Supernormal foam enrichment device and method

Abstract

The invention relates to a supernormal foam enrichment device and a supernormal foam enrichment method, belongs to the technical field of enrichment of metal ions in a solution, and solves the problem that an existing foam enrichment device is relatively low in enrichment ratio. The supernormal foam enrichment device comprises a column body with a closed inner cavity, a feeding hole and an air inlet which are formed in the lower part of the column body, and a pressure regulating valve arranged at the upper part of the column body, wherein a solution outlet is formed in the lower part of the column body, and a foam outlet is formed in the upper part of the column body. The column body of the device is closed, the pressure in the column body is adjusted through the pressure adjusting valve, air bubbles can be broken in the bubble floating process, bubbles containing target metal ions float, and therefore supernormal foam enrichment of the target metal ions is achieved, and the enrichment ratio of rare and precious metal ions is increased.

Description

Technical Field

[0001] The invention relates to the technical field of metal enrichment in solution, and in particular to an extraordinary foam enrichment device and method. Background Art

[0002] Precious metals have unique properties such as excellent electrical conductivity, ductility, heat resistance and corrosion resistance, and play an irreplaceable key role in many fields such as chemical metallurgy and integrated circuits. The reserves of precious metal resources in my country are limited, and they are mainly dispersed in bulk metal mines as associated metals. Most precious metals with similar properties replace each other in an isomorphic form, which makes their deep separation extremely difficult. At present, the separation of precious metals mainly uses roasting, acid leaching, alkaline leaching and other technical means to convert them into a dissolved state in the liquid phase, and then enrich the precious metal ions in the leachate.

[0003] The usual enrichment method is foam enrichment. The existing foam enrichment device is usually in an open state and enriches rare and precious metal ions under normal pressure. All rising bubbles enter the bubble layer and are directly discharged from the discharge port. The enrichment of this enrichment device is relatively low. Summary of the invention

[0004] In view of the above analysis, the embodiments of the present invention aim to provide an extraordinary foam enrichment device and method to solve the problem of relatively low enrichment ratio of existing foam enrichment devices.

[0005] On the one hand, an embodiment of the present invention provides an extraordinary foam enrichment device, the extraordinary foam enrichment device comprising a column with a closed inner cavity, a feed inlet and an air inlet arranged at the lower part of the column, and a pressure regulating valve arranged at the upper part of the column;

[0006] A solution outlet is arranged at the lower part of the column, and a foam outlet is arranged at the upper part of the column.

[0007] Preferably, a surfactant inlet is provided on the feed inlet.

[0008] Preferably, the extraordinary foam enrichment device also includes an online image and particle size analysis device, which includes a probe and a computer terminal, the probe is connected to the computer terminal, and the probe extends from the foam outlet into the foam layer in the column.

[0009] Preferably, the column is made of transparent material.

[0010] Preferably, the extraordinary foam enrichment device further comprises a high-speed camera, and the high-speed camera is arranged outside the column.

[0011] Preferably, a safety valve assembly is provided at the upper end of the column.

[0012] Preferably, the safety valve assembly comprises a shell, an upper cover and a piston, the shell is connected to the cylinder through a lower opening, the upper cover is located at the upper end opening of the shell, the piston is located in a cavity formed by the upper cover and the shell, the piston extends in the cavity along the up-down direction, the lower end of the piston abuts against the lower opening of the shell, a first spring is arranged on the outer periphery of the piston, the upper end of the first spring is connected to the upper cover, and the lower end of the first spring is connected to the lower part of the piston;

[0013] The housing is provided with a transverse channel, in which a steel ball, a second spring and a fixing block are sequentially arranged in a direction away from the piston, one end of the second spring is connected to the steel ball, and the other end is connected to the fixing block;

[0014] The shell is also provided with an air leakage channel, one end of which is connected with the transverse channel, and the other end of which is connected with the outside of the shell. The connection point between the air leakage channel and the transverse channel is located between the steel ball and the fixing block.

[0015] Preferably, an agitator is provided at the bottom of the inner cavity of the column.

[0016] On the other hand, the present invention also provides a super-normal foam enrichment method, using the above-mentioned super-normal foam enrichment device, the super-normal foam enrichment method comprises:

[0017] A feed liquid containing the target metal and a surfactant are introduced into the column through a feed inlet;

[0018] Introduce gas into the liquid in the column through the gas inlet to generate bubbles in the liquid;

[0019] The pressure in the column is adjusted by a pressure regulating valve, so that the air bubbles burst during the floating process, and the bubbles containing the target metal float up, thereby achieving extraordinary foam enrichment of the target metal.

[0020] Preferably, the size, morphology and number of bubbles are observed by the online image and particle size analysis device.

[0021] Compared with the prior art, the present invention can achieve at least one of the following beneficial effects:

[0022] 1. The column of the device of the present invention is closed, and a pressure regulating valve is arranged on the upper part of the column. Since the surface tension of air bubbles is greater than that of bubbles containing metal ions, air bubbles will be selectively broken under pressure environment to enrich bubbles containing rare and precious metal ions. Therefore, by adjusting the pressure in the column through the pressure regulating valve, the air bubbles can be broken during the floating process of the bubbles, and the bubbles containing the target metal ions can float up, thereby achieving extraordinary foam enrichment of the target metal ions and improving the enrichment ratio of the rare and precious metal ions.

[0023] 2. In the device and method of the present invention, the rupture of air bubbles allows the surfactant to return to the feed liquid system for recycling, thereby achieving efficient enrichment with low dosage of reagents.

[0024] 3. The device and method of the present invention couple the bubble theory of the flotation process and the distillation principle of the chemical process, which not only achieves the extraordinary enrichment of rare and precious metal ions, but also realizes the recycling of surfactants.

[0025] In the present invention, the above-mentioned technical solutions can also be combined with each other to achieve more preferred combination solutions. Other features and advantages of the present invention will be described in the subsequent description, and some advantages can become obvious from the description, or can be understood by practicing the present invention. The purpose and other advantages of the present invention can be realized and obtained through the contents particularly pointed out in the description and the drawings. BRIEF DESCRIPTION OF THE DRAWINGS

[0026] The drawings are only for the purpose of illustrating particular embodiments and are not to be considered limiting of the present invention. Like reference symbols denote like components throughout the drawings.

