Reverse flotation adsorption regulation type efficient regulator for high-calcium collophanite and preparation method of reverse flotation adsorption regulation type efficient regulator

Abstract

The invention discloses a high-calcium collophanite reverse flotation adsorption regulation type efficient regulator and a preparation method thereof. The efficient collophanite regulator comprises the following raw materials: a cation collecting agent, a non-polar collecting agent, a foaming agent and an activating agent. The reverse flotation application comprises the following steps that the prepared adjusting agent is added into a roughing chute, three times of reverse flotation scavenging are carried out, obtained middling products are used for preparing the low-phosphorus-concentration phosphate fertilizer, and foam serves as tailing products. The method is applied to reverse flotation of calcareous phosphorite collophanite, and indifference adsorption of the collecting agent to minerals can be reduced by regulating and controlling the adsorption behavior of the collecting agent. According to the technology, the middling grade and the concentrate phosphorus yield can be remarkably improved, the flotation operation efficiency is synchronously optimized, and the phosphorus resource utilization rate is substantially improved.

Description

Technical Field

[0001] The present invention relates to the technical field of phosphate rock flotation, and in particular to a high-calcium colloidal phosphate reverse flotation adsorption control type high-efficiency regulator and a preparation method thereof. Background Art

[0002] Phosphate rock, a non-renewable and non-recyclable strategic resource, is abundant in my country, but a significant portion of the reserves are low-grade phosphate rock, mostly composed of medium- and low-grade phosphate rock cemented with fine particles such as dolomite-like carbonates and siliceous materials. Impurities such as calcium, magnesium, and silicon in this ore are closely associated with the phosphorus-containing minerals, making separation difficult and resulting in high losses. Therefore, the development of suitable conditioning agents is urgently needed to achieve efficient utilization of phosphate rock resources. Reverse flotation is a common process for processing low- and medium-grade collophosphate ore. Current research on reverse flotation modifiers focuses on inhibiting phosphate rock by enhancing its hydrophilicity, thereby preventing it from floating. Traditional reverse flotation depressants are primarily inorganic acids such as phosphoric acid and sulfuric acid. However, as ore grade continues to decline, these depressants suffer from high dosages and poor effectiveness, leading to significant phosphorus loss from tailings and equipment corrosion. Furthermore, research on inhibitors for phosphate reverse flotation is limited. For example, a Chinese patent (publication number: CN106674274B) discloses a phosphate mineral depressant suitable for use in neutral or weakly alkaline conditions, which is more suitable for reverse flotation desiliconization. Although patents have reported the use of organophosphonic acids as phosphate mineral depressants, their limited effectiveness and high cost have limited practical application. Different from the mechanism of action of traditional inhibitors that achieve inhibition by changing the hydrophilicity and hydrophobicity of phosphate rock, the high-efficiency adjuster for reverse flotation of high-calcium colloidal phosphate rock proposed in the present invention aims to reduce the adsorption of anionic collectors. It focuses on reducing the adsorption of reagents by the pulp during the scavenging stage and increasing the chance of removing the reagents from the surface of the ore particles. It can reduce the indiscriminate adsorption of collectors on minerals, significantly improve the grade of middlings and the phosphorus recovery rate of concentrates, and simultaneously optimize the flotation operation efficiency. In summary, developing a conditioning agent that promotes the removal of collectors from ore particles is crucial for improving phosphorus recovery from low- and medium-grade collophosphates and addressing issues such as the limited applicability of traditional inhibitors, severe phosphorus loss in tailings, and equipment corrosion. This can significantly improve the grade of middlings and concentrate phosphorus recovery, while simultaneously optimizing flotation efficiency and substantially increasing phosphorus resource utilization. Summary of the Invention

[0003] The object of the present invention is to provide a high-efficiency adjusting agent for the reverse flotation of collophanite, which can alleviate the problem of large phosphorus loss in tailings in the existing reverse flotation technology for medium and low-grade high-calcium collophanite.

