Germanium extraction device for continuous fluidization cascade reaction

Abstract

The invention discloses a germanium extraction device for continuous fluidization cascade reaction, belongs to the technical field of germanium extraction, and is used for solving at least one problem in the prior art that the germanium extraction process is complicated, the time is long, the acid consumption is large, and the temperature is high. The germanium extraction device comprises a feeding unit, a fluidization oxidizer and a fluidization reducer which are connected in sequence, the fluidization oxidizer is provided with an oxidizing gas inlet, and germanium-containing smoke dust powder in the fluidization oxidizer is always in a fluidization state and is subjected to an oxidation reaction; the fluidization reducer is provided with a reducing gas inlet, and the germanium-containing smoke dust powder oxidized in the fluidization reducer is always in a fluidization state and is subjected to a reduction reaction. The method can be used for extracting germanium from the germanium-containing smoke dust powder.

Description

Technical Field

[0001] This invention belongs to the field of germanium extraction technology, and particularly relates to a germanium extraction device using a continuous fluidized stepwise reaction. Background Technology

[0002] Germanium is a rare dispersed metal and an important semiconductor material besides silicon. It is an essential metal in fields such as communications, computers, and healthcare. Germanium is present in natural coal deposits, but the content is generally quite low.

[0003] In existing technologies, germanium is typically extracted using the following methods:

[0004] Chinese patent application CN109402409A discloses a method for enriching germanium from germanium-containing lignite fly ash. The method involves mixing coal powder and a sulfiding agent to form pellets, followed by drying, heating, and high-temperature sulfidation for 2 to 6 hours. This method has drawbacks such as complex raw material preparation, long reduction time, and high energy consumption.

[0005] Chinese patent application CN116397114A discloses a method for extracting germanium from germanium-containing lignite. This method uses ammonia water as a leaching agent to directly leach germanium from germanium-containing lignite. The leaching process requires heating and pressurization, as well as a protective gas. It has disadvantages such as long leaching time, large amount of acid used, and long process.

[0006] Chinese patent application CN105907979A discloses a method for enriching germanium from lignite dust. The method involves mixing lignite dust with pulverized coal and lime, granulating the mixture, and then placing it into a heating furnace. The furnace is kept in a reducing atmosphere at a temperature of 1200℃ to 1500℃. The reduction and volatilization process lasts for 2 to 18 hours, and the dust is collected to obtain germanium-enriched material. This method also suffers from the problems of complex raw material preparation steps, high reduction temperature, and long reduction time. Summary of the Invention

[0007] Based on the above analysis, the present invention aims to provide a germanium extraction device for continuous fluidized stepwise reaction volatilization, in order to solve at least one of the problems of complex extraction processes, long time, large acid consumption, and high temperature in the current technology.

[0008] This invention provides a germanium extraction apparatus for a continuous fluidized bed step-reaction, comprising a feeding unit, a fluidized bed oxidizer, and a fluidized bed reducer connected in sequence;

[0009] The fluidized bed oxidizer is equipped with an oxidizing gas inlet. In the fluidized bed oxidizer, germanium-containing dust powder is always fluidized and undergoes an oxidation reaction.

[0010] The fluidized bed reducer has a reducing gas inlet, and the germanium-containing dust powder after oxidation is always fluidized and undergoes a reduction reaction in the fluidized bed reducer.

[0011] Furthermore, the feeding unit includes a feeding tank, a dry mill, and a buffer chamber connected in sequence, with the outlet of the buffer chamber connected to the fluidized bed oxidizer.

[0012] Furthermore, the feeding unit also includes a screw feeder, a feeding heater, and a straight feeder connected in sequence to the buffer bin. The discharge port at the bottom of the buffer bin is connected to the top inlet of the screw feeder, and the discharge port of the feeding heater is connected to the bottom of the fluidized bed oxidizer through the straight feeder.

[0013] Furthermore, the fluidized bed oxidizer includes an oxidation chamber, an oxidation insulation layer, and an oxidation heating assembly. The cavity wall of the oxidation chamber has a sandwich structure, the oxidation heating assembly is located in the sandwich, and the oxidation insulation layer is located on the outer wall of the oxidation chamber.