[0027] Figure 1 It is a schematic diagram of the structure of the super-normal foam enrichment device of the present invention.

[0028] Reference numerals:

[0029] 1-column; 2-feed port; 3-air inlet; 4-pressure regulating valve; 5-solution outlet; 6-foam outlet; 7-probe; 8-computer terminal; 9-high-speed camera; 10-agitator; 11-surfactant inlet; 12-pump; 13-housing; 14-piston; 15-first spring; 16-steel ball; 17-upper cover; 18-second spring; 19-fixed block; 20-air release channel. DETAILED DESCRIPTION

[0030] The preferred embodiments of the present invention are described in detail below in conjunction with the accompanying drawings, wherein the accompanying drawings constitute a part of this application and are used together with the embodiments of the present invention to illustrate the principles of the present invention, but are not used to limit the scope of the present invention.

[0031] In one aspect, the present invention provides an extraordinary foam enrichment device, such as Figure 1 As shown, the extraordinary foam enrichment device comprises a column 1 with a sealed inner cavity, a feed inlet 2 and an air inlet 3 arranged at the lower part of the column 1, and a pressure regulating valve 4 arranged at the upper part of the column 2;

[0032] A solution outlet is arranged at the lower part of the column, and a foam outlet is arranged at the upper part of the column.

[0033] During implementation, a slurry containing the target metal and a surfactant are introduced into the column 1 through the feed port 2; gas is introduced into the slurry in the column through the gas inlet 3 to generate bubbles in the slurry; the pressure in the column 1 is adjusted by the pressure regulating valve 4 so that during the floating process of the bubbles, the air bubbles (bubbles not containing the target metal) burst and the bubbles containing the target metal float up, thereby achieving extraordinary foam enrichment of the target metal.

[0034] Compared with the prior art, the column of the device of the present invention is closed, and a pressure regulating valve is arranged on the upper part of the column. Since the surface tension of air bubbles is greater than the surface tension of bubbles containing metal ions, the air bubbles will be selectively broken under the pressure environment to enrich the bubbles containing rare and precious metal ions. Therefore, by adjusting the pressure in the column through the pressure regulating valve, the air bubbles can be broken during the floating process of the bubbles, and the bubbles containing the target metal ions can float up, thereby achieving extraordinary foam enrichment of the target metal ions and improving the enrichment ratio of rare and precious metals.

[0035] Exemplarily, a surfactant inlet 11 is provided on the feed port 2 for introducing a surfactant. The surfactant can selectively capture target metal ions to form bubbles that rise together.

[0036] Exemplarily, the feed inlet 2 is located above the air inlet 3, which is conducive to the formation of bubbles in the feed liquid.

[0037] Exemplarily, the feed port 2 is located at 1 / 4-1 / 5 of the column height above the column bottom.

[0038] Exemplarily, the air inlet 3 is located above the column bottom at 1 / 6-1 / 7 of the column height and is on the same vertical line as the feed inlet 2 .

[0039] Exemplarily, the feed port 2 and the air inlet 3 are respectively connected to a pump 12 for providing power for the feed and the air.

[0040] Exemplarily, a solution outlet 5 is provided at the lower portion of the column 1 for discharging the solution after froth flotation.

[0041] Specifically, the solution outlet 5 is located at 1 / 8-1 / 9 of the column height above the column bottom and is arranged on the column wall opposite to the feed port 2 .

[0042] Exemplarily, a foam outlet 6 is provided at the upper portion of the column 1. Bubbles containing the target metal float to the bubble layer and are discharged from the foam outlet 6.

[0043] Specifically, the foam outlet 6 is located below the top of the column at 1 / 3-1 / 4 of the column height and on the same vertical line as the solution outlet 5 .

[0044] Exemplarily, the pressure regulating valve 4 is located at 1 / 5-1 / 6 of the column height below the column top. If the position is too low, the slurry may gush out during the pressure regulation process.

[0045] Exemplarily, the pressure regulating valve 4 is located higher than the foam outlet 6 to prevent the slurry from gushing out.

[0046] Exemplarily, the height difference between the pressure regulating valve 4 and the foam outlet 6 is 20-30 cm. This is because during the pressure relief process, rising bubbles in the liquid will cause the liquid level to rise briefly. The height difference is set to 20-30 cm to prevent the liquid from gushing out.

[0047] Exemplarily, the extraordinary foam enrichment device further includes an online image and particle size analysis device, which includes a probe 7 and a computer terminal 8, wherein the probe 7 is connected to the computer terminal 8, and the probe 7 extends from the foam outlet 6 into the foam layer in the column 1. The online image and particle size analysis device is used to observe the size, morphology and number of bubbles in the liquid system to adjust the optimal inflation flow rate of the air pump and the optimal stirring rate of the stirrer.

[0048] Exemplarily, the column 1 is made of transparent material.

[0049] Exemplarily, the column 1 is made of transparent glass.

[0050] Exemplarily, scale lines are provided on the column 1, and the volume of the feed liquid can be known through the scale lines.

[0051] Exemplarily, the extraordinary foam enrichment device further includes a high-speed camera 9, which is arranged outside the column 1. The high-speed camera 9 can quickly capture the moment of bubble bursting. Due to the different surface tensions of air bubbles and metal-containing bubbles, there are differences in bubble bursting under high-pressure environment. The high-speed camera 9 is used to record "bubbles carrying target metal ions continue to rise and enrich to the foam layer, and bubbles without target metal ions burst".

[0052] In order to avoid system failure caused by excessive pressure in the column, a safety valve assembly is provided at the upper end of the column 1. The safety valve assembly can relieve pressure when the pressure in the chamber of the column 1 is abnormal, thereby fine-tuning the pressure in the column cavity and reducing system failure. Under normal circumstances, the safety valve assembly does not work.

[0053] Specifically, the safety valve assembly includes a housing 13, an upper cover 17 and a piston 14. The housing 13 is connected to the cylinder 1 through a lower opening. The upper cover 17 is located at the upper end opening of the housing 13. The piston 14 is located in a cavity formed by the upper cover 17 and the housing 13. The piston 14 extends in the cavity in an up-down direction. The lower end of the piston 14 abuts against the lower opening of the housing 13. A first spring 15 is arranged on the periphery of the piston 14. The upper end of the first spring 15 is connected to the upper cover 17. The lower end of the first spring 15 is connected to the lower part of the piston 14.

