A preparation method of oxide ore combined collector

Abstract

The present invention relates to a method for preparing a combined collector for oxide ores. The method comprises mixing polyetheramine and sulfonated kerosene and stirring them uniformly. The resulting mixed reagent is placed in a water bath at 50-65°C for 30-60 minutes. An inorganic salt and water are then mixed with the heated mixed reagent in the water bath. The mixture is stirred on a heated magnetic stirrer at 50-65°C and a stirring speed of 100-200 r / min for 20-30 minutes. Finally, the solution is calibrated with water to form a dilute solution. Advantages of the method include: based on the concept of reagent combination, using polyetheramine as the main reagent and sulfonated kerosene and inorganic salt as auxiliary reagents, and utilizing the synergistic effect of the mixed reagents, the method enhances the selectivity of the collector and reduces the amount of expensive amine reagents. Furthermore, the method solves the problems of excessive foam viscosity and difficulty in defoaming during flotation with traditional amine collectors, resulting in sludging.

Description

Technical Field

[0001] The invention belongs to the field of flotation, and in particular relates to a method for preparing a combined collector for oxide ore. Background Art

[0002] my country is a country with abundant iron ore resources, but the iron ore grade is low and the endowment is poor, so it is necessary to obtain high-grade iron concentrate through flotation process. At present, the main iron ore flotation collectors are anionic collectors represented by oleic acid and cationic collectors represented by amines. The reagent system is complex when using anionic collectors, and Ca 2+ Ions act as activators, and the pH value must be above 11. Furthermore, since oleic acid-based anionic collectors have poor solubility and dispersibility at low temperatures, the mixing temperature must be above 90°C, the storage temperature must be 60-80°C, and the flotation slurry temperature must be around 35°C. This consumes a lot of energy during the flotation process. Cationic collectors require a relatively simple reagent system and can be prepared, stored, and sorted at room temperature.

[0003] Prior art patent application CN201710229419.8 discloses a composite cationic collector and its preparation method. This involves preparing a microemulsion using a mixture of sec-octanol and dodecylamine, a mixture of sec-octanol, kerosene, and dodecylamine, and a mixture of dodecylamine, kerosene, sec-octanol, a surfactant, and water. This microemulsion also functions as a frother during coal slime flotation. Patent application CN202011014678.7 discloses a composite collector for reducing flotation foam stability, its preparation method, and its application. This collector is prepared using dodecylamine, a sulfonate, and a solubilizer. This collector reduces cationic flotation foam stability, improves foam fluidity, and shortens the half-life of static defoaming during flotation.

[0004] Traditional amine collectors suffer from high foaming, sticky foam, poor fluidity, and difficulty in defoaming. They also require the addition of acid to dissolve in water, making large-scale industrial application difficult. Iron ore "iron-enhancing and silicon-reducing" agents also suffer from low selectivity, high temperatures required for preparation and use, high agent costs, and sticky foam.

[0005] As humans pay more attention to environmental protection, it is urgent to develop flotation agents with good collection performance and low temperature resistance in order to reduce the emission of greenhouse gases and dust, reduce flotation costs, and improve the economic benefits of mineral processing plants. Summary of the Invention

[0006] The purpose of the present invention is to provide a method for preparing a combined collector for oxide ore, simplify the reagent system, reduce the iron ore flotation temperature and reagent configuration temperature, reduce the reagent cost, and solve the problem of large-scale consumption of heating steam during the flotation process.

[0007] To achieve the above object, the present invention is implemented through the following technical solutions:

[0008] A method for preparing an oxide ore combined collector comprises the following steps:

[0009] 1) Mix polyetheramine and sulfonated kerosene and stir evenly;

[0010] 2) placing the mixed agent obtained in step 1) in a water bath at 50-65° C. for 30-60 minutes;

[0011] 3) mixing the inorganic salt and water with the mixed agent heated in a water bath;

[0012] 4) stirring the solution obtained in step 3) on a heated magnetic stirrer at a temperature of 50-65° C. and a stirring speed of 100-200 rpm for 20-30 min;

[0013] 5) The solution obtained in step 4) is standardized with water to be a dilute solution.

[0014] The molecular weight of the polyetheramine is 200-400, and the polyetheramine is bifunctional.

[0015] The preparation method of sulfonated kerosene comprises the following steps: thoroughly mixing kerosene with concentrated sulfuric acid in a volume ratio of 5:1 to 4:1, allowing the mixture to stand for stratification, discharging the waste acid in the lower layer, neutralizing the residual sulfuric acid with a sodium carbonate solution having a mass percentage of 5% to 8%, and finally washing the mixture with distilled water until the mixture is neutral.

