Method for flotation separation of barite and quartz

Abstract

The invention relates to a barite and quartz flotation separation method, which belongs to the technical field of mineral flotation, and comprises the following steps: crushing, grinding and screening raw ore; the granules are made into ore pulp, the ore pulp is placed in an inflatable flotation machine, a regulator, an inhibitor and a collecting agent are sequentially added, barite rough concentrate is enriched at the bottom of a flotation tank of the inflatable flotation machine, and a foam layer of the flotation machine is quartz-rich tailings; and the barite rough concentrate is placed in an inflatable flotation machine to be subjected to direct flotation, an inhibitor and a collecting agent are sequentially added, and an upper-layer foam product of the inflatable flotation machine is barite concentrate. According to the method, one-time reverse flotation and one-time direct flotation are adopted, the technological process is shortened, loss of barite in the flotation process is reduced, and the recovery rate and purity of the obtained barite concentrate can both reach 91% or above.

Description

Technical Field

[0001] The invention relates to the technical field of mineral flotation, in particular to a method for flotation separation of barite and quartz. Background Art

[0002] Barite is widely used in the fields of oil and gas, chemical industry, papermaking and medical treatment due to its high specific gravity, stable chemical properties, acid and alkali resistance, non-toxicity, radiation absorption and other advantages. Among them, 80-90% of barite is used as a weighting agent in the oil and gas industry, and 7-8% of barite is used to produce BaCl 2 、BaCO 3 and Ba(OH) 2 Raw materials for barium compounds such as barium. For oil drilling, barite is required to have high specific gravity and low carbonate content. The production of barium salts places higher requirements on the content of trace impurities in barite. With the mining and utilization of barite for many years, the trend of ore quality deterioration has become more and more obvious. At present, the utilization of mineral resources has become a consensus among people. Guizhou Province has also proposed the strategy of "rich mines and fine mining" in promoting high-quality development of the industry, which has put forward high requirements for the quality improvement of barite and the classified utilization of associated resources.

[0003] As the most commonly used mineral processing technology, flotation can usually effectively process barite ores with low grade, complex distribution and turbid composition. At present, due to the similar surface characteristics of fluorite and barite, and the irreplaceable position of fluorite in fluorine chemical industry, most of the research on barite purification is devoted to the separation of barite and fluorite, while there are very few studies on the flotation separation of barite and gangue minerals such as quartz and calcite. The existing process of separating and flotating barite and quartz is lengthy and requires a large amount of reagents. It usually requires multiple concentrations to improve the purity of barite, but this often leads to a decrease in the yield of barite. Therefore, it is urgent to find a flotation method with high separation efficiency and simple process. Summary of the invention

[0004] The object of the present invention is to provide a method for flotation separation of barite and quartz, shorten the process flow, reduce production costs, reduce the loss of barite during flotation, and improve the recovery rate and purity of barite concentrate.

[0005] The present invention provides a method for flotation separation of barite and quartz, which adopts the following technical scheme:

[0006] A method for flotation separation of barite and quartz, characterized in that it comprises the following steps:

[0007] S1. Crushing and grinding: Take the raw ore and crush it until the particle size of the raw ore is less than 1 cm, then put it in a ball mill for grinding to obtain granular material;

[0008] S2, closed-circuit screening: placing the granular material obtained in step S1 in a vibrating screen, the sieve aperture of the vibrating screen is 0.074 mm, and obtaining granular material with a particle size less than or equal to 0.074 mm;

[0009] S3, reverse flotation desiliconization: the granular material obtained by the treatment in step S2 is made into slurry, the slurry is placed in an aerated flotation machine, and a regulator, an inhibitor and a collector are added in sequence, the barite coarse concentrate is enriched at the bottom of the flotation tank of the aerated flotation machine, and the foam layer of the flotation machine is a quartz-rich tailings;

[0010] S4, positive flotation enrichment: the barite coarse concentrate obtained in step S3 is placed in an aerated flotation machine for positive flotation, and an inhibitor and a collector are added in sequence. The upper foam product of the flotation machine is the barite concentrate.

[0011] Preferably, step S2 further includes collecting the granular materials that have not passed through the sieve holes of the vibrating screen and placing them in the ball mill in step S1 for ball milling until all the granular materials pass through the sieve holes of the vibrating screen, and mixing the granular materials that pass through the sieve holes of the vibrating screen evenly.