[0054] The housing 13 is provided with a transverse channel, in which a steel ball 16, a second spring 18 and a fixing block 19 are sequentially arranged in a direction away from the piston, one end of the second spring 18 is connected to the steel ball 16, and the other end is connected to the fixing block 19;

[0055] The housing 13 is also provided with an air leakage channel 20 , one end of which is connected to the transverse channel, and the other end of which is connected to the outside of the housing 13 . The connection point between the air leakage channel 20 and the transverse channel is located between the steel ball 16 and the fixing block 19 .

[0056] When the pressure in the column 1 exceeds the safety range, the piston is pushed upward, and the gas enters the cavity formed by the shell 13 and the upper cover 17, further pushing the steel ball 16 to compress the second spring 18. As the steel ball 16 compresses the second spring 18, the air leakage channel 20 is exposed, and the gas is discharged along the air leakage channel 20, completing the pressure relief in sequence. Under normal working conditions, the steel ball 16 blocks the cavity in the valve, stabilizes the pressure, and realizes dust and water resistance.

[0057] Exemplarily, the upper cover 17 is threadedly connected to the housing 13. By rotating the upper cover 17, the pressure of the piston 14 on the lower opening of the housing 13 can be increased or decreased, thereby adjusting the threshold of the safety pressure.

[0058] Exemplarily, a stirrer 10 is disposed at the bottom of the inner cavity of the column 1. The stirrer 10 is conducive to the mixing of metal ions and bubbles in the feed liquid, so that the bubbles can more easily capture the target metal ions.

[0059] In a second aspect, the present invention further provides a supernormal foam enrichment method, using the above-mentioned supernormal foam enrichment device, the supernormal foam enrichment method comprises:

[0060] A feed solution containing target metal ions and a surfactant are introduced into the column through a feed inlet;

[0061] Introduce gas into the liquid in the column through the gas inlet to generate bubbles in the liquid;

[0062] The pressure in the column is adjusted by a pressure regulating valve, so that the air bubbles burst during the floating process, and the bubbles containing the target metal ions float up, thereby achieving extraordinary foam enrichment of the target metal ions.

[0063] Exemplarily, the feed solution may be bauxite leaching solution, fly ash leaching solution, smoke dust leaching solution and zinc smelting waste slag leaching solution.

[0064] It can be understood that the leachate is an ionic solution of an aqueous phase system.

[0065] Exemplarily, the target metal ions are gallium ions or germanium ions.

[0066] Exemplarily, the height of the liquid in the column 1 does not exceed 2 / 3 of the height of the column 1.

[0067] Exemplarily, the height of the liquid in the column 1 is 5-10 cm below the discharge port 6 .

[0068] Exemplarily, the size, morphology and number of bubbles are observed by the online image and particle size analysis device.

[0069] For the scheme of enriching gallium ions from bauxite leachate using the extraordinary foam enrichment method of the present invention, the preparation method of the bauxite leachate includes: under normal temperature conditions, the leaching solid-liquid ratio of bauxite to deionized water is 1:3-4, sulfuric acid is used as a leaching agent, the sulfuric acid concentration is 85-95%, and the bauxite leachate is obtained by stirring and leaching for 10-15 minutes.

[0070] Exemplarily, the components of the bauxite leachate include: gallium ions (0.01-0.02 g / L, about 0.003%-0.008%), lithium ions (0.2-0.5 g / L), aluminum ions (30.0-40 g / L), iron ions (2.0-4.0 g / L), sodium ions (1.0-2.0 g / L), potassium ions (0.1-0.3 g / L), calcium ions (0.3-0.5 g / L), zinc ions, magnesium ions, copper ions, lead ions, etc. It can be seen that the gallium ion content in the bauxite leachate is extremely low, which is difficult to enrich, and the main impurity ion aluminum ion content is high, which is similar to the radius of the gallium ion, both are zwitterions, and selective separation is difficult. The present invention adopts the above-mentioned extraordinary foam enrichment device, and at the same time adopts specific surfactants, appropriate material dosage, gas and its flow rate, column pressure, etc. to effectively improve the gallium ion enrichment ratio.

[0071] Illustratively, the viscosity of the bauxite leachate is 1.1-1.2 cSt.

[0072] Exemplarily, the surfactant used in the bauxite leachate is trans-2-nonene hydroxamic acid. The preparation method of trans-2-nonene hydroxamic acid is described in the paper "A novel sodium trans-2-nonene hydroxamate for the flotation separation of ilmenite and forsterite: Superior collecting and selectivity, Separation and Purification Technology 333 (2024) 125830".

[0073] Illustratively, in a mixture of bauxite leachate and surfactant, the mass concentration of the surfactant is 0.03-0.04%. Too high a mass concentration of the surfactant will cause the surfactant to capture other impurity ions, which will rise with the bubbles, thereby reducing the selectivity of the foam product. Too low a mass concentration of the surfactant will result in incomplete capture of the target metal ions, thereby reducing the recovery rate and the enrichment ratio.

[0074] Exemplarily, the flow rate of the mixture of bauxite leachate and surfactant is 90-120 mL / min. Too high a flow rate may damage the motor, and too low a flow rate may cause unnecessary waste of time.

[0075] Exemplarily, the stirring rate of the agitator is 80-120rpm. Too high a stirring rate will cause turbulence and instability of the liquid in the reaction chamber, and may also shear the bubbles, causing them to burst. Too low a stirring rate will cause uneven liquid and incomplete reaction between the surfactant and the target metal ion.

[0076] For example, the air flow rate of the air inlet is 0.2 to 0.4 m 3 / h, too large aeration flow rate will result in large and unstable bubbles, while too small aeration flow rate will result in too few bubbles, low efficiency in capturing target metal ions, and thus low recovery rate of foam products.

[0077] For example, the gas introduced into the gas inlet is hydrogen. Hydrogen provides a reducing environment, which can inhibit the Fe 2+ Converted to Fe 3+ , because hydroxamic acid reacts with Fe 3+ The complex is more stable, and the inhibitory effect can prevent iron ions from being entrained into the foam product in large quantities.