[0016] The inorganic salt is one or both of sodium sulfide and potassium chloride.

[0017] The solution obtained in step 4) comprises the following components by weight: 45% to 70% polyetheramine; 20% to 35% sulfonated kerosene; 5% to 25% inorganic salt; and 2% to 5% water.

[0018] The solution obtained in step 4) is a uniformly dispersed solution.

[0019] The mass concentration of the dilute solution is 0.1% to 5%.

[0020] Compared with the prior art, the present invention has the following beneficial effects:

[0021] 1. The present invention is based on the concept of reagent combination, with polyether ammonium as the main reagent, sulfonated kerosene and inorganic salt as auxiliary agents of the collector. The synergistic effect of the mixture of various reagents is utilized to enhance the selectivity of the collector and reduce the dosage of expensive amine reagents. At the same time, it solves the problems of excessive foam viscosity and difficulty in defoaming during the flotation process of traditional amine collectors, which causes the flotation to run.

[0022] 2. Polyether ammonium has strong bubble and capture performance and the foam produced is too stable, so its effect is poor when used alone. Sulfonated kerosene has certain capture performance and no foaming performance. When used in combination with polyether ammonium, it can reduce the amount of foam generated during the use of the agent and enhance the selectivity of the agent. A certain concentration of inorganic salt can increase the diameter of the bubbles at the initial stage of generation and reduce the stability of the foam. The collector prepared by the method of the present invention can realize the room temperature flotation of iron ore, effectively solving the problems of large-scale consumption of heating steam, waste of energy and increase of carbon emissions in the high-temperature flotation process. At the same time, due to the reduction of the operating temperature of the collector and the reduction of the amount used, the production cost and the degree of environmental pollution damage will be greatly reduced, which has good social benefits and good prospects for promotion and industrialization.

[0023] 3. The combined collector provided by the present invention can achieve a concentrate grade exceeding 65% and a tailings grade of approximately 18% for iron ore reverse flotation, which is close to the flotation performance of common amine collectors. The bubbles produced by the combined collector have a large initial diameter, a high liquid content, and rapid liquid loss, resulting in rapid bubble merger, growth, and collapse. The half-life of the bubbles is shorter than that of common amine collectors, indicating that the foam produced by the combined collector is relatively less stable and more conducive to flotation. DETAILED DESCRIPTION

[0024] The present invention will be described in detail below, but it should be noted that the implementation of the present invention is not limited to the following embodiments.

[0025] A method for preparing an oxide ore combined collector comprises the following steps:

[0026] 1) The raw materials are as follows by weight: polyetheramine 45% to 70%; sulfonated kerosene 20% to 35%; inorganic salt 5% to 25%; water 2% to 5%. The molecular weight of the polyetheramine is 200 to 400, and it is generally bifunctional.

[0027] Weigh polyetheramine and sulfonated kerosene according to the above ratio, put them into a beaker, and stir them evenly with a glass rod;

[0028] 2) Place the beaker containing the mixed drug in step 1) in a water bath at 50-65°C for 30-60 minutes;

[0029] 3) Weigh an inorganic salt and water in the above proportions and add them to the beaker in step 2). The inorganic salt is either sodium sulfide or potassium chloride, or both. Adding an appropriate amount of inorganic salt can shorten the foam half-life and prevent the foam from becoming overly stable.

[0030] 4) Place the solution obtained in step 3) on a heated magnetic stirrer and stir for 20-30 minutes at a temperature of 50-65°C and a stirring speed of 100-200 rpm to allow the combined collector to be fully mixed and dispersed, thereby improving the performance of the agent. Stirring is terminated when the liquid becomes a uniformly dispersed solution, at which point stirring is stopped.

[0031] 5) Transfer the solution obtained in step 4) to a volumetric flask and standardize it with water to a dilute solution with a concentration of 0.1% to 5% by mass. This dilute solution ensures that the collector is fully dissolved and dispersed in water and the amount of the agent added during use is within an appropriate range.

[0032] Preparation of sulfonated kerosene: Kerosene and concentrated sulfuric acid are thoroughly mixed in a separatory funnel at a volume ratio of 5:1 to 4:1. After standing and separating the layers, the waste acid layer is drained. The residual sulfuric acid is then neutralized with a 5% to 8% sodium carbonate solution (the end point is determined when no more bubbles appear). Finally, the mixture is washed with distilled water until neutral. Sulfonated kerosene prepared using this method prevents polymerization of unsaturated bonds, which can form viscous liquid polymers and reduce the performance of the agent. Furthermore, the sulfonation process allows the olefin to react with the acid to form an acidic sulfate ester, increasing its solubility in water.

