Preparation method and application of novel phosphorite reverse flotation collecting agent
The novel phosphate ore reverse flotation collector addresses low foaming and solubility issues by modifying alpha-hydroxyoleic acid with a prepolymer, achieving efficient and selective flotation without heating, thus improving production efficiency.
Patent Information
- Application Number
- CN202411381317.4
- Authority / Receiving Office
- CN · China
- Patent Type
- Applications(China)
- Current Assignee / Owner
- Filing Date
- 2024-09-30
- Publication Date
- 2024-12-31
AI Technical Summary
Existing phosphate ore reverse flotation collectors face challenges with low foaming properties, poor solubility, and limited collecting capacity, leading to increased energy consumption and reduced production efficiency due to the need for heating during flotation.
A novel phosphate ore reverse flotation collector is prepared by modifying alpha-hydroxyoleic acid with a prepolymer containing multi-double bond monomers and quaternary ammonium salt monomers, enhancing solubility, dispersibility, and adsorption capacity through controlled mass ratios and reactions to introduce active groups.
The modified collector exhibits high solubility, good dispersibility, and improved collecting capacity, allowing efficient flotation at room temperature with enhanced selectivity and reduced operational complexity.
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Abstract
Description
Technical Field
[0001] The invention relates to the field of ore flotation collectors, and in particular to a preparation method and application of a novel phosphate ore reverse flotation collector. Background Art
[0002] Phosphate is one of the most important non-metallic mineral resources in my country, and it is difficult to regenerate. It has important application value and is widely used in biology, agriculture, medicine and other fields. However, most of the phosphate in my country is high-magnesium phosphate, which is difficult to select. The useful minerals and gangue are very closely combined and difficult to separate. Flotation is a widely used mineral processing method, which can effectively separate phosphate ore and dolomite. It is divided into positive flotation and reverse flotation. Due to the large number of medium and low-grade collophosphates in our country, reverse flotation is widely used. The collector of reverse flotation is mainly fatty acid, which has strong collection ability, but poor selection. In addition, fatty acid collectors are difficult to dissolve at room temperature and have poor dispersibility in water. Heating is required during flotation, which increases energy consumption, increases production costs, and slows down production efficiency. Therefore, the synthesis of easily soluble and well-dispersed reverse flotation collectors has become the focus of research in this field.
[0003] Patent CN101293226B provides a carbonate phosphate reverse flotation collector and a preparation method thereof, which is composed of the following raw materials: bran oil acidified oil, soybean oil acidified oil, and a frother. The collector has strong collecting ability, high selectivity, small dosage and low temperature resistance, and is suitable for the beneficiation production of carbonate phosphate and various phosphate ores. However, the foaming property of the collector is low, and a large amount of frother needs to be added.
[0004] Patent CN106269286B discloses a method for preparing a sulfonated fatty acid phosphate ore reverse flotation collector. The method increases polar groups on fatty acids to enhance the complexation of carboxylic acids with calcium and magnesium ions to form a stable complex, thereby achieving the purpose of removing gangue minerals from the ore pulp; at the same time, the solubility of the collector at low temperatures is increased, and its resistance to low temperatures is enhanced, so that it can also float efficiently at room temperature. However, the collector has fewer polar groups and limited collection capacity.
[0005] Therefore, there is an urgent need for a new type of phosphate rock reverse flotation collector with high foaming property and good collecting ability. Summary of the invention
[0006] In order to overcome the above-mentioned deficiencies of the prior art, the present invention provides a novel phosphate ore reverse flotation collector with high foaming property, good solubility, high dispersibility, good collecting capacity and high mineral processing efficiency.
[0007] In order to achieve the above object, the technical solution adopted by the present invention is:
[0008] The first aspect of the present invention provides a method for preparing a novel phosphate ore reverse flotation collector, comprising the following steps:
[0009] S1. Dissolve a multi-double bond monomer, a quaternary ammonium salt monomer, and maleic anhydride in a solvent, add an initiator, and react at 50-60° C. with stirring for 1-2 hours to obtain a prepolymer;
[0010] S2. Add the prepolymer and α-hydroxyoleic acid obtained in step S1 into a reaction vessel, stir at 70-80° C. for 2-3 hours, and dry to obtain a novel phosphate rock reverse flotation collector.