[0014] Furthermore, the fluidized bed reducer includes a reduction chamber, a reduction insulation layer, and a reduction heating component. The chamber wall of the reduction chamber has a sandwich structure, the reduction heating component is located in the sandwich, and the reduction insulation layer is located on the outer wall of the reduction chamber.

[0015] Furthermore, the germanium extraction device also includes a feeding unit, through which the top of the fluidized bed oxidizer is connected to the bottom of the fluidized bed reducer.

[0016] Furthermore, the feeding unit includes a feeding heater and a screw feeder. The top of the fluidized bed oxidizer is connected to the top of the feeding heater, the bottom of the feeding heater is connected to the feed end of the screw feeder, and the discharge end of the screw feeder is connected to the bottom of the fluidized bed reducer.

[0017] Furthermore, the germanium extraction device also includes a discharge unit, with the top of the fluidized bed reducer connected to the inlet of the discharge unit.

[0018] Furthermore, the discharge unit includes a cooling tank and a belt conveyor connected in sequence to the fluidized bed reducer.

[0019] Furthermore, a discharge valve is installed on the connecting pipeline between the fluidized bed reducer and the cooling tank.

[0020] Compared with the prior art, the present invention can achieve at least one of the following beneficial effects:

[0021] A) The continuous fluidized bed reaction germanium extraction device provided by this invention uses solid waste (i.e. germanium-containing flue gas powder) generated from the combustion of germanium-containing coal as raw material for germanium extraction, which can improve the utilization rate of solid waste. In the fluidized bed oxidizer, germanium monoxide, germanium disulfide and germanium monosulfide in germanium-containing flue gas powder are converted into germanium dioxide, fixing germanium monoxide, germanium disulfide and germanium monosulfide, removing volatile impurities such as sulfur and arsenic, and destroying complex mineral structures. In the fluidized bed reducer, germanium dioxide is reduced to germanium monoxide. Taking advantage of the volatility of germanium monoxide, germanium enrichment is achieved by collecting flue gas containing germanium monoxide.

[0022] B) The germanium extraction device of continuous fluidized step reaction provided by the present invention keeps germanium-containing dust powder in a fluidized state under the action of reaction gas (oxidizing gas or reducing gas) and inert gas, which can fully contact the reaction gas to react, thereby effectively improving reaction efficiency, shortening reaction time, and improving germanium enrichment efficiency and enrichment extraction rate.

[0023] C) The continuous fluidized step reaction germanium extraction device provided by the present invention involves only oxidation and reduction reactions in the fluidized oxidizer and fluidized reducer during the germanium extraction process. The required reaction temperature is lower and easier to control. It does not require the use of corrosive agents, thereby effectively reducing energy consumption costs and improving the environmental friendliness of germanium extraction.

[0024] In this invention, the above-described technical solutions can be combined with each other to achieve more preferred combinations. Other features and advantages of this invention will be set forth in the following description, and some advantages may become apparent from the description or be learned by practicing the invention. The objects and other advantages of this invention can be realized and obtained from what is particularly pointed out in the description and drawings. Attached Figure Description

[0025] The accompanying drawings are for illustrative purposes only and are not intended to limit the invention. Throughout the drawings, the same reference numerals denote the same parts.

[0026] Figure 1 A schematic diagram of the germanium extraction apparatus for continuous fluidized stepwise reaction provided by the present invention;

[0027] Figure 2 This is a schematic diagram of the fluidized bed oxidizer in the continuous fluidized bed step reaction germanium extraction apparatus provided by the present invention.

[0028] Figure 3 This is a schematic diagram of the fluidized bed catalyst in the continuous fluidized bed step-reaction germanium extraction device provided by the present invention.

[0029] Figure label:

[0030] 1-Feeding tank; 2-Dry grinding mill; 3-Buffer silo; 4-Screw feeder; 5-Feeding heater; 6-Straight cylinder feeder; 7-Fluidized bed oxidizer; 71-Oxidation chamber; 72-Oxidation insulation layer; 73-Oxidation heating assembly; 8-Pushing heater; 9-Screw pusher; 10-Fluidized bed reducer; 101-Reduction chamber; 102-Reduction insulation layer; 103-Reduction heating assembly; 11-Discharge valve; 12-Cooling tank; 13-Belt conveyor. Detailed Implementation

[0031] The preferred embodiments of the present invention will now be described in detail with reference to the accompanying drawings, which constitute a part of the present invention and are used together with the embodiments of the present invention to illustrate the principles of the present invention, but are not intended to limit the scope of the present invention.

