CN103240184A - Rare earth ore collecting agent, preparation method and mineral separation process of low-grade refractory rare earth ore - Google Patents
Rare earth ore collecting agent, preparation method and mineral separation process of low-grade refractory rare earth ore Download PDFInfo
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Abstract
The invention relates to a rare earth ore collecting agent which is characterized by being prepared by reacting 4-7 parts by weight of 2-naphthalene hydroxyimino acid, 2-4 parts by weight of methyl salicylate and an aqueous solution containing 1-2 parts by weight of sodium hydroxide solid; the collecting agent has simple compatibility, easy preparation and low cost, can be used for the flotation of low-grade rare earth ores which are complex and difficult to separate, has good selectivity and collecting performance, and has no harsh requirements on the temperature and the pH value of a flotation system; the invention also provides a preparation method of the collecting agent, which is simple and convenient to operate, easy to control conditions and easy to implement; the invention also provides a mineral separation process of the low-grade refractory rare earth ore, and the high-grade and high-recovery rare earth concentrate is obtained by adopting a mineral separation method of flotation pre-enrichment-wet type strong magnetic separation purification.
Description
Technical field
The invention belongs to the technique of preparing field of rare earth, particularly relate to the ore-dressing technique that a kind of collecting agent, its preparation method and a kind of low-grade refractory that can be used for the Rare Earth Mine normal temperature flotation selects Rare Earth Mine.
Background technology
[0002] rare earth resources is described as the treasure-house of new century high-tech and functional material by people, and it is the strategic element of developing high-tech.The rare earth resources of China is very abundant, has found out that the rare earth reserves account for 80% of world's gross reserves.Simultaneously, China also is that global rare earth is consumed one of fastest-rising country, estimates in future, and the rare earth demand can constantly increase.The research of the technique of preparing of Rare Earth Mine, significant to the development of rare-earth trade.
With constantly carrying out of exploitation, selected Rare Earth Mine begins to occur situation such as grade decline, mineral composition complexity, disseminated grain size is tiny, tradition gravity treatment, magnetic separation technology more and more are difficult to adapt to, and the flotation beneficiation method of Rare Earth Mine more and more has consequence in numerous beneficiation methods.The key that the flotation sorting process can be obtained good result is to find strong, the selective good rare-earth mineral collector of a kind of collecting.
Traditional rare-earth mineral collector has good collecting performance to the thicker rare-earth mineral of grain size number, but the extremely low-grade Rare Earth Mine big for sludge content, that mineral composition is complicated then can't obtain good separating effect.
The H205 rare earth catching agent of being used widely aborning has good selective and collecting performance to the rare-earth mineral in Baogang's ore dressing plant gravity treatment rare earth rough concentrate.But when using it with Dechang big syneclise Rare Earth Mine screening test, result of the test is unsatisfactory.Dechang big syneclise Rare Earth Mine ore chats cement content is big, the mineral disseminated grain size is thin, and sludge RARE EARTH MINERALS IN content is bigger, and predictive desliming operation meeting reduces rare earth yield, causes the loss of rare-earth mineral and the waste of resource.When adopting direct flotation technology, the gangue mineral of embedding cloth complexity can influence the H205 rare earth catching agent to the collecting of rare-earth mineral in the ore, makes the selective decline of the rare-earth mineral of H205 to worsen separating effect.
Provide a kind of 1-hydroxyl 2-naphthalene first hydroximic acid collecting agent in the prior art " the synthetic collecting performance that reaches rare-earth mineral of 1-hydroxyl 2-naphthalene first hydroximic acid; Xu Jinqiu etc.; non-ferrous metal; the 54th the 3rd phase of volume; in August, 2002 ", compare with the collecting agent of other kind, this collecting agent has stronger collecting ability, and the actual collecting effect of Rare Earth Mine is better than the bigcatkin willow hydroximic acid.But the collecting agent of this single component selects the collecting ability of Rare Earth Mine relatively poor to low-grade refractory, only can be used for the flotation of high-grade Rare Earth Mine, and must could realize better collecting effect in the ore pulp system of meta-alkalescence.
Therefore, demand inventing a kind of novel rare-earth mineral collector urgently, can be used in the low-grade Rare Earth Mine flotation of complicated difficult choosing, and selective and collecting is good, simultaneously to temperature and the no specific (special) requirements of pH value of flotation system.
On the other hand, for rare-earth ore ore-dressing technology itself, the coarse grain rare earth ore generally adopts physical upgrading technologies such as traditional gravity treatment, magnetic separation to reclaim, and the particulate rare earth ore mainly adopts the floatation process of heating to reclaim.Carry out with the Rare Earth Mine exploitation, the selected grade of Rare Earth Mine descends year by year, and milling ore embedding cloth is complicated day by day, sludge content is big, and traditional single ore-dressing technique more and more is difficult to adapt to.