[0011] Preferably, the mass ratio of the multi-double bond monomer, the quaternary ammonium salt monomer and maleic anhydride is (4-6):(1-3):1.
[0012] In some embodiments, the mass ratio of the prepolymer to α-hydroxyoleic acid in step S2 is (0.3-0.5):1.
[0013] The reverse flotation collector obtained by modifying alpha-hydroxy oleic acid with a prepolymer has high solubility in water, does not need to be heated during flotation, and is easy to operate. In addition, the mass ratio of a multi-double bond monomer, a quaternary ammonium salt monomer and maleic anhydride is limited, and the prepared collector contains a large number of active groups, which can effectively adsorb elements such as calcium, magnesium, and iron in minerals, thereby improving the selectivity of the collector. In addition, by limiting the mass ratio of the prepolymer and the alpha-hydroxy oleic acid, the collector has high surface activity, improves its dispersibility, thereby improving the utilization rate of the collector, and can reduce surface tension while having good foaming properties, thereby improving flotation properties.
[0014] In some embodiments, the structure of the multi-double bond monomer is:
[0015]
[0016] The structure of quaternary ammonium salt monomers is:
[0017]
[0018] In some embodiments, the number average molecular weight of the prepolymer is 6000-7000.
[0019] In some embodiments, the method for preparing the multi-double bond monomer comprises the following steps: adding 1,5-hexadiene-3,4-diol, maleic anhydride, and benzodiquinone into a reaction container, stirring at 50-60° C. for 28-32 hours to obtain a multi-double bond monomer.
[0020] In some embodiments, the mass ratio of 1,5-hexadiene-3,4-diol to maleic anhydride is 1:(1.8-2.6).
[0021] The present invention obtains a copolymer monomer containing multiple double bonds and carboxyl groups through the reaction of 1,5-hexadiene-3,4-diol and maleic anhydride, and limits the mass ratio of 1,5-hexadiene-3,4-diol and maleic anhydride so that the maleic anhydride is hydrolyzed and ring-opened to react with a hydroxyl group of 1,5-hexadiene-3,4-diol, thereby ensuring that the obtained multi-double bond monomer has sufficient active groups, thereby improving the water solubility of the collector on one hand, and increasing the adsorption to minerals on the other hand, thereby improving the collection capacity.
[0022] In some embodiments, the method for preparing the quaternary ammonium salt monomer comprises the following steps:
[0023] (1) adding glycidyl ether to a 28-32 wt% methanol solution of dimethylamine, stirring the mixture at 45-55° C. for 5-6 h, and rotary evaporating the mixture to obtain compound 1;
[0024] (2) adding compound 1 obtained in step (1), acrylic acid and tetraisobutyl titanate into a reaction vessel, stirring at 70-80° C. for 5-6 hours, extracting, combining the organic phases, washing and drying, and separating by column chromatography to obtain compound 2;
[0025] (3) Compound 2 obtained in step (2) and sodium chloroacetate are added to ethanol, stirred at a constant temperature of 50-60° C. for 5-6 hours, and rotary evaporated and dried to obtain a quaternary ammonium salt monomer.
[0026] In some embodiments, the mass ratio of compound 1 to acrylic acid in step (2) is 1:(0.18-0.22).
[0027] In some embodiments, the mass ratio of compound 2 to sodium chloroacetate in step (3) is 1:(0.8-0.9).
[0028] The invention firstly opens the epoxy group of glycidyl ether and introduces a quaternary ammonium salt structure to obtain compound 1, then by limiting the mass ratio of compound 1 and acrylic acid, a hydroxyl group after the epoxy ring opening reacts with acrylic acid to obtain compound 2 with a double bond group, and then by a quaternary ammonium salt reaction, the mass ratio of compound 2 and sodium chloroacetate is limited to completely react the quaternary ammonium group in compound 2 to obtain a quaternary ammonium salt monomer with high surface activity and stability.
