Medicament for removing impurities from barite crude product through reverse flotation

Abstract

The invention provides an agent for removing impurities from barite crude products through reverse flotation, and belongs to the technical field of mineral separation. The medicament for removing the impurities from the barite crude product through the reverse flotation comprises an inhibitor, an activating agent and a collecting agent, the inhibitor is prepared from the following components in parts by mass: 20 to 35 parts of methyl thymol blue tetrasodium salt and 65 to 80 parts of 4-(2-pyridylazo)-resorcinol, the activating agent comprises the following components in parts by mass: 80-95 parts of aluminum potassium sulfate and 5-20 parts of scandium nitrate; the collecting agent is prepared from the following components in parts by mass: 1 to 5 parts of 8-hydroxyquinoline, 15 to 35 parts of alkyl substituted butanediamine, 20 to 40 parts of alkanoyl methylaminoacetic acid and 20 to 55 parts of alkyl sodium sulfonate. According to the method, efficient removal of fluorite, calcite and other impurities is achieved through the synergistic effect of the inhibitor, the activating agent and the collecting agent.

Description

Technical Field

[0001] The invention relates to the technical field of ore dressing, and in particular to a reagent for removing impurities from a crude barite product by reverse flotation. Background Art

[0002] Barite is a strategic non-metallic raw material mineral with the advantages of high density, poor solubility in water, non-toxicity, easy absorption of radiation, good filling properties, etc. It is widely used in the fields of petroleum, chemical industry, filler, medicine and military. Due to the scarcity of resources and their irreplaceability, the mining of barite is particularly important. However, with the large-scale mining over the years, the high-quality barite resources have been seriously over-consumed.

[0003] Since barite is often associated with calcium-containing resources such as fluorite and calcite, flotation technology has become the main process for producing high-quality barite concentrate. However, there are currently the following deficiencies in the flotation purification of barite:

[0004] (1) Collectors are generally made of oleic acid, oxidized paraffin soap and other ingredients. Such agents are widely available and low in cost, but have low selectivity for barite, fluorite and calcite. Especially when flotation separation of fine-grained minerals is performed, the selectivity of the agent deteriorates sharply. Therefore, the content of fluorite and calcite in barite concentrate is often seriously exceeded. In addition, this type of collector needs to heat the slurry in industrial applications to achieve a better effect, which greatly increases the production cost of the enterprise.

[0005] (2) Water glass is generally used as an inhibitor for gangue minerals such as calcite and fluorite in the flotation process, but the inhibitory effect of water glass is limited, causing some impurity minerals to still enter the concentrate product. In addition, the addition of water glass makes it difficult for the tailings to settle, and a large amount of tailings are suspended in the tailings pond. The tailings return water cannot be used, which not only wastes a lot of water resources but also poses a major safety hazard to the tailings pond. Summary of the invention

[0006] In view of this, an object of the present invention is to provide a reagent for removing impurities from a crude barite product by reverse flotation.

[0007] In order to achieve the above object, the present invention provides the following technical solutions:

[0008] One of the technical solutions of the present invention is a reagent for removing impurities from a crude barite product by reverse flotation, comprising an inhibitor, an activator and a collector;

[0009] The inhibitor comprises the following components in parts by mass: 20-35 parts of methylthymol blue tetrasodium salt and 65-80 parts of 4-(2-pyridyl azo)-resorcinol;

[0010] The activator comprises the following components in parts by mass: 80-95 parts of potassium aluminum sulfate and 5-20 parts of scandium nitrate;

[0011] The collector comprises the following components in parts by mass: 1-5 parts of 8-hydroxyquinoline, 15-35 parts of alkyl-substituted butanediamine, 20-40 parts of alkanoylmethylaminoacetic acid, and 20-55 parts of sodium alkyl sulfonate.

[0012] The second technical solution of the present invention is a method for removing fluorite and calcite from a crude barite product by reverse flotation, comprising the following steps:

[0013] The crude barite product is mixed with the inhibitor described in the above technical solution and then ground to obtain a grinding product, and the grinding product is prepared into a pulp and then flotation is performed;

[0014] The flotation is carried out using the activator and collector described in the above technical solution.

