CN113979442A - Dissolution inhibiting method for purifying quartz from fluorine-containing solid waste - Google Patents
Dissolution inhibiting method for purifying quartz from fluorine-containing solid waste Download PDFInfo
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Abstract
The application relates to the technical field of purifying quartz by using fluorine-containing solid wastes, and particularly discloses a dissolution inhibiting method for purifying quartz by using fluorine-containing solid wastes, which comprises the following treatment steps: performing acid leaching on the minerals and the acid leaching solution at the temperature of 10-90 ℃, wherein the acid leaching time is 10-80min, and the solid-to-liquid ratio of the minerals to the acid leaching solution is 1kg (1-3) L; the acid leaching solution consists of a strong acid solution and a dissolution inhibitor, wherein the strong acid dissolves out fluorine-containing substances and calcium-containing substances in minerals but does not dissolve out silicon dioxide, and the coordination capacity of the dissolution inhibitor and fluorine is greater than that of fluorine and silicon. The mineral and the acid leaching solution react under specific conditions to enable the fluorine-containing substance and the calcium-containing substance to be dissolved out but not to dissolve silicon dioxide, the coordination capacity of the dissolution inhibitor and fluorine is greater than that of fluorine and silicon, and the generated hydrofluoric acid preferentially reacts with the dissolution inhibitor to break continuous chemical reaction of silicon dissolved out by the hydrofluoric acid and play a role in dissolution inhibition.
Description
The priority basis of the present application includes: application No. 2021111612834, application No. 2021, 9/30, entitled "method and apparatus for preparing quartz from secondary tungsten tailings".
Technical Field
The application relates to the technical field of purifying quartz by using fluorine-containing solid wastes, in particular to a dissolution inhibiting method for purifying quartz by using fluorine-containing solid wastes.
Background
At present, some minerals (such as tungsten ore, fluorite, calcite, cryolite, ilmenite and the like) and tailings thereof contain fluorine-containing substances, solid wastes such as wet-process smelting slag, smoke dust and flue gas sediment, waste water and waste acid sediment and the like also contain fluorine-containing substances, a certain amount of even a large amount of silicon dioxide and other substances, and in order to recycle the fluorine-containing solid wastes, the fluorine-containing solid wastes are usually purified to obtain high-purity quartz. The fluorine-containing substances (fluorite and fluorapatite) in the fluorine-containing solid waste basically react with strong acid to generate hydrofluoric acid (HF). Hydrofluoric acid can react with silica in quartz and aluminosilicate rock mineral (such as mica, feldspar, etc.) to produce fluosilicic acid; the chemical reaction equation is as follows:
6HF+SiO2＝H2SiF6+2H2O；4HF+SiO2＝SiF4+2H2O；
3SiF4+3H2O＝2H2SiF6+H2SiO3；SiF4+3H2O＝H2SiO3+4HF；
H2SiF6＝SiF4+2HF；H2SiO3＝Si2O·H2O↓；
in the process of purifying quartz from fluorine-containing solid wastes, the prepared minerals contain fluorine-containing substances, so that the fluorine-containing substances cannot be separated from quartz and silicon dioxide by a strong acid decomposition method or a strong acid selective acid leaching method. If the treatment is carried out by a strong acid decomposition method and a strong acid selective acid leaching method, the hydrofluoric acid which generates the intermediate product can also generate continuous chemical reaction with silicon dioxide, aluminum oxide and silicon dioxide in an aluminosilicate-containing substance to generate fluosilicic acid by knowing that the strong acid reacts with the fluorine-containing substance; the obtained solution contains fluosilicic acid and fluosilicate, so that high-purity quartz cannot be obtained, the treatment and recovery difficulty is increased by the contained fluosilicic acid and fluosilicate, and even the treatment and recovery cannot be carried out sometimes, and the enterprise cost is high. Therefore, the technical problem to be overcome is needed in the process of purifying quartz by using fluorine-containing solid waste, which is how to prevent hydrofluoric acid from dissolving silicon dioxide.
Disclosure of Invention
In order to effectively prevent the silicon dioxide from dissolving out and reduce the enterprise cost, the application provides a dissolution inhibiting method for purifying quartz by using fluorine-containing solid wastes.
