CN1103111A - Making rare-earth material liquid from bastnae site - Google Patents
Making rare-earth material liquid from bastnae site Download PDFInfo
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Abstract
The invented technological process mixes the minerals of rare-earth and sodium carbonate or sodium hydrocarbonate in accordance with a proper proportion, through roasting, water washing, acid cleaning, primary acid leaching and secondary acid leaching, the leachate of primary acid leaching and leachate of secondary acid leaching and primary dregs are obtained. To the primary dregs the leachate of stcondary acid leaching is used as the leachate of primary acid leaching to proceed alkaline wash, after washed by water, the primary acid leaching and secondary acid leaching are separately proceeded. Said technological process features strong adaptabilit, no polluting environment, high decomposition rate of ore, high recovery rate of rare earth, small amount of dregs, low acidity of rare-earth raw material liquid and high rare-earth concentration.
Description
The present invention relates to wet method from rare earth ore concentrate, more specifically say so from f_c_ce_la concentrate, produce the processing method of rare earth mineral acid stock liquid by the roasting leaching.
In existing technology, decompose the method that bastnasite is produced rare earth raw material liquid, sulfuric acid process is arranged. processing methodes such as water flowing vapor-phase oxidation roasting method, sodium carbonate roasting method.
The sulfuric acid roasting method of Chinese patent literature CN86105043.6 report decomposes the processing method of producing the sulfuric acid rare earth stock liquid, be to be raw material with the Baotou rare earth ore deposit of containing more phosphorus, add sulfuric acid and carry out roasting, through the Baotou rare earth ore deposit behind the sulfuric acid baking, add entry and leach, and add magnesium oxide and remove impurity element, and obtain the vitriolic rare earth raw material liquid, this processing method is easy, is the good flow process of decomposing the Baotou rare earth ore deposit of containing more phosphorus.But fluorine is enriched in contaminate environment in the tail gas in this technical process, the health of harmful human body.And the concentration of resulting sulfuric acid rare earth stock liquid middle-weight rare earths is lower, only contains the mixed rare-earth oxide of tens grams in this stock liquid of every liter, and need obtain denseer rare earth raw material liquid will make the transition with the organic extraction method.
The molybdenum company of the U.S. carries out the decomposition of hamartite with the oxidizing roasting method that feeds water vapor, this technology is raw material with the hamartite that contains 60% rare earth oxide, hydrochloric acid with 10% carries out pickling to it, is dissolved in the impurity element of hydrochloric acid in the flush away ore, forms the pickling concentrate.Under the condition that feeds water vapor, in 800 ℃ the hamartite after overpickling is carried out oxidizing roasting, in the process that feeds steam roasting, remove fluorine (with hydrofluoric form), through the concentrate after the oxidizing roasting, leach with hydrochloric acid, after the solid-liquid separation, and obtain the rare earth chloride stock liquid of liquid phase, though can obtain containing the higher rare earth raw material liquid of rare-earth oxidation substrate concentration with this technical process.But,, be furnished with the hydrofluoric equipment of recovery and favorable protection measure with hydrofluoric form defluorination.As everyone knows, hydrogen fluoride has huge poison, does not reclaim it, does not have the favorable protection measure that health of operators is had very big influence, major polluting atmosphere environment again.
The people was also once arranged, and (" rare earth " rare earth is write group, the first volume 1978P219-P220 of metallurgical industry press) rare earth ore concentrate with the rare earth oxide that contains 50-60% is a raw material, at first carries out oxidizing roasting, leaches with sulfuric acid again, filter, and obtain leach liquor, and in leach liquor, add a certain amount of sodium sulfate, carry out the double salt precipitation of rare earth, filter, in the double salt of rare earth that obtains precipitation, add sodium hydroxide, carry out carrying out solid-liquid separation again after alkali changes.Dissolve with hydrochloric acid, filter, and make the rare earth chloride stock liquid.Can obtain containing the big rare earth raw material liquid of concentration of rare earth oxide with this technical process.But this technical process is long, cause the loss of rare earth through the sedimentation and filtration that repeatedly makes the transition. and the solubleness of double salt of rare earth is bigger, needs the free acid of higher concentration, operation inconvenience.In addition, because the solubleness of the double salt of heavy rare earths is bigger than the solubleness of the double salt of light rare earths, so the loss of heavy rare earths is even more serious, so the rare earth total recovery of this technical process is lower.
There is report to say that (" rare earth " rare earth is write group again, the first volume 1978P211-P212 of metallurgical industry press) to containing the collective concentrate that rare earth oxide is 20-35%, mix roasting collective concentrate and sodium carbonate mixture when temperature is 600-700 ℃ mutually with concentrate with the industrial sodium carbonate that is equivalent to concentrate weight 15-30%.In baked concentrate, add entry and carry out wet ball mill.Add about 80 ℃ water in the concentrate of crossing through the roasting wet ball mill, mix and stir half an hour, wash, filter, the hydrochloric acid that adds 0.3-0.6N in filter cake stirs in 60-70 ℃ and carried out pickling in 0.5 hour, filters the filter cake that obtains through pickling.Sulfuric acid with 4-5N carries out acidleach in 60-70 ℃ to the filter cake of crossing through overpickling.In leaching process, constantly stir the carrying out of accelerated reaction.Filter, obtain the leach liquor that sulfuric acid concentration is approximately 3N.Sulfuric acid with 0.5N washs slag, filters.Washing lotion and leach liquor merge and obtain rare earth raw material liquid.The advantage of this processing method is that cerium is oxidized to tetravalence when roasting is decomposed, for the extraction separation of cerium creates conditions, and for dissimilar rare earth ore concentrates certain adaptability is arranged all.In roasting process, do not produce obnoxious flavour yet, atmospheric environment is not polluted.The weak point of this technical process is that technical process is still longer, and the rare earth concentration of resulting leach liquor (rare earth raw material liquid) is low, and the acidity of sulfuric acid of leach liquor high (approximately 3N), is not easy to the carrying out of later purification separation technology.Cost is higher, and wastewater flow rate is more.