[0033] Compared with the single agent polyether ammonium, the collection performance of the oxide ore combination collector is lower, the selectivity is increased, and the foaming performance and the stability of the foam are reduced. It solves the problems of excessive foam viscosity and difficulty in defoaming during the flotation process of traditional amine collectors, such as trough leakage.

[0034] Using this combined collector for reverse flotation of iron ore can achieve a concentrate grade exceeding 65% and a tailings grade of 17.5%-19%, similar to the flotation performance of common amine collectors. The bubbles produced by the combined collector have a large initial diameter, contain a large amount of liquid in the foam, and lose liquid quickly, causing the bubbles to merge, grow, and burst. The half-life of the bubbles is shorter than that of common amine collectors, indicating that the foam produced by the combined collector is relatively less stable and more conducive to flotation.

[0035] The iron ore flotation depressant used in the following examples is corn starch with a mass concentration of 2.5%.

[0036] The pH adjusters used in the following examples are 5% sodium hydroxide solution and 5% dilute sulfuric acid.

[0037] The iron ore used in the following examples is a mixed magma hematite iron ore with an iron grade of 47%, wherein magnetite accounts for 55% of the total iron distribution rate and hematite accounts for 45%.

[0038] In the following examples, when iron ore flotation was performed, the slurry temperature was 20±1° C. and the pH value of the slurry was 9-9.5.

[0039] The iron ore flotation test steps in the following examples are as follows:

[0040] A 200g ore sample was poured into a 500ml flotation tank at a stirring speed of 1995r / min. A pH adjuster, inhibitor, and collector were added in sequence for testing. After flotation, the flotation concentrate and tailings were dried, weighed, sampled, assayed, tested, and calculated. The flotation process employed a 1-coarse, 1-fine, 3-sweep reverse flotation process.

[0041] Example 1

[0042] A method for preparing an oxide ore combined collector comprises the following steps:

[0043] 1) The raw materials are as follows by weight: 60% polyetheramine; 30% sulfonated kerosene; and 10% sodium sulfide. The molecular weight of the polyetheramine is 230, and it is bifunctional.

[0044] Weigh polyetheramine and sulfonated kerosene in proportion, put them into a beaker, and stir them evenly with a glass rod;

[0045] 2) Place the beaker containing the mixed drug from step 1) in a 60°C water bath for 30 minutes;

[0046] 3) Weigh sodium sulfide and water in proportion and add to the beaker in step 2);

[0047] 4) Place the solution obtained in step 3) on a heated magnetic stirrer and stir at 60°C and 200 rpm for 20 minutes. Stirring is terminated when the liquid becomes a uniformly dispersed solution. Stirring can be stopped at this point.

[0048] 5) The solution obtained in step (4) was transferred to a volumetric flask and standardized with water to a dilute solution with a mass concentration of 3.5%.

[0049] The preparation method of sulfonated kerosene is as follows: kerosene and concentrated sulfuric acid are thoroughly mixed in a separatory funnel at a volume ratio of 5:1, allowed to stand for stratification, the lower layer of waste acid is discharged, and then the residual sulfuric acid is neutralized with 5% sodium carbonate solution (the end point is determined when no bubbles appear), and finally washed with distilled water until neutral.

[0050] The prepared collector was used for iron ore reverse flotation test. The laboratory 0.5L was used, in which the roughing collector dosage was 90g / t, the fine collector dosage was 30g / t, and the inhibitor dosage was 450g / t. After 1 roughing, 1 fine and 3 sweep reverse flotation tests, flotation concentrate with a grade of 67.5% and flotation tailings with a grade of 18% were obtained.

[0051] Example 2

[0052] A method for preparing an oxide ore combined collector comprises the following steps:

[0053] 1) The raw materials are as follows by weight: 65% polyetheramine; 23% sulfonated kerosene; and 12% inorganic salt. The molecular weight of the polyetheramine is 230, and it is bifunctional.

[0054] Weigh a certain amount of polyetheramine and sulfonated kerosene in proportion, put them into a beaker, and stir them evenly with a glass rod;

[0055] 2) Place the beaker containing the mixed drug from step 1) in a 60°C water bath for 30 minutes;

[0056] 3) Weigh a certain amount of inorganic salt and water and add them to the beaker in step (2); the inorganic salt is a mixture of sodium sulfide and potassium chloride in a mass ratio of 1:1.

[0057] 4) The solution obtained in step 3) was placed on a heated magnetic stirrer and stirred at 60° C. and 200 rpm for 20 min. At this time, the liquid became a uniformly dispersed solution and stirring was stopped.

