CN111359774B - Method for recovering rare earth minerals from submarine sediments - Google Patents
Method for recovering rare earth minerals from submarine sediments Download PDFInfo
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Abstract
A method for recovering rare earth minerals from submarine sediments relates to the technical field of rare earth ore dressing. The method comprises pretreatment operation, roughing operation and fine selection operation, wherein the pretreatment operation comprises stirring and mixing the seabed sediment and a first regulator at the temperature of not lower than 40 ℃. And the roughing operation comprises the step of mixing the pretreated seabed sediment with a second regulator and a collecting agent for roughing to obtain rough concentrate and roughed tailings. The fine selection operation comprises the following steps: and (4) carrying out concentration for at least two times by taking the rough concentrate as a raw material for concentration operation to obtain rare earth concentrate, wherein a second regulator is added in each concentration. The method provided by the application can realize effective enrichment of the rare earth minerals in the submarine sediments and recovery of the rare earth minerals, and is simple to operate, stable in process, convenient for field management and strong in adaptability.
Description
Technical Field
The application relates to the technical field of rare earth ore dressing, in particular to a method for recovering rare earth minerals from submarine sediments.
Background
Rare earth metals are applied to the fields of electronics, chemical industry, metallurgy, machinery, energy and the like, and are praised as modern industrial vitamins. The existing rare earth metals are all derived from land rare earth resources, and through high-strength mining for more than half a century, the reserve and the guarantee period of the land rare earth resources are continuously reduced, so that the industrial requirements are increasingly difficult to meet.
In 2011, a great amount of rare earth elements are found in ocean bottom sediments in Japan, which attracts the attention of various countries. The existing research shows that compared with the rare earth resource on land, the rare earth resource in the submarine sediment has huge reserve, and the medium-heavy rare earth has higher proportion, thus being an important potential medium-heavy rare earth resource.
The rare earth-rich seafloor sediments are of various types and mainly comprise polymetallic soft mud, zeolite clay and ocean clay. The rare earth elements in the multi-metal soft mud are mostly present in iron manganese oxides and hydroxides related to submarine hydrothermal action, while the enrichment of the rare earth elements in zeolite clay and ocean clay is closely related to the mixing of phosphate, and the rare earth elements are mainly present in fish bone fragments equivalent to apatite components.
At present, relatively few data are available for mineral separation research on rare earth resources in submarine sediments, and the existing research mainly extracts rare earth elements in the submarine sediments through a direct acid leaching process, including a sulfuric acid method, a hydrochloric acid method and a nitric acid method. Because the submarine sediments are different from the rare earth ores on land, the conventional beneficiation method for the rare earth ores on land cannot be simply applied to the treatment of the rare earth resources on the submarine sediments, and a new rare earth beneficiation process technology needs to be developed pertinently.
In view of this, the present application is hereby presented.
Disclosure of Invention
The present application provides a method of recovering rare earth minerals from seafloor sediments to ameliorate the above problems.
The method for recovering rare earth minerals from seabed sediments according to the embodiment of the application comprises a pretreatment operation, a roughing operation and a concentrating operation.
Wherein the preprocessing operation comprises: mixing the seabed sediment and the first regulator under stirring at the temperature of not less than 40 ℃.
The roughing operation comprises the following steps: and (3) taking the seabed sediment obtained by pretreatment as flotation feed, mixing the seabed sediment with a second regulator and a collecting agent, and performing rough concentration to obtain rough concentrate and rough tailings.
The fine selection operation comprises the following steps: and (4) carrying out concentration for at least two times by taking the rough concentrate as a raw material for concentration operation to obtain rare earth concentrate, wherein a second regulator is added in each concentration.
Wherein the first conditioning agent comprises sodium carbonate.
According to the method for recovering the rare earth minerals from the seabed sediments, sodium carbonate in the first regulator adopted in the pretreatment step can not only adjust and stabilize the pH value of ore pulp, but also has strong dispersion effect. Therefore, the first regulator and the seabed sediment are stirred and mixed to further promote the first regulator to be fully contacted with the seabed sediment, the strong dispersion effect of the first regulator is effectively promoted under the condition that the temperature is not lower than 40 ℃, the synergistic effect of the first regulator and the seabed sediment is utilized to effectively strengthen, disperse and separate rare earth minerals, rare earth carrier minerals and gangue minerals such as aluminosilicate, silicate and iron-manganese oxide ore in the seabed sediment, the agglomeration phenomenon among the seabed sediment minerals is reduced, and then the rare earth minerals and the gangue minerals are subjected to targeted flotation treatment by adopting the collecting agent and the second regulator to obtain rare earth ore concentrate.