Purpose of the present invention just is to work out one and is applicable to the processing method of producing rare earth raw material liquid from bastnasite, the bastnasite that are produced from various places all has certain adaptability, in the roasting decomposition course, do not produce obnoxious flavour yet, and shortened process again, reduce and filter number of times, the rate of decomposition of bastnasite and the rate of recovery of rare earth are all increased significantly, the concentration of resulting rare earth raw material liquid middle-weight rare earths is big, and its acidity is low, is convenient to next step the purification and the carrying out of separating technology.
A kind of processing method of producing rare earth raw material liquid from bastnasite of the present invention, bastnasite and yellow soda ash or sodium hydroxide are mixed with suitable weight ratio, roasting, wash the calcining matter of ore deposit and yellow soda ash (or sodium hydroxide) with water, after the washing, after under agitation carrying out pickling with nitric acid or aqueous solution of hydrochloric acid, carry out solid-liquid separation, the aqueous solution with nitric acid, aqueous solution of hydrochloric acid, the leach liquor of acidleach for the second time, the mixed solution of the leach liquor of nitric acid or hydrochloric acid and acidleach for the second time a kind of leaching liquid wherein as acidleach for the first time, under agitation solid phase is carried out the acidleach first time, in the acidleach process, add reductive agent simultaneously, doubly (the cerium amount is to contain the cerium amount in the ore for the 0.7-4 that the quadrivalent cerium Restore All become the trivalent cerium theoretical amount for the amount of the reductive agent that is added, down together), the aqueous nitric acid that is added, aqueous hydrochloric acid, the leach liquor of acidleach for the second time, it is 0.01 mol/liter-0.6 mol liter that the amount of mixed solution a kind of solution wherein of the leach liquor of nitric acid or hydrochloric acid and acidleach for the second time makes the concentration of the free acid in the leach liquor of acidleach for the first time, carry out solid-liquid separation, the aqueous solution with nitric acid, aqueous solution of hydrochloric acid a kind of leaching liquid wherein as acidleach for the second time, under agitation solid phase is carried out the acidleach second time, in the acidleach process, add reductive agent simultaneously, the reduction dosage that is added is for becoming the quadrivalent cerium Restore All 0.7-4 times (the cerium amount is to contain the cerium amount in the ore) of trivalent cerium theoretical amount, the aqueous nitric acid that is added, aqueous hydrochloric acid wherein a kind of amount of solution to make the concentration of the free acid in the leach liquor of acidleach for the second time be 0.7 mol/liter-2.5 mol liter, isolate the leach liquor and the primary slag of acidleach for the second time after the filtration, the leach liquor of acidleach for the second time is used for acidleach for the first time, aqueous sodium hydroxide solution with 5%-40%, to carrying out alkali cleaning through the primary slag behind the secondary pickling, washing again is with the above-mentioned acidleach first time, the condition of acidleach is for the second time carried out acidleach for the first time and acidleach for the second time (leach liquor of second acidleach is used for acidleach for the first time) to the primary slag after the alkali cleaning washing.To be merged into the stock liquid of rare earth through the leach liquor of the leach liquor of the acidleach first time of the primary slag after alkali cleaning, the washing and the above-mentioned acidleach first time.The bastnasite aboundresources of China wherein contains RE phosphate hardly, and general bastnasite contains rare earth oxide 20-60%(weight percentage), used mineral are good with f_c_ce_la concentrate.Employed bastnasite is that its tap density of the bastnasite of Sichuan Province's Mianning is 3.03 gram/cubic centimetres through the bastnasite on ground such as the Sichuan Province of ore dressing Mianning in the technology of the present invention, and loose density is 2.3 gram/cubic centimetres, and its size-grade distribution is as follows:
Particle diameter (micron)〉720＜720＜216＜100＜61＜44
Accumulation % 4.4 95.6 60.5 28.4 10.1 9.5
Contain the 58.02%(weight percentage in the bastnasite, down together) rare earth oxide contains 29.46% cerium dioxide, contains 3.85% iron, contain 6.74% fluorine. consisting of of its ore middle-weight rare earths oxide compound, La2O3 is the 35.35%(weight percentage, down together), CeO2 is 50.08%, Pr6O11 is 4.03%, Nd2O3 is 10.09%, and Sm2O3 is 0.45%, and remaining rare earth oxide is all less than 0.10%.
The ore deposit alkali of bastnasite and alkali (yellow soda ash or sodium hydroxide) is than being 100/10-100/40.Ore deposit alkali ratio is lower than at 100/16 o'clock, and the rate of decomposition of concentrate is low.With the raising of alkali number in the ore deposit alkali ratio, its rate of decomposition increases gradually; Ore deposit alkali is than in the scope of 100/20-100/40, and little to the influence of rate of decomposition along with the increase of alkali number, used alkali is good with yellow soda ash. and the granularity of concentrate does not almost have any influence to its rate of decomposition.
The maturing temperature of the mixture after f_c_ce_la concentrate and yellow soda ash or sodium hydroxide mix is controlled between 500-800 ℃, and the 0.5-3 hour combustion time of roasting is in 500-750 ℃ temperature range.Along with the raising of maturing temperature, the increase of roasting time, its rate of decomposition increases thereupon; When roasting time one timing, its rate of decomposition improves with the raising of maturing temperature.Maturing temperature one timing, its rate of decomposition improves with the increase of roasting time.But, when selecting roasting condition, should consider to reduce the consumption of industrial chemicals as far as possible, guarantee that full technical process carries out smoothly.