[0029] The second aspect of the present invention provides an application of a novel phosphate rock reverse flotation collector. The collector is mixed with deionized water to prepare a 1-3wt% collector solution, and the added amount is 0.94-0.96kg / t.
[0030] Compared with the prior art, the present invention has the following beneficial effects:
[0031] 1. The reverse flotation collector obtained by prepolymer-modified α-hydroxyoleic acid in the present invention has high solubility in water, does not need to be heated during flotation, is simple to operate, and has high selectivity and collection capacity.
[0032] 2. The present invention obtains a copolymer monomer containing multiple double bonds and carboxyl groups through the reaction of 1,5-hexadiene-3,4-diol and maleic anhydride, and limits the mass ratio of 1,5-hexadiene-3,4-diol and maleic anhydride so that the maleic anhydride is hydrolyzed and ring-opened to react with a hydroxyl group of 1,5-hexadiene-3,4-diol, thereby ensuring that the obtained multi-double bond monomer has sufficient active groups, which improves the water solubility of the collector on the one hand, and increases the adsorption to minerals on the other hand, thereby improving the collection capacity.
[0033] 3. The present invention first opens the epoxy group of glycidyl ether and adds a quaternary ammonium salt structure to obtain compound 1, and then by limiting the mass ratio of compound 1 and acrylic acid, a hydroxyl group after the epoxy ring opening is reacted with acrylic acid to obtain compound 2 with a double bond group, and then by quaternary ammonium salt reaction, the mass ratio of compound 2 and sodium chloroacetate is limited to make the quaternary ammonium group in compound 2 completely react, and the obtained quaternary ammonium salt monomer with higher surface activity and stability can complex the metal ions of minerals and further improve the collection capacity. DETAILED DESCRIPTION
[0034] The present invention will be described below in conjunction with specific embodiments. It should be noted that the following examples and comparative examples are only used to illustrate the present invention and are not intended to limit the present invention. Other combinations and various modifications within the concept of the present invention may be performed without departing from the spirit or scope of the present invention.
[0035] In order to facilitate those skilled in the art to implement the present invention, some raw materials and manufacturers of the embodiments and comparative examples are described as follows:
[0036] The compounds and related reagents used in the following examples and comparative examples can all be purchased from the market.
[0037] Preparation Example 1
[0038] The preparation method of a multi-double bond monomer-A comprises the following steps: adding 5 g of 1,5-hexadiene-3,4-diol, 11.5 g of maleic anhydride, and 0.01 g of benzodiquinone into a reaction container, stirring at 55° C. for 30 hours, and obtaining a multi-double bond monomer-A.
[0039] Preparation Example 2
[0040] The preparation method of multi-double bond monomer-B is the same as that of Preparation Example 1, except that the amount of maleic anhydride added is 15 g.
[0041] Preparation Example 3
[0042] The preparation method of quaternary ammonium salt monomer-A comprises the following steps:
[0043] (1) Add 10 g of glycidyl ether to 200 ml of a 30 wt% dimethylamine methanol solution, stir and react at 50° C. for 5.5 h, and rotary evaporate to obtain compound 1;
[0044] (2) Add 10 g of compound 1 obtained in step (1), 2 g of acrylic acid, and 0.1 g of tetraisobutyl titanate into a reaction vessel and stir at 75° C. for 5.5 h, extract, combine the organic phases, wash with 300 ml of saturated sodium chloride solution, dry, and separate by column chromatography to obtain compound 2;
[0045] (3) Add 10 g of compound 2 obtained in step (2) and 8.5 g of sodium chloroacetate to 100 ml of anhydrous ethanol, stir at a constant temperature of 55° C. for 5.5 h, and rotary evaporate and dry to obtain quaternary ammonium salt monomer-A.
[0046] Preparation Example 4
[0047] The preparation method of quaternary ammonium salt monomer-B is the same as that of Preparation Example 3, except that the amount of acrylic acid added is 2.6 g.
[0048] Preparation Example 5
[0049] The preparation method of quaternary ammonium salt monomer-C is the same as that of Preparation Example 3, except that the amount of sodium chloroacetate added is 6 g.
