CN115216653A - Method for leaching weathering crust elution-deposited rare earth ore by using electric field - Google Patents
Method for leaching weathering crust elution-deposited rare earth ore by using electric field Download PDFInfo
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- C—CHEMISTRY; METALLURGY
- C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
- C22B—PRODUCTION AND REFINING OF METALS; PRETREATMENT OF RAW MATERIALS
- C22B59/00—Obtaining rare earth metals
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- C—CHEMISTRY; METALLURGY
- C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
- C22B—PRODUCTION AND REFINING OF METALS; PRETREATMENT OF RAW MATERIALS
- C22B3/00—Extraction of metal compounds from ores or concentrates by wet processes
- C22B3/04—Extraction of metal compounds from ores or concentrates by wet processes by leaching
- C22B3/045—Leaching using electrochemical processes
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- C—CHEMISTRY; METALLURGY
- C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
- C22B—PRODUCTION AND REFINING OF METALS; PRETREATMENT OF RAW MATERIALS
- C22B3/00—Extraction of metal compounds from ores or concentrates by wet processes
- C22B3/04—Extraction of metal compounds from ores or concentrates by wet processes by leaching
- C22B3/06—Extraction of metal compounds from ores or concentrates by wet processes by leaching in inorganic acid solutions, e.g. with acids generated in situ; in inorganic salt solutions other than ammonium salt solutions
- C22B3/08—Sulfuric acid, other sulfurated acids or salts thereof
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Abstract
The invention provides a method for strengthening weathering crust elution-deposited rare earth ore leaching mass transfer by using an electric field, which comprises the following steps: remodeling the collected weathering crust elution type rare earth ore sample to obtain a remodeled soil sample; injecting mineral leaching liquid from the top of the remolded soil sample for column leaching, applying an electric field parallel to the flowing direction of the mineral leaching liquid to the remolded soil sample, and collecting leaching liquid from the bottom of the remolded soil sample; the method improves the migration and permeation of the leaching solution in the ore body and strengthens the mass transfer process of the rare earth ions in the in-situ leaching process through the electro-physical and electrochemical actions generated by an external electric field, thereby improving the recovery rate of the rare earth and shortening the leaching period.
Description
Technical Field
The invention belongs to the technical field of efficient mining of ionic rare earth mines, and particularly relates to a method for leaching an enhanced weathering crust elution-deposited rare earth ore by using an electric field.
Background
Rare Earth elements (Rare Earth elements, abbreviated as REEs or RE) are a general name of 17 elements, are composed of scandium (Sc), yttrium (Y) and 15 lanthanides (Ln), have the names of "industrial vitamins" and "new material precursors", and have extremely wide applications in various fields of modern industrial systems, such as: aviation, electronics, medical treatment, superconduction, nuclear energy and other fields. China is a big rare earth country, and the rare earth resource reserves are abundant, wherein more than 70-80% of heavy rare earths are sourced from weathering crust elution type rare earth ores in south China globally, and the resource is also called as ion adsorption type rare earth ores because rare earth elements are adsorbed on the surfaces of clay minerals in an ionic state. The more active chemically cations are all capable of exchanging adsorbed rare earth ions, e.g. NH 4 + 、Na + 、Mg 2+ 、Ca 2+ 、Al 3+ And the like. The existing mining technology of the resources is an in-situ mining technology of ammonium sulfate leaching, namely under the condition of not excavating the earth surface, a certain amount of electrolyte solution is continuously injected into a rare earth ore body by using a liquid injection hole, rare earth ions are exchanged into the solution through the ion exchange effect and then flow out from a flow guide hole, a liquid collecting ditch is collected into a mother liquor pool, and finally rare earth elements are recovered after impurity removal and precipitation processes in a hydrometallurgy workshop.
