Device and method for measuring contents of calcium fluoride and carbonate in dolomite-containing fluorite mine

Abstract

The invention relates to the technical field of calcium fluoride determination, in particular to a device and a method for determining the content of calcium fluoride and carbonate in dolomite-containing fluorite mine, the device comprises a determination beaker and a watch glass covering the determination beaker, a plug ring is fixed on the bottom surface of the watch glass, and the plug ring is inserted into a beaker opening of the determination beaker; a swinging ball is rotationally connected to the center of the surface of the watch glass, and a stirring rod is inserted into the surface of the swinging ball and extends into the measuring beaker; the device has the beneficial effects that the swinging ball is rotationally connected to the center of the surface of the watch glass, the stirring rod is inserted into the surface of the swinging ball, and structures such as a reserved opening, a limiting ring and a rubber clamping piece are arranged, so that effective anti-falling limiting of the stirring rod is realized. During stirring, the stirring rod drives the swinging ball to swing in the reserved opening, the inclination amplitude of the rod body, extending into the measuring beaker, of the stirring rod can be flexibly adjusted, and different stirring requirements are met.

Description

TECHNICAL FIELD

[0001] The present application relates to the technical field of calcium fluoride determination, in particular to a device and method for measuring the content of calcium fluoride and carbonate in dolomite fluorite ore. BACKGROUND

[0002] In the process of measuring the content of calcium fluoride and carbonate in dolomite fluorite ore, the traditional measuring device has many inconveniences and defects.

[0003] On the one hand, in the stirring operation link, the ordinary stirring method is difficult to effectively prevent the stirring rod from falling off and limiting. During the stirring process, the stirring rod is easy to fall off from the device due to shaking or improper operation, which causes the stirring to be interrupted, not only affects the stirring efficiency, but also may cause the scattered material, resulting in waste of material and pollution of experimental environment, and even may affect the accuracy of the measurement result.

[0004] On the other hand, in the aspect of reagent feeding, the traditional method needs to frequently open the surface dish to add the required reagent into the measuring beaker. Each time the surface dish is opened, the inside of the measuring beaker is in contact with the outside environment, which may cause foreign matter to enter the measuring beaker, interfere with the measuring process, and affect the accuracy of the measuring result. Moreover, the frequent opening operation is tedious, increases the experimental steps and time cost, and reduces the overall measuring efficiency. SUMMARY

[0005] The present application aims to provide a device and method for measuring the content of calcium fluoride and carbonate in dolomite fluorite ore to solve the problems raised in the background.

[0006] To achieve the above-mentioned purpose, the present application provides the following technical scheme: a device for measuring the content of calcium fluoride and carbonate in dolomite fluorite ore, comprising a measuring beaker and a surface dish covering the top of the measuring beaker, the bottom surface of the surface dish is fixed with a plug ring, the plug ring is inserted into the cup opening of the measuring beaker, the surface of the surface dish is centrally rotationally connected with a swing ball, the surface of the swing ball is inserted with a stirring rod, the stirring rod extends into the measuring beaker, the top surface of the surface dish is fixed with an enclosure frame, the inside of the enclosure frame is fixed with a plurality of partitions to divide a plurality of storage spaces, the bottom surface of the surface dish is fixed with a plurality of dispensing boxes corresponding to the storage spaces, the top surface of the enclosure frame is screwed with a traction screw, the traction screw penetrates the surface dish, the bottom end of the traction screw is fixed with a traction handle, the traction handle penetrates the bottom plate of the dispensing box; a plurality of storage spaces store reagents for measurement respectively, after the traction screw in the corresponding storage space is upwardly screwed and extracted, the actual falling in the storage space falls into the dispensing box, at this time the dispensing box is blocked by the traction handle; after the traction screw is downwardly screwed to block the surface dish, the traction handle no longer blocks the bottom plate of the dispensing box, and the reagent in the dispensing box falls into the measuring beaker.

[0007] Preferably, the outer side of the plug ring is fixed with a rubber clamp ring, which is clamped between the plug ring and the inner wall of the measuring beaker to produce elastic deformation, and the outer ring of the surface dish is fixed with a silica gel sleeve, which is a circular plate with a "Fang" shape cross section.

[0008] Preferably, the surface of the surface dish is provided with a reserved port, and the upper and lower sides of the reserved port are provided with limiting rings, respectively fixed on the top surface of the surface dish and the bottom surface of the surface dish, and the limiting rings are circular plates with a "Fang" shape cross section, and the two limiting rings limit the swing ball in the reserved port, and the inner ring surface of the limiting ring is fixed with a rubber clamp piece one, which is clamped between the swing ball and the limiting ring to produce elastic deformation.

[0009] Preferably, the surface of the swing ball is provided with a through hole, the stirring rod penetrates through the through hole and extends into the measuring beaker, the bottom end of the through hole is fixed with a rubber scraping ring, the rubber scraping ring is sleeved on the stirring rod, and the inside of the through hole is fixed with a rubber clamp ring, which is clamped between the through hole and the stirring rod to produce elastic deformation.

[0010] Preferably, the enclosure frame is a circular frame with a "Fang" shape cross section, the top surface of the enclosure frame is provided with through holes two corresponding to the storage space, the surface of the surface dish is provided with through holes one corresponding to the through holes two, the top surface of the enclosure frame is fixed with silk sleeves corresponding to the through holes two, the traction screw rod is screwed with the silk sleeve, the bottom end of the traction screw rod is sleeved and fixed with an elastic plug ring one, and when the traction screw rod falls to block the surface dish, the elastic plug ring one is inserted into the through hole one.

[0011] Preferably, the surface of the traction screw rod is provided with a pressure relief hole, which is a "Fang" shaped hole.

[0012] Preferably, the bottom plate of the sub-packaging box is provided with a through hole three, the rod body of the traction handle is sleeved and fixed with an elastic plug ring two, after the bottom end of the traction screw rod is inserted into the surface of the surface dish, the elastic plug ring two is below the sub-packaging box, the through hole three leaks out, and after the traction screw rod is separated from the surface of the surface dish, the elastic plug ring two is inserted into the through hole three.

