CN1034744C - Method of extracting cerium-rich solution - Google Patents
Method of extracting cerium-rich solution Download PDFInfo
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- CN1034744C CN1034744C CN93120629A CN93120629A CN1034744C CN 1034744 C CN1034744 C CN 1034744C CN 93120629 A CN93120629 A CN 93120629A CN 93120629 A CN93120629 A CN 93120629A CN 1034744 C CN1034744 C CN 1034744C
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Abstract
The present invention relates to a method for extracting cerium-rich solution. Raw material is leached by acid primarily and secondarily to obtain lanthanum-rich leach solution of the primary acid leaching, leach solution of the secondary acid leaching and primary slag, and the leach solution of the secondary acid leaching is used as leaching solution for the primary acid leaching. The primary slag is leached by acid twice in the presence of reducing agents to obtain cerium-rich leach solution of the primary acid leaching in the presence of reducing agents, and leach solution of the secondary acid leaching in the presence of reducing agents is used as leaching solution of the primary acid leaching in the presence of reducing agents. The method has the advantages of strong adaptability, no environmental pollution, high recovery rates of cerium and rare earth, and small slag quantity and can be used for preparing two product solutions of rare earth.
Description
The present invention relates to a kind of hydrometallurgy and produce the method for cerium-rich solution.
At present, the separating and extracting method of cerium is a lot, all is based on quadrivalent cerium and the difference of other rare earth elements on chemical property, and cerium is separated with it.The processing method of extracting cerium mainly is divided into two kinds: a kind of is solvent extration, and another kind is a chemical precipitation method.
Reported a kind of preparation method of cerium oxide among the Chinese patent literature CN1060828 (application number 91110578.6), this processing method is that the trivalent cerium in the mishmetal all is oxidized to quadrivalent cerium, make mishmetal with sulfuric acid dissolution then, to concentration 90～130 grams per liter rare earth oxides (REO), in the mishmetal sulfuric acid liquid of acidity 0.5～1.2 mol, disposable adding sodium sulfate, its add-on is expressed as relational expression: REO: Na among the ∑ feed liquid A
2SO
4=1: 1～2, stirring reaction is 1～2 hour under 70 ℃～90 ℃ conditions, and reaction generates few cerium RE
3+Double salt precipitation C, filter immediately after reaction finishes, liquor B is Ce
4+Complex solution, in liquor B, add ferrous sulfate, its add-on is expressed as relational expression: Ce in the liquor B
4+: FeSO
4=1: 1～1.8, stirring reaction is 0.5～1 hour under 60 ℃～90 ℃ conditions, and reaction generates cerous sulfate sodium double salt precipitation, filters then, precipitation after the filtration is through reacting with caustic soda, change into cerous hydroxide, dissolving with hydrochloric acid becomes Cerium II Chloride then, adds oxalate precipitation again, oxalate precipitation after the filtration becomes cerium oxide 800 ℃ of calcinations, purity is 99.0～99.5%, direct yield 〉=90%, few cerium RE
3+Double salt precipitation C through 50 ℃ of hot water agitator treatings 0.5 hour, washing lotion is sent back to liquor B and is mixed, deposit C after the washing and caustic soda reaction change into oxyhydroxide, washing oxyhydroxide is to PH=7, filter, use dissolving with hydrochloric acid, the solution after the filtration is prepared into few cerium rare earth chloride crystalline product through concentrating, be precipitated as rich cerium rare earth hydrate, it be dissolved in the sulfuric acid then mix with feed liquid A.The advantage of this technical process is that resulting cerium oxide product purity is higher.But, needing repeatedly sedimentation and filtration, technical process is long, and complexity needs mass consumption industrial chemicals and water, electricity, and product cost is increased greatly.
Purpose of the present invention just is to work out a kind of new processing method of producing cerium oxide purity greater than 95% rich cerium product solution, make processing method technical process of the present invention simple, avoid multiple times of filtration to make the transition, significantly reduce the consumption of chemical raw material, facility investment is reduced greatly, the cost of product is reduced.
A kind of processing method of producing cerium-rich solution of the present invention, with bastnasite and yellow soda ash or the weight ratio uniform mixing of sodium hydroxide to suit, through roasting, washing, pickling, solid phase calcining matter after the solid-liquid separation, secondary slag after the alkali cleaning washing, above-mentioned solid phase calcining matter and through alkali cleaning, wherein a kind of of the mixture of the secondary slag after the washing is raw material, the aqueous solution with nitric acid, aqueous solution of hydrochloric acid, the leach liquor of acidleach for the second time, mixed solution a kind of solution wherein of the leach liquor of nitric acid or hydrochloric acid and acidleach for the second time is as the leaching liquid of the acidleach first time, under agitation raw material is carried out the acidleach first time, the aqueous nitric acid that is added, aqueous hydrochloric acid, the leach liquor of acidleach for the second time, 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, making the concentration of the free acid in the leach liquor of acidleach for the first time is 0.01 mol～0.6 mol, carries out solid-liquid separation; The aqueous solution with nitric acid, aqueous solution of hydrochloric acid a kind of solution wherein is as the leaching liquid of the acidleach second time, under agitation the raw material through acidleach is for the first time carried out the acidleach second time, the aqueous nitric acid that is added, the amount of aqueous hydrochloric acid, making the concentration of free acid in the leach liquor of acidleach for the second time is 0.7 mol～2.5 mol, after the filtration, isolate the leach liquor and the primary slag of acidleach for the second time, the leach liquor of acidleach for the second time is used for acidleach for the first time, the leach liquor of acidleach for the first time is a lanthanum rich rare earth solution, the aqueous solution with nitric acid, aqueous solution of hydrochloric acid, the leach liquor that acidleach under the reductive agent existence is arranged for the second time, nitric acid or hydrochloric acid and have for the second time reductive agent to exist mixed solution a kind