In the mining process, the infiltration and diffusion effects of the mineral leaching solution are key factors determining the recovery rate of the rare earth resources. However, since the clay content in the rare earth minerals accounts for 40% -70%, the rare earth minerals have the special properties of clay minerals, such as: small mineral particles, large specific surface area, easy formation of double electric layers in pores, physical expansion of mineral when meeting water in the leaching process and the like. Due to the characteristics, the mineral deposit has poor infiltration and diffusion effects of mineral leaching liquid, a longer leaching period, lower comprehensive recovery rate of rare earth resources and potential safety hazards of slopes in the mining process, so that the rapid development, popularization and application of the in-situ mineral leaching technology are limited. Therefore, the diffusion capacity of the mineral leaching solution in a soil body is enhanced, mineral leaching blind areas are reduced, the exchange effect of cations and rare earth ions in the mineral leaching solution is enhanced, the mass transfer process of rare earth is accelerated, the fact that the mineral leaching solution can be comprehensively and well transported and permeated in a rare earth ore body is always the key point for successful in-situ mineral leaching popularization, and the key scientific problem which needs to be solved urgently for efficiently developing weathering crust leaching type rare earth ore resources is how to accelerate the rare earth leaching rate, improve the recovery rate and guarantee the safe production of mines.
CN112853124B discloses a process method for in-situ leaching injection of ionic rare earth ore, which comprises the following steps: s1, punching: a plurality of transverse liquid injection holes are drilled at intervals on the side surface of the ionic rare earth ore body, and the transverse liquid injection holes transversely penetrate through the ore body or point to the center of the ore body from the periphery of the ore body; the plurality of transverse liquid injection holes are distributed in a multilayer manner in the height direction of the ore body, and the plurality of transverse liquid injection holes positioned in the same layer are distributed at intervals in the horizontal direction; s2, inserting a tube: inserting a hard long-strip object into each transverse liquid injection hole, and then inserting a connecting pipe into each transverse liquid injection hole along each hard long-strip object; s3, liquid injection and ore leaching: injecting an ore leaching agent into the transverse injection hole through a connecting pipe; s4, water injection and leaching: and injecting water into the transverse liquid injection hole through the connecting pipe. The technological method of the invention arranges a plurality of layers of transverse liquid injection holes, pressurizes and adjusts the flow and controls the liquid injection layer by layer and section; the ore leaching agent is prevented from forming runoff and directly penetrating through an ore body; the leaching rate of rare earth reaches more than 96 percent. However, the leaching time of the rare earth element is long and the efficiency is low by the process method.
CN105087925A discloses an auxiliary leaching agent for ion type rare earth ore leaching and an ore leaching method thereof. The leaching aid is a water-soluble aminopolycarboxylic acid compound, and leaching mineral liquid prepared by mixing the leaching agent and the leaching aid is used for leaching ionic rare earth ore. When the leaching aid is coordinated with the rare earth, a RE-N coordination compound can be formed through nitrogen atoms on amino groups, and a RE-O coordination compound can be formed through oxygen atoms on carboxyl groups, so that the complexing constant of the rare earth and the leaching aid is increased, the obtained rare earth complex is more stable, and the enhanced leaching effect is improved. The leaching aid is used in the ore leaching process, so that the rare earth leaching rate is improved, the dosage of the leaching aid is reduced, the production cost is reduced, and the ammonia nitrogen pollution is reduced.
CN112176209A discloses an ion type rare earth ore calcium salt system green extraction method, which uses calcium salt as an ore leaching agent, calcium oxide as a purification and impurity removal agent and calcium oxide as a precipitating agent, and uses a fluorine type salt form to recover the ore leaching agent, dechlorination and heavy metal elements, the whole process of the system is free of ammonia nitrogen and high-salt wastewater discharge, the process is smooth, the content of product impurities is low, the influence on the environment of a mine area after ore closing is small, and the ion type rare earth ore green environment-friendly exploitation can be realized. In addition, the method of the invention takes calcium chloride as a main material, and adds a small amount of acid regulating agents such as aluminum chloride, ferric chloride, ammonium chloride and the like, the formed composite salt mineral leaching agent is a main composition material of the mineral soil, compared with a mineral leaching system taking ammonium salt, magnesium salt, sodium salt and potassium salt as main materials, the composite salt mineral leaching agent has almost no influence on the environment, the leaching rate of rare earth and the leaching peak concentration of the rare earth can be effectively improved, the tailing phenomenon of the mineral leaching agent is reduced, the mineral leaching time is shortened, and the mineral leaching efficiency is improved. Although the extraction method improves the ore leaching efficiency, the system is complex and secondary pollution can be caused.
