CN115478182B - Preparation method of ionic rare earth leaching agent - Google Patents
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Abstract
The invention discloses a preparation method of an ionic rare earth leaching agent, which comprises the following steps: (1) Domesticating microorganisms by using a rare earth activated mineral powder culture medium to obtain a microorganism suspension; (2) Amplifying and culturing the microorganism suspension and the additive to obtain an amplifying culture solution; (3) And uniformly mixing the modified sesbania gum with the amplification culture solution to obtain the ionic rare earth leaching agent. The activated mineral powder has excellent cation exchange function after being activated, and the activated mineral powder and the ionic rare earth mineral powder are used as culture medium components to domesticate microorganisms, so that the microorganisms can survive in the ionic solution, and the leaching rate of the synergized leached ionic rare earth is improved.
Description
Technical Field
The invention belongs to the technical field of rare earth hydrometallurgy, and particularly relates to a preparation method of an ionic rare earth leaching agent.
Background
Rare earth resources are called as 'universal earth', and are important strategic reserve resources in China. The rare earth material is an important manufacturing raw material for permanent magnet, hydrogen storage, luminescence, catalysis and the like, and becomes a key resource for the important support and the tip national defense technology development of new material manufacturing. The rare earth resources in China are rich, the distribution pattern of the light rare earth in north and the heavy rare earth in south is formed, and the ecological damage is caused by the lag and excessive exploitation of the early rare earth technology, and meanwhile, the waste and the loss of the rare earth resources are also caused. The rare earth elements in the ionic rare earth ore are adsorbed on the weathered clay mineral in the state of hydration or hydroxyl hydration cations, such as kaolin, montmorillonite, the content is about 0.3-0.05%, when the rare earth ions meet electrolyte cations (K) + 、Na + 、Mg 2+ 、Ca 2+ 、NH 4 + Etc.) can be exchanged and resolved from clay minerals.
In recent years, the leaching technology mainly comprises an ammonium sulfate in-situ leaching technology formed by exploiting the ionic rare earth, but the total ammonia nitrogen in the leaching liquid causes pollution to water body, and the leaching technology is not in accordance with the development concept of parallel ecological friendliness and rare earth exploitation. Patent publication No. CN113699389A discloses a leaching and purifying method of rare earth concentrate, which takes hydrochloric acid solution as a leaching agent to act on rare earth concentrate powder, and stir under the condition to carry out a small test; however, the method uses hydrochloric acid, so that the leached slag is easy to acidify, meanwhile, the pH value of the supernatant is too low to be treated to the emission standard, in addition, the rare earth ore is used in a large amount in the actual exploitation process, and the production of the powder and the production under the stirring condition can increase a large amount of cost, so that the method is insufficient for providing technical reference for industrial exploitation of ionic rare earth. Patent publication No. CN113046579A discloses a method for leaching weathering crust leaching rare earth ore by biological and chemical synergy, wherein the leaching rate of ionic rare earth in a small test can reach 98.30%, the clean and efficient extraction of rare earth is realized on the premise of relieving environmental pollution, but a large number of chemical raw materials are used in the preparation process of a leaching agent, so that the rare earth extraction cost is increased. Patent publication No. CN113046552A discloses a method for leaching and weathering by using plant extractThe shell leaching process of producing RE ore includes extracting one or several kinds of oak, bamboo, wild jujube, rice husk and corn cob to obtain pyrolysed liquid or pyroligneous liquor, mixing with ammonium sulfate or magnesium sulfate, regulating pH value to 1-6 with sulfuric acid or sodium hydroxide, and leaching with ion type RE leaching rate up to 93.7%; but the method utilizes pyroligneous liquor to cooperate with NH + 4 The leaching of rare earth in an acidic environment is still unavoidable, and the supernatant fluid contains ammonia nitrogen, so that improvement is still needed. The literature sesbania gum and the influence of chemical modification products thereof on leaching of weathered crust leaching rare earth ores, rao Guohua and the like, hydrometallurgy, stage 2 (total 54 th stage), 6 months in 1995, pages P10-13, aims at the characteristics of weathered crust leaching rare earth ores, and carries out sodium hypochlorite oxidation modification, carboxymethylation modification and phosphorylation modification on the sesbania gum, so as to examine the influence of the original gum and modified gum on the leaching speed. Test results show that after sesbania gum is added, the filtration performance of a filter cake is improved, the diffusion resistance in the exchange process is reduced, the filtration strength is improved on the premise of guaranteeing the leaching rate of rare earth, the flocculation and filtration assisting effects are achieved, and the leaching rate still needs to be improved.
