CN104724746B - Method for recycling ardealite - Google Patents
Method for recycling ardealite Download PDFInfo
- Publication number
- CN104724746B CN104724746B CN201510081892.7A CN201510081892A CN104724746B CN 104724746 B CN104724746 B CN 104724746B CN 201510081892 A CN201510081892 A CN 201510081892A CN 104724746 B CN104724746 B CN 104724746B
- Authority
- CN
- China
- Prior art keywords
- ardealite
- rare earth
- earth metal
- solution
- slurry
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Expired - Fee Related
Links
Classifications
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01F—COMPOUNDS OF THE METALS BERYLLIUM, MAGNESIUM, ALUMINIUM, CALCIUM, STRONTIUM, BARIUM, RADIUM, THORIUM, OR OF THE RARE-EARTH METALS
- C01F11/00—Compounds of calcium, strontium, or barium
- C01F11/46—Sulfates
- C01F11/468—Purification of calcium sulfates
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
- C01B25/00—Phosphorus; Compounds thereof
- C01B25/02—Preparation of phosphorus
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01F—COMPOUNDS OF THE METALS BERYLLIUM, MAGNESIUM, ALUMINIUM, CALCIUM, STRONTIUM, BARIUM, RADIUM, THORIUM, OR OF THE RARE-EARTH METALS
- C01F17/00—Compounds of rare earth metals
- C01F17/20—Compounds containing only rare earth metals as the metal element
- C01F17/206—Compounds containing only rare earth metals as the metal element oxide or hydroxide being the only anion
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
- C01P2006/00—Physical properties of inorganic compounds
- C01P2006/80—Compositional purity
Landscapes
- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Inorganic Chemistry (AREA)
- Life Sciences & Earth Sciences (AREA)
- Geology (AREA)
- Manufacture And Refinement Of Metals (AREA)
Abstract
The invention discloses a method for recycling ardealite. The method comprises the following steps: (1) doping water and a grinding aid into ardealite to prepare ardealite slurry; (2) treating the ardealite slurry by using a 3.5-6.2% sulfuric acid solution to leach out solid phosphorus; (3) treating the ardealite slurry treated in the step (2) by using an 8-10% of sulfuric acid solution to leach out rare earth metals; (4) adjusting the pH value by using sulfuric acid, adsorbing the rare earth metals by using a cation exchanger, and performing desorption by using a desorption agent; (5) precipitating the rare earth metals from the solution by using oxalic acid; (6) rinsing, drying and roasting insoluble compounds of the rare earth metals; (7) performing a method of recycle leaching; and (8) performing separation by crystallization on calcium sulfate in a secondary mother solution in the step (3), and washing and drying. According to the method disclosed by the invention, phosphorus, rare earth metals and calcium sulfate in ardealite are leached out by stages, the leaching rate is high, the purity is high, the whole technological process is stable, the implementation manner is simple and effective, and the utilization ratio of resources is greatly improved.
Description
Technical field
The present invention relates to chemical industrial waste thing reclaim and environmental protection technical field, be specifically related to a kind of ardealite
The method of cycling and reutilization.
Background technology
Phosphogypsum slag occurs mainly with phosphorous chemical industry (phosphate fertilizer) industry, be produce high-concentration phosphate compound fertilizers be produce
A kind of industry by-product gypsum, ardealite be mainly composed of CaSO4 2H2O, pH value is about 1.5～4.5,
In acidity, moisture content is the highest, and contained free water can reach 20%-25%.There are some researches show, use wet
The enterprise of method defeated slag mode, inorganic fluoride (the not including calcium fluoride) concentration in its ardealite solid waste is more than
100mg/L, beyond the limit value of " hazardous waste judging standard leaching characteristic identification " (GB5085.3-2007),
Belong to hazardous waste, 2006, State Environmental Protection Administration once by qualitative for the phosphogypsum slag of two phosphatic fertilizer companies for danger
Danger refuse.Ardealite storage yard mainly has mountain valley-type type two ways pacifically, and ardealite storage yard takies a large amount of soil
Ground, relatively big to periphery ecology influence, ardealite storage yard is an artificial mud-rock flow with high potential energy simultaneously
Source, once has an accident, will cause huge disaster and loss to industrial and agricultural production and downstream people's lives and properties.