In view of the above, a new method needs to be researched to enhance the leaching efficiency of the rare earth elements in the ionic rare earth.
Disclosure of Invention
Aiming at the problems of low leaching efficiency, additional separation or pollution caused by an additionally added enhanced leaching agent and the like in the prior art, the invention provides a method for enhancing the leaching mass transfer of weathered crust leaching type rare earth ore by using an electric field.
In order to achieve the purpose, the invention adopts the following technical scheme:
the invention provides a method for strengthening weathering crust elution-deposited rare earth ore leaching mass transfer by using an electric field, which comprises the following steps:
remodeling the collected weathering crust elution-deposited rare earth ore sample to obtain a reconstructed soil sample;
injecting mineral leaching liquid from the top of the remolded soil sample for column leaching and leaching, applying an electric field parallel to the flow direction of the mineral leaching liquid to the remolded soil sample, and collecting leaching liquid from the bottom of the remolded soil sample.
The invention provides a method for strengthening weathering crust eluviation type rare earth ore leaching mass transfer by using an electric field, wherein the electric field is added in a rare earth leaching system, and the electro-physical and electrochemical actions generated by the electric field are combined with chemical leaching, so that the requirement of leaching efficiency can be fully met; the principle of electric field reinforced rare earth ion mass transfer mainly comprises the following two aspects: the first is that the rare earth leaching process is via the more active Mg 2+ RE adsorbed on the surface of the ore soil particles 3+ The RE in the pore solution of the leaching system is added into the pore solution of the ore body 3+ Moves downwards with the solution under the action of gravity, and on the other hand, RE in the solution system 3+ The movement along with seepage in disorder is changed into directional movement with higher speed. Secondly, clay particles in the weathering crust eluviation type rare earth ore have negative charges to form a combined water layer on the surface of the mineral particles, when an electric field is applied to a rare earth leaching body, the original static balance of the clay particles is broken, the thickness of an electric double layer of the clay particles is reduced, on one hand, the sectional area of a seepage channel is increased, the solution seepage resistance is reduced, and the seepage speed of a leaching solution is increased; on the other hand, water molecules adsorbed on the surfaces of the clay particles are subjected to a force moving towards the direction of the negative electrode to generate directional migration, and the positive charges drag free water around the water molecules to perform directional migration due to certain viscosity of the solution, so that electroosmosis is formed, and the seepage speed of the solution is improved.
Preferably, the remodeling is performed within a tubular container.
Preferably, the remodeling is performed by a method comprising: and adding the soil sample into a tubular container in batches, and sequentially compacting and shaving to obtain the remolded soil sample.
Preferably, the number of strokes and shaves is 1-3, and may be, for example, 1, 2 or 3.
Preferably, the electric field is applied by placing electrode pieces on the top and bottom of the remolded soil sample and connecting a power supply.
In the invention, the electric field applying mode is suitable for small and medium-sized soil samples in a laboratory, when the method is applied to the actual industry, the arrangement mode of the liquid injection holes and the flow guide holes provides a natural field for the arrangement position of the electrodes of the external electric field, the used equipment is simple, the operation is simple, and the external electric field assisted rare earth leaching has great potential for realizing industrial application.
Preferably, the electric field is applied at a time after the bottom of the reshaped soil sample begins to leach.
Preferably, the collection of leachate in this application refers to: continuously flowing the leachate at the bottom of the remolded soil sample to a container, transferring and collecting the leachate obtained in the container at intervals, and then carrying out labeling, testing and the like.
Preferably, the electric field is a direct current electric field.
Preferably, the strength of the electric field comprises 5-6V/cm, for example 5V/cm, 5.5V/cm or 6V/cm, but is not limited to the values listed, and other values not listed in this range are equally applicable.