[0013] Preferably, the rod body of the traction handle is sleeved and fixed with a shield, which is a circular plate with a "Fang" shape cross section.

[0014] A method for measuring the content of calcium fluoride and carbonate in dolomite fluorite ore, comprising the following steps: Sample preparation: prepare the sample according to GB / T22564 standard, process the sample to a particle size of less than 0.063mm, and dry at 105°C±5°C for 2 hours, and then cool to room temperature in a dryer; Reagent preparation: using analytical reagents and water meeting the requirements of GB / T6682 or its equivalent purity, prepare the following reagents: 1+9 acetic acid, 1+1 hydrochloric acid, 1+2 triethanolamine, 200g / L potassium hydroxide solution, boric acid, CMP mixed indicator, calcium indicator, KB indicator, buffer solution with pH value of 10, 0.01000mol / L calcium standard solution and 0.0200mol / L EDTA standard titration solution; Calcium carbonate content determination of filtrate: take 0.25g sample, accurate to 0.0001g, put it in a 100ml measuring beaker, add 10ml acetic acid, room temperature for 30 minutes, shake every 5 minutes, then filter with fast qualitative filter paper, and wash the measuring beaker and residue with water; put the filtrate in a 500ml conical flask, dilute with water to about 120ml, add triethanolamine, potassium hydroxide solution and calcium indicator, titrate with 0.02mol / L EDTA standard titration solution until the green color changes to blue as the end point, record the volume of EDTA standard titration solution consumed; correct the calcium carbonate content of the filtrate, the correction formula is: W=W' / 0.98-0.15, where W' is the measured mass percentage of calcium carbonate in the filtrate, 0.98 is the dissolution rate of calcium carbonate, and 0.15 is the correction value of calcium fluoride dissolution amount; Magnesium content determination of filtrate: add hydrochloric acid to the filtrate after titration of calcium carbonate, then add PH10 buffer solution and KB indicator, titrate with 0.02mol / L EDTA standard solution until the pink color disappears and blue color appears as the end point, record the volume of EDTA standard solution consumed; Total calcium and total magnesium content determination in sample: take 0.1000g sample, add boric acid and hydrochloric acid, heat and boil for 10-15 minutes, shake from time to time, rinse with water after the sample is almost dry, and add appropriate amount of water to cool; add triethanolamine, potassium hydroxide solution and CMP mixed indicator to the solution, titrate with 0.02mol / L EDTA standard titration solution until the green fluorescence of the test solution disappears, record the volume of EDTA standard solution consumed to determine the total calcium content; add hydrochloric acid to the filtrate after titration of total calcium, then add PH10 buffer solution and KB indicator, titrate with 0.02mol / L EDTA standard solution until the pink color disappears and blue color appears as the end point, record the volume of EDTA standard solution consumed to determine the total magnesium content; Result calculation: according to the measured data, the mass fraction of calcium carbonate in the filtrate, total calcium in the sample, magnesium in the filtrate and total magnesium in the sample is calculated respectively; finally, according to the mass fraction of total calcium, total magnesium, calcium carbonate in the filtrate and magnesium in the filtrate, combined with the correction formula, the final mass fraction of calcium fluoride and calcium carbonate in the sample is calculated, and the calculation formula is respectively: Calcium carbonate mass fraction calculation in filtrate: ωCaCO 3滤 =C×(V1-V01 ) X 40.08*100 / M1 / 1000; Calcium mass fraction in sample is calculated as follows: ωCa total = C x (V2-V 02 ) X 40.08*100 / M1 / 1000; Magnesium mass fraction in filtrate is calculated as follows: ωMg 液 = C x (V3-V 03 ) X 24.31*100 / M1 / 1000; Calcium mass fraction in sample is calculated as follows: ωMg 总 = C x (V4-V 04) ) X 24.31*100 / M1 / 1000; Calcium fluoride mass fraction in sample is calculated as follows: ; Calcium carbonate mass fraction in sample is calculated as follows: ωCaCO3=ωCaCO 3液 + (ωMg 总 - ωMg 液 ) *100 / 24.31-0.15.

[0015] Compared with the prior art, the present application has the following beneficial effects: The device and method for measuring calcium fluoride and carbonate content in dolomite fluorite ore provided by the present application realize effective anti-disengagement and limiting of the stirring rod by centrally rotating and connecting the swing ball on the surface of the watch glass, inserting the stirring rod into the surface of the swing ball, and arranging the reserved opening, the limiting ring and the rubber clamping piece and other structures. When stirring, the swing ball swings in the reserved opening driven by the stirring rod, and the inclination range of the rod body of the stirring rod inserted into the inside of the measuring beaker can be flexibly adjusted to meet different stirring requirements. At the same time, the rubber clamping ring is clamped between the stirring rod and the through hole, and the rubber clamping piece is clamped between the swing ball and the limiting ring, which avoids the scattering of the material stirred in the inside of the measuring beaker, guarantees the stability and reliability of the stirring process, improves the stirring efficiency, and also helps to obtain more accurate measurement results.

[0016] The present application is characterized in that a protective frame is arranged on the top of the surface dish, a plurality of storage spaces are separated in the protective frame for storing reagents, corresponding sub-packaging boxes are arranged on the bottom surface of the surface dish, and the reagent dispensing control is realized through traction screw, traction handle and other components. When in use, only by rotating the traction screw, the reagent can be controlled to fall into the sub-packaging box from the storage space, and then fall into the measuring beaker from the sub-packaging box. The whole process does not need to open the surface dish, effectively avoids the foreign matter into the measuring beaker, ensures the relative closure and purity of the measuring environment, and improves the accuracy of the measuring result. Meanwhile, the surface of the sub-packaging box is provided with a scale, so that the required reagent amount can be conveniently measured and dispensed, the operation process is simplified, time is saved, and the overall measuring efficiency is improved. BRIEF DESCRIPTION OF DRAWINGS

[0017] Figure 1 It is a structural schematic view of the present application; Figure 2 It is a structural schematic view of the present application; Figure 1 It is a structural sectional view of A-A in the present application; Figure 3 It is a structural schematic view of the present application; Figure 2 It is an enlarged structural schematic view of B in the present application; Figure 4 It is an enlarged structural schematic view of C in the present application; Figure 2 It is an enlarged structural schematic view of D in the present application; Figure 5 Figure 2 It is an enlarged structural schematic view of D in the present application; Figure 6 It is a schematic view of the surface dish and the ring connection structure of the present application; Figure 7 It is a schematic view of the protective frame and the partition plate connection structure of the present application; Figure 8 It is a schematic view of the surface dish and the limiting ring connection structure of the present application; Figure 9 It is a schematic view of the traction screw and the traction handle connection structure of the present application.