In recent years, the generation amount of ardealite is quickly increasing always, is increased to by 11,000,000 tons of 2000
More than 4000 in 2008 ten thousand tons, the biggest 4000-7000 of the amount of generation ten thousand tons/year over 2010, accumulative volume of cargo in storage
More than 100,000,000 tons.To the end of the year 2011, China is accumulative has piled up more than 300,000,000 tons of ardealites, and every year with
50000000 tons of yield increase；To the end of the year 2010, whole world industrial phosphogypsum is stacked total amount and has been reached 5,600,000,000 tons,
Every annual meeting increases 1.1 hundred million～1.5 hundred million tons newly, and newly-increased quantity also can be double during 2025 to the year two thousand forty.
The effective rate of utilization of whole world ardealite is only about 4.5%, and the effective rate of utilization of China's ardealite is not enough
10%, National Development and Reform Committee in 2013 is that the comprehensive utilization of ardealite proposes comprehensive utilization ratio in 2015 and reaches
To the target of 30%；In " industry by-product gypsum comprehensive utilization instruction ", the Ministry of Industry and Information Technology is then
Proposing for the end of the year 2015, ardealite comprehensive utilization ratio to bring up to 40%.But the most do not obtain
Application very well, current comprehensive utilization ratio only about 10%, year, utilization was at 400～5,000,000 tons.
At present, the comprehensive utilization technique of ardealite mainly has building material technology, cement joint production sulphuric acid and cement
Retarder technology etc., these technology due in ardealite containing free sulphuric acid, phosphoric acid and Fluohydric acid., they
Gypsum Fibrosum preparata can be made when building, structural material to be corrosive, or to the model of Gypsum Fibrosum prefabricated component processed, set
Standby generation is corroded, and the most also extends the setting time of Gypsum Fibrosum, and actual effect is unsatisfactory.Ardealite is located a little
Reason can serve as cement retarder, it is possible to make building block for building or brick, but consumption is limited, it is difficult to from all
Upper solution ardealite accumulates.So, the most all work out more preferable ardealite Application way being devoted to.
Ardealite is actually impure Gypsum Fibrosum, and impurity comprises a large amount of rare earth metal.If can impurity with
Gypsum Fibrosum is kept completely separate, and not only can get high-purity, the high purity plaster of high whiteness, and impurity slag is gone back after enrichment again
The raw material refining rare earth metal can be become.High purity plaster is had many uses general, and the whiteness high with it and purity can
For industries such as rubber, plastics, coating, papermaking, medicine, food, it is used for manufacturing senior building materials and decoration
Material, high-quality crystal whisker of gypsum etc., can substitute the top quality natural gypsum comprehensively.Have full resource utilization only
It is only the final outlet of ardealite.Developing rapidly of phosphorous chemical industry, increases the demand of sulphuric acid, and China's sulfur money
Source lacks, major part dependence on import sulfur Sulphuric acid.Therefore, impurity and Gypsum Fibrosum are kept completely separate become wholly-owned source
Change the key utilizing ardealite.High purity white gypsum product content reaches more than 99%, containing 20 in impurity
Remaining kind metal, wherein most is rare earth metal, and ardealite utilization rate nearly 100% the most just can be thorough
The end, solves this global problem of ardealite recycling.
Summary of the invention
Present invention solves the technical problem that a kind of method being to provide ardealite cycling and reutilization, whole technique
Process is steady, and ardealite utilization rate is high, has significant economic benefit.