The method for recovering the rare earth minerals from the seabed sediments can effectively improve the grade of the concentrate and ensure the better recovery rate of the rare earth minerals while realizing the effective enrichment of the rare earth minerals in the seabed sediments, effectively inhibits high-content easy-floating fine mud and iron-manganese oxidized ore in the rare earth minerals, and has the advantages of simple operation, stable flow, convenient field management and strong adaptability.
In addition, the method for recovering rare earth minerals from the seabed sediment according to the embodiment of the application has the following additional technical characteristics:
the first conditioning agent may comprise only sodium carbonate, but if only sodium carbonate is used, the rare earth concentrate is of lower grade although the recovery of the rare earth concentrate obtained is higher.
In order to solve the above problem, optionally, the first conditioning agent includes sodium carbonate and sodium hydroxide.
The sodium hydroxide is a strong base, has certain cleaning and corrosion effects on the surfaces of metal minerals, can promote the dispersion effect among the minerals, exposes metal ions on the surfaces of the minerals, provides more adsorption sites for the adsorption of the collecting agent on the surfaces of the rare earth minerals, and is matched with sodium carbonate to effectively improve the grade of rare earth concentrate.
In some embodiments illustrated herein, the first conditioning agent comprises: 40-70 parts by mass of sodium carbonate and 20-50 parts by mass of sodium hydroxide.
The proportion is reasonable, and the enhanced dispersion separation effect of the first regulator keeps a better range.
Optionally, the second conditioning agent comprises: 30-50 parts by mass of sodium silicate, 10-30 parts by mass of aluminum potassium sulfate, 10-30 parts by mass of sodium fluosilicate and 10-30 parts by mass of ferrous sulfate.
In the second regulator, sodium silicate and potassium aluminum sulfate have stronger selective inhibition and flocculation agglomeration effects on silicate and aluminosilicate minerals; the sodium fluosilicate can inhibit silicate minerals and has certain activation effect on rare earth minerals; the ferrous sulfate has a certain inhibiting effect on iron-manganese oxide ores in the ore pulp; the addition of the second regulator can effectively inhibit gangue minerals dispersed by the first regulator, and the second regulator is matched with the first regulator to reduce the entrainment effect of foam on fine mud in the flotation process.
Optionally, the collector comprises: 30-50 parts by mass of 3-hydroxy-2-naphthalene hydroxamic acid, 30-50 parts by mass of sodium fatty acid methyl ester sulfonate, 10-30 parts by mass of ether alkyl phosphate and 3-10 parts by mass of tributyl phosphate.
The collecting agent is good in proportioning, minerals prefabricated and activated by the second regulator are effectively collected, the 3-hydroxy-2-naphthalene hydroxyoxime acid is a strong effective collecting agent of rare earth minerals, is commonly used for flotation of rare earth minerals such as xenotime, bastnaesite, monazite and the like, and has the characteristics of strong collecting capacity and good selectivity, the sodium fatty acid methyl ester sulfonate and the ether alkyl phosphate have strong collecting capacity on rare earth associated minerals such as apatite and the like, the rare earth carrier minerals can be effectively recovered and are matched with the second regulator, so that the overall recovery rate of the rare earth is improved, the tributyl phosphate has a certain defoaming effect, the foam amount formed by the fatty acid collecting agent in the flotation process can be adjusted by adding the collecting agent in a proper amount, the entrainment phenomenon of excessive foam on fine mud is effectively reduced, the overall flotation condition is improved, and the recovery rate of the rare earth minerals is effectively improved.
In combination with the first aspect, the present application illustrates some embodiments wherein the method of recovering rare earth minerals from seafloor sediments further comprises a scavenger operation comprising: and carrying out scavenging for at least one time by taking the rougher tailings as scavenging raw materials to obtain scavenged middlings and scavenged first tailings, wherein a second regulator and a collecting agent are added in each scavenging.
Returning the scavenging middlings obtained by the first scavenging to the pretreatment operation for pretreatment, and returning the scavenging middlings obtained by the other scavenging to the previous scavenging step for scavenging.
Through the operation, the mineral aggregate in the scavenging middlings is reinforced and dispersed again, the mineral aggregate in the roughing operation is reduced as far as possible, meanwhile, the rare earth minerals can be effectively enriched, the rare earth minerals are prevented from being lost, and the recovery rate is improved. Wherein the first tailings are discharged.