Preferably, the shape of the electrode sheet comprises a mesh shape.
Preferably, the electrode plate is made of titanium-plated ruthenium-iridium or graphite.
Preferably, the electrode tabs include a positive electrode tab and a negative electrode tab.
Preferably, the positive plate is placed on top of the remolded soil sample.
Preferably, the negative electrode sheet is arranged at the bottom of the remolded soil sample.
Preferably, the solute of the mineral leach solution comprises magnesium sulphate heptahydrate.
Preferably, the concentration of the leachate is 1.99 to 2.01% by mass, for example 1.99%, 1.9995%, 2%, 2.005% or 2.01%, but is not limited to the values listed, and other values not listed within this range are equally applicable.
Preferably, the time for leaching the column is 100-480min, such as 100min, 180min, 240min, 320min, 400min or 480min, but is not limited to the recited values, and other values not recited in the range of values are equally applicable.
Preferably, the time of the column leaching starts with the injection of the leaching solution until the rare earth concentration in the rare earth leaching solution remains substantially unchanged and below the minimum industrial exploitation level.
Preferably, the manner of collecting the leachate comprises intermittent collection or uniform collection.
Preferably, when batch collection is used for collecting the leachate, the time for column leaching is 479-481min, such as 479min, 479.5min, 480min, 480.5min or 481min, but is not limited to the values recited, and other values not recited in this range are equally applicable;
preferably, when the collected leachate is collected uniformly, the time for column leaching is 129-131min, such as 129min, 129.5min, 130min, 130.5min or 131min, but not limited to the values listed, and other values not listed in the range of the values are also applicable;
preferably, when intermittent collection is used for the collection of the leachate, the total time for applying the electric field is 59-61min, such as 59min, 59.5min, 60min, 60.5min or 61min, but not limited to the values listed, and other values not listed in this range are equally applicable;
preferably, when uniform collection is used for the collection of the leachate, the total time for applying the electric field is 19-21min, for example 19min, 19.5min, 20min, 20.5min or 21min, but is not limited to the values listed, and other values not listed in this range are equally applicable. Preferably, the type of means for injecting the mineral spirits comprises a peristaltic material delivery device.
Preferably, the infusion rate of the mineral dip is 0.99-1.01 mL-min -1 For example, the concentration may be 0.99 mL/min -1 、0.995mL·min -1 、1mL·min -1 、1.005mL·min -1 Or 1.01 mL/min -1 However, the numerical values recited are not intended to be limiting, and other numerical values not recited within the numerical range may be equally applicable.
Preferably, the remolded soil sample is washed by injecting the top water after the mineral leaching solution is injected.
Preferably, the mineral leaching liquid is injected and then top water washing is not injected according to leaching conditions.
Preferably, the top water comprises deionized water.
Preferably, the type of means for injecting the head water comprises a peristaltic material delivery device.
Preferably, the injection rate of the top water is 0.99-1.01 mL-min -1 For example, it may be 0.99mL · min -1 、0.995mL·min -1 、1mL·min -1 、1.005mL·min -1 Or 1.01 mL/min -1 However, the numerical values recited are not intended to be limiting, and other numerical values not recited within the numerical range may be equally applicable.
As a preferred embodiment of the present invention, the method comprises the steps of:
adding the collected weathered crust eluviation type rare earth ore sample into a tubular container, compacting for 1-3 times and shaving to obtain a remolded soil sample; carrying out column leaching on the remolded soil sample, and using a peristaltic material conveying device for 0.99-1.01 mL/min -1 Injecting ore leaching solution with the mass concentration of 1.99-2.01% and the solute of magnesium sulfate heptahydrate from the top of the remolded soil sample, applying an electric field with the strength of 5-6V/cm and parallel to the flowing direction of the ore leaching solution to the remolded soil sample, placing a positive plate on the top of the remolded soil sample, placing a negative plate on the bottom of the remolded soil sample and connecting a power supply, wherein the positive plate and the negative plate comprise a titanium net or a graphite net plated with iridium ruthenium; intermittently or uniformly collecting leachate from the bottom of the remolded soil sample, wherein when intermittent collection is adopted, the time for leaching and leaching the column is 479-481min, and the total time for applying an electric field is 59-61min; when uniform collection is adopted, the time for column leaching is 129-131min, and the total time for applying the electric field is 19-21min.
