Barite direct flotation collector and method of preparation thereof

Abstract

The application provides a barite positive flotation collector and a preparation method thereof, and relates to the technical field of ore dressing. The barite positive flotation collector is prepared from raw materials including the following components in parts by weight: 2-2.5 parts of sodium alkyl sulfonate, 3.5-4 parts of sulfonated oleic acid, 0.6-0.7 parts of a defoaming agent and 0.2-0.3 parts of a stabilizer. The barite positive flotation collector has high selectivity, high ore carrying capacity and good dispersibility, and can achieve excellent flotation effect on barite, thereby improving the concentrate recovery rate and the ore dressing efficiency. The preparation method of the barite positive flotation collector comprises the steps of sulfonated oleic acid preparation and collector preparation. The method has a simple process and is green and environmentally-friendly. The prepared collector has excellent effect and low cost, and is beneficial to production and use.

Description

Technical Field

[0001] The present application relates to the field of mineral processing technology, and in particular to a barite positive flotation collector and a preparation method thereof. Background Art

[0002] Barite is the most common mineral of barium, composed of barium sulfate. It occurs in low-temperature hydrothermal veins, such as quartz-barite and fluorite-barite veins, often coexisting with galena, sphalerite, chalcopyrite, and cinnabar. It can also occur in sedimentary rocks as nodules, often found in sedimentary manganese deposits and shallow marine muddy and sandy sedimentary rocks. Within the residual clay overburden of weathered residual deposits, it often forms nodules or blocks. It is chemically stable, insoluble in water and hydrochloric acid, and non-magnetic and non-toxic.

[0003] Barite is widely used as a weighting agent in oil and gas drilling muds, and its consumption in barium chemicals, fillers and other fields is also increasing year by year. However, most barite ores are of low grade and closely associated with other metal and non-metallic ores. In the early days, high-quality barite concentrates were separated mainly through jigging and spiral chutes. These traditional methods can only be used for high-grade ores with impurities that have a large difference in specific gravity from barite. They are difficult to achieve good results for low-grade and difficult-to-separate barite ores with fine-grained particles. Therefore, it is necessary to develop an efficient barite flotation collector. Summary of the Invention

[0004] The purpose of the present application is to provide a barite positive flotation collector with high selectivity, strong ore-carrying capacity and good dispersibility. The collector can achieve excellent flotation effect on barite and improve concentrate recovery rate and mineral processing efficiency.

[0005] Another object of the present application is to provide a method for preparing a barite positive flotation collector, which has a simple process, is green and environmentally friendly, and the prepared product collector has excellent effect, low cost, and is conducive to production and use.

[0006] The technical solution of this application is as follows:

[0007] On the one hand, an embodiment of the present application provides a barite positive flotation collector, which is prepared from raw materials including the following ingredients, in parts by weight: 2 to 2.5 parts of sodium alkyl sulfonate, 3.5 to 4 parts of sulfonated oleic acid, 0.6 to 0.7 parts of defoaming agent and 0.2 to 0.3 parts of stabilizer.

[0008] On the other hand, the present invention also provides a method for preparing a barite flotation collector, which comprises the following steps:

[0009] Preparation of sulfonated oleic acid: Heat oleic acid and add sulfonating agent dropwise, and react at constant temperature to prepare sulfonated oleic acid for later use;

[0010] Preparation of collector: sodium alkyl sulfonate, defoamer, stabilizer and prepared sulfonated oleic acid are added with water and stirred for reaction to obtain a finished collector.

[0011] Compared with the prior art, the embodiments of the present application have at least the following advantages or beneficial effects:

[0012] In response to the first aspect, an embodiment of the present application provides a barite positive flotation collector, which is prepared from raw materials including the following ingredients, in parts by weight: 2 to 2.5 parts of sodium alkyl sulfonate, 3.5 to 4 parts of sulfonated oleic acid, 0.6 to 0.7 parts of defoaming agent and 0.2 to 0.3 parts of stabilizer.