[0018] In the figure: measuring beaker 1, surface dish 2, silica gel sleeve 201, reserved port 202, limiting ring 203, rubber clamping piece one 2031, through hole one 204, ring 3, rubber clamping ring 301, swing ball 4, perforation 401, rubber scraping ring 402, stirring rod 403, rubber clamping ring 404, protective frame 5, partition plate 501, through hole two 502, wire sleeve 503, traction screw 504, pressure relief hole 5041, elastic ring one 5042, sub-packaging box 6, through hole three 601, traction handle 7, elastic ring two 701, shield 702. DETAILED DESCRIPTION

[0019] ​In order to make the purpose, technical scheme of the present application, and the advantages are clearer, more complete, and more clearly understood, the embodiments of the present application are further described in detail below with reference to the drawings. It should be understood that the specific embodiments described herein are part of the embodiments of the present application, rather than all embodiments, and are used to explain the embodiments of the present application, and are not used to limit the embodiments of the present application. All other embodiments obtained by those skilled in the art without creative labor fall within the scope of the present application.

[0020] Embodiment one, please refer to Figures 1 to 9 The present application provides a technical scheme: a device for measuring the content of calcium fluoride and carbonate in dolomite fluorite ore, comprising a measuring beaker 1 and a surface dish 2 covering the top of the measuring beaker 1. The bottom surface of the surface dish 2 is fixed with a plug ring 3, which is inserted into the mouth of the measuring beaker 1. The outer side of the plug ring 3 is fixed with a rubber clamp ring 301, which is clamped between the plug ring 3 and the inner wall of the measuring beaker 1 to produce elastic deformation. The outer ring of the surface dish 2 is fixed with a silica gel sleeve 201, which is a circular plate with a "H" shaped cross section. In use, the surface dish 2 covers the top of the measuring beaker 1, at this time the plug ring 3 is inserted into the mouth of the measuring beaker 1, the surface dish 2 blocks the mouth of the measuring beaker 1, and because the rubber clamp ring 301 is clamped between the plug ring 3 and the measuring beaker 1, the rubber clamp ring 301 rebounds to avoid the plug ring 3 from shaking on the measuring beaker 1, so that the surface dish 2 is stably covered on the measuring beaker 1, avoiding the liquid inside the measuring beaker 1 from splashing outwards.

[0021] In order to realize the anti-displacement and limiting of the stirring rod 403, the following content is proposed: The surface of the surface dish 2 is rotationally connected with a swing ball 4, the surface of the swing ball 4 is inserted with a stirring rod 403, the stirring rod 403 extends into the measuring beaker 1, the surface of the surface dish 2 is provided with a reserved port 202, the upper and lower sides of the reserved port 202 are provided with limiting rings 203, the two limiting rings 203 are respectively fixed on the top surface of the surface dish 2 and the bottom surface of the surface dish 2, and the limiting rings 203 are circular plates with a table shape, the two limiting rings 203 limit the swing ball 4 in the reserved port 202, and the inner ring surface of the limiting ring 203 is fixed with a rubber clamp 2031, which is clamped between the swing ball 4 and the limiting ring 203 to produce elastic deformation; the surface of the swing ball 4 is provided with a perforation 401, the stirring rod 403 extends into the measuring beaker 1 after penetrating through the perforation 401, the bottom end of the perforation 401 is fixed with a rubber scraping ring 402, which is sleeved on the stirring rod 403, and the inside of the perforation 401 is fixed with a rubber clamp ring 404, which is clamped between the perforation 401 and the stirring rod 403 to produce elastic deformation.

[0022] The specific process of mixing the materials in the measuring beaker 1 by the stirring rod 403 is as follows: After the materials that need to be stirred are added into the measuring beaker 1, the watch glass 2 is covered on the measuring beaker 1, then the top of the stirring rod 403 is pinched by the finger, the stirring rod 403 is rotated in the circumferential direction, the swinging ball 4 swings in the reserved opening 202 when the stirring rod 403 rotates, the inclination range of the rod body of the stirring rod 403 that extends into the measuring beaker 1 can be adjusted, the rubber clamping ring 404 is clamped between the stirring rod 403 and the perforated hole 401, and the swinging ball 4 and the limiting ring 203 clamps the rubber clamping piece 2031, so that the materials stirred in the measuring beaker 1 are prevented from scattering out, when the stirring rod 403 is pulled out from the swinging ball 4, the rubber scraping ring 402 can scrape the residual liquid on the surface of the stirring rod 403 and drop it into the measuring beaker 1.

