CN103103351A - Method for preparing high-purity calcium carbonate for saponifying rare earth extraction agent - Google Patents
Method for preparing high-purity calcium carbonate for saponifying rare earth extraction agent Download PDFInfo
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- CN103103351A CN103103351A CN2013100378256A CN201310037825A CN103103351A CN 103103351 A CN103103351 A CN 103103351A CN 2013100378256 A CN2013100378256 A CN 2013100378256A CN 201310037825 A CN201310037825 A CN 201310037825A CN 103103351 A CN103103351 A CN 103103351A
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Abstract
The invention discloses a method for preparing high-purity calcium carbonate for rare earth extraction and saponification of an organic phase. The method is performed according to the following steps of: 1, ammonolysis: dissolving lime by ammonium chloride; 2, filtering ammonolysis mixture, preparing high-purity calcium carbonate for saponifying the rare earth extraction agent; 3, carbonization: introducing saponifying reaction side product carbon dioxide from a step 6 so as to generate calcium carbonate; 4, filtering carbonization mixed solution; 5, drying, thereby obtaining high-purity calcium carbonate; and 6, saponifying: carrying out saponifying reaction to high-purity calcium carbonate and organic phase containing air loaded acidic extraction agent, clearing, and separating, wherein the organic phase of the upper layer is the saponified extraction agent. The method disclosed by the invention has the advantages that the purity of calcium carbonate product is high, the content of impurities such as Fe, Al and Si is low, the acid non-soluble substance is avoided, the process is simple, the ammonium chloride is recycled, and the like. The saponifying by using the method is the same as the saponifying by using liquid ammonia and liquid alkali, the extraction agent obtained by the methods all can achieve the theoretical extracting ability, and the purpose of extraction separation is achieved.
Description
Technical field
The present invention relates to a kind of method that high-purity calcium carbonate is used for the saponification rare-earth extractant for preparing.
Background technology
Liquid-liquid extraction refers to utilize two or more immiscible or substantially immiscible liquid phase through the technology of row separation, it is a kind of process of another liquid phase that needed material is transferred to from a liquid phase, is specially adapted to chemical property close and be difficult to use in the element that ordinary method is separated.
Extracting and separating is a kind of important Wet-process metallurgy method, most of extracting and separating is carried out under acidic conditions, its extracting power and water balance acidity are inversely proportional to, the hydrogen ion that metal ion of general extraction will be replaced some amount enters water, increase along with acidity, the extraction liquid extracting power descends rapidly, so extracted organic phase need to carry out saponification with sodium hydroxide or ammoniacal liquor before extractive reaction, is referred to as soda soap or ammonia soap.The saponification organic phase is with after Element Extraction carries out ion-exchange, and Element Extraction is treated in the organic phase load, and organic phase can be recycled after stripping, and water is the salts solution of sodium or ammonia, generally as discharge of wastewater or processing again.
As the rare earth saponifying agent, there is following defective in ammoniacal liquor with sodium hydroxide: enter extraction system although there is advantage in the relative liquid caustic soda of liquefied ammonia and can introduce other foreign ions on price, it generates waste water and has NH
4+, the waste water of its generation all need carry out evaporative crystallization, and the ammonia salt in waste water is crystallized out, and could process qualified discharge, and the energy of consumption is too large, and processing cost is high, and very harsh to the requirement of equipment.Sodium hydroxide is made saponifying agent, environmental protection treatment cost during saponification, but production cost increases.
ZL200410050948.4 " rare earth extraction separates the making method of acidic extractant saponification organic phase " is disclosed is: with calcium oxide, calcium hydroxide or magnesium hydroxide and acidic extractant generation saponification reaction, after the clarification phase-splitting, the acidic extractant on upper strata is the saponification organic phase.The shortcoming of this technique just is the constantly accumulation and can't getting rid of in the saponification system of saponifying agent impurities, causes that extracting and separating line three-phase increases, organic blackening, profit phase-splitting are unclear, carry serious, separating effect variation secretly.Given this, the lime purification becomes the derivative problem of calcium soap naturally.