[0013] In the above embodiment, in its raw material components, sodium alkyl sulfonate has a complexing ability for barium ions, and by using sodium alkyl sulfonate, the selectivity of the product collector to barite ore can be effectively enhanced, and the capture flotation effect is improved. Sulfonated oleic acid is the product obtained by sulfonation of oleic acid by a sulfonating agent, and it also has a strong complexing ability for barium ions; In contrast, sodium alkyl sulfonate has good water solubility, but its carbon chain is shorter, and the floating speed after adsorption on the mineral surface is slower, while the sulfonated oleic acid carbon chain is longer, and its hydrophobicity is strong, and the floating speed after adsorption on the mineral surface is faster, and the two are used in combination with each other, which can further enhance the capture flotation effect of the product collector, and also help control the amount of reagent used in the production process, thereby saving reagent costs. At the same time, when using sodium alkyl sulfonate and sulfonated oleic acid, there may be a situation where flotation foam is too rich, for which it is necessary to control the foam; By adding defoamers and stabilizers, flotation foam can be effectively controlled, thereby preventing adverse phenomena such as running grooves in industrial production processes, more conducive to actual production use, and helping to further enhance the use effect of product collectors.

[0014] Such a barite positive flotation collector has high selectivity for barite ore and good dispersibility, can effectively collect and float barite ore, has low reagent cost, and has extremely high practical value.

[0015] Furthermore, in some embodiments of the present application, the defoaming agent is tributyl phosphate; and the stabilizer is polydimethylsiloxane.

[0016] In the above examples, tributyl phosphate is a colorless, nearly odorless liquid with low surface tension and slight solubility in water. Polydimethylsiloxane also has low surface tension, is heat-resistant and cold-resistant, is non-toxic and odorless, is physiologically inert, and has good chemical stability. The combination of tributyl phosphate and polydimethylsiloxane effectively controls excess foam during flotation, thereby preventing undesirable phenomena such as sluicing and further enhancing the capture and flotation efficiency of barite.

[0017] Furthermore, in some embodiments of the present application, the above-mentioned sodium alkyl sulfonate is sodium dodecyl sulfonate or sodium octadecyl sulfonate.

[0018] Furthermore, in some embodiments of the present application, the sulfonated oleic acid is prepared by reacting oleic acid and a sulfonating agent.

[0019] In the above embodiment, oleic acid is sulfonated by a sulfonation reaction to prepare sulfonated oleic acid, which has a strong ability to complex barium ions and good hydrophobicity, can float quickly, and improve flotation efficiency.

[0020] Furthermore, in some embodiments of the present application, the oleic acid is any one of soybean oleic acid, corn oleic acid or peanut oleic acid; and the sulfonating agent is concentrated sulfuric acid.

[0021] In view of the second aspect, the present application also provides a method for preparing a barite positive flotation collector, which comprises the following steps:

[0022] Preparation of sulfonated oleic acid: Heat oleic acid and add sulfonating agent dropwise, and react at constant temperature to prepare sulfonated oleic acid for later use;

[0023] Preparation of collector: sodium alkyl sulfonate, defoamer, stabilizer and prepared sulfonated oleic acid are added with water and stirred for reaction to obtain a finished collector.

[0024] In the above-described embodiment, oleic acid is first placed in a reactor and heated, then sulfonating agent is slowly added dropwise, sulfonated oleic acid is prepared by isothermal sulfonation reaction, for subsequent use. Then sodium alkyl sulfonate, defoamer, stabilizer and prepared sulfonated oleic acid are taken in proportion, it is placed in a stirred tank and heated and stirred reaction, and finally a milky paste is obtained, which is product collector. Whole preparation method flow is simple, and it is easy to large-scale production, and the product collector obtained by production is excellent in capturing flotation effect on barite, with low cost, and flotation production efficiency can be effectively improved.

[0025] Furthermore, in some embodiments of the present application, during the preparation process of the sulfonated oleic acid, oleic acid is heated to 90° C., and then a sulfonating agent is added dropwise, and the reaction is carried out at a constant temperature for 1 hour to prepare the sulfonated oleic acid.

[0026] In the above embodiment, the reaction temperature and time are controlled and the sulfonating agent is added slowly to ensure the normal progress of the reaction and the quality of the product sulfonated oleic acid, which is more conducive to production and application.

[0027] Furthermore, in some embodiments of the present application, in the preparation process of the sulfonated oleic acid, the amount of oleic acid used is 28.2 g, and the amount of the sulfonating agent used is 9.8 g.

[0028] Furthermore, in some embodiments of the present application, during the preparation of the collector, the weight ratio of the added raw materials to water is 3:2.

[0029] In the above embodiment, by controlling the amount of raw materials, the production cost is saved while ensuring the quality of the product collector, which is more conducive to actual production application.