Disclosure of Invention
The invention aims to solve the technical problems and provide a preparation method of an ion type rare earth leaching agent which is pollution-free, economical, safe and environment-friendly and has high rare earth leaching rate.
In order to achieve the above purpose, the technical scheme of the invention is as follows:
the preparation method of the ionic rare earth leaching agent comprises the following steps:
(1) Domesticating microorganisms by using a rare earth activated mineral powder culture medium to obtain a microorganism suspension;
(2) Amplifying and culturing the microorganism suspension and the additive to obtain an amplifying culture solution;
(3) And uniformly mixing the modified sesbania gum with the amplification culture solution to obtain the ionic rare earth leaching agent.
As a further technical scheme, the acclimatization in the step (1) is implemented by inoculating microorganisms into a rare earth activated mineral powder culture mediumMedium culture, initial microbial inoculation amount is not less than 1.2X10 7 Inoculating at 15-60 deg.c for 36-240 hr to obtain microbe suspension; the microorganism is one or more of actinomycetes and saccharomycetes; the rare earth activated mineral powder culture medium consists of 2-30 g/L of carbon source, 5-15 g/L of nitrogen source, 1-10 g/L of growth factor, 0.42-4.2 g/L of inorganic salt, 0.52-10 g/L of rare earth activated mineral powder and the balance of water.
As a further technical scheme, the actinomycetes are Micromonospora, the saccharomycetes are candida or pichia pastoris, and the carbon source is one or more of fructose, lignin, calcium carbonate and protein; the nitrogen source is one or more of amino acid, protein, nitrate, peptone and urea; the growth factor is one or more of yeast extract, corn steep liquor and wort; the inorganic salt is a combination of potassium nitrate, sodium chloride, potassium phosphate, magnesium sulfate and ferric sulfate; the rare earth activated mineral powder is a combination of ionic rare earth mineral powder and activated mineral powder.
As a further technical scheme, the dosage of the potassium nitrate is 0.1-1.2 g/L, the dosage of the sodium chloride is 0.1-0.9 g/L, the dosage of the potassium phosphate is 0.07-0.7 g/L, the dosage of the magnesium sulfate is 0.1-0.9 g/L, the dosage of the ferric sulfate is 0.05-0.5 g/L, the dosage of the ionic rare earth mineral powder is 0.5-4 g/L, and the dosage of the activated mineral powder is 0.02-6 g/L.
As a further technical scheme, the amplification culture is carried out in the step (2), the culture temperature is 15-60 ℃, the culture time is 36-240 hours, the additive is activated mineral powder, the additive is added according to 1-6% of the mass of the amplification culture solution, and the volume ratio of the microorganism suspension to the amplification culture solution is 1:10000-1:50.
As a further technical scheme, the preparation method of the activated mineral powder comprises the steps of adding an activating agent into active metal-containing mineral powder according to weight percentage, and roasting at 400-900 ℃ for 0.5-5 hours, wherein the activating agent is one or more of calcium chloride, sodium chloride, potassium carbonate, magnesium carbonate and calcium carbonate, and the active metal-containing mineral powder is one or more of mica powder, feldspar powder and bentonite; the usage amount of the activator is 5% -40% of the weight of the mineral powder containing active metals.
As a further technical scheme, the mica powder is lepidolite powder; the feldspar powder is one or two of potassium feldspar mineral powder and sodium feldspar mineral powder.
As a further technical scheme, the modification method of the sesbania gum in the step (3) comprises the steps of adding Tianjiao g to 5.0g of a strong alkali solid and 1.0g to 6.5 g of the strong alkali solid into 100 mL monochloroacetic acid solution, stirring for 5min to 60 min at the temperature of 10 ℃ to 35 ℃ to enable the solution to be in a strong alkaline environment, then stirring for 1 min to 6h strongly at the temperature of 40 ℃ to 80 ℃, and carrying out suction filtration and separation to obtain the alkali metal modified carboxymethyl sesbania gum.
As a further technical proposal, the additive amount of the modified sesbania gum is 0.05 to 0.2 percent of the mass of the ionic rare earth leaching agent
The modified chemical equation of the alkali metal modified carboxymethyl sesbania gum in the invention is as follows:
(1) Preparation of an alkali metal monochloroacetate solution: clCH (ClCH) 2 COOH+ MeOH ==ClCH 2 COOMe+ H 2 O
(2) Alkali metal modified carboxymethyl Tianjiao: [ C 6 H 7 O 2 (OH) 3 ] n Ten nClCH2 COOMe= = = = [ C 6 H 7 O 2 (OH) 2 OCH 2 COOMe] n Ten nMECl+nH 2 O
Me is Na or K metal.