Compared with the prior art, the invention has the beneficial effects that:
(1) The invention provides a method for strengthening weathering crust elution type rare earth ore leaching mass transfer by using an electric field, wherein the electric field is added in a rare earth leaching system, the rare earth ion leaching speed is accelerated by using the electromigration action and the electromigration action generated by the electric field, and the peak value of leached rare earth moves forwards;
(2) The method for strengthening the leaching mass transfer of the weathering crust elution-deposited rare earth ore by using the electric field has the advantages that the used equipment and the operation are simple and convenient, the rare earth leaching is assisted by the external electric field, the cost is low, no pollution is caused, no additional separation step is caused, and the separation efficiency is further improved;
(3) The method for strengthening weathering crust elution type rare earth ore leaching mass transfer by using the electric field provided by the invention is based on the principle of an in-situ leaching process, almost has no obstacle in the actual scene of transferring from a middle sample to a small sample to rare earth leaching, and has the potential of expanded application.
Detailed Description
For the purpose of facilitating an understanding of the present invention, the present invention will now be described by way of examples. It should be understood by those skilled in the art that the examples are only for the understanding of the present invention and should not be construed as the specific limitations of the present invention.
The technical solution of the present invention is further explained by the following embodiments.
In one embodiment, the invention provides a method for strengthening leaching mass transfer of weathering crust elution type rare earth ore by using an electric field, which comprises the following steps:
adding the collected weathered crust eluviation type rare earth ore sample into a tubular container, compacting for 1-3 times and shaving to obtain a remolded soil sample; leaching and leaching the remolded soil sample by using a column, and conveying the remolded soil sample by using a peristaltic material conveying device at a speed of 0.99-1.01 mL/min -1 Injecting ore leaching solution with the mass concentration of 1.99-2.01% and the solute of magnesium sulfate heptahydrate from the top of the remolded soil sample, applying an electric field with the strength of 5-6V/cm in the direction vertical to the ground to the remolded soil sample, placing a positive plate on the top of the remolded soil sample, placing a negative plate on the bottom of the remolded soil sample and connecting a power supply, wherein the positive plate and the negative plate comprise a ruthenium-iridium plated titanium net or a graphite net; intermittently or uniformly collecting leachate from the bottom of the remolded soil sample, wherein when intermittent collection is adopted, the time for leaching and leaching the column is 479-481min, and the total time for applying an electric field is 59-61min; when uniform collection is adopted, the time for column leaching is 129-131min, and the electric field is appliedThe total time is 19-21min.
It is understood that processes or substitutions and variations of conventional data provided by embodiments of the present invention are within the scope and disclosure of the present invention.
In the following examples and comparative examples, weathered crust eluviation type rare earth ore with the ion phase rare earth grade of 0.0472% is selected, sufficient and dry ore soil is uniformly prepared into soil samples with the water content of 13%, 108g of the soil samples are respectively taken after uniform mixing and are loaded into leaching columns with the diameter of 4cm, and the ore loading heights are uniform and 6cm.
Example 1
The embodiment provides a method for strengthening leaching mass transfer of weathering crust elution-type rare earth ore by using an electric field, which comprises the following steps:
adding the collected weathered crust eluviation type rare earth ore sample into a leaching column, compacting for 2 times and shaving to obtain a remolded soil sample; saturating the remolded soil sample with deionized water for 1h after the remolded soil sample begins to liquid out of the bottom; continuously injecting heptahydrate magnesium sulfate mineral leaching liquid with the mass concentration of 2% from the top of the remolded soil sample by using a peristaltic pump, keeping the height of a liquid injection water head to be 1cm, intermittently collecting rare earth mother liquid every 0.5h, applying an electric field with the strength of 6V/cm to the remolded soil sample in the direction vertical to the ground after 1 st mother liquid collection, placing a positive plate on the top of the remolded soil sample, placing a negative plate on the bottom of the remolded soil sample, and connecting a power supply, wherein the positive plate and the negative plate are titanium meshes plated with ruthenium and iridium; the time of the external electric field is from the end of the 1 st collection to the end of the 3 rd collection, and the cumulative time is 60min; and after 480min of accumulative column leaching and leaching, stopping injecting and collecting the solution, and collecting the leaching solution for 16 times in an accumulative way.