Through the calcining matter of baked f_c_ce_la concentrate and yellow soda ash or sodium hydroxide, water washs it, fluorochemical and unreacted yellow soda ash that flush away can be water-soluble.Its method is in stirring down, adds entry (tap water, distilled water, ion exchanged water wherein a kind of), washs under 30-80 ℃ temperature, and temperature is lower than 30 ℃, and to wash fluorine efficient low, and the high more fluorine efficient of washing of temperature is high more.Stopping to stir and treat to carry out solid-liquid separation with dumping method or siphonage after the sedimentation, so carry out 1-8 time, is good with 3-6 time again.Till washing is 7-8 to the PH of its water lotion.The speed that stirs when washing with water is as the criterion to have stirred solid materials, and the speed of stirring is little to the washing effect influence.The water that is added during washing makes solid-to-liquid ratio be controlled at 1: 1.5-5, again with 1: 1-2 is for well, the concentrate amount of the amount of solid phase to be added.
Carry out pickling after the washing, the method of pickling is under the temperature of room temperature to 80 ℃, in stirring, add entry (tap water, a kind ofly in distilled water, the ion exchanged water) and nitric acid or hydrochloric acid, it is 4.5-6 that the amount of adding nitric acid or hydrochloric acid makes the pH value of last pickle solution, solid-to-liquid ratio during pickling is controlled at 1: 1.5-5, again with 1: 2-3 is good, the amount of solid phase is in the amount of the f_c_ce_la concentrate that added, when pickling, the speed that stirs also is to be as the criterion to have stirred solid materials, and the speed of stirring is little to the pickling effect influence.Stop to stir and treat to carry out solid-liquid separation with dumping method or siphonage after the solid materials sedimentation, the pH value of isolated liquid phase pickle solution is 4.5-6, carries out a pickling usually.
Carry out the acidleach first time after the pickling.Its method is, with leach liquor, nitric acid or the hydrochloric acid of the aqueous solution of nitric acid, aqueous solution of hydrochloric acid, acidleach for the second time and mixed solution a kind of leaching liquid wherein of the leach liquor of acidleach for the second time, under agitation solid phase is carried out the acidleach first time in 50-100 ℃ as the acidleach first time.In acidleach first time process, add reductive agent simultaneously, the amount of the reductive agent that is added for the 0.7-4 that the quadrivalent cerium Restore All become the trivalent cerium theoretical amount doubly, 1-2.5 with its theoretical amount doubly is advisable again, and it is 0.01 mol-0.6 mol/liter that leach liquor, nitric acid or the hydrochloric acid of the aqueous nitric acid that is added, aqueous hydrochloric acid, acidleach for the second time and the amount of mixed solution a kind of solution wherein of the leach liquor of acidleach for the second time make the concentration of free acid in the leach liquor of the acidleach first time.Again with 0.1 mol/liter-0.6 mol liter for well, the reductive agent that is added can be wherein a kind of of hydrogen peroxide, Sulfothiorine, S-WAT, sulfurous gas, Sodium Nitrite, water-soluble divalent iron salt, but is good to add hydrogen peroxide (hydrogen peroxide).Because corresponding impurity element is introduced in other affiliation that add of former dose, can produce adverse influence to later technology.Added hydrogen peroxide (hydrogen peroxide) can be that concentration is the hydrogen peroxide of 5-30%, again with 30% hydrogen peroxide for well.The amount of used hydrogen peroxide for the 0.7-4 that the quadrivalent cerium Restore All become the trivalent cerium theoretical amount doubly, the 1-2.5 with theoretical amount doubly is advisable again.The hydrogen peroxide add-on is The more the better, but make cost up, because except that the discrete bastnasite, the content of cerium dioxide is between 20-35% in most of bastnasites, can also be controlled at 20 kilograms of-110 kilograms/bastnasites per ton so add the amount of hydrogen peroxide, again be controlled at 60 kilograms-90 kilograms/whenever ram the loose soil with a stone-roller after sowing bastnasite for well, be that reductive agent is when carrying out first time acidleach with the hydrogen peroxide, the acidleach temperature generally is controlled at 50-100 ℃, the temperature of acidleach is high more, helps the leaching of rare earth element more.But hydrogen peroxide its decomposition reaction below 70 ℃ the time is very slow, surpasses 85 ℃ of its decomposition rates and accelerates, and is advisable so the temperature of acidleach for the first time and acidleach for the second time is controlled at 70-85 ℃.The stirring velocity of (acidleach for the first time and acidleach for the second time) is as the criterion to have stirred solid materials when acidleach, and its stirring velocity influences not quite the result of acidleach.The solid phase of (acidleach for the first time and acidleach for the second time) and the solid-to-liquid ratio of leaching liquid are controlled at 1 during acidleach: 1.5-4.5, again in 1: 2.0-3.0 is (the concentrate amount of the amount of solid phase to be added).The extraction time of (acidleach for the first time and acidleach for the second time) was controlled at 0.1-2 hour when acidleach, was advisable with 0.5-1.1 hour again.
When acidleach for the first time finishes, stop to stir treat the solid materials sedimentation after, carry out solid-liquid separation with dumping method or siphonage, the leach liquor of isolated liquid phase acidleach for the first time places container interior stand-by.