The principle of the invention is that the excellent ion cation exchange properties of organic acid, various proteases and mineral powder generated in the microbial metabolism process are utilized, and the permeation performance of the leaching agent is improved by cooperatively adding the modified sesbania gum through complexation or ion exchange, so that the effect of improving the leaching rate of ionic rare earth is achieved.
Compared with the prior art, the invention has the beneficial effects that:
1. the activated mineral powder has excellent cation exchange function after being activated, and the activated mineral powder and the ionic rare earth mineral powder are used as culture medium components to domesticate microorganisms, so that the microorganisms can survive in the ionic solution, and the leaching rate of the synergized leached ionic rare earth is improved.
2. The leaching agent is nontoxic and pollution-free, the supernatant fluid does not contain ammonia nitrogen after the leaching agent precipitates rare earth, the water pollution source is eliminated from the process source, and in addition, potassium ions can improve soil, so that the leaching agent is not polluted after the rare earth slag is leached, and the soil quality of the slag is improved, so that the leaching agent is an environment-friendly leaching agent.
3. The ionic rare earth leaching agent is obtained by the amplification culture of domesticated microorganisms and ionic rare earth mineral powder in nature in combination with activated mineral powder, and active metal-containing mineral powder such as mica powder, feldspar powder, bentonite and the like serving as raw materials of the activated mineral powder is prepared from K + 、Na + 、Mg 2+ 、Ca 2+ The chemical elements consist of the same chemical elements, and the natural reserves are rich; sesbania gum is a product obtained by processing and separating sesbania seeds, and is a natural high-molecular compound (the molecular weight of the sesbania gum is 250000), so that the raw material cost is reduced, and the sesbania gum is economical and environment-friendly.
Drawings
FIG. 1 is a diagram of a detection report of an ionic rare earth ore used in the present invention;
FIG. 2 is an XRD pattern of activated mineral powder according to example 3 of the present invention;
FIG. 3 is an SEM image of activated mineral powder according to example 3 of the present invention;
FIG. 4 is an EDS chart of activated mineral powder of example 3 of the present invention;
FIG. 5 is a graph showing the detection report of the rare earth leaching concentration of the ion-type rare earth leaching agent of the embodiment 3 after being applied to the rare earth raw ore;
FIG. 6 is comparative example 1 (NH) 4 ) 2 SO 4 The leaching agent is applied to a rare earth leaching concentration detection report chart after rare earth raw ores;
FIG. 7 is a sample of comparative example 2 (NH 4 ) 2 SO 4 A rare earth leaching concentration detection report chart after the modified sesbania gum leaching agent is applied to rare earth raw ores;
FIG. 8 is a graph showing the detection report of the rare earth leaching concentration after the amplification culture solution of comparative example 3 is applied to the rare earth raw ore as a leaching agent.
Detailed Description
The present invention will be described in further detail with reference to examples, but the embodiments of the present invention are not limited to the scope indicated by the examples.
The ionic rare earth ore and the ionic rare earth ore powder mentioned in the embodiment of the invention are obtained from ionic rare earth in Cenxi city of Guangxi Zhang autonomous region, and the ore powder is dry powder of which the particle size is less than 200 meshes. The detection report is shown in figure 1, and the mineral sample rare earth content is as follows: full phase 0.12% and ionic phase 0.062%.
The rare earth existing form in the ionic rare earth ore can be divided into 4 phases: the rare earth composite material comprises a water-soluble phase, an exchangeable ion phase, a mineral phase and a colloidal phase, wherein the proportion of the four phases is less than 0.0001%, 50% -90%, 1% -10% and 5% -40% of the total amount of rare earth. The water-soluble phase rare earth can be dissociated in the part of rare earth resources in water, and the exchangeable ion phase rare earth refers to rare earth resources adsorbed on clay by hydroxyl or water and hydroxyl; mineral phases refer to rare earth ions that make up the mineral lattice or are dispersed and formed in the rock mineral, and colloidal rare earth refers to water-insoluble rare earth oxides or hydroxides, especially rare earth resources that are adsorbed on iron/manganese oxides. Among the four rare earth resources, the gel phase rare earth and the mineral rare earth cannot be adopted by direct displacement leaching, but are converted into an ionic form by adopting strong acid such as sulfuric acid hydrochloric acid or adding roasting acid leaching, so that cation displacement leaching which is more active than rare earth can be adopted. The invention mainly aims at leaching exchangeable ion phases in mineral rare earth, and all phases mentioned in the embodiment refer to the sum of four phases of rare earth.