[0023] In order to temporarily store the reagent on the top of the watch glass 2 by the enclosure frame 5, and to realize the reagent needed to be put into the measuring beaker 1 without opening the watch glass 2, the following contents are proposed: The top surface of the surface dish 2 is fixed with a surrounding frame 5, the inside of the surrounding frame 5 is fixed with a plurality of partitions 501 to divide a plurality of storage spaces, the bottom surface of the surface dish 2 is fixed with a plurality of sub-packing boxes 6 corresponding to the storage spaces one by one, the top surface of the surrounding frame 5 is screwed with a traction screw rod 504, the traction screw rod 504 penetrates the surface dish 2, the bottom end of the traction screw rod 504 is fixed with a traction handle 7, the traction handle 7 penetrates the bottom plate of the sub-packing box 6; a plurality of storage spaces respectively store reagents for determination, after the traction screw rod 504 in the corresponding storage space is screwed upwards to extract, the actual falling in the storage space falls into the sub-packing box 6, at this time the sub-packing box 6 is blocked by the traction handle 7; after the traction screw rod 504 is screwed downwards to block the surface dish 2, the traction handle 7 no longer blocks the bottom plate of the sub-packing box 6, the reagent in the sub-packing box 6 falls into the determination beaker 1; the surrounding frame 5 is a circular frame with a section of a "Fang" character, the top surface of the surrounding frame 5 is provided with through holes two 502 corresponding to the storage spaces one by one, the surface of the surface dish 2 is provided with through holes one 204 corresponding to the through holes two 502 one by one, the top surface of the surrounding frame 5 is fixed with a silk sleeve 503 corresponding to the through holes two 502 one by one, the traction screw rod 504 and the silk sleeve 503 are screwed, the bottom end of the traction screw rod 504 is fixed with a elastic plug ring one 5042, when the traction screw rod 504 falls to block the surface dish 2, the elastic plug ring one 5042 is inserted in the through hole one 204; the surface of the traction screw rod 504 is provided with a pressure relief hole 5041, the pressure relief hole 5041 is a "Fang" character hole; the bottom plate of the sub-packing box 6 is provided with a through hole three 601, the rod body of the traction handle 7 is fixed with an elastic plug ring two 701, after the bottom end of the traction screw rod 504 is inserted in the surface of the surface dish 2, the elastic plug ring two 701 is below the sub-packing box 6, the through hole three 601 leaks out, after the traction screw rod 504 is separated from the surface of the surface dish 2, the elastic plug ring two 701 is inserted in the through hole three 601; the rod body of the traction handle 7 is fixed with a shield 702, the shield 702 is a table type ring plate structure.

[0024] The reagent needs to be stored in the storage space in advance, in order to facilitate the replenishment to the storage space, the top surface of the containment frame 5 is provided with a filling opening, and a plug is screwed in the filling opening. The above-mentioned replenishment operation is a mature technology, and therefore is not limited too much; when the reagent in the storage space needs to be poured into the measuring beaker 1, the traction screw 504 is quickly screwed upwards, the traction screw 504 drives the elastic plug ring one 5042 to be separated from the through hole one 204, at the same time, the traction screw 504 drives the traction handle 7 to move upwards, the elastic plug ring two 701 at the bottom end of the traction handle 7 is inserted into the through hole three 601, at this time, the reagent in the storage space falls into the sub-packaging box 6 through the through hole one 204, the surface of the sub-packaging box 6 is provided with a scale, the scale on the surface of the sub-packaging box 6 can be observed through the measuring beaker 1, the actual amount of the reagent to be poured is measured through the sub-packaging box 6, the elastic plug ring one 5042 is pushed into the through hole one 204 by quickly screwing the traction screw 504 downwards, the bottom of the storage space is sealed, at the same time, the traction handle 7 is lowered to drive the elastic plug ring two 701 to be separated from the through hole three 601, the reagent measured in the sub-packaging box 6 falls into the measuring beaker 1 through the through hole three 601, then the multiple materials in the measuring beaker 1 are stirred through the stirring rod 403.

[0025] Device for measuring calcium fluoride and carbonate content in dolomite fluorite ore I. Initial preparation of the device: Ensure that the measuring beaker 1, the surface dish 2, the plug ring 3, the rubber clamping ring 301, the silica gel sleeve 201, the swing ball 4, the stirring rod 403, the containment frame 5, the partition plate 501, the sub-packaging box 6, the traction screw 504, the traction handle 7 and other components are complete and undamaged.

[0026] Cover the surface dish 2 on the top of the measuring beaker 1, and insert the plug ring 3 into the cup opening of the measuring beaker 1. At this time, the rubber clamping ring 301 is clamped between the plug ring 3 and the inner wall of the measuring beaker 1 to produce elastic deformation, the silica gel sleeve 201 at the outer ring of the surface dish 2 plays an auxiliary stabilizing role, ensuring that the surface dish 2 is stably covered on the measuring beaker 1, preventing the internal stirring liquid from splashing.

[0027] II. Reagent storage: A filling opening is formed on the top surface of the containment frame 5, and a plug is screwed in the filling opening (this is a mature technology, which ensures that the plug is tightly sealed). Open the plug, and store the reagents for measurement in the multiple storage spaces in the containment frame 5 through the filling opening. After storage is completed, tighten the plug.

[0028] Three, stirring operation: add the material to be stirred into the measuring beaker 1. Pinch the top of the stirring rod 403 with your fingers, and rotate the stirring rod 403 in a circular motion. As the stirring rod 403 rotates, it causes the swing ball 4 to swing in the reserved port 202 of the surface dish 2, thereby adjusting the inclination of the rod body of the stirring rod 403 extending into the interior of the measuring beaker 1, and achieving the mixing and stirring of the material. In this process, the rubber clamp ring 404 is clamped between the stirring rod 403 and the through hole 401, and the swing ball 4 and the rubber clamp piece 1 203 in the limiting ring 203 serve as anti-disengagement limiting, preventing the material inside the measuring beaker 1 from scattering.

[0029] Four, reagent delivery: when it is necessary to deliver reagents into the measuring beaker 1, quickly screw the traction screw 504 upwards. The traction screw 504 causes the elastic plug ring 1 5042 to be pulled away from the through hole 1 204, and simultaneously causes the traction handle 7 to move upwards, and the elastic plug ring 2 701 at the bottom end of the traction handle 7 is inserted into the through hole 3 601. At this time, the reagent in the storage space falls into the sub-packaging box 6 through the through hole 1 204. The scale on the surface of the sub-packaging box 6 is observed through the measuring beaker 1, and the actual amount to be delivered is measured according to the need. Quickly screw the traction screw 504 downwards, push the elastic plug ring 1 5042 into the through hole 1 204, and achieve the plugging of the bottom of the storage space. At the same time, the traction handle 7 is lowered, causing the elastic plug ring 2 701 to be pulled away from the through hole 3 601, and the measured reagent in the sub-packaging box 6 falls into the measuring beaker 1 through the through hole 3 601.