[0004] To achieve the above object, the technical solutions adopted by the present invention are as follows: A regulator for reverse flotation of collophosphate, comprising the following components in parts by weight: 22-38 parts of a cationic collector, 10-16 parts of a non-polar collector, 14-20 parts of a foaming agent, and 24-32 parts of an activator.

[0005] Similarly, it can be understood that the mass ratio of cationic collector, non-polar collector, foaming agent and activator is (22-38): (10-16): (14-20): (24-32) for compounding.

[0006] In some embodiments, 1 portion is 1 Kg.

[0007] Preferably, the cationic collector is one or more of didecyl secondary ammonium, tallow propylene diamine, distearyl stearamide, dicocoyl dimethyl quaternary ammonium chloride, and mixed ammonium-11. The cationic collector and the phosphate rock reagent form ion-pair complexes in the solution through electrostatic interaction, resulting in a decrease in the concentration of the free reagent, reducing the effective amount of the phosphate rock reagent migrating to the surface of the phosphate mineral, and thus reducing the adsorption of the reagent to the phosphate mineral.

[0008] Didecyl secondary ammonium chloride (Guangdong Fangxin Biotechnology Co., Ltd.), tallow propylene diamine (manufacturer: Clariant), distearyl stearamide (Shanghai Jixiang Biotechnology Co., Ltd.), dicocoyl dimethyl quaternary ammonium chloride (Shandong Xingguang Chemical Co., Ltd.) and mixed ammonium-11 (Shenyang Metallurgical Mineral Processing Reagent Factory).

[0009] Preferably, the non-polar collector is one or more of motor oil (mineral type), white essential oil, liquid paraffin, anthracene oil, pine oil, tall oil, and 3-isooctylidinedane. The non-polar collector competes with the phosphate rock collector, blocking its adsorption sites, reducing selectivity, and thus impairing its effectiveness. Phosphate rock collectors act in the roughing stage of the process, primarily capturing calcium-magnesium gangue to achieve phosphate mineral separation. These primarily include natural fatty acids (such as oleic acid and linoleic acid), fatty acid soaps (such as sodium oleate and tall oil soap), modified fatty acids (such as emulsified fatty acids and hydroxy fatty acids), and blended products. In this embodiment, the phosphate rock collector in the roughing stage is primarily oleic acid.

[0010] Preferably, the foaming agent is one or more of diacetone alcohol, 3-butylene glycol, camphor white oil, pine oil, eucalyptus oil, propylene glycol isopropyl ether, ethylene glycol glycidyl ether, and 1-methyl-isoamyl alcohol. The foaming agent occupies active sites on the surface of the phosphate rock through hydrogen bonding or electrostatics, hindering the chemical adsorption of the phosphate rock reagent, thereby reducing phosphate rock loss. Preferably, the activator is one or more of ferrous sulfate, aluminum nitrate, aluminum sulfate, aluminum chloride, and polyaluminum silicate sulfate. The activator modifies the chemical properties of the mineral surface, exposing more active sites or changing the surface charge, making it easier for the mineral to interact with the phosphate rock reagent, thereby reducing the consumption of the phosphate rock reagent by impurities.

[0011] The method for preparing the high-calcium collophosphate reverse flotation adsorption control type high-efficiency adjusting agent comprises the following steps: 1) Evenly mix appropriate amounts of a non-polar collector and a foaming agent to obtain solution A; 2) Add appropriate amounts of cationic collector, active agent and water to solution A to obtain solution B; 3) Solution B is subjected to ultrasonic emulsification operation to obtain a high-efficiency adjusting agent for reverse flotation of collophosphate.

[0012] Preferably, the solid content of the solution B in step (2) is 73%-82%.

[0013] The high-calcium collophosphate reverse flotation adsorption control type high-efficiency regulator is used in the reverse flotation sweeping operation process of medium and low-grade calcium collophosphate.

[0014] Preferably, the phosphate rock reagent is an anionic fatty acid collector for reverse flotation of collophosphate rock.