Example 1:
(1) Preparing activated mineral powder: 20 g anhydrous calcium chloride is added into 100g and 200 meshes of potassium feldspar mineral powder, and the mixture is roasted for 1 hour at 750 ℃ to obtain activated mineral powder for standby.
(2) Preparation of potassium-modified carboxymethyl Tianjiao: in a vacuum glove box, 1.0g of Tianjiao and 1.5. 1.5 g potassium hydroxide were added to 100 mL monochloroacetic acid solution, the solution was stirred at 21℃for 30min under strongly basic ambient conditions, followed by 60℃temperatureStirring strongly at a temperature of 2.5 h, suction filtering, separating, washing with alcohol for 2 times to obtain potassium modified carboxymethyl Tianjiao, denoted SG-CH 2 COOK is reserved.
(3) Preparing a microorganism suspension: inoculating candida into culture medium for domestication, wherein the microbial inoculum size is 1.5X10 7 The domestication temperature is 30 ℃ and the domestication time is 120 hours, and the culture medium contains 6.0 g/L peptone, 6.0 g/L amino acid, 22g/L fructose, 4.5 g/L yeast extract, 0.3 g/L potassium nitrate, 0.4 g/L sodium chloride, 0.4 g/L potassium phosphate, 0.2 g/L magnesium sulfate, 0.1g/L ferric sulfate, 1.2 g/L ionic rare earth mineral powder, 0.03 g/L activated mineral powder and the balance water, so as to obtain a microorganism suspension.
(4) Preparing an amplification culture solution: 21. adding 27 g activated mineral powder obtained in the step (1) and 5m L microorganism suspension obtained in the step (3) into 1L distilled water at the temperature of DEG C, and performing amplification culture for 48 hours to obtain an amplification culture solution.
(5) Preparing an ionic rare earth leaching agent: adding 0.8 of SG-CH obtained in the step (2) g to 1L of the amplification culture solution obtained in the step (4) 2 And COOK, uniformly mixing to obtain the ionic rare earth leaching agent.
(6) And (3) vertically fixing a cylindrical hollow tube with phi 90 multiplied by 450mm, sleeving a filter screen on the bottom of the column, adding 500g of ionic rare earth ore, dripping 250g of the ionic rare earth leaching agent, slowly adding clear water after the leaching agent is dripped, washing the leaching agent from an ore body, and collecting the leaching agent to obtain 320 mL. The rare earth leaching rate is 97.12 percent.
The pH value of the supernatant liquid after the leaching solution precipitates out the rare earth is 8.2, the COD value is 68.9 mg/L, the ammonia nitrogen is 5.29 mg/L and other detection indexes all accord with the emission standard of rare earth industrial pollutants GB/T26451-2011.
Example 2:
(1) Preparing activated mineral powder: 20 g anhydrous calcium chloride is added into 100g and 200 meshes of lepidolite mineral powder, and the mixture is roasted for 1 hour at 750 ℃ to obtain activated mineral powder for standby.
(2) Preparation of potassium-modified carboxymethyl Tianjiao: in a vacuum glove box, 1.5 g of Tianjiao and 4.2 potassium hydroxide were added to 100 mL of monochloroacetic acid solution and stirred at 21℃Stirring for 30min to obtain solution under strongly alkaline condition, stirring at 60deg.C for 2.5 times h, suction filtering, separating, and alcohol washing for 2 times to obtain potassium modified carboxymethyl Tianjiao, denoted SG-CH 2 COOK is reserved.
(3) Preparing a microorganism suspension: inoculating Pichia pastoris into culture medium for domestication, wherein the microorganism inoculation amount is 1.5X10 7 The domestication temperature is 30 ℃ and the domestication time is 120 hours, and the culture medium contains 6.0 g/L peptone, 6.0 g/L amino acid, 22g/L fructose, 4.5 g/L yeast extract, 0.3 g/L potassium nitrate, 0.4 g/L sodium chloride, 0.4 g/L potassium phosphate, 0.2 g/L magnesium sulfate, 0.1g/L ferric sulfate, 1.2 g/L ionic rare earth mineral powder, 0.03 g/L activated mineral powder and the balance water, so as to obtain a microorganism suspension.
