A collector for collecting carbon and silicon by reverse flotation, and its preparation method and use

Abstract

The present invention relates to a collector for collecting carbon and silicon by reverse flotation, and a preparation method and use thereof. The collector comprises a cyclohexane acid imidazoline derivative, mineral oil and ether alcohol. The use comprises using the collector to reverse flotate and remove carbon and silicon from phosphogypsum waste residue, specifically as follows: mixing and stirring the phosphogypsum waste residue slurry with the collector, and performing reverse flotation operation to obtain silicon-containing carbon tailings and phosphogypsum concentrate. The reverse flotation collector can realize an economical and efficient phosphogypsum mixed flotation and silicon-carbon removal process in a strongly acidic environment, which not only improves the grade and whiteness of phosphogypsum, but also ensures a high recovery rate of phosphogypsum, and provides qualified raw materials for multi-path large-scale utilization of phosphogypsum.

Description

Technical Field

[0001] The invention relates to the field of solid waste beneficiation in the phosphorus chemical industry, and in particular to a collector for collecting carbon and silicon by reverse flotation, and a preparation method and application thereof. Background Art

[0002] At present, due to the low utilization rate of phosphogypsum, less than 10%, a large amount of land is used to store phosphogypsum, occupying precious land resources. In addition, the highly acidic phosphogypsum contains soluble phosphorus and fluorine, which will cause secondary pollution to the environment. Therefore, the harmless treatment and comprehensive utilization of phosphogypsum are urgent issues that need to be solved in the field of bulk solid waste resource disposal.

[0003] At present, the more mature process for industrial application of phosphogypsum flotation desiliconization and decarbonization is the reverse flotation decarbonization-positive flotation desiliconization process under a strongly acidic environment. This process uses mineral oil + frother for reverse flotation decarbonization, and then uses amine cationic collectors for positive flotation desiliconization. It is generally a one coarse and two fine process, with the middling ore returned.

[0004] For example, CN113695085A discloses a combined collector for desiliconization and carbon removal of phosphogypsum and a method for preparing a solution thereof, wherein the combined collector comprises a benzyl quaternary ammonium salt, a non-polar oil and / or an alcohol. The agent can achieve synchronous desiliconization and decarbonization in a strongly acidic environment, and the whiteness of the phosphogypsum concentrate can be increased from about 43 to 48-50, the desiliconization rate is 30-40%, and the content of calcium sulfate dihydrate can be increased by about 3 points. Although siliconization and carbon removal can be performed synchronously, the desiliconization rate is relatively low, only about 30%, and the content of calcium sulfate dihydrate in phosphogypsum is increased by only about 3 points. It is suitable for the reprocessing of phosphogypsum with relatively good quality, but not for phosphogypsum with a content of calcium sulfate dihydrate below 90%.

[0005] CN102500469A discloses a process for desiliconization and impurity removal of phosphogypsum by reverse flotation, wherein 1-15 kg / t of a regulator (caustic soda, water glass, lime, hydrochloric acid, etc.) and 1-10 kg / t of a collector (fatty acid, amine collector) are added to the phosphogypsum slurry, and the silicon dioxide content of the phosphogypsum can be reduced from 8-13% to less than 3% through one or two reverse flotation operations. However, there are problems such as large dosage of reagents, high reagent costs, and general desiliconization selectivity.

[0006] CN114308398A discloses a method for flotation washing, decolorization and purification of phosphogypsum, wherein ether diamine is added to the phosphogypsum slurry to perform three-coarse and one-sweep reverse flotation to obtain decolorized and purified phosphogypsum, and then a dispersant is added and fine impurities are removed by classification, and the finished high-purity phosphogypsum is obtained by concentration, filtration and drying. The desiliconization selectivity is average and the recovery rate of phosphogypsum is low.

