CN113138254A - Device and method for measuring fluorine content in slag melting agent for metallurgy - Google Patents
Device and method for measuring fluorine content in slag melting agent for metallurgy Download PDFInfo
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- CN113138254A CN113138254A CN202110458727.4A CN202110458727A CN113138254A CN 113138254 A CN113138254 A CN 113138254A CN 202110458727 A CN202110458727 A CN 202110458727A CN 113138254 A CN113138254 A CN 113138254A
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- 229910052731 fluorine Inorganic materials 0.000 title claims abstract description 81
- 239000011737 fluorine Substances 0.000 title claims abstract description 81
- YCKRFDGAMUMZLT-UHFFFAOYSA-N Fluorine atom Chemical compound [F] YCKRFDGAMUMZLT-UHFFFAOYSA-N 0.000 title claims abstract description 80
- 239000003795 chemical substances by application Substances 0.000 title claims abstract description 34
- 239000002893 slag Substances 0.000 title claims abstract description 33
- 238000002844 melting Methods 0.000 title claims abstract description 27
- 230000008018 melting Effects 0.000 title claims abstract description 27
- 238000005272 metallurgy Methods 0.000 title claims abstract description 20
- 238000000034 method Methods 0.000 title claims description 29
- 238000004821 distillation Methods 0.000 claims abstract description 74
- 239000010453 quartz Substances 0.000 claims abstract description 49
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N silicon dioxide Inorganic materials O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 claims abstract description 49
- NBIIXXVUZAFLBC-UHFFFAOYSA-N Phosphoric acid Chemical compound OP(O)(O)=O NBIIXXVUZAFLBC-UHFFFAOYSA-N 0.000 claims abstract description 40
- 238000006243 chemical reaction Methods 0.000 claims abstract description 36
- 229910000147 aluminium phosphate Inorganic materials 0.000 claims abstract description 20
- 238000009833 condensation Methods 0.000 claims abstract description 20
- 230000005494 condensation Effects 0.000 claims abstract description 20
- 239000004816 latex Substances 0.000 claims abstract description 20
- 229920000126 latex Polymers 0.000 claims abstract description 20
- 238000010438 heat treatment Methods 0.000 claims abstract description 19
- 230000005540 biological transmission Effects 0.000 claims abstract description 7
- 238000005259 measurement Methods 0.000 claims abstract description 4
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 41
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 claims description 33
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 claims description 28
- PEDCQBHIVMGVHV-UHFFFAOYSA-N Glycerine Chemical compound OCC(O)CO PEDCQBHIVMGVHV-UHFFFAOYSA-N 0.000 claims description 24
- 229920001971 elastomer Polymers 0.000 claims description 23
- 239000007788 liquid Substances 0.000 claims description 21
- 238000004448 titration Methods 0.000 claims description 17
- 229910052742 iron Inorganic materials 0.000 claims description 14
- 239000000243 solution Substances 0.000 claims description 13
- 239000000498 cooling water Substances 0.000 claims description 8
- 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 claims description 6
- 239000012086 standard solution Substances 0.000 claims description 6
- 238000005303 weighing Methods 0.000 claims description 6
- 241001411320 Eriogonum inflatum Species 0.000 claims description 4
- 229910021536 Zeolite Inorganic materials 0.000 claims description 3
- 239000012159 carrier gas Substances 0.000 claims description 3
- 239000008367 deionised water Substances 0.000 claims description 3
- 229910021641 deionized water Inorganic materials 0.000 claims description 3
- HNPSIPDUKPIQMN-UHFFFAOYSA-N dioxosilane;oxo(oxoalumanyloxy)alumane Chemical compound O=[Si]=O.O=[Al]O[Al]=O HNPSIPDUKPIQMN-UHFFFAOYSA-N 0.000 claims description 3
- 238000002474 experimental method Methods 0.000 claims description 3
- 239000010457 zeolite Substances 0.000 claims description 3
- 239000012153 distilled water Substances 0.000 claims description 2
- 239000007789 gas Substances 0.000 claims description 2
- 238000002360 preparation method Methods 0.000 claims description 2
- 239000000839 emulsion Substances 0.000 claims 1
- 239000002904 solvent Substances 0.000 claims 1
- 239000002253 acid Substances 0.000 abstract description 8
- 239000002699 waste material Substances 0.000 abstract description 5
- 230000009286 beneficial effect Effects 0.000 abstract description 4
- VLTRZXGMWDSKGL-UHFFFAOYSA-N perchloric acid Chemical compound OCl(=O)(=O)=O VLTRZXGMWDSKGL-UHFFFAOYSA-N 0.000 description 9
- 238000000354 decomposition reaction Methods 0.000 description 6
- 238000011084 recovery Methods 0.000 description 5
- PUZPDOWCWNUUKD-UHFFFAOYSA-M sodium fluoride Chemical compound [F-].[Na+] PUZPDOWCWNUUKD-UHFFFAOYSA-M 0.000 description 4