(4) Preparing an amplification culture solution: 21. adding 27 g activated mineral powder obtained in the step (1) and 5m L microorganism suspension obtained in the step (3) into 1L distilled water at the temperature of DEG C, and performing amplification culture for 48 hours to obtain an amplification culture solution.
(5) Preparing an ionic rare earth leaching agent: adding 0.8 of SG-CH obtained in the step (2) g to 1L of the amplification culture solution obtained in the step (4) 2 And COOK, uniformly mixing to obtain the ionic rare earth leaching agent.
(6) And (3) vertically fixing a cylindrical hollow tube with phi 90 multiplied by 450mm, sleeving a filter screen on the bottom of the column, adding 500g of ionic rare earth ore, then dripping 250g of the ionic rare earth leaching agent, slowly adding clear water after the leaching agent is dripped, washing the leaching agent from the ore body, and collecting 315mL of leaching agent. The rare earth leaching rate is 92.41 percent.
The pH value of the supernatant liquid after the leaching solution precipitates out the rare earth is 8.5, the COD value is 14.29 mg/L, the ammonia nitrogen is 5.96 mg/L and other detection indexes all accord with the emission standard of rare earth industrial pollutants GB/T26451-2011.
Example 3:
(1) Preparing activated mineral powder: 20 g anhydrous calcium chloride is added into 100g and 200 meshes of bentonite mineral powder, and the mixture is roasted for 1 hour at 750 ℃ to obtain activated mineral powder for standby. The obtained activated mineral powder was examined, and the results are shown in fig. 2 to 4.
(2) Preparation of Potassium modified carboxymethylTianjiao: in a vacuum glove box, adding Tianjiao g of 2.0g of potassium hydroxide and 4.2g of potassium hydroxide into 100 mL monochloroacetic acid solution, stirring for 30min at 21 ℃ to ensure that the solution is in a strong alkaline environment, then strongly stirring for 2.5 h at 60 ℃, carrying out suction filtration separation, and carrying out alcohol washing for 2 times to obtain potassium modified carboxymethyl Tianjiao which is named SG-CH 2 COOK is reserved.
(3) Preparing a microorganism suspension: inoculating candida into culture medium for domestication, wherein the microbial inoculum size is 1.5X10 7 The domestication temperature is 30 ℃ and the domestication time is 120 hours, and the culture medium contains 6.0 g/L peptone, 6.0 g/L amino acid, 22g/L fructose, 4.5 g/L yeast extract, 0.3 g/L potassium nitrate, 0.4 g/L sodium chloride, 0.4 g/L potassium phosphate, 0.2 g/L magnesium sulfate, 0.1g/L ferric sulfate, 1.2 g/L ionic rare earth mineral powder, 0.03 g/L activated mineral powder and the balance water, so as to obtain a microorganism suspension.
(4) Preparing an amplification culture solution: 21. adding 27 g activated mineral powder obtained in the step (1) and 5m L microorganism suspension obtained in the step (3) into 1L distilled water at the temperature of DEG C, and performing amplification culture for 48 hours to obtain an amplification culture solution.
(5) Preparing an ionic rare earth leaching agent: adding 0.3 of SG-CH obtained in the step (2) g to 1L of the amplification culture solution obtained in the step (4) 2 And COOK, uniformly mixing to obtain the ionic rare earth leaching agent.
(6) And (3) vertically fixing a cylindrical hollow tube with phi 90 multiplied by 450mm, sleeving a filter screen on the bottom of the column, adding 500g of ionic rare earth ore, then dripping 250g of the ionic rare earth leaching agent, slowly adding clear water after the leaching agent is dripped, washing the leaching agent from an ore body, and collecting the leaching agent to obtain 300 mL. The rare earth leaching rate is 98.71 percent.
The pH value of the supernatant liquid after the leaching solution precipitates out the rare earth is 8.46, the COD value is 36.5 mg/L, the ammonia nitrogen is 6.49 mg/L and other detection indexes all accord with the emission standard of rare earth industrial pollutants GB/T26451-2011.
Example 4:
(1) Preparing activated mineral powder: 5g of anhydrous sodium chloride is added into 100g of 200-mesh albite mineral powder, and the mixture is roasted for 5 hours at 400 ℃ to obtain activated mineral powder for later use. And detecting the obtained activated mineral powder.
(2) Preparation of sodium modified carboxymethyl Tianjiao: in a vacuum glove box, 3.0g of Tianjiao and 5.0g potassium hydroxide are added into 100 mL monochloroacetic acid solution, the solution is stirred for 60 min at 15 ℃ to ensure that the solution is in a strong alkaline environment, then the solution is stirred for 6h at 40 ℃ with strong force, the solution is separated by suction filtration, and the alcohol washing liquid is separated for 2 times to obtain sodium modified carboxymethyl Tianjiao which is recorded as SG-CH 2 COONa is reserved.