After carrying out the acidleach first time, carry out the acidleach second time.The aqueous solution, aqueous solution of hydrochloric acid a kind of leaching liquid as acidleach for the second time wherein with nitric acid under agitation carry out the acidleach second time to solid phase.In the acidleach process, add reductive agent simultaneously, the amount of the reductive agent that is added (for example hydrogen peroxide) for the 0.7-4 that the quadrivalent cerium Restore All become the trivalent cerium theoretical amount doubly, 1-2.5 in theoretical amount doubly is advisable again, and to make the concentration of the leach liquor free acid of acidleach for the second time be 0.7 mol-2.5 mol/liter for (cerium amount containing the cerium amount in the ore, down with) aqueous nitric acid that is added, the amount of aqueous hydrochloric acid.Be advisable with 0.7 mol/liter-2 mol/liter again.The reductive agent that is added can be wherein a kind of of hydrogen peroxide, Sulfothiorine, S-WAT, sulfurous gas, Sodium Nitrite, water-soluble divalent iron salt, but is good to add hydrogen peroxide as reductive agent.Added hydrogen peroxide can be that concentration is the hydrogen peroxide of 5-30%, and the hydrogen peroxide with 30% is for well.The amount of the hydrogen peroxide that is added for the 0.7-4 that the quadrivalent cerium Restore All become cerous theoretical amount doubly, the 1-2.5 with theoretical amount doubly is advisable again.Add hydrogen peroxide amount also can be controlled at 20 kilograms of-110 kilograms/bastnasites per ton, to be controlled at 60 kilograms of-90 kilograms/bastnasites per ton for well, the temperature of acidleach for the second time also can be controlled in 50-100 ℃, again to be controlled at 70-85 ℃ for good again.Its stirring velocity is as the criterion to have stirred solid materials, and its stirring velocity also influences not quite the result of the acidleach second time.The solid-to-liquid ratio of solid phase and leaching liquid is controlled at 1 during acidleach for the second time: 1.5-4.5, again in 1: 2.0-3.0 is (the concentrate amount of the amount of solid phase to be added).Extraction time also was controlled at 0.1-2 hour when secondary pickling, again with 0.5-1.1 hour for well.
After acidleach for the second time, filter, carry out 1-2 washing again for good.Filtering method has methods such as filter press technique, centrifuging, suction filtration, but is advisable with filter press technique.Filter back water (distilled water, ion exchanged water, tap water wherein a kind of) washing 1-2 time, obtain the leach liquor of the leach liquor of primary slag and the acidleach second time as the acidleach first time.
Because through behind the secondary pickling, filter and in the primary slag of water washing, still contain rare earth oxide about 2 percent, 30, so must be further processed to primary slag.At first primary slag is carried out alkali cleaning.So-called alkali cleaning is exactly under agitation, adds the sodium hydroxide solution of 5-40%, under 70-110 ℃ temperature, stirs 0.5-4.0 hour, filters, and washes again.General alkali cleaning is carried out once.The concentration of used sodium hydroxide solution is the 5-40%(weight percentage during alkali cleaning), the concentration of sodium hydroxide solution is lower than 5%, and the rate that washes out of fluorine and the rate of decomposition of ore are all low, along with the raising of naoh concentration.The rate that washes out of fluorine and the rate of decomposition in ore deposit improve thereupon.Concentration sodium hydroxide is high more good more, and the temperature of alkali cleaning is high more good more.When concentration sodium hydroxide greater than 20% the time, fluorine wash out rate and rate of decomposition all reaches more than 98%.So concentration sodium hydroxide is good with 20-30%.In the influence tabulation 1 of concentration sodium hydroxide to the rate that washes out of fluorine and ore resolution ratio.
Table 1 naoh concentration is to the influence of the rate of decomposition of the rate that washes out of fluorine and ore
The slag that slag in the acid leaching liquor heavily restrains slag content ore of washing of the fluorine of alkali contains
Concentration goes out rate % REO content REO% rate of decomposition % fluorine %
Gram/liter
5% 73.45 65.80 17.0 30.13 82.34 _
10% 80.21 68.45 16.5 28.93 83.54 _
15% 91.35 73.34 14.0 20.37 90.20 1.13
20% 98.48 80.21 10.5 0.74 99.32 0.67
25% 98.78 80.31 8.0 0.43 99.88 0.65
30% 99.00 80.33 8.0 0.21 99.94 0.58
REO represents rare earth oxide in the table 1.The experimental technique of obtained data is to get 50 gram f_c_ce_la concentrates through roasting, washing in the table 1, acidleach for the first time, and acidleach for the second time obtains primary slag.Under 100 ℃ temperature, stirred 3 hours again, carry out alkali cleaning after, carry out the acidleach first time with nitric acid, acidleach is for the second time filtered, and is washed with water to the PH-7 of washing water.Rare-earth oxidation substrate concentration in the table 1 in the acid leaching liquor is the concentration after the leach liquor of the leach liquor of acidleach for the first time and acidleach for the second time merges.The rate of washing out of fluorine comprises the cumulative amount of data such as concentrate processing.The leach liquor volume is 370 milliliters, and exhausted sodium hydroxide is recyclable during alkali cleaning recycles.Temperature is high more good more during alkali cleaning.The speed that stirs is as the criterion to have stirred solid materials.Its stirring velocity is little to the alkali cleaning effect influence.Under agitation the time of carrying out alkali cleaning with sodium hydroxide solution generally was controlled at 0.5-4.0 hour.The rate of decomposition of the amount of washing out of fluorine and ore improves along with the increase of alkali cleaning time, so the alkali cleaning time is controlled at 2-4 hour for good.The alkali cleaning time sees Table 2 to the rate that washes out of fluorine and the influence of ore resolution ratio.
The time of table 2 alkali cleaning is to the influence of the rate of decomposition of the rate that washes out of fluorine and ore
The slag in the acid leaching liquor washed of alkali cleaning time fluorine heavily restrains slag and includes ore
Hour go out rate % REO content REO% rate of decomposition
Gram/liter %
0.5 76.34 69.89 16.0 32.50 82.07
1.0 79.41 72.35 15.5 28.41 84.82
1.5 81.28 74.21 15.0 26.30 86.40
2.0 84.51 76.40 14.0 22.50 88.36
2.5 90.45 79.92 13.0 10.11 95.46
3.0 99.28 83.01 10.0 0.23 99.92
3.5 99.37 83.41 10.0 0.47 99.84
4.0 99.50 83.39 10.0 0.11 99.96
The experiment condition and the table 1 of table 2 are basic identical, and only different is that other conditions are constant, and the time of alkali cleaning changes.Solid-to-liquid ratio is the bigger the better when carrying out alkali cleaning.
After the alkali cleaning under agitation water wash, the temperature of washing is controlled at 30-95 ℃, the speed of stirring the same during with alkali cleaning is as the criterion to have stirred solid materials, solid-to-liquid ratio is the bigger the better, wash 3-10 time, be good with 4-6 time, the PH that makes water lotion is 7-8.