- 238000000926 separation method Methods 0.000 description 3
- ZAMOUSCENKQFHK-UHFFFAOYSA-N Chlorine atom Chemical compound [Cl] ZAMOUSCENKQFHK-UHFFFAOYSA-N 0.000 description 2
- KRHYYFGTRYWZRS-UHFFFAOYSA-M Fluoride anion Chemical compound [F-] KRHYYFGTRYWZRS-UHFFFAOYSA-M 0.000 description 2
- 238000002479 acid--base titration Methods 0.000 description 2
- 238000004458 analytical method Methods 0.000 description 2
- 239000000460 chlorine Substances 0.000 description 2
- 229910052801 chlorine Inorganic materials 0.000 description 2
- 230000001684 chronic effect Effects 0.000 description 2
- 238000001514 detection method Methods 0.000 description 2
- 238000010586 diagram Methods 0.000 description 2
- 238000003912 environmental pollution Methods 0.000 description 2
- 239000000376 reactant Substances 0.000 description 2
- 239000011775 sodium fluoride Substances 0.000 description 2
- 235000013024 sodium fluoride Nutrition 0.000 description 2
- 230000000007 visual effect Effects 0.000 description 2
- OYPRJOBELJOOCE-UHFFFAOYSA-N Calcium Chemical compound [Ca] OYPRJOBELJOOCE-UHFFFAOYSA-N 0.000 description 1
- 238000009835 boiling Methods 0.000 description 1
- 239000011575 calcium Substances 0.000 description 1
- 229910052791 calcium Inorganic materials 0.000 description 1
- BRPQOXSCLDDYGP-UHFFFAOYSA-N calcium oxide Chemical compound [O-2].[Ca+2] BRPQOXSCLDDYGP-UHFFFAOYSA-N 0.000 description 1
- 239000000292 calcium oxide Substances 0.000 description 1
- ODINCKMPIJJUCX-UHFFFAOYSA-N calcium oxide Inorganic materials [Ca]=O ODINCKMPIJJUCX-UHFFFAOYSA-N 0.000 description 1
- 238000009749 continuous casting Methods 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 239000003085 diluting agent Substances 0.000 description 1
- 238000007599 discharging Methods 0.000 description 1
- 238000005485 electric heating Methods 0.000 description 1
- 238000009851 ferrous metallurgy Methods 0.000 description 1
- 150000002221 fluorine Chemical class 0.000 description 1
- -1 fluorine ions Chemical class 0.000 description 1
- 150000002500 ions Chemical class 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- 239000000463 material Substances 0.000 description 1
- 239000002184 metal Substances 0.000 description 1
- 229910052751 metal Inorganic materials 0.000 description 1
- VLTRZXGMWDSKGL-UHFFFAOYSA-M perchlorate Inorganic materials [O-]Cl(=O)(=O)=O VLTRZXGMWDSKGL-UHFFFAOYSA-M 0.000 description 1
- 230000001681 protective effect Effects 0.000 description 1
- 238000000197 pyrolysis Methods 0.000 description 1
- 238000007789 sealing Methods 0.000 description 1
- 239000000779 smoke Substances 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 239000008399 tap water Substances 0.000 description 1
- 235000020679 tap water Nutrition 0.000 description 1
- VGBPIHVLVSGJGR-UHFFFAOYSA-N thorium(4+);tetranitrate Chemical compound [Th+4].[O-][N+]([O-])=O.[O-][N+]([O-])=O.[O-][N+]([O-])=O.[O-][N+]([O-])=O VGBPIHVLVSGJGR-UHFFFAOYSA-N 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
- G01N31/00—Investigating or analysing non-biological materials by the use of the chemical methods specified in the subgroup; Apparatus specially adapted for such methods
- G01N31/16—Investigating or analysing non-biological materials by the use of the chemical methods specified in the subgroup; Apparatus specially adapted for such methods using titration
- G01N31/166—Continuous titration of flowing liquids
-
- 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
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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
- G01N1/38—Diluting, dispersing or mixing samples
-
- 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
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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)
- Molecular Biology (AREA)
- Engineering & Computer Science (AREA)
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Abstract
The invention discloses a device for measuring the fluorine content in a slag melting agent for metallurgy, which comprises a steam transmission part, a sample reaction part and a condensation collection part, wherein the reaction part comprises a triangular flask, a heating device, a quartz distillation fluorine measuring tube and a thermometer; the inlet of the quartz distillation fluorine measuring tube is connected with the outlet of the steam conveying part through a latex tube, and the outlet of the quartz distillation fluorine measuring tube is connected with the condensation collecting part through a latex tube. According to the invention, high-boiling-point phosphoric acid is used as reaction acid, the temperature change range is expanded, the temperature is controlled in an oil bath mode, the reaction temperature can be accurately controlled, the accuracy of the measurement result is improved, the waste of the sample and the reaction acid is reduced due to the design of the slender quartz distillation fluorine measuring tube, the overall cost of the device is low, the application range is wide, and the device is beneficial to popularization and use.