of solution wherein of leach liquor of acidleach down as the leaching liquid that the acidleach under the reductive agent existence is arranged for the first time, under agitation primary slag is carried out having for the first time the acidleach of reductive agent under existing, in the acidleach process, add reductive agent simultaneously, (the cerium amount is to contain the cerium amount in the ore in order the quadrivalent cerium Restore All is become 0.7～4 times of trivalent cerium theoretical amount for the amount of the reductive agent that is added, contain in the ore and contain cerium amount meter in cerium amount and/or the secondary slag, down together), the aqueous nitric acid that is added, aqueous hydrochloric acid, the leach liquor that acidleach under the reductive agent existence is arranged for the second time, nitric acid or hydrochloric acid and the amount of mixed solution a kind of solution wherein of the leach liquor of the acidleach of reductive agent under existing is arranged for the second time, making the concentration of free acid in the leach liquor that the acidleach under the reductive agent existence is arranged for the first time is 0.01 mol～0.6 mol, carries out solid-liquid separation; The aqueous solution with nitric acid, wherein a kind of solution of aqueous solution of hydrochloric acid is as the leaching liquid that the acidleach under the reductive agent existence is arranged for the second time, under agitation primary slag is carried out having for the second time the acidleach of reductive agent under existing, add reductive agent in the acidleach process, add reductive agent amount (the cerium amount is to contain the cerium amount in the ore in order quadrivalent cerium is reduced into 0.7～4 times of trivalent cerium theoretical amount, contain in the ore and contain cerium amount meter in cerium amount and/or the secondary slag, down together), the aqueous nitric acid that is added, aqueous hydrochloric acid wherein a kind of amount of solution to make the concentration of free acid in the leach liquor that the acidleach of reductive agent under existing arranged for the second time be 0.7 mol～2.5 mol, isolate leach liquor and secondary slag that the acidleach under the reductive agent existence is arranged for the second time after the filtration, have for the second time reductive agent to exist the leach liquor of acidleach down to be used for having for the first time reductive agent to have acidleach down, it is cerium-rich solution product liquid that the leach liquor of the acidleach under the reductive agent existence is arranged the first time.
Operational conditions such as the method for used bastnasite, ore deposit alkali ratio, maturing temperature, roasting time, washing, the pickling of bastnasite and yellow soda ash or sodium hydroxide when roasting and condition are on November 26th, 1993 with the application number 93114910.X applying date fully, invention and created name be " producing rare earth raw material liquid " from bastnasite narrated identical.
Bastnasite and yellow soda ash or sodium hydroxide with suitable weight ratio uniform mixing after, and through roasting, washing, pickling, solid phase calcining matter after the solid-liquid separation, secondary slag after the alkali cleaning washing, above-mentioned solid phase calcining matter and through alkali cleaning, the mixture of the secondary slag after the washing is wherein a kind of to be raw material, the aqueous solution with nitric acid, aqueous solution of hydrochloric acid, the leach liquor of acidleach for the second time, mixed solution a kind of solution wherein of the leach liquor of nitric acid or hydrochloric acid and acidleach for the second time is as the leaching liquid of the acidleach first time, under agitation raw material is carried out the acidleach first time in 50～100 ℃, the aqueous nitric acid that is added, aqueous hydrochloric acid, the leach liquor of acidleach for the second time, 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, making the concentration of free acid in the leach liquor of acidleach for the first time is 0.01 mol～0.6 mol, again with 0.1 mol～0.6 mol for well.When carrying out the acidleach first time, acidleach for the second time, the acidleach temperature generally is controlled at 50～100 ℃, and the temperature of acidleach is high more, helps the leaching of rare earth element more, is advisable but the temperature of acidleach for the first time and acidleach for the second time is controlled at 70～95 ℃.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, 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: 1.5～4.5 (grams per milliliters) during acidleach, are (amount of solid phase is with the ore deposit amount that is added, the ore deposit amount that is added and/or the amount of secondary slag) in 1: 2～3 (grams per milliliters) again.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 decantation or siphonage, the leach liquor of isolated liquid phase acidleach for the first time is a lanthanum rich rare earth solution, places in the container as a kind of lanthanum rich rare earth product solution.
After carrying out the acidleach first time, carry out the acidleach second time, with the aqueous solution of nitric acid, aqueous solution of hydrochloric acid a kind of solution wherein leaching liquid as the acidleach second time, under agitation 50～100 ℃ are carried out the acidleach second time to raw material, it is 0.7 mol～2.5 mol that the aqueous nitric acid that is added, the amount of aqueous hydrochloric acid make the concentration of free acid in the leach liquor of acidleach for the second time, be advisable with 0.7 mol～2.0 mol again, when carrying out second time acidleach, temperature is controlled at 50～100 ℃, again to be controlled at 70～95 ℃ for good.Stirring velocity during acidleach for the second time 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: 1.5～4.5 (grams per milliliters) during acidleach for the second time, be (amount of solid phase is with the ore deposit amount that is added, the ore deposit amount and/or the secondary quantity of slag that are added) in 1: 2.0～3.0 (grams per milliliters) again, extraction time also was controlled at 0.1～2 hour during acidleach for the second time, again with 0.5～1.1 hour for well.
After the acidleach second time, filter, carry out 1～2 washing again for good.Filtering method has methods such as filter press technique, centrifuging, suction filtration, but suction filtration is advisable.Filter back water (distilled water, ion exchanged water, tap water wherein a kind of) washing 1～2 time, obtain the leaching liquid of the leach liquor of primary slag and acidleach for the second time as the acidleach first time.