[0030] Furthermore, in some embodiments of the present application, the following step is also included: the prepared finished collector is formulated into an aqueous solution with a solid content of 2 wt % for standby use.

[0031] In the above embodiment, when used in actual production, the prepared product collector is formulated into an aqueous solution with a solid content of 2 wt% to better control the amount of the agent used, save agent costs while meeting production needs, and improve production efficiency. DETAILED DESCRIPTION

[0032] To make the purpose, technical solutions and advantages of the examples of the present application clearer, the technical solutions in the examples of the present application will be described clearly and completely below. Where specific conditions are not specified in the examples, conventional conditions or conditions recommended by the manufacturer are used. Where the manufacturer of the reagents or instruments is not specified, they are all conventional products that can be purchased commercially.

[0033] It should be noted that the term "comprising" or any other variant thereof is intended to cover non-exclusive inclusion, so that a process, method, article or device comprising a series of elements includes not only those elements, but also includes other elements not explicitly listed, or also includes elements inherent to such process, method, article or device. In the absence of further restrictions, the elements defined by the sentence "comprising..." do not exclude the presence of other identical elements in the process, method, article or device comprising the above elements. In the absence of conflict, the embodiments in this application and the features in the embodiments may be combined with each other.

[0034] The features and performance of the present application are further described in detail below with reference to the embodiments.

[0035] Example 1

[0036] This embodiment provides a barite positive flotation collector, which is prepared by the following method:

[0037] Preparation of sulfonated oleic acid: Heat 28.2 g of soybean oleic acid to 90°C, then add 9.8 g of concentrated sulfuric acid dropwise and react at this temperature for 1 hour to obtain sulfonated oleic acid, which is then set aside.

[0038] Preparation of collector: 200 g of sodium octadecylsulfonate, 62 g of tributyl phosphate, 25 g of polydimethylsiloxane and 350 g of prepared sulfonated oleic acid were added with 425 g of water and stirred at 70° C. for 1 h to prepare a finished collector.

[0039] Example 2

[0040] This embodiment provides a barite positive flotation collector, which is prepared by the following method:

[0041] Preparation of sulfonated oleic acid: Heat 28.2 g of corn oleic acid to 90°C, then add 9.8 g of concentrated sulfuric acid dropwise and react at this temperature for 1 hour to obtain sulfonated oleic acid, which is then set aside.

[0042] Preparation of collector: 250 g of sodium dodecyl sulfate, 70 g of tributyl phosphate, 20 g of polydimethylsiloxane and 400 g of prepared sulfonated oleic acid were added with 493 g of water and stirred at 75° C. for 2 h to prepare a finished collector.

[0043] Example 3

[0044] This embodiment provides a barite positive flotation collector, which is prepared by the following method:

[0045] Preparation of sulfonated oleic acid: Heat 28.2 g of peanut oleic acid to 90°C, then add 9.8 g of concentrated sulfuric acid dropwise and react at this temperature for 1 hour to obtain sulfonated oleic acid, which is then set aside.

[0046] Preparation of collector: 220 g of sodium octadecylsulfonate, 60 g of tributyl phosphate, 30 g of polydimethylsiloxane and 380 g of prepared sulfonated oleic acid were added with 460 g of water and stirred at 75° C. for 1.5 h to prepare a finished collector.

[0047] Test Example 1

[0048] A barite flotation collector provided in Example 1 of the present application was used to perform a coarse and three fine flotation on a barite ore sample from Guizhou. The chemical composition of the ore sample is shown in Table 1:

[0049] Table 1

[0050] element <![CDATA[BaSO4]]> <![CDATA[SiO2]]> CaO <![CDATA[Al2O3]]> <![CDATA[CaF2]]> MgO Pb content% 60.74 24.37 4.36 3.71 0.17 1.56 0.19

[0051] The flotation process is as follows:

[0052] Ore pre-treatment: For the crushing of raw ore, the grinding fineness is less than -200 mesh, accounting for 67.35%.