[0078] Exemplarily, the pressure in the column is adjusted to 0.2-0.3MPa by a pressure regulating valve. If the pressure is too low, it is difficult to rupture air bubbles and the surfactant cannot be recycled. If the pressure is too high, the bubbles in the column will rupture indiscriminately, making it difficult to enrich the foam product at the top of the column, and the product recovery rate and enrichment ratio will be reduced.

[0079] For the scheme of enriching gallium ions from fly ash leachate using the extraordinary foam enrichment method of the present invention, the preparation method of the fly ash leachate includes: quantitatively weighing fly ash, the leaching temperature is 110-115°C, the leaching solid-liquid ratio of fly ash to deionized water is 1:10-12, hydrochloric acid is used as the leaching agent, the hydrochloric acid concentration is 15-20%, and the fly ash leachate is obtained by stirring and leaching for 2-2.5 hours.

[0080] Exemplarily, the components of fly ash leachate include: gallium ions (0.6-0.9 g / L), silicon ions (26.0-33.0 g / L), aluminum ions (22.0-26.0 g / L), calcium ions (1.0-1.5 g / L), iron ions (0.7-1.1 g / L), arsenic ions, zinc ions, magnesium ions, etc. It can be seen that the high silicon ion content in the fly ash leachate will lead to a high viscosity of the fly ash leachate, so that the adhesion between the target metal ions and the impurity metal ions is large, and it is not easy to achieve selective enrichment. The present invention achieves efficient enrichment of gallium ions in fly ash leachate by adopting an extraordinary foam enrichment device, and at the same time coordinating a high surfactant dosage, material and gas flow rate, stirring rate and column pressure.

[0081] Exemplarily, the viscosity of the fly ash leachate is 3.2-3.5 cSt.

[0082] Exemplarily, the surfactant used in the fly ash leachate is tributyl phosphate.

[0083] Exemplarily, in the mixture of fly ash leachate and surfactant, the mass concentration of the surfactant is 0.07-0.09%. Too high a concentration of the surfactant will cause the surfactant to capture other impurity ions and rise with the bubbles, thereby reducing the selectivity of the foam product. Too low a concentration of the surfactant will cause incomplete capture of the target metal ions, thereby reducing the recovery rate and the enrichment ratio.

[0084] Exemplarily, the flow rate of the mixture of fly ash leachate and surfactant is 50-60 mL / min. The fly ash leachate has a high viscosity. When the flow rate is too large, more power is required, which may damage the motor. If the flow rate is too small, unnecessary time waste will be caused.

[0085] Exemplarily, the stirring rate of the agitator is 280-350rpm. A stirring rate that is too high will cause turbulence and instability of the feed liquid in the reaction chamber, and may also shear the bubbles, causing the bubbles to burst. A stirring rate that is too low will cause uneven feed liquid and incomplete reaction of the surfactant and the target metal ion. In addition, a stirring rate that is too low will make it difficult to achieve ion dispersion.

[0086] For example, the air flow rate of the air inlet is 0.7 to 1.2 m 3 / h, too large aeration flow rate will result in large and unstable bubbles, while too small aeration flow rate will result in too few bubbles, low efficiency in capturing target metal ions, and thus low recovery rate of foam products.

[0087] For example, the gas introduced into the air inlet is air. The fly ash leachate has fewer impurity ions in the solution environment than bauxite and zinc smelting waste slag. Air is used as the gas atmosphere, no gas cylinder is required, it is easy to prepare, and the operating cost is low.

[0088] Exemplarily, the pressure in the column is adjusted to 0.8-1.2MPa by a pressure regulating valve. If the pressure is too low, it is difficult to rupture air bubbles and the surfactant cannot be recycled. If the pressure is too high, the bubbles in the column will rupture indiscriminately, making it difficult to enrich the foam product at the top of the column, and the product recovery rate and enrichment ratio will be reduced.

[0089] For the scheme of enriching germanium ions from smoke dust leachate using the extraordinary foam enrichment method of the present invention, the preparation method of the smoke dust leachate includes: weighing germanium-containing zinc oxide smoke, the leaching temperature is 60-70°C, the leaching solid-liquid ratio of smoke dust to deionized water is 1:7-8, sulfuric acid is used as a leaching agent, the sulfuric acid concentration is 10-12%, and stirring and leaching for 1-2 hours to obtain the germanium-containing zinc oxide smoke dust leachate.

[0090] Exemplarily, the components of the smoke leachate include: germanium ions (0.1-0.3 g / L), zinc ions (30.0-42.0 g / L), lead ions (0.02-0.08 g / L), iron ions (0.5-1.0 g / L), sulfur ions, arsenic ions, etc. It can be seen that the smoke leachate has a simple composition and a low impurity content, but because the boiling points of arsenic ions and germanium ions in the impurity ions are similar, it is difficult to achieve high efficiency and selectivity when enriching germanium ions through the traditional process-chlorination distillation. The present invention adopts the above-mentioned extraordinary foam enrichment device, which does not consider the boiling point. The method is based on the fact that the surface tension of air bubbles is greater than that of bubbles containing metal ions, and the air bubbles will be selectively broken under pressure, thereby enriching bubbles containing germanium ions.

[0091] Exemplarily, the viscosity of the smoke extract is 1.4-1.8 cSt.

[0092] Exemplarily, the surfactant used in the smoke leachate is dodecylamine.

[0093] Exemplarily, in the mixture of smoke extract and surfactant, the mass concentration of the surfactant is 0.03-0.04%. Too high a concentration will cause the surfactant to capture other impurity ions and rise with the bubbles, thereby reducing the selectivity of the foam product. Too low a concentration will result in incomplete capture of the target metal ions, thereby reducing the recovery rate and the enrichment ratio.

[0094] Exemplarily, the flow rate of the mixture of the smoke extract and the surfactant is 70-85 mL / min. Too high a flow rate may damage the motor, and too low a flow rate may cause unnecessary waste of time.

[0095] Exemplarily, the stirring rate of the agitator is 180-220rpm. Too high a stirring rate will cause turbulence and instability of the liquid in the reaction chamber, and may also shear the bubbles, causing them to burst. Too low a stirring rate will cause uneven liquid and incomplete reaction between the surfactant and the target metal ion.

[0096] For example, the air flow rate of the air inlet is 0.2 to 0.4 m 3 / h, too large aeration flow rate will result in large and unstable bubbles, while too small aeration flow rate will result in too few bubbles, low efficiency in capturing target metal ions, and thus low recovery rate of foam products.

