measuring method of fluorine in a kind of calcirm-fluoride.
Background technique
Fluorine is one of element widely distributed in nature, mainly with CaF2Form exist, and be enriched in firefly extensively
In stone, rock phosphate in powder.CaF at present2It is mainly used for metallurgy, chemical industry and the big industry of building materials three, but with fluorination work comprehensive utilization technique
Develop in depth and breadth, CaF2Application in other industry is also constantly being expanded, and strategic position and significance also become more
Exacerbation is wanted.In metallurgical industry, CaF2With the fusing point that can reduce infusibility substance, promotes clinker flowing, keep slag and metal fine
The features such as separating, desulfurization, dephosphorization in smelting process, enhancing the forging property and tensile strength of metal.Therefore, it is as fluxing agent
It is widely used in smelting iron and steel and ferroalloy production, changes iron process and non-ferrous metal metallurgy.In building materials industry, CaF2It is wide
General to be applied in the productions of products such as glass, ceramics, cement, dosage accounts for the 2nd in China, wherein in glass industry,
CaF2It is added as fluxing agent, opacifier, it can promote the fusing of glass raw material；In manufacture of cement, CaF2As mineralizer plus
Enter.CaF2The sintering temperature of furnace charge can be reduced, clinker liquid phase viscosity when reducing fuel consumption, while can also enhance sintering promotes
The formation of tricalcium silicate；In ceramic industry, CaF2It is mainly used as enamel, it can be played in enamel production process helps color and help
Molten effect；CaF2It is also applied in porcelain enamel industry and cast stone production, but either in metallurgy industry, building material industry, can all exist
High-temperature lower part is divided calcirm-fluoride to decompose and form gaseous fluorides and is escaped, and not only causes the pollution of environment, also will form corrosivity
Stronger hydrofluoric acid and corrode equipment, reduce the service life of production equipment.Therefore, it realizes to various source different content fluorine
Precise determination, strict control CaF2Additional amount then becomes most important.
However up to the present, the measurement of fluorine is to survey after calcium arbitration law measures calcium content to convert by calcirm-fluoride in calcirm-fluoride
Gained, method is cumbersome, and time-consuming, and this method is on the basis of carrying out pretreated to sample with flux potassium hydroxide, knot
Fluoride ion selective electrode method is closed, has accomplished the simple and efficient Accurate Determining of fluorine content in calcirm-fluoride.
Summary of the invention
The purpose of the present invention is to provide a kind of measuring methods of fluorine in calcirm-fluoride, it is characterised in that uses flux potassium hydroxide
On the basis of pretreated to sample progress, in conjunction with fluoride ion selective electrode method, accomplish that the simplicity of fluorine content in calcirm-fluoride is fast
Prompt Accurate Determining.
Realize that the work step of the object of the invention measuring method is as follows:
(1) sample ore to be determined is crushed, ground, granularity≤200 mesh.
(2) above-mentioned sample ore is placed in Muffle furnace, under the action of flux potassium hydroxide, is decomposed in silver crucible.
(3) slag in crucible is leached with hot water, diluted hydrochloric acid dissolution to it is limpid, be filtered, washed and constant volume.
(4) it is divided to and takes sample solution that five drop citric acid-sodium citrate buffers and two drop bromines are added in 50ml volumetric flask
The green indicator solution of cresols, is neutralized to that solution is blue with the sodium hydroxide solution of 200 g/L, then is adjusted with the nitric acid solution of (1+5)
Solution is in yellow just.The citric acid-sodium citrate buffer 20ml that pH value is 5 is added and is diluted to scale with deionized water,
It is poured into dry 50ml beaker, is inserted into fluoride ion selective electrode and saturated calomel electrode, stirred in the constant speed of magnetic stirring apparatus
Under, potential value when balance is measured, E1 is recorded as.Addition 1mg/ml fluorine standard solution 0.5ml measures its potential value again and is recorded as
E2。
Fluorine content (w) is calculated as follows
In formula: m1- addition fluorine standard solution is equivalent to fluorine quality, g；
59.16-with the theoretical value of this special slope of the energy that measures of experiment (59.16 at 25 DEG C)；
M-absorption sample solution is equivalent to the quality of sample, g；
The potential difference (i.e. E2-E1) that Δ E-front and back measures twice, mV；
Arclog-antilogarithm.