[0007] However, the return water in the reverse flotation decarbonization-positive flotation desiliconization process must be reused according to quality. Positive flotation desiliconization has more flotation and less suppression, large flotation foam, high fixed investment and energy consumption, and complex process flow. At the same time, reverse flotation desiliconization in a strong alkaline environment requires multiple filter pressing-ore washing to adjust the pH value of the phosphogypsum slurry from strong acidity to weak acidity, and then add a large amount of lime to control the slurry pH to about 10 before reverse flotation desiliconization. Although the desiliconization rate is high, reaching about 80%, the strongly acidic return water from multiple washings cannot be reused, the beneficiation cost is high, and a large amount of lime enters the phosphogypsum concentrate, which also has an adverse effect on the application of phosphogypsum for building materials, such as reducing the strength of gypsum.

[0008] In summary, the treatment of phosphogypsum waste residue in the art still has problems such as complicated treatment process and poor silicon-carbon removal effect, which leads to poor whiteness and low grade of the obtained phosphogypsum product. Summary of the invention

[0009] In view of the problems existing in the prior art, the purpose of the present invention is to provide a collector for capturing carbon and silicon by reverse flotation, and a preparation method and use thereof, which can realize an economical and efficient mixed flotation silicon-carbon removal process for phosphogypsum in a strongly acidic environment, which not only improves the grade and whiteness of phosphogypsum, but also ensures a high recovery rate of phosphogypsum, thereby providing qualified raw materials for the multi-path large-scale utilization of phosphogypsum.

[0010] To achieve this object, the present invention adopts the following technical solutions:

[0011] In a first aspect, the present invention provides a collector for collecting carbon silicon by reverse flotation, wherein the collector comprises a cyclohexane acid imidazoline derivative, mineral oil and ether alcohol.

[0012] The collector provided by the present invention is compounded with specific cyclohexane acid imidazoline derivatives, mineral oil and ether alcohol, and can achieve the simultaneous removal of carbon and silicon in phosphogypsum through a reverse flotation process, thereby improving the indicators of phosphogypsum products, reducing the silicon dioxide content of phosphogypsum, and significantly improving the whiteness of phosphogypsum, which is conducive to further full utilization of phosphogypsum.

[0013] In the present invention, the mineral oil may be a mixture of saturated hydrocarbons and unsaturated hydrocarbons, such as diesel, kerosene or transformer oil, etc., whichever is commonly used in the art.

[0014] As a preferred technical solution of the present invention, the cycloalkanoic acid imidazoline derivative includes imidazoline quaternary ammonium salt.

[0015] Preferably, the ether alcohol comprises butyl ether alcohol.

[0016] In the present invention, the ether alcohol is a single substance, that is, an ether containing a hydroxyl group, rather than a mixture of ether and alcohol, such as propylene glycol butyl ether, 1,2-propylene glycol ether, dipropylene glycol butyl ether or propylene glycol methyl ether.

[0017] As a preferred technical solution of the present invention, the collector comprises 4-6 parts of cyclohexane acid imidazoline derivative, 1-2 parts of mineral oil and 1-2 parts of ether alcohol in parts by weight.

[0018] In the present invention, the cycloalkane acid imidazoline derivative in the collector is 4-6 parts by weight, for example, it can be 4 parts, 4.2 parts, 4.4 parts, 4.6 parts, 4.8 parts, 5 parts, 5.2 parts, 5.4 parts, 5.6 parts, 5.8 parts or 6 parts, but is not limited to the listed values, and other unlisted values ​​within this range are also applicable.

[0019] In the present invention, the mineral oil in the collector is 1-2 parts by weight, for example, it can be 1 part, 1.1 parts, 1.2 parts, 1.3 parts, 1.4 parts, 1.5 parts, 1.6 parts, 1.7 parts, 1.8 parts, 1.9 parts or 2 parts, but is not limited to the listed values, and other unlisted values ​​within this range are also applicable.

[0020] In the present invention, the ether alcohol in the collector is 1-2 parts by weight, for example, it can be 1 part, 1.1 parts, 1.2 parts, 1.3 parts, 1.4 parts, 1.5 parts, 1.6 parts, 1.7 parts, 1.8 parts, 1.9 parts or 2 parts, but is not limited to the listed values, and other unlisted values ​​within this range are also applicable.