Optionally, in the scavenging operation, the dosage of the second regulator used in the first scavenging is 0.5-2 kg/t of raw ore, and the dosage of the collector is 0.1-1 kg/t of raw ore; the dosage of the second regulator adopted by the rest scavenging is 1/5-1/2 of the first scavenging, and the dosage of the collecting agent adopted by the rest scavenging is 1/5-1/2 of the first scavenging.
The amount is reasonable, the purposes of adjustment and collection are achieved, meanwhile, waste of the second adjusting agent and the collecting agent is prevented, and cost is reasonably controlled.
In some embodiments, the second conditioning agent is used in an amount of 0.5-2 kg/t raw ore in the first fine selection in the fine selection operation; in the other fine selections, the dosage of the second regulator is 1/10-1/2 of the first fine selection.
In some embodiments, in combination with the first aspect, the method for recovering rare earth minerals from seafloor sediments further comprises a middling recleaning operation, the middling recleaning operation comprising: and respectively merging the concentrated middlings obtained by the first concentration and the second concentration in the concentration operation, and adding a second regulator and a collecting agent for flotation to obtain middlings and recleaning rough concentrates and second tailings.
And returning the middling recleaning rough concentrate to the first concentration and carrying out concentration treatment, and carrying out delay return on the concentrated middling obtained by the other times of concentration as a raw material for concentration operation to the previous concentration step.
Through the operation, the cooperation high-efficient collector and the second adjustment agent of pertinence are discharged by the second tailing with the most slime of sneaking into the choice operation, reduce the easy interference of flotation slime to the choice flow, reduce the middlings circulation volume of choice operation, improve the stability of flotation flow to can effectively improve the enrichment effect of rare earth concentrate. Wherein the second tailings are discharged.
Optionally, in the middling recleaning operation, the amount of the second modifier is 0.5-2 kg/t of raw ore, and the amount of the collector is 0.1-1 kg/t of raw ore.
The amount is reasonable, the purposes of adjustment and collection are achieved, meanwhile, the waste of the second adjusting agent and the collecting agent is prevented, and the cost is reasonably controlled.
In some embodiments, the amount of the first conditioning agent used in the pretreatment operation is 5-15 kg/t of raw ore.
The amount is reasonable, the purpose of strengthening dispersion and separation is achieved, meanwhile, waste of the second regulator and the collecting agent is prevented, and cost is reasonably controlled.
In some embodiments, in combination with the first aspect, the second conditioning agent is used in an amount of 2-10 kg/t raw ore and the collecting agent is used in an amount of 1-5 kg/t raw ore in the roughing operation.
In combination with the first aspect, the present application illustrates some embodiments wherein the seafloor sediment is mixed with the first conditioning agent under agitation at 40-80 ℃.
Optionally, the stirring speed of stirring and mixing is 500-1500 r/min, and the stirring time is 10-30 min.
Under the conditions, the reinforced separation and dispersion effect is good, the energy consumption is effectively saved, and the economic benefit is good.
The beneficial effects of the method for recovering rare earth minerals in the seabed sediment provided by the embodiment of the application comprise:
aiming at the problem that rare earth minerals are difficult to effectively enrich and recover due to high clay mineral content, fine mineral granularity and serious agglomeration phenomenon in the submarine sediments, the method provided by the application is adopted to intensively disperse the submarine sediments at the temperature of not less than 40 ℃ through the combined action of stirring and a first regulator, so that the agglomeration phenomenon among minerals is reduced; and adding a second targeted regulator to inhibit slime, and adopting a high-efficiency collecting agent to intensively collect the rare earth minerals. The invention effectively avoids the problems of large medicament consumption, unsatisfactory rare earth recovery effect, easy generation of a large amount of acid wastewater and the like of the direct acid leaching process, the return water can be directly recycled, and the invention has the advantages of simple operation, stable flow, convenient field management and strong adaptability.
Drawings
In order to more clearly illustrate the technical solutions of the embodiments of the present application, the drawings that are required to be used in the embodiments will be briefly described below, it should be understood that the following drawings only illustrate some embodiments of the present application and therefore should not be considered as limiting the scope, and for those skilled in the art, other related drawings can be obtained from the drawings without inventive effort.
Fig. 1 is a schematic flow diagram of a method of recovering rare earth minerals from a seafloor deposit provided by the present application.
Detailed Description
In order to make the objects, technical solutions and advantages of the embodiments of the present application clearer, the technical solutions in the embodiments of the present application will be clearly and completely described below. The examples, in which specific conditions are not specified, were carried out according to conventional conditions or conditions recommended by the manufacturer. The reagents or instruments used are not indicated by the manufacturer, and are all conventional products available commercially.