The dissolution inhibiting method for purifying quartz by using fluorine-containing solid waste adopts the following technical scheme:
a dissolution inhibiting method for purifying quartz by using fluorine-containing solid waste comprises the following processing steps: performing acid leaching on the minerals and the acid leaching solution at the temperature of 30-90 ℃, wherein the acid leaching time is 20-80min, and the solid-to-liquid ratio of the minerals to the acid leaching solution is 1kg (1-3) L;
the acid leaching solution consists of a strong acid solution and a dissolution inhibitor, and the volume mass ratio of the strong acid solution to the dissolution inhibitor is 1L (25-200 g); the strong acid dissolves out the fluorine-containing substances and the calcium-containing substances in the minerals but does not dissolve out silicon dioxide, and the coordination capacity of the dissolution inhibitor and fluorine is larger than that of fluorine and silicon.
By adopting the technical scheme, the acid leaching solution can leach fluorine-containing substances and calcium-containing substances but not dissolve silicon dioxide, and because the coordination capacity of the dissolution inhibitor and fluorine is greater than that of fluorine and silicon, the generated intermediate product hydrofluoric acid preferentially reacts with the dissolution inhibitor to interrupt the continuous chemical reaction of silicon dissolved by hydrofluoric acid, so that the dissolution inhibitor plays a role in dissolution inhibition, and meanwhile, the generated product does not leach silicon dioxide.
The minerals and the acid leaching solution are placed in a specific temperature condition in a specific proportion and react for a certain time to enable the fluorine-containing substances and the calcium-containing substances to be dissolved out, the dissolution inhibitor interrupts the continuous chemical reaction of silicon dissolved out by hydrofluoric acid, and the dissolution of silicon dioxide is effectively prevented, so that the purified quartz has higher purity, and meanwhile, the production cost of enterprises is reduced.
Preferably, the dissolution inhibitor is boric acid or a borate.
By adopting the technical scheme, the selection of the dissolution inhibitor is optimized, and the coordination capacity of fluorine and boron is stronger than that of fluorine and silicon. When fluorine, boron and silicon exist in the reaction system, hydrofluoric acid reacts with boric acid or borate to generate fluoroboric acid and does not react with silicon dioxide, so that the dissolution inhibiting effect can be achieved.
Preferably, the strong acid solution is a hydrochloric acid solution or a nitric acid solution.
By adopting the technical scheme, the hydrochloric acid solution and the nitric acid solution are convenient for dissolving out fluorine-containing substances, calcium-containing substances and the like so as to be beneficial to separating the fluorine-containing substances from quartz and silicon dioxide, hydrofluoric acid and corresponding salt substances are generated by reaction, and the dissolution inhibitor can interrupt the hydrofluoric acid to dissolve out the silicon dioxide so as to be beneficial to the purified quartz to have higher purity.
Preferably, the strong acid solution is a hydrochloric acid solution, and the dissolution inhibitor is boric acid.
By adopting the technical scheme, the selection of the strong acid solution is optimized to reduce the production cost of enterprises, and because the nitric acid solution has high price and stronger corrosivity on equipment when reacting with fluorine-containing substances, the subsequent recycling process of the generated nitrate is more complicated, and the production cost of the enterprises is high, the hydrochloric acid is usually selected as the strong acid solution.
The selection of the dissolution inhibitor is optimized, the treatment and recovery costs of the product are considered together besides the dissolution inhibitor, and the boric acid is preferably used as the dissolution inhibitor because the borate is used as the dissolution inhibitor, new impurity ions are introduced, the subsequent recovery and reuse processes are more complicated, the equipment requirement is higher, and the production and equipment investment costs of enterprises are increased.
Preferably, the volume mass ratio of the hydrochloric acid solution to the boric acid is 1L (75-125) g.
By adopting the technical scheme, the dosage ratio of the hydrochloric acid solution to the boric acid is further optimized, the dissolution resistance of the acid leaching solution to minerals is further improved, the dissolution of silicon dioxide is reduced, and the purity of the purified quartz is improved.
Preferably, the concentration of hydrochloric acid is 3 to 6 mol/L.
By adopting the technical scheme, if the concentration of the hydrochloric acid is too high, the volatility is strong, the influence on the environment and the human body is certain, and the acid leaching reaction is also carried out at a certain temperature, so that the volatilization of the hydrochloric acid solution is promoted, the equipment loss is large, and the enterprise cost is high; if the concentration of the hydrochloric acid is too low, the fluorine-containing substances cannot be completely dissolved, so that the aim of extracting the purity of the quartz cannot be achieved, and meanwhile, the speed of dissolving the fluorine-containing substances is too low, the treatment time is long, so that the production cost of an enterprise is increased; the concentration of the hydrochloric acid solution is optimized, the dissolution inhibiting effect of the acid leaching solution on minerals is improved, and meanwhile, the production cost of enterprises is reduced.