[0015] The present invention discloses the following technical effects:

[0016] The inhibitor in the present invention can greatly increase the hydrophilicity of barite, reduce the amount of barite entering the foam product with fluorite and calcite during flotation, and thus improve the recovery rate of barite; the inhibitor also has a strong inhibitory effect on some fluorite minerals, but the Sc in the activator 3+ The presence of Ca on the surface of fluorite and calcite 2+ It can form a multi-component complex with 8-hydroxyquinoline in the collector, thereby increasing the hydrophobicity of the surface of fluorite and calcite minerals, creating favorable conditions for flotation separation; the synergy between the four substances in the collector can achieve a good removal effect on impurity minerals such as fluorite, calcite, silicate, iron oxide, aluminum oxide, etc. in the crude barite product. DETAILED DESCRIPTION

[0017] Various exemplary embodiments of the present invention will now be described in detail. This detailed description should not be considered as limiting the present invention, but should be understood as a more detailed description of certain aspects, features, and embodiments of the present invention.

[0018] It should be understood that the terms described in the present invention are only for describing a particular embodiment and are not intended to limit the present invention. In addition, for the numerical range in the present invention, it should be understood that each intermediate value between the upper and lower limits of the scope is also specifically disclosed. The intermediate value in any stated value or stated range, and each smaller range between any other stated value or intermediate value in the described range is also included in the present invention. The upper and lower limits of these smaller ranges can be independently included or excluded in the scope.

[0019] Unless otherwise indicated, all technical and scientific terms used herein have the same meanings as those generally understood by those skilled in the art. Although the present invention describes only preferred methods and materials, any methods and materials similar or equivalent to those described herein may also be used in the implementation or testing of the present invention. All documents mentioned in this specification are incorporated by reference to disclose and describe the methods and / or materials associated with the documents. In the event of a conflict with any incorporated document, the content of this specification shall prevail.

[0020] It will be apparent to those skilled in the art that various modifications and variations may be made to the specific embodiments of the present invention description without departing from the scope or spirit of the present invention. Other embodiments derived from the present invention description will be apparent to the skilled artisan. The present invention description and examples are exemplary only.

[0021] The words “include,” “including,” “have,” “contain,” etc. used in this document are open-ended terms, meaning including but not limited to.

[0022] One of the technical solutions of the present invention is a reagent for removing impurities from a crude barite product by reverse flotation, comprising an inhibitor, an activator and a collector;

[0023] The inhibitor comprises the following components in parts by mass: 20-35 parts of methylthymol blue tetrasodium salt and 65-80 parts of 4-(2-pyridyl azo)-resorcinol;

[0024] The activator comprises the following components in parts by mass: 80-95 parts of potassium aluminum sulfate and 5-20 parts of scandium nitrate;

[0025] The collector comprises the following components in parts by mass: 1-5 parts of 8-hydroxyquinoline, 15-35 parts of alkyl-substituted butanediamine, 20-40 parts of alkanoylmethylaminoacetic acid, and 20-55 parts of sodium alkyl sulfonate.

[0026] In some embodiments of the present invention, the reagent used for reverse flotation to remove impurities from the crude barite product consists of an inhibitor, an activator and a collector;

[0027] The inhibitor is composed of the following components in parts by mass: 20-35 parts of methylthymol blue tetrasodium salt and 65-80 parts of 4-(2-pyridyl azo)-resorcinol;

[0028] The structural formula of the methylthymol blue tetrasodium salt is:

[0029]

[0030] The structural formula of the 4-(2-pyridyl azo)-resorcinol is:

[0031]

[0032] The activator is composed of the following components in parts by mass: 80-95 parts of potassium aluminum sulfate and 5-20 parts of scandium nitrate;

[0033] The collector is composed of the following components in parts by mass: 1-5 parts of 8-hydroxyquinoline, 15-35 parts of alkyl-substituted butanediamine, 20-40 parts of alkanoylmethylaminoacetic acid and 20-55 parts of sodium alkyl sulfonate.

[0034] In some embodiments of the present invention, the structural formula of the alkyl-substituted butanediamine is:

[0035]

[0036] In the formula, R=C10-C14 saturated or unsaturated alkyl; preferably, the alkyl-substituted butanediamine is N-dodecyl-1,4-butanediamine.