(3) Preparing a microorganism suspension: inoculating candida into culture medium for domestication, wherein the microbial inoculum size is 1.5X10 7 The domestication temperature is 15 ℃ and the domestication time is 240 hours, the culture medium contains 3.0 g/L protein, 2.0 g/L urea, 2g/L lignin, 1g/L corn steep liquor, 0.1g/L potassium nitrate, 0.1g/L sodium chloride, 0.07 g/L potassium phosphate, 0.1g/L magnesium sulfate, 0.05g/L ferric sulfate, 0.5g/L ionic rare earth mineral powder, 0.02 g/L activated mineral powder and the balance of water, and a microorganism suspension is obtained.
(4) Preparing an amplification culture solution: 2.5g of the activated mineral powder obtained in the step (1) and 5. 5m L of the microorganism suspension obtained in the step (3) were added to 250mL of distilled water at 15℃to conduct amplification culture for 240 hours to obtain an amplification culture solution.
(5) Preparing an ionic rare earth leaching agent: to 250ml of the amplification culture broth obtained in the step (4), 0.125g of SG-CH obtained in the step (2) was added 2 And COOK, uniformly mixing to obtain the ionic rare earth leaching agent.
(6) And (3) vertically fixing a cylindrical hollow tube with phi 90 multiplied by 450mm, sleeving a filter screen on the bottom of the column, adding 500g of ionic rare earth ore, then dripping 250g of the ionic rare earth leaching agent, slowly adding clear water after the leaching agent is dripped, washing the leaching agent from the ore body, and collecting the leaching agent 305 mL. The rare earth leaching rate is 93.25 percent.
The pH value of the supernatant liquid after the leaching solution precipitates out the rare earth is 8.4, the COD value is 27.9mg/L, the ammonia nitrogen is 7.69 and mg/L, and other detection indexes all accord with the emission standard of rare earth industrial pollutants GB/T26451-2011.
Example 5:
(1) Preparing activated mineral powder: 40g of anhydrous calcium carbonate is added into 100g of bentonite with 200 meshes, and the mixture is roasted for 0.5 hour at 900 ℃ to obtain activated mineral powder for standby. And detecting the obtained activated mineral powder.
(2) Preparation of potassium-modified carboxymethyl Tianjiao: in a vacuum glove box, adding Tianjiao and 5.0g potassium hydroxide (2.5 g) into 100 mL monochloroacetic acid solution, stirring at 35deg.C for 5min to make the solution under strong alkaline condition, stirring at 80deg.C for 1 hr, suction filtering, separating, washing with alcohol for 2 times to obtain potassium modified carboxymethyl Tianjiao, denoted SG-CH 2 COOK is reserved.
(3) Preparing a microorganism suspension: inoculating candida into culture medium for domestication, wherein the microbial inoculum size is 1.5X10 7 The domestication temperature is 60 ℃ and the domestication time is 36 hours, and the culture medium contains 10.0 g/L peptone, 5.0 g/L amino acid, 30g/L calcium carbonate, 10g/L malt extract, 1.2 g/L potassium nitrate, 0.9g/L sodium chloride, 0.7 g/L potassium phosphate, 0.9g/L magnesium sulfate, 0.5g/L ferric sulfate, 4g/L ionic rare earth mineral powder, 6g/L activated mineral powder and the balance of water, so as to obtain a microorganism suspension.
(4) Preparing an amplification culture solution: at 60 ℃, adding 3kg of the activated mineral powder obtained in the step (1) and 5m L of the microorganism suspension obtained in the step (3) into 50L of distilled water for amplification culture for 36 hours to obtain an amplification culture solution.
(5) Preparing an ionic rare earth leaching agent: 100g of SG-CH obtained in step (2) was added to 50L of the amplification culture solution obtained in step (4) 2 And COOK, uniformly mixing to obtain the ionic rare earth leaching agent.
(6) And (3) vertically fixing a cylindrical hollow tube with phi 90 multiplied by 450mm, sleeving a filter screen on the bottom of the column, adding 500g of ionic rare earth ore, then dripping 250g of the ionic rare earth leaching agent, slowly adding clear water after the leaching agent is dripped, washing the leaching agent from an ore body, and collecting the leaching agent to obtain 300 mL. The rare earth leaching rate is 92.76 percent.