The low-grade refractory of present REO grade＜3% selects the ore-dressing technique of Rare Earth Mine to mainly contain:
(1) gravity treatment-strong magnetic process integration: raw ore REO grade 2.5%, adopt primary grinding, ore grain size-0.074 millimeter accounts for about 80%, adopt the gravity separation technology flow process of slimer one roughing, once purging selection, can obtain rare earth rough concentrate productive rate 4.9%, REO grade 24.8%, the index of the rate of recovery 48.66%.The rare earth rough concentrate is entered strong magnetic separation operation obtain rare earth ore concentrate productive rate 1.7%, REO grade 54.8%, the index of the rate of recovery 37.2%.The low-grade Rare Earth Mine chats cement content of REO grade＜3% is big and sludge middle rare earth distributive law is higher, in the gravity tailings in this process loss excessive, can't obtain the Rare Earth Mine concentrate of qualified grade and the desirable rate of recovery.
(2) floatation process of heating, raw ore REO grade 2.5%, adopt primary grinding, ore grain size-0.074 millimeter accounts for about 80%, adopts flotation desliming in advance, will remove to the part sludge in the ore deposit, to reduce it to the influence of follow-up flotation operation, the sludge productive rate is that 9.8%, REO grade is 2.9%, and the rate of recovery is 11.35% index.Product after the desliming (35 ℃ ~ 50 ℃) and cooperate with the suitable rare earths high-efficient collecting agent under the condition of heating can obtain productive rate and be 1.8%, the REO grade is 45%, the rate of recovery is 32.41% floatation indicators (to raw ore).This technology medicament is expensive, and needs to heat in the flotation operation process, and energy consumption is big, and the Job Operations inclement condition is difficult to control, is difficult to obtain desirable production target.
Existing ore-dressing technique technology is reformed, can be rare earth, the scarce resource of country's saving and new increase preciousness, realize resource to greatest extent, make ecological environment be improved significantly, reach the purpose that realizes environmental benefit, economic benefit and social benefit combination and sustainable development.
Therefore, find a kind ofly need not to heat, process conditions are easy to control, Rare Earth Mine rate of recovery height, novel rare-earth ore deposit method for floating that concentrate grade is good, become another problem that the present invention tries hard to solve.
Summary of the invention
One of purpose of the present invention is to provide a kind of Rare Earth Mine collecting agent, and compatibility is simple, and preparation easily, with low cost, can be used in the low-grade Rare Earth Mine flotation of complicated difficult choosing, select performance and collecting functional, simultaneously to temperature and the no harsh requirement of pH value of flotation system.
Rare Earth Mine collecting agent of the present invention, by weight, it is by 4 ~ 7 parts of 2-naphthalene first hydroximic acids, and 2 ~ 4 parts of gaultherolins make with the reactant aqueous solution that contains 1 ~ 2 part of sodium hydrate solid;
The structural formula of described 2-naphthalene first hydroximic acid is
Compare with the 1-hydroxyl 2-naphthalene first hydroximic acid collecting agent of existing one-component, the present invention be 2-naphthalene first hydroximic acid and gaultherolin separately with the reactant mixture of sodium hydroxide solution, sorting and the collecting of collecting agent are significantly improved, medicament is stronger to the adaptability that system temperature changes in the floatation process, can in wideer pulp density scope, realize the flotation under the normal temperature condition, be specially adapted to the rare-earth ore ore-dressing that sludge content is big, the mineral disseminated grain size is thin, gangue mineral constitutes complexity, and obtain good flotation effect.Collecting agent chemical property of the present invention is stable, non-corrosiveness, and toxicity is little, and is non-inflammable, the good stability that shady and cool director's phase stores.Be understandable that collecting agent of the present invention also can be used for the flotation of high-grade Rare Earth Mine simultaneously.
Preferably, described Rare Earth Mine collecting agent, by weight, by 5 ~ 6 parts of hydroximic acids, 2 ~ 3.5 parts of gaultherolins make with the reactant aqueous solution that contains 1 ~ 2 part of sodium hydrate solid.In described preferable range, collecting agent selects the collecting better effects if of Rare Earth Mine to low-grade refractory.