Description
Technical Field
The invention relates to a method for carrying out chemical analysis on a material, in particular to a device and a method for measuring the content of fluorine in a slag melting agent for metallurgy.
Background
The fluoride is widely applied in the ferrous metallurgy production, the continuous casting protective slag, the KR calcium oxide-based desulfurizer and most of slagging agents can not separate from the fluoride, the fluorine reduces the melting point and viscosity of slag charge in the metallurgical slag, improves the reaction kinetic conditions of slag and metal or slag and inclusions, plays the role of fluxing agent and diluting agent, and is beneficial to the smooth process and the improvement of the billet quality.
The detection method of the fluorine ions adopts an ion selective electrode method, a pyrolysis method and a distillation separation volumetric method more commonly. The method belongs to a distillation separation volumetric method, and conventional distillation separation volumetric methods such as a method for measuring thorium nitrate titration of the fluorine content of GB/T6730.26-2017 iron ore, a device and a method for measuring fluorine salt in a calcium-based desulfurizer CN 110346508A require that the distillation temperature is kept at 130-140 ℃, because the distillation is incomplete when the temperature is lower than 130 ℃, perchlorate is subjected to excessive temperature and is subjected to smoke distillation, so that the end point observation is influenced. And the samples are decomposed by adding perchloric acid and phosphoric acid, and the actual operation is difficult to control due to the narrow temperature range, so that the error influence is caused. Although the CN 110346508A solves the temperature stability problem by connecting an electric heating jacket with a relatively expensive thyristor temperature controller, the problems of unobvious color change at the titration end point and perchloric acid waste and pollution still exist.
Disclosure of Invention
The invention aims to provide a measuring device and a measuring method which are simple in structure, strong in practicability, accurate, safe and less in pollution and waste, aiming at the defects of the prior art.
In order to achieve the above object, the present invention provides an apparatus for measuring fluorine content in a slag melting agent for metallurgy, the apparatus comprising a vapor delivery portion, a sample reaction portion, and a condensation collection portion, wherein:
the steam delivery part is used for generating steam and comprises a heating device, a distillation flask, an iron support, a safety pipe, a water stop clamp, an air guide bent pipe and a rubber plug; the distillation flask is fixed by an iron support, the bottom of the distillation flask provides heat for the heating device, the mouth of the distillation flask is connected with a safety tube and an air guide bent tube by a rubber plug, the upper part of the safety tube is connected with a latex tube, and the air guide bent tube is connected with a quartz distillation fluorine measuring tube by the latex tube;
the sample reaction part is used for providing condition devices required by sample reaction, and comprises a triangular flask, a heating device, a rubber plug, a quartz distillation fluorine measuring tube and a thermometer; the mouth of the triangular flask is respectively connected with a quartz distillation fluorine measuring tube and a thermometer by a rubber plug, and the bottom of the thermometer is basically level with the quartz distillation fluorine measuring tube; the outlet of the quartz distillation fluorine measuring tube is connected with the condensation collecting part through a latex tube;
the condensation is collected the part and is included condenser pipe, iron stand platform, rubber buffer, ox horn pipe and collection container, the condenser pipe is fixed by the iron stand platform, and vapor after the reaction gets into the condenser pipe condensation via rubber buffer and condenser pipe interface under vapor promotes and becomes liquid, and the cooling water gets into the condenser pipe by the condenser pipe water inlet after being connected cold water source by latex tube, and the condenser pipe delivery port is connected through latex tube and is discharged and cool off, and ox horn pipe is by rubber buffer and condenser pipe exit linkage, and collection container arranges ox horn pipe below in and is used for collecting the distillate.