Preferably, in the acid leaching step, the acid leaching temperature is 40-70 ℃.
By adopting the technical scheme, the acid leaching temperature is optimized, so that the boric acid is completely dissolved, the treatment effect of the acid leaching solution is improved, and the production cost is controlled. The solubility of boric acid at different temperatures in table 1 shows that the solubility of boric acid in 1L of aqueous solution is 115.4g at 50 ℃, while the solubility of solid boric acid added after optimization is 75-125g in 1L of acid leachate, and the dissolution of boric acid at different temperatures shows that boric acid in 1L of acid leachate can not be completely dissolved when the temperature is lower than 40 ℃; but the higher the temperature is, the production cost is increased, the volatility of the hydrochloric acid solution is increased, and the temperature is controlled to be 40-70 ℃ better for improving the treatment effect of the acid leaching solution and reducing the production cost of enterprises.
TABLE 1 solubility of boric acid at different temperatures
| Temperature/. degree.C | 20 | 30 | 40 | 50 | 60 | 70 | 80 | 90 |
| Dissolution rate g/%) | 5.04 | 6.72 | 8.72 | 11.54 | 14.81 | 18.62 | 23.63 | 30.38 |
Preferably, in the acid leaching step, the acid leaching time is 30-60 min.
By adopting the technical scheme, the reaction time of acid leaching is optimized so as to further control the leaching of fluorine-containing substances but not the silica, effectively prevent the silica from being leached by hydrofluoric acid and improve the purity of the purified quartz.
Preferably, in the acid leaching step, the solid-to-liquid ratio of the mineral to the acid leaching solution is 1kg (1-1.4) L.
By adopting the technical scheme, the solid-liquid ratio of the minerals and the acid leaching solution is further optimized so as to facilitate stirring in the reaction process, if the minerals are too much, the stirring difficulty is increased, the reaction is not facilitated to be effectively carried out, and if the acid leaching solution is too much, the amount of the minerals processed in a single batch is small, and the processing batches are increased, so that the processing cost of an enterprise is increased, therefore, the solid-liquid ratio is further optimized to 1kg (1-1.4) L to be better.
In summary, the present application has the following beneficial effects:
1. the acid leachate can dissolve the fluorine-containing substance and the calcium-containing substance but can not dissolve silicon dioxide, because the coordination capacity of fluorine and boron is stronger than that of fluorine and silicon. When fluorine, boron and silicon exist in a reaction system, hydrofluoric acid reacts with boric acid or borate to generate fluoroboric acid and does not react with silicon dioxide, so that continuous chemical reaction of dissolving silicon out of hydrofluoric acid is interrupted, and the effect of dissolution inhibition is achieved. The mineral and the acid leaching solution are placed in a specific temperature condition under a specific proportion and react for a certain time to enable the fluorine-containing substances and the calcium-containing substances in the mineral to be dissolved out but not to dissolve silicon dioxide, so that the purified quartz has higher purity.
2. The concentration of the hydrochloric acid solution, the acid leaching time, the acid leaching temperature and the solid-liquid ratio of the minerals to the acid leaching solution are further optimized, so that the leaching of fluorine-containing substances is further controlled, but the silicon dioxide is not leached, the silicon dioxide is effectively prevented from being leached by hydrofluoric acid, the purity of the purified quartz is improved, and the production cost of enterprises is reduced.
Detailed Description
The present application will be described in further detail with reference to examples.
Examples
Example 1
A dissolution inhibiting method for purifying quartz by using fluorine-containing solid waste comprises the following processing steps: 10kg of mineral and 10L of acid leaching solution are subjected to an acid leaching process under the conditions that the temperature is 30 ℃ and the stirring speed is 90 r/min, and the acid leaching time is 20 min. The acid leachate is prepared by mixing 3mol/L hydrochloric acid solution and boric acid according to the volume mass ratio of 1L:25g, and as the density of the 3-6mol/L hydrochloric acid solution is 1.02-1.1kg/L, for the convenience of calculation and representation, the density of the hydrochloric acid solution used in the application is equal to 1kg/L, namely the mass of the 1L hydrochloric acid solution is 1kg, and the acid leachate is prepared according to the above ratio, wherein the mass ratio of the boric acid to the hydrochloric acid solution is 0.025: 1, namely the mass ratio of the boric acid in the hydrochloric acid solution is 2.5%, and the boric acid ratio is hereinafter referred to as boric acid ratio.