Summary of the invention
The object of the present invention is to provide a kind of method that high-purity calcium carbonate is used for the saponification rare-earth extractant for preparing, to improve the purity of calcium carbonate, reach theoretical extracting power.
In order to reach above-mentioned purpose, solution of the present invention is:
A kind of high-purity calcium carbonate for preparing carries out according to the following steps for the method for saponification rare-earth extractant:
Step 1, ammonia solution are used chloride leach solution lime;
Step 2, filtration ammonia solution mixture, the preparation high-purity calcium carbonate is used for the saponification rare-earth extractant;
Step 3, carbonization pass into step 6 saponification reaction by product carbonic acid gas in filtrate, generate calcium carbonate;
Step 4, filtration carbonization mixed solution;
Step 5, drying make purity calcium carbonate;
Step 6, saponification, purity calcium carbonate with contain the organic phase generation saponification reaction that idling carries acidic extractant, the byproduct of reaction carbon dioxide collection turns back to the step 3 carbonization, the clarification phase-splitting after, the organic phase on upper strata is Saponified Extractants.
Wherein, step 1 ammonia solution is to add ammonium chloride solution and unslaked lime in the enamel kiln of stirring rake is housed, and makes CaO and NH
4The Cl reaction, NH
4Cl concentration is controlled between 2-5 mol/L, and the reaction times was at 1-2 hour.
It is that ammonia solution mixture is added in the vacuum filtration groove that step 2 is filtered ammonia solution mixture, ageing 1-2 hour, carries out solid-liquid separation.
The step 3 carbonization is that the filtered filtrate of ammonia solution mixture is joined in carbonating tower, passes into the by product CO of step 6 saponification reaction
2, carburizing reagent occurs, the Ca ion solubility of carbonization terminal point in the liquid lower than 0.01mol/L or pH less than 7 as standard, carbonization time is controlled in 40-80min.
It is that the carbonization mixture is added in the vacuum filtration groove that step 4 is filtered the carbonization mixed solution, ageing 1-6 hour, carry out solid-liquid separation, and filtrate is NH
4Cl solution returns to step 1 ammonia solution process, filter cake CaCO
3Next process that enters solid continues to process.
The step 5 drying is CaCO
3Solid is put into loft drier, carries out drying operation under the condition of 200-500 ℃.
The step 6 saponification is dried CaCO
3And carry out saponification reaction in airtight, the container for the treatment of stirring rake that contains that organic phase that idling carries acidic extractant adds, reaction product is the calcium soap organic phase of load calcium ion, CO
2Collection turns back to the step 3 carbonization process and uses.
After adopting such scheme, it is high that technique of the present invention has calcium carbonate product purity, and the impurity such as Fe, Al, Si are low, and without acid non-soluble substance, technique is simple, the advantages such as ammonium chloride recycle.Use this method saponification with the same with the liquid caustic soda saponification with liquefied ammonia, extraction agent all can reach theoretical extracting power, realizes the purpose of extracting and separating.
Principle of the present invention: in the lime of high-temperature calcination, the silicon existence form is more, exists with silicon-dioxide, silicate form, removes with solid phase under this condition.The Fe, the Al that exist exist with the high oxide form substantially, and the Fe oxide compound is water insoluble, is insoluble to alkali; The Al oxide compound, water insoluble, be insoluble to weak base, can remove after filtration with solid phase form for these two kinds.Even Fe, the Al of part exist with oxyhydroxide, so according to NH
3H
2The K of O
b=1.8 * 10
-5, Ca (OH)
2K
sp=5.5 * 10
-6, Fe (OH)
3K
sp=3 * 10
-39, Fe (OH)
2K
sp=3 * 10
-16,
2 NH
4 ++ Ca (OH)
2=Ca
2++ 2 NH
3H
2O, K
c=1.7 * 10
4, react completely, exist with ionic species,
2 NH
4 ++ Fe (OH)
2=Fe
2++ 2 NH
3H
2O, K
c=1.7 * 10
-1, do not react Fe (OH)
2Continuation exists with solid phase and removes by filter,
3 NH
4 ++ Fe (OH)
3=Fe
3++ 3 NH
3H
2O, K
c=1.7 * 10
-24, do not react Fe (OH)
3Continuation exists with solid phase and removes by filter,
Al (OH)
3Though be the soda acid ampholyte, but also be insoluble to weak base, remove by filter with solid phase form.