[0015] Preferably, the medium-low grade calcareous collophosphate has a P2O5 grade of 18%-24%, a MgO content of 6%-9%, and an Al2O3 content of 1%-2%; and the dosage of the adjusting agent is 0.2-0.4 kg / t.

[0016] Compared with the prior art, the present invention has the following beneficial effects: (1) The adjusting agent of the present invention can precisely regulate adsorption, thereby reducing the adsorption energy barrier of the slurry to the agent during the scavenging stage and increasing the desorption rate of the collector. Compared with traditional inhibitors, it is more targeted and has a stronger effect.

[0017] (2) The regulator of the present invention optimizes the action of the reagent, avoids indiscriminate adsorption of the reagent, improves the grade of the middlings and the phosphorus yield of the concentrate, simultaneously optimizes the efficiency of the flotation operation, reduces the amount of inorganic acid used, and reduces the mineral processing cost and the residual reagent in the tailings.

[0018] (3) The inhibitory mechanism of the present invention on phosphate rock is universally enhanced and does not rely on changes in the hydrophilicity of the mineral surface. It is suitable for medium and low-grade collophosphate ores with different calcium and magnesium impurity contents, and can stably regulate the adsorption balance within the slurry pH range of 3-5. BRIEF DESCRIPTION OF THE DRAWINGS

[0019] Figure 1 This is a flow chart of the method for using the reverse flotation high-efficiency adjusting agent of the present invention. DETAILED DESCRIPTION

[0020] The following will be combined with the specific embodiments of the present invention to clearly and completely describe the technical solutions in the embodiments of the present invention. Obviously, the embodiments described are only part of the embodiments of the present invention, not all of the embodiments. Based on the embodiments of the present invention, all other embodiments obtained by ordinary technicians in this field without making any creative efforts shall fall within the scope of protection of the present invention.

[0021] Example 1 Preparation of a high-efficiency phosphate adjuster for a calcareous phosphorite-type phosphate rock in Sichuan. The main components of the ore include P2O522.3%, MgO6.63%, and Al2O31.4%. Reverse flotation is performed at room temperature to remove calcium impurities. The formula of the high-efficiency phosphate adjuster and the reverse flotation process are as follows: (1) Preparation of a high-efficiency phosphate rock adjuster: Take 13 parts of white essential oil and 16 parts of diacetone alcohol, mix them evenly, and stir until they are completely dissolved to obtain solution A; take 15 parts of solution A, take 28 parts of dicocoyl dimethyl ammonium chloride, take 24 parts of aluminum sulfate, and add 20 parts of distilled water to obtain solution B. Ultrasonic emulsification operation is performed on solution B. After completion, let it stand for 5 to 10 minutes to observe whether the system is a uniform milky white liquid with no oil layer floating. Finally, a high-efficiency phosphate rock adjuster is obtained.

[0022] (2) The calcareous phosphorite-type collophosphate ore is crushed and then ground to a grinding fineness of -0.074 mm accounting for 70% to 75%. Water is added to adjust the pulp concentration to 30% to 33%.

[0023] (3) At room temperature, 0.23 kg / t of the high-efficiency phosphate adjuster prepared in step (1) was added to the roughing chute. After three scavenging operations on the flotation machine, the final test concentrate grade was measured to be 31.64%, the middling grade was 23.6%, the tailings phosphorus was 3.6%, the concentrate yield was 94.62%, and the scavenging efficiency was 43.8%.

[0024] (4) Considering that the regulator remains in the middlings and returns to affect the adsorption of the roughing collector, the process uses the middlings for the production of phosphate fertilizers with low phosphorus concentration.

[0025] Comparative Example 1 The method and steps are the same as those in Example 1, except that the cationic collector is removed from the formula of the high-efficiency phosphate rock adjuster, and reverse flotation is performed. The test results show that the test concentrate grade is 31.56%, the middling grade is 16.8%, the tailings phosphorus is 8.62%, the concentrate recovery rate is 84.40%, and the scavenging efficiency is 11.61%.