Primary slag after alkali cleaning, washing carries out the acidleach first time and acidleach for the second time (secondary acidleach leach liquor is used for acidleach for the first time) with the condition of the above-mentioned acidleach first time, acidleach for the second time to the primary slag after alkali cleaning, washing.Will be to the leach liquor of the acidleach first time of the primary slag after alkali cleaning, washing and the stock liquid of leach liquor merging the becoming rare earth of the above-mentioned acidleach first time.The acidity of the free acid in the rare earth raw material liquid is generally 0.01-0.6 mol/liter, again with 0.1-0.6 mol/liter for well.
The acidity of the free acid in the leach liquor of secondary pickling is measured with the neutralization titration that the those of ordinary skill under this area is all known.With Zn-EDTA or Ca-EDTA is sequestering agent, with the blue mixture indicator of methyl red-methyne, carries out titration with standard caustic soda solution.If weakly acid soln can be measured its pH value with the PH meter.
Our experiments show that, processing method of the present invention is applicable to the bastnasite that contains 20% rare earth oxide of each real estate fully, contains the bastnasite of 36.9% rare earth oxide, contains the bastnasite of 46.06% rare earth oxide, its rate of decomposition is all more than 99.9%, and rare earth yield is all more than 97%.
Resulting rare earth raw material liquid can be through the raw material of suitable purification as the promotor of the raw material of agricultural rare earth nitrate and other plant-growths that contain rare earth, add oxalic acid and generate the rare-earth oxalate precipitation, become rare earth oxide in 800 ℃ of calcinations again, also it can be concentrated and make rare earth chloride crystallization or rare earth nitrate crystallization, can be used as the raw material of extracting and separating single rare earth again.
The advantage of processing method of the present invention just is:
1. processing method suitability of the present invention is strong, be applicable to that the bastnasite that produces from various places produces rare earth raw material liquid, in the process of roasting decomposing ore, do not produce the obnoxious flavour that contains fluorochemical, avoided pollution, help operator's health environment.
2. compare with existing technology and reduced filtering number of times, shortened technical process, simplified operating process, reduced the consumption and the cost of industrial chemicals.Improve the rate of decomposition of bastnasite and the rate of recovery of rare earth, greatly reduced the quantity of slag.Slag middle-weight rare earths constituent content is little.
Since with nitric acid, salt acid substitution sulfuric acid as leaching liquid, the rare earth raw material liquid middle-weight rare earths concentration of gained is big; Owing to taked secondary pickling, with the leach liquor of the acidleach second time leaching liquid as the acidleach first time, reduced sour consumption, reduced the acidity in the rare earth raw material liquid, increase the concentration of rare earth raw material liquid middle-weight rare earths, be convenient to next step the purification and the carrying out of separating technology.
4. fluorine is washed out with the form of Sodium Fluoride, has improved the concentration that washes out of fluorine, is convenient to the recovery and the comprehensive utilization of fluorine.
With following embodiment processing method of the present invention is further described, will helps the understanding of the present invention and advantage thereof, and not as the qualification to protection domain of the present invention.Protection scope of the present invention is decided by claims.
Embodiment 1
F_c_ce_la concentrate 250 gram and the yellow soda ash that will contain 58.01% rare earth oxide, with ore deposit alkali than 100/20(weight ratio) mix, carried out roasting 1 hour in 650 ℃, under agitation with the fluorine of tap water in the calcining matter of 70 ℃ of washing ore deposits and yellow soda ash, solid-to-liquid ratio is 1: the concentrate amount of the amount of 2(solid phase to be added), washed 20 minutes at every turn, stop to stir and treat to carry out solid-liquid separation with the siphonage or the method for dumping after the sedimentation, so carry out 3 times, wash to the PH of water lotion be 7.5.The cumulative volume of water lotion is 1475 milliliters, wherein fluorine-containing 5.19 gram/liters.Washing back adds entry and drips 4 mol/liter under 80 ℃ aqueous nitric acid carries out the PH-5 that pickling makes last pickle solution, pickling 20 minutes, solid-to-liquid ratio during pickling is 1: the amount of 2.5(solid phase is in the amount of the bastnasite that added), pickling once, pickle solution is 480 milliliters, wherein contains 1.28 gram/liter rare earth oxides, 0.89 gram/liter calcium, 0.33 gram/liter magnesium, 5.79 gram/liter barium.
Carry out the acidleach first time after the pickling, its method is to use the leaching liquid of the leach liquor of the acidleach second time that contains free acid 1 mol/liter nitric acid of preparation already as the acidleach first time, under agitation the solid phase after separating is carried out the acidleach first time in 82 ℃, in acidleach first time process, add 30% hydrogen peroxide simultaneously, the amount that hydrogen peroxide added is for being reduced into quadrivalent cerium one times of three cerium theoretical amount, add the amount of the leach liquor of the acidleach second time that contains free acid 1 mol/liter nitric acid of preparation already, making the free acid in the leach liquor of acidleach for the first time is 0.1 mol/liter nitric acid.Solid-to-liquid ratio during acidleach for the first time is 1: the concentrate amount of the amount of 2.5(solid phase to be added), acidleach 1 hour, the volume of the leach liquor of acidleach is for the first time merged into 700 milliliters, wherein contain 173.7 gram/liter rare earth oxides, 0.96 gram/liter calcium, 0.24 gram/liter magnesium, 0.24 gram/liter barium, 0.19 gram/liter iron.
For the first time after the acidleach, stop to stir treat the solid materials sedimentation after, carry out solid-liquid separation with dumping method or siphonage, the leach liquor of the isolated liquid phase acidleach first time places in the container.