[0037] In some embodiments of the present invention, the structural formula of the alkanoylmethylaminoacetic acid is:

[0038]

[0039] In the formula, R2=C17-C20 saturated or unsaturated alkyl; preferably, the alkanoylmethylaminoacetic acid is oleoylmethylaminoacetic acid, and the structural formula is:

[0040]

[0041] In some embodiments of the present invention, the structural formula of the sodium alkyl sulfonate is:

[0042]

[0043] In the formula, Y=C12-C18 saturated or unsaturated alkyl, preferably, the sodium alkyl sulfonate is sodium dodecyl sulfonate.

[0044] The second technical solution of the present invention is a method for removing fluorite and calcite from a crude barite product by reverse flotation, comprising the following steps:

[0045] The crude barite product is mixed with the inhibitor described in the above technical solution and then ground to obtain a grinding product, and the grinding product is prepared into a pulp and then flotation is performed;

[0046] The flotation is carried out using the activator and collector described in the above technical solution.

[0047] In some embodiments of the present invention, the flotation is specifically:

[0048] Step 1. Adding the activator and collector described in the above technical solution to the slurry for the first flotation to obtain the first concentrate and the first tailings;

[0049] Step 2. After the first concentrate is prepared into a pulp, the flotation process in step 1 is repeated; after a total of n flotations, a barite concentrate and an nth tailing are obtained;

[0050] Said 4≤n≤6.

[0051] In some embodiments of the present invention, the dosage of the inhibitor is 500 g / t of crude barite product.

[0052] In some embodiments of the present invention, in each flotation process, the amount of the activator is 100-400 g / t barite crude product, and the amount of the collector is 200-1200 g / t barite crude product. When adding the activator in flotation, potassium aluminum sulfate is added first, and then scandium nitrate is added, and the interval between the addition of the two agents is 3-5 minutes; when adding the collector in flotation, 8-hydroxyquinoline, alkyl-substituted butanediamine, alkanoylmethylaminoacetic acid, and sodium alkyl sulfonate are mixed in proportion to prepare an aqueous solution and then added.

[0053] In the present invention, as the number of flotation increases, the dosage of the activator (potassium aluminum sulfate, scandium nitrate) and the collector (8-hydroxyquinoline, alkyl-substituted butanediamine, alkanoylmethylaminoacetic acid, sodium alkyl sulfonate) is gradually reduced. For example, when the number of flotation is 5, the dosage of the activator in the first, second, third, fourth, and fifth flotation processes is 400 g / t of raw ore, 300 g / t of raw ore, 200 g / t of raw ore, 200 g / t of raw ore, and 100 g / t of raw ore, respectively. The dosage of the collector in the first, second, third, fourth, and fifth flotation processes is 1200 g / t of raw ore, 800 g / t of raw ore, 600 g / t of raw ore, 400 g / t of raw ore, and 200 g / t of raw ore, respectively.

[0054] In some embodiments of the present invention, after the first flotation is completed, the step of scavenging the first tailings is also included.

[0055] In some embodiments of the present invention, the scavenging specifically comprises: preparing the first tailings into ore pulp, and then scavenging to obtain scavenged concentrate and final tailings;

[0056] The scavenged concentrate is mixed with the second tailings and returned to the first scavenging, and the nth tailings are returned to the n-1th flotation; 4≤n≤6. The present invention reuses the tailings through the scavenging step, reducing the waste of fluorite resources. In addition, no additional reagents need to be added during the scavenging, which is green, environmentally friendly and resource-saving.

[0057] The working principle of the agent used for reverse flotation to remove impurities from the crude barite product in the present invention is as follows:

[0058] The inhibitor provided by the present invention includes methylthymol blue tetrasodium salt and 4-(2-pyridyl azo)-resorcinol. The two agents contain a large number of hydrophilic groups such as hydroxyl, carboxyl, and sulfonic acid groups in the molecules. After being adsorbed on the surface of barite, the hydrophilicity of barite can be greatly increased, and the amount of barite entering the foam product with fluorite and calcite during flotation can be reduced, thereby improving the recovery rate of barite. At the same time, because the water solubility of the two agents is poor, the two agents are added to the ball mill in a powder state, thereby increasing the intensity and time of the action of the agents with the barite, and improving the effect of the agents.