The technical scheme is that a kind of method of ardealite cycling and reutilization comprises the following steps:
(1) ardealite slurry is prepared: ardealite and water are mixed according to the ratio of 1:3-5, stirring, stand
0.2-0.5h, mixes the grinding aid relative to amount of the mixture 0.08-0.12%, then uses ball mill ball milling, system
Become ardealite slurry；
(2) solid phosphorus is leached: process ardealite slurry with the sulfuric acid solution of 3.5-6.2%, by weight, add
Ratio between the sulphuric acid entered and ardealite slurry is 1:3.2-4.0, temperature is controlled at 28-34 DEG C, at stirring
Managing 0.4-0.6 hour, stand 3-5h, leach solid phosphorus, solid phosphorus is separated from a mother solution,
Phosphorus residue purified water is washed, and reclaims once washing liquid, returns again in ardealite slurry；
(3) rare earth metal is leached: the sulphuric acid of ardealite slurry continuation 8-10% step (2) processed
Solution processes, and by weight, the ratio between the sulphuric acid of addition and ardealite slurry is 1:1.2-2.8, by temperature
Degree controls at 64-72 DEG C, and stir process 0.5-1.5 hour leaches insoluble black slag, is rare earth metal,
Through filtering, rare earth metal is separated from secondary mother liquid, wash by purified water, stay secondary washing liquid to treat
With；
(4) conversion rare earth compound becomes solution: comprise a large amount of rare earth metal, warp in the black slag after washing
The L-AA of 11-15% can be added as the raw material of refinement rare earth metal, then adjusts with sulphuric acid after enrichment again
Joint pH value, to 1.5-2.0, acts on 0.4-1.2h at 70-80 DEG C, with cationite absorption rare earth gold
Belong to, wash with water, remove insoluble impurity, adsorption liquid use again strippant desorbing, described strippant be nitric acid,
Hydrochloric acid, calcium nitrate, the mixture of calcium chloride, apply pulse Vacuum effect during whole；
(5) precipitation again of rare earth metal: introduce oxalic acid in the solution of rare earth compound, generate dilute
The insoluble compound of earth metal, is settled out from solution, uses film filter to isolate from infusion solution
Come；
(6) smelting of rare earth metal: the insoluble compound of the rare earth metal separated rinses, is dried,
Calcining, prepares the oxide of rare earth metal；
(7) method of circulating leaching is used to carry out, by a mother solution of step (2) in each cyclic process
It is incorporated in step (3) with once washing liquid, the secondary washing liquid of step (3) is circulated throughout at the next one
Journey is re-introduced in step (2)；
(8) by the secondary mother liquid of step (3), being incorporated in vacuum type plusator, starting impulse is sent out
Raw device, changes mother solution condition, makes the crystal of calcium sulfate of dissolving separate out, then through filter pressing, primary water is through the dress that catchments
Put discharge, washing, it is dried to obtain high-purity sulphuric acid calcium.
In such scheme, in described step (1), grinding aid is polymerized polyalcohol, adds a small amount of grinding aid,
It is possible to prevent particle aggregation, improves material fluidity, thus improve grinding efficiency, shorten milling time.
In such scheme, described step (4) cationic exchanger is strongly acidic cation-exchange,
Mainly contain highly acid reactive group such as sulfonic group (-SO3H), this ion exchange resin to various sun from
The exchange rate of son is the highest.
In such scheme, nitric acid, hydrochloric acid, calcium nitrate, calcium chloride in the strippant in described step (4)
Mol ratio be 8:5:3:1.Strong acid cooperates with slaine, and desorption effect is more preferable.
In such scheme, strippant described in described step (4) is 2-5:1 with the mass ratio of adsorption liquid.
In such scheme, changing mother solution condition in described step (8) is: with the cooling speed of 0.3 DEG C/min
Degree, reduces mother solution temperature to 2-8 DEG C.
Compared with prior art, it provides the benefit that the present invention: by the phosphorus in ardealite, rare earth metal, sulfur
Acid calcium leaches stage by stage, and each stage leaching rate is the highest, and its purity of each composition leached is the highest；
The method using circulating leaching, is effectively improved the utilization rate of resource, economizes on resources；Whole technical process is steady,
Embodiment is simply effective, serves good refuse cycling and reutilization effect, protects environment.
Detailed description of the invention
In order to enable the auditor especially public of Patent Office to be more clearly understood from the technical spirit of the present invention
And beneficial effect, applicant will elaborate by way of example below, but retouches embodiment
Stating not is the restriction to the present invention program, any the most pro forma according to done by present inventive concept
Rather than substantial equivalent transformation is regarded as technical scheme category.
