Emulsion type collecting agent prepared based on oil-water two-phase emulsifier phase composition transformation method and preparation method and application thereof

Abstract

The invention discloses an emulsion type collecting agent prepared on the basis of an oil-water two-phase emulsifier phase composition transformation method and a preparation method and application of the emulsion type collecting agent, and the emulsion type collecting agent with the total mass fraction of 100 is prepared from 20-40 parts of an oily collecting agent, 1-5 parts of a W / O emulsifier, 4-10 parts of an O / W emulsifier and a plurality of parts of water. When the emulsion type collecting agent is prepared, the HLB value of a system can be accurately controlled by adjusting the mass ratio of the W / O emulsifier to the O / W emulsifier, the phase transformation process from W / O emulsion to bicontinuous phase and O / W emulsion is achieved, and then the emulsion type collecting agent with excellent performance is prepared. The average particle size of the emulsion type collecting agent is about 0.5 mu m, compared with a traditional oily collecting agent, the emulsion type collecting agent is better in dispersity, smaller in particle size and larger in specific surface area, the collision and adhesion probability of the collecting agent and particles is remarkably increased, and the low-rank coal interface hydrophobic modification effect and the flotation recovery rate are improved.

Description

Technical Field

[0001] The invention belongs to the technical field of mineral flotation process intensification, and particularly relates to an emulsion collector prepared based on an oil-water two-phase emulsifier phase composition transformation method, and a preparation method and application thereof. Background Art

[0002] Coal slime is a mixture of clean coal particles, kaolinite, quartz, montmorillonite, calcite and other common minerals, among which clean coal particles are the final desired product, while coal slime minerals such as kaolinite, quartz and montmorillonite are usually used as abandoned tailings. Flotation is an effective way to improve the quality of coal slime, but low-rank coal has a low degree of metamorphism, and its surface contains rich oxygen-containing functional groups (such as hydroxyl, carboxyl, etc.) and a developed pore structure, resulting in poor surface hydrophobicity. Conventional oily collectors (such as diesel and kerosene) are difficult to effectively adsorb on the surface of coal particles during flotation, resulting in low flotation efficiency and poor selectivity. In addition, the high porosity of low-rank coal will adsorb a large amount of collectors, resulting in a significant increase in the amount of drugs used, which not only increases production costs, but also aggravates environmental pollution. At the same time, the oxygen-containing functional groups on the surface of low-rank coal easily form hydrogen bonds with water molecules, further reducing its floatability, making the application effect of traditional collectors in the flotation of low-rank coal far lower than that of high-rank coal. Therefore, developing a new technology that can effectively improve the hydrophobicity of low-rank coal and significantly reduce the amount of collector used has become a key issue that needs to be urgently addressed in the field of efficient low-rank coal sorting.

[0003] As an efficient carrier of oily collectors, emulsions can significantly improve the adsorption efficiency of collectors on the surface of low-rank coal and reduce the amount of collectors used through the strong adsorption capacity and high specific surface area of ​​nano-micron droplets. However, traditional emulsion preparation methods (such as mechanical stirring and high-pressure homogenization) are difficult to achieve nano-micron dispersion of droplets, and have poor stability. They are prone to stratification, agglomeration or rupture during flotation, and cannot meet the needs of low-rank coal flotation. In addition, the particle size distribution of traditional emulsions is relatively wide, making it difficult to achieve uniform adsorption of collectors on the surface of low-rank coal, further limiting their application effect. Summary of the invention

[0004] In view of the deficiencies of the prior art, the present invention provides an emulsion-type collector prepared based on the phase composition transformation method of an oil-water two-phase emulsifier, and a preparation method and application thereof. The present invention can accurately control the HLB value of the system by adjusting the mass ratio of the W / O emulsifier to the O / W emulsifier, realize the phase transformation process from the W / O emulsion to the bicontinuous phase and the O / W emulsion, and then successfully prepare an emulsion-type collector with a smaller particle size, effectively solving the problem of low collision adhesion efficiency caused by the excessively large emulsion particle size and poor stability, thereby meeting the flotation production needs of the coal preparation plant. The technical solution provided by the present invention is as follows:

[0005] In the first aspect of the present invention, there is provided an emulsion-type collector prepared by a method based on the phase composition transformation of an oil-water biphasic emulsifier, which comprises 20 - 40 parts of an oily collecting agent, 1 - 5 parts of a W / O emulsifier, 4 - 10 parts of an O / W emulsifier and several parts of water, and is formulated into an emulsion-type collector with a total mass fraction of 100.

[0006] The oily collecting agent is any one or a mixture of several of diesel oil, kerosene, gasoline, oleic acid esters, oleic acid, erucic acid, coconut oil amine or octadecyl amine.

[0007] The W / O emulsifier (water-in-oil emulsifier) is any one or a mixture of several of Span, glycerol monostearate, sodium oleate or sodium erucate.

[0008] The O / W emulsifier (oil-in-water emulsifier) is any one or a mixture of several of Tween, fatty alcohol polyoxyethylene ether, polyoxyethylene stearate or fatty alcohol polyoxyethylene ether carboxylate sodium.

[0009] In the second aspect of the present invention, there is provided a preparation method of an emulsion-type collector prepared by a method based on the phase composition transformation of an oil-water biphasic emulsifier. This method does not require high shear force or homogenization equipment, reduces the input of mechanical energy, and reduces the risk of demulsification. The specific steps are as follows:

[0010] (1) Weigh 20 - 40 parts of an oily collecting agent, 1 - 5 parts of a W / O emulsifier and 4 - 10 parts of an O / W emulsifier by mass fraction and mix them in a container to obtain a mixed agent.

[0011] (2) Magnetically stir the mixed agent in the container at a rotation speed of 800 - 1000 r / min for a shearing time of 5 - 10 min to fully mix the oil phase and avoid unstable emulsification caused by local concentration differences in the subsequent process, so as to obtain a mixed oil phase.

[0012] (3) Slowly add water to the mixed oil phase in (2) at a constant rate of 0.05 - 0.5 mL / min using a micro syringe until the solution weight reaches 100 parts, and stir the mixture at a rotation speed of 200 - 300 r / min during the addition process to obtain an emulsion-type collector product.

[0013] With the addition of deionized water, the emulsion realizes the transformation from W / O to bicontinuous phase and then to O / W. In the embodiments of the present invention, an emulsion with an average particle size of about 400 - 710 nm is prepared, and further an emulsion with a particle size of 407.3 - 703.3 nm is prepared.

[0014] In the third aspect of the present invention, there is provided an application of an emulsion-type collector prepared by a method based on the phase composition transformation of an oil-water biphasic emulsifier in the flotation of coal slime.

[0015] Further, the slime is low-rank coal.

[0016] Specifically, the application method is as follows: adjust the concentration of the low-rank coal slurry, add an emulsion-type collector, and after mixing evenly with the slurry, add a foaming agent, stir and mix evenly, and then carry out aeration flotation.

[0017] Among them, the concentration of the flotation slurry is 60-100 g / L, and the dosage of the emulsion-type collector is 2-3 kg per ton of coal.

[0018] The added foaming agent is one or a mixture of sec-octanol, methyl isobutyl carbinol, and pine oil. Sec-octanol is selected for the test, and the dosage is 0.1-1 kg per ton of dry coal for flotation; after adding the foaming agent, the pulp is adjusted for 30 s, and then aeration flotation is carried out.

[0019] Among them, the aeration volume is 0.1-0.3 m 3 / h, the stirring speed is 1500-2000 r / min, and the flotation time is about 2-3 min.