In the acid leaching solution, boric acid is completely dissolved in hydrochloric acid solution under a certain temperature condition, and the volume change is negligible, so that the volume of the acid leaching solution used in the application is regarded as the volume of the hydrochloric acid solution, namely the solid-to-liquid ratio of minerals to the acid leaching solution is 1: 1;
the selected mineral is secondary tungsten tailings, and is waste tailings obtained by purifying fluorite and mica again after the tungsten tailings are ground again, so that most tailings are fine in size fraction due to the fact that the tailings are ground again, the tailings belong to micro-fine-size tailings, and the fluorite and the mica in a part of micro-fine-size fractions are intergrowths, monomer decomposition is not obtained, and quartz cannot be purified through a physical ore dressing mode. The analysis of the mineral phase in the secondary tungsten tailings is shown in table 2.
TABLE 2
Examples 2-17 differed from example 1 in the conditions, and the process conditions for examples 1-17 are shown in Table 3.
Table 3 process conditions for examples 1-17
| Solid-to-liquid ratio | Boric acid ratio/%) | Temperature/. degree.C | Time/min | Hydrochloric acid concentration mol/L | |
| Example 1 | 1:1 | 2.5 | 30 | 20 | 3 |
| Example 2 | 1:1.4 | 2.5 | 30 | 20 | 3 |
| Example 3 | 1:3 | 2.5 | 30 | 20 | 3 |
| Example 4 | 1:1 | 7.5 | 30 | 20 | 3 |
| Example 5 | 1:1 | 10 | 30 | 20 | 3 |
| Example 6 | 1:1 | 12.5 | 30 | 20 | 3 |
| Example 7 | 1:1 | 20 | 30 | 20 | 3 |
| Example 8 | 1:1 | 10 | 40 | 20 | 3 |
| Example 9 | 1:1 | 10 | 50 | 20 | 3 |
| Example 10 | 1:1 | 10 | 70 | 20 | 3 |
| Examples11 | 1:1 | 10 | 90 | 20 | 3 |
| Example 12 | 1:1 | 10 | 50 | 30 | 3 |
| Example 13 | 1:1 | 10 | 50 | 50 | 3 |
| Example 14 | 1:1 | 10 | 50 | 60 | 3 |
| Example 15 | 1:1 | 10 | 50 | 80 | 3 |
| Example 16 | 1:1 | 10 | 50 | 30 | 4 |
| Example 17 | 1:1 | 10 | 50 | 30 | 6 |
Example 18
The difference from example 16 is that the raw material secondary tungsten tailings were replaced with fluorite tailings, wherein the fluorite tailings comprise 95% of quartz, 3% of fluorite, 1% of feldspar and 1% of mica, and the rest is the same as example 16.
Example 19
The difference from example 16 is that hydrochloric acid was replaced with nitric acid, and the rest was the same as example 16.
Example 20
The difference from example 16 is that boric acid was replaced with sodium borate, and the rest was the same as example 16.
Comparative example
Comparative example 1
The difference from example 16 is that the acid leachate contained no boric acid, and the rest was the same as example 16.
Comparative example 2
The difference from the example 16 is that the solid-to-liquid ratio of the mineral to the acid leachate is 1: 0.5, the rest is the same as in example 16.
Comparative example 3
The difference from example 16 is that the acid leaching temperature is 5 ℃ and the acid reaction time is 20min, and the rest is the same as example 16.
Performance test
The mass before mineral acid leaching of examples 1 to 20 and comparative example 1 was recorded as M1, the mass after the acid leaching process was recorded as M2,% dissolution ═ M1-M2) × 100%/M1, the dissolution rate of the minerals was calculated, the content of silica in examples 1 to 20 and comparative examples 1 to 3 was measured according to JC/T1021-2007 "analytical methods for nonmetallic minerals and rock chemistry", and the results of the dissolution rate and the silica content of examples 1 to 20 were recorded in table 4 and the results of examples 16 and comparative examples 1 to 3 were recorded in table 5.