The existing research mainly extracts rare earth elements in the rare earth elements by a direct acid leaching process, and comprises a sulfuric acid method, a hydrochloric acid method and a nitric acid method. Because the submarine sediments are different from the land rare earth ores, the conventional beneficiation method for the land rare earth ores cannot be simply applied to the treatment of the submarine sediment rare earth resources.
Through research, the reasons that the conventional beneficiation method for the land rare earth ore cannot be simply applied to the treatment of the rare earth resource of the submarine sediment are mainly as follows: because the content of gangue minerals such as aluminosilicate minerals and silicate minerals in the seabed sediments is high, the granularity of the gangue minerals, rare earth minerals and rare earth carrier minerals is mostly less than 5um, the agglomeration phenomenon among the minerals is very serious, and the effective enrichment of rare earth elements is difficult to realize by the conventional flotation process treatment; if the acid leaching process is adopted, the consumption of a leaching agent is extremely high, the cost is high, a large amount of iron-manganese oxidized ore exists, the subsequent rare earth extraction and separation effects are seriously influenced, and the rare earth minerals in the rare earth are difficult to effectively recover.
Based on the cognition, the method for recovering the seabed sediments with high clay mineral content, fine mineral granularity and serious agglomeration phenomenon is provided.
The method for recovering rare earth minerals from seafloor sediments according to the embodiments of the present application will be described in detail below.
Referring to fig. 1, a method of recovering rare earth minerals from a seafloor sediment, comprising:
s1, preprocessing operation, wherein the preprocessing operation comprises the following steps: mixing the seabed sediment and the first regulator at the temperature of not lower than 40 ℃. That is, the seabed sediment is used as ore feeding and is heated, stirred and mixed with the first conditioning agent.
Wherein, the stirring can adopt a magnetic stirrer.
The specific operation of stirring and mixing may be to add the first regulator into the bottom sediment, heat and stir the mixture to mix the first regulator and the bottom sediment uniformly, or to heat the bottom sediment to a temperature of not less than 40 ℃ and add the first regulator while stirring. The latter stirring and mixing method ensures that the two are fully contacted, and through the coordination of temperature, stirring and the first regulator, rare earth minerals and rare earth carrier minerals in the submarine sediments and gangue minerals such as aluminosilicate, silicate and iron-manganese oxide ore are dispersed and separated strongly, so that the agglomeration phenomenon among the submarine sediments is reduced.
Optionally, the temperature of the pretreatment operation is 40 to 80 ℃, for example, the temperature of the pretreatment operation is 40 ℃, 50 ℃, 60 ℃, 70 ℃, the temperature range is good in economic benefit, the stirring rate of the pretreatment operation is 500 to 1500r/min, for example, the stirring rate is 500r/min, 600r/min, 800r/min, 900r/min, 1000r/min, 1300r/min, 1400r/min, etc., and the stirring time is 10 to 30min, for example, the stirring time is 10min, 15min, 20min, 25min, 30min, etc.
The first conditioning agent comprises sodium carbonate.
Optionally, the first conditioning agent comprises sodium carbonate and sodium hydroxide.
That is, the first conditioning agent may consist of only sodium carbonate, or may consist of sodium carbonate and sodium hydroxide.
Specifically, the first conditioning agent comprises: 40-70 parts by mass of sodium carbonate and 20-50 parts by mass of sodium hydroxide.
In the pretreatment operation, the dosage of the first regulator is 5-15 kg/t of raw ore, for example, the dosage of the first regulator is 5kg/t of raw ore, 7kg/t of raw ore, 10kg/t of raw ore, 13kg/t of raw ore or 15kg/t of raw ore, wherein in the application, 5-15 kg/t of raw ore means 5-15 kg per ton of seabed sediment; the dosage of the medicament in the form of the medicament in the document indicates the meaning, and the numerical values are different, so that the detailed description is not repeated.
It should be noted that the first conditioning agent is not added in any other operations than the pretreatment operation.
S2, roughing operation, wherein the roughing operation comprises the following steps: and (3) taking the seabed sediment obtained by pretreatment as flotation feed, mixing the seabed sediment with a second regulator and a collecting agent, and performing rough concentration to obtain rough concentrate and rough tailings.
Wherein the second regulator comprises sodium silicate, aluminum potassium sulfate, sodium fluosilicate and ferrous sulfate.
Optionally, the second conditioning agent comprises: 30-50 parts by mass of sodium silicate, 10-30 parts by mass of aluminum potassium sulfate, 10-30 parts by mass of sodium fluosilicate and 10-30 parts by mass of ferrous sulfate.