[0021] In a second aspect, the present invention provides a method for preparing the catalyst as described in the first aspect, the preparation method comprising: mixing a cyclohexane acid imidazoline derivative, mineral oil and ether alcohol according to a formula to obtain the collector.

[0022] In a third aspect, the present invention provides a use of the catalyst as described in the first aspect, wherein the use comprises using the collector to perform reverse flotation decarbonization and desiliconization on phosphogypsum waste residue, as follows:

[0023] The phosphogypsum waste slag slurry is mixed and stirred with the collector, and reverse flotation operation is performed to obtain silicon-carbon tailings and phosphogypsum concentrate.

[0024] As a preferred technical solution of the present invention, the phosphogypsum waste slag slurry is obtained by slurrying phosphogypsum waste slag and water;

[0025] Preferably, the phosphogypsum waste residue comprises, by mass percentage, 80-85% of CaSO4·2H2O, 5-10% of SiO2, and ≤2.0% of organic carbon.

[0026] In the present invention, the mass percentage of CaSO4·2H2O in the phosphogypsum waste slag is 80-85%, for example, it can be 80%, 80.5%, 81%, 81.5%, 82%, 82.5%, 83%, 83.5%, 84%, 84.5% or 85%, etc., but is not limited to the listed values, and other unlisted values ​​within the range are also applicable.

[0027] In the present invention, the mass percentage of SiO2 in the phosphogypsum waste slag is 5-10%, for example, it can be 5%, 5.5%, 6%, 6.5%, 7%, 7.5%, 8%, 8.5%, 9%, 9.5% or 10%, etc., but is not limited to the listed values, and other unlisted values ​​within the range are also applicable.

[0028] In the present invention, the mass percentage of organic carbon in the phosphogypsum waste is ≤2%, for example, it can be 2%, 1.9%, 1.8%, 1.7%, 1.6%, 1.5%, 1.4%, 1.3%, 1.2%, 1.1%, 1%, 0.9%, 0.8%, 0.7%, 0.6%, 0.5%, 0.4%, 0.3%, 0.2% or 0.1%, etc., but is not limited to the listed values, and other unlisted values ​​within the range are also applicable.

[0029] As a preferred technical solution of the present invention, the slurry concentration of the phosphogypsum waste slurry is 20-45wt%, for example, it can be 20wt%, 21wt%, 22wt%, 23wt%, 24wt%, 25wt%, 26wt%, 27wt%, 28wt%, 29wt%, 30wt%, 31wt%, 32wt%, 33wt%, 34wt%, 35wy%, 36wt%, 37wt%, 38wt%, 39wt%, 40wt%, 41wt%, 42wt%, 43wt%, 44wt% or 45wt%, etc., but is not limited to the listed values, and other unlisted values ​​within the range are also applicable.

[0030] In the present invention, wt% refers to mass percentage.

[0031] Preferably, the pH value of the phosphogypsum waste slurry is 0.5-2, for example, it can be 0.5, 0.6, 0.7, 0.8, 0.9, 1, 1.1, 1.2, 1.3, 1.4, 1.5, 1.6, 1.7, 1.8, 1.9 or 2, but is not limited to the listed values, and other unlisted values ​​within this range are also applicable.

[0032] Preferably, the solid particles of -0.074 mm in the phosphogypsum waste slurry account for 60-70% of the mass of all solid particles, for example, it can be 60%, 61%, 62%, 63%, 64%, 65%, 66%, 67%, 68%, 69% or 70%, etc., but is not limited to the listed values, and other unlisted values ​​within this range are also applicable.

[0033] In the present invention, -0.074 mm refers to the undersize product obtained by sieving with a 0.074 mm sieve.

[0034] As a preferred technical solution of the present invention, the mixing and stirring time is 3-5min, for example, it can be 3min, 3.2min, 3.4min, 3.6min, 3.8min, 4min, 4.2min, 4.4min, 4.6min, 4.8min or 5min, but is not limited to the listed values, and other unlisted values ​​within the range are also applicable.