[0030] Five, subsequent stirring: after the reagent delivery is completed, the stirring rod 403 is used again to stir the various materials inside the measuring beaker 1, ensuring that the materials are fully mixed and reacted.

[0031] Six, stirring rod cleaning: when the stirring rod 403 needs to be extracted, the rubber scraping ring 402 will scrape the residual liquid on the surface of the stirring rod 403 into the measuring beaker 1, avoiding pollution or waste caused by liquid residue.

[0032] Example Two, on the basis of Example One, a method for determining the content of calcium fluoride and carbonate in dolomite fluorite ore is proposed, including the following steps: I. Scope The method is suitable for determining the content of calcium fluoride and calcium carbonate in dolomite fluorite ore, and the determination range (mass fraction of calcium fluoride) is ≥1%; it has a wide range of applications. It is mainly used for determining the content of calcium fluoride and calcium carbonate in dolomite-containing fluorite ore, concentrate, flotation tailings and other ore samples.

[0033] II. Normative reference documents GB / T 6682 Specifications and test methods for water for analytical laboratories GB / T 12806 Laboratory glassware, single-marked volumetric flask GB / T 12807 Laboratory glassware, graduated pipette GB / T 12808 Laboratory glassware - Single-marked pipets GB / T 22564 Sampling and sample preparation of fluorite GB / T 5195.1 Determination of calcium fluoride content in fluorite GB / T 5195.2 Determination of carbonate content in fluorite III. PRINCIPLE The sample is leached with dilute acetic acid and filtered. The calcium carbonate and magnesium content of the filtrate is determined. The sample is then decomposed with hydrochloric acid and boric acid and the total calcium and magnesium content is determined. The magnesium content of the residue is obtained by subtracting the magnesium content of the filtrate from the total magnesium. The calcium content of the dolomite in the residue is calculated from the magnesium content of the residue. The calcium fluoride content is obtained by subtracting the calcium content of the dolomite and the calcium carbonate content of the filtrate from the total calcium content. The calcium carbonate content is obtained by adding the calcium carbonate equivalent of the calcium content of the dolomite in the residue to the calcium carbonate content of the filtrate. A correction is applied to the final calcium fluoride and calcium carbonate results because a small amount of calcium fluoride is dissolved by the acetic acid leach.

[0034] This method solves the problem of dolomite dissolution when leaching with acetic acid. The accurate calculation of the amount of dolomite dissolved makes the measured calcium fluoride content more clear, reasonable, reliable and close to the true value. The process is simple and fast and is suitable for the needs of mine production, laboratory testing and other fields.

[0035] IV. REAGENTS Unless otherwise stated, only reagents of recognized analytical purity and water of grade 3 or better conforming to GB / T 6682 were used in the analysis.

[0036] 4.1 Acetic acid, 1 + 9 4.2 Hydrochloric acid, 1 + 1 4.3 Triethanolamine, 1 + 2 4.4 Potassium hydroxide, 200 g / L 4.5 Boric acid 4.6 CMP mixed indicator: accurately weigh 1.0 g of calcein, 1.0 g of methylthymols blue and 0.2 g of phenolphthalein, mix with 50 g of potassium nitrate which has been dried at 105-110°C, and store in a ground glass stoppered bottle for use.

[0037] 4.7 Calcium indicator: accurately weigh 0.12 g of thymols phthalein, 0.2 g of calcein and 20 g of potassium sulfate, mix and store in a ground glass stoppered bottle for use.

[0038] 4.8 kB indicator: accurately weigh 1.0 g of acid chrome blue K, 2.5 g of naphthol green B and 50 g of dried potassium nitrate, mix and store in a ground glass stoppered bottle for use.

[0039] 4.9 Buffer solution pH value is 10. (68 g of ammonium chloride is dissolved in 400 ml of water, 570 ml of ammonia water is added, and water is diluted to 1000 ml, and mixed well.) 4.10 Calcium standard solution: 0.01000 mol / L Take 1.0008 g of calcium carbonate (>99.9%) previously dried at 105℃-110℃ for 2h and cooled to room temperature in a desiccator, in a 400 ml beaker, cover with a watch glass, slowly add 25 ml of hydrochloric acid (4.2), after the calcium carbonate is dissolved, add 100 ml of water, heat to boiling, drive off the carbon dioxide, cool to room temperature. Transfer the solution to a 1000 ml volumetric flask, dilute to the mark with water, mix well.

[0040] 4.11 EDTA standard titration solution: 0.0200 mol / L.

[0041] (a) Preparation: Take 7.45 g of EDTA (reference material) previously dried in a 105℃ oven for 1h, in a 400 ml beaker, add 200 ml of water, heat to dissolve completely, cool to room temperature, transfer the entire solution to a 1000 ml volumetric flask and dilute to the mark.

[0042] (b) Calibration: Take 25.00 ml of calcium standard solution (4.8) in triplicate, place in 250 ml beakers, dilute to 100 ml with water, add 5 ml of triethanolamine (4.3), 20 ml of potassium hydroxide solution (4.4), add an appropriate amount of CMP indicator (4.6), titrate with EDTA standard titration solution (4.9) to the end point when the green fluorescence of the test solution disappears (observe on a black background pad). Do a blank test at the same time. The range of the volume of EDTA consumed by the three calcium standard solutions should not exceed 0.10 ml, otherwise it should be recalibrated.

[0043] (c) Calculation: C=0.0100*25 / (V-V0) / 1000 Where: C----the concentration of EDTA standard titration solution, mol / L; V----the average value of the volume of EDTA standard titration solution consumed in titrating the three calcium standard solutions, ml; V0----the volume of EDTA standard titration solution consumed in the blank test, ml.