TABLE 4 results of the experiments of examples 1 to 20
TABLE 5 test results
| Example 16 | Comparative example 1 | Comparative example 2 | Comparative example 3 | |
| Dissolution rate/%) | 1.44 | 4.46 | 0.82 | 0.22 |
| SiO2％ | 99.17 | 95.16 | 98.30 | 97.90 |
As can be seen from examples 1 to 3 in combination with table 4, by adjusting the solid-to-liquid ratio between the mineral raw material and the acid leachate, the amount of the acid leachate is increased, the dissolution rate of the mineral is increased, but the purity of silica in the mineral is not significantly improved, because the content of boric acid is constant, when the acid leachate is large, the reaction is facilitated, but the amount of the mineral processed in a single batch is small, and the processing batch needs to be increased for processing the same amount of mineral, so that the processing cost of an enterprise is increased, and the processing cost for recovering and processing the waste acid leachate with the same amount of mineral is increased, so that the solid-to-liquid ratio between the mineral and the acid leachate is preferably 1: 1.
As can be seen from examples 1 and 4 to 7 in combination with table 4, when the concentration of boric acid is 7.5% to 12.5%, the dissolution rate is very small, and when the concentration of boric acid is greater than 12.5%, the dissolution rate is not substantially changed, and when the percentage of boric acid is adjusted to 7.5% to 12.5%, that is, the dosage ratio of the hydrochloric acid solution to boric acid is optimized, the dissolution rate of minerals can be in a required range, the dissolution resistance of acid leachate to minerals can be improved, the dissolution of silica can be reduced, and the quality of the prepared product can be improved, and when the percentage of boric acid is 10%, that is, the dosage ratio of hydrochloric acid solution to boric acid is 1L: more preferably 100 g.
As can be seen from examples 5 and examples 8 to 11 in combination with Table 4, the change of the dissolution rate from the purity of silica in the mineral was small at the acid leaching temperature of 40 to 70 ℃, the dissolution rate began to decrease at 70 ℃, the decrease of the dissolution rate was large at 90 ℃, and the purity of silica in the mineral was also decreased because the hydrochloric acid concentration was decreased due to the large volatilization of hydrochloric acid at higher temperature, resulting in a part of fluorite not being dissolved; the acid leaching temperature is adjusted to be 40-70 ℃, so that the complete dissolution of boric acid is facilitated, the complete dissolution time of fluorite is shortened, the treatment effect of acid leaching liquid is improved, and the production cost is controlled.
It can be seen from examples 9 and 12 to 15 in combination with tables 4 and 7 that if the leaching time is less than 30min, the dissolution rate decreases and the purity of silica in the mineral is also low because a part of fluorite is not dissolved, and if the acid leaching time is 30 to 60min, the dissolution rate and the purity of silica in the mineral are slightly changed, and the dissolution rate starts to increase after exceeding 60min, and if the leaching time is 80min, the dissolution rate becomes significantly higher in example 15, but the purity of silica in the mineral is hardly increased and even slightly decreased because too long, so that a small part of quartz is dissolved. Therefore, the acid leaching time is adjusted to be 30-60min so as to further control the dissolution of the fluorine-containing substances but not the dissolution of the silicon dioxide, and effectively prevent the silicon dioxide from being dissolved by hydrofluoric acid. Therefore, the acid leaching production cost can be reduced when the temperature is 40-70 ℃ and the time is 30-60min, and the reaction is better for 30min under the condition that the temperature is 50 ℃.
By combining the examples 12 and 16 to 17 with tables 4 and 7, it can be seen that the adjustment of the concentration of the hydrochloric acid solution not only improves the dissolution inhibiting effect of the acid leachate on minerals, but also reduces the production cost of enterprises; if the concentration of the hydrochloric acid is too high, although the time required for dissolving all fluorite is shortened to a certain extent, the purity of silicon dioxide in minerals is not obviously improved, and meanwhile, the hydrochloric acid has too high concentration and strong volatility and has certain influence on the environment and human bodies, and the acid leaching reaction also reacts at a certain temperature and has a promoting effect on the volatilization of the hydrochloric acid solution, so that the equipment loss is large, and the adverse factor of high enterprise cost exists; if the concentration of hydrochloric acid is too low, the fluorine-containing substance cannot be completely dissolved, and the purpose of improving the purity of quartz cannot be achieved, and at the same time, the speed of dissolving the fluorine-containing substance is too slow, the treatment time is long, and it is more preferable to use a hydrochloric acid solution having a concentration of 4 mol/L.