Optionally, the collector comprises: 30-50 parts by mass of 3-hydroxy-2-naphthalene hydroxamic acid, 30-50 parts by mass of sodium fatty acid methyl ester sulfonate, 10-30 parts by mass of ether alkyl phosphate and 3-10 parts by mass of tributyl phosphate.
Optionally, in the roughing operation, the amount of the second conditioning agent is 2-10 kg/t of raw ore, for example, the amount of the second conditioning agent is 2kg/t of raw ore, 5kg/t of raw ore, 7kg/t of raw ore, 9kg/t of raw ore or 10kg/t of raw ore, and the amount of the collecting agent is 1-5 kg/t of raw ore, for example, the amount of the collecting agent is 1kg/t of raw ore, 2kg/t of raw ore, 4kg/t of raw ore or 5kg/t of raw ore.
In practical application, the roughing flotation time is 6-10 min.
S3, scavenging operation, wherein the scavenging operation comprises the following steps: carrying out scavenging for at least one time by taking the rougher tailings as scavenging raw materials to obtain scavenged middlings and scavenged first tailings, wherein a second regulator and a collecting agent are added in each scavenging; returning the scavenged middlings obtained by the first scavenging to the pretreatment operation for pretreatment, and returning the scavenged middlings obtained by the other scavenging to the previous scavenging step for scavenging.
Wherein, at least one time of scavenging is, for example, one time, two times, three times, etc., and those skilled in the art can select the scavenging according to actual requirements.
And when the scavenging is at least twice, continuously carrying out the scavenging for at least two times, and finally obtaining scavenged middlings which correspond to the scavenging for each time one by one and the final first tailings, wherein the first tailings are discharged.
Optionally, the scavenging is performed for 1-2 times, and the circulating amount of the scavenged middling is moderate.
Optionally, in the scavenging operation, the dosage of the second conditioning agent used in the first scavenging is 0.5-2 kg/t of raw ore, for example, the dosage of the second conditioning agent used in the first scavenging is 0.5kg/t of raw ore, 1kg/t of raw ore, 1.3kg/t of raw ore, 1.6kg/t of raw ore or 2kg/t of raw ore, and the dosage of the collecting agent is 0.1-1 kg/t of raw ore, for example, the dosage of the collecting agent is 0.1kg/t of raw ore, 0.3kg/t of raw ore, 0.5kg/t of raw ore, 0.7kg/t of raw ore or 1kg/t of raw ore; the dosage of the second regulator adopted by the rest scavenging is 1/5-1/2 of the first scavenging, and the dosage of the collecting agent adopted by the rest scavenging is 1/5-1/2 of the first scavenging.
In practical application, the scavenging flotation time is 4-6 min each time.
S4, selecting operation, wherein the selecting operation comprises the following steps: and (4) carrying out concentration for at least two times by taking the rough concentrate as a raw material for concentration operation to obtain rare earth concentrate, wherein a second regulator is added in each concentration.
At least two beneficiating runs are, for example, two, three, five or seven beneficiating runs, and optionally a total of three to five beneficiating runs are performed on the beneficiating run.
Optionally, in the concentration operation, in the first fine separation, the dosage of the second regulator is 0.5-2 kg/t of raw ore, for example, the dosage of the second regulator is 0.5kg/t of raw ore, 0.7kg/t of raw ore, 0.9kg/t of raw ore, 1kg/t of raw ore, 1.3kg/t of raw ore, 1.5kg/t of raw ore, 1.7kg/t of raw ore or 2kg/t of raw ore; in the other fine selections, the dosage of the second regulator is 1/10-1/2 of the first fine selection.
Optionally, in practical application, in each concentration operation, the flotation time is 4-6 min, for example, 4min, 5min, 5.5min, or 6 min.
S5, middling recleaning operation, wherein the middling recleaning operation comprises the following steps: respectively merging the concentrated middlings obtained by the first concentration and the second concentration in the concentration operation, and adding a second regulator and a collecting agent for flotation to obtain middlings, namely, recleaning rough concentrates and second tailings; and returning the middling recleaning rough concentrate to the first concentration and carrying out concentration treatment, and carrying out concentration treatment on the other concentrated middling obtained by concentration in a forward delay manner and returning to the previous concentration step.
Under the above conditions, the circulation volume of the middlings in the concentration is moderate.
Optionally, in the middling recleaning operation, the amount of the second modifier is 0.5-2 kg/t of raw ore, for example, the amount of the second modifier is 0.5kg/t of raw ore, 0.8kg/t of raw ore, 1kg/t of raw ore, 1.2kg/t of raw ore, 1.5kg/t of raw ore, 1.7kg/t of raw ore, or 2kg/t of raw ore, and the amount of the collector is 0.1kg/t of raw ore, 0.3kg/t of raw ore, 0.5kg/t of raw ore, 0.7kg/t of raw ore, or 1kg/t of raw ore.