[0020] Compared with the prior art, the beneficial effects of the present invention are as follows:

[0021] (1) The emulsion-type collector prepared by the present invention based on the phase inversion composition (PIC) method of the oil-water double-phase emulsifier provides a brand-new flotation reagent for the flotation of low-rank coal. Compared with traditional hydrocarbon oil collectors and ordinary emulsion-type collectors, this emulsion has a smaller particle size (nanometer to micrometer level) and excellent dispersibility, which can significantly increase the collision probability and adhesion efficiency between the emulsion and coal particles, thereby effectively improving the hydrophobic modification effect of the low-rank coal interface and the separation efficiency from gangue minerals, and solving the problem of low flotation efficiency of low-rank coal.

[0022] (2) By regulating the ratio of the oil-water double-phase emulsifier, the present invention can prepare a nano-microemulsion with high stability and strong adsorption ability. This emulsion can uniformly cover the oxygen-containing functional groups and pore structures on the surface of low-rank coal, significantly reduce the specific surface area of coal particles, reduce the ineffective adsorption of the collector, and thus greatly reduce the dosage of the collector and save production costs.

[0023] (3) The emulsion-type collector prepared by the present invention has excellent kinetic and thermodynamic stability, can maintain a uniformly dispersed state during long-term storage and transportation, and is not prone to stratification, coalescence or rupture. In addition, this emulsion can still maintain stable performance after high-speed stirring or a large amount of water dilution during the actual flotation process, which provides convenience for coal preparation production.

[0024] (4) The emulsion-type collector designed by the present invention can flexibly adjust the emulsifier formula and preparation process according to the surface characteristics (such as oxygen-containing functional group content, pore structure, etc.) of different low-rank coals, showing high adaptability and flexibility.

[0025] (5) The emulsion-type collector prepared by the phase composition transformation (PIC) method adopted in the present invention has a simple and efficient process, does not require high-energy-consuming equipment, can complete the preparation of the emulsion at normal temperature or a lower temperature, significantly reduces the production cost and energy consumption, and is suitable for large-scale industrial application. Description of the Drawings

[0026] The attached drawings forming a part of the present invention are used to provide a further understanding of the present invention. The schematic embodiments and descriptions thereof of the present invention are used to explain the present invention and do not constitute an improper limitation to the present invention.

[0027] Figure 1 Macrophotographs of the emulsion-type collectors prepared in Examples 1-6.

[0028] Figure 2 Microscopic morphology photographs of the emulsion-type collectors prepared in Examples 1-6.

[0029] Figure 3 Particle size distribution data of the emulsion-type collectors prepared in Examples 1-6.

[0030] Figure 4 ΔBS dynamic stability curves of the emulsion-type collectors prepared in Examples 1-6.

[0031] Figure 5 Contact angle changes of the coal samples treated with the emulsion-type collectors prepared in Examples 1-6.

[0032] Wherein, Figures 1 - 5 The example marks in the examples are marked as instances. Detailed Embodiments

[0033] In order to help practitioners in the professional field better understand this technological innovation, the following will provide a detailed interpretation of the excellent practices of this technology. However, the following practical cases do not specifically limit the protection scope of this innovation.

[0034] In the actual operation of the present invention, the experimental conditions are not specifically specified and are all carried out according to the conventional operations and conditions in this field. The materials used are commercially available products if not otherwise specified.

[0035] Example 1

[0036] An emulsion-type collector prepared by the phase composition transformation (PIC) method based on an oil-water biphasic emulsifier, and its components are calculated by mass fraction and include: 20% of a collector agent, 2% of a W / O emulsifier, 8% of an O / W emulsifier, and 70% of water. Among them, the collector is diesel oil, the W / O emulsifier is Span-80, and the O / W emulsifier is Tween-80.

[0037] The nano-collector is prepared according to the following steps:

[0038] (1) Weigh each component by mass fraction: weigh 20 parts of diesel, 2 parts of Span-80, 8 parts of Tween-80, and 70 parts of deionized water.

[0039] (2) Put the weighed diesel, Span-80, and Tween-80 into a beaker and mix them evenly on a magnetic stirrer (rotation speed is 1000 r / min, stirring time is 5 min, at room temperature) to prepare a mixed oil phase with an HLB value of 12.78.