As can be seen from examples 16 and 18, the dissolution rate and silica content of the final product obtained by using different types of raw materials vary depending on the components of the raw materials. Example 19 replaced hydrochloric acid with nitric acid, and example 20 replaced boric acid with sodium borate, and the dissolution rate and silica content of the products obtained in examples 19 and 20 were substantially the same as those of example 16, but in the actual production process, the products of examples 19 and 20 were more complicated in the subsequent recycling process, and the cost of the enterprise was higher.
It can be seen from example 16 and comparative example 1 in combination with table 5 that the acid leachate of comparative example 1 does not contain boric acid, the dissolution rate of minerals is significantly increased, and hydrofluoric acid generated after the reaction of hydrochloric acid and fluorine-containing substances also reacts with quartz silica, so that the content of the prepared product silica is lower than that of the raw material, and the product silica cannot achieve the dissolution inhibiting effect and cannot achieve the purpose of purifying quartz.
As can be seen from example 16 and comparative example 2 in combination with table 5, in comparative example 2, the amount of minerals is too large, the amount of acid leachate is too small, and the solid-to-liquid ratio between the minerals and the acid leachate is unbalanced, so that not only can the impurities in the minerals be completely dissolved, but also the minerals are too large, which increases the difficulty of stirring, and is not beneficial to the effective reaction, so that the dissolution rate in the minerals is low, and the purity of the quartz is improved to a very small extent because the fluorite is contained in the obtained quartz product for complete dissolution, and the purification purpose desired by the present application cannot be achieved.
It can be seen from example 16 and comparative example 3 in combination with Table 5 that the acid leaching temperature in comparative example 3 is too low to facilitate the reaction, and the purity of the resultant quartz product is substantially unchanged from the purity of the mineral before acid leaching, and the intended purpose of dissolving impurities to purify the quartz cannot be achieved.
The secondary tungsten tailings of example 16 and the minerals obtained from the acid leaching process, and the fluorite tailings of example 18 and the minerals obtained from the acid leaching process were subjected to calcium fluoride detection and calcium fluoride dissolution rate calculation, respectively, to verify the dissolution of the fluorine-containing solid wastes after acid leaching, and the results are shown in table 6.
TABLE 6
From the above table, it can be known that the dissolution rate of fluorite in the secondary tungsten tailings after acid leaching reaches 99.74%, the dissolution rate of fluorite in the fluorite tailings after acid leaching reaches 99.66%, and all the fluorite can be considered to be completely dissolved within the related error range.
As most of fluorine-containing substances in the solid waste are calcium fluoride (fluorite), the content of the calcium fluoride in different solid wastes is different, and the related reaction of the calcium fluoride and acid leachate is as follows:
2HCl+CaF2＝CaCl2+2HF；4HF+H3BO3＝HBF4+3H2O；
as can be seen from the above reaction equation, the amount of the acid leachate is in direct proportion to the mass of the fluorine-containing substances in the solid to be acid-leached, and the amount of the acid leachate is increased when the content of the fluorine-containing substances in the solid to be acid-leached is increased. If the quality of the fluorine-containing substances in the acid leached solid is high, the measures are adopted; under the condition that the content of boric acid in the acid leaching solution is not changed and the concentration of hydrochloric acid is not changed, the solid-liquid ratio of the acid leaching solution is increased, namely the using amount of the acid leaching solution is increased; secondly, under the condition that the solid-to-liquid ratio of acid leaching is not changed, the concentration of hydrochloric acid and the content of boric acid in the acid leaching solution are increased. Comprehensively considering, when the solid-liquid ratio is unchanged and the ratio of boric acid is constant, the required time for dissolving all calcium fluoride is obtained through the changes of the acid leaching temperature, the reaction time and the concentration of hydrochloric acid.
To further investigate the time required for the total dissolution of different amounts of calcium fluoride in the above acid leaching process, the following experiments were performed.
Test of the time required for the complete dissolution of various amounts of calcium fluoride in fluorine-containing solid waste
The test steps are as follows: changing the mass of calcium fluoride under the process conditions that the concentration of hydrochloric acid is 3mol/L, 4mol/L and 6mol/L, the temperature is 40-70 ℃, the boric acid accounts for 10%, and the solid-liquid ratio is 1:1 (namely 1kg of fluorine-containing mineral and 1L of hydrochloric acid), wherein the mass of calcium fluoride is recorded as m1, the mass of mineral is recorded as m2, and the content of calcium fluoride is m1 x 100%/m 2; the test results of the above conditions are reported in table 7.