Two of purpose of the present invention is to provide a kind of method for preparing described Rare Earth Mine collecting agent, comprises the steps:
Step 1, synthetic: as to take by weighing the 2-naphthoic acid of 1 weight portion in enamel reaction still, add 2 ~ 4 weight portion methyl alcohol, be stirred to the concentrated sulfuric acid that abundant dissolving back adds 0.3 ~ 0.5 weight portion, reaction is 30-35 hour under the reflux state, leaves standstill complete back to be crystallized and filters, discard filtrate, obtain crystal;
Step 2, esterification: get the crystallization of step 1 gained, add 10% the hydroxylamine hydrochloride aqueous solution in the ratio of solid masses 2:1 ~ 3, adding sodium hydroxide solution regulator solution pH value subsequently is 9 ~ 10, under 35 ℃ of-55 ℃ of conditions, reacting at least 4 hours then, is that 10% dilute sulfuric acid is acidified to pH=4 ~ 5 with mass fraction, filtration drying obtains 2-naphthalene first hydroximic acid;
Step 3, saponification: with step 2 gained 2-naphthalene first hydroximic acid, gaultherolin and sodium hydrate aqueous solution mixing, the water-bath heating was stirred 30 minutes at least, to reacting completely, obtained the good yellowish-brown liquid of light transmission, was the Rare Earth Mine collecting agent in described ratio.
Preparation method of the present invention is easy and simple to handle, and condition is easily controlled, and implements easily.
Three of purpose of the present invention is to provide a kind of low-grade refractory to select the ore-dressing technique of Rare Earth Mine, comprises the steps:
(1) gets raw ore, add after the fragmentation that water is sized mixing and ore grinding to the ore weight of granularity-0.074 millimeter accounts for raw ore gross weight 80% ~ 88%;
(2) add water in step (1) the gained ore pulp and size mixing to pulp density be 20 ~ 30%, carry out substep then and roughly select, obtain roughly selecting concentrate and rougher tailings, described substep is roughly selected and is at least twice flotation; In this step, during each flotation, in ore pulp, add inhibitor, described Rare Earth Mine collecting agent and foaming agent successively;
(3) the described concentrate of roughly selecting is carried out that two-stage is selected at least, obtain flotation concentrate and chats at different levels;
(4) the described flotation concentrate that obtains in the step (3) is carried out strong magnetic purification operation, obtain strong magnetic concentrate, it is qualified rare earth ore concentrate product.
Ore-dressing technique of the present invention is applicable to the flotation of the low-grade Rare Earth Mine of REO grade＜3%, and particularly sludge content difficulty big, mineral embedding cloth complexity is selected the flotation of rare earth ore, has effectively enlarged the REO grade scope of selected raw ore, has saved rare-earth ore resource.
Compared with prior art, the beneficiation method that the present invention adopts flotation preenrichment-wet high-intensity magnetic separation to purify first, before this by flotation preenrichment mineral aggregate, flotation is to add inhibitor, collecting agent and foaming agent in ore pulp, selected after the flotation, selected gained concentrate adopts wet high-intensity magnetic separation (high intensity magnetic separation is used for removing non magnetic gangue mineral) to purify again.
The omnidistance normal-temperature operation of the present invention get final product, need not heat in the operation, and technology is strong to thermal adaptability, and reaction condition is simple and be easy to control, has overcome effectively that temperature influences big deficiency to flotation operation in the common process, and energy consumption is low.On the other hand, technological process of the present invention is short, and in the whole technology, need not the pH value, and operation is further simplified.
Preferably, step (1) is all carried out under normal temperature condition to the operation of step (4), and described foaming agent is oily by weight (1 ~ 3) by terpenic oil and ether alcohol: 1 mixes.Terpenic oil and ether alcohol oil is composite for the Rare Earth Mine flotation, can under the less situation of consumption, obtain to bubble preferably effect, froth bed is stable in the floatation process, compared with prior art, this foaming agent not only consumption is few, foam stabilization, and compatibility is simple, when improving flotation effect, definite effective has been alleviated the pressure that the three wastes are handled, and has reduced reagent cost.
Preferably, during step (2) the middle first time of flotation, the inhibitor consumption is that 1.0 ~ 2.0kg/t raw ore, collector dosage are 1.0 ~ 2.0kg/t raw ore, the foaming agent consumption is 0.04 ~ 0.08kg/t raw ore, during step (2) the middle second time of flotation, the inhibitor consumption is that 0.5 ~ 1.0kg/t raw ore, collector dosage are 0.5 ~ 1.0kg/t raw ore, and the foaming agent consumption is 0.01 ~ 0.04kg/t raw ore, and described inhibitor is waterglass.During twice flotation, dosing control is comparatively suitable in described scope, and consumption is lower than described scope, and flotation effect reduces, and consumption is higher than described scope, and flotation effect promotes not obvious, and reagent cost rises.
Preferably, step (3) carry out three grades selected, when the first order is selected, in ore pulp, add water glass, the waterglass consumption is 50 ~ 100g/t raw ore, the selected and third level in the second level is selected to be the blank selected of not adding medicine.Can be understood that, the present invention is owing to passed through aforesaid improvement, make the selected operation of step (3) obtain further to improve, comprise that selected needs of the first order add a spot of inhibitor, adopt the blank selected purpose of inventing of can realizing and the selected and third level in the second level is selected, reduce reagent cost.
