CN109112305A - A kind of fluorine-containing Rare Earth Mine defluorinate extract technology - Google Patents
A kind of fluorine-containing Rare Earth Mine defluorinate extract technology Download PDFInfo
- Publication number
- CN109112305A CN109112305A CN201811272683.0A CN201811272683A CN109112305A CN 109112305 A CN109112305 A CN 109112305A CN 201811272683 A CN201811272683 A CN 201811272683A CN 109112305 A CN109112305 A CN 109112305A
- Authority
- CN
- China
- Prior art keywords
- fluorine
- rare earth
- defluorinate
- containing rare
- extract technology
- 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.)
- Pending
Links
Classifications
-
- C—CHEMISTRY; METALLURGY
- C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
- C22B—PRODUCTION AND REFINING OF METALS; PRETREATMENT OF RAW MATERIALS
- C22B3/00—Extraction of metal compounds from ores or concentrates by wet processes
- C22B3/04—Extraction of metal compounds from ores or concentrates by wet processes by leaching
- C22B3/06—Extraction of metal compounds from ores or concentrates by wet processes by leaching in inorganic acid solutions, e.g. with acids generated in situ; in inorganic salt solutions other than ammonium salt solutions
- C22B3/10—Hydrochloric acid, other halogenated acids or salts thereof
-
- C—CHEMISTRY; METALLURGY
- C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
- C22B—PRODUCTION AND REFINING OF METALS; PRETREATMENT OF RAW MATERIALS
- C22B3/00—Extraction of metal compounds from ores or concentrates by wet processes
- C22B3/20—Treatment or purification of solutions, e.g. obtained by leaching
- C22B3/22—Treatment or purification of solutions, e.g. obtained by leaching by physical processes, e.g. by filtration, by magnetic means, or by thermal decomposition
-
- C—CHEMISTRY; METALLURGY
- C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
- C22B—PRODUCTION AND REFINING OF METALS; PRETREATMENT OF RAW MATERIALS
- C22B59/00—Obtaining rare earth metals
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
- Y02P10/00—Technologies related to metal processing
- Y02P10/20—Recycling
Landscapes
- Chemical & Material Sciences (AREA)
- Engineering & Computer Science (AREA)
- Geology (AREA)
- Life Sciences & Earth Sciences (AREA)
- General Life Sciences & Earth Sciences (AREA)
- Manufacturing & Machinery (AREA)
- Environmental & Geological Engineering (AREA)
- Materials Engineering (AREA)
- Mechanical Engineering (AREA)
- Metallurgy (AREA)
- Organic Chemistry (AREA)
- Geochemistry & Mineralogy (AREA)
- Inorganic Chemistry (AREA)
- Manufacture And Refinement Of Metals (AREA)
Abstract
The invention belongs to rare earth fluorine resources to purify recovery technology field, and in particular to a kind of fluorine-containing Rare Earth Mine defluorinate extract technology.In the present invention, fluorine-containing rare earth is leached under high acid environment first with boric acid and KCl system, after leachate is then filtered residue, without acid-base accommodation, it is washed after being directly precipitated by spontaneous nucleation, the high-purity fluorine potassium borate product of technical grade can be obtained.Defluorinate extract technology provided by the invention, tests prove that, there is the features such as mineral defluorinate efficient stable, rare earth leaching rate is high, fluorine can efficiently use and commercialization, and output rare-earth liquid concentration is high, and process is short；Meanwhile being compared with other methods the waste water yield that can be reduced more than half；In addition, having extensive and good applicability, it is suitable for all types of fluorine-containing rare-earth minerals and its all kinds of fluorine-containing Rare Earth Derivatives.
Description
Technical field
The present invention relates to rare earth fluorine resources to purify recovery technology field, and in particular to a kind of fluorine-containing Rare Earth Mine defluorinate leaching work
Skill.
Background technique
There are mainly two types of for the fluorine-containing rare-earth mineral decomposition leaching technology of rare-earth trade now:
1, it sulfuric acid roasting method: is roasted after the concentrated sulfuric acid and rare-earth mineral mixing, rare earth fluoride or phosphoric acid rare earth is made to be converted into sulphur
Acid rare earth, part fluorine is escaped in the form of hydrogen fluoride gas in roasting process, and the difficult operating cost of the fluorine-containing processing of baking tail gases is high.