TABLE 7
As can be seen from table 7, under the condition of constant solid-to-liquid ratio and constant hydrochloric acid concentration, the time required for dissolving an equal amount of calcium fluoride is reduced with the increase of temperature, when the temperature reaches 70 ℃, the hydrochloric acid solution volatilizes faster, and when the content of calcium fluoride is 6%, the calcium fluoride can not be completely dissolved. When the temperature is 50 ℃, the hydrochloric acid concentration is increased, the time required for dissolving all calcium fluoride is shorter, the dissolved calcium fluoride has higher quality, but the hydrochloric acid concentration is higher, the volatility is stronger, the influence on the environment and the human body is caused, the corrosion on equipment is high, the requirements on the performance and the corrosion resistance of the equipment are higher, and the investment on production equipment and production cost is increased. In the process of purifying quartz from fluorine-containing solid wastes, the fluorine content in the fluorine-containing minerals after physical ore dressing is usually less than 1.5%, so that the acid leaching process is better under the condition that the solid-liquid ratio is 1:1, the temperature is 50 ℃, the hydrochloric acid concentration is 4mol/L and the calcium fluoride with the content of less than 3% in the fluorine-containing minerals can be completely dissolved in 30min of reaction by combining the consideration of the acid leaching temperature, the acid leaching time and the cost. When the content of calcium fluoride in the fluorine-containing mineral is more than 3 percent, the aim of completely dissolving the calcium fluoride can be achieved by increasing any one or more of the solid-to-liquid ratio, the temperature and the concentration of hydrochloric acid and boric acid.
In the continuous production of quartz purified from fluorine-containing solid waste, the solid waste is subjected to an acid leaching process, and the product after the reaction contains fluoboric acid, and the following experiment is carried out in order to verify that the obtained quartz is not dissolved by the fluoboric acid.
Experimental verification that fluoboric acid does not dissolve quartz
Selecting quartzite (sandy silicalite) mineral for carrying out related experiments, wherein the main impurities of the quartzite are aluminosilicate and carbonate rock mineral, the main impurities of the aluminosilicate mineral are feldspar and mica, the mica accounts for 3%, and SiO in the mica2About 45.2% of Al2O3About 38.5%, K2O accounts for about 11.8%, and further contains a small amount of Na, Ca, Mg, Ti, Cr, Mn, Fe, F, etc. A small amount of K is replaced by Na, Ca, Mg,Fe, etc. The main impurity of carbonate rock mineral is calcite (chemical formula is CaCO)3) And secondly dolomite (chemical formula CaCO)3·MgCO3)。
100kg of quartzite mineral (SiO)298.35 percent) under the conditions of 10 percent of boric acid, 50 ℃ of temperature, 30min of reaction time, 1:1 of solid-liquid ratio and 90 r/min of stirring speed, the quartzite mineral after the acid leaching operation is dissolved by 0.663kg, and the dissolution rate is 0.66 percent. The elemental content of the quartzite minerals before acid leaching, the elemental content of the quartzite minerals after acid leaching and the elemental content of the acid-leached liquid after acid leaching were measured according to JC/T1021-2007 method for chemical analysis of nonmetallic minerals and rocks, and the results are shown in Table 8.
TABLE 8
It is known that 0.663kg of mica is dissolved in 100kg of quartzite mineral after acid leaching operation, and the dissolution rate of mica is as follows, assuming that 0.663kg of mica is totally mica and quartz is not dissolved, the dissolved mica is: (0.663 kg/3.0 kg) × 100% ═ 22.1%, theoretically, the contents of silica, alumina, and potassium oxide in the acid-leached quartzite mineral were:
the difference from the actual test result of 98.76% was 0.04%.
The difference value between the actual detection result and 0.88 percent is 0.03 percent
The difference from the actual test result of 0.271% was 0.007%.
The contents of silicon dioxide, aluminum oxide and potassium oxide in the acid leaching solution after mineral acid leaching are respectively as follows;
the difference from the actual measurement result 2.984(g/L) was 0.013(g/L)
The difference from the actual detection result 2.549(g/L) was 0.004(g/L)
The difference from the actual measurement result of 0.598(g/L) is-0.184 (g/L), because a small amount of K in mica is replaced by Na, Ca, Mg, Fe, etc., and thus the actual measurement result is slightly lower than the theoretical content.