[0035] Preferably, the stirring speed of the mixed stirring is 1.5-2 m / s, for example, it can be 1.5 m / s, 1.6 m / s, 1.7 m / s, 1.8 m / s, 1.9 m / s or 2 m / s, but is not limited to the listed values, and other unlisted values ​​within the range are also applicable.

[0036] As a preferred technical solution of the present invention, the reverse flotation operation is performed at least once.

[0037] Preferably, the addition amount of the collector is 100-1000g / t, for example, it can be 100g / t, 150g / t, 200g / t, 250g / t, 300g / t, 350g / t, 400g / t, 450g / t, 500g / t, 550g / t, 600g / t, 650g / t, 700g / t, 750g / t, 800g / t, 850g / t, 900g / t, 950g / t or 1000g / t, but is not limited to the listed values, and other unlisted values ​​within the range are equally applicable.

[0038] In the present invention, the amount of collector added is the total amount added in the flotation operation, rather than the single amount added. When multiple reverse flotations are used, the amount of collector added in each stage can be adjusted according to the impurity content and tests.

[0039] In the present invention, g / t refers to adding a corresponding mass g of flotation collector to a certain amount of phosphogypsum waste residue.

[0040] In the present invention, the number of times the reverse flotation operation is performed can be designed according to the content of silicon and carbon in the phosphogypsum waste residue. In multiple reverse flotations, the obtained phosphogypsum product is obtained by mixing the phosphogypsum concentrate obtained in each reverse flotation.

[0041] Preferably, the reverse flotation operation is open circuit reverse flotation.

[0042] As a preferred technical solution of the present invention, the use includes using the collector to perform reverse flotation decarbonization and desiliconization on phosphogypsum waste residue, as follows:

[0043] The phosphogypsum waste slurry is mixed and stirred with the collector, and reverse flotation is performed to obtain silicon-carbon tailings and phosphogypsum concentrate;

[0044] The phosphogypsum waste slurry is obtained by slurrying the phosphogypsum waste slurry and water; the phosphogypsum waste slurry includes, by mass percentage, 80-85% of CaSO4·2H2O, 5-10% of SiO2, and ≤2.0% of organic carbon; the slurry concentration of the phosphogypsum waste slurry is 20-45wt%; the pH value of the phosphogypsum waste slurry is 0.5-2; the solid particles of -0.074mm in the phosphogypsum waste slurry account for 60-70% of the mass of all solid particles;

[0045] The mixing and stirring time is 3-5 minutes; the mixing and stirring speed is 1.5-2 m / s; the adding amount of the collector is 100-1000 g / t; the reverse flotation operation is performed at least once; and the reverse flotation operation is open circuit reverse flotation.

[0046] According to the above scheme, water is added to the phosphogypsum waste residue to make a slurry, and the slurry flows into the stirring tank. Then, a reverse flotation collector is added to the stirring tank for stirring and selective adsorption. The slurry-made material enters the reverse flotation system. The mineralized foam scraped out by the scraper is the tailings, which are discharged and piled up after dense filtration. The product in the tank is high-quality phosphogypsum, which enters the water washing system after filtration. The backwater generated by the tailings and phosphogypsum concentrate can be fully recycled to reduce the consumption of reagents and water resources.

[0047] Compared with the prior art solutions, the present invention has the following beneficial effects:

[0048] (1) By using a specific compound reagent, through one or two reverse flotation operations, the silicon-containing minerals and organic matter in the phosphogypsum waste residue are mixed and removed simultaneously, which not only reduces the silicon dioxide content of the phosphogypsum (≤2.85%), but also significantly improves the whiteness of the phosphogypsum (≥53).

[0049] (2) Only one collector is introduced in the flotation process, the process is simple and the reagent cost is low. The return water does not need to be separated and reused or specially treated, and can be fully reused, which saves reagent and water resource consumption and does not pollute the environment.