Preferably, comprise that also the selected gained chats of step (3) first order is carried out chats to be selected again, it is to add water glass 0.1 ~ 0.3kg/t raw ore and collecting agent 0.1 ~ 0.3kg/t raw ore and flotation in the ore pulp of the selected gained chats of the first order that described chats selects again; Again the selected gained chats in step (3) second level and the selected gained chats of the third level are returned in the former selected operation and select again.
Preferably, comprise that also rougher tailings is carried out at least twice to be scanned, scanning for the first time is to add water glass 100 ~ 500g/t raw ore, collecting agent 100 ~ 500g/t raw ore and foaming agent 10 ~ 40g/t raw ore in ore pulp successively, obtain sweeping a concentrate and sweep a mine tailing, scanning for the second time is to add water glass 100 ~ 300g/t raw ore, collecting agent 100 ~ 300g/t raw ore and foaming agent 10 ~ 20g/t raw ore in the mine tailing ore pulp successively to sweeping, and obtains sweeping two concentrate and final flotation tailing; To sweep a concentrate mixes with the selected gained chats of step (3) first order and carries out chats and select.In this preferred version, mine tailing is scanned and can be guaranteed the optimum recovery rate of technology to reduce the REO grade of discharging mine tailing.On the other hand, will sweep a concentrate and mix with the selected gained chats of the first order and carry out chats and select again, and can reduce the flotation operation sludge to the influence of separation index, reduce the sludge internal circulating load in the chats.
Beneficial effect of the present invention:
The medicament that the present invention obtains is the good yellowish-brown liquid of light transmission, compatibility is simple, preparation is easy, in ore pulp, be easy to disperse, chemical property is stable, non-corrosiveness, toxicity is little, non-inflammable, can store in the shady and cool director phase, the more important thing is that it has good selective and collecting to rare-earth mineral, can be used in the Rare Earth Mine flotation that Rare Earth Mine, particularly sludge content are big, the mineral disseminated grain size is thin, gangue mineral is complicated, temperature and acid-base value to flotation system during application do not have harsh requirement, applicability is strong, has stronger market popularization value.
Ore-dressing technique of the present invention, its temperature applicable range is wide, even need not heat, and just can obtain excellent beneficiating technology index.Compare with traditional gravity treatment-magnetic separation process, the ore-dressing technique that adopts the application to propose not only can obtain the more dressing product of good quality, also greatly reduce the loss of rare-earth mineral in product from failing, guaranteed the rate of recovery of rare-earth mineral, realized the maximization of economic benefit; Compare with the floatation process of heating, the process that adopts the application to propose can obtain more high-quality dressing product, carries out under the flotation operation normal temperature condition, save the process of heating of flotation operation, improve production environment, reduced production cost simultaneously largely, improved recovery rate in ore-dressing.
The specific embodiment
The present invention is further illustrated below in conjunction with the specific embodiment.
One, preparation hydroximic acid:
Embodiment 1
Take by weighing the 2-naphthoic acid of 30kg in enamel reaction still, add 60Kg methyl alcohol in reactor, after treating to dissolve fully, add the 9Kg concentrated sulfuric acid while stir, reaction is 30 hours under the heating reflux state, leaves standstill to crystallization complete; Take by weighing the 30Kg crystallization, add 10% the hydroxylamine hydrochloride aqueous solution in the ratio of solid masses 2:1, to make the pH value of solution value be 9 to the dropping sodium alkaline aqueous solution again, solution temperature to 35 ℃ temperature then raises, be 10% sulfuric acid adjusting pH to 4 with mass fraction behind the reaction 5h, filter, filter residue is dried, obtain 2-naphthalene first hydroximic acid.
Get 2-naphthalene first hydroximic acid 30Kg and with the gaultherolin mixing of 15Kg, add the aqueous solution that contains the 5Kg sodium hydrate solid then, water-bath heating and in 20 ℃ of insulated and stirred 2 hours obtains the ore dressing of rare earth collecting agent.
Utilize this medicament that raw material (from the big syneclise Rare Earth Mine in Dechang, Sichuan) is carried out the experiment of flotation rare earth.Dechang big syneclise Rare Earth Mine sludge content is big, head grade low (the REO grade only is 2.5%).This experiment is at former technological process and mog, carries out the contrast of embodiment 1 and former medicine under the identical prerequisite of pulp density, adopts a closed circuit production procedure that slightly sweeps three essences, experimental result table 1:
Table 1 embodiment 1 and the contrast of former drug effect fruit index
Embodiment 2
Take by weighing the 2-naphthoic acid of 25kg in enamel reaction still, add 60Kg methyl alcohol in the reactor, treat that solid dissolves fully after, add the 9Kg concentrated sulfuric acid while stirs, heat under the reflux state and reacted 35 hours, leave standstill to crystallization complete then; Take by weighing the 2-naphthalene first hydroximic acid that obtains 25Kg, adding mass fraction in the ratio of solid masses 1:1 is 10% the hydroxylamine hydrochloride aqueous solution, to make the pH value of solution value be 10 to the dropping sodium alkaline aqueous solution again, solution temperature to 45 ℃ then raises, react after 6 hours, be that 10% sulfuric acid acidation is 4 to pH with mass fraction, filtration is dried, and obtains 2-naphthalene first hydroximic acid.