With the nitric acid of 9 mol/liter leaching liquid as the acidleach second time, under agitation solid phase is carried out the acidleach second time in 80 ℃, add 30% hydrogen peroxide in the acidleach process simultaneously, the amount that hydrogen peroxide added is for becoming the quadrivalent cerium Restore All 1 times of trivalent cerium theoretical amount.The amount that adds the nitric acid of 9 mol/liter, making the concentration of free acid of the leach liquor of acidleach for the second time is 1 mol/liter.The solid-to-liquid ratio of solid phase and leaching liquid is 1 during acidleach for the second time: the concentrate amount of the amount of 2.0(solid phase to be added), the extraction time of acidleach for the second time is 0.5 hour, the volume of the leach liquor of acidleach is for the second time merged into 200 milliliters, wherein contain 145.5 gram/liter rare earth oxides, 0.14 gram/liter calcium, 0.21 gram/liter magnesium, 0.51 gram/liter barium.
Get the back through acidleach for the second time and filter, wash secondary with water, obtain the leach liquor of primary slag and acidleach for the second time with press filtration.
Primary slag is carried out an alkali cleaning, and alkali cleaning is exactly the solution that under agitation adds 30% sodium hydroxide, stirs 3 hours in 101 ℃, filters, and water washs again, and the temperature of washing is 90 ℃, washes 6 times, and the PH that makes water lotion is 7.5.
Through alkali cleaning, primary slag after the washing is with the condition of the above-mentioned acidleach first time and the acidleach for the second time of present embodiment, and to through alkali cleaning, the primary slag after the washing carries out acidleach first time and the acidleach second time.Will be through the leach liquor of the acidleach first time of the primary slag after the alkali cleaning washing stock liquid with leach liquor merging the becoming rare earth of the above-mentioned acidleach first time, acidity is 0.1 mol/liter nitric acid.Slag weighs 36.0 grams, and slag rate 14.4% contains rare earth oxide 0.17% in the slag, and the rate of recovery of ore resolution ratio 99.96% rate rare earth is 97.5%.
Embodiment 2
Its operation is substantially with embodiment 1, and only different is that ore deposit alkali is than 100/30(weight ratio), carried out roasting 0.7 hour in 750 ℃, with tap water wash to PH be 7.2, the cumulative volume of water lotion is 1475 milliliters, wherein fluorine-containing 5.88 gram/liters, the PH of the pickle solution of pickling is 6, pickle solution is 480 milliliters, wherein contains 0.86 gram/liter rare earth oxide, 0.87 gram/liter calcium, 0.20 gram/liter magnesium, 5.60 gram/liter barium.
Carry out the acidleach first time after the pickling, the acidleach temperature is 75 ℃, the amount that hydrogen peroxide added is for being reduced into quadrivalent cerium 1.5 times of trivalent cerium theoretical amount, add the leach liquor that contains the acidleach second time of free acid 1 mol/liter nitric acid among the embodiment 1, making the free acid in the leach liquor of acidleach for the first time is 0.2 mol/liter nitric acid.Solid-to-liquid ratio is 1: the concentrate amount of the amount of 2.5(solid phase to be added), acidleach 0.7 hour, the volume of the leach liquor of acidleach for the first time is 700 milliliters, wherein contain 172.4 gram/liter rare earth oxides, 1.02 gram/liter calcium, 0.18 gram/liter magnesium, 0.29 gram/liter barium, 0.34 gram/liter iron.
After the acidleach for the first time, with 10 mol/liter nitric acid is the leaching liquid of acidleach for the second time, under agitation solid phase is carried out the acidleach second time in 75 ℃, add 30% hydrogen peroxide simultaneously in the acidleach process, the amount that hydrogen peroxide added is for becoming the quadrivalent cerium Restore All 1.5 times of trivalent cerium theoretical amount.The amount that adds the nitric acid of 10 mol/liter, making the concentration of free acid of the leach liquor of acidleach for the second time is 2 mol/liter.Solid-to-liquid ratio is 1: the concentrate amount of the amount of 2.0(solid phase to be added), the extraction time of acidleach is 1 hour, and the volume of the leach liquor of acidleach is for the second time merged into 200 milliliters, wherein contain 148.6 gram/liter rare earth oxides, 0.21 gram/liter calcium, 0.66 gram/liter magnesium, 0.34 gram/liter barium.
Primary slag is carried out an alkali cleaning, and alkali cleaning is with 20% aqueous sodium hydroxide solution, stirs 2.5 hours in 90 ℃, and water washs again, and the temperature of washing is 95 ℃, washes 4 times, and the PH that makes water lotion is 8.0.
Through alkali cleaning, primary slag after the washing above-mentioned acidleach first time of present embodiment and the condition of second acidleach, primary slag after alkali cleaning, washing is carried out the acidleach first time, acidleach for the second time, the acidity of the stock liquid of rare earth is 0.2 mol/liter nitric acid, slag weighs 36.0 grams, and slag rate 14.4% contains rare earth oxide 0.14% in the slag, ore resolution ratio 100%, the rate of recovery of rare earth are 99%.
Embodiment 3
Its operation is substantially with embodiment 1, only different is that ore deposit alkali is than 100/16(weight ratio), in 550 in ℃ carrying out roasting 3 hours, wash to PH7 with tap water, the cumulative volume of water lotion is 1475 milliliters, wherein fluorine-containing 5.89 gram/liters, the PH of the pickle solution of pickling are 5.5, and the pickling volume is 480 milliliters, wherein contain 0.84 gram/liter rare earth oxide, 0.88 gram/liter calcium, 0.21 gram/liter magnesium, 5.64 gram/liter barium.
Carry out the acidleach first time after the pickling, 70 ℃ of acidleach temperature, the amount that hydrogen peroxide added is for being reduced into quadrivalent cerium 3.0 times of trivalent cerium theoretical amount, the mixed solution that adds the aqueous nitric acid of the leach liquor of the acidleach second time that contains free acid 2 mol/liter nitric acid among the embodiment 2 and 7 mol/liter, making the free acid in the leach liquor of acidleach for the first time is 0.4 mol/liter nitric acid, solid-to-liquid ratio during acidleach for the first time is 1: the concentrate amount of the amount of 2.5(solid phase to be added), acidleach 2 hours, the volume of the leach liquor of acidleach is for the first time merged into 700 milliliters, wherein contain 177 gram/liter rare earth oxides, 1.24 gram/liter calcium, 0.38 gram/liter magnesium, 0.49 gram/liter barium, 0.15 gram/liter iron.