[0059] The activator provided by the present invention includes potassium aluminum sulfate and scandium nitrate, wherein the aluminum ions in the potassium aluminum sulfate can react with the fluoride ions on the surface of fluorite to generate [AlF6] 3- The presence of sulfate can react with Ba on the surface of barite to activate the fluorite. 2+ The reaction generates BaSO4, which further enhances the inhibitory effect on barite. 3+ The presence of Ca on the surface of fluorite and calcite 2+ It forms a multi-component complex Ca[Sc(OX)4]2 (OX represents 8-hydroxyquinoline) with 8-hydroxyquinoline in the collector, thus creating favorable conditions for the flotation of fluorite and calcite.

[0060] The collector provided by the present invention includes 8-hydroxyquinoline, which alone cannot react with Ca 2+ reaction occurs, but when Sc 3+ When it exists, a ternary complex Ca[Sc(OX)4]2 (OX represents 8-hydroxyquinoline) can be generated, thereby increasing the hydrophobicity of the surface of fluorite and calcite; the presence of alkyl-substituted butanediamine can further remove silicate and clay impurities represented by silicon dioxide in the crude barite product; the presence of alkanoylmethylaminoacetic acid and sodium alkyl sulfonate can further enhance the removal efficiency of impurities such as fluorite, calcite, aluminum trioxide, and iron trioxide and reduce the cost of the combined reagent. In addition, because the non-polar group of 8-hydroxyquinoline is relatively short, the reagent can only increase the hydrophobicity of the mineral surface after adsorption on the surface of fluorite and calcite and cannot effectively float and separate fluorite and calcite. The presence of alkyl-substituted butanediamine, alkanoylmethylaminoacetic acid and sodium alkyl sulfonate can greatly increase the stability of bubbles in the pulp, thereby playing a good role in capturing fluorite and barite with 8-hydroxyquinoline adsorbed on the surface. The synergy of the four collectors can effectively remove impurity minerals such as fluorite, calcite, silicate, iron oxide, aluminum oxide, etc. in the crude barite product.

[0061] In order to better understand the present invention, the content of the present invention is further explained below in conjunction with the embodiments, but the content of the present invention is not limited to the following embodiments.

[0062] Example 1

[0063] In terms of weight, the inhibitor is: 25 parts of methylthymol blue tetrasodium salt, 75 parts of 4-(2-pyridylazo)-resorcinol; the activator is: 85 parts of potassium aluminum sulfate, 15 parts of scandium nitrate; the capture agent is: 2 parts of 8-hydroxyquinoline, 30 parts of N-dodecyl-1,4-butanediamine, 20 parts of oleoylmethylaminoacetic acid, and 48 parts of sodium dodecyl sulfonate.

[0064] Example 2

[0065] In terms of weight, the inhibitor is: 20 parts of methylthymol blue tetrasodium salt, 80 parts of 4-(2-pyridylazo)-resorcinol; the activator is: 90 parts of potassium aluminum sulfate, 10 parts of scandium nitrate; the collector is: 1 part of 8-hydroxyquinoline, 20 parts of N-dodecyl-1,4-butanediamine, 40 parts of oleoylmethylaminoacetic acid, and 39 parts of sodium dodecyl sulfonate.

[0066] Example 3

[0067] In terms of weight, the inhibitor is: 30 parts of methylthymol blue tetrasodium salt, 70 parts of 4-(2-pyridylazo)-resorcinol; the activator is: 93 parts of potassium aluminum sulfate, 7 parts of scandium nitrate; the collector is: 2 parts of 8-hydroxyquinoline, 20 parts of N-dodecyl-1,4-butanediamine, 32 parts of oleoylmethylaminoacetic acid, and 32 parts of sodium dodecyl sulfonate.

[0068] Example 4

[0069] In terms of weight, the inhibitor is: 35 parts of methylthymol blue tetrasodium salt, 65 parts of 4-(2-pyridylazo)-resorcinol; the activator is: 85 parts of potassium aluminum sulfate, 15 parts of scandium nitrate; the collector is: 1 part of 8-hydroxyquinoline, 25 parts of N-dodecyl-1,4-butanediamine, 30 parts of oleoylmethylaminoacetic acid, and 44 parts of sodium dodecyl sulfonate.