[0050] (3) The reverse flotation process is suitable for a strong acidic environment and is compatible with the pH environment of the slurry after phosphogypsum slurry adjustment. It also has a high silicon content in the tailings foam and can be directly used as a tailings storage or soil conditioner. The foam has good fluidity.

[0051] (4) This process can achieve a high recovery rate of phosphogypsum, which means that most of the phosphogypsum becomes qualified raw materials for building materials, acid production and cement production after reverse flotation and mixed flotation to remove impurities. This significantly increases the consumption of phosphogypsum and is conducive to the sustainable development of the phosphorus chemical industry. BRIEF DESCRIPTION OF THE DRAWINGS

[0052] Figure 1 It is a schematic diagram of the process of reverse flotation capture of carbon silicon provided by the present invention;

[0053] Figure 2 It is the process flow chart of Application Example 1 of the present invention.

[0054] The present invention is further described in detail below. However, the following examples are only simplified examples of the present invention and do not represent or limit the scope of protection of the present invention. The scope of protection of the present invention shall be subject to the claims. DETAILED DESCRIPTION

[0055] To better illustrate the present invention and facilitate understanding of the technical solution of the present invention, typical but non-limiting embodiments of the present invention are as follows:

[0056] Example 1

[0057] This embodiment provides a collector for collecting carbon and silicon by reverse flotation, wherein the collector comprises, by weight, 5 parts of a cyclohexane acid imidazoline derivative, 1 part of a mineral oil, and 1 part of an ether alcohol;

[0058] The cyclohexane acid imidazoline derivative is imidazoline quaternary ammonium salt, the ether alcohol is butyl ether alcohol, and the mineral oil is diesel and kerosene in a mass ratio of 1:1;

[0059] The above reagents are mixed according to the formula.

[0060] Example 2

[0061] This embodiment provides a collector for collecting carbon and silicon by reverse flotation. The collector comprises, by weight, 6 parts of cyclohexane acid imidazoline derivative, 2 parts of mineral oil and 1 part of ether alcohol.

[0062] The cyclohexane acid imidazoline derivative is imidazoline quaternary ammonium salt, the ether alcohol is butyl ether alcohol, and the mineral oil is diesel;

[0063] The above reagents are mixed according to the formula.

[0064] Example 3

[0065] This embodiment provides a collector for collecting carbon and silicon by reverse flotation. The collector comprises 4 parts of cyclohexane acid imidazoline derivative, 1 part of mineral oil and 2 parts of ether alcohol in parts by weight.

[0066] The cyclohexane acid imidazoline derivative is imidazoline quaternary ammonium salt, the ether alcohol is butyl ether alcohol, and the mineral oil is transformer oil and kerosene;

[0067] The above reagents are mixed according to the formula.

[0068] The imidazoline quaternary ammonium salt in the above-mentioned embodiment is the imidazoline quaternary ammonium salt (RT-90G) produced by Jinan Fine.

[0069] Furthermore, the present invention provides a specific use process of the obtained collector, such as Figure 1 As shown, the process is as follows: water is added to the phosphogypsum paste, i.e., the waste residue, to adjust the pulp, and the pulp concentration is controlled to be 20wt-45wt%, and the pulp pH value is 0.5-2.0; after the obtained strong acidic pulp is mixed and stirred with the reverse flotation collector, one or two mixed reverse flotation operations are performed to obtain silicon-carbon tailings and phosphogypsum concentrate according to the impurity content in the phosphogypsum paste.

[0070] The specific application process is as follows:

[0071] Application Example 1

[0072] This embodiment provides a method for beneficiation of phosphogypsum by simultaneous desiliconization and decarbonization, such as Figure 2 As shown, the phosphogypsum is produced by a semi-hydrated-dihydrate wet phosphoric acid process in Hubei Province. The silicon-containing minerals in the ore are mainly fine-grained quartz and wollastonite. The mass fraction of CaSO4·2H2O is 84.10%, the mass fraction of SiO2 is 7.32%, the mass fraction of organic carbon is 0.53%, and the whiteness is 31.