After the acidleach for the first time, with concentrated nitric acid is the leaching liquid of acidleach for the second time, under agitation solid phase is carried out the acidleach second time in 70 ℃, add 30% hydrogen peroxide in the acidleach process, the amount that hydrogen peroxide added is for becoming the quadrivalent cerium Restore All 3.0 times of trivalent cerium theoretical amount.The amount that adds concentrated nitric acid, making the concentration of free acid of the leach liquor of acidleach for the second time is 2.5 mol/liter.Solid-to-liquid ratio is 1: the concentrate amount of the amount of 2.0(solid phase to be added), the extraction time of acidleach is 0.6 hour, and the volume of the leach liquor of acidleach is for the second time merged into 200 milliliters, wherein contains 138 gram/liter rare earth oxides, 0.17 gram/liter calcium, 0.64 gram/liter magnesium.
Primary slag is carried out an alkali cleaning, and alkali cleaning is with 20% aqueous sodium hydroxide solution, stirs 2.5 hours in 90 ℃, and water washs again, and the temperature of washing is 95 ℃, washes 5 times, and the PH that makes water lotion is 7.
Through alkali cleaning, primary slag after the washing condition of the above-mentioned acidleach first time of present embodiment and acidleach for the second time, primary slag after alkali cleaning, washing is carried out the acidleach first time, acidleach for the second time, the acidity of the stock liquid of rare earth is 0.4 mol/liter nitric acid, slag weighs 32 grams, and slag rate 12.8% contains rare earth oxide 0.12% in the slag, ore resolution ratio 100%, the rate of recovery of rare earth are 98.5%.
Embodiment 4
Its operation is substantially with embodiment 1, and only different is that ore deposit alkali is than 100/25(weight ratio), in 750 ℃, carried out roasting 0.7 hour, wash to PH-7 with tap water, the cumulative volume of water lotion is 1475 milliliters, wherein fluorine-containing 5.83 gram/liters, the PH of the pickle solution of pickling is 6, the pickling volume is 480 milliliters, wherein contains 0.89 gram/liter rare earth oxide, 0.86 gram/liter calcium, 0.22 gram/liter magnesium, 5.65 gram/liter barium.
Carry out the acidleach first time after the pickling, 80 ℃ of acidleach temperature, the amount that hydrogen peroxide added is for being reduced into quadrivalent cerium 1.1 times of trivalent cerium theoretical amount, add the leach liquor that contains the acidleach second time of free acid 2.5 mol/liter nitric acid among the embodiment 3, making the free acid in the leach liquor of acidleach for the first time is 0.3 mol/liter nitric acid, solid-to-liquid ratio during acidleach for the first time is 1: the concentrate amount of the amount of 2.5(solid phase to be added), acidleach 1.5 hours, the volume of the leach liquor of acidleach is for the first time merged into 700 milliliters, wherein contain 170.0 gram/liter rare earth oxides, 0.68 gram/liter calcium, 0.59 gram/liter magnesium, 0.54 gram/liter barium, 0.13 gram/liter iron.
After the acidleach for the first time, with 10 mol/liter nitric acid is the leaching liquid of acidleach for the second time, under agitation solid phase is carried out the acidleach second time in 80 ℃, add 30% hydrogen peroxide in the acidleach process, the amount that hydrogen peroxide added is for becoming the quadrivalent cerium Restore All 1.1 times of trivalent cerium theoretical amount.The amount that adds 10 mol/liter nitric acid, making the leach liquor of acidleach for the second time is 0.8 mol/liter.Solid-to-liquid ratio is 1: the concentrate amount of the amount of 2.0(solid phase to be added), the extraction time of acidleach is 1.1 hours, the volume of the leach liquor of acidleach is for the second time merged into 200 milliliters, wherein contain 161.2 gram/liter rare earth oxides, 0.16 gram/liter calcium, 0.47 gram/liter magnesium, 0.09 gram/liter barium.
Primary slag is carried out an alkali cleaning, and alkali cleaning is with 23% aqueous sodium hydroxide solution, stirs 2.5 hours in 93 ℃, and water washs again, and the temperature of washing is 89 ℃, washes 6 times, and the PH that makes water lotion is 7.
Through alkali cleaning, primary slag after the washing above-mentioned acidleach first time of present embodiment and the condition of second acidleach, primary slag after alkali cleaning, washing is carried out the acidleach first time, acidleach for the second time, the acidity of the stock liquid of rare earth is 0.3 mol/liter nitric acid, slag weighs 31.0 grams, and slag rate 12.4% contains rare earth oxide 0.23% in the slag, ore resolution ratio 100%, the rate of recovery of rare earth are 97%.
Embodiment 5
Its working method and condition are substantially the same manner as Example 1, only different is to contain rare earth oxide 46.06%200 grams in the ore, the merging volume of the leach liquor of acidleach for the first time is 400 milliliters, wherein contain 185.8 gram/liter rare earth oxides, 0.99 gram/liter calcium, 0.12 gram/liter magnesium, 1.35 gram/liter barium, 0.53 gram/liter iron, the volume of the leach liquor of acidleach is for the second time merged into 200 milliliters, wherein contains 106.5 gram/liter rare earth oxides, 0.40 gram/liter calcium, 0.25 gram/liter magnesium, barium trace, 0.43 gram/liter iron, slag weighs 31.5 grams, contain rare earth oxide 0.34% in the slag, ore resolution ratio 99.9%, the rate of recovery of rare earth is 97.7%.