The aqueous solution with nitric acid, aqueous solution of hydrochloric acid, the leach liquor that acidleach under the reductive agent existence is arranged for the second time, nitric acid or hydrochloric acid and have for the second time reductive agent to exist mixed solution a kind of solution wherein of leach liquor of acidleach down as the leaching liquid that the acidleach under the reductive agent existence is arranged for the first time, under agitation primary slag carried out have for the first time the acidleach of reductive agent under existing in 50～100 ℃, in the process of acidleach, add reductive agent simultaneously, the amount of the reductive agent that is added is for becoming the quadrivalent cerium Restore All 0.7～4 times of trivalent cerium theoretical amount, be advisable with 1～2.5 times of its theoretical amount again, the aqueous nitric acid that is added, aqueous hydrochloric acid, the leach liquor that acidleach under the reductive agent existence is arranged for the second time, nitric acid or hydrochloric acid and to have for the second time reductive agent to exist the amount of mixed solution a kind of solution wherein of the leach liquor of acidleach down to make the concentration of free acid in the leach liquor that the acidleach under the reductive agent existence is arranged for the first time be 0.01 mol～0.6 mol, again with 0.1 mol～0.6 mol 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 the affiliation that adds of other reductive agents, later technology is produced adverse influence.The hydrogen peroxide that is added (hydrogen peroxide) can be that concentration is the hydrogen peroxide of 5～30% (weight percentage), again with 30% hydrogen peroxide for well, the amount of used hydrogen peroxide is for becoming the quadrivalent cerium Restore All 0.7～4 times of trivalent cerium theoretical amount, is advisable with 1～2.5 times of theoretical amount again.The hydrogen peroxide add-on is The more the better, but product cost is increased.Because except that the discrete bastnasite, the content of cerium dioxide is between 20～35% in most of bastnasites, also can be controlled at 20 kilograms～110 kilograms/bastnasite per ton so add the amount of hydrogen peroxide, again to be controlled at 60 kilograms～90 kilograms/bastnasite per ton for well.Be reductive agent when carrying out having for the first time the acidleach of reductive agent under existing with the hydrogen peroxide, the acidleach temperature generally is controlled at 50～100 ℃, the high more leaching that helps rare earth element more of the temperature of acidleach.But hydrogen peroxide is below 70 ℃ the time, and its decomposition reaction is slow, surpasses 85 ℃ of its decomposition rates and accelerates, and is advisable so have reductive agent to have acidleach down for the first time and have the temperature of the acidleach under the reductive agent existence to be controlled at 70～85 ℃ for the second time.The stirring velocity that (acidleach and the acidleach that has for the second time in the presence of the reductive agent in the presence of the reductive agent is arranged) for the first time when acidleach is as the criterion to have stirred solid materials, its stirring velocity influences not quite the result of acidleach, the solid-to-liquid ratio of solid phase and leaching liquid is 1: 1.5～4.5 (grams per milliliters) when having for the first time reductive agent to have acidleach down, be (the ore deposit amount of the amount of solid phase with 1: 2.0～3.0 (grams per milliliters) again to be added, the ore deposit amount and/or the secondary quantity of slag meter that are added), the extraction time that (acidleach and the acidleach that has for the second time under the reductive agent existence under the reductive agent existence is arranged) for the first time during acidleach was controlled at 0.1～2 hour, was advisable with 0.5～1.1 hour again.
When the acidleach that has for the first time reductive agent to exist finishes, stop to stir treat the solid materials sedimentation after, carry out solid-liquid separation with decantation or siphonage, it is the product liquid of cerium-rich solution that isolating liquid phase has the leach liquor of the acidleach of reductive agent under existing for the first time.
After carrying out having for the first time the acidleach under the reductive agent existence, carry out having for the second time the acidleach under the reductive agent existence.The aqueous solution with nitric acid, aqueous solution of hydrochloric acid a kind of solution wherein is as the leaching liquid that the acidleach under the reductive agent existence is arranged for the second time, under agitation to through there being for the first time reductive agent to exist sour impregnated primary slag down to carry out having for the second time the acidleach of reductive agent under existing, in the acidleach process, add reductive agent simultaneously, the amount of the reductive agent that is added is for becoming the quadrivalent cerium Restore All 0.7～4 times of trivalent cerium theoretical amount, being advisable with 1～2.5 times of theoretical amount again, (the cerium amount is to contain the cerium amount in the ore, contain in the ore and contain cerium amount meter in cerium amount and/or the secondary slag), the aqueous nitric acid that is added, it is 0.7 mol～2.5 mol that the amount of aqueous hydrochloric acid a kind of solution wherein makes the concentration of the free acid in the leach liquor that the acidleach under the reductive agent existence is arranged for the second time, is advisable with 0.7 mol～2 mol 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.The hydrogen peroxide that is added can be that concentration is the hydrogen peroxide of 5～30% (weight percentage), hydrogen peroxide with 30% is for well, the amount of the hydrogen peroxide that is added is for becoming the quadrivalent cerium Restore All 0.7～4 times of cerous theoretical amount, is advisable with 1～2.5 times of theoretical amount again.The amount of the hydrogen peroxide that is added also can be controlled at 20 kilograms～110 kilograms/bastnasite per ton, again to be controlled at 60 kilograms～90 kilograms/bastnasite per ton for well.Have for the second time the acidleach temperature under the reductive agent existence also to be controlled at 50～100 ℃, to be controlled at 70～85 ℃ for good, its stirring velocity is as the criterion to have stirred solid materials again, and its stirring velocity also influences not quite the result that the acidleach under the reductive agent existence is arranged for the second time.When the acidleach under the reductive agent existence is arranged for the second time, the solid-to-liquid ratio of solid phase and leaching liquid is controlled at 1: 1.5～4.5 (grams per milliliters), is (amount of solid phase is with the ore deposit amount that is added, the ore deposit amount and/or the secondary quantity of slag that are added) in 1: 2.0～3.0 (grams per milliliters) again.When the acidleach that for the second time has in the presence of the reductive agent, extraction time also was controlled at 0.1～2 hour, again with 0.5～1.1 hour for well.Isolate leach liquor and secondary slag that the acidleach under the reductive agent existence is arranged for the second time after the filtration, have for the second time reductive agent to exist the leach liquor of acidleach down to be used for having for the first time reductive agent to have acidleach down, it is the product liquid of cerium-rich solution that the leach liquor of the acidleach under the reductive agent existence is arranged the first time.
To the secondary slag that the acidleach after-filtration is separated under the reductive agent existence is arranged through secondary, to carry out 1～2 washing for good, the method for its filtration and washing such as above-mentioned filtered water are identical when washing the preparation primary slag.