[0058] 5) The solution obtained in step (4) was transferred to a volumetric flask and standardized with water to a dilute solution with a mass concentration of 3.5%.

[0059] The preparation method of sulfonated kerosene is as follows: kerosene and concentrated sulfuric acid are thoroughly mixed in a separatory funnel at a volume ratio of 5:1, allowed to stand for stratification, the lower layer of waste acid is discharged, and then the residual sulfuric acid is neutralized with 5% sodium carbonate solution (the end point is determined when no bubbles appear), and finally washed with distilled water until neutral.

[0060] The prepared collector was used for iron ore reverse flotation test. The laboratory 0.5L was used, in which the roughing collector dosage was 80g / t, the fine collector dosage was 20g / t, and the inhibitor dosage was 450g / t. After 1 roughing, 1 fine and 3 sweep reverse flotation tests, a flotation concentrate with a grade of 67% and a flotation tailings with a grade of 18.2% were obtained.

[0061] Example 3

[0062] A method for preparing an oxide ore combined collector comprises the following steps:

[0063] 1) The raw materials are as follows by weight: 60% polyetheramine; 35% sulfonated kerosene; and 5% potassium chloride. The polyetheramine has a molecular weight of 300 and is bifunctional.

[0064] Weigh a certain amount of polyetheramine and sulfonated kerosene in proportion, put them into a beaker, and stir them evenly with a glass rod;

[0065] 2) Place the beaker containing the mixed drug in step 1) in a 65°C water bath for 30 minutes;

[0066] 3) Weigh a certain amount of potassium chloride and water and add them to the beaker in step 2);

[0067] 4) Place the solution obtained in step 3) on a heated magnetic stirrer and stir for 20 minutes at a temperature of 65°C and a stirring speed of 200 r / min. Stirring ends when the liquid becomes a uniformly dispersed solution and stirring can be stopped at this time.

[0068] 5) The solution obtained in step 4) was transferred to a volumetric flask and standardized with water to a dilute solution with a mass concentration of 3.5%.

[0069] The preparation method of sulfonated kerosene is as follows: kerosene and concentrated sulfuric acid are thoroughly mixed in a separatory funnel at a volume ratio of 5:1, allowed to stand for stratification, the lower layer of waste acid is discharged, and then the residual sulfuric acid is neutralized with 5% sodium carbonate solution (the end point is determined when no bubbles appear), and finally washed with distilled water until neutral.

[0070] The prepared collector was used in an iron ore reverse flotation test. A 0.5L laboratory sample was used in which the roughing collector dosage was 80g / t, the fine collector dosage was 30g / t, and the inhibitor dosage was 450g / t. After 1 roughing, 1 fine, and 3 sweep reverse flotation tests, a flotation concentrate with a grade of 67.8% and a flotation tailing with a grade of 18.5% were obtained.

Claims

1. A method for preparing an oxide ore combined collector, characterized in that: The following steps are involved: 1) Mixing polyetheramine and sulfonated kerosene and stirring them evenly; the molecular weight of the polyetheramine is 200 to 400, and the polyetheramine is bifunctional; 2) placing the mixed agent obtained in step 1) in a water bath at 50-65° C. for 30-60 minutes; 3) mixing the inorganic salt and water with the mixed agent heated in a water bath; 4) stirring the solution obtained in step 3) on a heated magnetic stirrer at a temperature of 50-65° C. and a stirring speed of 100-200 rpm for 20-30 min; 5) The solution obtained in step 4) is standardized with water to be a dilute solution.

2. The method for preparing an oxide ore combined collector according to claim 1, characterized in that: The preparation method of sulfonated kerosene comprises the following steps: thoroughly mixing kerosene with concentrated sulfuric acid in a volume ratio of 5:1 to 4:1, allowing the mixture to stand for stratification, discharging the waste acid in the lower layer, neutralizing the residual sulfuric acid with a sodium carbonate solution having a mass percentage of 5% to 8%, and finally washing the mixture with distilled water until the mixture is neutral.

3. The method for preparing an oxide ore combined collector according to claim 1, characterized in that: The inorganic salt is one or both of sodium sulfide and potassium chloride.

4. The method for preparing an oxide ore combined collector according to claim 1, characterized in that: The solution obtained in step 4) comprises the following components by weight: 45% to 70% polyetheramine; 20% to 35% sulfonated kerosene; 5% to 25% inorganic salt; and 2% to 5% water.

5. The method for preparing an oxide ore combined collector according to claim 1, characterized in that: The solution obtained in step 4) is a uniformly dispersed solution.

6. The method for preparing an oxide ore combined collector according to claim 1, characterized in that: The mass concentration of the dilute solution is 0.1% to 5%.