[0073] (1) slurrying the above-mentioned phosphogypsum raw paste, i.e., the waste residue, to control the slurry concentration to be 35% and the slurry pH value to be 1.0;

[0074] (2) the ore pulp obtained in step (1) enters a mixing tank and is mixed with a reverse flotation collector, and then enters a flotation machine for reverse flotation desiliconization and decarbonization roughing operation 1, thereby obtaining a silicon-carbon tailing 1 and a phosphogypsum concentrate 1; the phosphogypsum concentrate 1 enters an intermediate box of a flotation machine and is mixed with a reverse flotation mixed flotation collector, and then enters a flotation machine for reverse flotation desiliconization and decarbonization roughing operation 2, thereby obtaining a silicon-carbon tailing 2 and a phosphogypsum concentrate 2;

[0075] (3) The silicon-carbon tailings 1 and the silicon-carbon tailings 2 obtained in step (2) are combined into a total tailings, and the phosphogypsum concentrate 2 is filtered, dried at 45° C., and then aged to obtain a final phosphogypsum concentrate.

[0076] Wherein, the amount of reverse flotation collector added in the roughing 1 process of step (2) is 60 g / t; the amount of reverse flotation collector added in the roughing 2 process is 240 g / t;

[0077] The phosphogypsum concentrate finally obtained in this application example has a CaSO4·2H2O mass fraction of 92.50%, a SiO2 mass fraction of 2.51%, and a whiteness of 57.

[0078] Application Example 2

[0079] The present embodiment provides a beneficiation method for simultaneous desiliconization and decarbonization of phosphogypsum, wherein the phosphogypsum is produced by a dihydrate wet-process phosphoric acid process in Hubei Province, the silicon-containing minerals in the ore are mainly fine-grained quartz and wollastonite, the mass fraction of CaSO4·2H2O is 83.85%, the mass fraction of SiO2 is 8.67%, the mass fraction of organic carbon is 0.65%, and the whiteness is 27.

[0080] The method comprises the following steps:

[0081] (1) slurrying the above-mentioned phosphogypsum raw paste, i.e., the waste residue, to control the slurry concentration to be 30% and the slurry pH value to be 1.5;

[0082] (2) the ore pulp obtained in step (1) enters a mixing tank and is mixed with a reverse flotation collector, and then enters a flotation machine for reverse flotation desiliconization and decarbonization roughing operation 1, thereby obtaining a silicon-carbon tailing 1 and a phosphogypsum concentrate 1; the phosphogypsum concentrate 1 enters an intermediate box of a flotation machine and is mixed with a reverse flotation mixed flotation collector, and then enters a flotation machine for reverse flotation desiliconization and decarbonization roughing operation 2, thereby obtaining a silicon-carbon tailing 2 and a phosphogypsum concentrate 2;

[0083] (3) The silicon-carbon tailings 1 and the silicon-carbon tailings 2 obtained in step (2) are combined into a total tailings, and the phosphogypsum concentrate 2 is filtered and dried at 45° C. to obtain a final phosphogypsum concentrate.

[0084] Wherein, the amount of reverse flotation collector added in the roughing 1 process of step (2) is 300 g / t; the amount of reverse flotation collector added in the roughing 2 process is 100 g / t;

[0085] The phosphogypsum concentrate finally obtained in this application example has a CaSO4·2H2O mass fraction of 93.10%, a SiO2 mass fraction of 2.85%, and a whiteness of 53.

[0086] Application Example 3

[0087] The present embodiment provides a beneficiation method for simultaneous desiliconization and decarbonization of phosphogypsum, wherein the phosphogypsum is produced by a dihydrate wet-process phosphoric acid process in Sichuan, the silicon-containing minerals in the ore are mainly fine-grained quartz and wollastonite, the mass fraction of CaSO4·2H2O is 86.85%, the mass fraction of SiO2 is 7.05%, the mass fraction of organic carbon is 0.35%, and the whiteness is 38.