[0040] (3) Slowly add the weighed deionized water in (1) to the mixed oil phase at a speed of 0.5 mL / min using a syringe, and at the same time, stir the mixture with a magnetic stirrer at a speed of 250 r / min to achieve the transformation of the emulsion from W / O to bicontinuous phase and then to O / W. When the addition of deionized water is completed, a uniform and stable emulsion-type collector can be prepared, and the average particle size of the emulsion is 491.3 nm.

[0041] Example 2

[0042] An emulsion-type collector prepared by the phase inversion composition (PIC) method based on oil-water biphasic emulsifier and its preparation method and application. Its components by mass fraction include: 25% of collector agent, 1% of W / O emulsifier, 4% of O / W emulsifier, and 70% of water. Among them, the collector is diesel, the W / O emulsifier is Span-80, and the O / W emulsifier is Tween-80.

[0043] The nano-collector is prepared according to the following steps:

[0044] (1) Weigh each component by mass fraction: weigh 25 parts of diesel, 1 part of Span-80, 4 parts of Tween-80, and 70 parts of deionized water.

[0045] (2) Put the weighed diesel, Span-80, and Tween-80 into a beaker and mix them evenly on a magnetic stirrer (rotation speed is 1000 r / min, stirring time is 5 min, at room temperature) to prepare a mixed oil phase with an HLB value of 12.78.

[0046] (3) Slowly add the weighed deionized water in (1) to the mixed oil phase at a speed of 0.5 ml / min using a syringe, and at the same time, stir the mixture with a magnetic stirrer at a speed of 250 r / min to achieve the transformation of the emulsion from W / O to bicontinuous phase and then to O / W. When the addition of deionized water is completed, a uniform and stable emulsion-type collector can be prepared, and the average particle size of the emulsion is 516.7 nm.

[0047] Example 3

[0048] An emulsion-type collector prepared by the phase inversion composition (PIC) method of oil-water biphasic emulsifier, its preparation method and application, the components are calculated by mass fraction, including: collector agent 20%, W / O emulsifier 2% and O / W emulsifier 8%, water 70%, wherein the collector is diesel oil, the W / O emulsifier is glycerol monostearate, and the O / W emulsifier is polyoxyethylene stearate.

[0049] The nano-collector is prepared according to the following steps:

[0050] (1) Weigh each component by mass fraction: weigh 20 parts of diesel oil, 2 parts of glycerol monostearate, 8 parts of polyoxyethylene stearate, and 70 parts of deionized water.

[0051] (2) Put the weighed diesel oil, glycerol monostearate, and polyoxyethylene stearate in a beaker and mix them evenly on a magnetic stirrer (rotation speed is 1000 r / min, stirring time is 5 min, room temperature) to prepare a mixed oil phase with an HLB value of 13.96.

[0052] (3) Slowly drop the deionized water weighed in (1) into the mixed oil phase at a speed of 0.5 ml / min using a syringe, and at the same time use a magnetic stirrer to stir the mixture at a speed of 250 r / min to achieve the transformation of the emulsion from W / O to bicontinuous phase and then to O / W. When the addition of deionized water is completed, a uniform and stable emulsion-type collector can be prepared, and the average particle size of the emulsion is 494.6 nm.

[0053] Example 4

[0054] An emulsion-type collector prepared by the phase inversion composition (PIC) method of oil-water biphasic emulsifier, its preparation method and application, the components are calculated by mass fraction, including: collector agent 25%, W / O emulsifier 1% and O / W emulsifier 4%, water 70%, wherein the collector is diesel oil, the W / O emulsifier is glycerol monostearate, and the O / W emulsifier is polyoxyethylene stearate.

[0055] The nano-collector is prepared according to the following steps:

[0056] (1) Weigh each component by mass fraction: weigh 25 parts of diesel oil, 1 part of glycerol monostearate, 4 parts of polyoxyethylene stearate, and 70 parts of deionized water.