By above ammonia solution, impurity conversion is insolubles, and by filtering, product purity is greatly enhanced.Product C aCl
2Obtain the high-purity calcium carbonate product by following reaction
NH
3H
2O(l)+?CaCl
2(l)+CO
2(g)=CaCO
3↓+NH
4Cl(l)
After the high-purity calcium carbonate oven dry, as rare earth extraction saponification agent and blank acid organic saponification reaction
CaCO
3+2HA=CaA
2+H
2O+CO
2↑
Saponification is organic as extraction agent, CO
2Recycling is as the raw material of carbonization process, and the utilization of the raw material of assurance maximizes.
General scheme can be write as: CaO+2HA=CaA
2+ H
2O
The maximum characteristics of this flow process are exactly to realize that unslaked lime is purified and the recirculation of raw material is used, the CO of unslaked lime purification step
2Generally need to add CO
2The source, but CaCO is used in the ingenious recovery of the present invention program
3Product C O with blank organic reaction
2As carbonized stock, realize the purpose of purification and saponification.
Description of drawings
Fig. 1 is schema of the present invention.
Embodiment
As shown in Figure 1, concrete operations of the present invention such as following.
Step 1, ammonia solution are used chloride leach solution lime.Add ammonium chloride solution and unslaked lime in the enamel kiln of stirring rake is housed, makes CaO and NH
4The Cl reaction.This reaction is solid-liquid reaction, the lay special stress on mass transfer process, and reaction need not heated, and the reaction times got final product at 1-2 hour.This process will be considered the concentration of ammonium chloride, and the too little conversion unit of concentration can be very large, the restriction production capacity; The ammonia concn of the too large generation of concentration is higher, and the volatility of ammoniacal liquor is obviously strengthened, and the ammoniacal liquor loss strengthens.Generally, NH
4Cl concentration is controlled between 2-5 mol/L.To utilize simultaneously collection and confinement of gases and storing unit to reclaim Ammonia recovery in process, guarantee the utilization ratio of material, reduce the wastage.
Step 2, filtration ammonia solution mixture.Ammonia solution mixture is added in the vacuum filtration groove, carry out solid-liquid separation, make iron, aluminium, silicon in the lime raw material
DengImpurity separates with calcium.Liquid gives over to next step raw material, and filter cake is drained placement.After the ammonia solution, CaO generates CaCl
2Solution, the impurity such as the Mg in lime, Fe, Al, Si exist with the slags such as its oxide compound, oxyhydroxide, salt or colloidal form.So carried out again filter operation in 1-2 hour after wanting thing ageing for some time to be mixed after the ammonia solution.
Step 3, carbonization.The filtered filtrate of ammonia solution mixture is joined in carbonating tower, pass into CO
2, carburizing reagent occurs.CaCl
2Solution generates CaCO
3Solid, ammonia soln generates NH
4Cl solution.This process reaction belongs to gas liquid reaction, and mass transfer process is crucial, notice that the gas at carbonating tower top is wanted recycle.The carbonization terminal point generally the Ca ion solubility in the liquid lower than 0.01mol/L or PH less than 7 as standard, the carbonization time general control is in 40-80min.
CO
2Replenish and recycle the cost that has a strong impact on this technique.Carbonic acid gas can be by following several approach: one, CaCO
3The Roasting Decomposition preparation is by roasting CaCO
3Obtain carbonic acid gas, reaching does not affect the ventilation system of existing electrical kiln effect, but cost is higher, application example: light calcium carbonate; Two, rare earth carbonate or rare-earth oxalate calcination degradation production degradation production CO
2, relate to the transformation of electrical kiln exhaust system, affect rare earth oxide calcination atmosphere; Three, saponification reaction CO
2
The different CO of form 1
2Source scheme relative merits relatively
Maximize angle from material utilization and consider, " saponification reaction product " is preferred plan, CO
2Recirculation is utilized, the CO that utilizes simultaneously rare-earth oxalate and carbonate decomposition to produce
2, be also CO as a supplement
2The important channel of air-loss.