In practical application, the flotation time for middling recleaning is 4-6 min.
In this application, recovery is the ratio of the total amount of rare earth in the concentrate product to the total amount of rare earth in the seafloor sediment (flotation feed).
The features and properties of the present application are described in further detail below with reference to examples.
Example 1
A method for recovering rare earth minerals from seabed sediment is used for mineral separation and enrichment of the rare earth minerals in the seabed sediment, wherein in the embodiment, the seabed sediment is the seabed sediment which is collected from the middle sea area of the Pacific ocean, and the minerals mainly comprise illite, feldspar, chlorite, halite and quartz, and are secondly apatite, iron manganese oxide, calcite, ilmenite, mica, barite, zircon and the like, the average particle size of the minerals is 4.5 mu m, the content of a sample REO is 0.096%, 50% of rare earth elements are existed in the apatite, about 40% of the rare earth elements are existed in independent rare earth minerals such as monazite, xenotime and the like, and a small amount of the rare earth elements are distributed in iron manganese oxide and clay minerals.
The method for recovering rare earth minerals from seabed sediments specifically comprises the following steps:
s1, preprocessing the operation, wherein the preprocessing operation comprises: mixing the submarine sediment at 60 ℃ with the first conditioning agent for 20min under the action of a magnetic stirrer at the stirring speed of 800 r/min.
Wherein the first regulator is formed by mixing 60 parts by mass of sodium carbonate and 40 parts by mass of sodium hydroxide; the dosage of the first regulator is 10kg/t raw ore.
S2, roughing operation, wherein the roughing operation comprises the following steps: and adding a second regulator into the pretreated seabed sediment, stirring for 5min, adding a collecting agent, stirring for 2min, and performing roughing to obtain rough concentrate and rough tailings.
Wherein the second regulator is formed by mixing 40 parts by mass of sodium silicate, 25 parts by mass of aluminum potassium sulfate, 20 parts by mass of sodium fluosilicate and 15 parts by mass of ferrous sulfate; the amount of the second regulator is 6kg/t raw ore. The collecting agent is formed by mixing 40 parts by mass of 3-hydroxy-2-naphthalene hydroxyoxime acid, 40 parts by mass of fatty acid methyl ester sodium sulfonate, 15 parts by mass of ether alkyl phosphate and 5 parts by mass of tributyl phosphate; the amount of the collector used was 4kg/t of raw ore. The roughing flotation time is 8 min.
S3, scavenging operation, wherein the scavenging operation comprises the following steps: and adding a second regulator and a collector into the roughed tailings, and performing scavenging for 2 times to obtain 2 scavenged middlings and first tailings.
When the first scavenging is carried out, the using amount of the second regulator is 2kg/t of raw ore, and the using amount of the collecting agent is 0.5kg/t of raw ore; during the second scavenging, the dosage of the second conditioning agent is 1/4 during the first scavenging, and the dosage of the collecting agent is 1/5 during the first scavenging. The flotation time of each scavenging is 5 min. And returning the first scavenging middlings to the pretreatment operation for pretreatment operation, and returning the second scavenging middlings to the first scavenging operation for scavenging as scavenging raw materials.
S4, selecting operation, wherein the selecting operation comprises the following steps: and (4) carrying out concentration by taking the rough concentrate as a raw material for concentration operation to obtain rare earth concentrate, wherein a second regulator is added for each concentration.
Wherein, when the first concentration is carried out, the dosage of the second regulator is 1kg/t of raw ore; when the second fine concentration is carried out, the dosage of the second regulator is 0.5kg/t of raw ore; when the concentration is carried out for the third time, the dosage of the second regulator is 0.25kg/t raw ore; in the fourth concentration, the dosage of the second regulator is 0.1kg/t raw ore. The flotation time is 5min for each concentration. And (4) combining the concentrated middlings obtained by the first concentration and the concentrated middlings obtained by the second concentration, and carrying out middling recleaning operation in the step S5, wherein the concentrated middlings obtained by the third and fourth concentrations are taken as raw materials of the concentration operation and are all sequentially returned to the previous concentration step for concentration treatment, namely, the concentrated middlings obtained by the third concentration are taken as raw materials of the second concentration treatment, and the concentrated middlings obtained by the fourth concentration are taken as raw materials of the third concentration treatment.