[0057] (2) Put the weighed diesel oil, glycerol monostearate, and polyoxyethylene stearate in a beaker and mix them evenly on a magnetic stirrer (rotation speed is 1000 r / min, stirring time is 5 min, room temperature) to prepare a mixed oil phase with an HLB value of 13.96.

[0058] (3) Slowly add the deionized water weighed in (1) to the mixed oil phase at a rate of 0.5 ml / min using a syringe, and at the same time, stir the mixture with a magnetic stirrer at a speed of 250 r / min to achieve the transformation of the emulsion from W / O to bicontinuous phase and then to O / W. When the addition of deionized water is completed, a homogeneous and stable emulsion-type collector can be prepared, and the average particle size of the emulsion is 703.3 nm.

[0059] Example 5

[0060] An emulsion-type collector prepared by the phase inversion composition (PIC) method based on oil-water biphasic emulsifier and its preparation method and application. The components are calculated by mass fraction and include: 20% of collector agent, 2% of W / O emulsifier, 8% of O / W emulsifier, and 70% of water. The collector is octadecylamine, the W / O emulsifier is glycerol monostearate, and the O / W emulsifier is polyoxyethylene stearate.

[0061] The nano-collector is prepared according to the following steps:

[0062] (1) Weigh each component by mass fraction: weigh 20 parts of octadecylamine, 2 parts of glycerol monostearate, 8 parts of polyoxyethylene stearate, and 70 parts of deionized water.

[0063] (2) Put the weighed octadecylamine, glycerol monostearate, and polyoxyethylene stearate in a beaker and mix them evenly on a magnetic stirrer (rotation speed: 1000 r / min, stirring time: 5 min, room temperature) to prepare a mixed oil phase with an HLB value of 13.96.

[0064] (3) Slowly add the deionized water weighed in (1) to the mixed oil phase at a rate of 0.5 ml / min using a syringe, and at the same time, stir the mixture with a magnetic stirrer at a speed of 250 r / min to achieve the transformation of the emulsion from W / O to bicontinuous phase and then to O / W. When the addition of deionized water is completed, a homogeneous and stable emulsion-type collector can be prepared, and the average particle size of the emulsion is 407.3 nm.

[0065] Example 6

[0066] An emulsion-type collector prepared by the phase inversion composition (PIC) method based on oil-water biphasic emulsifier and its preparation method and application. The components are calculated by mass fraction and include: 25% of collector agent, 1% of W / O emulsifier, 4% of O / W emulsifier, and 70% of water. The collector is octadecylamine, the W / O emulsifier is glycerol monostearate, and the O / W emulsifier is polyoxyethylene stearate.

[0067] The nano-collector is prepared according to the following steps:

[0068] (1) Weigh each component by mass fraction: weigh 25 parts of octadecylamine, 1 part of glycerol monostearate, 4 parts of polyethylene glycol stearate, and 70 parts of deionized water.

[0069] (2) Put the weighed octadecylamine, glycerol monostearate, and polyethylene glycol stearate in a beaker and mix them evenly on a magnetic stirrer (rotation speed is 1000 r / min, stirring time is 5 min, at room temperature) to prepare a mixed oil phase with an HLB value of 13.96.

[0070] (3) Use a syringe to slowly drip the weighed deionized water in (1) into the mixed oil phase at a speed of 0.5 ml / min, and at the same time use a magnetic stirrer to stir the mixture at a speed of 250 r / min to achieve the transformation of the emulsion from W / O to bicontinuous phase and then to O / W. When the addition of deionized water is completed, a uniform and stable emulsion-type collector can be prepared, and the average particle size of the emulsion is 637.9 nm.

[0071] Example 7

[0072] An emulsion-type collector prepared by the phase inversion composition (PIC) method based on an oil-water biphasic emulsifier, the components of which are in mass fraction, including: 20% of collector agent, 2% of W / O emulsifier, 8% of O / W emulsifier, and 70% of water. The collector is diesel, the W / O emulsifier is Span-80, and the O / W emulsifier is Tween-80.