[0088] The method comprises the following steps:

[0089] (1) slurrying the phosphogypsum paste, i.e., the waste residue, to control the slurry concentration to be 45% and the slurry pH value to be 0.8;

[0090] (2) the ore pulp obtained in step (1) enters a mixing tank, is mixed with a reverse flotation collector, and then enters a flotation machine for reverse flotation desiliconization and decarbonization roughing operations to obtain silicon-carbon tailings 1 and phosphogypsum concentrate 1;

[0091] (3) The silicon-carbon tailings 1 obtained in step (2) are the final tailings, and the phosphogypsum concentrate 2 is filtered and then dried at 45°C to form the final phosphogypsum concentrate.

[0092] Wherein, the amount of reverse flotation collector added during the roughing process of step (2) is 350 g / t;

[0093] The phosphogypsum concentrate finally obtained in this application example has a CaSO4·2H2O mass fraction of 94.52%, a SiO2 mass fraction of 2.28%, and a whiteness of 58.

[0094] Application Example 4

[0095] The only difference from Application Example 3 is that the cyclohexanecarboxylic acid imidazoline derivative in the collector used in the reverse flotation process is replaced by an equal amount of cyclohexanecarboxylic acid.

[0096] The phosphogypsum concentrate finally obtained in this application example has a CaSO4·2H2O mass fraction of 86.25%, a SiO2 mass fraction of 7.08%, and a whiteness of 40.

[0097] Application Example 5

[0098] The only difference from Application Example 3 is that the alcohol ether in the collector used in the reverse flotation process is replaced by an equal amount of butanol.

[0099] The phosphogypsum concentrate finally obtained in this application example has a CaSO4·2H2O mass fraction of 92.25%, a SiO2 mass fraction of 3.78%, and a whiteness of 42.

[0100] Application Example 6

[0101] The only difference from Application Example 3 is that the alcohol ether in the collector used in the reverse flotation process is replaced by an equal amount of butyl ether.

[0102] The phosphogypsum concentrate finally obtained in this application example has a CaSO4·2H2O mass fraction of 92.38%, a SiO2 mass fraction of 3.85%, and a whiteness of 41.

[0103] Application Example 7

[0104] The only difference from Application Example 3 is that the alcohol ether in the collector used in the reverse flotation process is replaced by a mixture of butanol and butyl ether in equal amounts and proportions.

[0105] The phosphogypsum concentrate finally obtained in this application example has a CaSO4·2H2O mass fraction of 92.15%, a SiO2 mass fraction of 3.69%, and a whiteness of 41.

[0106] Application Example 8

[0107] The only difference from Application Example 3 is that the alcohol ether in the collector used in the reverse flotation process is replaced by an equal amount of C10 ether amine.

[0108] The phosphogypsum concentrate finally obtained in this application example has a CaSO4·2H2O mass fraction of 88.28%, a SiO2 mass fraction of 6.34%, and a whiteness of 43.

[0109] It can be seen from the results of the above embodiments and application examples that the composite collector provided by the present invention can effectively remove silicon and carbon from phosphogypsum under strong acidic conditions, which not only reduces the silicon dioxide content of phosphogypsum, but also significantly improves the whiteness of phosphogypsum. Furthermore, the process is simple and the cost of the reagent is low. The return water can be fully reused without separation and special treatment, which saves the consumption of reagents and water resources and does not pollute the environment.

[0110] It is stated that the present invention illustrates the detailed structural features of the present invention through the above embodiments, but the present invention is not limited to the above detailed structural features, that is, it does not mean that the present invention must rely on the above detailed structural features to be implemented. Those skilled in the art should understand that any improvement of the present invention, equivalent replacement of the components selected by the present invention, addition of auxiliary components, selection of specific methods, etc., all fall within the protection scope and disclosure scope of the present invention.

[0111] The preferred embodiments of the present invention are described in detail above. However, the present invention is not limited to the specific details in the above embodiments. Within the technical concept of the present invention, a variety of simple modifications can be made to the technical solution of the present invention, and these simple modifications all belong to the protection scope of the present invention.