[0026] The results of Example 1 and Comparative Example 1 show that when preparing a high-efficiency reverse flotation adjuster, the lack of a cationic collector will increase the effective adsorption of an anionic collector on phosphate rock, increase the loss of phosphorus in the tailings, and reduce the phosphorus yield.

[0027] Example 2 Preparation of a high-efficiency collophosphate adjusting agent for a calcareous phosphorite-type collophosphate ore in Sichuan. The main components of the ore include P2O519.35%, MgO8.7%, and Al2O31.33%. Reverse flotation is performed to remove calcium impurities at room temperature. The formula of the high-efficiency phosphate adjusting agent and the reverse flotation process are as follows: (1) Preparation of high-efficiency phosphate rock adjuster: Take 15 parts of engine oil (ore type) and 14 parts of ethylene glycol glycidyl ether, mix them evenly, and stir until they are completely dissolved to obtain solution A; take 18 parts of solution A, take 25 parts of mixed amine-11, take 28 parts of crystalline aluminum chloride, and add 22 parts of distilled water to obtain solution B. Ultrasonic emulsification operation is performed on solution B. After completion, let it stand for 5 to 10 minutes to observe whether the system is a uniform milky white liquid with no oil layer floating. Finally, a high-efficiency phosphate rock adjuster is obtained.

[0028] (2) The calcareous phosphorite-type collophosphate ore is crushed and then ground to a grinding fineness of -0.074 mm accounting for 70% to 75%. Water is added to adjust the pulp concentration to 30% to 33%.

[0029] (3) At room temperature, 0.35 kg / t of the high-efficiency phosphate adjuster prepared in step (1) was added to the roughing chute. After three scavenging operations on the flotation machine, the final test concentrate grade was measured to be 30.76%, the middling grade was 25.41%, the tailings phosphorus content was 5.2%, the concentrate yield was 89.81%, and the scavenging efficiency was 44.28%.

[0030] (4) Considering that the regulator remains in the middlings and returns to affect the adsorption of the roughing collector, the process uses the middlings for the production of phosphate fertilizers with low phosphorus concentration.

[0031] Comparative Example 2 The method and steps are the same as those in Example 2, except that the non-polar collector is removed from the formula of the high-efficiency phosphate rock adjuster, and reverse flotation is performed. The test results show that the test concentrate grade is 30.72%, the middling grade is 18.3%, the tailings phosphorus is 11.2%, the concentrate recovery rate is 66.29%, and the scavenging efficiency is 9.88%.

[0032] The results of Example 2 and Comparative Example 2 show that when preparing a high-efficiency reverse flotation adjuster, the lack of a non-polar collector will increase the selectivity of the anionic collector for phosphate rock capture, increase the loss of phosphorus in the tailings, and reduce the phosphorus yield.

[0033] Example 3 Preparation of a high-efficiency phosphate adjusting agent for a calcareous phosphorite-type phosphate rock in Sichuan. The main components of the ore include P2O523.21%, MgO5.7%, and Al2O31.21%. Reverse flotation is performed at room temperature to remove calcium impurities. The formula of the high-efficiency phosphate adjusting agent and the reverse flotation process are as follows: (1) Preparation of a high-efficiency phosphate rock adjuster: Take 12 parts of 3-isooctylhydroindane and 18 parts of eucalyptus oil, mix them evenly, and stir until they are completely dissolved to obtain solution A; take 16 parts of solution A, take 30 parts of didecyl secondary amine, take 25 parts of polyaluminum silicate sulfate, and add 24 parts of distilled water to obtain solution B. Ultrasonic emulsification operation is performed on solution B. After completion, let it stand for 5 to 10 minutes to observe whether the system is a uniform milky white liquid with no oil layer floating. Finally, a high-efficiency phosphate rock adjuster is obtained.