Get the 2-naphthalene first hydroximic acid of 25Kg and the gaultherolin of 15Kg and mix, add the aqueous solution contain the 10Kg sodium hydrate solid then, the water-bath heating and under 23 ℃ of temperature conditions insulated and stirred 2 hours, obtain the Rare Earth Mine collecting agent.
Utilize the present invention that raw material (from the Rare Earth Mine of Weishan, Shandong) has been carried out the experiment of flotation rare earth.The contrast of former medicine and embodiment 2 is carried out in this experiment under the identical prerequisite of former mog and pulp density, adopt a closed circuit production procedure that slightly sweeps three essences, and experimental result sees Table 2:
Table 2 embodiment 2 and the contrast of former drug effect fruit index
Embodiment 3
Take by weighing the 2-naphthoic acid of 30kg in enamel reaction still, add 60Kg methyl alcohol again, after treating to dissolve fully, stir to add the 9Kg concentrated sulfuric acid, reaction is 33 hours under the heating reflux state, leaves standstill to crystallization fully, filters and obtains crystallization; Take by weighing the 30Kg crystallization, adding mass fraction in the ratio of solid masses 2:3 is 10% the hydroxylamine hydrochloride aqueous solution, to make the pH value of solution value be 10 to the dropping sodium alkaline aqueous solution again, be heated to 55 ℃ of temperature, react after 5 hours with mass fraction be 10% sulfuric acid acidation to pH be 5, filtering solution dries the filter residue that obtains, and obtains 2-naphthalene first hydroximic acid;
Get the gaultherolin mixing of 30Kg2-naphthalene first hydroximic acid and 30Kg, add the aqueous solution that contains the 15Kg sodium hydrate solid again, the water-bath heating was also stirred 2 hours under 25 ℃ of temperature conditions, obtained the Rare Earth Mine collecting agent.
Utilize the present invention that raw material (from Sichuan Mianning Rare Earth Mine) has been carried out the experiment of flotation rare earth.This experiment is all carried out the contrast of former medicine and embodiment 3 under the identical prerequisite at mog, pulp density, adopts a closed circuit production procedure that slightly sweeps three essences, and experimental result sees Table 3:
Table 3 embodiment 3 and the contrast of former drug effect fruit index
More than the contrast effect of 3 embodiment and former medicine show that the present invention is improving a lot aspect product grade and the rate of recovery improving.
Two, sort Rare Earth Mine
Embodiment 4
Selecting the big syneclise Rare Earth Mine in Dechang, Sichuan for use is the raw ore that present embodiment is handled, and Dechang big syneclise Rare Earth Mine sludge content is big, REO grade 2.34%.
Concrete treatment process is:
1, ore grinding: with the rare-earth original ore fragmentation, add water size mixing to ore milling concentration be 60%, ore grinding to the content of-0.074mm grade is 83% then, add again water size mixing to pulp density be 30%;
2, under the normal temperature condition step 1 gained ore pulp (20 ℃ of slurry temperatures) is carried out roughly selecting operation twice, when the first step is roughly selected, the inhibitor consumption is that 1.5kg/t raw ore, collector dosage are the 1.0kg/t raw ore, the foaming agent consumption is the 0.04kg/t raw ore, obtains the first step and roughly selects concentrate and first step rougher tailings; First step rougher tailings was carried out for second step roughly select, the inhibitor consumption is that 0.5kg/t raw ore, collector dosage are the 0.5kg/t raw ore, and the foaming agent consumption is 0.01kg/t, obtains for second step at last to roughly select concentrate and rougher tailings; The used inhibitor of twice flotation is waterglass; Foaming agent is terpenic oil, and collecting agent is hydroximic acid collecting agent.
3, the first step is roughly selected concentrate and second step and roughly select the concentrate merging as the flotation rough concentrate, under the normal temperature (20 ℃ of slurry temperatures) carry out three grades selected, the selected glass 0.05kg/t raw ore that adds water of the first order, selected and the third level in the second level is selected to be the blank selected of adding medicine not, obtains the REO grade and be 28% flotation concentrate and chats at different levels;
4, to the REO grade be 28% rare earth flotation concentrate, carry out the wet high-intensity magnetic sorting, magnetic field intensity is 12000Oe, and strong magnetic concentrate is qualified rare earth ore concentrate product, and its REO grade is 55%, and the rate of recovery is 50%.