[0044] Five, instruments In the analysis, only the usual laboratory instruments and equipment are used. Unless otherwise specified, the volumetric flasks used should meet the requirements of GB / T12806, the graduated pipettes and single scale pipettes should meet the requirements of GB / T12807 and GB / T12808 respectively.

[0045] Six, sample preparation 6.1 Prepare the sample according to GB / T 22564.

[0046] 6.2 The sample should be ground to a particle size of less than 0.063 mm, dried at a temperature of 105 °C ± 5 °C for 2 h, and cooled to room temperature in a desiccator.

[0047] Seven, analysis procedure 7.1 Number of determinations At least two independent determinations should be made on the same sample (6.2).

[0048] 7.2 Sample mass Weigh 0.25 g of the sample to the nearest 0.0001 g.

[0049] 7.3 Blank test A blank test should be made with the sample.

[0050] 7.4 Analysis procedure 7.4.1 Determination of calcium carbonate content in the filtrate 7.4.1.1 Place the sample (7.2) in a 100 ml beaker, add 10 ml of acetic acid (4.1), cover with a watch glass, and let stand at room temperature for 30 min, shaking every 5 min.

[0051] 7.4.1.2 Filter with a rapid qualitative filter paper. Wash the beaker with water 3 times and wash the residue with water 3 times. Place the filtrate in a 500 ml conical flask and dilute with water to about 120 ml.

[0052] 7.4.1.3 Slowly add 10 ml of triethanolamine solution (4.3) to the resulting filtrate (7.4.1.2), add 20 ml of potassium hydroxide solution (4.4), add 0.1 g to 0.2 g of calcium indicator (4.7), and titrate with 0.02 mol / l EDTA standard titration solution (4.9) until the green color changes to blue.

[0053] 7.4.2 Correction of calcium carbonate content While the calcium carbonate is separated by leaching with dilute acetic acid, a small amount of calcium fluoride will also be dissolved. Moreover, the high content of calcium carbonate is not completely dissolved, and through actual measurement, the dissolution rate of high content calcium carbonate is 98%, and the dissolution amount of calcium fluoride is 0.15%.

[0054] Therefore, the mass percentage of calcium carbonate in the filtrate should be W = W / 0.98 - 0.15 7.4.3 Determination of magnesium content in the filtrate 7.4.3.1 The titrated calcium carbonate filtrate (7.4.1.3) is added to 25 ml of the hydrochloric acid (4.2) acidified solution, shaken, 10 ml of the pH 10 buffer (4.9) is added, and 0.1-0.2 g of the KB indicator (4.8) is added. Titration is carried out with the 0.02 mol / l EDTA standard solution until the pink color disappears and a blue color appears as the end point. The volume of the EDTA standard solution consumed is recorded, and a blank test is carried out.

[0055] 7.4.3.2 Determination of total calcium in the sample The sample is weighed at 0.1000 g, 0.42 g of boric acid (4.5) is added, 8 ml of hydrochloric acid (4.2) is added, a glass dish is placed on top, shaken, and placed on an electric hot plate at 180°C to boil for 10-15 min. The bottom is shaken from time to time. When no white precipitate is formed, the sample is boiled until it is almost dry (wet salt-like), the surface dish and the cup wall are rinsed with water, an appropriate amount of water is added to about 40 ml, and the water is added to 200 ml after cooling.

[0056] 7.4.3.3 Determination of total calcium The solution is slowly added with 10 ml of the triethanolamine solution (4.3), 20 ml of the potassium hydroxide solution (4.4) is added under constant stirring with a polytetrafluoroethylene stirring rod, 0.1-0.2 g of the CMP mixed indicator (4.6) is added, and titration is carried out with the 0.02 mol / l EDTA standard titration solution (4.9) until the green fluorescence of the test solution disappears (observed on a black background). The volume of the EDTA standard solution consumed is recorded.

[0057] 7.4.3.4 Determination of total magnesium The titrated total calcium filtrate (7.4.3.3) is added to 25 ml of the hydrochloric acid (4.2) acidified solution, shaken, 10 ml of the pH 10 buffer (4.9) is added, and 0.1-0.2 g of the KB indicator (4.8) is added. Titration is carried out with the 0.02 mol / l EDTA standard solution until the pink color disappears and a blue color appears as the end point. The volume of the EDTA standard solution consumed is recorded, and a blank test is carried out.

[0058] Eight Result calculation 8.1 Calculation of the mass fraction of calcium carbonate in the filtrate ωCaCO 3滤 = C x (V1-V 01 ) x 100.09*100 / M1 / 1000 / 0.98-0.15 In the formula: ωCaCO 3滤- --- the mass fraction of calcium carbonate in the filtrate, %; 100.09 --- the atomic mass of calcium carbonate, g / mol; C - concentration of EDTA standard titration solution, mol / L; V1 - volume of EDTA standard titration solution consumed for titration of calcium carbonate content in the filtrate, ml; V 01 - volume of EDTA standard titration solution consumed for blank test, ml; M1 - sample mass, 0.25 g; 0.98 - calcium carbonate dissolution amount; 0.15 - correction value for calcium fluoride content.

[0059] 8.2 Calculation of total calcium mass fraction in the sample ωCa total = C x (V2-V 02 ) x 40.08 * 100 / M1 / 1000 where: ωCa 总 - total calcium mass fraction in the sample, %; 40.08 - molar mass of calcium, g / mol; C - concentration of EDTA standard titration solution, mol / L; V2 - volume of EDTA standard titration solution consumed for titration of total calcium ions, mL; V 02 - volume of EDTA standard titration solution consumed for blank test, mL; M1 - sample mass, 0.1000 g.

[0060] 8.3 Calculation of magnesium mass fraction in the filtrate ωMg 液 = C x (V3-V 03 ) x 24.31 * 100 / M1 / 1000 where: ωMg 液 - magnesium mass fraction in the filtrate, %; 24.31 - molar mass of magnesium, g / mol; C - concentration of EDTA standard titration solution, mol / L; V3 - volume of EDTA standard solution consumed for titration of magnesium amount in the filtrate, mL; V 03 - volume of EDTA standard titration solution consumed for blank test, mL; M1 - sample mass, 0.2500 g.