[0012] Preferably, the adjusting agent in step S3 includes HCl and NaOH;

[0013] The pH of the slurry in step S3 is 10.

[0014] Preferably, the inhibitor in step S3 comprises corn starch and / or aluminum sulfate.

[0015] Preferably, when the inhibitors corn starch and aluminum sulfate are used in step S3, corn starch is added first, and then aluminum sulfate is added;

[0016] The dosage of corn starch is 1300-1600g / t, and the dosage of aluminum sulfate is 300-500g / t.

[0017] Preferably, in the process of adding corn starch in step S3, corn starch, NaOH, and water are mixed separately, heated to 80° C. and magnetically stirred until the solution is transparent, and then immediately added to the ore slurry;

[0018] The mass ratio of corn starch to NaOH is 4:1.

[0019] Preferably, the inhibitor in step S4 includes Na 2 SiO 3 ;

[0020] Na 2 SiO 3 The dosage is 800g / t, Na 2 SiO 3 The modulus is 2.

[0021] Preferably, the collector in step S3 and step S4 is dodecylamine;

[0022] The amount of dodecylamine used in step S3 is 240 g / t, and the amount of dodecylamine used in step S4 is 120 g / t.

[0023] Preferably, after adding dodecylamine in step S3, glacial acetic acid is also added in an amount having the same molar number as the dodecylamine in step S3;

[0024] In step S4, after adding dodecylamine, glacial acetic acid is added in the same mole number as that of dodecylamine in step S4.

[0025] Preferably, the rotation speed of the air-filled flotation machine in step S3 and step S4 is 1800 r / min, and the air flow rate is 0.05 ml / h.

[0026] In summary, the present invention includes the following beneficial technical effects:

[0027] 1. In this application, the barite concentrate in the raw ore is selectively separated through one reverse flotation and one forward flotation, which shortens the process flow, reduces the production cost, and reduces the serious loss of barite concentrate during the flotation process. The recovery rate and purity of the obtained barite concentrate can reach more than 91%.

[0028] 2. In this application, corn starch and aluminum sulfate are used as inhibitors of barite in reverse flotation. Under the synergistic effect of the mixed inhibitor, the inhibitory effect is stronger than that of a single inhibitor. Aluminum sulfate can complex with the hydroxyl groups in corn starch to enhance the stability of starch molecules. Corn starch and aluminum sulfate can improve the hydrophilicity of barite. SO 4 2- 、Al(OH) 4 - Plasma forms a complex with corn starch, which can form a dense and uniform adsorption layer on the surface of barite, thereby enhancing its inhibitory effect on barite and hindering the subsequent adsorption of dodecylamine on the surface of barite.

[0029] 3. In this application, corn starch, NaOH, and water were mixed separately, heated to 80°C and magnetically stirred until the solution was transparent, and then immediately added to the slurry to increase the solubility of corn starch. BRIEF DESCRIPTION OF THE DRAWINGS

[0030] Figure 1 This is a process flow chart of a method for flotation separation of barite and quartz in the present application. DETAILED DESCRIPTION

[0031] The present invention is further described in detail below in conjunction with the accompanying drawings and embodiments.

[0032] Example

[0033] Example 1

[0034] Reference Figure 1 , a method for flotation separation of barite and quartz, comprising the following steps:

[0035] 1) Take the raw ore and crush it. The barite content of the raw ore is 66.48%, the quartz content is 28.83%, and the content of other impurity minerals is 4.69%. The impurity minerals are mainly mica, gibbsite, and magnetite; crush the raw ore until the particle size is less than 1 cm, and then place it in a ball mill for grinding to obtain granular material, and place the granular material in a vibrating screen. The aperture of the vibrating screen is 0.074 mm, so as to obtain granular material with a particle size less than or equal to 0.074 mm; collect the granular material that does not pass through the sieve hole of the vibrating screen, and re-place it in the ball mill for ball milling until all the granular material passes through the sieve hole of the vibrating screen, and mix the granular material that passes through the sieve hole of the vibrating screen evenly;