[0032] This invention provides a germanium extraction apparatus for a continuous fluidized stepwise reaction, see [link to relevant documentation]. Figure 1 It includes a feeding unit, a fluidized bed oxidizer 7 and a fluidized bed reducer 10 connected in sequence.

[0033] The fluidized bed oxidizer 7 is provided with an oxidizing gas (e.g., air or oxygen) inlet. In the fluidized bed oxidizer 7, germanium-containing dust powder is always fluidized and undergoes an oxidation reaction.

[0034] The fluidized bed reducer 10 is provided with a reducing gas (e.g., CO) inlet. In the fluidized bed reducer 10, the germanium-containing dust powder that has been oxidized is always fluidized and undergoes a reduction reaction.

[0035] Specifically, the reaction formula in fluidized bed oxidizer 7 is as follows:

[0036] 2GeO + O2 → 2GeO2;

[0037] GeS2+3O2→GeO2+2SO2;

[0038] GeS + 2O2 → GeO2 + SO2;

[0039] The reaction formula in fluidized bed reducer 10 is as follows:

[0040] GeO2(s) + CO(g) = GeO(g) + CO2(g)

[0041] Compared with existing technologies, the continuous fluidized bed reaction germanium extraction device provided by this invention, on the one hand, uses solid waste (i.e. germanium-containing flue gas powder) generated from the combustion of germanium-containing coal as raw material for germanium extraction, which can improve the utilization rate of solid waste. In the fluidized bed oxidizer, germanium monoxide, germanium disulfide, and germanium monosulfide in the germanium-containing flue gas powder are converted into germanium dioxide, fixing germanium monoxide, germanium disulfide, and germanium monosulfide, removing volatile impurities such as sulfur and arsenic, and destroying complex mineral structures. In the fluidized bed reducer 10, germanium dioxide is reduced to germanium monoxide. Taking advantage of the volatility of germanium monoxide, germanium enrichment can be achieved by collecting the flue gas containing germanium monoxide.

[0042] On the other hand, the germanium-containing dust powder is always fluidized under the action of the reaction gas (i.e., oxidizing gas or reducing gas), which allows the germanium-containing dust powder to fully contact and react with the reaction gas, thereby effectively improving the reaction efficiency, shortening the reaction time, and improving the enrichment efficiency and enrichment extraction rate of germanium.

[0043] On the other hand, in the process of germanium extraction, only oxidation and reduction reactions are involved in the fluidized bed oxidizer 7 and fluidized bed reducer 10. The required reaction temperature is lower and easier to control. There is no need to use corrosive agents, which can effectively reduce energy consumption costs and improve the environmental friendliness of germanium extraction.

[0044] To achieve continuous feeding, the feeding unit specifically includes a feeding tank 1, a dry mill 2, and a buffer chamber 3 connected in sequence. In practice, germanium-containing dust powder is fed into the dry mill 2 through the feeding tank 1. The dry mill 2 contains grinding media (e.g., ceramic ball media, steel ball media, or irregularly shaped media) to grind the germanium-containing dust powder, reduce its particle size, and break the particles to facilitate subsequent reactions. The discharge port of the dry mill 2 is connected to the feed port at the top of the buffer chamber 3. The buffer chamber 3 stores and buffers the germanium-containing dust powder to achieve continuous feeding during the processing.

[0045] To facilitate the smooth movement of germanium-containing dust powder in the germanium extraction device, the feeding unit also includes a screw feeder 4, a feeding heater 5, and a straight feeder 6 connected in sequence to the buffer chamber 3. The discharge port at the bottom of the buffer chamber 3 is connected to the top inlet of the screw feeder 4. After passing through the screw feeder 4, the germanium-containing dust powder is fed into the feeding heater 5. The feeding heater 5 heats the germanium-containing dust powder to raise its temperature to 600℃~800℃ to facilitate the subsequent oxidation reaction. The discharge port of the feeding heater 5 is connected to the bottom of the fluidized bed oxidizer 7 through the straight feeder 6.