S5, middling recleaning operation, wherein the middling recleaning operation comprises the following steps: and merging the concentrated middlings obtained by the first concentration and the concentrated middlings obtained by the second concentration, and adding a second regulator and a collecting agent to perform primary rough concentration to obtain middlings, namely, the recleaning rough concentrate and the second tailings.
Wherein the dosage of the second regulator is 1kg/t of raw ore; the amount of the collector used was 0.5kg/t of raw ore. And returning the obtained middling recleaning rough concentrate to the first concentration operation for concentration treatment. The flotation time for the combined beneficiated middlings re-selection operation was 5 min.
Specifically, by the treatment of the embodiment 1 of the invention, most of aluminosilicate, silicate gangue minerals and iron-manganese oxide ores are inhibited in tailings, and the rare earth minerals are effectively enriched.
Finally, the following results are obtained through laboratory closed-loop tests: the REO content of the concentrate is 10.56 percent, and the recovery rate of the rare earth is 40.86 percent; this shows that the method for recovering rare earth minerals from seafloor sediments provided by the embodiment 1 of the invention can effectively enrich rare earth minerals in seafloor sediments and can obtain higher rare earth recovery rate.
Test examples
The applicant has set up comparative examples 1-6.
Of these, comparative example 1 differs from example 1 only in that: in the pretreatment operation of comparative example 1, the seabed sediment was stirred and mixed with the first conditioner at 30 ℃.
Comparative example 2 differs from example 1 only in that: in the pretreatment operation of comparative example 2, the bottom sediment was mixed with the first conditioner under stirring at 60 ℃, wherein the first conditioner was only sodium carbonate commonly used in the art, and no sodium hydroxide was added.
Comparative example 3 differs from example 1 only in that: in the pretreatment operation of comparative example 3, the seabed sediment was stirred at 60 ℃ without adding the first conditioning agent.
Comparative example 4 differs from example 1 only in that: in comparative example 4 no second conditioner was added.
Comparative example 5 differs from example 1 only in that: the second modifier used in comparative example 5 is sodium silicate and sodium fluorosilicate, which are commonly used in the art, and is mixed from 80 parts by mass of sodium silicate and 20 parts by mass of sodium fluorosilicate, unlike example 1.
Comparative example 6 differs from example 1 only in that: the collector used in comparative example 6 was salicylhydroxamic acid and sodium oleate, which are commonly used in the art, and is mixed with 50 parts by mass of salicylhydroxamic acid and 50 parts by mass of sodium oleate, unlike in example 1.
Finally, a laboratory closed-loop test shows that: the REO content of the concentrate and the rare earth recovery in comparative examples 1-6 are shown in table 1.
Table 1 comparative example test results
| Concentrate REO content (%) | Rare earth recovery (%) | |
| Comparative example 1 | 5.75 | 30.45 |
| Comparative example 2 | 8.12 | 41.08 |
| Comparative example 3 | 4.86 | 36.62 |
| Comparative example 4 | 5.81 | 39.56 |
| Comparative example 5 | 7.70 | 40.33 |
| Comparative example 6 | 9.55 | 36.73 |
According to table 1:
compared with the example 1, the comparative examples 1 and 3 respectively can obtain that the heating and the addition of the first regulator have certain promotion effects on the improvement of the grade and the recovery rate of the rare earth in the concentrate in the pretreatment operation.
Compared with the embodiment 1, the first conditioning agent used in the method can effectively improve the rare earth grade of the concentrate in the pretreatment operation compared with the conventional conditioning agent sodium carbonate, and the comparison example 2 can obtain the effect.
Compared with the embodiment 1, the comparative examples 4 and 5 respectively have certain promotion effects on the improvement of the concentrate rare earth grade and the recovery rate in the flotation operation by adding the second regulator. Compared with the embodiment 1, the second regulator provided by the application can effectively improve the rare earth grade of the concentrate and has a certain promotion effect on the improvement of the recovery rate compared with the common regulator in the field.
Compared with the embodiment 1, the combined collector used in the method can effectively improve the recovery rate of rare earth and has better selectivity in flotation operation compared with the conventional rare earth collector.
In conclusion, it can be seen that the technical scheme provided by the application effectively improves the grade of the rare earth concentrate on the whole and keeps a better rare earth recovery rate through the synergistic cooperation of the steps of temperature, the first regulator, the second regulator, the collecting agent, screening and the like.
In conclusion, the method for recovering the rare earth minerals from the seabed sediments, which is provided by the application, can effectively recover the rare earth minerals from the seabed sediments, effectively improve the grade of rare earth concentrate and obtain a better rare earth recovery rate, and is simple to operate, stable in process, convenient for field management and strong in adaptability.