[0070] Example 5

[0071] In terms of weight, the inhibitor is: 50 parts of methylthymol blue tetrasodium salt, 50 parts of 4-(2-pyridylazo)-resorcinol; the activator is: 95 parts of potassium aluminum sulfate, 5 parts of scandium nitrate; the collector is: 1 part of 8-hydroxyquinoline, 25 parts of N-dodecyl-1,4-butanediamine, 30 parts of oleoylmethylaminoacetic acid, and 44 parts of sodium dodecyl sulfonate.

[0072] The samples processed in Examples 1 to 5 of the present invention are crude products of barite gravity separation in Shangluo, Shaanxi. The flotation temperature is 23±2° C., and a reverse flotation closed-circuit process is adopted. The specific operation process is as follows: the barite coarse product is ball-milled to -0.074mm accounting for more than 85%, and an inhibitor (methylthymol blue tetrasodium salt and 4-(2-pyridyl azo)-resorcinol) is added during the grinding process at a rate of 500g / t of the original ore. After the grinding product is made into a slurry with a mass concentration of 35%, potassium aluminum sulfate and scandium nitrate (the total amount of potassium aluminum sulfate and scandium nitrate is 400g / t of the original ore) are added in sequence, and a collector (8-hydroxyquinoline, alkyl-substituted butanediamine, alkanoylmethylaminoacetic acid, and sodium alkyl sulfonate are mixed to form an aqueous solution and added. In the following process, the collector is added in the same way) 1200g / t of the original ore is then roughly selected to obtain the first concentrate and the first tailings. After the first concentrate is made into a slurry with a mass concentration of 30%, potassium aluminum sulfate, scandium nitrate (the total amount of potassium aluminum sulfate + scandium nitrate is 300g / t of the original ore), and a collector 80 0g / t of original ore is subjected to the first concentration to obtain the second concentrate and the second tailings; after the second concentrate is made into a slurry of appropriate concentration, potassium aluminum sulfate, scandium nitrate (the total amount of potassium aluminum sulfate + scandium nitrate is 200g / t of original ore), and 600g / t of collector are added in sequence to carry out the second concentration to obtain the third concentrate and the third tailings; after the third concentrate is made into a slurry with a mass concentration of 25%, potassium aluminum sulfate, scandium nitrate (the total amount of potassium aluminum sulfate + scandium nitrate is 200g / t of original ore), and 400g / t of collector are added in sequence to carry out the third concentration to obtain the fourth concentrate and the fourth tailings; after the fourth concentrate is made into a slurry with a mass concentration of 25%, potassium aluminum sulfate, scandium nitrate (the total amount of potassium aluminum sulfate + scandium nitrate is 100g / t of original ore), and 200g / t of collector are added in sequence to carry out the fourth concentration to obtain the barite concentrate and the fifth tailings. The first tailings were made into a slurry with a mass concentration of 40%, and then scavenged without adding any reagents to obtain the sixth concentrate and the sixth tailings. The sixth concentrate and the second tailings were combined to make a slurry with a mass concentration of 50% and entered the ball mill. After grinding to -0.045mm, accounting for 75%, it was returned to the roughing selection. The third tailings returned to the first selection, the fourth tailings returned to the second selection, and the fifth tailings returned to the third selection. After each reagent was added, it was stirred for about 3 minutes before adding the next reagent.

[0073] Table 1 shows the grade and recovery of BaSO4 in the barite concentrate obtained after the closed-circuit flotation test using the reagent system of Examples 1 to 5 of the present invention. The data in Table 1 show that after the barite crude product is subjected to one roughing, four fine cleaning and one scavenging by the method of the present invention, a barite concentrate with a BaSO4 grade of 97.37% to 98.51% and a recovery rate of 85.62% to 88.67% can be obtained, wherein the grade of CaF2 is 0.59% to 1.21%, the grade of CaCO3 is 0.09% to 0.30%, the grade of Fe2O3 is 0.05% to 0.15%, the grade of Al2O3 is 0.10% to 0.12%, and the grade of SiO2 is 0.62% to 0.82%.