[0036] 2) Mix the granular material obtained in step 1) with water to prepare a pulp, wherein the mass concentration of the pulp is 20%, place the pulp in an aerated flotation machine, add HCl and NaOH to make the pH of the pulp 10, then mix corn starch and NaOH in water to obtain a mixed solution, heat to 80° C. and stir magnetically until the mixed solution is transparent, and immediately add the mixed solution to the pulp, wherein the amount of corn starch is 1600 g / t, and the mass ratio of corn starch to NaOH is 4:1. , add enough water to make the solution transparent; then add aluminum sulfate, the amount of aluminum sulfate is 400g / t; finally add dodecylamine and glacial acetic acid, the amount of dodecylamine is 240g / t, and the molar number of glacial acetic acid is the same as the molar number of dodecylamine; start the aerated flotation machine, set the speed of the aerated flotation machine to 1800r / min, the aeration flow rate to 0.05ml / h, the barite coarse concentrate is enriched at the bottom of the flotation tank of the aerated flotation machine, and the foam layer of the flotation machine is quartz-rich tailings;

[0037] 3) Place the barite concentrate obtained in step 2) in an aerated flotation machine and add Na 2 SiO 3 , where Na 2 SiO 3 The dosage is 800g / t, Na 2 SiO 3 The modulus is 2, and then dodecylamine and glacial acetic acid are added. The amount of dodecylamine is 120g / t, and the molar number of glacial acetic acid is the same as the molar number of dodecylamine. Start the aerated flotation machine, set the speed of the aerated flotation machine to 1800r / min, the aeration flow rate to 0.05ml / h, and the upper foam product of the aerated flotation machine is barite concentrate.

[0038] The purity of the barite concentrate prepared in Example 1 was detected to be 92.83%, and the barite recovery rate was 91.12%.

[0039] Example 2

[0040] A method for flotation separation of barite and quartz, which is different from Example 1 in that 1300 g / t of corn starch and 500 g / t of aluminum sulfate are added, and the remaining steps are the same as those in Example 1.

[0041] The purity of the barite concentrate obtained in Example 2 was detected to be 90.26%, and the barite recovery rate was 89.19%.

[0042] Example 3

[0043] A method for flotation separation of barite and quartz, which is different from Example 1 in that aluminum sulfate is not added, and the remaining steps are the same as those in Example 1.

[0044] The purity of the barite concentrate obtained in Example 3 was detected to be 88.75%, and the barite recovery rate was 87.96%.

[0045] Example 4

[0046] A method for flotation separation of barite and quartz, which is different from Example 1 in that corn starch is not added, and the remaining steps are the same as those in Example 1.

[0047] The purity of the barite concentrate prepared in Example 4 was detected to be 87.35%, and the barite recovery rate was 85.67%.

[0048] Comparative Example

[0049] Comparative Example 1

[0050] A method for flotation separation of barite and quartz, which is different from Example 1 in that step 3) in Example 1 is not included, and the remaining steps are the same as those in Example 1.

[0051] Comparative Example 2

[0052] A method for flotation separation of barite and quartz, which is different from Comparative Example 1 in that the amount of aluminum sulfate used is 380 g / t, and the remaining steps are the same as those of Comparative Example 1.

[0053] Comparative Example 3

[0054] A method for flotation separation of barite and quartz, which is different from Comparative Example 1 in that the amount of aluminum sulfate used is 420 g / t, and the remaining steps are the same as those of Comparative Example 1.

[0055] Comparative Example 4

[0056] A method for flotation separation of barite and quartz, which is different from Comparative Example 1 in that the amount of aluminum sulfate used is 440 g / t, and the remaining steps are the same as those of Comparative Example 1.

[0057] Comparative Example 5

[0058] A method for flotation separation of barite and quartz, which is different from Comparative Example 1 in that the amount of aluminum sulfate used is 460 g / t, and the remaining steps are the same as those of Comparative Example 1.

[0059] Comparative Example 6

[0060] A method for flotation separation of barite and quartz, which is different from Comparative Example 1 in that aluminum sulfate is not added, and the remaining steps are the same as those of Comparative Example 1.

[0061] Comparative Example 7

[0062] A method for flotation separation of barite and quartz, which is different from Comparative Example 6 in that the amount of corn starch added is 1300 g / t, and the remaining steps are the same as those of Comparative Example 6.

[0063] Comparative Example 8

[0064] A method for flotation separation of barite and quartz, which is different from Comparative Example 6 in that the amount of corn starch added is 1400 g / t, and the remaining steps are the same as those of Comparative Example 6.

[0065] Comparative Example 9

[0066] A method for flotation separation of barite and quartz, which is different from Comparative Example 6 in that the amount of corn starch added is 1500 g / t, and the remaining steps are the same as those of Comparative Example 6.