[0061] 8.4 Total magnesium mass fraction in the sample ωMg 总 = C x (V4-V 04)24.31 - molar mass of magnesium, g / mol; wherein: ωMg 总 - mass fraction of total magnesium in the sample, %; 24.31 - molar mass of magnesium, g / mol; C - concentration of the EDTA standard titration solution, mol / L; V4 - volume of the EDTA standard solution consumed for titration of the magnesium amount in the sample, mL; V 04 - volume of the EDTA standard titration solution consumed in the blank test, mL; M1 - sample mass, 0.1000 g.

[0062] 8.5 Calculation of the final mass fraction of calcium fluoride in the sample

[0063] wherein: ωCaF2- mass fraction of the final calcium fluoride, %; 24.31 - molar mass of magnesium, g / moL; 40.08 - molar mass of calcium, g / mol; 78.08 - molar mass of calcium fluoride, g / mol; ωCa - mass fraction of total calcium in the sample, %; ωCaCO 3液 - mass fraction of calcium carbonate in the filtrate, %; ωMg 总 - mass fraction of total magnesium in the sample, %; ωMg 液 - mass fraction of magnesium in the filtrate, %; 100.09 - molar mass of calcium carbonate, g / mol; 0.15 - correction value for the calcium fluoride content.

[0064] 8.6 Calculation of the final mass fraction of calcium carbonate in the sample ωCaCO3= ωCaCO 3液 + (ωMg 总 - ωMg 液 )* 100 / 24.31 - 0.15 wherein: ωCaCO3- mass fraction of calcium carbonate in the sample, %; ωCaCO 3液 - mass fraction of calcium carbonate in the filtrate, %; ωMg 总 - mass fraction of total magnesium in the sample, %; ωMg 液 Mass fraction of magnesium in filtrate, % 100.09 - molar mass of calcium carbonate, g / mol 24.31 - molar mass of magnesium, g / mol 0.15 - correction value for calcium fluoride content.

[0065] While embodiments of the application have been shown and described, it is to be understood that the embodiments described are merely divergences of the principles and spirit of the application and that numerous modifications, changes, substitutions, and alterations can be made thereto without departing from the spirit and scope of the application as defined by the appended claims and their equivalents.

Claims

1. An apparatus for determining the calcium fluoride and carbonate content in dolomite-fluorite ore, comprising a measuring beaker (1) and a watch glass (2) covering the measuring beaker (1), characterized in that: A plug ring (3) is fixed to the bottom surface of the watch glass (2). The plug ring (3) is inserted into the cup mouth of the measuring beaker (1). A swing ball (4) is rotatably connected to the center of the surface of the watch glass (2). A stirring rod (403) is inserted into the surface of the swing ball (4). The stirring rod (403) extends into the measuring beaker (1). A protective frame (5) is fixed to the top surface of the watch glass (2). A plurality of partition plates (501) are fixed inside the protective frame (5) to divide into a plurality of storage spaces. A plurality of dispensing boxes (6) corresponding to the storage spaces one by one are fixed to the bottom surface of the watch glass (2). A traction screw rod (504) is screwed to the top surface of the protective frame (5). The traction screw rod (504) penetrates through the watch glass (2). A traction handle (7) is fixed to the bottom end of the traction screw rod (504). The traction handle (7) penetrates through the bottom plate of the dispensing box (6). Reagents for measurement are stored in the plurality of storage spaces respectively. After the traction screw rod (504) in the corresponding storage space is screwed upward to extract, the actual in the storage space falls into the dispensing box (6). At this time, the dispensing box (6) is blocked by the traction handle (7). After the traction screw rod (504) is screwed downward to block the watch glass (2), the traction handle (7) no longer blocks the bottom plate of the dispensing box (6), and the reagent in the dispensing box (6) falls into the measuring beaker (1).

2. The apparatus for determining the content of calcium fluoride and carbonate in dolomite-fluorite ore according to claim 1, characterized in that: A rubber clamping ring (301) is sleeved and fixed on the outer side of the plug ring (3). The rubber clamping ring (301) is clamped between the plug ring (3) and the inner wall of the measuring beaker (1) to generate elastic deformation. A silica gel sleeve (201) is sleeved and fixed at the outer ring of the watch glass (2). The silica gel sleeve (201) is a circular ring plate with a "匚" - shaped cross - section.

3. The apparatus for determining the calcium fluoride and carbonate content in dolomite-fluorite ore according to claim 1, characterized in that: A reserved port (202) is formed on the surface of the watch glass (2). Limiting rings (203) are provided on both the upper and lower sides of the reserved port (202). The two limiting rings (203) are respectively fixed to the top surface and the bottom surface of the watch glass (2). And the limiting rings (203) are in the shape of a stepped circular ring plate. The two limiting rings (203) limit the swing ball (4) in the reserved port (202). And a rubber clamping piece one (2031) is fixed to the inner ring surface of the limiting ring (203). The rubber clamping piece one (2031) is clamped between the swing ball (4) and the limiting ring (203) to generate elastic deformation.

4. The apparatus for determining the content of calcium fluoride and carbonate in dolomite-fluorite ore according to claim 1, characterized in that: A through - hole (401) is formed on the surface of the swing ball (4). The stirring rod (403) penetrates through the through - hole (401) and then extends into the measuring beaker (1). A rubber scraping ring (402) is fixed to the bottom end of the through - hole (401). The rubber scraping ring (402) is sleeved on the stirring rod (403). And a rubber clamping ring (404) is fixed inside the through - hole (401). The rubber clamping ring (404) is clamped between the through - hole (401) and the stirring rod (403) to generate elastic deformation.