Furthermore, the volume of a distillation flask in the steam transmission part is 500-2000 mL, the internal liquid is distilled water or deionized water, and a small amount of zeolite is preset at the bottom of the distillation flask to prevent bumping.
Further, the volume of the triangular flask in the sample reaction part is 1000-2000 mL, and the internal bath liquid is glycerol.
Further, the thermometer in the sample reaction part has an effective measurement range of 100-300 ℃.
The invention also provides a method for measuring the fluorine content in the slag melting agent for metallurgy, which comprises the following steps:
step one, providing and assembling the measuring device, opening a heating device to heat the liquid in the distillation flask to boil, opening a water stop clamp at an outlet of a safety tube, keeping water vapor communicated with the atmosphere, closing the water stop clamp at the latex tube, and stopping the water vapor from entering a reaction part;
step two, weighing a slagging agent sample with the mass m, adding the slagging agent sample into a quartz distillation fluorine measuring tube, then adding phosphoric acid, covering a ground bottle stopper, placing the quartz distillation fluorine measuring tube into a triangular flask with an oil bath, and opening a heating device of a sample reaction part to heat the triangular flask;
step three, when the temperature of the oil bath in the triangular flask rises to 130 ℃, immediately closing a water-stopping clamp at the outlet of the safety pipe, opening the water-stopping clamp at the outlet of the air guide bent pipe, and then introducing water vapor into a quartz distillation fluorine measuring pipe of the sample reaction part from the vapor transmission part; the vapor is used as carrier gas and solution to condense the vapor generated by the sample reaction part through the condensation collection part and then enters the collection container;
step four, adding a phenolphthalein indicator into a collection container containing distillate, titrating with a standard sodium hydroxide solution with the concentration of C, finishing titration when the indicator turns red and does not change color within 30s, and recording the volume of the consumed standard sodium hydroxide as V;
step five, blank experiment: opening the water stop clamp, closing the water stop clamp, taking down the quartz distillation fluorine measuring tube, replacing the new quartz distillation fluorine measuring tube only added with phosphoric acid, wherein the volume of the added phosphoric acid is the same as that of the phosphoric acid added in the step two, then, repeating the step three and the step four, and after titration is finished, recording the volume of the consumed standard sodium hydroxide solution as V0；
Sixthly, theoretically calculating, wherein the percent of fluorine in the slag melting agent is as follows:
in the formula:
c-concentration of standard sodium hydroxide solution, mol/L;
v is the volume of standard solution consumed by the titration sample, mL;
V0titration of the volume of standard solution consumed by the blank, mL;
m-weighing the mass of the sample, g;
19-molar mass of fluorine, g/mol.
Furthermore, in the second step, the liquid level of the oil bath in the Erlenmeyer flask exceeds the liquid level of the quartz distillation fluorine measuring tube, so that the oil bath in the Erlenmeyer flask is heated uniformly.
Furthermore, in the second step, the sample preparation granularity of the slag melting agent is less than or equal to 120 meshes.
Further, in the second step, the volume of phosphoric acid added into the quartz distillation fluorine measuring tube is 5-20 m.
Further, in the second step and the third step, the oil bath temperature is controlled to be 130-180 ℃.
Furthermore, in the third step, the volume of the liquid condensed by distillation is not less than 100 mL.