[0067] Comparative Example 10

[0068] A method for flotation separation of barite and quartz, which is different from Comparative Example 6 in that the amount of corn starch added is 1700 g / t, and the remaining steps are the same as those of Comparative Example 6.

[0069] Comparative Example 11

[0070] A method for flotation separation of barite and quartz, which is different from Comparative Example 6 in that the pH of the slurry is 2.5, and the remaining steps are the same as those of Comparative Example 6.

[0071] Comparative Example 12

[0072] A method for flotation separation of barite and quartz, which is different from Comparative Example 6 in that the pH of the slurry is 5, and the remaining steps are the same as those of Comparative Example 6.

[0073] Comparative Example 13

[0074] A method for flotation separation of barite and quartz, which is different from Comparative Example 6 in that the pH of the slurry is 7.5, and the remaining steps are the same as those of Comparative Example 6.

[0075] Comparative Example 14

[0076] A method for flotation separation of barite and quartz, which is different from Comparative Example 6 in that the pH of the slurry is 12.5, and the remaining steps are the same as those of Comparative Example 6.

[0077] Comparative Example 15

[0078] A method for flotation separation of barite and quartz, which is different from Comparative Example 11 in that, in the process of adding the inhibitor in step 2), corn starch is directly added to the slurry without mixing the corn starch and NaOH, and the remaining steps are the same as Comparative Example 11.

[0079] Comparative Example 16

[0080] A method for flotation separation of barite and quartz, which is different from Comparative Example 11 in that glacial acetic acid is not added during the process of adding a collector in step 2), and glacial acetic acid is not added during the process of adding a collector in step 3), and the remaining steps are the same as Comparative Example 11.

[0081] Test results

[0082] The barite ores prepared in Comparative Examples 1-16 were tested respectively to test the purity of the barite rough concentrate and the barite recovery rate in reverse flotation. The test results are shown in Table 1.

[0083] Table 1 is the test results of Comparative Examples 1-11 and Comparative Examples 1-6

[0084]

[0085] According to Table 1 and in combination with the test results of Example 1 and Comparative Example 1, it can be seen that the present application adopts a process of one reverse flotation and one forward flotation, firstly enriches the barite at the bottom of the flotation tank, and then captures it into the foam layer by forward flotation to obtain a barite concentrate with a purity and a recovery rate of 92.83% and 91.12%, respectively. The purity of the barite rough concentrate and the recovery rate of barite in Example 1 are better than the test results of Comparative Example 1 using only one reverse flotation process.

[0086] According to Table 1 and the test results of Examples 1-4, it can be seen that the present application uses a combination of corn starch and aluminum sulfate to inhibit barite, and its separation effect is enhanced compared with that of a single corn starch as an inhibitor. When the aluminum sulfate dosage is 400 g / t, it can show a relatively good barite crude concentrate purity and barite recovery rate. This shows that the addition of aluminum sulfate can enhance the inhibitory effect of corn starch on barite. On the one hand, SO generated by the hydrolysis and ionization of aluminum sulfate 42- Ba on the barite surface 2+ The reaction generates the stable phase BaSO 4 On the other hand, aluminum sulfate and corn starch interacted with each other to form a cross-linked structure, which improved the stability and adhesion of the mixed inhibitor.

[0087] According to Table 1 and in combination with the test results of Examples 7-11 and Comparative Examples 1-6, it can be seen that as the amount of corn starch increases, the barite grade and recovery first increase and then decrease, reaching a threshold value when the amount of corn starch is 1600g / t. The active groups such as -OH and -O- in corn starch are mainly adsorbed on the surface of barite through hydrogen bonding. As the amount of corn starch increases, the molecular weight increases and the active groups increase, causing the adsorption to be stronger, and the hydrophobicity of the barite surface also decreases, and the purity and recovery rate are improved. When the corn starch concentration is increased to 1700g / t, the purity of the barite rough concentrate decreases, because the corn starch is in excess in the solution, and the target minerals and non-target minerals are indiscriminately suppressed. This shows that the single inhibitor corn starch has an inhibitory effect on barite, but the selectivity is not strong enough.