5. The apparatus for determining the content of calcium fluoride and carbonate in dolomite-fluorite ore according to claim 1, characterized in that: The enclosure frame (5) is a circular ring frame with a "C"-shaped cross-section. Through holes two (502) corresponding to the storage spaces one by one are provided on the top surface of the enclosure frame (5). Through holes one (204) corresponding to the through holes two (502) one by one are provided on the surface of the watch glass (2). Threaded sleeves (503) corresponding to the through holes two (502) one by one are fixed on the top surface of the enclosure frame (5). The traction screw (504) is screwed with the threaded sleeve (503). An elastic plug ring one (5042) is sleeved and fixed at the bottom end of the traction screw (504). When the traction screw (504) drops to block the watch glass (2), the elastic plug ring one (5042) is inserted into the through hole one (204).

6. The apparatus for determining the content of calcium fluoride and carbonate in dolomite-fluorite ore according to claim 5, characterized in that: A pressure relief hole (5041) is provided on the surface of the traction screw (504). The pressure relief hole (5041) is a "C"-shaped hole.

7. The apparatus for determining the calcium fluoride and carbonate content in dolomite-fluorite ore according to claim 1, characterized in that: Through holes three (601) are provided on the bottom plate of the dispensing box (6). An elastic plug ring two (701) is sleeved and fixed on the rod body of the traction handle (7). After the bottom end of the traction screw (504) is inserted into the surface of the watch glass (2), the elastic plug ring two (701) is located below the dispensing box (6), and the through holes three (601) are exposed. After the traction screw (504) is separated from the surface of the watch glass (2), the elastic plug ring two (701) is inserted into the through holes three (601).

8. The apparatus for determining the calcium fluoride and carbonate content in dolomite-fluorite ore according to claim 1, characterized in that: A shielding cover (702) is sleeved and fixed on the rod body of the traction handle (7). The shielding cover (702) has a frustum-shaped ring plate structure.

9. A method for determining the calcium fluoride and carbonate content in dolomite-fluorite ore, using the apparatus described in any one of claims 1-8, characterized in that: The method includes the following steps: Specimen preparation: Prepare specimens according to the GB / T22564 standard, process the specimens to a particle size less than 0.063 mm, dry them at 105°C ± 5°C for 2 hours, and then place them in a dryer to cool to room temperature; Reagent preparation: Use analytical pure reagents and distilled water of grade three or above conforming to GB / T6682 or water with equivalent purity to prepare the following reagents: acetic acid of 1+9, hydrochloric acid of 1+1, triethanolamine of 1+2, potassium hydroxide solution of 200 g / L, boric acid, CMP mixed indicator, calcium indicator, KB indicator, buffer solution with a pH value of 10, calcium standard solution of 0.01000 mol / L, and EDTA standard titration solution of 0.0200 mol / L; Determination of calcium carbonate content in the filtrate: Weigh 0.25 g of the specimen, accurate to 0.0001 g, place it in a 100 ml measuring beaker (1), add 10 ml of acetic acid, place it at room temperature for 30 minutes, shake it once every 5 minutes, then filter it with a fast qualitative filter paper, and wash the measuring beaker (1) and the residue with water; Place the filtrate in a 500 ml conical flask, dilute it with water to about 120 ml, add triethanolamine, potassium hydroxide solution and calcium indicator, and titrate it with 0.02 mol / L EDTA standard titration solution until the color changes from light green to blue as the end point, and record the volume of the consumed EDTA standard titration solution; Correct the calcium carbonate content in the filtrate. The correction formula is: W = W' / 0.98 - 0.15, where W' is the measured mass percentage of calcium carbonate in the filtrate, 0.98 is the calcium carbonate dissolution rate, and 0.15 is the correction value for the dissolution amount of calcium fluoride; Determination of magnesium content in filtrate: Acidify the filtrate after titrating calcium carbonate with hydrochloric acid, then add pH 10 buffer and KB indicator, and titrate with 0.02 mol / L EDTA standard solution until the pink color disappears and turns blue as the endpoint. Record the volume of EDTA standard solution consumed. Determination of total calcium and total magnesium content in the sample: Weigh 0.1000 g of sample, add boric acid and hydrochloric acid, heat to boiling for 10-15 minutes, shaking occasionally during the process. After the sample is nearly dry, rinse with water and add an appropriate amount of water to cool. Add triethanolamine, potassium hydroxide solution and CMP mixed indicator to the solution, and titrate with 0.02 mol / L EDTA standard solution until the green fluorescence of the test solution disappears. Record the volume of EDTA standard solution consumed to determine the total calcium content. Add hydrochloric acid to the filtrate after titrating the total calcium, then add pH10 buffer and KB indicator. Titrate with 0.02 mol / L EDTA standard solution until the pink color disappears and turns blue as the endpoint. Record the volume of EDTA standard solution consumed to determine the total magnesium content. Results Calculation: Based on the measured data, the mass fractions of calcium carbonate in the filtrate, total calcium in the sample, magnesium in the filtrate, and total magnesium in the sample were calculated respectively. Finally, based on the mass fractions of total calcium, total magnesium, calcium carbonate in the filtrate, and magnesium in the filtrate, and combined with the correction formula, the final mass fractions of calcium fluoride and calcium carbonate in the sample were calculated. The calculation formulas are as follows: Calculation of the mass fraction of calcium carbonate in the filtrate: ωCaCO 3滤 =C×(V1-V 01 )×100.09*100 / M1 / 1000 / 0.98-0.15; Calculation of total calcium mass fraction in sample: ωCa 总 =C× (V2-V 02 ) X40.08*100 / M1 / 1000 ; Calculation of the mass fraction of magnesium in the filtrate: ωMg 液 =C×(V3-V 03 )×24.31*100 / M1 / 1000; Mass fraction of total magnesium in the sample: ωMg 总 =C×(V4-V 04) ×24.31*100 / M1 / 1000; Calculation of the final mass fraction of calcium fluoride in the sample: ； Calculation of the final calcium carbonate mass fraction in the sample: ωCaCO3=ωCaCO 3液 +(ωMg 总 -ωMg 液 )*100 / 24.31-0.15。

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