[0053] Direct flotation enrichment: add 166g of raw ore to the flotation tank, add a certain amount of tap water to prepare the slurry, stir thoroughly, first add 1.5kg / t of water glass (5%) as a pH adjuster, stir for 2 minutes, then add 1.5kg / t of the prepared collector, stir for 4 minutes, aerate and bubbling, and then perform positive flotation at room temperature to scrape out BaSO4 minerals, with a scraping time of 5 minutes; filter and dry the tailings, add the concentrate to the flotation tank and tap water to prepare the slurry, add 0.2kg / t of water glass (5%) as a pH adjuster, stir for 2 minutes, aerate and bubbling, and then perform the first step of selection to scrape out BaSO4 The middlings are filtered and dried, the concentrate is added to the flotation tank and tap water for slurry preparation, 0.15 kg / t of water glass (5%) as a pH adjuster is added, stirred for 2 minutes, and after aeration and bubbling, the second step of finely selecting and scraping out BaSO4 minerals is carried out, the scraping time is 5 minutes, the middlings are filtered and dried, the concentrate is added to the flotation tank and tap water for slurry preparation, 0.15 kg / t of water glass (5%) as a pH adjuster is added, stirred for 2 minutes, and after aeration and bubbling, the third step of finely selecting and scraping out BaSO4 minerals is carried out, the scraping time is 5 minutes, and the middlings and concentrates are filtered and dried separately.

[0054] The Guizhou barite ore was floated using a barite positive flotation collector provided in Example 1 of the present application, and the BaSO4 content of the final concentrate was 98.74%, and the recovery rate reached 94.15%.

[0055] Test Example 2

[0056] A barite flotation collector provided in Example 2 of the present application was used to perform a coarse and three fine flotation on a barite ore sample from Sichuan. The chemical composition of the ore sample is shown in Table 2:

[0057] Table 2

[0058] element <![CDATA[BaSO4]]> <![CDATA[SiO2]]> CaO <![CDATA[Al2O3]]> <![CDATA[CaF2]]> MgO REO Pb content% 18.92 30.81 0.44 8.95 12.65 1.09 3.94 0.64

[0059] The flotation process is as follows:

[0060] Ore pre-treatment: For the crushing of raw ore, the grinding fineness is less than -200 mesh, accounting for 59.74%.

[0061] Direct flotation enrichment: add 166g of raw ore to the flotation tank, add a certain amount of tap water to prepare the slurry, stir thoroughly, first add 1.2kg / t of water glass (5%) as a pH adjuster, stir for 2 minutes, then add 1.0kg / t of the prepared collector, stir for 4 minutes, aerate and bubbling, and then perform positive flotation at room temperature to scrape out BaSO4 minerals, with a scraping time of 5 minutes; filter and dry the tailings, add the concentrate to the flotation tank and tap water to prepare the slurry, add 0.2kg / t of water glass (5%) as a pH adjuster, stir for 2 minutes, aerate and bubbling, and then perform the first step of concentrating to scrape out BaSO4 The middlings are filtered and dried, the concentrate is added to the flotation tank and tap water for slurry preparation, 0.15 kg / t of water glass (5%) as a pH adjuster is added, stirred for 2 minutes, and after aeration and bubbling, the second step of finely selecting and scraping out BaSO4 minerals is carried out, the scraping time is 5 minutes, the middlings are filtered and dried, the concentrate is added to the flotation tank and tap water for slurry preparation, 0.15 kg / t of water glass (5%) as a pH adjuster is added, stirred for 2 minutes, and after aeration and bubbling, the third step of finely selecting and scraping out BaSO4 minerals is carried out, the scraping time is 5 minutes, and the middlings and concentrates are filtered and dried separately.

[0062] The Sichuan barite ore was floated using a barite positive flotation collector provided in Example 2 of the present application, and the resulting concentrate had a BaSO4 content of 97.36% and a recovery rate of 89.72%.

[0063] Test Example 3

[0064] A barite flotation collector provided in Example 3 of the present application was used to perform a coarse and three fine flotation on a barite ore sample from Gansu. The chemical composition of the ore sample is shown in Table 3:

[0065] Table 3

[0066] element <![CDATA[BaSO4]]> <![CDATA[SiO2]]> CaO <![CDATA[Al2O3]]> <![CDATA[CaF2]]> MgO Ag Cu content% 63.24 32.10 0.12 0.55 1.85 0.02 1.188 0.112

[0067] The flotation process is as follows:

[0068] Ore pre-treatment: For the crushing of raw ore, the grinding fineness is less than -200 mesh, accounting for 71.65%.