[0073] The nano-collector is prepared according to the following steps:

[0074] (1) Weigh each component by mass fraction: weigh 20 parts of diesel, 2 parts of Span-80, 8 parts of Tween-80, and 70 parts of deionized water.

[0075] (2) Put the weighed diesel, Span-80, and Tween-80 in a beaker and mix them evenly on a magnetic stirrer (rotation speed is 1000 r / min, stirring time is 5 min, at room temperature) to prepare a mixed oil phase with an HLB value of 12.78.

[0076] (3) Use a syringe to slowly drip the weighed deionized water in (1) into the mixed oil phase at a speed of 1 mL / min, and at the same time use a magnetic stirrer to stir the mixture at a speed of 250 r / min. After the addition of deionized water is completed, it is found that the emulsion has stratified within a short time, indicating that the stability of the emulsion is poor or the emulsion has not been successfully prepared. This is because the rapid addition of water causes a sudden change in the local HLB value, and the emulsifier molecules cannot be rearranged to the new interface in time, skipping the phase inversion critical point.

[0077] Test example: Performance test:

[0078] In Examples 1 to 6, emulsion collectors with good performance were prepared. The emulsion collectors prepared in Examples 1 to 6 were applied and tested to illustrate the effects of Examples 1 to 6.

[0079] (1) Macroscopic morphology characterization of the emulsion collector

[0080] Taking the emulsion collectors prepared in Examples 1 to 6 as examples, their properties were tested. Specifically:

[0081] As Figure 1 shown are the macroscopic photos of the emulsion collectors prepared in 1 - 6. It can be seen from Figure 1 them that the emulsion collectors present a milky white macroscopic morphology.

[0082] (2) Microscopic morphology characterization of the emulsion collector

[0083] Taking the emulsion collectors prepared in Examples 1 to 6 as examples, their properties were tested. Specifically:

[0084] As Figure 2 shown are the microscopic morphology photos of the emulsion collectors prepared in 1 - 6 obtained by using an optical microscope (Nikon Corporation, Japan). It can be seen from Figure 2 them that the emulsion collectors have a concentrated particle size distribution, good uniformity, and an average particle size of about 0.5 μm.

[0085] (3) Particle size distribution characterization of the emulsion collector

[0086] Taking the emulsion collectors prepared in Examples 1 to 6 as examples, their properties were tested. Specifically:

[0087] The particle size of the emulsion collector described or prepared in the present invention was analyzed by a nano particle size analyzer (Nano ZSE, Malvern Panalytical, UK). The average particle size of the obtained emulsion collector is about 0.5 μm. The test results of the particle size distribution are shown in Figure 3 .

[0088] (4) Dynamic stability characterization of the emulsion collector

[0089] Taking the emulsion collectors prepared in Examples 1 to 6 as examples, their properties were tested. Specifically:

[0090] As Figure 4 shown are the ΔBS dynamic stability analysis curves of the emulsion collectors prepared in Examples 1 - 6 obtained by using a TURBISCAN multiple light scattering instrument (Formulaction Company, France). It can be seen from Figure 4 them that the emulsion collectors all have high stability, but with the decrease in the amount of surfactant used, the stability of the emulsion decreases slightly.

[0091] In addition, to visually compare the improvement of the hydrophobicity of coal samples by different emulsion collectors, a contact angle measuring instrument (JC2000D, China) was used to measure the contact angle of the coal samples treated with the emulsion collector. The results of the contact angle are shown in Figure 5 , and the specific data are shown in Table 1. The addition of the emulsion collector significantly increases the contact angle of the coal surface. This is because the emulsifier and the oil-phase collector have a synergistic adsorption effect on the coal surface, covering the surface hydrophilic polar groups, thereby improving the surface hydrophobicity and flotation performance.