The secondary slag carries out alkali cleaning again after washing, so-called alkali cleaning is exactly under agitation, add 5～40% (weight percentage, sodium hydroxide solution down together) under 70～110 ℃ temperature, stirred 0.5～4 hour, filter and wash again, general alkali cleaning is carried out once, and used concentration sodium hydroxide during alkali cleaning is 5～40%, 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 of ore 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% (weight percentage).
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.Washing 3～10 times, is good with 4～6 times, and the PH that makes water lotion is 7～8, to the secondary slag of separating after the acidleach under the reductive agent existence is arranged through secondary, can be used as raw material again after alkali cleaning, washing.It is the product liquid of cerium-rich solution that the leach liquor of the acidleach under the reductive agent existence is arranged for the first time, the acidity of free acid generally is 0.01 mol～0.6 mol in the cerium-rich solution and in the lanthanum rich rare earth solution, again with 0.1 mol～0.6 mol for well, identical in the leach liquor of all acidleach (not having the acidleach of reductive agent under having acidleach down and the reductive agent existence being arranged) described in the mensuration of the acidity of free acid such as the application number 93114910.X Chinese patent literature.
The advantage of processing method of the present invention just is:
1. compared with the prior art shorten technical process, simplified operating process, reduced the consumption of industrial chemicals, reduced the cost of product, the rate of decomposition of bastnasite and the rate of recovery of rare earth, the rate of recovery of cerium is all high, and the quantity of slag is little, and slag middle-weight rare earths constituent content is low.
2. technical process of the present invention can be produced two kinds of product solutions, and a kind of is that the ratio of cerium/total amount of rare earth is greater than 95% rich cerium product solution and a kind of lanthanum rich rare earth solution.Since with nitric acid, salt acid substitution sulfuric acid as leaching liquid, taked secondary pickling, with the leach liquor of the acidleach second time (do not have reductive agent to exist and have reductive agent to exist) leaching liquid as the acidleach first time (do not have reductive agent to exist and have reductive agent to exist).Reduced sour consumption, reduced the acidity in rich cerium product solution and the lanthanum rich rare earth solution again, increased cerium and concentrations of rare-earth in rich cerium product liquid, the lanthanum rich rare earth solution, the purification of being convenient to next step with separate, purity can be used as glass fining agent greater than 95% cerium dioxide product.
3. do not produce the obnoxious flavour that contains fluorochemical in technological process of the present invention, avoided the pollution to environment, help health of operators, 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 understanding 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 100 gram and the yellow soda ash that will contain 58.02% rare earth oxide, mix than 100/20 (weight ratio) with ore deposit alkali, carried out roasting 1 hour in 650 ℃, under agitation with the fluorine of tap water in the solid phase calcining matter of 70 ℃ of washing ore deposits and yellow soda ash, solid-to-liquid ratio is 1: 2 (grams per milliliter, the concentrate amount of the amount of solid phase to be added), each washing 20 minutes, stop to stir, treat to carry out solid-liquid separation with siphonage or decantation after the sedimentation, so carry out 3 times, wash to the PH of water lotion be 7.5.Pickling is carried out in 80 ℃ of aqueous nitric acid that add entry and splash into 4 mol in washing back, and the PH that makes last pickle solution is 5.Pickling 20 minutes.Solid-to-liquid ratio during pickling is 1: 2.5 (grams per milliliter, the amount of solid phase is in the amount of the bastnasite that added), and pickling once.With through above-mentioned roasting, washing, pickling, solid phase calcining matter after the solid-liquid separation is the raw material leaching liquid of the leach liquor of the acidleach second time that contains free acid 1 mol nitric acid of preparation already as the acidleach first time, under agitation raw material is carried out the acidleach first time in 95 ℃, it is 0.1 mol that the amount of leach liquor of the acidleach second time that contains free acid 1 mol nitric acid of preparation already that is added makes the concentration of free acid in the leach liquor of acidleach for the first time, solid-to-liquid ratio during acidleach for the first time is 1: 3 (grams per milliliter, the concentrate amount of the amount of solid phase to be added), acidleach 1 hour, the leach liquor of acidleach for the first time is a lanthanum rich rare earth solution.
For the first time after the acidleach, stop to stir treat the solid materials sedimentation after, carry out solid-liquid separation with decantation or siphonage, isolated liquid phase, the leach liquor of acidleach for the first time is a kind of lanthanum rich rare earth product solution, places in the container.
With the nitric acid of 9 mol leaching liquid as the acidleach second time, under agitation the raw material through acidleach is for the first time carried out the acidleach second time in 95 ℃, the nitric acid amount of 9 mol that added, making the concentration of the free acid in the leach liquor of acidleach for the second time is 1 mol.The solid-to-liquid ratio of solid phase and leaching liquid is 1: 3.0 (grams per milliliter, the concentrate amount of the amount of solid phase to be added) during acidleach for the second time, and the time of acidleach for the second time is 0.5 hour.
Through filtering with suction method after the acidleach for the second time, wash secondary with water, obtain the leach liquor of primary slag and acidleach for the second time, the leach liquor of acidleach for the second time is used for acidleach for the first time.The leach liquor of acidleach for the first time is a lanthanum rich rare earth solution, wherein contain 40.52 grams per liter rare earth oxides (RE0), contain 1.47 grams per liter cerium dioxides, contain 75.8% rare earth oxide in the primary slag, 64.7% cerium dioxide, the ratio of cerium dioxide/rare earth oxide is 85.4%.