Embodiment 6
Its working method and condition are substantially the same manner as Example 1, only different has been with salt acid substitution nitric acid, the merging volume of the leach liquor of acidleach for the first time is 900 milliliters, wherein contain 176.9 gram/liter rare earth oxides, 1.3 gram/liter calcium, 0.85 gram/liter magnesium, 11.7 gram/liter barium, 8.7 gram/liter iron, the volume of the leach liquor of acidleach is for the second time merged into 300 milliliters, wherein contains 144.2 gram/liter rare earth oxides, 0.8 gram/liter calcium, 0.33 gram/liter magnesium, 5.9 gram/liter barium, 5.9 gram/liter iron, slag rate 12.6%, contain rare earth oxide 0.57% in the slag, rare earth ore rate of decomposition 99.9%, the rate of recovery of rare earth are 98.3%.
Claims (13)
1, a kind of processing method of from bastnasite, producing rare earth raw material liquid, with bastnasite and yellow soda ash or sodium hydroxide, mix with suitable weight ratio, roasting, wash the calcining matter of ore deposit and yellow soda ash or sodium hydroxide with water, under agitation carry out pickling, solid-liquid separation after the washing with nitric acid or aqueous solution of hydrochloric acid, it is characterized in that
(1) aqueous solution of usefulness nitric acid, aqueous solution of hydrochloric acid, the leach liquor of acidleach for the second time, the mixed solution of the leach liquor of nitric acid or hydrochloric acid and acidleach for the second time a kind of leaching liquid wherein as acidleach for the first time, under agitation solid phase is carried out the acidleach first time, add reductive agent in the acidleach process, doubly (the cerium amount is to contain the cerium amount in the ore for the 0.7-4 that the quadrivalent cerium Restore All become the trivalent cerium theoretical amount for the amount of the reductive agent that is added, down together), the aqueous nitric acid that is added, aqueous hydrochloric acid, the leach liquor of acidleach for the second time, the mixed solution of the leach liquor of nitric acid or hydrochloric acid and acidleach for the second time is a kind of amount of solution wherein, making the concentration of free acid in the leach liquor of acidleach for the first time is 0.01 mol/liter-0.6 mol liter, carry out solid-liquid separation
(2) aqueous solution of usefulness nitric acid, aqueous solution of hydrochloric acid a kind of leaching liquid wherein as acidleach for the second time, under agitation solid phase is carried out the acidleach second time, add reductive agent in the acidleach process, the amount of the reductive agent that is added for the 0.7-4 that the quadrivalent cerium Restore All become the trivalent cerium theoretical amount doubly, the aqueous nitric acid that is added, the amount of aqueous hydrochloric acid, making the concentration of the free acid in the leach liquor of acidleach for the second time is 0.7 mol/liter-2.5 mol/liter, isolate the leach liquor and the primary slag of acidleach for the second time after the filtration, the leach liquor of acidleach for the second time is used for acidleach for the first time
(3) with the aqueous solution of the sodium hydroxide of 5-40%, to carrying out alkali cleaning through the primary slag behind the secondary pickling, washing again
(4) with the condition of the above-mentioned acidleach first time, acidleach for the second time the primary slag after alkali cleaning, washing is carried out the acidleach first time and acidleach for the second time, the leach liquor of acidleach for the second time is used for acidleach for the first time.
(5) will be through the leach liquor merging of leach liquor and the above-mentioned acidleach first time of the acidleach first time of the primary slag after alkali cleaning, the washing.
2, produce the processing method of rare earth raw material liquid according to a kind of of claim 1 from bastnasite, it is characterized in that the reductive agent that is added is a hydrogen peroxide.
3, produce the processing method of rare earth raw material liquid according to a kind of of claim 2 from bastnasite, it is characterized in that the concentration of hydrogen peroxide is the 5-30%(weight percentage).
4, produce the processing method of rare earth raw material liquid according to a kind of of claim 1 from bastnasite, it is characterized in that, when acidleach for the first time, acidleach for the second time, the temperature of acidleach is 50-100 ℃.
5, produce the processing method of rare earth raw material liquid according to a kind of of claim 4 from bastnasite, it is characterized in that, the temperature of acidleach for the first time, acidleach for the second time is 70-85 ℃.
6, produce the processing method of rare earth raw material liquid according to a kind of of claim 4 from bastnasite, it is characterized in that the solid-to-liquid ratio of solid phase and leaching liquid is 1 during acidleach: 1.5-4.5.
7, produce the processing method of rare earth raw material liquid according to a kind of of claim 6 from bastnasite, it is characterized in that solid-to-liquid ratio is 1: 2.0-3.0.
8, produce the processing method of rare earth raw material liquid according to a kind of of claim 1 from bastnasite, it is characterized in that, the concentration of the free acid of the leach liquor of acidleach for the first time is 0.1 mol-0.6 mol/liter.
9, produce the processing method of rare earth raw material liquid according to a kind of of claim 1 from bastnasite, it is characterized in that, the concentration of the free acid of the leach liquor of acidleach for the second time is 0.7 mol/liter-2 mol/liter.
10, produce the processing method of rare earth raw material liquid according to a kind of of claim 1 from bastnasite, it is characterized in that,, carry out 1-2 washing through acidleach second time after-filtration.
11, produce the processing method of rare earth raw material liquid according to a kind of of claim 1 from bastnasite, it is characterized in that concentration sodium hydroxide is 20-30% during alkali cleaning.
12, produce the processing method of rare earth raw material liquid according to a kind of of claim 1 or 11 from bastnasite, it is characterized in that the temperature during alkali cleaning is 70-110 ℃, stirred 0.5-4 hour.
13, produce the processing method of rare earth raw material liquid according to a kind of of claim 2 from bastnasite, it is characterized in that, the amount of the hydrogen peroxide of the reductive agent that is added for the 1-2.5 that the quadrivalent cerium Restore All become the trivalent cerium theoretical amount doubly.
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| CN93114910A CN1034743C (en) | 1993-11-26 | 1993-11-26 | Making rare-earth material liquid from bastnae site |
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