Compared with the prior art, the invention has the beneficial effects that:
1) only phosphoric acid is used for decomposing the sample, so that the interference of chlorine generated by perchloric acid decomposition can be avoided, the titration can adopt acid-base titration with more obvious color change, the visual error of artificial titration is reduced, and only phosphoric acid is used, so that the decomposition temperature range can be increased to 130-180 ℃, and the control is easier compared with 130-140 ℃;
2) the temperature is controlled by utilizing the relatively chronic heat conduction property of the glycerol and adopting the mode of immersing a quartz fluorine measuring tube into an oil bath for indirect heating, so that the problem that the temperature is difficult to control is completely solved.
3) Only a small amount of phosphoric acid decomposition samples and the slender characteristic of the quartz fluorine measuring tube are adopted, so that the reaction is concentrated, the utilization rate of acid is improved, and the waste of the acid and the environmental pollution are reduced.
4) The whole device is low in cost, strong in universality and convenient to popularize and apply.
Description of the drawings:
FIG. 1 is a schematic structural diagram of an embodiment of the present invention;
FIG. 2 is a schematic diagram of the internal structure of a quartz distillation fluorine measuring tube;
wherein: 1 is a steam conveying part, 2-1 and 2-2 are heating devices, 3 is a distillation flask, 4-1 and 4-2 are iron stand tables, 5 is a safety tube, 6-1 and 6-2 are water stoppers, 7 is an air guide bent tube, 8-1, 8-2, 8-3 and 8-4 are rubber stoppers, 9-1, 9-2, 9-3, 9-4 and 9-5 are latex tubes, 10 is a sample reaction part, 11 is a triangular flask, 12 is a quartz distillation fluorine measuring tube, 13 is a thermometer, 14 is a condensation collecting part, 15 is a condenser, 16 is a condenser water inlet, 17 is a condenser water outlet, 18 is a ox horn tube, and 19 is a collecting container.
Detailed Description
For a better understanding of the present invention, the present invention will be further described with reference to the accompanying drawings and specific examples, but the present invention is not limited to the following examples:
the device for measuring the fluorine content in the slag melting agent for metallurgy, as shown in fig. 1, comprises a vapor transmission part 1, a sample reaction part 10 and a condensation collection part 14, wherein the vapor transmission part 1 is used for generating vapor, the vapor is used as a carrier gas and a solution to dissolve a reactant generated by the reaction part 10, and the reactant is condensed by the condensation collection part 14 and then enters a collection container 19, and the device comprises a heating device 2, a distillation flask 3, an iron support 4, a safety tube 5, a water stop clamp 6-1, a water stop clamp 6-2, an air guide bent tube 7 and a rubber plug 8-1; the distillation flask 3 is fixed by an iron support 4, the bottom of the distillation flask provides heat for the heating device 2, the mouth of the distillation flask 3 is connected with a safety tube 5 and an air guide bent tube 7 by a rubber plug 8-1, the upper part of the safety tube is connected with a latex tube 6-1, and the air guide bent tube 7 is connected with a quartz distillation fluorine measuring tube 12 by a latex tube 9-2; the reaction part 10 is used for providing condition devices required by sample reaction, and comprises an Erlenmeyer flask 11, a heating device 2-2, a rubber plug 8-2, a quartz distillation fluorine measuring tube 12 and a thermometer 13; the mouth of the triangular flask 11 is connected with a quartz distillation fluorine measuring tube 12 and a thermometer 13 by a rubber stopper 8-2 in a dividing way, a sample and reaction acid are added into the quartz distillation fluorine measuring tube 12, the liquid level of bath liquid in the triangular flask 11 exceeds the liquid level in the quartz distillation fluorine measuring tube 12, and the bottom of the thermometer 11 is basically level with the quartz distillation fluorine measuring tube 12. The outlet of the quartz distillation fluorine detecting tube 12 is connected with a condensation collecting part 14 through a latex tube 9-3. The condensation collecting part 14 comprises a condensing pipe 15, an iron support 4-2 rubber plug 8-3, a rubber plug 8-4, a horn tube 18 and a collecting container 19, the condensing pipe 15 is fixed by the iron support 4-2, steam after reaction is pushed by steam to enter the condensing pipe 15 through the rubber plug 8-3 and a condensing pipe 15 interface by a latex pipe 9-3 to be condensed into liquid, cooling water is connected with a cold water source by the latex pipe 9-4 and then enters the condensing pipe 15 through a condensing pipe water inlet 16, the cooling water is discharged through the latex pipe 9-5 and is cooled through a condensing pipe water outlet 17, the horn tube 18 is connected with a condensing pipe outlet by the rubber plug 8-4, and the collecting container 19 is arranged below the horn tube 18 to collect distillate.