Example 2
The embodiment provides a method for strengthening leaching mass transfer of weathering crust elution type rare earth ore by using an electric field, which is different from the embodiment 1 only in that the electric field intensity applied during column leaching is 4V/cm.
Example 3
The embodiment provides a method for strengthening leaching mass transfer of weathering crust elution type rare earth ore by using an electric field, which is different from the embodiment 1 only in that the electric field intensity applied during column leaching is 8V/cm.
Comparative example 1
The present comparative example provides a method for leaching mass transfer of weathering crust eluviation type rare earth ore, which is different from example 1 only in that no electric field is applied during column leaching.
The methods provided in examples 1 to 3 and comparative example 1 are shown in table 1, which shows the mass of rare earth (in terms of rare earth oxide) in each leachate collected intermittently, the yield, and other relevant properties.
TABLE 1
In table 1, since the rare earth content in the first leaching solution was very low, close to 0, no statistics were made.
Example 4
The embodiment provides a method for strengthening leaching mass transfer of weathering crust elution-type rare earth ore by using an electric field, which comprises the following steps:
adding the collected weathered crust elution-deposited rare earth ore sample into a tubular container, compacting for 2 times and shaving to obtain a remolded soil sample; 1 mL/min by using a peristaltic material conveying device -1 Firstly injecting 2% magnesium sulfate heptahydrate mineral leaching solution from the top of the remolded soil sample, wherein the ratio of the total injection amount of the mineral leaching solution to the liquid-solid volume of the remolded soil sample is 0.4; after the liquid begins to flow out from the bottom for 10min, applying an electric field with the strength of 6V/cm, which is vertical to the ground direction, to the remolded soil sample, placing a positive plate on the top of the remolded soil sample, placing a negative plate on the bottom of the remolded soil sample and switching on a power supply, wherein the switching-on time is 20min, and the positive plate and the negative plate comprise ruthenium and iridium plated materialsA titanium mesh or a graphite mesh; and accumulating the leaching and leaching time of the column for 130min, uniformly collecting the rare earth mother liquor at one time when the bottom of the remolded soil sample does not outflow any more, and ending the experiment.
Example 5
This example provides a method for using electric field to enhance leaching mass transfer of rare earth ore in weathering crust elution, which is different from example 4 only in that the duration of the electric field applied in the column leaching is 10min.
Example 6
The embodiment provides a method for strengthening leaching mass transfer of weathering crust elution type rare earth ore by using an electric field, and the method is different from the embodiment 4 only in that the duration of the electric field applied during column leaching is 30min.
Example 7
This example provides a method for using electric field to enhance leaching mass transfer of rare earth ore in weathering crust elution, which is different from example 4 only in that the duration of the electric field applied in the column leaching is 40min.
Comparative example 2
This comparative example provides a method of weathering crust elution mass transfer leaching of rare earth ore, which differs from example 4 only in that no electric field is applied during column leaching.
The methods provided in examples 4 to 7 and comparative example 2, using the cumulative rare earth mass (in terms of rare earth oxide), cumulative liquor collection rate, and the like, in the uniformly collected leachate, are shown in table 2.