Embodiment 1: a kind of method of ardealite cycling and reutilization, comprises the following steps:
(1) prepare ardealite slurry: 200kg is contained the ardealite of the rare earth element of 0.45% and water according to
The ratio mixing of 1:3, stirring, stand 0.2h, mix the grinding aid relative to amount of the mixture 0.08%,
Described grinding aid is polymerized polyalcohol, adds a small amount of grinding aid, is possible to prevent particle aggregation, improves material stream
Dynamic property, thus improve grinding efficiency, shorten milling time, then use ball mill ball milling, make ardealite slurry；
(2) solid phosphorus is leached: the sulfuric acid solution with 3.5% processes ardealite slurry, by weight, addition
Ratio between sulphuric acid and ardealite slurry is 1:3.2, temperature is controlled at 28 DEG C, stir process 0.4 hour,
Standing 3h, leach solid phosphorus, solid phosphorus is separated from a mother solution, and phosphorus residue purification is washed
Wash, reclaim once washing liquid, return again in ardealite slurry；
(3) rare earth metal is leached: ardealite slurry step (2) processed continues the sulfuric acid solution with 8%
Processing, by weight, the ratio between the sulphuric acid of addition and ardealite slurry is 1:1.2, temperature is controlled
64 DEG C, stir process 0.5 hour, leaches insoluble black slag, is rare earth metal, through filtering, by rare earth
Metal is separated from secondary mother liquid, washs by purified water, stays secondary washing liquid stand-by；
(4) conversion rare earth compound becomes solution: comprise a large amount of rare earth metal, warp in the black slag after washing
The L-AA of 11% can be added as the raw material of refinement rare earth metal, then regulates with sulphuric acid after enrichment again
PH value, to 1.5, acts on 0.4h at 70 DEG C, adsorbs rare earth metal, described cation with cationite
Exchanger is strongly acidic cation-exchange, mainly contain highly acid reactive group such as sulfonic group (-
SO3H), this ion exchange resin is the highest to the exchange rate of various cationes, is washed with water and washs, and removes
Insoluble impurity, adsorption liquid uses strippant desorbing, described strippant to be nitric acid, hydrochloric acid, calcium nitrate, chlorination again
The mixture of calcium, described nitric acid, hydrochloric acid, calcium nitrate, the mol ratio of calcium chloride are 8:5:3:1, strong acid with
Slaine cooperates, and desorption effect is more preferable, and wherein, described strippant is 2:1 with the mass ratio of adsorption liquid,
Meanwhile, during whole, pulse Vacuum effect is applied；
(5) precipitation again of rare earth metal: introduce oxalic acid in the solution of rare earth compound, generate dilute
The insoluble compound of earth metal, is settled out from solution, uses film filter to isolate from infusion solution
Come；
(6) smelting of rare earth metal: the insoluble compound of the rare earth metal separated rinses, is dried,
Calcining, prepares the oxide of rare earth metal；
(7) method of circulating leaching is used to carry out, by a mother solution of step (2) in each cyclic process
It is incorporated in step (3) with once washing liquid, the secondary washing liquid of step (3) is circulated throughout at the next one
Journey is re-introduced in step (2)；
(8) by the secondary mother liquid of step (3), being incorporated in vacuum type plusator, starting impulse is sent out
Raw device, changes mother solution condition, and with the cooling rate of 0.3 DEG C/min, reduction mother solution temperature, to 2 DEG C, makes molten
The crystal of calcium sulfate solved separates out, then through filter pressing, primary water is discharged through captation, and washing is dried to obtain height
Pure calcium sulfate.
Result: 200kg ardealite, analyzes method with ICP-AES and is analyzed its chemical composition, contain
Rare earth element is 0.46%, containing P2O5Being 2.16%, i.e. containing rare earth element is 0.9kg, containing P2O5For
4.32kg, with the sample analysis of ICPMS (inductively coupled plasma mass spectrometry), result demonstrates rare earth element
The response rate be 91.4%, insoluble P2O5Leaching rate reach 90.7%, the high-purity sulphuric acid calcium finally given
Its purity is 99.72%.
Embodiment 2: a kind of method of ardealite cycling and reutilization, comprises the following steps:
(1) prepare ardealite slurry: 200kg is contained the ardealite of the rare earth element of 0.45% and water according to
The ratio mixing of 1:4, stirring, stand 0.35h, mix the grinding aid relative to amount of the mixture 0.1%,
Described grinding aid is polymerized polyalcohol, adds a small amount of grinding aid, is possible to prevent particle aggregation, improves material stream
Dynamic property, thus improve grinding efficiency, shorten milling time, then use ball mill ball milling, make ardealite slurry；
(2) solid phosphorus is leached: the sulfuric acid solution with 4.85% processes ardealite slurry, by weight, addition
Ratio between sulphuric acid and ardealite slurry is 1:3.6, temperature is controlled at 31 DEG C, stir process 0.5 hour,
Standing 4h, leach solid phosphorus, solid phosphorus is separated from a mother solution, and phosphorus residue purification is washed
Wash, reclaim once washing liquid, return again in ardealite slurry；
(3) rare earth metal is leached: ardealite slurry step (2) processed continues the sulfuric acid solution with 9%