[0050] Preparation Example 6
[0051] The preparation method of monomer 1 comprises the following steps:
[0052] (1) Add 10 g of allyl glycidyl ether to 200 ml of a 30 wt % methanol solution of dimethylamine, stir and react at 50° C. for 5.5 h, and rotary evaporate to obtain compound 1;
[0053] (2) Add 10 g of compound 1 obtained in step (1) and 8.5 g of sodium chloroacetate to 100 ml of anhydrous ethanol, stir at 55° C. for 5.5 h, and perform rotary evaporation and dry to obtain monomer 1.
[0054] Preparation Example 7
[0055] The preparation method of Monomer 2 comprises the following steps: adding 5 g of propylene alcohol, 11.5 g of maleic anhydride, and 0.01 g of benzodiquinone into a reaction container, stirring at 55° C. for 30 hours, and obtaining Monomer 2.
[0056] Example 1
[0057] A method for preparing a novel phosphate rock reverse flotation collector comprises the following steps:
[0058] S1, 5g of multi-double bond monomer-A, 2g of quaternary ammonium salt monomer-A, and 1g of maleic anhydride were dissolved in 50ml of DMF, and 10ml of DMF solution containing 0.1g of azobisisobutyronitrile was added dropwise for 5min, and the mixture was stirred at 55°C to obtain a prepolymer with a number average molecular weight of 6441;
[0059] S2. Add 4 g of the prepolymer obtained in step S1 and 10 g of α-hydroxyoleic acid into a reaction container, stir at 75° C. for 2.5 h, and dry to obtain a novel phosphate rock reverse flotation collector.
[0060] Example 2
[0061] A method for preparing a novel phosphate rock reverse flotation collector comprises the following steps:
[0062] S1, dissolve 4g of multi-double bond monomer-A, 1g of quaternary ammonium salt monomer-A, and 1g of maleic anhydride in 50ml of DMF, dropwise add 10ml of DMF solution dissolved with 0.1g of azobisisobutyronitrile, stir at 50°C for 5min to complete the dropwise addition, and obtain a prepolymer with a number average molecular weight of 6187;
[0063] S2. Add 3 g of the prepolymer obtained in step S1 and 10 g of α-hydroxyoleic acid into a reaction container, stir at 70° C. for 3 h, and dry to obtain a novel phosphate rock reverse flotation collector.
[0064] Example 3
[0065] A method for preparing a novel phosphate rock reverse flotation collector comprises the following steps:
[0066] S1, dissolving 6g of multi-double bond monomer-A, 3g of quaternary ammonium salt monomer-A, and 1g of maleic anhydride in 50ml of DMF, adding dropwise 10ml of DMF solution containing 0.1g of azobisisobutyronitrile, stirring and reacting at 60°C, to obtain a prepolymer with a number average molecular weight of 6876;
[0067] S2. Add 5 g of the prepolymer obtained in step S1 and 10 g of α-hydroxyoleic acid into a reaction container, stir at 80° C. for 2 h, and dry to obtain a novel phosphate rock reverse flotation collector.
[0068] Example 4
[0069] A novel phosphate rock reverse flotation collector and a preparation method thereof. The specific implementation method is the same as that of Example 1, except that the multi-double bond monomer-A is replaced by the multi-double bond monomer-B in equal amounts.
[0070] Example 5
[0071] A novel phosphate ore reverse flotation collector and a preparation method thereof. The specific implementation manner is the same as that of Example 1, except that the number average molecular weight of the prepolymer is 8974.
[0072] Example 6
[0073] A novel phosphate rock reverse flotation collector and a preparation method thereof. The specific implementation method is the same as that of Example 1, except that an equal amount of quaternary ammonium salt monomer-A is replaced by a quaternary ammonium salt monomer-B.
[0074] Example 7
[0075] A novel phosphate rock reverse flotation collector and a preparation method thereof. The specific implementation method is the same as that of Example 1, except that the quaternary ammonium salt monomer-A is replaced by the quaternary ammonium salt monomer-C in equal amounts.