Embodiment 5
Repeat the operation of embodiment 4, difference is: collecting agent is to be made with the aqueous solution reaction that contains 2 parts of sodium hydrate solids by 4 parts of 2-naphthalene first hydroximic acids, 4 parts of gaultherolins.Recording the magnetic concentrate product grade at last is 57%, and the rate of recovery is 55%.
Embodiment 6
Repeat the operation of embodiment 4, difference is: the foaming agent mixture that to be terpenic oil mixes by weight 2:1 with pure ether oil, collecting agent are to be reacted by 4 parts of 2-naphthalene first hydroximic acids, 4 parts of gaultherolins and the aqueous solution that contains 2 parts of sodium hydrate solids to make.
Recording the magnetic concentrate product grade at last is 58%, and the rate of recovery is 63%.
Embodiment 7
Repeat the operation of embodiment 4, difference is: a, foaming agent are the mixture that terpenic oil and pure ether oil mix by weight 2:1; B, collecting agent are to be made with the aqueous solution reaction that contains 2 parts of sodium hydrate solids by 4 parts of 2-naphthalene first hydroximic acids, 4 parts of gaultherolins; After obtaining rougher tailings in c, the step 2, rougher tailings is carried out scanning for twice, when scanning for the first time, in ore pulp, add water glass 100g/t raw ore, collecting agent 100g/t raw ore and foaming agent 10g/t raw ore successively, scan for the first time and obtain sweeping a concentrate and sweep a mine tailing, when scanning operation for the second time, add water glass 100g/t raw ore, collecting agent 100g/t raw ore and foaming agent 10g/t ton raw ore in the mine tailing ore pulp successively to sweeping, scan for the second time and obtain sweeping two concentrate and final flotation tailing.To sweep a concentrate and mix as chats with the selected gained chats of the first order, and carry out chats and be elected to be industry again, chats adds water glass 0.1kg/t raw ore and collecting agent 0.15kg/t raw ore when selecting again; D, that the flotation concentrate in the step (3) is carried out high intensity magnetic separation is selected.
Obtaining the REO grade at last is 60.05%, and the rate of recovery is 66.43% rare earth ore concentrate, records simultaneously in the mine tailing, and the REO grade is 0.81%.
Embodiment 8
The raw ore (the REO grade is 2.8%) that present embodiment selects for use Weishan, Shandong Rare Earth Mine to handle for the present invention.
Repeat the operation of embodiment 7, difference is that a, rare-earth original ore ore grinding to the content less than 200 orders part are 80%; B, foaming agent are the mixture that terpenic oil and pure ether oil mix by weight 3:1; C, collecting agent are to be made with the aqueous solution reaction that contains 2 parts of sodium hydrate solids by 4 parts of 2-naphthalene first hydroximic acids, 4 parts of gaultherolins; D, reagent dosage was waterglass 1.0kg/t raw ore, collecting agent 1.0kg/t raw ore and foaming agent 0.05kg/t raw ore when step 2 first step was roughly selected, and reagent dosage was waterglass 0.5kg/t raw ore, collecting agent 0.5kg/t raw ore, foaming agent 0.02kg/t raw ore when second step roughly selected; E, the waterglass consumption was the 0.1kg/t raw ore when step 3 first order was selected, and f, dosing is when scanning for the first time: waterglass 0.2kg/t raw ore, collecting agent 0.2kg/t raw ore, foaming agent 0.02kg/t raw ore; Dosing is waterglass 0.1kg/t raw ore, collecting agent 0.1kg/t raw ore and foaming agent 0.01kg/t raw ore when scanning for the second time; When selecting again, f, chats add 0.15 kg water glass and 0.1 kilogram of hydroximic acid collecting agent successively as floating agent by raw ore per ton; Flotation concentrate in g, the step (3) is purified through the wet high-intensity magnetic sorting, obtains grade and be 61%, the rate of recovery is 67.49% magnetic concentrate, records simultaneously in the mine tailing, and the REO grade is 0.94%.
Embodiment 9
The raw ore of selecting for use Sichuan Mianning Rare Earth Mine to handle for the present invention, the REO grade of the low-grade Rare Earth Mine of Mianning is 2.3%.