[0034] (2) The calcareous phosphorite-type collophosphate ore is crushed and then ground to a grinding fineness of -0.074 mm accounting for 70% to 75%. Water is added to adjust the pulp concentration to 30% to 33%.

[0035] (3) At room temperature, 0.28 kg / t of the high-efficiency phosphate rock adjuster prepared in step (1) was added to the roughing chute. After three scavenging operations on the flotation machine, the final test concentrate grade was 31.41%, the middling grade was 23.45%, the tailings phosphorus content was 3.84%, the concentrate yield was 95.08%, and the scavenging efficiency was 42.25%.

[0036] (4) Considering that the regulator remains in the middlings and returns to affect the adsorption of the roughing collector, the process uses the middlings for the production of phosphate fertilizers with low phosphorus concentration.

[0037] Comparative Example 3 The method and steps are the same as those in Example 3, except that the frother is removed from the formula of the high-efficiency phosphate rock adjuster, and reverse flotation is performed. The test results show that the test concentrate grade is 31.46%, the middling grade is 17.39%, the tailings phosphorus is 9.77%, the concentrate recovery rate is 83.99%, and the scavenging efficiency is 10.54%.

[0038] The results of Example 3 and Comparative Example 3 show that when preparing a high-efficiency reverse flotation adjuster, the lack of a frother will increase the chemical adsorption of the anion collector on the phosphate rock, increase the loss of phosphorus in the tailings, and reduce the phosphorus yield.

[0039] Example 4 Preparation of a high-efficiency phosphate ore adjusting agent for a calcareous phosphorite-type phosphate ore in Sichuan. The main components of the raw ore include P2O520.67%, MgO7.63%, and Al2O31.52%. Reverse flotation is carried out to remove calcium impurities at room temperature. The formula of the high-efficiency phosphate ore adjusting agent and the reverse flotation process are as follows: (1) Preparation of a high-efficiency phosphate rock adjuster: Take 13 parts of liquid paraffin and 16 parts of camphor white oil, mix them evenly, and stir until they are completely dissolved to obtain solution A; take 14 parts of solution A, take 33 parts of tallow propylene diamine, take 24 parts of aluminum nitrate, and add 28 parts of distilled water to obtain solution B. Ultrasonic emulsification operation is performed on solution B. After completion, let it stand for 5 to 10 minutes to observe whether the system is a uniform milky white liquid with no oil layer floating. Finally, a high-efficiency phosphate rock adjuster is obtained.

[0040] (2) The calcareous phosphorite-type collophosphate ore is crushed and then ground to a grinding fineness of -0.074 mm accounting for 70% to 75%. Water is added to adjust the pulp concentration to 30% to 33%.

[0041] (3) At room temperature, 0.25 kg / t of the high-efficiency phosphate adjuster prepared in step (1) was added to the roughing chute. After three scavenging operations on the flotation machine, the final test concentrate grade was measured to be 31.74%, the middling grade was 25.64%, the tailings phosphorus content was 5.4%, the concentrate yield was 89.02%, and the scavenging efficiency was 33.88%.

[0042] (4) Considering that the regulator remains in the middlings and returns to affect the adsorption of the roughing collector, the process uses the middlings for the production of phosphate fertilizers with low phosphorus concentration.

[0043] Comparative Example 4 The method and steps are the same as those in Example 4, except that the activator is removed from the formula of the efficient phosphate rock adjuster, and reverse flotation is performed. The test results show that the test concentrate grade is 31.67%, the middling grade is 19.24%, the tailings phosphorus is 9.44%, the concentrate recovery rate is 77.40%, and the scavenging efficiency is 11.92%.

[0044] The results of Example 4 and Comparative Example 4 show that when preparing a high-efficiency reverse flotation adjuster, the lack of an activator will increase the consumption of anionic collectors by impurities, increase the dosage of the reagent, affect the ion concentration of the system, increase the loss of phosphorus in the tailings, and reduce the phosphorus yield.