[0046] For details regarding the structure of the fluidized bed oxidizer 7, please refer to [link / reference]. Figure 2It includes an oxidation chamber 71, an oxidation insulation layer 72, and an oxidation heating component 73. The cavity wall of the oxidation chamber 71 has a sandwich structure, and the oxidation heating component 73 is located in the sandwich to heat the germanium-containing dust powder in the oxidation chamber 71. The oxidation insulation layer 72 is located on the outer wall of the oxidation chamber 71 to keep the oxidation chamber 71 warm. A protective gas inlet (e.g., an inert gas inlet) is opened at the bottom of the oxidation chamber 71, and an oxidizing gas inlet is opened in the middle of the oxidation chamber 71. The germanium-containing dust powder in the fluidized oxidizer 7 is in a fluidized state, which fixes germanium monoxide, germanium disulfide, and germanium monosulfide, removes volatile impurities such as sulfur and arsenic, and destroys complex mineral structures.

[0047] For the structure of the fluidized bed reducer 10, see [link to relevant documentation]. Figure 3 It includes a reduction chamber 101, a reduction insulation layer 101, and a reduction heating component 103. The cavity wall of the reduction chamber 101 has a sandwich structure. The reduction heating component 103 is disposed in the sandwich and is used to heat the oxidized germanium-containing dust powder in the reduction chamber 101. The reduction insulation layer 101 is disposed on the outer wall of the reduction chamber 101 to keep the reduction chamber 101 warm. The bottom of the reduction chamber 101 has a protective gas inlet (e.g., an inert gas inlet) and a reducing gas inlet. In this way, the germanium-containing dust powder in the fluidized bed reducer 10 is in a fluidized state, reducing germanium dioxide to germanium monoxide. Then, taking advantage of the volatility of germanium monoxide, germanium enrichment is achieved by collecting the flue gas containing germanium monoxide.

[0048] In order to transport the oxidized germanium-containing dust powder from the fluidized bed oxidizer 7 to the fluidized bed reducer 10, the aforementioned continuous fluidized bed step reaction germanium extraction device also includes a feeding unit. The top of the fluidized bed oxidizer 7 is connected to the bottom of the fluidized bed reducer 10 through the feeding unit, which provides power to the oxidized germanium-containing dust powder.

[0049] Specifically, the feeding unit includes a feeding heater 8 and a screw feeder 9. The top of the fluidized bed oxidizer 7 is connected to the top of the feeding heater 8, the bottom of the feeding heater 8 is connected to the feed end of the screw feeder 9, and the discharge end of the screw feeder 9 is connected to the bottom of the fluidized bed reducer 10. In this way, the feeding heater 8 heats the oxidized germanium-containing dust powder, raising its temperature to 1100℃~1350℃ to facilitate the subsequent reduction reaction. The discharge port of the feeding heater 8 is connected to the bottom of the fluidized bed catalyst via the screw feeder 9.

[0050] In order to achieve smooth discharge of the waste material after processing, the germanium extraction device of continuous fluidized step reaction mentioned above also includes a discharge unit, and the top of the fluidized reducer 10 is connected to the feed port of the discharge unit.

[0051] Specifically, the discharge unit includes a cooling tank 12 and a belt conveyor 13 connected in sequence to the fluidized bed reducer 10. A discharge valve 11 is provided on the connecting pipe between the fluidized bed reducer 10 and the cooling tank 12 to control the actual discharge volume. The cooling tank 12 is used to cool the tail material after reduction so that the tail material is cooled to below 80°C.

[0052] Secondly, the present invention provides another germanium extraction apparatus for continuous fluidized bed stepwise reaction, the structure of which is basically the same as the germanium extraction apparatus for continuous fluidized bed stepwise reaction provided in the first aspect, the difference being:

[0053] It is worth noting that since germanium monoxide, germanium disulfide, and germanium monosulfide have different oxidation reaction temperature ranges (germanium monoxide oxidation temperature (250℃~300℃) < germanium monosulfide oxidation temperature (400℃~500℃) < germanium disulfide oxidation temperature (600℃~700℃), and all three undergo oxidation reactions in the same chamber, in order to ensure the sufficiency of the reactions, the temperature inside the fluidized bed oxidizer 7 needs to be controlled to be higher than the oxidation reaction temperature of germanium disulfide. However, this will not only lead to violent oxidation reactions of germanium monoxide and germanium monosulfide, but also increase energy consumption.