[0092] Table 1. Contact angle test results

[0093]

[0094] Using the emulsion collector prepared by the present invention to carry out low-rank coal flotation, including the following steps:

[0095] Adjust the concentration of the coal slurry to be floated to 80 g / L, add the emulsion collector, stir and mix evenly, wait for 2 min, then add the frother, stir and mix evenly, wait for 30 s, and inflate for flotation. Among them, the air inflow is 0.1 m 3 / h, the stirring speed is 1800 r / min, and the flotation time is about 3 min.

[0096] It should be noted that the coal sample used in the test is long-flame coal, and the feed ash content is 7.54%. The raw coal is crushed, screened, blended and reduced, and then an analytical coal sample with a particle size less than 0.5 mm is prepared according to the "Preparation Method of Coal Samples" (GB474-1984). The test method is carried out according to the "Unit Flotation Test Method in Coal Preparation Laboratory" (GB4758-1984) for performance detection. The pulp concentration is 80 g / L, the stirring speed of the flotation machine is 2300 r / min, the air inflow is 0.2 m 3 / (m 2 ·min), the flotation time is 5 min, and the dosage of the reagent is 600 g / t.

[0097] Furthermore, it should be noted that in Comparative Example 1 of the experiment, the conventional flotation reagent diesel was selected, with a dosage of 1000 g / t, and the frother was fixed as sec-octanol, with a dosage of 500 g / t; in other examples, the frother can also be one or a mixture of sec-octanol, methyl isobutyl carbinol, and pine oil.

[0098] The specific test results are shown in Table 2.

[0099] Table 2. Performance test results

[0100]

[0101]

[0102] As can be seen from Table 2, compared with the control sample test results, under the condition that the ash content of the flotation clean coal obtained after using the emulsion collector prepared in Examples 1-6 of the present invention is similar, the clean coal yield, flotation efficiency, etc. are significantly improved. This is because by emulsifying the traditional non-polar oil collector into nano-sized droplets, the contact area with the surface of low-rank coal is significantly increased. At the same time, the surfactant molecules in the emulsifier are adsorbed directionally on the hydrophobic region of the coal particles and cover the hydrophilic oxygen-containing groups, reducing the surface hydrophilicity. In addition, an "oil bridge" is formed between the coal particles and the bubbles, strengthening the adhesion force among the three, thereby significantly improving the floatability and selectivity of the coal particles. Finally, while reducing the dosage of the collector, the clean coal yield is significantly increased (compared with the traditional collector). This further verifies the advantage of the new emulsion collector in the selectivity of low-rank coal, thus effectively improving the flotation performance of low-rank coal.

[0103] To intuitively reflect the effect of cost savings, assume that the annual production of a coal preparation plant is 1 million tons, of which the proportion of slime is 0.15. The unit price of the traditional collector (diesel) is 5000 yuan / ton, and the unit price of the emulsion collector is 7000 yuan / ton (slightly higher due to the cost of the emulsifier). Then the cost of the traditional collector in one year is 1 kg / ton * 1 million tons * 0.15 * 5000 yuan / ton = 750,000 yuan, and the cost of the emulsion collector in one year is 1 kg / ton * 1 million tons * 0.15 * 7000 yuan / ton = 1.05 million yuan. Although the cost of the emulsion collector in one year is higher, due to the significant increase in the clean coal yield under the same dosage, the actual unit cost is significantly reduced. Taking Example 1 as an example: the clean coal output cost per unit raw coal of the traditional collector is 750,000 yuan / (1 million tons * 0.15 * 23.88%) = 20.94 yuan / ton of clean coal, while the clean coal output cost per unit raw coal of the emulsion collector is 1.05 million yuan / (1 million tons * 0.15 * 84.77%) = 8.26 yuan / ton of clean coal. Although the unit price of the emulsified collector is 40% higher, due to the significant increase in the clean coal output, the reagent cost per unit of clean coal is significantly reduced (from 20.94 yuan / ton to 8.26 yuan / ton).