All calcirm-fluoride arbitration law first measures calcirm-fluoride to fluorine measuring method in a conventional manner always in calcirm-fluoride so far
Amount, finally converse fluorine content, but existing chemical method surveys calcirm-fluoride and operates shadow relatively complicated, vulnerable to interfering ion
Ring, result that time-consuming inaccuracy, this method using flux potassium hydroxide to sample progress it is pretreated on the basis of, in conjunction with fluorine ion
Electrodes selective method has accomplished the measurement of fluorine content in calcirm-fluoride, the advantage is that time-consuming short, process is simple and direct, as a result accurately may be used
It leans on.
Specific embodiment
Example 1
It weighs 0.3999g 1# calcirm-fluoride (granularity≤200 mesh) and is accurate to 0.0001, (doing reagent blank with sample), which is placed in, to be filled
It in the silver crucible of 6.0052 g potassium hydroxide, covers crucible and stays a gap, be placed in high temperature and decomposed 8 minutes at 680 DEG C, take out
Crucible and rotate it is slightly cold, be placed in 500ml beaker, be added 20~50ml hot water, cap upper surface ware, falls off to fusant immediately
Afterwards, crucible and lid (being cleaned with the glass bar with rubber tip) are cleaned with hot water and a small amount of 1:5 hydrochloric acid solution.It drips under constant stirring
Add hydrochloric acid solution until solution is limpid.Beaker is removed, rinses surface plate and wall of cup with deionized water, it is cooling, it is dry with Medium speed filter paper
It filters and is washed with deionized acid non-soluble substance 5 times or more, collect filtrate and cleaning solution is settled to 500mL.
Take 10ml sample solution that five drop citric acid-sodium citrate buffers and two drop bromine first are added in 50ml volumetric flask
The green indicator solution of phenol, is neutralized to that solution is blue with the sodium hydroxide solution of 200 g/L, then is adjusted with the nitric acid solution of (1+5) molten
Liquid is in yellow just.The citric acid-sodium citrate buffer 20ml that pH value is 5 is added and is diluted to scale with deionized water, inclines
Enter in dry 50ml beaker, is inserted into fluoride ion selective electrode and saturated calomel electrode, under the constant speed stirring of magnetic stirring apparatus,
Potential value when balance is measured, is recorded as -158.Be added 1mg/ml fluorine standard solution 0.5ml measure again its potential value be recorded as-
150。
Fluorine content (w) is calculated as follows
=17.11%
Example 2
It weighs 0.2009g 2# calcirm-fluoride (granularity≤200 mesh) and is accurate to 0.0001, (doing reagent blank with sample), which is placed in, to be filled
It in the silver crucible of 4.0031 g potassium hydroxide, covers crucible and stays a gap, be placed in high temperature and decomposed 10 minutes at 700 DEG C, taken
Out crucible and rotate it is slightly cold, be placed in 500ml beaker, be added 20~50ml hot water, cap upper surface ware, falls off to fusant immediately
Afterwards, crucible and lid (being cleaned with the glass bar with rubber tip) are cleaned with hot water and a small amount of 1:3 hydrochloric acid solution.It drips under constant stirring
Add hydrochloric acid solution until solution is limpid.Beaker is removed, rinses surface plate and wall of cup with deionized water, it is cooling, it is dry with Medium speed filter paper
It filters and is washed with deionized acid non-soluble substance 5 times or more, collect filtrate and cleaning solution is settled to 500mL.