[0076] Example 8
[0077] A novel phosphate rock reverse flotation collector and a preparation method thereof. The specific implementation method is the same as that of Example 1, except that the amount of prepolymer added is 8g.
[0078] Comparative Example 1
[0079] A novel phosphate rock reverse flotation collector and a preparation method thereof. The specific implementation method is the same as that of Example 1, except that the multi-double bond monomer -A is replaced by monomer 2 in equal amounts.
[0080] Comparative Example 2
[0081] A novel phosphate rock reverse flotation collector and a preparation method thereof. The specific implementation method is the same as that of Example 1, except that the quaternary ammonium salt monomer-A is replaced by monomer 1 in equal amounts.
[0082] Performance Testing
[0083] 1. Flotation test
[0084] A medium-low-grade refractory collophanite from Hubei was selected for the experiment. The elemental analysis of the raw ore of the collophanite is shown in Table 1:
[0085] Table 1
[0086] Components <![CDATA[P2O5]]> MgO <![CDATA[SiO2]]> CaO <![CDATA[Fe2O3]]> <![CDATA[Al2O3]]> other Mass fraction % 26.7 4.5 5.5 50.7 1.6 1.9 9.1
[0087] Reverse flotation process:
[0088] (1) Pretreatment: 1000 g of crushed ore was wet-ground, with the mass ratio of ore to deionized water being 1:1, ground for 15 min, and passed through a 200-mesh sieve.
[0089] (2) Reverse flotation: 170 g of ground ore was added to the flotation tank, water was added to adjust the slurry, and the mixture was stirred evenly. 13 kg / t of 15 wt% sulfuric acid solution was added, and the mixture was stirred for 1 min. Then, 5 kg / t of 85 wt% phosphoric acid solution was added, and the mixture was stirred for 1 min. Then, 0.95 kg / t of 2 wt% collector solution was added, and the mixture was stirred for 5 min. After aeration and bubbling, the gangue minerals were flotated out by reverse flotation at room temperature. The scraping time was 6 min. The concentrate in the flotation tank was collected, and the P2O5 content was determined according to GB / T1871.1-1995. The recovery rate was calculated as follows: Recovery rate (%) = (weight of P2O5 in the concentrate / weight of P2O5 in the ore) × 100%
[0090] The experimental results are shown in Table 2.
[0091] Table 2
[0092] Group <![CDATA[P2O5%]]> <![CDATA[Recovery rate of P2O5 %]]> Example 1 34.15 94.01 Example 2 33.90. 90.99 Example 3 34.02 92.94 Example 4 33.42 90.21 Example 5 33.01 89.98 Example 6 32.93 85.03 Example 7 31.99 83.56 Example 8 31.05 81.45 Comparative Example 1 30.67 76.16 Comparative Example 2 30.11 73.91
[0093] By comparing the experimental data of Examples 1-3 in Table 2, it can be seen that the reverse flotation collector has good selectivity and a high recovery rate of phosphorus; by comparing Example 4 with Example 1, it can be seen that the change in the ratio of 1,5-hexadiene-3,4-diol and maleic anhydride in the multi-double bond monomer may cause the hydroxyl group to be completely reacted, the polar group to be reduced, and the recovery rate to be reduced; by comparing Example 5 with Example 1, it can be seen that the molecular weight of the prepolymer increases, which may cause the dissolution to slow down at room temperature and the recovery rate to decrease; by comparing Example 6 with Example 1, it can be seen that the change in the ratio of compound 1 and acrylic acid in the quaternary ammonium salt monomer may cause an increase in the number of double bonds and a decrease in the degree of crosslinking. Increase, the solubility of the collector decreases, and the recovery rate decreases; compared with Example 7 and Example 1, it can be seen that the change in the ratio of sodium chloroacetate and compound 2 in the quaternary ammonium salt monomer may lead to a decrease in the adsorption capacity of the ore and a decrease in the recovery rate; compared with Example 8 and Implementation 1, it can be seen that the change in the ratio of the prepolymer and α-hydroxyoleic acid may lead to a decrease in foaming and a decrease in the recovery rate; compared with Example 1, it can be seen that in Monomer 2, allyl alcohol is used to react with maleic anhydride, the number of active groups is reduced, and the recovery rate is significantly reduced; compared with Example 2 and Example 1, it can be seen that the number of quaternary ammonium groups in Monomer 1 is reduced, and the recovery rate is further reduced.