[0054] Therefore, based on the different densities of germanium monoxide, germanium disulfide, and germanium monosulfide (density of germanium disulfide < density of germanium monoxide and density of germanium monosulfide), the fluidized bed oxidizer 7 has two oxidation modes, namely the first oxidation mode and the second oxidation mode. During the germanium extraction process, the fluidized bed oxidizer 7 is in the first oxidation mode and the second oxidation mode in sequence.

[0055] Specifically, when the fluidized bed oxidizer 7 is in the first oxidation mode, the inert gas supply and oxidation heating component 73 are in the on state, the inert gas supply flow rate is in the first flow rate range, the heating temperature of the fluidized bed oxidizer 7 is in the first temperature range (600℃~700℃), the germanium disulfide in the germanium-containing dust powder is fluidized and undergoes oxidation reaction in the middle and upper parts of the fluidized bed oxidizer 7, while germanium monoxide and germanium monosulfide are located in the lower part of the fluidized bed oxidizer 7 and are not fluidized. The oxidation heating component 73 is not installed in the lower part of the fluidized bed oxidizer 7, therefore, germanium monoxide and germanium monosulfide do not undergo oxidation reaction.

[0056] When the fluidized bed oxidizer 7 is in the second oxidation mode, the inert gas supply flow rate is increased so that the inert gas supply flow rate is within the second flow range. The inert gas supply flow rate corresponding to the second flow range is greater than the inert gas supply flow rate corresponding to the first flow range. The oxidation heating component 73 is in the off state. Germanium monoxide and germanium sulfide located at the bottom of the fluidized bed oxidizer 7 are fluidized under the action of the inert gas and blown to the middle and upper parts of the fluidized bed oxidizer 7 to carry out the oxidation reaction using the residual heat of the fluidized bed oxidizer 7.

[0057] In this way, by utilizing the density difference between germanium disulfide and germanium monoxide and germanium monosulfide, as well as the inert gas supply flow rate, germanium disulfide is separated from germanium monoxide and germanium monosulfide. This allows germanium disulfide to undergo oxidation in the middle and upper parts of the fluidized bed oxidizer 7. Due to the large interparticle density, it can fully interact with the oxidizing gas and undergo a rapid and thorough oxidation reaction. After the germanium disulfide reaction is complete, the inert gas supply flow rate is increased, causing germanium monoxide and germanium monosulfide to be fluidized and undergo oxidation. At this time, since the fluidized bed oxidizer 7 still has residual heat from the first oxidation mode, there is no need to turn on the oxidation heating component 73 to allow germanium monoxide and germanium monosulfide to undergo oxidation. This not only effectively reduces energy consumption but also avoids the violent oxidation reaction of germanium monoxide and germanium monosulfide at high temperatures, thereby ensuring the overall safety of the equipment.

[0058] Example 1

[0059] This embodiment employs a continuous fluidized bed reaction germanium extraction device to extract germanium from germanium-containing dust powder. The raw material used is high-sulfur germanium-containing dust powder, whose composition, calculated by mass percentage, includes Ge 1.03%, Si 6.23%, S 4.35%, Al 0.23%, Fe 2.36%, Ca 1.63%, Zn 40.01%, Pb 15.63%, and other elements.

[0060] The specific extraction process includes the following steps:

[0061] Step 1: The germanium-containing dust powder after combustion is fed into the dry grinder through the feeder for dry grinding. The grinding product is required to have a particle size of less than 0.045mm and a mass content of less than 75%. The germanium-containing dust powder after drying is fed into the buffer bin and then fed into the screw feeder through the bottom of the buffer bin.

[0062] Step 2: The screw feeder rotates and drives the germanium-containing dust powder to the top of the feed heater. The feed heater heats the germanium-containing dust powder, raising its temperature to 700±20℃.

[0063] Step 3: The heated germanium-containing dust powder is fed into the fluidized bed oxidizer through a straight cylinder feeder. The germanium-containing dust powder is fluidized under the action of inert gas, and the temperature is maintained at 700±20℃. At the same time, air or oxygen is introduced. The residence time of the germanium-containing dust powder in the fluidized bed oxidizer is 30 minutes, so that germanium monoxide, germanium disulfide and germanium monosulfide in the germanium-containing dust powder are converted into germanium dioxide.