TABLE 2
| Cumulative leaching rare earth mass (mg) | Cumulative liquid yield (%) | |
| Example 4 | 37.91 | 85.55 |
| Example 5 | 35.69 | 80.54 |
| Example 6 | 36.04 | 81.49 |
| Example 7 | 35.27 | 79.57 |
| Comparative example 2 | 35.97 | 81.17 |
From the data in tables 1 and 2 we can see that:
(1) In the method for reinforcing leaching mass transfer of the weathering crust elution type rare earth ore by using the electric field provided in the embodiments 1 and 4, the electric field is applied when the rare earth element is leached by the opposite column, and the optimal electric field intensity and the optimal electric field application time are adopted, so that the leaching rate of the rare earth is improved in the intermittent collection method, and the leaching peak value is advanced to the 2 nd leaching; higher yield of rare earth elements is also obtained, the mass of the leached rare earth is more than or equal to 44.13mg during intermittent collection, the cumulative liquid yield is more than or equal to 99.58%, the mass of the leached rare earth is more than or equal to 37.91mg during uniform collection, and the cumulative liquid yield is more than or equal to 85.55%;
(2) As can be seen by combining examples 1-3 and comparative example 1, the applied field strength of example 1 was 6V/cm, the cumulative leaching rate of rare earth was 7.68% for the first 2 collections, and the cumulative leaching rate of rare earth was 64.24% for the first 4 collections, whereas the rare earth mass was only 0.03mg, and 0mg for the 2 nd collection leachate of examples 2-3 and comparative example 1, the cumulative leaching rates of rare earth were only 52.19%, 52.16%, and 45.84% for the first 4 collections, as compared to the applied field strengths of examples 2-3 of 4V/cm and 8V/cm, respectively, and comparative example 1 with no applied field; as can be seen, an electric field of 6V/cm is added in the rare earth leaching system, and rare earth ions are detected in advance in the rare earth leaching solution collected at the 2 nd time; with the increase of the leaching time, the cumulative leaching rate of the sample under the action of the electric field after the 3 rd leaching is finished reaches 45.87 percent, and is improved by 32.48 times compared with the cumulative leaching rate of the sample under the condition of the comparative example 1 without the electric field. Similarly, when the 4 th and 5 th leaching are finished, the cumulative leaching rate of the sample under the action of the electric field is obviously higher, which indicates that the application of the electric field in the rare earth leaching system and the optimization of the electric field strength can promote the mass transfer leaching of the rare earth, the higher leaching rate can be achieved in the same leaching time, and the leaching time is greatly shortened;
(3) It can be seen from the combination of examples 4-7 and comparative example 2 that the time of applying the electric field was 20min for example 4, 10min, 30min and 40min for comparative example 2, respectively, and no electric field was applied for comparative example 2, the cumulative leached rare earth mass for example 4 was 37.91mg, and the cumulative liquid yield was 85.55%, while the cumulative leached rare earth mass for examples 5-7 and comparative example 2 was only 35.69mg, 36.04mg, 35.27mg and 35.97mg, respectively, and the cumulative liquid yields were only 80.54%, 81.49%, 79.57% and 81.17%, respectively; it can be seen that an electric field of 6V/cm is added in the rare earth leaching system, under the condition of the optimized electrifying time length, the concentration of the rare earth in the leaching solution is higher than that of the leaching solution without the electric field sample, and under the condition that the volumes of the collected leaching solutions are basically consistent, the quality and the leaching rate of the finally leached rare earth are also higher, which indicates that the added electric field is beneficial to improving the recovery rate of rare earth resources and reducing the dosage of the leaching solution, the dosage of the leaching agent is reduced to a certain extent, and the mining cost is reduced.
In summary, according to the method for reinforcing leaching mass transfer of the weathering crust eluviation type rare earth ore by using the electric field, the electric field is applied to the rare earth leaching system, the electro-physical and electrochemical actions generated by the electric field are combined with chemical leaching, the requirements on leaching efficiency, cost, environmental protection and the like can be fully met, based on the principle of the in-situ leaching process, the arrangement mode of the liquid injection holes and the flow guide holes provides a natural field for the arrangement position of the electrodes of the applied electric field, the used equipment is simple, the operation is simple, and the possibility of realizing industrial application of the rare earth leaching assisted by the applied electric field is provided.
The applicant declares that the above description is only a specific embodiment of the present invention, but the scope of the present invention is not limited thereto, and it should be understood by those skilled in the art that any changes or substitutions that can be easily conceived by those skilled in the art within the technical scope of the present invention are within the scope and disclosure of the present invention.