[0045] Comparative Example 5 The method and steps were the same as those in Example 1, without using any adjusting agent, and reverse flotation was performed. The final test concentrate grade was 31.64%, the middling grade was 18.77%, the tailings phosphorus was 8.1%, the concentrate yield was 85.59%, and the scavenging efficiency was 15.62%.

[0046] Comparative Example 6 The method and steps were the same as those in Example 1. A conventional inorganic acid (phosphoric acid or sulfuric acid) was used as a depressant, and reverse flotation was performed. The final measured test ore grade was 20.62%, tailings phosphorus was 7.8%, concentrate yield was 86.07%, and scavenging efficiency was 18.22%.

[0047] The above embodiments are used to explain the technical solutions of the present invention. However, the present invention is not limited to the above embodiments, that is, it does not mean that the present invention must rely on the above specific embodiments to be implemented. Any improvements made by those skilled in the art based on the present invention, or equivalent substitutions of materials used in the present invention, etc., fall within the scope of protection of the patent.

Claims

1. High-calcium collophosphate reverse flotation adsorption control type high-efficiency regulator, characterized by: The regulator comprises the following components in parts by weight: 22-38 parts of a cationic collector, 10-16 parts of a non-polar collector, 14-20 parts of a foaming agent, and 24-32 parts of an activator.

2. The high-calcium collophosphate reverse flotation adsorption control type efficient adjusting agent according to claim 1, characterized in that: The cationic collector is one or more of didecyl secondary amine, tallow propylene diamine, distearyl stearamide, bis-cocoyl dimethyl quaternary ammonium chloride and mixed ammonium-11.

3. The high-calcium collophosphate reverse flotation adsorption control type efficient adjusting agent according to claim 1, characterized in that: The non-polar collector is one or more of motor oil (mineral type), white essential oil, liquid paraffin, anthracene oil, pine oil, tall oil, and 3-isooctyl hydrogenated indane.

4. The high-calcium collophosphate reverse flotation adsorption control type efficient adjusting agent according to claim 1, characterized in that: The foaming agent is one or more of diacetone alcohol, 3-butylene glycol, camphor white oil, pine oil, eucalyptus oil, propylene glycol isopropyl ether, ethylene glycol glycidyl ether, and 1-methyl-isoamyl alcohol.

5. The high-calcium collophosphate reverse flotation adsorption control type efficient adjusting agent according to claim 1, characterized in that: The activator is one or more of ferrous sulfate, aluminum nitrate, aluminum sulfate, aluminum chloride, and polysilicate aluminum sulfate.

6. A method for preparing a high-calcium collophosphate reverse flotation adsorption control type high-efficiency adjusting agent according to any one of claims 1 to 5, characterized in that: The following steps are involved: 1) Evenly mix appropriate amounts of a non-polar collector and a foaming agent to obtain solution A; 2) Add appropriate amounts of cationic collector, active agent and water to solution A to obtain solution B; 3) Solution B is subjected to ultrasonic emulsification operation to obtain a high-efficiency adjusting agent for reverse flotation of collophosphate.

7. The method for preparing the high-calcium collophosphate reverse flotation adsorption control type efficient adjusting agent according to claim 6, characterized in that: The mass ratio of the non-polar collector and the foaming agent in step (1) is (0.5-1.2): (1.0-2.0); the mass ratio of the solution A to the cationic collector, the active agent, and the water in step (2) is (0.5-1.0): (1.2-1.5): (1.0-2.0):

1.

8. The high-efficiency adjusting agent for reverse flotation of collophanite according to claims 1-5 or the adjusting agent obtained by the preparation method according to any one of claims 6-7 is used in the reverse flotation and scavenging process of high-calcium phosphorus block rock type collophanite.

9. The use according to claim 8, characterized in that: The collophanite is a medium-low grade high-calcium phosphorite rock type collophanite, with a P2O5 grade of 18%-24%, a MgO content of 6%-9%, and an Al2O3 content of 1%-2%.

10. The use according to claim 8, characterized in that: The dosage of the regulator is 0.2-0.4kg / t.

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