[0097] For example, the gas introduced into the air inlet is air. The solution environment of the smoke leaching solution has fewer impurity ions than that of bauxite and zinc smelting waste slag. Air is used as the gas atmosphere, no gas cylinder is required, it is easy to prepare, and the operating cost is low.

[0098] Exemplarily, the pressure in the column is adjusted to 0.4-0.5MPa by a pressure regulating valve. If the pressure is too low, it is difficult to rupture air bubbles and the surfactant cannot be recycled. If the pressure is too high, the bubbles in the column will rupture indiscriminately, making it difficult to enrich the foam product at the top of the column, and the product recovery rate and enrichment ratio will be reduced.

[0099] For the scheme of enriching germanium ions from zinc smelting waste slag leaching solution using the extraordinary foam enrichment method of the present invention, the preparation method of the zinc smelting waste slag leaching solution includes: weighing the zinc smelting waste slag, the leaching temperature is 65-75°C, the leaching solid-liquid ratio of the zinc smelting waste slag to deionized water is 1:3-5, sulfuric acid is used as a leaching agent, the sulfuric acid concentration is 20-25%, and stirring and leaching for 2-3 hours to obtain the zinc smelting waste slag leaching solution.

[0100] Illustratively, the components of the zinc smelting waste slag leachate include: germanium ions (0.8-1.2 g / L), zinc ions (18.0-24.0 g / L), cadmium ions (5.5-7.0 g / L), lead ions (0.1-0.4 g / L), copper ions (1.5-1.8 g / L), iron ions (1.9-2.4 g / L), arsenic ions, cobalt ions, nickel ions, gold ions, etc. It can be seen that the zinc ion content in the zinc smelting waste slag leachate is relatively high, and there are many types of precious metals (such as cadmium, arsenic, cobalt, nickel, and gold), making it difficult to achieve efficient and selective enrichment of germanium ions in the leachate. The present invention adopts the above-mentioned extraordinary foam enrichment device. The method is based on the fact that the surface tension of air bubbles is greater than the surface tension of bubbles containing metal ions. Air bubbles will be selectively broken under a pressure environment to enrich bubbles containing germanium ions. Therefore, by adjusting the pressure in the column through a pressure regulating valve, the air bubbles can be broken during the floating process of the bubbles, and the bubbles containing germanium ions can float up, thereby realizing extraordinary foam enrichment of germanium ions and improving the enrichment ratio of germanium ions.

[0101] Exemplarily, the viscosity of the zinc smelting waste slag leaching solution is 2-2.5 cSt.

[0102] For example, the surfactant used in the zinc smelting waste slag leaching solution is a mixture of pyrogallol and dodecylamine, wherein pyrogallol acts as a complexing agent to capture germanium ions, and then reacts with the surfactant dodecylamine in the feed solution to make the germanium ions float out with bubbles.

[0103] Exemplarily, the mass ratio of pyrogallol to dodecylamine is 1:3-3.5.

[0104] For example, in a mixture of zinc smelting waste slag leachate and surfactant, the mass concentration of the surfactant is 0.05-0.06%. Too high a concentration will cause the surfactant to capture other impurity ions and rise with the bubbles, thereby reducing the selectivity of the foam product. Too low a concentration will result in incomplete capture of the target metal ions, thereby reducing the recovery rate and the enrichment ratio.

[0105] Exemplarily, the flow rate of the mixture of zinc smelting waste slag leaching solution and surfactant is 50-60 mL / min. Too large a flow rate may damage the motor, and too small a flow rate may cause unnecessary waste of time.

[0106] Exemplarily, the stirring rate of the agitator is 230-260 rpm. Too high a stirring rate will cause turbulence and instability of the liquid in the reaction chamber, and may also shear the bubbles, causing them to burst. Too low a stirring rate will cause uneven liquid and incomplete reaction between the surfactant and the target metal ion.

[0107] For example, the air flow rate of the air inlet is 0.4-0.6m 3 / h, too large aeration flow rate will result in large and unstable bubbles, while too small aeration flow rate will result in too few bubbles, low efficiency in capturing target metal ions, and thus low recovery rate of foam products.

[0108] For example, the gas introduced into the air inlet is carbon dioxide. The surface of carbon dioxide bubbles is positively charged, and the complexation of germanium and pyrogallol is negatively charged. The electrostatic effect can assist the bubbles in capturing germanium-containing ions and inhibit the bubbles from capturing positive ions of gas impurities, thereby increasing the germanium ion enrichment ratio.

[0109] Exemplarily, the pressure in the column is adjusted to 0.6-0.7MPa by a pressure regulating valve. If the pressure is too low, it is difficult to rupture air bubbles and the surfactant cannot be recycled. If the pressure is too high, the bubbles in the column will rupture indiscriminately, making it difficult to enrich the foam product at the top of the column, and the product recovery rate and enrichment ratio will be reduced.

[0110] The following is a further explanation of the super foam enrichment device and method of the present invention through specific examples.

[0111] Example 1

[0112] This embodiment provides an extraordinary foam enrichment device.