With the leach liquor that has the second time of containing free acid 1 mol nitric acid for preparing already reductive agent to have an acidleach down as there being for the first time reductive agent to have the leaching liquid of acidleach down, under agitation in 82 ℃ of acidleach of primary slag being carried out having the first time under the reductive agent existence.In the process that the acidleach in the presence of the reductive agent is arranged for the first time, add 30% hydrogen peroxide simultaneously, the amount that hydrogen peroxide added is for being reduced into quadrivalent cerium one times of trivalent cerium theoretical amount, have reductive agent to have the leach liquor of acidleach down the second time of containing free acid 1 mol/liter nitric acid that adds preparation already, making the concentration of free acid in the leach liquor that the acidleach under the reductive agent existence is arranged for the first time is 0.1 mol nitric acid, solid-to-liquid ratio when having for the first time reductive agent to have acidleach down is 1: 3.0 (grams per milliliter, the ore deposit amount of the amount of solid phase to be added), acidleach 1 hour, it is the product liquid of cerium-rich solution that the leach liquor of the acidleach under the reductive agent existence is arranged for the first time.
After having for the first time reductive agent to have acidleach down, stop to stir treat the solid materials sedimentation after, carry out solid-liquid separation with decantation or siphonage, isolated liquid phase has the leach liquor cerium-rich solution of the acidleach under the reductive agent existence for the first time, places in the container.
With the nitric acid of 9 mol as the leaching liquid that the acidleach of reductive agent under existing arranged for the second time, under agitation primary slag is carried out having for the second time the acidleach of reductive agent under existing in 80 ℃, in the acidleach process that has for the second time in the presence of the reductive agent, add 30% hydrogen peroxide simultaneously, the amount that hydrogen peroxide added is for becoming the quadrivalent cerium Restore All 1 times of trivalent cerium theoretical amount, the nitric acid amount that adds 9 mol, making the concentration of the free acid of the leach liquor that the acidleach under the reductive agent existence is arranged for the second time is 1 mol, when having for the second time reductive agent to have acidleach down, the solid-to-liquid ratio of solid phase and leaching liquid is 1: 3.0 (grams per milliliter, the concentrate amount of the amount of solid phase to be added), the extraction time of the acidleach under the reductive agent existence being arranged for the second time is 0.5 hour.
After having for the second time reductive agent to have acidleach down, filter with suction method, wash secondary with water, obtain the secondary slag and have reductive agent to have the leach liquor of acidleach down for the second time, there is for the second time reductive agent to exist the leach liquor of acidleach down to be used for having for the first time acidleach under the reductive agent existence, it is the product liquid of cerium-rich solution that the leach liquor of the acidleach under the reductive agent existence is arranged for the first time, wherein contain 39.87 grams per liter rare earth oxides (REO), 29.0 grams per liter cerium dioxide, the ratio of cerium dioxide/rare earth oxide is 97.82%, contain 35.0% rare earth oxide in the secondary slag, 17.3% cerium dioxide, the ratio of cerium dioxide/rare earth oxide is 49.4%.
The secondary slag is carried out an alkali cleaning, and alkali cleaning is exactly under agitation to add 30% sodium hydroxide solution, 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.Secondary slag after alkali cleaning, washing can mix as raw material with the solid phase calcining matter after roasting, washing, pickling, solid-liquid separation again separately as raw material, returns in the technical process of beginning.
Example 2
Its operation is substantially with embodiment 1, and only different is, alkali ratio in ore deposit is 100/30 (weight ratio), carries out roasting 0.7 hour in 750 ℃, with tap water wash to PH be 7.2.The PH of the pickle solution of pickling is 6.
Carry out the acidleach first time after the pickling, the temperature of acidleach is 75 ℃, add among the embodiment 1 and contain the leach liquor that free acid concentration is the acidleach second time of 1 mol nitric acid, making the concentration of free acid in the leach liquor of acidleach for the first time is 0.2 mol nitric acid, solid-to-liquid ratio is 1: 2.5 (grams per milliliter, the concentrate amount of the amount of solid phase to be added), acidleach 0.7 hour, the leach liquor of acidleach for the first time is a lanthanum rich rare earth solution.
After the acidleach for the first time, with 10 mol salpeter solutions is the leaching liquid of acidleach for the second time, under agitation raw material is carried out the acidleach second time in 75 ℃, the amount that adds the nitric acid of 10 mol, making the concentration of free acid in the leach liquor of acidleach for the second time is 2 mol, solid-to-liquid ratio is 1: 2.5 (grams per milliliter, the concentrate amount of the amount of solid phase to be added), and it is 1 hour that acidleach goes out the time.
Through filtering with suction method after the acidleach for the second time, wash secondary with water, the leach liquor that obtains primary slag and acidleach for the second time is used for acidleach for the first time, the leach liquor of acidleach for the first time is a lanthanum rich rare earth solution, wherein contain 41.28 grams per liter rare earth oxides, contain 0.94 grams per liter cerium dioxide, contain 75.7% rare earth oxide in the primary slag, 65.0% cerium dioxide, the ratio of cerium dioxide/rare earth oxide is 86.1%.
Primary slag is carried out having for the first time the acidleach of reductive agent under existing, the temperature of acidleach is 75 ℃, the add-on of hydrogen peroxide is for being reduced into quadrivalent cerium 1.5 times of trivalent cerium theoretical amount, adding has reductive agent to have the leach liquor of acidleach down the second time of containing free acid 1 mol nitric acid among the embodiment 1, making the concentration of free acid in the leach liquor that has reductive agent to have acidleach down for the first time is 0.2 mol nitric acid, solid-to-liquid ratio is 1: 2.5 (grams per milliliter, the concentrate amount of the amount of solid phase to be added), acidleach 0.7 hour, it is the product liquid of cerium-rich solution that the leach liquor of the acidleach under the reductive agent existence is arranged for the first time.
After acidleach under the reductive agent existence is arranged for the first time, with 10 mol nitric acid is the leaching liquid that the acidleach under the reductive agent existence is arranged for the second time, under agitation primary slag is carried out having for the second time the acidleach of reductive agent under existing in 75 ℃, in the acidleach process that has for the second time in the presence of the reductive agent, add 30% hydrogen peroxide simultaneously, 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 10 mol nitric acid, making the concentration of the free acid of the leach liquor that has reductive agent to have following acidleach for the second time is 2 mol, solid-to-liquid ratio is 1: 2.5 (grams per milliliter, the concentrate amount of the amount of solid phase to be added), leaching time is 1 hour.