Processing, by weight, the ratio between the sulphuric acid of addition and ardealite slurry is 1:2, temperature is controlled
68 DEG C, stir process 1 hour, leaches insoluble black slag, is rare earth metal, through filtering, by rare earth gold
Belong to and separating from secondary mother liquid, wash by purified water, stay secondary washing liquid stand-by；
(4) conversion rare earth compound becomes solution: comprise a large amount of rare earth metal, warp in the black slag after washing
The L-AA of 13% can be added as the raw material of refinement rare earth metal, then regulates with sulphuric acid after enrichment again
PH value to 1.75, at 75 DEG C act on 0.8h, adsorb rare earth metal with cationite, described sun from
Sub-exchanger is strongly acidic cation-exchange, mainly contain highly acid reactive group such as sulfonic group (-
SO3H), this ion exchange resin is the highest to the exchange rate of various cationes, is washed with water and washs, and removes
Insoluble impurity, adsorption liquid uses strippant desorbing, described strippant to be nitric acid, hydrochloric acid, calcium nitrate, chlorination again
The mixture of calcium, described nitric acid, hydrochloric acid, calcium nitrate, the mol ratio of calcium chloride are 8:5:3:1, strong acid with
Slaine cooperates, and desorption effect is more preferable, and wherein, described strippant with the mass ratio of adsorption liquid is
3.5:1, meanwhile, applies pulse Vacuum effect during whole；
(5) precipitation again of rare earth metal: introduce oxalic acid in the solution of rare earth compound, generate dilute
The insoluble compound of earth metal, is settled out from solution, uses film filter to isolate from infusion solution
Come；
(6) smelting of rare earth metal: the insoluble compound of the rare earth metal separated rinses, is dried,
Calcining, prepares the oxide of rare earth metal；
(7) method of circulating leaching is used to carry out, by a mother solution of step (2) in each cyclic process
It is incorporated in step (3) with once washing liquid, the secondary washing liquid of step (3) is circulated throughout at the next one
Journey is re-introduced in step (2)；
(8) by the secondary mother liquid of step (3), being incorporated in vacuum type plusator, starting impulse is sent out
Raw device, changes mother solution condition, and with the cooling rate of 0.3 DEG C/min, reduction mother solution temperature, to 5 DEG C, makes molten
The crystal of calcium sulfate solved separates out, then through filter pressing, primary water is discharged through captation, and washing is dried to obtain height
Pure calcium sulfate.
Result: 200kg ardealite, analyzes method with ICP-AES and is analyzed its chemical composition, contain
Rare earth element is 0.46%, containing P2O5Being 2.16%, i.e. containing rare earth element is 0.9kg, containing P2O5For
4.32kg, with the sample analysis of ICPMS (inductively coupled plasma mass spectrometry), result demonstrates rare earth element
The response rate be 91.7%, insoluble P2O5Leaching rate reach 91.3%, the high-purity sulphuric acid calcium finally given
Its purity is 99.75%..
Embodiment 3: a kind of method of ardealite cycling and reutilization, comprises the following steps:
(1) prepare ardealite slurry: 200kg is contained the ardealite of the rare earth element of 0.45% and water according to
The ratio mixing of 1:5, stirring, stand 0.5h, mix the grinding aid relative to amount of the mixture 0.12%,
Described grinding aid is polymerized polyalcohol, adds a small amount of grinding aid, is possible to prevent particle aggregation, improves material stream
Dynamic property, thus improve grinding efficiency, shorten milling time, then use ball mill ball milling, make ardealite slurry；
(2) solid phosphorus is leached: the sulfuric acid solution with 6.2% processes ardealite slurry, by weight, addition
Ratio between sulphuric acid and ardealite slurry is 1:4.0, temperature is controlled at 34 DEG C, stir process 0.6 hour,
Standing 5h, leach solid phosphorus, solid phosphorus is separated from a mother solution, and phosphorus residue purification is washed
Wash, reclaim once washing liquid, return again in ardealite slurry；
(3) rare earth metal is leached: it is molten that ardealite slurry step (2) processed continues the sulphuric acid with 10%
Liquid processes, and by weight, the ratio between the sulphuric acid of addition and ardealite slurry is 1:2.8, by temperature control
At 72 DEG C, stir process 1.5 hours, leaches insoluble black slag, is rare earth metal, through filtering, by dilute
Earth metal is separated from secondary mother liquid, washs by purified water, stays secondary washing liquid stand-by；
(4) conversion rare earth compound becomes solution: comprise a large amount of rare earth metal, warp in the black slag after washing
The L-AA of 15% can be added as the raw material of refinement rare earth metal, then regulates with sulphuric acid after enrichment again
PH value, to 2.0, acts on 1.2h at 80 DEG C, adsorbs rare earth metal, described cation with cationite
Exchanger is strongly acidic cation-exchange, mainly contain highly acid reactive group such as sulfonic group (-
SO3H), this ion exchange resin is the highest to the exchange rate of various cationes, is washed with water and washs, and removes
Insoluble impurity, adsorption liquid uses strippant desorbing, described strippant to be nitric acid, hydrochloric acid, calcium nitrate, chlorination again