[0113] The device comprises a column 1 with a closed inner cavity, a feed port 2 and an air inlet 3 arranged at the lower part of the column 1, and a pressure regulating valve 4 arranged at the upper part of the column 2. A surfactant inlet 11 is arranged on the feed port 2, and the feed port 2 is located above the air inlet 3, and the feed port 2 is located at 1 / 4 of the column height above the column bottom. The air inlet 3 is located at 1 / 6 of the column height above the column bottom, and is in the same vertical line as the feed port. The feed port 2 and the air inlet 3 are respectively connected to a pump 12. A solution outlet 5 is arranged at the lower part of the column 1, and the solution outlet 5 is located at 1 / 8 of the column height above the column bottom, opposite to the feed port. A foam outlet 6 is arranged at the upper part of the column 1. The foam outlet 6 is located at 1 / 3 of the column height below the column top, and is in the same vertical line as the solution outlet. The pressure regulating valve 4 is located higher than the foam outlet 6, and the height difference between the pressure regulating valve 4 and the foam outlet 6 is 25 cm. The extraordinary foam enrichment device also includes an online image and particle size analysis device, which includes a probe 7 and a computer terminal 8. The probe 7 is connected to the computer terminal 8, and the probe 7 extends from the foam outlet 6 into the foam layer in the column 1. The column 1 is made of transparent glass. The extraordinary foam enrichment device also includes a high-speed camera 9, which is arranged on the outside of the column 1. A safety valve assembly is arranged at the upper end of the column 1, and the safety valve assembly includes an outer shell 13, an upper cover 17 and a piston 14. The outer shell 13 is connected to the column 1 through a lower opening, and the upper cover 17 is located at the upper end opening of the outer shell 13. The piston 14 is located in a cavity formed by the upper cover 17 and the outer shell 13. The piston 14 extends in the cavity in the up and down directions, and the lower end of the piston 14 is against the lower opening of the outer shell 13. A first spring 15 is arranged on the periphery of the piston 14, and the upper end of the first spring 15 is connected to the upper cover 17. The first spring 15 is provided on the outer periphery of the piston 14. The lower end of 15 is connected to the lower part of the piston 14; the shell 13 is provided with a transverse channel, and the steel ball 16, the second spring 18 and the fixed block 19 are arranged in sequence in the transverse channel in the direction away from the piston, one end of the second spring 18 is connected to the steel ball 16, and the other end is connected to the fixed block 19; the shell 13 is also provided with a degassing channel 20, one end of the degassing channel 20 is connected to the transverse channel, and the other end is connected to the outside of the shell 13, and the connection point of the degassing channel 20 and the transverse channel is located between the steel ball 16 and the fixed block 19. When the pressure in the column 1 exceeds the safety range, the piston is pushed upward, and the gas enters the cavity formed by the shell 13 and the upper cover 17, further pushing the steel ball 16 to compress the second spring 18. As the steel ball 16 compresses the second spring 18, the degassing channel 20 is exposed, and the gas is discharged along the degassing channel 20, completing the pressure relief in sequence. Under normal working conditions, the steel ball 16 blocks the cavity in the valve, stabilizes the pressure and realizes dust and water resistance. The upper cover 17 is threadedly connected to the shell 13. By rotating the upper cover 17 , the pressure of the piston 14 on the lower opening of the housing 13 can be increased or decreased, thereby adjusting the threshold of the safety pressure.A stirrer 10 is arranged at the bottom of the inner cavity of the column 1 .

[0114] Example 2-1

[0115] This embodiment provides an extraordinary foam enrichment method, using the extraordinary foam enrichment device of Example 1 to enrich gallium ions from bauxite leachate. The method comprises:

[0116] (1) Under normal temperature conditions, the leaching solid-liquid ratio of bauxite to deionized water is 1:3, sulfuric acid is used as the leaching agent, the sulfuric acid concentration is 85%, and the leaching is stirred for 10 minutes to obtain a bauxite leachate with a viscosity of 1.1 cSt. The bauxite leachate contains 0.015 g / L of gallium ions, 0.36 g / L of lithium ions, 36.5 g / L of aluminum ions, 2.95 g / L of iron ions, 1.22 g / L of sodium ions, 0.17 g / L of potassium ions, 0.37 g / L of calcium ions, zinc ions, magnesium ions, copper ions, lead ions, etc.;

[0117] (2) introducing a mixture of bauxite leachate and a surfactant at a flow rate of 90 mL / min into the column through a feed port, wherein the concentration of the surfactant in the mixture is 0.04 wt.%, the surfactant is trans-2-nonenehydroxamic acid, and the stirring rate of the stirrer is 100 rpm;

[0118] (3) Hydrogen is introduced into the liquid in the column through the air inlet to generate bubbles in the liquid. The aeration flow rate is 0.3m 3 / h;

[0119] (4) The pressure in the column is adjusted by a pressure regulating valve, and the chamber pressure is 0.3 MPa, so that during the process of bubble floating, the air bubbles burst and the bubbles containing the target metal ions float up, thereby achieving extraordinary foam enrichment of the target metal ions. The bubble size under the inflation flow rate is recorded using an online image and particle size analysis device, and the equilibrium state of bubble floating and bursting is observed by a high-speed camera. After the process is stable, the concentrations of the gallium ion solution and gallium ion foam at the bottom and top outlets are measured, and the average value is taken after multiple records, and the gallium metal ion enrichment ratio is calculated to be 174.

[0120] Example 2-2

[0121] This example provides an extraordinary foam enrichment method similar to Example 2-1, except that the flow rate of the mixture of bauxite leachate and surfactant is 80 mL / min.

[0122] The gallium metal ion enrichment ratio is 165.

[0123] Example 2-3

[0124] This embodiment provides an extraordinary foam enrichment method similar to that of Embodiment 2-1, except that the stirring speed of the stirrer is 70 rpm.

[0125] The gallium metal ion enrichment ratio is 150.

[0126] Embodiment 2-4

[0127] This embodiment provides a super foam enrichment method similar to that of embodiment 2-1, except that the aeration flow rate is 0.1 m 3 / h.

[0128] The gallium metal ion enrichment ratio is 161.

[0129] Embodiment 2-5

[0130] This embodiment provides an extraordinary foam enrichment method similar to that of Embodiment 2-1, except that the pressure in the column is 0.1 MPa.

[0131] The gallium metal ion enrichment ratio is 154.

[0132] Embodiment 2-6

[0133] This example provides a super foam enrichment method similar to that of Example 2-1, except that the concentration of the surfactant in the mixture is 0.02 wt.%.

[0134] The gallium metal ion enrichment ratio is 147.

[0135] Embodiment 2-7

[0136] This embodiment provides an extraordinary foam enrichment method similar to that of Embodiment 2-1, except that air is introduced into the slurry in the column through the air inlet.

[0137] The gallium metal ion enrichment ratio is 113.