[0074] Table 1 Grade and recovery of BaSO4 in barite concentrate

[0075]

[0076]

[0077] When the alkyl-substituted butanediamine is N-hexadecyl-1,4-butanediamine, the alkanoylmethylaminoacetic acid is laurylmethylaminoacetic acid, and the sodium alkyl sulfonate is sodium hexadecyl sulfonate, the present invention also conducts an experiment of reverse flotation to remove impurities such as fluorite and calcite from the crude barite product. The experimental results show that when other alkyl-substituted butanediamines, alkanoylmethylaminoacetic acid, and sodium alkyl sulfonate are selected, the effect of reverse flotation to remove impurities such as fluorite and calcite from the crude barite product is equivalent to that of Examples 1-5, and due to space reasons, it will not be repeated here.

[0078] In summary, the method for removing impurities such as fluorite and calcite by reverse flotation from crude barite products provided by the present invention can increase the grade of BaSO4 by more than 15 percentage points, and the grades of CaF2, CaCO3, Fe2O3, Al2O3, and SiO2 in the final concentrate can be reduced to below 1.21%, 0.30%, 0.15%, 0.12%, and 0.82%, respectively.

[0079] In the absence of conflict, the above embodiments and features in the embodiments may be combined with each other.

[0080] The above description is only a preferred embodiment of the present invention and is not intended to limit the present invention. Any modifications, equivalent substitutions, improvements, etc. made within the spirit and principle of the present invention should be included in the protection scope of the present invention.

Claims

1. A reagent for removing impurities from a crude barite product by reverse flotation, characterized in that: Includes inhibitors, activators and collectors; The inhibitor comprises the following components in parts by mass: 20-35 parts of methylthymol blue tetrasodium salt and 65-80 parts of 4-(2-pyridyl azo)-resorcinol; The activator comprises the following components in parts by mass: 80-95 parts of potassium aluminum sulfate and 5-20 parts of scandium nitrate; The collector comprises the following components in parts by mass: 1-5 parts of 8-hydroxyquinoline, 15-35 parts of alkyl-substituted butanediamine, 20-40 parts of alkanoylmethylaminoacetic acid, and 20-55 parts of sodium alkyl sulfonate.

2. The agent for removing impurities from a crude barite product by reverse flotation according to claim 1, characterized in that: The structural formula of the alkyl-substituted butanediamine is: Wherein, R = C10-C14 saturated or unsaturated alkyl; The structural formula of the alkanoylmethylaminoacetic acid is: Wherein, R2=C17-C20 saturated or unsaturated alkyl; The structural formula of the sodium alkyl sulfonate is: In the formula, Y = C12-C18 saturated or unsaturated alkyl.

3. A method for removing fluorite and calcite from a crude barite product by reverse flotation, characterized in that: The following steps are involved: The crude barite product is mixed with the inhibitor described in claim 1 and then ground to obtain a grinding product, and the grinding product is prepared into a pulp and then flotation is performed; The flotation is carried out using the activator and collector described in claim 1.

4. The method for removing fluorite and calcite by reverse flotation from a crude barite product according to claim 3, characterized in that: The flotation is specifically: Step 1. Adding the activator and collector described in claim 1 to the slurry for the first flotation to obtain a first concentrate and a first tailings; Step 2. After the first concentrate is prepared into a pulp, the flotation process in step 1 is repeated; after a total of n flotations, a barite concentrate and an nth tailing are obtained; Said 4≤n≤6.

5. The method for removing fluorite and calcite by reverse flotation from a crude barite product according to claim 3, characterized in that: The dosage of the inhibitor is 500 g / t of crude barite product.

6. The method for removing fluorite and calcite from a crude barite product by reverse flotation according to claim 4, characterized in that: In each flotation process, the dosage of the activator is 100-400 g / t of crude barite product, and the dosage of the collector is 200-1200 g / t of crude barite product.

7. The method for removing fluorite and calcite from a crude barite product by reverse flotation according to claim 4, characterized in that: After the first flotation is completed, the method further includes the step of scavenging the first tailings.

8. The method for removing fluorite and calcite from a crude barite product by reverse flotation according to claim 7, characterized in that: The scavenging specifically comprises: preparing the first tailings into ore pulp, and then scavenging to obtain scavenged concentrate and final tailings; The scavenged concentrate is mixed with the second tailings and returned to the first scavenging, and the nth tailings are returned to the n-1th flotation; Said 4≤n≤6.

Images