[0064] Step 4: The oxidized germanium-containing dust powder enters the feeder heater for heating, raising the temperature of the oxidized germanium-containing dust powder to 1100±20℃. Then, it is fed into the fluidized bed reducer by the screw feeder. The oxidized germanium-containing dust powder becomes fluidized under the action of inert gas, and the temperature is maintained at 1100±20℃. At the same time, a reducing gas is introduced. The residence time of the germanium-containing dust powder in the fluidized bed reducer is 50 minutes, so that germanium dioxide is reduced to germanium monoxide.

[0065] Step 5: Collect the vaporized germanium monoxide and calculate that the germanium volatilization rate is over 99.5%.

[0066] The above description is only a preferred embodiment of the present invention, but the scope of protection of the present invention is not limited thereto. Any changes or substitutions that can be easily conceived by those skilled in the art within the scope of the technology disclosed in the present invention should be included within the scope of protection of the present invention.

Claims

1. A germanium extraction apparatus using a continuous fluidized bed stepwise reaction, characterized in that, It includes a feeding unit, a fluidized bed oxidizer, and a fluidized bed reducer connected in sequence; The fluidized bed oxidizer is equipped with an oxidizing gas inlet, and germanium-containing dust powder is always fluidized and undergoes an oxidation reaction in the fluidized bed oxidizer; The fluidized bed reducer has a reducing gas inlet, and the germanium-containing dust powder oxidized in the fluidized bed reducer is always fluidized and undergoes a reduction reaction.

2. The germanium extraction apparatus for continuous fluidized bed step-reaction according to claim 1, characterized in that, The feeding unit includes a feeding tank, a dry mill, and a buffer chamber connected in sequence, and the outlet of the buffer chamber is connected to the fluidized bed oxidizer.

3. The germanium extraction apparatus for continuous fluidized bed step-reaction according to claim 2, characterized in that, The feeding unit also includes a screw feeder, a feeding heater and a straight feeder connected in sequence to the buffer bin. The discharge port at the bottom of the buffer bin is connected to the top inlet of the screw feeder, and the discharge port of the feeding heater is connected to the bottom of the fluidized bed oxidizer through the straight feeder.

4. The germanium extraction apparatus for continuous fluidized bed step-reaction according to claim 1, characterized in that, The fluidized bed oxidizer includes an oxidation chamber, an oxidation insulation layer, and an oxidation heating assembly. The wall of the oxidation chamber has a sandwich structure, the oxidation heating assembly is disposed in the sandwich, and the oxidation insulation layer is disposed on the outer wall of the oxidation chamber.

5. The germanium extraction apparatus for continuous fluidized bed step-reaction according to claim 1, characterized in that, The fluidized bed reducer includes a reduction chamber, a reduction insulation layer, and a reduction heating component. The wall of the reduction chamber is a sandwich structure, the reduction heating component is disposed in the sandwich, and the reduction insulation layer is disposed on the outer wall of the reduction chamber.

6. The germanium extraction apparatus for continuous fluidized bed step-reaction according to claim 1, characterized in that, The germanium extraction device also includes a feeding unit, and the top of the fluidized oxidizer is connected to the bottom of the fluidized reducer through the feeding unit.

7. The germanium extraction apparatus for continuous fluidized bed step-reaction according to claim 6, characterized in that, The feeding unit includes a feeding heater and a screw feeder. The top of the fluidized bed oxidizer is connected to the top of the feeding heater, the bottom of the feeding heater is connected to the feed end of the screw feeder, and the discharge end of the screw feeder is connected to the bottom of the fluidized bed reducer.

8. The germanium extraction apparatus for continuous fluidized bed step-reaction according to claim 1, characterized in that, The germanium extraction device also includes a discharge unit, and the top of the fluidized bed reducer is connected to the inlet of the discharge unit.

9. The germanium extraction apparatus for continuous fluidized bed step-reaction according to claim 8, characterized in that, The discharge unit includes a cooling tank and a belt conveyor connected in sequence to the fluidized bed reducer.

10. The germanium extraction apparatus for continuous fluidized bed step-reaction according to claim 9, characterized in that, A discharge valve is provided on the connecting pipe between the fluidized bed reducer and the cooling tank.

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