[0138] Example 3-1

[0139] This embodiment provides an extraordinary foam enrichment method, using the extraordinary foam enrichment device of Example 1 to enrich gallium ions from fly ash leachate. The method comprises:

[0140] (1) fly ash was weighed quantitatively, the leaching temperature was 110°C, the solid-liquid ratio of fly ash to deionized water was 1:10, hydrochloric acid was used as the leaching agent, the hydrochloric acid concentration was 15%, and the leaching was stirred for 2 hours to obtain a fly ash leaching solution with a viscosity of 3.2 cSt. The fly ash leaching solution contained 0.73 g / L gallium ions, 29.98 g / L silicon ions, 24.42 g / L aluminum ions, 1.35 g / L calcium ions, 0.98 g / L iron ions, arsenic ions, zinc ions, magnesium ions, etc.;

[0141] (2) a mixture of fly ash leachate and a surfactant is introduced into the column through a feed port at a flow rate of 50 mL / min, wherein the concentration of the surfactant in the mixture is 0.07 wt.%, the surfactant is tributyl phosphate, and the stirring speed of the stirrer is 300 rpm;

[0142] (3) Air is introduced into the liquid in the column through the air inlet to generate bubbles in the liquid. The air flow rate is 0.8m 3 / h;

[0143] (4) The pressure in the column is adjusted by a pressure regulating valve, and the chamber pressure is 0.9 MPa, so that during the bubble floating process, the air bubbles burst and the bubbles containing the target metal ions float up, thereby achieving extraordinary foam enrichment of the target metal ions. The bubble size under the inflation flow rate is recorded using an online image and particle size analysis device, and the equilibrium state of bubble floating and bursting is observed by a high-speed camera. After the process is stable, the concentrations of gallium solution and gallium foam at the bottom and top outlets are measured, and the average value is taken after multiple records, and the gallium metal ion enrichment ratio is calculated to be 156.

[0144] Example 3-2

[0145] This embodiment provides an extraordinary foam enrichment method similar to that of Embodiment 3-1, except that the flow rate of the mixture of fly ash leachate and surfactant is 40 mL / min.

[0146] The gallium metal ion enrichment ratio is 145.

[0147] Example 3-3

[0148] This embodiment provides an extraordinary foam enrichment method similar to that of Embodiment 3-1, except that the stirring speed of the stirrer is 260 rpm.

[0149] The gallium metal ion enrichment ratio is 142.

[0150] Embodiment 3-4

[0151] This embodiment provides a super foam enrichment method similar to that of embodiment 3-1, except that the aeration flow rate is 0.5 m 3 / h.

[0152] The gallium metal ion enrichment ratio is 141.

[0153] Embodiment 3-5

[0154] This embodiment provides an extraordinary foam enrichment method similar to that of Embodiment 3-1, except that the pressure in the column is 0.6 MPa.

[0155] The gallium metal ion enrichment ratio is 136.

[0156] Embodiment 3-6

[0157] This example provides a super foam enrichment method similar to that of Example 3-1, except that the concentration of the surfactant in the mixture is 0.05 wt.%.

[0158] The gallium metal ion enrichment ratio is 131.

[0159] Example 4-1

[0160] This embodiment provides an extraordinary foam enrichment method, using the extraordinary foam enrichment device of Example 1 to enrich germanium ions from smoke leaching liquid. The method comprises:

[0161] (1) Weighing a germanium-containing zinc oxide dust sample, leaching at a temperature of 60° C., a solid-liquid ratio of dust to deionized water of 1:7, using sulfuric acid as a leaching agent, a sulfuric acid concentration of 10%, stirring and leaching for 1 h to obtain a germanium-containing zinc oxide dust leachate with a viscosity of 1.4 cSt. In the dust leachate, germanium ions are 0.21 g / L, zinc ions are 36.18 g / L, lead ions are 0.06 g / L, iron ions are 0.751 g / L, sulfur ions, arsenic ions, etc.;

[0162] (2) introducing a mixture of smoke extract and a surfactant at a flow rate of 80 mL / min into the column through the feed port, wherein the concentration of the surfactant in the mixture is 0.04 wt.%, the surfactant is dodecylamine, and the stirring speed of the stirrer is 200 rpm;

[0163] (3) Air is introduced into the liquid in the column through the air inlet to generate bubbles in the liquid. The air flow rate is 0.3m 3 / h;

[0164] (4) The pressure in the column is adjusted by a pressure regulating valve, and the chamber pressure is 0.4 MPa, so that during the process of bubble floating, the air bubbles burst and the bubbles containing the target metal ions float up, thereby achieving extraordinary foam enrichment of the target metal ions. The bubble size under the inflation flow rate is recorded using an online image and particle size analysis device, and the equilibrium state of bubble floating and bursting is observed by a high-speed camera. After the process is stable, the concentrations of the germanium solution and germanium foam at the bottom and top outlets are measured, and the average value is taken after multiple records, and the germanium metal ion enrichment ratio is calculated to be 168.

[0165] Example 4-2

[0166] This embodiment provides an extraordinary foam enrichment method similar to that of Embodiment 4-1, except that the flow rate of the mixture of the smoke extract and the surfactant is 60 mL / min.

[0167] The germanium metal ion enrichment ratio is 157.

[0168] Example 4-3

[0169] This embodiment provides an extraordinary foam enrichment method similar to that of Embodiment 4-1, except that the stirring speed of the stirrer is 160 rpm.

[0170] The germanium metal ion enrichment ratio is 150.

[0171] Example 4-4

[0172] This embodiment provides a super foam enrichment method similar to that of embodiment 4-1, except that the aeration flow rate is 0.1 m 3 / h.

[0173] The germanium metal ion enrichment ratio is 142.

[0174] Embodiment 4-5

[0175] This embodiment provides an extraordinary foam enrichment method similar to that of Embodiment 4-1, except that the pressure in the column is 0.2 MPa.

[0176] The germanium metal ion enrichment ratio is 149.

[0177] Embodiment 4-6

[0178] This example provides a super foam enrichment method similar to that of Example 4-1, except that the concentration of the surfactant in the mixture is 0.02 wt.%.

[0179] The germanium metal ion enrichment ratio is 140.