After the acidleach under the reductive agent existence is arranged for the second time, filter with suction method, wash secondary with water, obtain the secondary slag and have reductive agent to have the leach liquor of acidleach down for the second time, there is for the second time reductive agent to exist the leach liquor of acidleach down to be used for having for the first time acidleach under the reductive agent existence, the leach liquor that acidleach under the reductive agent existence is arranged for the first time, product solution for cerium-rich solution, wherein contain 40.15 grams per liter rare earth oxides, 39.25 the grams per liter cerium dioxide, the ratio of cerium dioxide/rare earth oxide is 97.76%, contains 34.0% rare earth oxide in the secondary slag, 16.5% cerium dioxide, the ratio 48.5% of cerium dioxide/rare earth oxide.
The secondary slag is carried out an alkali cleaning, and alkali lye is 20% aqueous sodium hydroxide solution, and in 90 ℃ of stirrings 2.5 hours, water washed again, and the temperature of washing is 95 ℃, washes 4 times, and the PH that makes water lotion is 8.0.
Embodiment 3
Its operation is basically with embodiment 1, and only different is, alkali ratio in ore deposit is 100/16 (weight ratio), carries out roasting 3 hours in 550 ℃, with tap water wash to PH be 7, the pickle solution PH of pickling is 5.
Carry out the acidleach first time after the pickling, the temperature of acidleach is 70 ℃, add the concentration that contains free acid among the embodiment 2 and be the mixed solution of the aqueous nitric acid of the leach liquor of the acidleach second time of 2 mol nitric acid and 7 mol, making the concentration of free acid in the leach liquor of acidleach for the first time is 0.4 mol, solid-to-liquid ratio is 1: 2.5 (grams per milliliter, the concentrate amount of the amount of solid phase to be added), acidleach 0.7 hour, the leach liquor of acidleach for the first time is a lanthanum rich rare earth solution.
After the acidleach for the first time, with concentrated nitric acid is the leaching liquid of acidleach for the second time, under agitation raw material is carried out the acidleach second time in 70 ℃, the amount that adds concentrated nitric acid, making the concentration of free acid in the leach liquor of acidleach for the second time is 2.5 mol, solid-to-liquid ratio is 1: 2.5 (grams per milliliter, the concentrate amount of the amount of solid phase to be added), and leaching time is 0.6 hour.
Through filtering with suction method after the acidleach for the second time, wash with water 2 times, the leach liquor that obtains primary slag and acidleach for the second time is used for acidleach for the first time, the leach liquor of acidleach for the first time is a lanthanum rich rare earth solution, wherein contain 40.95% rare earth oxide, 1.05 grams per liter cerium dioxides contain 76.3% rare earth oxide in the primary slag, 65.8% cerium dioxide, the ratio of cerium dioxide/rare earth oxide is 86.2%.
Primary slag is carried out having for the first time the acidleach of reductive agent under existing, the temperature of acidleach is 70 ℃, the add-on of hydrogen peroxide is for being reduced into quadrivalent cerium 3.0 times of trivalent cerium theoretical amount, add the leach liquor that has the second time of containing free acid concentration 2 mol nitric acid among the embodiment 2 reductive agent to have acidleach down and the mixed solution of 7 mol aqueous nitric acid, making the concentration of free acid in the leach liquor that has reductive agent to have acidleach down for the first time is 0.4 mol nitric acid.Solid-to-liquid ratio is 1: 2.5 (grams per milliliter, the concentrate amount of the amount of solid phase to be added), acidleach 2 hours, and it is the product solution of cerium-rich solution that the leach liquor of the acidleach under the reductive agent existence is arranged for the first time.
After acidleach under the reductive agent existence is arranged for the first time, with concentrated nitric acid is the leaching liquid that the acidleach under the reductive agent existence is arranged for the second time, under agitation primary slag is carried out having for the second time the acidleach of reductive agent under existing in 70 ℃, in the acidleach process that has for the second time in the presence of the reductive agent, add 30% hydrogen peroxide simultaneously, 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 in the leach liquor that the acidleach under the reductive agent existence is arranged for the second time is 2.5 mol nitric acid, solid-to-liquid ratio is 1: 2.5 (grams per milliliter, the concentrate amount of the amount of solid phase to be added), acidleach is 0.6 hour.
After the acidleach under the reductive agent existence is arranged the second time, filter with suction method, wash secondary with water, obtain secondary slag and the leach liquor that acidleach under the reductive agent existence is arranged for the second time.There is for the second time reductive agent to exist the leach liquor of acidleach down to be used for having for the first time acidleach under the reductive agent existence.Having for the first time reductive agent to have the leach liquor of acidleach down is the product liquid of cerium-rich solution, wherein contain 40.25 grams per liter rare earth oxides, 39.02 grams per liter cerium dioxide, the ratio of cerium dioxide/rare earth oxide is 96.94%, contain 34.5% rare earth oxide in the secondary slag, 17.1% cerium dioxide, the ratio of cerium dioxide/rare earth oxide is 49.6%.
The secondary slag is carried out an alkali cleaning, and alkali lye is 20% aqueous sodium hydroxide solution, and in 90 ℃ of stirrings 2.5 hours, water washed, and the temperature of washing is 95 ℃, washes 5 times, and the PH that makes water lotion is 7.
Embodiment 4
Its operation is basically with embodiment 1, and only different is that ore deposit alkali ratio is 100/25 (weight ratio), carries out roasting 0.7 hour in 750 ℃, with tap water wash to PH be 7, the pickle solution PH of pickling is 6.
Carry out the acidleach first time after the pickling, the temperature of acidleach is 80 ℃, adding the concentration that contains free acid among the embodiment 3 is the leach liquor of the acidleach second time of 2.5 mol nitric acid, making the concentration of free acid in the leach liquor of acidleach for the first time is 0.3 mol nitric acid, solid-to-liquid ratio is 1: 2.5 (grams per milliliter, the concentrate amount of the amount of solid phase to be added), acidleach 1.5 hours, the leach liquor of acidleach for the first time is a lanthanum rich rare earth solution.