Take 5ml sample solution that five drop citric acid-sodium citrate buffers and two drop bromine first are added in 50ml volumetric flask
The green indicator solution of phenol, is neutralized to that solution is blue with the sodium hydroxide solution of 200 g/L, then is adjusted with the nitric acid solution of (1+5) molten
Liquid is in yellow just.The citric acid-sodium citrate buffer 20ml that pH value is 5 is added and is diluted to scale with deionized water, inclines
Enter in dry 50ml beaker, is inserted into fluoride ion selective electrode and saturated calomel electrode, under the constant speed stirring of magnetic stirring apparatus,
Potential value when balance is measured, is recorded as -162.Be added 1mg/ml fluorine standard solution 0.5ml measure again its potential value be recorded as-
148。
Fluorine content (w) is calculated as follows
=34.41%
Example 3
It weighs 3# calcirm-fluoride 0.1005g (granularity≤200 mesh) and is accurate to 0.0001, (doing reagent blank with sample), which is placed in, to be filled
It in the silver crucible of 2.0052 g potassium hydroxide, covers crucible and stays a gap, be placed in high temperature and decomposed 15 minutes at 720 DEG C, taken
Out crucible and rotate it is slightly cold, be placed in 500ml beaker, be added 20~50ml hot water, cap upper surface ware, falls off to fusant immediately
Afterwards, crucible and lid (being cleaned with the glass bar with rubber tip) are cleaned with hot water and a small amount of 1:1 hydrochloric acid solution.Under constant stirring after
It is continuous that 1:1 hydrochloric acid solution is added dropwise until solution is limpid.Beaker is removed, rinses surface plate and wall of cup with deionized water, it is cooling, use middling speed
Filter Paper Dry is filtered and is washed with deionized acid non-soluble substance 5 times or more, collects filtrate and cleaning solution is settled to 500mL.
Take 5ml sample solution that five drop citric acid-sodium citrate buffers and two drop bromine first are added in 50ml volumetric flask
The green indicator solution of phenol, is neutralized to that solution is blue with the sodium hydroxide solution of 200 g/L, then is adjusted with the nitric acid solution of (1+5) molten
Liquid is in yellow just.The citric acid-sodium citrate buffer 20ml that pH value is 5 is added and is diluted to scale with deionized water, inclines
Enter in dry 50ml beaker, is inserted into fluoride ion selective electrode and saturated calomel electrode, under the constant speed stirring of magnetic stirring apparatus,
Potential value when balance is measured, is recorded as -163.Be added 1mg/ml fluorine standard solution 0.5ml measure again its potential value be recorded as-
143。
Fluorine content (w) is calculated as follows
=42.23%
Fluorine content analyzes result in 1 calcirm-fluoride of table
| Embodiment | Different samples | Potential changing value | Fluorine content (%) | Theoretical value (%) | Relative error |
| 1 | Calcirm-fluoride 1# | 8 | 17.11 | 17.13 | 0.12% |
| 2 | Calcirm-fluoride 2# | 14 | 34.41 | 34.68 | 0.78% |
| 3 | Calcirm-fluoride 3# | 20 | 42.19 | 42.60 | 0.96% |
Illustrate: the theoretical value of calcirm-fluoride sample is converted after measuring fluorination calcium value by calcirm-fluoride arbitration law in table 1.
It can be seen from Table 1 that this analysis method is preferable for the measurement reproducibility of fluorine in different calcirm-fluoride, relative error
Between 0.12%~0.96%.
Claims (5)
1. the measuring method of fluorine in a kind of calcirm-fluoride, it is characterised in that key step is as follows:
(1) sample ore to be determined is crushed, ground, granularity≤200 mesh；
(2) above-mentioned sample ore is placed in Muffle furnace, under the action of flux potassium hydroxide, is decomposed in silver crucible；
(3) slag in crucible is leached with hot water, diluted hydrochloric acid dissolution to it is limpid, be filtered, washed and constant volume；
(4) it is divided to and takes sample solution that five drop citric acid-sodium citrate buffers and two drop bromine cresols are added in 50ml volumetric flask
Green indicator solution, is neutralized to that solution is blue with the sodium hydroxide solution of 200 g/L, then adjusts solution with the nitric acid solution of (1+5)
Just it is in yellow, the citric acid-sodium citrate buffer 20ml that pH value is 5 is added and is diluted to scale with deionized water, is poured into
In dry 50ml beaker, it is inserted into fluoride ion selective electrode and saturated calomel electrode, under the constant speed stirring of magnetic stirring apparatus, is surveyed
Potential value when must balance, is recorded as E1；
Addition 1mg/ml fluorine standard solution 0.5ml measures its potential value again and is recorded as E2；
Fluorine content (w) is calculated as follows:
In formula: m1- addition fluorine standard solution is equivalent to fluorine quality, g；
59.16-with the theoretical value of this special slope of the energy that measures of experiment (59.16 at 25 DEG C)；
M-absorption sample solution is equivalent to the quality of sample, g；
The potential difference (i.e. E2-E1) that Δ E-front and back measures twice, mV；
Arclog-antilogarithm.