Fluorine in sulfuric acid process process feed liquid can be with by-product ice crystal, but its long flow path, and auxiliary facility is more, at high cost.Sulphur on the whole
Acid system leaching rate is high, but reagent consumption is big, and brine waste yield is big, and the utilization rate of fluorine is not high.
2, sodium-hydroxide method: converting rare earth fluoride or phosphoric acid rare earth using sodium hydroxide, generates sodium fluoride or phosphorus
Then sour sodium needs massive laundering to wash ore pulp, then dissolving with hydrochloric acid.Transformation time is long in technical process, fluoride waste yield
Greatly, processing is difficult, and fluorine resource wastes substantially.
As the above analysis, both the above rare-earth mineral leaching technology exist process flow is long, waste water yield is big,
Waste water fluorinated volume is higher, the not high problem of fluorine resource utilization in rare earth.At the same time, in above-mentioned technique, due to returning for villiaumite
Receipts mostly use the mode of organic extraction to carry out, and extraction step is more and cumbersome, and there is also larger for used organic extract
Pollution problem, recycling and post-processing trouble.
Summary of the invention
The present invention provides a kind of fluorine-containing Rare Earth Mine defluorinate extract technologies, it is therefore intended that passes through the change of extract technology route
And optimization, to solve the problems, such as fluorine Resource Access complex process and rate of recovery deficiency in existing rare earth extract technology.
The technical solution adopted by the invention is as follows:
A kind of fluorine-containing Rare Earth Mine defluorinate extract technology, which comprises the following steps:
1) reaction kettle is added after crushing fluorine-containing rare-earth mineral, boric acid and potassium chloride is then added, forms mixture；
2) concentrated hydrochloric acid is added into reaction kettle and adjusts the acidity of mixture in kettle to 3~8N, and forming solid-to-liquid ratio is 1:(4
~10) solidliquid mixture；
3) after reaction kettle heating, after carrying out 1~5h of Leach reaction under conditions of 80~110 DEG C, it is separated by solid-liquid separation to obtain slag
And feed liquid；
4) feed liquid is after crystallisation by cooling, then is separated by solid-liquid separation, and obtains thick potassium fluoborate and peracid feed liquid；
5) thick potassium fluoborate obtains purification potassium fluoborate successively after pickling, washing, centrifugal dehydration, drying.
Further, the fluorine-containing Rare Earth Mine is bastnaesite, mixed rare earth concentrates or fluorine-containing rare earth by-product；It is fluorine-containing dilute
Native by-product can be rare earth fluoride, fluorine rare earth oxide, impure fluorine rare earth oxide, etc..
Further, in step 1, fluorine-containing rare-earth mineral is rear after crushing to cross the use of 100~300 meshes.The mesh that mineral crush
Be increase contact area, improve reaction speed, reduce the reaction time.Mineral granularity control is in 100~300 purposes the reason is that grain
Spend the big reaction time it is too long be unfavorable for industrialized production, after the meticulous leaching of granularity can argillization, cause to be separated by solid-liquid separation difficult；It crushes
Mesh number preferably can be 100 mesh, 120 mesh, 180 mesh, 240 mesh and 300 mesh.
Further, in step 1, mole of boron element contained by the mole and boric acid of fluorine element contained by fluorine-containing rare-earth mineral
The ratio of amount is 1: (4.8~10)；I.e. first according to the fluorinated volume in the fluorine-containing rare-earth mineral as raw material, according to fluorine from minerals
It is completely converted into KBF4Theoretical amount needed for calculating boric acid, then boric acid actual use measures 1.2~2.5 times of theoretical amount.
Further, in step 1, the mass ratio between boric acid and potassium chloride is 1: (0.9~1.15).In above-mentioned boric acid and
The ratio and boric acid of potassium chloride correspond to mineral it is enough under the premise of, by be added potassium chloride amount difference, can be according to practical feelings
Condition adjustment reaction system is excessive in potassium chloride or is in that boric acid is excessive, to guarantee KBF4Quantum of output.
Further, in step 2, the mass concentration of concentrated hydrochloric acid is 30%.The high acid environment that concentrated hydrochloric acid is formed, a side
The decomposition that face is conducive to each element in fluorine-containing Rare Earth Mine is precipitated, while improving solubility of the boric acid in feed liquid and guaranteeing that fluorine ion is complete
Portion forms fluoro boron acid ion, can effectively improve reaction rate, reduces the reaction time.