[0088] According to Table 1 and the test results of Comparative Examples 6 and 7-14, it can be seen that in the pH range of 2.5-12.5, when corn starch is used as a single inhibitor, the grade and recovery rate of barite increase first and then decrease with the increase of pH value, indicating that the flotation of barite in a neutral or weak alkaline environment is more favorable than that in a strong acid or strong alkaline environment. Under acidic conditions, the main active component of DDA is RNH 3 + It has a strong adsorption capacity on the negatively charged surface of barite, which causes the barite to be floated to the foam layer in an acidic environment, and the recovery rate is reduced.

[0089] According to Table 1 and the test results of Comparative Examples 11-16, it can be seen that the solubility of corn starch and dodecylamine has a great influence on the purity and recovery rate of barite. Since corn starch not treated with NaOH and dodecylamine not treated with glacial acetic acid are insoluble in water, their active sites and reactive groups are difficult to be exposed in the slurry, making the separation of barite and quartz difficult.

[0090] The above are all preferred embodiments of the present invention, and are not intended to limit the protection scope of the present invention. Therefore, any equivalent changes made based on the structure, shape, and principle of the present invention should be included in the protection scope of the present invention.

Claims

1. A method for flotation separation of barite and quartz, characterized in that: The following steps are involved: S1. Crushing and grinding: Take the raw ore and crush it until the particle size of the raw ore is less than 1 cm, then put it in a ball mill for grinding to obtain granular material; S2, closed-circuit screening: placing the granular material obtained in step S1 in a vibrating screen, the sieve aperture of the vibrating screen is 0.074 mm, and obtaining granular material with a particle size less than or equal to 0.074 mm; S3, reverse flotation desiliconization: the granular material obtained by the treatment in step S2 is made into slurry, the slurry is placed in an aerated flotation machine, and a regulator, an inhibitor and a collector are added in sequence, the barite coarse concentrate is enriched at the bottom of the flotation tank of the aerated flotation machine, and the foam layer of the flotation machine is a quartz-rich tailings; S4, positive flotation enrichment: the barite rough concentrate obtained in step S3 is placed in an aerated flotation machine for positive flotation, and an inhibitor and a collector are added in sequence. The upper foam product of the aerated flotation machine is the barite concentrate.

2. A method for flotation separation of barite and quartz according to claim 1, characterized in that: The step S2 also includes collecting the granular materials that have not passed through the sieve holes of the vibrating screen and placing them in the ball mill in step S1 for ball milling until all the granular materials pass through the sieve holes of the vibrating screen, and mixing the granular materials that pass through the sieve holes of the vibrating screen uniformly.

3. A method for flotation separation of barite and quartz according to claim 1, characterized in that: The adjusting agent in step S3 includes HCl and NaOH; The pH of the slurry in step S3 is 10.

4. A method for flotation separation of barite and quartz according to claim 1, characterized in that: The inhibitor in step S3 includes corn starch and / or aluminum sulfate.

5. A method for flotation separation of barite and quartz according to claim 4, characterized in that: When the inhibitor in step S3 is corn starch and aluminum sulfate, corn starch is added first, and then aluminum sulfate is added; The dosage of corn starch is 1300-1600g / t, and the dosage of aluminum sulfate is 300-500g / t.

6. A method for flotation separation of barite and quartz according to claim 5, characterized in that: In the process of adding corn starch in step S3, corn starch, NaOH and water are mixed to obtain a mixed solution, which is heated to 80° C. and magnetically stirred until the mixed solution is transparent, and then the mixed solution is immediately added to the ore pulp; The mass ratio of corn starch to NaOH is 4:

1.

7. The method for flotation separation of barite and quartz according to claim 1, characterized in that: The inhibitor in step S4 includes Na2SiO3; The dosage of Na2SiO3 is 800g / t, and the modulus of Na2SiO3 is 2.

8. The method for flotation separation of barite and quartz according to claim 1, characterized in that: The collector in step S3 and step S4 is dodecylamine; The amount of dodecylamine used in step S3 is 240 g / t, and the amount of dodecylamine used in step S4 is 120 g / t.

9. A method for flotation separation of barite and quartz according to claim 8, characterized in that: After adding dodecylamine in step S3, glacial acetic acid is added in an amount having the same molar number as that of dodecylamine in step S3; In step S4, after adding dodecylamine, glacial acetic acid is added in the same mole number as that of dodecylamine in step S4.

10. The method for flotation separation of barite and quartz according to claim 1, characterized in that: The rotation speed of the air-filled flotation machine in step S3 and step S4 is 1800 r / min, and the air flow rate is 0.05 ml / h.

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