The mixture of calcium, described nitric acid, hydrochloric acid, calcium nitrate, the mol ratio of calcium chloride are 8:5:3:1, strong acid with
Slaine cooperates, and desorption effect is more preferable, and wherein, described strippant is 5:1 with the mass ratio of adsorption liquid,
Meanwhile, during whole, pulse Vacuum effect is applied；
(5) precipitation again of rare earth metal: introduce oxalic acid in the solution of rare earth compound, generate dilute
The insoluble compound of earth metal, is settled out from solution, uses film filter to isolate from infusion solution
Come；
(6) smelting of rare earth metal: the insoluble compound of the rare earth metal separated rinses, is dried,
Calcining, prepares the oxide of rare earth metal；
(7) method of circulating leaching is used to carry out, by a mother solution of step (2) in each cyclic process
It is incorporated in step (3) with once washing liquid, the secondary washing liquid of step (3) is circulated throughout at the next one
Journey is re-introduced in step (2)；
(8) by the secondary mother liquid of step (3), being incorporated in vacuum type plusator, starting impulse is sent out
Raw device, changes mother solution condition, and with the cooling rate of 0.3 DEG C/min, reduction mother solution temperature, to 8 DEG C, makes molten
The crystal of calcium sulfate solved separates out, then through filter pressing, primary water is discharged through captation, and washing is dried to obtain height
Pure calcium sulfate.
Result: 200kg ardealite, analyzes method with ICP-AES and is analyzed its chemical composition, contain
Rare earth element is 0.46%, containing P2O5Being 2.16%, i.e. containing rare earth element is 0.9kg, containing P2O5For
4.32kg, with the sample analysis of ICPMS (inductively coupled plasma mass spectrometry), result demonstrates rare earth element
The response rate be 92.5%, insoluble P2O5Leaching rate reach 92.4%, the high-purity sulphuric acid calcium finally given
Its purity is 99.83%.
Last it is noted that above example is only in order to illustrate technical scheme, rather than it is limited
System；Although the present invention being described in detail with reference to previous embodiment, those of ordinary skill in the art
It is understood that the technical scheme described in previous embodiment still can be modified by it, or to wherein
Portion of techniques feature carries out equivalent；And these amendments or replacement, do not make the basis of appropriate technical solution
Matter departs from the spirit and scope of embodiment of the present invention technical scheme.
Claims (6)
1. the method for an ardealite cycling and reutilization, it is characterised in that comprise the following steps:
(1) ardealite slurry is prepared: ardealite and water are mixed, stirring, stand, mix relative to mixture
The grinding aid of total amount 0.08-0.12%, then use ball mill ball milling, make ardealite slurry；
(2) leach solid phosphorus: process ardealite slurry with the sulfuric acid solution of 3.5-6.2%, the sulphuric acid of addition with
Ratio between ardealite slurry is 1:3.2-4.0, and temperature is at 28-34 DEG C, and action time is 0.4-0.6 hour,
Leaching solid phosphorus, be separated out by solid phosphorus, obtain a mother solution, phosphorus residue with water washs, and reclaims one
Secondary cleaning mixture, returns again in ardealite slurry；
(3) rare earth metal is leached: the sulphuric acid of ardealite slurry continuation 8-10% step (2) processed
Solution process, the sulphuric acid of addition and ardealite slurry between ratio be 1:1.2-2.8, temperature at 64-72 DEG C,
Action time is 0.5-1.5 hour, leaches insoluble black slag, is rare earth metal, through filtering, by rare earth
Metal is separated, and obtains secondary mother liquid, washs solid, stays secondary washing liquid stand-by；
(4) conversion rare earth compound becomes solution: comprise a large amount of rare earth metal, warp in the black slag after washing
With sulfur acid for adjusting pH value to 1.5-2.0, cation can be used as the raw material of refinement rare earth metal again after enrichment
Exchanger absorption rare earth metal, washes with water, removes insoluble impurity, and adsorption liquid uses strippant desorbing again,
To the solution of rare earth compound, described strippant is the mixing of nitric acid, hydrochloric acid, calcium nitrate, calcium chloride
Thing, applies pulse Vacuum effect during whole；
(5) precipitation again of rare earth metal: introduce oxalic acid in the solution of rare earth compound, generate dilute
The insoluble compound of earth metal, is settled out from solution, uses film filter to separate from solution；
(6) smelting of rare earth metal: the insoluble compound of the rare earth metal separated rinses, is dried,
Calcining, prepares the oxide of rare earth metal；
(7) method of circulating leaching is used to carry out, by a mother solution of step (2) in each cyclic process
It is incorporated in step (3) with once washing liquid, the secondary washing liquid of step (3) is circulated throughout at the next one
Journey is re-introduced in step (2)；
(8) by the secondary mother liquid of step (3), change mother solution condition, make the crystal of calcium sulfate of dissolving separate out,
Through filter pressing, wash, be dried to obtain high-purity sulphuric acid calcium.