The above description is only a preferred embodiment of the present application and is not intended to limit the present application, and various modifications and changes may be made to the present application by those skilled in the art. Any modification, equivalent replacement, improvement and the like made within the spirit and principle of the present application shall be included in the protection scope of the present application.
Claims (9)
1. A method of recovering rare earth minerals from seafloor sediments, comprising:
a pre-processing job, the pre-processing job comprising: stirring and mixing the seabed sediment and a first regulator at the temperature of 40-80 ℃;
roughing operation, including: taking the seabed sediment obtained by pretreatment as flotation feed, mixing the seabed sediment with a second regulator and a collecting agent for roughing to obtain rough concentrate and rough tailings;
a beneficiation operation, the beneficiation operation comprising: performing concentration for at least two times by taking the rough concentrate as a raw material for concentration operation to obtain rare earth concentrate, wherein the second regulator is added in each concentration;
wherein the first regulator consists of 40-70 parts by mass of sodium carbonate and 20-50 parts by mass of sodium hydroxide;
the second conditioning agent comprises: 30-50 parts by mass of sodium silicate, 10-30 parts by mass of aluminum potassium sulfate, 10-30 parts by mass of sodium fluosilicate and 10-30 parts by mass of ferrous sulfate;
the collector comprises: 30-50 parts by mass of 3-hydroxy-2-naphthalene hydroxamic acid, 30-50 parts by mass of sodium fatty acid methyl ester sulfonate, 10-30 parts by mass of ether alkyl phosphate and 3-10 parts by mass of tributyl phosphate.
2. The method of recovering rare earth minerals from seafloor sediments according to claim 1, wherein the method of recovering rare earth minerals from seafloor sediments further comprises a scavenger operation comprising: carrying out scavenging for at least one time by taking the rougher tailings as scavenging raw materials to obtain scavenged middlings and scavenged first tailings, wherein the second regulator and the collecting agent are added in each scavenging;
returning the scavenging middlings obtained by the first scavenging to the pretreatment operation for pretreatment, and returning the scavenging middlings obtained by the other scavenging to the previous scavenging step for scavenging.
3. The method for recovering rare earth minerals from seabed sediments according to claim 2, wherein the second regulator is used for the first scavenging in the scavenging operation in an amount of 0.5-2 kg/t raw ore, and the collector is used in an amount of 0.1-1 kg/t raw ore; the dosage of the second regulator adopted by the rest scavenging is 1/5-1/2 of the first scavenging, and the dosage of the collector adopted by the rest scavenging is 1/5-1/2 of the first scavenging.
4. The method for recovering rare earth minerals from seafloor sediments according to claim 2, wherein in the concentration operation, the dosage of the second regulator is 0.5-2 kg/t of raw ore in the first concentration; and in the other fine selections, the dosage of the second regulator is 1/10-1/2 of the first fine selection.
5. The method of recovering rare earth minerals from seafloor sediments according to claim 1, wherein the method of recovering rare earth minerals from seafloor sediments further comprises a middling recleaning operation comprising: respectively merging the concentrated middlings obtained by the first concentration and the second concentration in the concentration operation, and adding the second regulator and the collecting agent for flotation to obtain middling recleaning rough concentrate and second tailings;
and returning the middling recleaning rough concentrate to the first concentration for concentration treatment, and carrying out concentration treatment on the other concentrated middling obtained by concentration in a continuous delay manner and returning the concentrated middling to the previous concentration step.
6. The method for recovering rare earth minerals from seabed sediments according to claim 5, wherein the dosage of the second regulator in the middling recleaning operation is 0.5-2 kg/t of raw ore, and the dosage of the collector is 0.1-1 kg/t of raw ore.
7. The method for recovering rare earth minerals from seafloor sediments according to any one of claims 1 to 6, wherein the amount of the first conditioning agent used in the pretreatment operation is 5 to 15kg/t of raw ore.
8. The method for recovering rare earth minerals from seafloor sediments according to any one of claims 1 to 6, wherein the dosage of the second regulator in the roughing operation is 2 to 10kg/t of raw ore and the dosage of the collecting agent is 1 to 5kg/t of raw ore.
9. The method for recovering rare earth minerals from seafloor sediments as claimed in claim 1, wherein the stirring speed of the stirring and mixing is 500-1500 r/min, and the stirring time is 10-30 min.
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| CN112474064B (en) * | 2020-10-23 | 2022-06-24 | 核工业北京化工冶金研究院 | Compound collecting agent and application thereof in complex rare earth ore flotation |
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