Claims (10)
1. A method for strengthening leaching mass transfer of weathering crust elution-deposited rare earth ore by using an electric field is characterized by comprising the following steps:
remodeling the collected weathering crust elution-deposited rare earth ore sample to obtain a reconstructed soil sample;
injecting mineral leaching liquid from the top of the remolded soil sample for column leaching, applying an electric field parallel to the flowing direction of the mineral leaching liquid to the remolded soil sample, and collecting leaching liquid from the bottom of the remolded soil sample.
2. The method of claim 1, wherein the remodeling is performed within a tubular container;
preferably, the remodeling is performed by a method comprising: adding the soil sample into a tubular container in batches, compacting and shaving in sequence to obtain a remolded soil sample;
preferably, the number of said strikes and shaves is 1-3.
3. The method of claim 1 or claim 2, wherein the electric field is applied by placing electrode pads on the top and bottom of the remodeled soil sample and applying a power source.
4. The method according to any one of claims 1 to 3, wherein the electric field is a direct current electric field;
preferably, the strength of the electric field is 5-6V/cm.
5. The method of claim 3 or 4, wherein the shape of the electrode sheet comprises a mesh;
preferably, the electrode plate is made of titanium-plated ruthenium-iridium or graphite.
6. The method according to any one of claims 3 to 5, wherein the electrode tabs comprise a positive tab and a negative tab;
preferably, the positive plate is placed on the top of the remolded soil sample;
preferably, the negative electrode sheet is arranged at the bottom of the remolded soil sample.
7. The method of any one of claims 1 to 6, wherein the solutes of the pregnant leach solution comprise magnesium sulfate heptahydrate;
preferably, the mass concentration of the mineral leaching solution is 1.99-2.01%;
preferably, the manner of collecting the leachate comprises intermittent collection or uniform collection;
preferably, when the collection of the mineral leaching solution adopts intermittent collection, the time of column leaching is 479-481min;
preferably, when the collected mineral leaching solution is collected uniformly, the time for leaching and leaching the column is 129-131min;
preferably, when the mineral leaching liquid is collected intermittently, the total time for applying the electric field is 59-61min;
preferably, when uniform collection is adopted for collecting the mineral leaching solution, the total time for applying the electric field is 19-21min.
8. A method according to any one of claims 1 to 7, wherein the type of apparatus for injecting the mineral leach solution includes a peristaltic material delivery apparatus;
preferably, the infusion rate of the mineral dip is 0.99-1.01 mL-min -1 。
9. The method according to any one of claims 1 to 8, wherein the remolded soil sample is washed by injecting top water after the completion of the injection of the mineral leaching solution;
preferably, the top water comprises deionized water;
preferably, the type of means for injecting the head water comprises a peristaltic material conveying means;
preferably, the injection rate of the top water is 0.99-1.01 mL-min -1 。
10. Method according to any of claims 1-9, characterized in that the method comprises the steps of:
adding the collected weathered crust eluviation type rare earth ore sample into a tubular container, compacting for 1-3 times and shaving to obtain a remolded soil sample; leaching and leaching the remolded soil sample by using a column, and conveying the remolded soil sample by using a peristaltic material conveying device at a speed of 0.99-1.01 mL/min -1 Injecting ore leaching solution with the mass concentration of 1.99-2.01% and the solute of magnesium sulfate heptahydrate from the top of the remolded soil sample, applying an electric field with the strength of 5-6V/cm and parallel to the flowing direction of the ore leaching solution to the remolded soil sample, placing a positive plate on the top of the remolded soil sample, placing a negative plate on the bottom of the remolded soil sample and connecting a power supply, wherein the positive plate and the negative plate comprise a titanium net or a graphite net plated with iridium ruthenium; intermittently or uniformly collecting leachate from the bottom of the remolded soil sample, wherein when intermittent collection is adopted, the time for leaching and leaching the column is 479-481min, and the total time for applying an electric field is 59-61min; when uniform collection is adopted, the time for leaching the column is 129-131min, and the total time for applying the electric field is 19-21min.
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