In the invention, the liquid level of the glycerol in the triangular flask 11 exceeds the height of the sample and the acid in the quartz distillation fluorine measuring tube, the condensation tube 15 is cooled by tap water and is cooled from low to high, namely, the glycerol flows in from a cooling water inlet 16, and the glycerol flows out from a cooling water outlet 17.
The volume of the distillation flask 3 used in the embodiment is 1000mL, 1/2-2/3 volume of deionized water is filled in the distillation flask, and 5-6 pieces of zeolite are placed to prevent bumping.
In the examples, the volume of a flask 11 used was 2000mL, the internal bath was glycerol, and the liquid level was 1/2-2/3, based on the height of the reaction solution in the quartz distillation fluorimeter tube 12.
Preferably, the thermometer in this embodiment has an effective measurement range of 100 ℃ to 300 ℃.
Furthermore, the device for measuring the content of the fluorine in the slag melting agent for metallurgy is used for implementing the method for measuring the content of the fluorine in the slag melting agent for metallurgy.
Specifically, the method for measuring the fluorine content in the slag melting agent for metallurgy comprises the following steps:
step one, providing and assembling the measuring device, heating a steam part 1 to boiling, taking down a water stop clamp 6-1 at an outlet of a safety tube 5, keeping the water steam communicated with the atmosphere, and sealing a latex tube 9-2 at the connection part of an air guide bent tube 7 and a quartz distillation fluorine measuring tube 12 by using the water stop clamp 6-2;
weighing fluorine-containing metallurgical slag with the mass m, adding the fluorine-containing metallurgical slag into a quartz distillation fluorine measuring tube 12, adding phosphoric acid, covering a ground bottle stopper, placing the ground bottle stopper into an oil bath of a triangular flask 11, and starting a heating device 2-2 of a reaction part 10 to heat the oil bath;
and step three, opening the condensation collecting part 14 to cool water, wherein the water flow direction flows in from the lower part of the condensation pipe 15, namely a cooling water inlet 16, and flows out from the higher part of the condensation pipe 15, namely a cooling water outlet 17, to a water outlet for discharging. When the oil bath temperature reaches 130 ℃, immediately closing a water stop valve 6-1 at the outlet of a safety pipe 5, opening a water stop valve 6-2 at the outlet of an air guide bend 7, and keeping the temperature of a thermometer at 130-180 ℃;
step four, when the volume of the distillate is more than or equal to 100mL, taking down the distillate, finishing the distillation process, replacing a new distillate collecting container 19, adding a phenolphthalein indicator into the distilled liquid, titrating the liquid by using a standard sodium hydroxide solution with the concentration of C until the red color does not change within 30 seconds, and marking the volume of the consumed sodium hydroxide as V;
step five, blank experiment: opening a water stop clamp 6-1 at the outlet of the safety tube 5, closing a gas guide bent tube 7 and a water stop clamp 6-2, taking down the quartz distillation fluorine measuring tube 12, replacing the new quartz distillation fluorine measuring tube 12 only added with phosphoric acid, connecting the quartz distillation fluorine measuring tube with the new quartz distillation fluorine measuring tube, and performing the same steps as the third step and the fourth step, and finally recording the titration volume as V0；
Step six, calculating an analysis result as follows:
in the formula:
c-concentration of standard sodium hydroxide solution, mol/L;
v is the volume of standard solution consumed by the titration sample, mL;
V0titration of the volume of standard solution consumed by the blank, mL;
m-weighing the mass of the sample, g;
19-molar mass of fluorine, g/mol.
According to the technical scheme, 3 samples of the slagging agent are randomly selected to carry out a method repeatability test so as to verify the precision of the measuring device, and the obtained results are shown in the following table 1.