After the acidleach for the first time, with 10 mol nitric acid is the leaching liquid of acidleach for the second time, under agitation raw material is carried out the acidleach second time in 80 ℃, the amount that adds 10 mol nitric acid, making the concentration of free acid in the leach liquor of acidleach for the second time is 0.8 mol, solid-to-liquid ratio is 1: 2.5 (grams per milliliter, the concentrate amount of the amount of solid phase to be added), and leaching time is 1.1 hours.
Through filtering with suction method after the acidleach for the second time, wash with water 2 times, obtain the leach liquor (being used for acidleach for the first time) of primary slag and acidleach for the second time, the leach liquor of acidleach for the first time is a lanthanum rich rare earth solution, wherein contain 40.82 grams per liter rare earth oxides, 1.24 grams per liter cerium dioxides contain 76.7% rare earth oxide in the primary slag, 66.0% cerium dioxide, the ratio of cerium dioxide/rare earth oxide is 85.94%.
Primary slag is carried out having for the first time the acidleach of reductive agent under existing, the temperature of acidleach is 80 ℃, the add-on of hydrogen peroxide is for being reduced into quadrivalent cerium 1.1 times of trivalent cerium theoretical amount, adding the concentration that contains free acid among the embodiment 3 is the leach liquor that acidleach under the reductive agent existence is arranged the second time of 2.5 mol nitric acid, and making the concentration of free acid in the leach liquor that has reductive agent to have acidleach down for the first time is 0.3 mol nitric acid.Solid-to-liquid ratio 1: 2.5 (grams per milliliter, the concentrate amount of the amount of solid phase) to be added, acidleach 1.5 hours.It is the product solution of cerium-rich solution that the leach liquor of the acidleach under the reductive agent existence is arranged for the first time.
After acidleach under the reductive agent existence is arranged for the first time, be the leaching liquid that the acidleach under the reductive agent existence is arranged for the second time with 10 mol nitric acid.Under agitation primary slag is carried out having for the second time the acidleach of reductive agent under existing in 80 ℃, in the acidleach process that has for the second time in the presence of the reductive agent, add 30% hydrogen peroxide simultaneously, 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 nitric acid, making the concentration of free acid in the leach liquor that the acidleach under the reductive agent existence is arranged for the second time is 0.8 mol nitric acid, solid-to-liquid ratio is 1: 2.5 (grams per milliliter, the concentrate amount of the amount of solid phase to be added), the extraction time of acidleach is 1.1 hours.
After the acidleach under the reductive agent existence is arranged the second time, filter with suction method, wash secondary with water, obtain secondary slag and the leach liquor that acidleach under the reductive agent existence is arranged for the second time.There is for the second time reductive agent to exist the leach liquor of acidleach down to be used for having for the first time acidleach under the reductive agent existence.It is the product liquid of cerium-rich solution that the leach liquor of the acidleach under the reductive agent existence is arranged for the first time, wherein contain 41.30 grams per liter rare earth oxides, 39.82 grams per liter cerium dioxide, the ratio of cerium dioxide/rare earth oxide is 96.42%, contain 34.2% rare earth oxide in the secondary slag, 16.7% cerium dioxide, the ratio of cerium dioxide/rare earth oxide is 48.83%.
The secondary slag is carried out an alkali cleaning, and alkali cleaning is with 23% 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.
Claims (20)
1. method of producing cerium-rich solution, it is characterized in that, with bastnasite and yellow soda ash or the weight ratio uniform mixing of sodium hydroxide to suit, through roasting, washing, pickling, solid phase calcining matter after the solid-liquid separation, through the secondary slag of alkali cleaning washing, above-mentioned solid phase calcining matter and be raw material through wherein a kind of of the mixture of the secondary slag of alkali cleaning, washing
(1) aqueous solution of usefulness nitric acid, aqueous solution of hydrochloric acid, the leach liquor of acidleach for the second time, mixed solution a kind of solution wherein of the leach liquor of nitric acid or hydrochloric acid and acidleach for the second time is as the leaching liquid of the acidleach first time, under agitation raw material is carried out the acidleach first time, the aqueous nitric acid that is added, aqueous hydrochloric acid, the leach liquor of acidleach for the second time, 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, making the concentration of free acid in the leach liquor of acidleach for the first time is 0.01 mol～0.6 mol, carry out solid-liquid separation
(2) with the aqueous solution of nitric acid, aqueous solution of hydrochloric acid a kind of solution wherein leaching liquid as the acidleach second time, under agitation the raw material through acidleach is for the first time carried out the acidleach second time, the aqueous nitric acid that is added, the amount of aqueous hydrochloric acid, making the concentration of free acid in the leach liquor of acidleach for the second time is 0.7 mol～2.5 mol, after the filtration, isolate the leach liquor and the primary slag of acidleach for the second time, the leach liquor of acidleach for the second time is used for acidleach for the first time
(3) aqueous solution of usefulness nitric acid, aqueous solution of hydrochloric acid, the leach liquor that the acidleach of reductive agent existence is arranged for the second time, nitric acid or hydrochloric acid and have for the second time reductive agent to exist mixed solution a kind of solution wherein of leach liquor of acidleach down as the leaching liquid that the acidleach under the reductive agent existence is arranged for the first time, under agitation primary slag is carried out having for the first time the acidleach of reductive agent under existing, in the acidleach process, add reductive agent simultaneously, the amount of the reductive agent that is added, for the quadrivalent cerium Restore All being become 0.7～4 times of trivalent cerium theoretical amount, the aqueous nitric acid that is added, aqueous hydrochloric acid, the leach liquor that acidleach under the reductive agent existence is arranged for the second time, nitric acid or hydrochloric acid and the amount of mixed solution a kind of solution wherein of the leach liquor of the acidleach of reductive agent under existing is arranged for the second time, making the concentration of free acid in the leach liquor that the acidleach under the reductive agent existence is arranged for the first time is 0.01 mol～0.6 mol, carry out solid-liquid separation, it is cerium-rich solution that the leach liquor of the acidleach under the reductive agent existence is arranged for the first time
(4) aqueous solution of usefulness nitric acid, wherein a kind of solution of aqueous solution of hydrochloric acid is as the leaching liquid that the acidleach under the reductive agent existence is arranged for the second time, under agitation primary slag is carried out having for the second time the acidleach of reductive agent under existing, add reductive agent in the acidleach process, add reductive agent amount for quadrivalent cerium being reduced into 0.7～4 times of trivalent cerium theoretical amount, the aqueous nitric acid that is added, aqueous hydrochloric acid is a kind of amount of solution wherein, making the concentration of free acid in the leach liquor that the acidleach under the reductive agent existence is arranged for the second time is 0.7 mol～2.5 mol, isolate the leach liquor and the secondary slag that have for the second time reductive agent to have acidleach down after the filtration, have reductive agent to exist the leach liquor of acidleach down to be used for having for the first time acidleach under the existence of reducing for the second time.