[0112] It should also be noted that the various specific technical features described in the above specific embodiments can be combined in any suitable manner without contradiction. In order to avoid unnecessary repetition, the present invention will not further describe various possible combinations.

[0113] In addition, various embodiments of the present invention may be arbitrarily combined, and as long as they do not violate the concept of the present invention, they should also be regarded as the contents disclosed by the present invention.

Claims

1. A collector for collecting carbon and silicon by reverse flotation, characterized in that: The collectors include cyclohexane acid imidazoline derivatives, mineral oil and ether alcohol.

2. The collector according to claim 1, characterized in that The cycloalkanoic acid imidazoline derivatives include imidazoline quaternary ammonium salts.

3. The collector according to claim 1, characterized in that The ether alcohol includes butyl ether alcohol.

4. The collector according to claim 1 or 2, characterized in that The collector comprises, by weight, 4-6 parts of cyclohexane acid imidazoline derivative, 1-2 parts of mineral oil and 1-2 parts of ether alcohol.

5. The method for preparing a collector according to any one of claims 1 to 4, characterized in that: The preparation method comprises: mixing cyclohexane acid imidazoline derivatives, mineral oil and ether alcohol according to a formula to obtain the collector.

6. The use of a collector according to any one of claims 1 to 4, characterized in that: The use includes using the collector to perform reverse flotation decarbonization and desiliconization on phosphogypsum waste residue, as follows: The phosphogypsum waste slag slurry is mixed and stirred with the collector, and reverse flotation operation is performed to obtain silicon-carbon tailings and phosphogypsum concentrate.

7. The use according to claim 6, characterized in that The phosphogypsum waste slurry is obtained by slurrying the phosphogypsum waste slag and water.

8. The use according to claim 7, characterized in that The phosphogypsum waste residue comprises, by mass percentage, 80-85% of CaSO4·2H2O, 5-10% of SiO2, and ≤2.0% of organic carbon.

9. The use according to claim 6, characterized in that The phosphogypsum waste slurry has a slurry concentration of 20-45wt%.

10. The use according to claim 6, characterized in that: The pH value of the phosphogypsum waste slurry is 0.5-2.

11. The use according to claim 6, characterized in that: In the phosphogypsum waste slurry, solid particles with a diameter of -0.074 mm account for 60-70% of the mass of all solid particles.

12. The use according to claim 6, characterized in that: The mixing and stirring time is 3-5 minutes.

13. The use according to claim 6, characterized in that: The stirring speed of the mixing and stirring is 1.5-2m / s.

14. The use according to claim 6, characterized in that The reverse flotation operation is performed at least once.

15. The use according to claim 6, characterized in that: The added amount of the collector is 100-1000g / t.

16. The use according to claim 6, characterized in that The reverse flotation operation is open circuit reverse flotation.

17. The use according to claim 6, characterized in that: The use includes using the collector to perform reverse flotation decarbonization and desiliconization on phosphogypsum waste residue, as follows: The phosphogypsum waste slurry is mixed and stirred with the collector, and reverse flotation is performed to obtain silicon-carbon tailings and phosphogypsum concentrate; The phosphogypsum waste slurry is obtained by slurrying the phosphogypsum waste slag and water; The phosphogypsum waste slag comprises, by mass percentage, 80-85% of CaSO4·2H2O, 5-10% of SiO2, and ≤2.0% of organic carbon; the slurry concentration of the phosphogypsum waste slag slurry is 20-45wt%; the pH value of the phosphogypsum waste slurry is 0.5-2; the solid particles of -0.074mm in the phosphogypsum waste slurry account for 60-70% of the mass of all solid particles; The mixing and stirring time is 3-5 minutes; the mixing and stirring speed is 1.5-2 m / s; the adding amount of the collector is 100-1000 g / t; the reverse flotation operation is performed at least once; and the reverse flotation operation is open circuit reverse flotation.

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