Table 1 shows the results of the precision test of fluorine content in the slag melting agent (n ═ 6)
As can be seen from Table 1, the relative standard deviation is less than or equal to 0.50%, which shows that the method has better precision.
In order to verify the accuracy of the technical scheme of the invention, the invention adopts a recovery test for further introduction, wherein the recovery test is carried out by adding reference sodium fluoride, sodium fluoride with different contents (converted into fluorine content) is added into the slagging agent according to the experimental conditions for standard recovery, and the obtained results are shown in table 2.
Table 2 shows the results of the recovery test
As can be seen from Table 2, the recovery rate is 96.2-103.4%, which indicates that the method is accurate and reliable.
As can be seen from the comprehensive table 1 and the table 2, the detection device and the method have the advantages of high accuracy, good reproducibility, small pollution and low cost for analyzing the fluorine content in the slag melting agent, and are beneficial to popularization and application.
In summary, compared with the prior art, the method has the advantages that only phosphoric acid is used for decomposing the sample, so that chlorine interference generated by perchloric acid decomposition can be avoided, titration can be performed by acid-base titration with more obvious color change, the visual error of artificial titration is reduced, only phosphoric acid is used, the decomposition temperature range can be increased to 130-180 ℃, and the method is easier to control compared with 130-140 ℃; the temperature is controlled by utilizing the relatively chronic heat conduction property of the glycerol and adopting the mode of immersing a quartz fluorine measuring tube into an oil bath for indirect heating, so that the problem that the temperature is difficult to control is completely solved. Only a small amount of phosphoric acid decomposition samples and the slender characteristic of the quartz fluorine measuring tube are adopted, so that the reaction is concentrated, the utilization rate of acid is improved, and the waste of the acid and the environmental pollution are reduced. The whole device is low in cost, strong in universality and convenient to popularize and apply.
It should be understood that although the present description refers to embodiments, not every embodiment contains only a single technical solution, and such description is for clarity only, and those skilled in the art should make the description as a whole, and the technical solutions in the embodiments can also be combined appropriately to form other embodiments understood by those skilled in the art.
Claims (10)
1. A device for measuring the fluorine content in a slag melting agent for metallurgy is characterized by comprising a steam transmission part (1), a sample reaction part (10) and a condensation collection part (14), wherein:
the steam delivery part (1) is used for generating steam, and the steam delivery part (1) comprises a heating device (2-1), a distillation flask (3), an iron stand (4), a safety pipe (5), a water stop clamp (6-1), a water stop clamp (6-2), an air guide bent pipe (7) and a rubber plug (8-1); the distillation flask (3) is fixed by an iron support (4), the bottom of the distillation flask provides heat for the heating device (2-1), the mouth of the distillation flask (3) is connected with a safety tube (5) and an air guide bent tube (7) by a rubber plug (8-1), the upper part of the safety tube (5) is connected with a latex tube (6-1), and the air guide bent tube (7) is connected with a quartz distillation fluorine measuring tube (12) by the latex tube (9-2);
the sample reaction part (10) is used for providing condition devices required by sample reaction, and comprises a triangular flask (11), a heating device (2-2), a rubber plug (8-2), a quartz distillation fluorine measuring tube (12) and a thermometer (13); the opening of the triangular flask (11) is respectively connected with a quartz distillation fluorine measuring tube (12) and a thermometer (13) through a rubber plug (8-2), and the bottom of the thermometer (13) is basically flush with the quartz distillation fluorine measuring tube (12); the outlet of the quartz distillation fluorine measuring tube (12) is connected with a condensation collecting part (14) through a latex tube (9-3);
condensation collection part (14) include condenser pipe (15), iron stand platform (4-2), rubber buffer (8-3), rubber buffer (8-4), ox horn pipe (18) and collection container (19), condenser pipe (15) are fixed by iron stand platform (4-2), and cooling water gets into condenser pipe (15) by condenser pipe water inlet (16), and it cools off to connect condenser pipe delivery port (17) through emulsion tube (9-5) and discharge, and ox horn pipe (18) are by rubber buffer (8-4) and condenser pipe exit linkage, and collection container (19) are arranged in ox horn pipe (18) below and are used for collecting the distillate.