Step 4, filtration carbonization mixed solution filter.The carbonization mixture is added in the vacuum filtration groove, carry out solid-liquid separation.Filtrate is NH
4Cl solution returns to step 1 ammonia solution process, filter cake CaCO
3Next process that enters solid continues to process.The granular size of calcium carbonate in the carbonization mixed solution when just stopping carbonization differing, and what have is very little, if filter this moment, and easily occurs leaking wearing phenomenon.So want ageing for some time, after growing up, particle carries out again filter operation, and digestion time was controlled between 1～6 hour.
Step 5, drying.CaCO
3Solid is put into loft drier, carries out drying operation under the condition of 200-500 ℃.The purpose of this process is to remove moisture remaining in calcium carbonate and remaining Ammonia.This process will be noted the performance of ventilating of loft drier.
Get off by this series of steps, the insolubles in unslaked lime, Fe, aluminium etc. can effectively be removed, and purity improves greatly, and following table is the impurity situation before and after three different batches unslaked limes are purified:
The foreign matter content situation of raw material before and after form 2 is purified
Step 6, saponification.Dried CaCO
3And contain in airtight, the container for the treatment of stirring rake that organic phase (as naphthenic acid, P507, C272 etc.) that idling carries acidic extractant adds by the ratio of saponification deg requirement and carry out saponification reaction.After reaction product clarification phase-splitting, the acidic extractant on upper strata is that the calcium soap organic phase of load calcium ion enters the extracting and separating system; CO
2Collection turns back to carbonization process and uses.Dried lime moisture content is few, contains the Ammonia substances content all in the ppm level, so the Ammonia that the calcium soap of load calcium ion is carried secretly in organic is few, meets environmental requirement.
Whether in calcium carbonate and organic acid reaction process, react fully particularly important: suppose that the saponification utilization ratio does not reach 100%, illustrated that part calcium carbonate has neither part nor lot in reaction, its place to go is inferred as: molecule enters organic, pollutes organic; The another one place to go is exactly filter residue, and calcium carbonate powder possesses certain oil absorption, and the quantity of slag increases, and causes organic consumption to increase.Thereby investigate the calcium carbonate utilization ratio situation under different saponification deg conditions of weighing, design series of experiments.Can find out from experimental result, in the situation that saponification value is lower than 0.6.The utilization ratio of calcium carbonate all reaches more than 99, but along with the continuation of saponification deg improves, utilization ratio significantly reduces, and organic blackout level of residue simultaneously increases, thereby the recommendation saponification value will be lower than 0.6.
Calcium carbonate utilization ratio situation under the different saponification degs of form 3
Embodiment 1
The ammonium chloride that adds 1 cube of 4mol/L in the enamel kiln of 2 cubes, adding the calcium total amount is 87% unslaked lime 129Kg.Stir 40min; Ageing 30min; Filter, filter residue press dry to be deposited, and filtrate passes in the carbonating tower of 2 cubes.Pass into CO at carbonating tower
2Carburizing reagent occurs, and recycling of overhead gas got mixed solution and measured calcium contents in liquid, stops carbonization during lower than 0.01mol/L when calcium contents.Carbonization mixed solution ageing 30min filters, and it is that the baking oven of 300 ℃ is dried that filter cake is put into temperature, and filtrate is reclaimed lime use to be dissolved, and the time is 50min.Blank organic (as the naphthenic acid, P507, C272 etc.) of calcium carbonate and the extracting and separating line of oven dry presses saponification value 0.54mol/L, reacts the CO that generates in process in the container that required ratio joins is airtight, be with stirring
2Collect storage and treat that carbonization process uses, the saponification organic phase enters extraction system.