2. the measuring method of fluorine in a kind of calcirm-fluoride according to claim 1, it is characterised in that: accurately weigh calcirm-fluoride sample
0.1~0.8g of product, flux 2~10g of potassium hydroxide, is accurate to 0.0001g.
3. the measuring method of fluorine in a kind of calcirm-fluoride according to claim 1, it is characterised in that: using potassium hydroxide to examination
Sample is decomposed, and decomposition temperature is 650~750 DEG C, the resolving time 8~15 minutes.
4. the measuring method of fluorine in a kind of calcirm-fluoride according to claim 1, it is characterised in that: slag is soaked with hot water
Out, with 1:5~1:1 diluted hydrochloric acid dissolution to limpid.
5. the measuring method of fluorine in a kind of calcirm-fluoride according to claim 1, it is characterised in that: with flux potassium hydroxide
On the basis of pretreated to sample progress, in conjunction with fluoride ion selective electrode method, accomplish that the simplicity of fluorine content in calcirm-fluoride is quasi-
Really measurement.
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Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN113776904A (en) * | 2021-08-27 | 2021-12-10 | 柳州钢铁股份有限公司 | Method for measuring calcium fluoride in fluorite |
Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| EP0125368A1 (en) * | 1983-12-05 | 1984-11-21 | Pharmacia ENI Diagnostics Inc. | A method of immunoassay detection by reaction-rate potentiometry using fluoride ion-selective electrode |
| CN108344789A (en) * | 2017-01-24 | 2018-07-31 | 华北理工大学 | A kind of method of fluorine content in measurement continuous casting covering slag |
| CN109596683A (en) * | 2018-11-05 | 2019-04-09 | 包头钢铁（集团）有限责任公司 | A method of fluorine content in measurement gypsum, silica |
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2019
- 2019-06-15 CN CN201910518382.XA patent/CN110133067A/en active Pending
Patent Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| EP0125368A1 (en) * | 1983-12-05 | 1984-11-21 | Pharmacia ENI Diagnostics Inc. | A method of immunoassay detection by reaction-rate potentiometry using fluoride ion-selective electrode |
| CN108344789A (en) * | 2017-01-24 | 2018-07-31 | 华北理工大学 | A kind of method of fluorine content in measurement continuous casting covering slag |
| CN109596683A (en) * | 2018-11-05 | 2019-04-09 | 包头钢铁（集团）有限责任公司 | A method of fluorine content in measurement gypsum, silica |
Non-Patent Citations (4)
| Title |
|---|
| 商检群: "《氟石检验》", 31 October 1978, 中国财政经济出版社 * |
| 李强 等: "氟离子选择电极法测定磷酸中的氟", 《磷肥与复肥》 * |
| 马列: "《化学检验（水泥）》", 30 November 2006, 中国建材工业出版社 * |
| 高德池: "氟离子选择电极法测定磷酸中氟含量", 《磷肥与复肥》 * |
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN113776904A (en) * | 2021-08-27 | 2021-12-10 | 柳州钢铁股份有限公司 | Method for measuring calcium fluoride in fluorite |
| CN113776904B (en) * | 2021-08-27 | 2024-03-01 | 柳州钢铁股份有限公司 | Method for determining calcium fluoride in fluorite |
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Application publication date: 20190816 |