The pH value of the supernatant liquid after the leaching solution precipitates out the rare earth is 8.51, the COD value is 41.7mg/L, the ammonia nitrogen is 11.22 mg/L and other detection indexes all accord with the emission standard of rare earth industrial pollutants GB/T26451-2011.
Comparative experiments
Comparative example 1: adding 0.15 mol/L (NH) to 500 mL distilled water 4 ) 2 SO 4 Stirring uniformly to obtain a leaching agent B; collecting the leachate 325mL.
Comparative example 2: adding 0.15 mol/L (NH) to 500 mL distilled water 4 ) 2 SO 4 And 0.15 g potassium modified carboxymethyl Tianjiao of example 3, and uniformly stirring to obtain a leaching agent C. Collecting the leachate 340 mL.
Comparative example 3: the amplification medium of example 3 was used as the leaching agent D. 325mL of leachate was obtained by collection.
The same leaching procedure was used as in example 3: the cylindrical hollow tube with phi 90 multiplied by 450mm is vertically fixed, a filter screen is sleeved on the bottom of the column, 500g of 0.062 percent of ionic rare earth ore is added, then 250g of the rare earth leaching agent of the comparative examples one to ten is dripped, clear water is slowly added after the dripping of the leaching agent is finished, the leaching agent is washed out of the ore body, and collection is stopped after the quality of the leaching agent exceeds 250 mL. The obtained leachate was sent to the test, the results are shown in table 1, and the test elements are shown in fig. 5 to 8.
TABLE 1
As can be seen from table 1:
(1) Comparative example 1 and comparative example 2 illustrate that, in a conventional (NH 4 ) 2 SO 4 When the modified sesbania gum is used as a leaching agent, the modified sesbania gum is beneficial to improving the leaching rate of ionic rare earth;
(2) Example 3 and comparative example 3 demonstrate that the microorganism suspension amplification broth and the modified sesbania gum have synergistic effect of leaching ionic rare earth.
(3) Example 3 and comparative example 2, and comparative example 1 and comparative example 3 each show that the leaching effect of the ionic rare earth is superior to that of the conventional (NH) 4 ) 2 SO 4 Leaching agent, microorganism suspension amplification culture solution of embodiment 3 of the invention synergistically modifies sesbania gum to ionic rare earthThe leaching rate is highest.
The above embodiments are merely specific examples for further detailed description of the object, technical solution and advantageous effects of the present invention, and the present invention is not limited thereto. Any modification, equivalent replacement, improvement, etc. made within the scope of the present disclosure are included in the scope of the present invention.
Claims (7)
1. The preparation method of the ionic rare earth leaching agent is characterized by comprising the following steps:
(1) Domesticating microorganisms by using a rare earth activated mineral powder culture medium to obtain a microorganism suspension; the microorganism is one or more of actinomycetes and saccharomycetes; the rare earth activated mineral powder culture medium consists of 2-30 g/L carbon source, 5-15 g/L nitrogen source, 1-10 g/L growth factor, 0.42-4.2 g/L inorganic salt, 0.52-10 g/L rare earth activated mineral powder and the balance water; the rare earth activated mineral powder is a combination of ionic rare earth mineral powder and activated mineral powder;
(2) Amplifying and culturing the microorganism suspension and the additive to obtain an amplifying culture solution; the additive is activated mineral powder;
(3) Uniformly mixing the modified sesbania gum with the amplification culture solution to obtain an ionic rare earth leaching agent;
adding Tianjiao g to 5.0g of 0.0 g to 6.5 g of strong alkali solid into 100 mL g of monochloroacetic acid solution, stirring for 5 to 60 minutes at the temperature of between 10 and 35 ℃ to enable the solution to be in a strong alkaline environment, then strongly stirring for 1 to 6h at the temperature of between 40 and 80 ℃, and carrying out suction filtration separation to obtain alkali metal modified carboxymethyl Tianjiao;
the preparation method of the activated mineral powder comprises the steps of adding an activating agent into the mineral powder containing active metals according to weight percentage, and roasting at 400-900 ℃ for 0.5-5 hours, wherein the activating agent is one or more of calcium chloride, sodium chloride, potassium carbonate, magnesium carbonate and calcium carbonate, and the mineral powder containing active metals is one or more of mica powder, feldspar powder and bentonite; the usage amount of the activator is 5% -40% of the weight of the mineral powder containing active metals.