Repeat the operation of embodiment 8, difference is: a, be 88% with rare-earth original ore ore grinding to the content less than 200 orders part, sizing mixing behind the ore grinding to pulp density is that 20%, b, foaming agent are terpenic oil and the pure ether oil mixture that mixes of 2:1 by weight; C, collecting agent are to be made with the aqueous solution reaction that contains 2 parts of sodium hydrate solids by 4 parts of 2-naphthalene first hydroximic acids, 4 parts of gaultherolins; It is waterglass 2.0kg/t raw ore, collecting agent 2.0 kg/t raw ores and foaming agent 0.08 kg/t raw ore that d, the first step are roughly selected dosing; Dosing was waterglass 1.0 kg/t raw ores, collecting agent 1.0 kg/t raw ores and foaming agent 0.04 kg/t raw ore when second step roughly selected; E, dosing was waterglass 0.1 kg/t raw ore when the first order was selected; F, the second level is selected and the third level selected be blank selected, three grades of selected chats that obtain return in the upper level operation successively; G, dosing is waterglass 0.5 kg/t raw ore, collecting agent 0.5kg/t raw ore and foaming agent 0.04 kg/t raw ore when scanning for the first time; Dosing is 0.3kg/t raw ore, collecting agent 0.3 kg/t raw ore and foaming agent 0.02 kg/t raw ore when scanning for the second time; Dosing was 0.3 kg/t raw ore and collecting agent 0.3 kg/t raw ore when h, chats selected again.Obtain grade at last and be 65%, the rate of recovery is 85% magnetic concentrate, the REO grade that records mine tailing simultaneously is 0.35%.
The ore dressing effect of the embodiment of the invention 7 technology ore dressing effects and existing technology is compared result such as table 1
Table 1 application technology and index that existing technology obtains contrast
Need to prove at last; above embodiment is only unrestricted for explanation technical scheme of the present invention; although with reference to preferred embodiment technical scheme of the present invention is had been described in detail; those skilled in the art are to be understood that; can make amendment or be equal to replacement technical scheme of the present invention; and not breaking away from aim of the present invention and scope, it all should be encompassed in the middle of protection scope of the present invention.
Claims (9)
1. Rare Earth Mine collecting agent is characterized in that: by weight, it is by 4 ~ 7 parts of 2-naphthalene first hydroximic acids, and 2 ~ 4 parts of gaultherolins make with the reactant aqueous solution that contains 1 ~ 2 part of sodium hydrate solid;
The structural formula of described 2-naphthalene first hydroximic acid is
。
2. according to the described Rare Earth Mine collecting agent of claim 1, it is characterized in that: by weight, by 5 ~ 6 parts of hydroximic acids, 2 ~ 3.5 parts of gaultherolins make with the reactant aqueous solution that contains 1 ~ 2 part of sodium hydrate solid.
3. prepare the method for described Rare Earth Mine collecting agent, it is characterized in that: comprise the steps:
Step 1, synthetic: as to take by weighing the 2-naphthoic acid of 1 weight portion in enamel reaction still, add 2 ~ 4 weight portion methyl alcohol, be stirred to the concentrated sulfuric acid that abundant dissolving back adds 0.3 ~ 0.5 weight portion, reaction is 30-35 hour under the reflux state, leaves standstill complete back to be crystallized and filters, discard filtrate, obtain crystal;
Step 2, esterification: get the crystallization of step 1 gained, add 10% the hydroxylamine hydrochloride aqueous solution in the ratio of solid masses 2:1 ~ 3, adding sodium hydroxide solution regulator solution pH value again is 9 ~ 10, under 35 ℃ of-55 ℃ of conditions, reacting at least 4 hours then, is that 10% dilute sulfuric acid is acidified to pH=4 ~ 5 with mass fraction, filtration drying obtains 2-naphthalene first hydroximic acid;
Step 3, saponification: with step 2 gained 2-naphthalene first hydroximic acid, gaultherolin and sodium hydrate aqueous solution mixing, the water-bath heating was stirred 30 minutes at least, to reacting completely, obtained the good yellowish-brown liquid of light transmission, was the Rare Earth Mine collecting agent in described ratio;
The saponification equation:
C
11H
9NO
2+NaOH=?C
11H
8NO
2Na+H
2O
C
8H
8O
3+NaOH=?C
7H
7O
3Na+CH
2O。
4. rare-earth ore ore-dressing technology is characterized in that: comprise the steps:
(1) gets raw ore, add after the fragmentation that water is sized mixing and ore grinding to the ore weight of granularity-0.074 millimeter accounts for raw ore gross weight 80% ~ 88%;
(2) add water in step (1) the gained ore pulp and size mixing to pulp density be 20 ~ 30%, carry out substep then and roughly select operation, obtain roughly selecting concentrate and rougher tailings, described substep is roughly selected operation and is comprised at least twice flotation, during each flotation, in ore pulp, add inhibitor, described Rare Earth Mine collecting agent and foaming agent successively;
(3) the described concentrate of roughly selecting is carried out that two-stage is selected at least, obtain flotation concentrate and chats at different levels;
(4) the described flotation concentrate that obtains in the step (3) is carried out strong magnetic separation, obtain strong magnetic concentrate, it is qualified concentrate product.
5. dressing rare-earth ore technology according to claim 4, it is characterized in that: step (1) is all carried out under normal temperature condition to the operation of step (4), described foaming agent be by terpenic oil and ether alcohol oil by weight (1 ~ 3): 1 mixes.