From the above calculations it can be seen that: the theoretical contents of silicon dioxide, aluminum oxide and potassium oxide in the quartzite mineral after acid leaching are basically consistent with the actual content of the detection result. And the contents of silicon dioxide, aluminum oxide and potassium oxide in the acid leaching solution after mineral acid leaching are basically consistent with the actual detection result. Therefore, the judgment can be made; what is actually dissolved by the fluoboric acid in the quartzite mineral is mica, not quartz (SiO)2) The quartz is not dissolved by the fluoroboric acid.
To further investigate whether the quartz with higher purity was dissolved, a quartz sample (silica content 99.99%, respectively) was prepared by mixing 500g of quartz sample at 90 ℃, 80min for reaction, 1: 3. the dissolution rate of quartz was measured in a sealed apparatus with varying concentration of fluoroboric acid under the condition of 4mol/L hydrochloric acid, and the results are shown in Table 9.
TABLE 9 dissolution of 99.9% quartz purity
As can be seen from the data in table 5,
the quartz with 99.99 percent of silicon dioxide content used in the test is not dissolved by the fluoroboric acid under the conditions of 90 ℃ of temperature, 80min of reaction time, 1.0:3.0 of solid-to-liquid ratio and 6 percent of fluoroboric acid concentration. After the fluoroboric acid concentration is greater than 6%, the quartz begins to be slowly dissolved by the fluoroboric acid, while the fluoroboric acid concentration produced under the conditions of the present application is less than 6%. Therefore, under the condition of most soluble, namely the temperature is 90 ℃, the reaction time is 80min, and the solid-to-liquid ratio is 1: 3; the quartz sample is not dissolved by the fluoboric acid, so the quartz product (especially the product with high silicon dioxide content) generated in the continuous purification production process of the quartz in a factory is not dissolved under the milder dissolution condition, and the high-purity quartz can be finally obtained.
The present embodiment is only for explaining the present application, and it is not limited to the present application, and those skilled in the art can make modifications of the present embodiment without inventive contribution as needed after reading the present specification, but all of them are protected by patent law within the scope of the claims of the present application.
Claims (9)
1. A dissolution inhibiting method for purifying quartz by using fluorine-containing solid waste is characterized by comprising the following processing steps: performing acid leaching on the minerals and the acid leaching solution at the temperature of 30-90 ℃, wherein the acid leaching time is 20-80min, and the solid-to-liquid ratio of the minerals to the acid leaching solution is 1kg (1-3) L;
the acid leaching solution consists of a strong acid solution and a dissolution inhibitor, and the volume mass ratio of the strong acid solution to the dissolution inhibitor is 1L (25-200 g); the strong acid dissolves out the fluorine-containing substances and the calcium-containing substances in the minerals but does not dissolve out silicon dioxide, and the coordination capacity of the dissolution inhibitor and fluorine is larger than that of fluorine and silicon.
2. The dissolution retarding method for purifying quartz from fluorine-containing solid waste according to claim 1, wherein: the dissolution inhibitor is boric acid or borate.
3. The dissolution retarding method for purifying quartz from fluorine-containing solid waste according to claim 2, wherein: the strong acid solution is hydrochloric acid solution or nitric acid solution.
4. The dissolution retarding method for purifying quartz from fluorine-containing solid wastes according to any one of claims 1 to 3, characterized in that: the strong acid solution is hydrochloric acid solution, and the dissolution inhibitor is boric acid.
5. The dissolution retarding method for purifying quartz from fluorine-containing solid waste according to claim 4, wherein: the volume mass ratio of the hydrochloric acid solution to the boric acid is 1L (75-125) g.
6. The dissolution retarding method for purifying quartz from fluorine-containing solid waste according to claim 4, wherein: the concentration of the hydrochloric acid is 3-6 mol/L.
7. The dissolution retarding method for purifying quartz from fluorine-containing solid waste according to claim 1, wherein: in the acid leaching process, the acid leaching temperature is 40-70 ℃.
8. The dissolution retarding method for purifying quartz by using fluorine-containing solid wastes as claimed in claim 1 or 7, wherein: in the acid leaching process, the acid leaching time is 30-60 min.
9. The dissolution retarding method for purifying quartz from fluorine-containing solid waste according to claim 1, wherein: in the acid leaching process, the solid-to-liquid ratio of the minerals to the acid leaching solution is 1kg (1-1.4) L.
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