2. The method for preparing the ionic rare earth leaching agent according to claim 1, wherein the method comprises the following steps: the domestication in the step (1) is to inoculate the microorganism into the rare earth activated mineral powder culture medium for culture, and the initial microorganism inoculum size is more than or equal to 1.2 multiplied by 10 7 The inoculation temperature is 15-60 ℃ and the domestication time is 36-240 hours per mL, and the microorganism suspension is obtained.
3. The method for preparing the ionic rare earth leaching agent according to claim 2, wherein the method comprises the following steps: the actinomycetes are Micromonospora, the saccharomycetes are candida or pichia pastoris, and the carbon source is one or more of fructose, lignin, calcium carbonate and protein; the nitrogen source is one or more of amino acid, protein, nitrate, peptone and urea; the growth factor is one or more of yeast extract, corn steep liquor and wort; the inorganic salt is a combination of potassium nitrate, sodium chloride, potassium phosphate, magnesium sulfate and ferric sulfate.
4. The method for preparing an ionic rare earth leaching agent according to claim 3, wherein: the potassium nitrate is 0.1-1.2 g/L, the sodium chloride is 0.1-0.9 g/L, the potassium phosphate is 0.07-0.7 g/L, the magnesium sulfate is 0.1-0.9 g/L, the ferric sulfate is 0.05-0.5 g/L, the ionic rare earth mineral powder is 0.5-4 g/L, and the activated mineral powder is 0.02-6 g/L.
5. The method for preparing the ionic rare earth leaching agent according to claim 1, wherein the method comprises the following steps: the amplification culture is carried out in the step (2), the culture temperature is 15-60 ℃, the culture time is 36-240 hours, the additive is added according to 1-6% of the mass of the amplification culture solution, and the volume ratio of the microorganism suspension to the amplification culture solution is 1:10000-1:50.
6. The method for preparing the ionic rare earth leaching agent according to claim 1, wherein the method comprises the following steps: the mica powder is lepidolite mineral powder; the feldspar powder is one or two of potassium feldspar mineral powder and sodium feldspar mineral powder.
7. The method for preparing the ionic rare earth leaching agent according to claim 1, wherein the method comprises the following steps: the addition amount of the modified sesbania gum is 0.05-0.2% of the mass of the ionic rare earth leaching agent.
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| CN202211242468.2A CN115478182B (en) | 2022-10-11 | 2022-10-11 | Preparation method of ionic rare earth leaching agent |
| PCT/CN2023/117024 WO2024008214A1 (en) | 2022-10-11 | 2023-09-05 | Preparation method for ionic rare earth leaching agent |
| LU505245A LU505245B1 (en) | 2022-10-11 | 2023-09-05 | Method for recovering indium from waste target materials |
| AU2023237173A AU2023237173A1 (en) | 2022-10-11 | 2023-09-05 | Preparation method of ionic rare earth leaching agent |
| ZA2023/09467A ZA202309467B (en) | 2022-10-11 | 2023-10-10 | Method for preparing the in2se3 nanomaterials for photocatalytic degradation of tetracycline |
| ZA2023/09468A ZA202309468B (en) | 2022-10-11 | 2023-10-10 | Method for preparing sheet tin disulfide nanomaterial for efficient adsorption of organic dyes |
| ZA2023/09466A ZA202309466B (en) | 2022-10-11 | 2023-10-10 | Preparation method of ionic rare earth leaching agent |
| LU505259A LU505259B1 (en) | 2022-10-11 | 2023-10-12 | METHOD FOR PREPARING THE In2Se3 NANOMATERIALS FOR PHOTOCATALYTIC DEGRADATION OF TETRACYCLINE |
| LU505260A LU505260B1 (en) | 2022-10-11 | 2023-10-12 | Method for preparing sheet tin disulfide nanomaterial for efficient adsorption of organic dyes |
| LU505258A LU505258B1 (en) | 2022-10-11 | 2023-10-12 | Combined protection smelting furnace and smelting method for antimony |
| ZA2024/00277A ZA202400277B (en) | 2022-10-11 | 2024-01-08 | Preparation method of ionic rare earth leaching agent |
| ZA2024/00279A ZA202400279B (en) | 2022-10-11 | 2024-01-08 | Method for preparing sheet tin disulfide nanomaterial for efficient adsorption of organic dyes |
| ZA2024/00278A ZA202400278B (en) | 2022-10-11 | 2024-01-08 | Method for preparing the in2se3 nanomaterials for photocatalytic degradation of tetracycline |
| LU506046A LU506046B1 (en) | 2022-10-11 | 2024-01-08 | Method for preparing sheet tin disulfide nanomaterial for efficient adsorption of organic dyes |
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