[0094] The above description is only a preferred embodiment of the present invention and does not limit the present invention in any form. Although the present invention has been disclosed as a preferred embodiment as above, it is not used to limit the present invention. Any technician familiar with this profession can make some changes or modifications to equivalent embodiments of equivalent changes using the technical contents disclosed above without departing from the scope of the technical solution of the present invention. However, any simple modification, equivalent change and modification made to the above embodiments based on the technical essence of the present invention without departing from the content of the technical solution of the present invention still fall within the scope of the technical solution of the present invention.
Claims
1. A method for preparing a novel phosphate rock reverse flotation collector, characterized in that: The following steps are involved: S1, dissolving a multi-double bond monomer, a quaternary ammonium salt monomer, and maleic anhydride in a solvent, adding an initiator, and stirring at 50-60° C. for 1-2 hours to obtain a prepolymer; S2. Add the prepolymer and α-hydroxyoleic acid obtained in step S1 into a reaction vessel, stir at 70-80° C. for 2-3 hours, and dry to obtain a novel phosphate rock reverse flotation collector.
2. The method for preparing a novel phosphate rock reverse flotation collector according to claim 1, characterized in that: The mass ratio of the prepolymer to α-hydroxyoleic acid in step S2 is (0.3-0.5):
1.
3. The method for preparing a novel phosphate rock reverse flotation collector according to claim 1, characterized in that: The structure of the multi-double bond monomer is: The structure of quaternary ammonium salt monomers is:
4. The method for preparing a novel phosphate rock reverse flotation collector according to claim 1, characterized in that: The number average molecular weight of the prepolymer is 6000-7000.
5. The method for preparing a novel phosphate rock reverse flotation collector according to claim 3, characterized in that: The preparation method of the multi-double bond monomer comprises the following steps: adding 1,5-hexadiene-3,4-diol, maleic anhydride and benzodiquinone into a reaction container, stirring at 50-60° C. for 28-32 hours, and obtaining the multi-double bond monomer.
6. The method for preparing a novel phosphate rock reverse flotation collector according to claim 5, characterized in that: The mass ratio of the 1,5-hexadiene-3,4-diol to maleic anhydride is 1:(1.8-2.6).
7. The method for preparing a novel phosphate rock reverse flotation collector according to claim 3, characterized in that: The preparation method of the quaternary ammonium salt monomer comprises the following steps: (1) adding glycidyl ether to a 28-32 wt % methanol solution of dimethylamine, stirring the mixture at 45-55° C. for 5-6 h, and rotary evaporating the mixture to obtain compound 1; (2) adding compound 1 obtained in step (1), acrylic acid and tetraisobutyl titanate into a reaction vessel, stirring at 70-80° C. for 5-6 hours, extracting, combining the organic phases, washing and drying, and separating by column chromatography to obtain compound 2; (3) Compound 2 obtained in step (2) and sodium chloroacetate are added to ethanol, stirred at a constant temperature of 50-60° C. for 5-6 hours, and rotary evaporated and dried to obtain a quaternary ammonium salt monomer.
8. The method for preparing a novel phosphate rock reverse flotation collector according to claim 7, characterized in that: In the step (2), the mass ratio of compound 1 to acrylic acid is 1:(0.18-0.22).
9. The method for preparing a novel phosphate rock reverse flotation collector according to claim 7, characterized in that: In the step (3), the mass ratio of compound 2 to sodium chloroacetate is 1:(0.8-0.9).
10. An application of a collector obtained by the preparation method of the novel phosphate ore reverse flotation collector according to claims 1-9, characterized in that: The collector is mixed with deionized water to prepare a 1-3 wt % collector solution, and the added amount is 0.94-0.96 kg / t.