Embodiment 2
The ammonium chloride that adds 1 cube of 3mol/L in the inner lining glass fiber reinforced plastic pot of 2 cubes, adding the calcium total amount is 92% unslaked lime 91 Kg.Stir 60min; Ageing 20min; Filter, filter residue press dry to be deposited, and filtrate passes in the carbonating tower of 2 cubes.Pass into CO at carbonating tower
2Carburizing reagent occurs, and recycling of overhead gas got mixed solution and measured calcium contents in liquid, stops carbonization when calcium concn is 0.005mol/L.Carbonization mixed solution ageing 20min filters, and it is that the baking oven of 300 ℃ is dried that filter cake is put into temperature, and filtrate is reclaimed lime use to be dissolved, and the time is 50min.Blank organic (as the naphthenic acid, P507, C272 etc.) of calcium carbonate and the extracting and separating line of oven dry presses saponification value 0.54mol/L, reacts the CO that generates in process in the container that required ratio joins is airtight, be with stirring
2Collect storage and treat that carbonization process uses, the saponification organic phase enters extraction system.
Embodiment 3
The ammonium chloride that adds 0.5 cube of 2mol/L in the inner lining glass fiber reinforced plastic pot of 2 cubes, adding the calcium total amount is 95% unslaked lime 29 Kg.Stir 20min; Ageing 10min; Filter, filter residue press dry to be deposited, and filtrate passes in the carbonating tower of 1 cube.Pass into CO at carbonating tower
2Carburizing reagent occurs, and the recycling of overhead gas stops carbonization less than 7 the time as pH.Carbonization mixed solution ageing 10min filters, and it is that the baking oven of 400 ℃ is dried that filter cake is put into temperature, and filtrate is reclaimed lime use to be dissolved, and the time is 50min.Blank organic (as the naphthenic acid, P507, C272 etc.) of calcium carbonate and the extracting and separating line of oven dry be by saponification value 0.54mol/L, reacts the CO that generates in process in the container that required ratio joins is airtight, be with stirring
2Collect storage and treat that carbonization process uses, the saponification organic phase enters extraction system.
Embodiment 4 adds the ammonium chloride of 2 cubes of 3.5mol/L in the enamel kiln of 3 cubes, and adding the calcium total amount is 78% unslaked lime 251Kg.Stir 70min; Ageing 40min; Filter, filter residue press dry to be deposited, and filtrate passes in the carbonating tower of 3 cubes.Pass into CO at carbonating tower
2Carburizing reagent occurs, and recycling of overhead gas got mixed solution and measured calcium contents in liquid, stops carbonization when calcium concn is 0.01mol/L.Carbonization mixed solution ageing 50min filters, and it is that the baking oven of 400 ℃ is dried that filter cake is put into temperature, and filtrate is reclaimed lime use to be dissolved, and the time is 50min.Blank organic (as the naphthenic acid, P507, C272 etc.) of calcium carbonate and the extracting and separating line of oven dry presses saponification value 0.54mol/L, reacts the CO that generates in process in the container that required ratio joins is airtight, be with stirring
2Collect storage and treat that carbonization process uses, the saponification organic phase enters extraction system.
Embodiment 5
The ammonium chloride that adds 2 cubes of 3.5mol/L in the enamel kiln of 3 cubes, adding the calcium total amount is 69% unslaked lime 284Kg.Stir 80min; Ageing 60min; Filter, filter residue press dry to be deposited, and filtrate passes in the carbonating tower of 3 cubes.Pass into CO at carbonating tower
2Carburizing reagent occurs, and recycling of overhead gas stops carbonization when PH equals 7.Carbonization mixed solution ageing 60min filters, and it is that the baking oven of 500 ℃ is dried that filter cake is put into temperature, and filtrate is reclaimed lime use to be dissolved, and the time is 50min.Blank organic (as the naphthenic acid, P507, C272 etc.) of calcium carbonate and the extracting and separating line of oven dry presses saponification value 0.5mol/L, reacts the CO that generates in process in the container that required ratio joins is airtight, be with stirring
2Collect storage and treat that carbonization process uses, the organic extraction system that enters of saponification.