2. The apparatus for measuring the fluorine content of the slag melting agent for metallurgy according to claim 1, wherein: the volume of a distillation flask (3) in the steam delivery part (1) is 500-2000 mL, the internal liquid is distilled water or deionized water, and a small amount of zeolite is preset at the bottom of the flask to prevent bumping.
3. The device for measuring the content of fluorine in the slag melting agent for metallurgy according to claim 1, is characterized in that: the volume of the triangular flask in the sample reaction part (10) is 1000-2000 mL, and the internal bath liquid is glycerol.
4. The device for measuring the content of fluorine in the slag melting agent for metallurgy according to claim 1, is characterized in that: the effective measurement range of the thermometer (13) in the sample reaction part (10) is 100-300 ℃.
5. A method for measuring the fluorine content in a slag melting agent for metallurgy is characterized by comprising the following steps:
step one, providing and assembling the measuring device in claims 1-4, opening a heating device (2-1) to heat the liquid in the distillation flask (3) to boil, opening a water-stopping clamp (6-1) at the outlet of a safety tube (5), keeping the water vapor communicated with the atmosphere, closing the water-stopping clamp (6-2) at the latex tube (9-2), and not introducing the water vapor into a reaction part (10);
weighing a slagging agent sample with the mass m, adding the slagging agent sample into a quartz distillation fluorine measuring tube (12), then adding phosphoric acid, covering a ground bottle stopper, placing the quartz distillation fluorine measuring tube (12) into a triangular flask (11) filled with an oil bath, and opening a heating device (2-2) of a sample reaction part (10) to heat the triangular flask (11);
step three, when the temperature of the oil bath in the triangular flask (11) rises to 130 ℃, immediately closing the water stop clamp (6-1) at the outlet of the safety tube (5), opening the water stop clamp (6-2) at the outlet of the gas guide bent tube (7), and then introducing water vapor into the quartz distillation fluorine measuring tube (12) of the sample reaction part (10) from the vapor transmission part (1); the vapor is used as carrier gas and solvent, and the vapor generated by the sample reaction part (10) is condensed by the condensation collection part (14) and then enters the collection container (19);
step four, adding a phenolphthalein indicator into a distillate-containing collecting container (19), titrating by using a standard sodium hydroxide solution with the concentration of C, finishing titration when the indicator turns red and does not change color within 30s, and recording the volume of the consumed standard sodium hydroxide as V;
step five, blank experiment: opening the water-stop clamp (6-1), closing the water-stop clamp (6-2), taking down the quartz distillation fluorine measuring tube (12), replacing a new quartz distillation fluorine measuring tube (12) only added with phosphoric acid, wherein the volume of the added phosphoric acid is the same as that of the phosphoric acid added in the step two, then, repeating the step three and the step four, and after titration is finished, recording the volume of the consumed standard sodium hydroxide solution as V0；
Sixthly, theoretically calculating, wherein the percent of fluorine in the slag melting agent is as follows:
in the formula:
c-concentration of standard sodium hydroxide solution, mol/L;
v is the volume of standard solution consumed by the titration sample, mL;
V0titration of the volume of standard solution consumed by the blank, mL;
m-weighing the mass of the sample, g;
19-molar mass of fluorine, g/mol.
6. The method for measuring the fluorine content in the slag melting agent for metallurgy according to claim 5, is characterized in that: in the second step, the oil bath liquid level in the Erlenmeyer flask (11) exceeds the liquid level of the quartz distillation fluorine measuring tube (12), so that the oil bath in the Erlenmeyer flask (11) is heated uniformly.
7. The method for measuring the fluorine content in the slag melting agent for metallurgy according to claim 5, is characterized in that: and in the second step, the volume of phosphoric acid added into the quartz distillation fluorine measuring tube (12) is 5-20 mL.
8. The method for measuring the fluorine content in the slag melting agent for metallurgy according to claim 5, is characterized in that: and in the second step, the sample preparation granularity of the slag melting agent is less than or equal to 120 meshes.
9. The method for measuring the fluorine content in the slag melting agent for metallurgy according to claim 5, is characterized in that: and the oil bath temperature in the second step and the third step is controlled to be 130-180 ℃.
10. The method for measuring the fluorine content in the slag melting agent for metallurgy according to claim 5, is characterized in that: in the third step, the volume of the liquid condensed by distillation is not less than 100 mL.
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