6. rare-earth mineral normal temperature sorting process according to claim 5, it is characterized in that: during step (2) the middle first time of flotation, the inhibitor consumption is 1.0 ~ 2.0kg/t raw ore, collector dosage is 1.0 ~ 2.0kg/t raw ore, and the foaming agent consumption is 0.04 ~ 0.08kg/t raw ore, during step (2) the middle second time of flotation, the inhibitor consumption is 0.5 ~ 1.0kg/t raw ore, collector dosage is 0.5 ~ 1.0kg/t raw ore, and the foaming agent consumption is 0.01 ~ 0.04kg/t raw ore, and described inhibitor is waterglass.
7. low-grade complex difficulty according to claim 6 is selected the ore-dressing technique of Rare Earth Mine, it is characterized in that: step (3) carry out three grades selected, when the first order is selected, in ore pulp, add water glass, the waterglass consumption is 50 ~ 100 gram/t raw ores, and the selected and third level in the second level is selected to be the blank selected of not adding medicine.
8. low-grade complex difficulty according to claim 7 is selected the ore-dressing technique of Rare Earth Mine, it is characterized in that: comprise that also the selected gained chats of step (3) first order is carried out chats to be selected again, it is to add water glass 0.1 ~ 0.3kg/t raw ore and collecting agent 0.1 ~ 0.3kg/t raw ore and flotation in the ore pulp of the selected gained chats of the first order that described chats selects again; Again the selected gained chats in step (3) second level and the selected gained chats of the third level are returned in the upper level flotation operation and select again.
9. low-grade complex difficulty according to claim 8 is selected the ore-dressing technique of Rare Earth Mine, it is characterized in that:
Comprise that also rougher tailings is carried out at least twice to be scanned, scanning for the first time is to add water glass 100 ~ 500g/t raw ore, collecting agent 100 ~ 500g/t raw ore and foaming agent 10 ~ 40g/t raw ore in ore pulp successively, obtain sweeping a concentrate and sweep a mine tailing, scanning for the second time is to add water glass 100 ~ 300g/t raw ore, collecting agent 100 ~ 300g/t raw ore and foaming agent 10 ~ 20g/t raw ore in the mine tailing ore pulp successively to sweeping, and obtains sweeping two concentrate and final flotation tailing; To sweep a concentrate and step (3) for the first time selected gained chats mix and carry out chats and select again.
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| CN104148189A (en) * | 2014-08-08 | 2014-11-19 | 西北矿冶研究院 | Rare earth mineral collecting agent |
| CN106040436A (en) * | 2016-05-27 | 2016-10-26 | 中国地质科学院矿产综合利用研究所 | Low-temperature-resistant rare earth ore flotation collector, preparation method and application thereof |
| CN106423573A (en) * | 2016-10-28 | 2017-02-22 | 江西理工大学 | Application method of ester-based hydroximic acid collecting agent to mineral flotation |
| CN106563561A (en) * | 2016-08-31 | 2017-04-19 | 李梅 | Method of improving rare earth grade of hybrid rare earth ores |
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| CN104148189B (en) * | 2014-08-08 | 2016-08-17 | 西北矿冶研究院 | Rare earth mineral collecting agent |
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| CN106563561A (en) * | 2016-08-31 | 2017-04-19 | 李梅 | Method of improving rare earth grade of hybrid rare earth ores |
| CN106423573B (en) * | 2016-10-28 | 2020-01-10 | 江西理工大学 | Application method of ester hydroxamic acid collecting agent in mineral flotation |
| CN106423573A (en) * | 2016-10-28 | 2017-02-22 | 江西理工大学 | Application method of ester-based hydroximic acid collecting agent to mineral flotation |
| CN108144752A (en) * | 2017-12-20 | 2018-06-12 | 宁波市鄞州智伴信息科技有限公司 | A kind of rare earth catching agent formula and preparation method thereof |
| CN108970812A (en) * | 2018-05-16 | 2018-12-11 | 汕头市国富锆钛实业有限公司 | The beneficiation method of beach placer |
| CN109395887A (en) * | 2018-12-11 | 2019-03-01 | 崔源发 | A kind of rare-earth ore ore-dressing method |
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| CN112439551A (en) * | 2020-11-02 | 2021-03-05 | 西部(重庆)地质科技创新研究院有限公司 | Synthesis process of rare earth collecting agent |
| CN112246429A (en) * | 2020-11-05 | 2021-01-22 | 江西铜业集团有限公司 | Scrubbing pretreatment method before magnetic separation of flotation bulk concentrate of fluorine-carbon-cerium type rare earth ore |
| CN112246429B (en) * | 2020-11-05 | 2022-08-12 | 江西铜业集团有限公司 | Scrubbing pretreatment method before magnetic separation of flotation bulk concentrate of fluorine-carbon-cerium type rare earth ore |
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