The method of a kind of ardealite cycling and reutilization the most according to claim 1, it is characterised in that described step
Suddenly in (1), grinding aid is polymerized polyalcohol.
The method of a kind of ardealite cycling and reutilization the most according to claim 1, it is characterised in that described step
Suddenly (4) cationic exchanger is strongly acidic cation-exchange.
The method of a kind of ardealite cycling and reutilization the most according to claim 1, it is characterised in that described step
Suddenly in the strippant in (4), nitric acid, hydrochloric acid, calcium nitrate, the mol ratio of calcium chloride are 8:5:3:1.
The method of a kind of ardealite cycling and reutilization the most according to claim 1, it is characterised in that described step
Suddenly strippant described in (4) is 2-5:1 with the mass ratio of adsorption liquid.
The method of a kind of ardealite cycling and reutilization the most according to claim 1, it is characterised in that described step
Suddenly changing mother solution condition in (8) is: with the cooling rate of 0.3 DEG C/min, reduce mother solution temperature to 2-8 DEG C.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201510081892.7A CN104724746B (en) | 2015-02-15 | 2015-02-15 | Method for recycling ardealite |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201510081892.7A CN104724746B (en) | 2015-02-15 | 2015-02-15 | Method for recycling ardealite |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN104724746A CN104724746A (en) | 2015-06-24 |
| CN104724746B true CN104724746B (en) | 2017-01-11 |
Family
ID=53449250
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN201510081892.7A Expired - Fee Related CN104724746B (en) | 2015-02-15 | 2015-02-15 | Method for recycling ardealite |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN104724746B (en) |
Families Citing this family (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN106977123A (en) * | 2017-03-31 | 2017-07-25 | 合肥学院 | A kind of citric acid for being used to remove impurity fluorine in ardealite adds water the process washed |
Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101186284A (en) * | 2007-12-18 | 2008-05-28 | 贵州蓝天科大矿业发展有限公司 | Method for preparing phosphoric acid from phosphorus block ore by wet method and extracting rare earth from phosphorus block ore |
| CN101451200A (en) * | 2007-11-29 | 2009-06-10 | 北京有色金属研究总院 | Rare-earth enrichment recovery method from phosphorite |
| CN102382979A (en) * | 2011-11-03 | 2012-03-21 | 沈阳化工大学 | Technique for extracting rare earth from rare earth tailing and preparing calcium sulfate whiskers |
| CN102639729A (en) * | 2010-09-14 | 2012-08-15 | 双子贸易开放式股份公司 | Method for extracting rare earth elements from phosphogypsum |
| RU2014108085A (en) * | 2014-03-03 | 2014-06-27 | Федеральное государственное бюджетное учреждение науки Институт химии и технологии редких элементов и минерального сырья им. И.В. Тананаева Кольского научного центра Российской академии наук (ИХТРЭМС КНЦ РАН) | METHOD FOR PROCESSING PHOSPHOGYPS |
-
2015
- 2015-02-15 CN CN201510081892.7A patent/CN104724746B/en not_active Expired - Fee Related
Patent Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101451200A (en) * | 2007-11-29 | 2009-06-10 | 北京有色金属研究总院 | Rare-earth enrichment recovery method from phosphorite |
| CN101186284A (en) * | 2007-12-18 | 2008-05-28 | 贵州蓝天科大矿业发展有限公司 | Method for preparing phosphoric acid from phosphorus block ore by wet method and extracting rare earth from phosphorus block ore |
| CN102639729A (en) * | 2010-09-14 | 2012-08-15 | 双子贸易开放式股份公司 | Method for extracting rare earth elements from phosphogypsum |
| CN102382979A (en) * | 2011-11-03 | 2012-03-21 | 沈阳化工大学 | Technique for extracting rare earth from rare earth tailing and preparing calcium sulfate whiskers |
| RU2014108085A (en) * | 2014-03-03 | 2014-06-27 | Федеральное государственное бюджетное учреждение науки Институт химии и технологии редких элементов и минерального сырья им. И.В. Тананаева Кольского научного центра Российской академии наук (ИХТРЭМС КНЦ РАН) | METHOD FOR PROCESSING PHOSPHOGYPS |