Claims (7)
1. one kind prepares the method that high-purity calcium carbonate is used for the saponification rare-earth extractant, it is characterized in that carrying out according to the following steps:
Step 1, ammonia solution are used chloride leach solution lime;
Step 2, filtration ammonia solution mixture, the preparation high-purity calcium carbonate is used for the saponification rare-earth extractant;
Step 3, carbonization pass into step 6 saponification reaction by product carbonic acid gas in filtrate, generate calcium carbonate;
Step 4, filtration carbonization mixed solution;
Step 5, drying make purity calcium carbonate;
Step 6, saponification, purity calcium carbonate with contain the organic phase generation saponification reaction that idling carries acidic extractant, the byproduct of reaction carbon dioxide collection turns back to the step 3 carbonization, the clarification phase-splitting after, the organic phase on upper strata is Saponified Extractants.
2. a kind of high-purity calcium carbonate for preparing for the method for saponification rare-earth extractant, is characterized in that step 1 ammonia solution is to add ammonium chloride solution and unslaked lime in the enamel kiln of stirring rake is housed, and makes CaO and NH as claimed in claim 1
4The Cl reaction, NH
4Cl concentration is controlled between 2-5 mol/L, and the reaction times was at 1-2 hour.
3. a kind of high-purity calcium carbonate for preparing for the method for saponification rare-earth extractant, is characterized in that it is that ammonia solution mixture is added in the vacuum filtration groove that step 2 is filtered ammonia solution mixture, ageing 1-2 hour, carries out solid-liquid separation as claimed in claim 1.
4. a kind of high-purity calcium carbonate for preparing for the method for saponification rare-earth extractant, is characterized in that the step 3 carbonization is that the filtered filtrate of ammonia solution mixture is joined in carbonating tower, passes into the by product CO of step 6 saponification reaction as claimed in claim 1
2, carburizing reagent occurs, the Ca ion solubility of carbonization terminal point in the liquid lower than 0.01mol/L or PH less than 7 as standard, carbonization time is controlled in 40-80min.
5. a kind of high-purity calcium carbonate for preparing for the method for saponification rare-earth extractant, is characterized in that it is that the carbonization mixture is added in the vacuum filtration groove that step 4 is filtered the carbonization mixed solution as claimed in claim 1, ageing 1-6 hour, carry out solid-liquid separation, and filtrate is NH
4Cl solution returns to step 1 ammonia solution process, filter cake CaCO
3Next process that enters solid continues to process.
6. a kind of high-purity calcium carbonate for preparing for the method for saponification rare-earth extractant, is characterized in that the step 5 drying is CaCO as claimed in claim 1
3Solid is put into loft drier, carries out drying operation under the condition of 200-500 ℃.
7. a kind of high-purity calcium carbonate for preparing for the method for saponification rare-earth extractant, is characterized in that the step 6 saponification is dried CaCO as claimed in claim 1
3And carry out saponification reaction in airtight, the container for the treatment of stirring rake that contains that organic phase that idling carries acidic extractant adds, reaction product is the calcium soap organic phase of load calcium ion, CO
2Collection turns back to the step 3 carbonization process and uses.
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| CN104480305A (en) * | 2014-10-16 | 2015-04-01 | 福建省长汀金龙稀土有限公司 | An organic matter recovery process in a rare earth extraction separating process |
| CN107400779A (en) * | 2017-06-30 | 2017-11-28 | 中铝广西有色金源稀土有限公司 | A kind of calcium carbonate saponification P507 method |
| CN111547757A (en) * | 2020-05-28 | 2020-08-18 | 四川省冕宁县方兴稀土有限公司 | Method for producing low-calcium lanthanum oxide product by extraction and precipitation linkage |
| CN113200560A (en) * | 2021-05-19 | 2021-08-03 | 江永县潇湘化工有限公司 | Process method for circularly preparing nano calcium carbonate |
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| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
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| CN113200560A (en) * | 2021-05-19 | 2021-08-03 | 江永县潇湘化工有限公司 | Process method for circularly preparing nano calcium carbonate |
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Application publication date: 20130515 |