[0104] The above are only the preferred embodiments of the present invention and are not intended to limit the present invention. For those skilled in the art, the present invention can have various changes and modifications. Any modification, equivalent replacement, improvement, etc. made within the spirit and principle of the present invention shall be included within the protection scope of the present invention.

Claims

1. An emulsion collector prepared by a phase composition transformation method of an oil-water biphasic emulsifier, characterized in that, Prepare an emulsion collector with a total mass fraction of 100 parts by mixing 20 - 40 parts of an oily collector agent, 1 - 5 parts of a W / O emulsifier, 4 - 10 parts of an O / W emulsifier and several parts of water.

2. The emulsion-type collector prepared by the phase composition transformation method of the oil-water biphasic emulsifier according to claim 1, wherein The oily collector agent is any one or a mixture of diesel, kerosene, gasoline, oleic acid esters, oleic acid, erucic acid, coconut oil amine or octadecyl amine.

3. The emulsion collector prepared by the oil-water biphasic emulsifier phase composition transformation method according to claim 1, wherein, The W / O emulsifier is any one or a mixture of Span, glycerol monostearate, sodium oleate or sodium erucate.

4. The emulsion-type collector prepared by the phase composition transformation method of the oil-water biphasic emulsifier according to claim 1, characterized in that The O / W emulsifier is any one or a mixture of Tween, fatty alcohol polyoxyethylene ether, polyoxyethylene stearate or fatty alcohol polyoxyethylene ether carboxylate sodium.

5. A preparation method of an emulsion-type collector prepared by a phase composition transformation method of an oil-water biphasic emulsifier, characterized in that It includes the following steps: Step 1: Weigh 20 - 40 parts of the oily collector agent, 1 - 5 parts of the W / O emulsifier and 4 - 10 parts of the O / W emulsifier by mass fraction and mix them in a container to obtain a mixed agent. Step 2: Magnetically stir the mixed agent in the container at a rotation speed of 800 - 1000 r / min for a shearing time of 5 - 10 min to obtain a mixed oil phase. Step 3: Use a micro syringe to add water to the mixed oil phase in Step 2 at a constant speed of 0.05 - 0.5 mL / min until the solution weight reaches 100 parts, and stir the mixture at a rotation speed of 200 - 300 r / min during the addition process to obtain an emulsion collector product.

6. The preparation method of the emulsion collector prepared by the phase composition transformation method of the oil-water biphasic emulsifier according to claim 5, characterized in that, In the step, the water addition speed is 0.5 mL / min.

7. The preparation method of the emulsion-type collector prepared by the oil-water biphasic emulsifier phase composition transformation method according to claim 5, characterized in that, The average particle size of the obtained emulsion collector product is 400 - 710 nm.

8. Application of the emulsion collector prepared by the phase composition transformation method of the oil - water double - phase emulsifier according to any one of claims 1 - 4 in the flotation of slime.

9. Use of the emulsion-type collector prepared by the phase composition transformation method of the oil-water biphasic emulsifier in coal slime flotation according to claim 8, characterized in that, The slime is low - rank coal.

10. Use of the emulsion-type collector prepared by the phase composition transformation method of the oil-water biphasic emulsifier according to claim 9 in the flotation of slime, characterized in that The method of the application is as follows: modulating the concentration of low-order coal slurry, adding an emulsion-type collector, waiting until it is uniformly mixed with the slurry, adding a foaming agent, stirring and mixing evenly, and then performing air flotation; the concentration of the flotation slurry is 60-100 g / L, and the dosage of the emulsion-type collector is 2-3 kg per ton of coal; the foaming agent is one or a mixture of sec-octanol, methyl isobutyl carbinol, and pine oil. After adding the foaming agent, the pulp is adjusted and air flotation is carried out; the air inflow rate is 0.1-0.3 m 3 / h, the stirring speed is 1500-2000 r / min, and the flotation time is 2-3 min.

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