[0069] Direct flotation enrichment: Add 166g of raw ore to the flotation tank, add a certain amount of tap water to prepare the slurry, stir thoroughly, first add 1.5kg / t of water glass (5%) as a pH adjuster, stir for 2 minutes, then add 1.8kg / t of the collector prepared above, stir for 4 minutes, aerate and bubbling, and then perform positive flotation at room temperature to scrape out BaSO4 minerals, with a scraping time of 5 minutes; the tailings are filtered and dried, and the concentrate is added to the flotation tank and tap water to prepare the slurry, and 0.5kg / t of water glass (5%) as a pH adjuster is added, stirred for 2 minutes, aerated and bubbling, and then the first step of concentration is performed to scrape out BaSO4. The middlings are filtered and dried, the concentrate is added to the flotation tank and tap water for slurry preparation, 0.20 kg / t of water glass (5%) as a pH adjuster is added, stirred for 2 minutes, and after aeration and bubbling, the second step of finely selecting and scraping out BaSO4 minerals is carried out, the scraping time is 5 minutes, the middlings are filtered and dried, the concentrate is added to the flotation tank and tap water for slurry preparation, 0.15 kg / t of water glass (5%) as a pH adjuster is added, stirred for 2 minutes, and after aeration and bubbling, the third step of finely selecting and scraping out BaSO4 minerals is carried out, the scraping time is 5 minutes, and the middlings and concentrates are filtered and dried separately.

[0070] The Gansu barite ore was floated using a barite positive flotation collector provided in Example 2 of the present application, and the resulting concentrate had a BaSO4 content of 97.98% and a recovery rate of 93.58%.

[0071] Experiments have shown that by using a barite positive flotation collector provided in this application to float barite ore samples, a concentrate product with a BaSO4 content greater than 97% can be obtained, with a recovery rate greater than 89% and excellent flotation effect.

[0072] In summary, the present application embodiment provides a kind of barite positive flotation collector and its preparation method, such a kind of barite positive flotation collector, it has high selectivity to barite ore, good dispersibility, can effectively capture and flotate barite ore, and low reagent cost, with extremely high practical value. The preparation method process is simple, is convenient for large-scale production, and the product collector produced has excellent barite capture and flotation effect, low cost, and can effectively improve flotation production efficiency.

[0073] The embodiments described above are part of the embodiments of the present application, rather than all of the embodiments. The detailed description of the embodiments of the present application is not intended to limit the scope of the present application for protection, but merely represents selected embodiments of the present application. Based on the embodiments in the present application, all other embodiments obtained by ordinary technicians in this field without making creative efforts are within the scope of protection of this application.

Claims

1. A barite positive flotation collector, characterized in that: The invention is prepared from the following raw materials by weight: 2 to 2.5 parts of sodium alkyl sulfonate, 3.5 to 4 parts of sulfonated oleic acid, 0.6 to 0.7 parts of defoaming agent and 0.2 to 0.3 parts of stabilizer, wherein the defoaming agent is tributyl phosphate; the stabilizer is polydimethylsiloxane, wherein: The sulfonated oleic acid is prepared by reacting soybean oleic acid, corn oleic acid or peanut oleic acid with concentrated sulfuric acid at 90°C.

2. A barite positive flotation collector according to claim 1, characterized in that, The sodium alkyl sulfonate is sodium dodecyl sulfonate or sodium octadecyl sulfonate.

3. A method for preparing a barite flotation collector, for preparing a barite flotation collector according to any one of claims 1 to 2, characterized in that: It includes the following steps: Preparation of sulfonated oleic acid: heat any one of soybean oleic acid, corn oleic acid or peanut oleic acid, add concentrated sulfuric acid dropwise, and react at a constant temperature to prepare sulfonated oleic acid, which is then set aside; Preparation of collector: sodium alkyl sulfonate, defoamer, stabilizer and prepared sulfonated oleic acid are added with water and stirred for reaction to obtain a finished collector.

4. The method for preparing a barite positive flotation collector according to claim 3, wherein In the preparation process of the sulfonated oleic acid, oleic acid is heated to 90° C., and then a sulfonating agent is added dropwise, and the reaction is carried out at a constant temperature for 1 hour to prepare the sulfonated oleic acid.

5. The method for preparing a barite positive flotation collector according to claim 3, wherein: During the preparation of the collector, the weight ratio of the added raw materials to water is 3:

2.

6. The method for preparing a barite positive flotation collector according to claim 3, wherein: During the preparation of the collector, the reaction is stirred at 70-75° C. for 1-2 hours.

7. The method for preparing a barite positive flotation collector according to claim 3, wherein: The method further comprises the following steps: preparing the prepared finished collector into an aqueous solution with a solid content of 2 wt % for standby use.