Also Published As
| Publication number | Publication date |
|---|---|
| CN104724746A (en) | 2015-06-24 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN101607834B (en) | Preparation method for preparing potash fertilizer and producing sulfuric acid simultaneously employing mineral with potassium, ardealite and high-sulphur coal | |
| CN102383179B (en) | A kind of method that industrial waste acid and phosphogypsum fully utilize | |
| CN104211099B (en) | Resource recycling method of industrial phosphogypsum waste residues | |
| CN104986789B (en) | Method for preparing alpha-semi-hydrated gypsum in controllable mode through acid wastewater produced by producing titanium dioxide | |
| CN107814370B (en) | Circulating environment-friendly process method for preparing phosphate concentrate, product and application thereof | |
| CN102050487B (en) | Acidolysis method in titanium dioxide production technology adopting sulfuric acid process | |
| CN105601066B (en) | The method that fluorine-containing sludge refines calcirm-fluoride | |
| CN114105171A (en) | Method for recycling and comprehensively utilizing lepidolite and lithium hydroxide prepared by method | |
| CN104261473B (en) | A kind of preparation method of Vanadium Pentoxide in FLAKES | |
| CN106744721A (en) | The recovery separation method and application of sulfuric acid and dissolubility titanium in titanium white waste acid | |
| CN104445431A (en) | Method for preparing high-purity iron oxide red from pyrites slag | |
| CN114605094B (en) | Method for improving whiteness and purity of phosphogypsum by combination of dressing and smelting | |
| CN103819228A (en) | Method for preparing potash fertilizer and alumina silicate from potash feldspar | |
| CN113697790A (en) | Method for preparing phosphoric acid by hydrochloric acid wet process combining organic solvent extraction and water back extraction | |
| CN104445281B (en) | Trichlorosilane elution circuit waste residue method of comprehensive utilization | |
| CN107827114B (en) | Method for recovering phosphorus in wet-process phosphoric acid concentrated slag acid and co-producing dihydrate gypsum and sodium fluosilicate | |
| CN106629806A (en) | Method for producing dihydrate gypsum from waste liquid in laterite nickel ore wet process | |
| CN104724746B (en) | Method for recycling ardealite | |
| CN108439451A (en) | The method for preparing precipitated calcium carbonate using ardealite | |
| CN110732543B (en) | Method for jointly producing cement clinker and ammonia water by electrolyzing metal manganese waste residue and gypsum | |
| CN106865724A (en) | The processing method of tantalum and niobium hydrometallurgy raffinate and comprehensive wastewater | |
| CN110395751B (en) | Method for extracting lithium sulfate from lepidolite | |
| CN110734093B (en) | Method for co-producing manganese hydroxide and sulfuric acid or ammonium sulfite by electrolyzing metal manganese waste residue | |
| CN111392754B (en) | Method and equipment for purifying calcium chloride from fluorine-containing solid waste | |
| CN108467945A (en) | A kind of processing method of slag, titanium white waste acid |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| C06 | Publication | ||
| PB01 | Publication | ||
| C10 | Entry into substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| C41 | Transfer of patent application or patent right or utility model | ||
| TA01 | Transfer of patent application right |
Effective date of registration: 20161014 Address after: 261061 Dongfeng East Street, high tech Zone, Shandong, Weifang, China, 5147 Applicant after: Weifang College Address before: 261061 No. 5147 Dongfeng East Street, Weifang hi tech Zone, Shandong Province, Weifang University Applicant before: Tai Xishi |
|
| GR01 | Patent grant | ||
| GR01 | Patent grant | ||
| CF01 | Termination of patent right due to non-payment of annual fee |
Granted publication date: 20170111 Termination date: 20190215 |
|
| CF01 | Termination of patent right due to non-payment of annual fee |