[0180] Example 5-1

[0181] This embodiment provides an extraordinary foam enrichment method, using the extraordinary foam enrichment device of Example 1 to enrich germanium ions from zinc smelting waste slag leaching solution. The method comprises:

[0182] (1) Weighing zinc smelting waste slag, leaching temperature of 65° C., leaching solid-liquid ratio of zinc smelting waste slag to deionized water of 1:3, using sulfuric acid as leaching agent, sulfuric acid concentration of 20%, stirring and leaching for 2 h to obtain zinc smelting waste slag leaching solution, viscosity of 2.1 cSt, zinc smelting waste slag leaching solution, germanium ion 0.98 g / L, zinc ion 21.77 g / L, cadmium ion 6.20 g / L, lead ion 0.24 g / L, copper ion 1.68 g / L, iron ion 2.12 g / L, arsenic ion, cobalt ion, nickel ion, gold ion, etc.;

[0183] (2) a mixture of zinc smelting waste leaching solution and a surfactant is introduced into the column through a feed port at a flow rate of 50 mL / min, wherein the concentration of the surfactant in the mixture is 0.06 wt.%, and the surfactant is a mixture of pyrogallol and dodecylamine (the mass ratio of pyrogallol to dodecylamine is 1:3.2), and the stirring speed of the stirrer is 250 rpm;

[0184] (3) Carbon dioxide is introduced into the liquid in the column through the air inlet to generate bubbles in the liquid. The aeration flow rate is 0.5m 3 / h;

[0185] (4) The pressure in the column is adjusted by a pressure regulating valve, and the chamber pressure is 0.6 MPa, so that during the process of bubble floating, the air bubbles burst and the bubbles containing the target metal ions float up, thereby achieving extraordinary foam enrichment of the target metal ions. The bubble size under the inflation flow rate is recorded using an online image and particle size analysis device, and the equilibrium state of bubble floating and bursting is observed by a high-speed camera. After the process is stable, the concentrations of the germanium solution and the germanium foam at the bottom and top outlets are measured, and the average value is taken after multiple records, and the germanium metal ion enrichment ratio is calculated to be 124.

[0186] Example 5-2

[0187] This embodiment provides an extraordinary foam enrichment method similar to that of Embodiment 5-1, except that the flow rate of the mixture of zinc smelting waste slag leachate and surfactant is 40 mL / min.

[0188] The germanium metal ion enrichment ratio is 120.

[0189] Example 5-3

[0190] This embodiment provides an extraordinary foam enrichment method similar to that of Embodiment 5-1, except that the stirring speed of the stirrer is 210 rpm.

[0191] The germanium metal ion enrichment ratio is 114.

[0192] Example 5-4

[0193] This embodiment provides a super foam enrichment method similar to that of embodiment 5-1, except that the aeration flow rate is 0.3 m 3 / h.

[0194] The germanium metal ion enrichment ratio is 117.

[0195] Example 5-5

[0196] This embodiment provides an extraordinary foam enrichment method similar to that of Embodiment 5-1, except that the pressure in the column is 0.4 MPa.

[0197] The germanium metal ion enrichment ratio is 112.

[0198] Embodiment 5-6

[0199] This example provides a super foam enrichment method similar to that of Example 5-1, except that the concentration of the surfactant in the mixture is 0.03 wt.%.

[0200] The germanium metal ion enrichment ratio is 106.

[0201] Embodiment 5-7

[0202] This embodiment provides an extraordinary foam enrichment method similar to that of Embodiment 5-1, except that air is introduced into the slurry in the column through the air inlet.

[0203] The germanium metal ion enrichment ratio is 94.

[0204] Comparative Example 1

[0205] This comparative example uses a conventional method to enrich gallium ions from the bauxite leachate of Example 2, that is, the upper end of the column is open, there is no pressure regulating valve and safety valve assembly, and other conditions are the same as Example 2.

[0206] The enrichment ratio of Comparative Example 1 is 69.

[0207] The above description is only a preferred specific implementation manner of the present invention, but the protection scope of the present invention is not limited thereto. Any changes or substitutions that can be easily conceived by any technician familiar with the technical field within the technical scope disclosed by the present invention should be covered within the protection scope of the present invention.

Claims

1. An extraordinary foam enrichment device, characterized in that: The extraordinary foam enrichment device comprises a column with a sealed inner cavity, a feed inlet and an air inlet arranged at the lower part of the column, and a pressure regulating valve arranged at the upper part of the column; A solution outlet is arranged at the lower part of the column, and a foam outlet is arranged at the upper part of the column.

2. The super foam enrichment device according to claim 1, characterized in that: The feed port is provided with a surfactant inlet.

3. The super foam enrichment device according to claim 2, characterized in that: The extraordinary foam enrichment device also includes an online image and particle size analysis device, which includes a probe and a computer terminal. The probe is connected to the computer terminal, and the probe extends from the foam outlet into the foam layer in the column.

4. The super foam enrichment device according to claim 1, characterized in that: The column is made of transparent material.

5. The super foam enrichment device according to claim 4, characterized in that: The extraordinary foam enrichment device further comprises a high-speed camera, which is arranged outside the column.

6. The super foam enrichment device according to claim 1, characterized in that: A safety valve assembly is arranged at the upper end of the column.

7. The super foam enrichment device according to claim 6, characterized in that: The safety valve assembly includes a shell, an upper cover and a piston. The shell is connected to the cylinder through a lower opening. The upper cover is located at the upper end opening of the shell. The piston is located in a cavity formed by the upper cover and the shell. The piston extends in the cavity along the up-down direction. The lower end of the piston abuts against the lower opening of the shell. A first spring is arranged on the outer periphery of the piston. The upper end of the first spring is connected to the upper cover. The lower end of the first spring is connected to the lower part of the piston. The housing is provided with a transverse channel, in which a steel ball, a second spring and a fixing block are sequentially arranged in a direction away from the piston, one end of the second spring is connected to the steel ball, and the other end is connected to the fixing block; The shell is also provided with an air leakage channel, one end of which is connected with the transverse channel, and the other end of which is connected with the outside of the shell. The connection point between the air leakage channel and the transverse channel is located between the steel ball and the fixing block.

8. The super foam enrichment device according to claim 1, characterized in that: A stirrer is arranged at the bottom of the inner cavity of the column.

9. A method for enriching extraordinary foam, characterized in that: The super-normal foam enrichment device according to any one of claims 1 to 8 is used, and the super-normal foam enrichment method comprises: A feed liquid containing the target metal and a surfactant are introduced into the column through a feed inlet; Introduce gas into the liquid in the column through the gas inlet to generate bubbles in the liquid; The pressure in the column is adjusted by a pressure regulating valve, so that the air bubbles burst during the floating process, and the bubbles containing the target metal float up, thereby achieving extraordinary foam enrichment of the target metal.

10. The method for enriching extraordinary foam according to claim 9, characterized in that: The size, morphology and quantity of the bubbles are observed by the online image and particle size analysis device.

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