2. according to a kind of method of producing cerium-rich solution of claim 1, it is characterized in that the reductive agent that is added is a hydrogen peroxide.
3. according to a kind of method of producing cerium-rich solution of claim 2, it is characterized in that the concentration of hydrogen peroxide is 5～30% (weight percentage).
4. according to a kind of method of producing cerium-rich solution of claim 2, it is characterized in that the amount of the reductive agent hydrogen peroxide that is added is for becoming the quadrivalent cerium Restore All 1～2.5 times of trivalent cerium theoretical amount.
5. according to a kind of method of producing cerium-rich solution of claim 1, it is characterized in that when acidleach for the first time, acidleach for the second time, the temperature of acidleach is 50～100 ℃.
6. according to a kind of method of producing cerium-rich solution of claim 5, it is characterized in that when acidleach for the first time, acidleach for the second time, the temperature of acidleach is 70～95 ℃.
7. according to a kind of method of producing cerium-rich solution of claim 1, it is characterized in that the acidleach under the reductive agent existence is arranged for the first time, when the acidleach under the reductive agent existence was arranged for the second time, the temperature of acidleach was 50～100 ℃.
8. according to a kind of method of producing cerium-rich solution of claim 7, it is characterized in that the acidleach under the reductive agent existence is arranged for the first time, when the acidleach under the reductive agent existence was arranged for the second time, the temperature of acidleach was 70～85 ℃.
9. according to a kind of method of producing cerium-rich solution of claim 1, it is characterized in that when acidleach for the first time, acidleach for the second time, solid phase is than 1: 1.5～4.5 (grams per milliliters) with the solid-liquid of leaching liquid, extraction time is 0.1～2 hour.
10. according to a kind of method of producing cerium-rich solution of claim 1, it is characterized in that when having reductive agent to have acidleach down for the first time, for the second time, the solid-to-liquid ratio of solid phase and leaching liquid is 1: 1.5～4.5 (grams per milliliters), extraction time is 0.1～2 hour.
11. a kind of method of producing cerium-rich solution according to claim 1 is characterized in that, the concentration of free acid is 0.1 mol～0.6 mol in the leach liquor of acidleach for the first time.
12. a kind of method of producing cerium-rich solution according to claim 1 is characterized in that, the concentration of free acid is 0.7 mol～2.0 mol in the leach liquor of acidleach for the second time.
13. a kind of method of producing cerium-rich solution according to claim 1 is characterized in that, having the reductive agent existence to descend the concentration of free acid in the leach liquor of acidleach for the first time is 0.1 mol～0.6 mol.
14. a kind of method of producing cerium-rich solution according to claim 1 is characterized in that, having the reductive agent existence to descend the concentration of free acid in the leach liquor of acidleach for the second time is 0.7 mol～2.0 mol.
15. a kind of method of producing cerium-rich solution according to claim 1 is characterized in that, through acidleach second time after-filtration, carries out 1～2 washing.
16. a kind of method of producing cerium-rich solution according to claim 1 is characterized in that, through the acidleach after-filtration under the reductive agent existence is arranged for the second time, carries out 1～2 washing.
17. a kind of method of producing cerium-rich solution according to claim 1 is characterized in that, during the alkali cleaning of secondary slag, concentration sodium hydroxide is 5～40% (weight percentage).
18. a kind of method of producing cerium-rich solution according to claim 17 is characterized in that, during the alkali cleaning of secondary slag, concentration sodium hydroxide is 20～30% (weight percentage).
19. a kind of method of producing cerium-rich solution according to claim 17 or 18 is characterized in that the temperature the during alkali cleaning of secondary slag is 70～110 ℃, stirs 0.5～4 hour.
20. a kind of method of producing cerium-rich solution according to claim 17 or 18 is characterized in that, after the alkali cleaning of secondary slag, and washing, the temperature of washing is 30～95 ℃, washes 3～10 times.
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| Application Number | Priority Date | Filing Date | Title |
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| CN93120629A CN1034744C (en) | 1993-12-07 | 1993-12-07 | Method of extracting cerium-rich solution |
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| CN93120629A CN1034744C (en) | 1993-12-07 | 1993-12-07 | Method of extracting cerium-rich solution |
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| CN1034744C true CN1034744C (en) | 1997-04-30 |
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| CN104278164B (en) * | 2014-09-29 | 2016-05-18 | 乐山盛和稀土股份有限公司 | Grade is at the fluorine carbonated rare earth ore deposit of 62%-72% treatment process |
| CN106148710A (en) * | 2016-08-19 | 2016-11-23 | 包头华美稀土高科有限公司 | A kind of process of recovering rare earth from cerium oxide waste material |
| CN111321307A (en) * | 2020-03-07 | 2020-06-23 | 江苏北矿金属循环利用科技有限公司 | Process for efficiently recovering palladium from palladium-containing waste catalyst |
| CN115369246B (en) * | 2022-04-11 | 2024-04-30 | 长沙市丰程有色金属材料有限责任公司 | Recovery method of monazite excellent slag |
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