Further, in step 3, Leach reaction is carried out also while under conditions of being condensed back, to avoid adding
Solution evaporation under the conditions of temperature in reaction system ensure that each material concentration and system acidity are stablized in reaction system, promote
Leach the process with defluorination reaction.
Further, in step 4, the process of crystallisation by cooling is specially that feed liquid is naturally cooled to 15~35 DEG C, thus directly
Connect the separation and Extraction that potassium fluoborate is realized using potassium fluoborate solubility and the positively related Variation Features of temperature；Compared to existing skill
Need to recycle the fluorine element in Extraction of rare earth mine in art by the way of multistep organic extraction, crystallisation by cooling process is simpler
It is convenient, without excessive control parameter, more operability and the fact, while also reducing the extraction cost and correlation of fluorine element
The possible environmental pollution of process institute and personnel safety risk.
Further, it in step 5, when carrying out pickling to thick potassium fluoborate, is carried out using 1~6N hydrochloric acid, and washing times
It is 1 time.It is advantageous in that using above-mentioned equivalent concentration hydrochloric acid, washed potassium fluoborate can be effectively prevent to hydrolyze, on the one hand
The yield of potassium fluoborate is improved, on the other hand potassium fluoborate can be effectively prevent to hydrolyze, and then ensure that subsequent dehydration
In filterability.In addition, hydrochloric acid can be volatilized automatically in subsequent drying process with drying, to accomplish not remain, protect
The purity of potassium fluoborate product is demonstrate,proved.
Further, it in step 5, when being washed to thick potassium fluoborate, is carried out using cold water.It is washed by cold water, into
One step has washed the water-solubility impurity in potassium fluoborate, further improves the purity of potassium fluoborate product.
Further, the defluorinate extract technology further includes step 6, the step 6 specifically: gained in step 4 is high
After sour feed liquid reduces acidity by way of soaking mine again, it is separated by solid-liquid separation to obtain deacidification feed liquid and solid impurity, deacidification filtrate is used
It is recycled in the extraction of rare earth element, impurity is for being added reaction kettle circular treatment in step 2.This process, on the one hand can be not
The purpose that feed liquid deacidification is realized in the case where using sodium hydroxide, to reduce the dosage of sodium hydroxide, on the other hand into one
Step is improved to the hydrionic utilization rate of high concentration is remained in feed liquid, reduces the usage amount of hydrochloric acid in whole process；Therefore, originally
Process can further increase the economic benefit of defluorinate extract technology.In addition, mine used in mineral used in leaching mine process and step 1
The type and granularity of object are consistent；The amount of the used mineral of mine process is soaked, simultaneously to soak gained deacidification feed liquid after mine separation
Acidity value be suitable for downstream rare earth element extraction process acidity requirements subject to.
In conclusion compared with the prior art, the invention has the advantages that:
(1) through the invention, mineral defluorinate efficient stable, rare earth leaching rate are high, fluorine can efficiently use and commercialization, produce
Rare-earth liquid concentration is high out, and process is short, is compared with other methods the waste water yield that can be reduced more than half；
(3) present invention is suitable for all types of fluorine-containing rare-earth minerals and its all kinds of fluorine-containing Rare Earth Derivatives, has extensive and good
Good applicability；
(4) potassium fluoborate product is extracted by spontaneous nucleation, needs not move through soda acid adjustment, and subsequent high containing rare earth element
The mode of leaching mine is taken to carry out in the deacidification of sour feed liquid, industry is whole to adjust pH value without using alkaline matter, simplifies work
Skill step, has saved the use of the alkaline conditioners such as sodium hydroxide, therefore saves the process time, reduces process costs；
(5) simple process, process only relate to the conventional simple operations such as heating for dissolving, filtering, decrease temperature crystalline precipitation, safely may be used
It leans on, and requires the equipment that uses less, operator is required lower, therefore operating cost is low, good in economic efficiency；
(6) each reagent toxicity used in technique is small, environmental pollution is low, environmentally friendly.
Specific embodiment
All features disclosed in this specification can be with any other than mutually exclusive feature and/or step
Mode combines.
Embodiment 1
A kind of fluorine-containing Rare Earth Mine defluorinate extract technology, which comprises the following steps:
1) fluorine-containing rare-earth mineral is crushed and is crossed after 100~300 meshes and reaction kettle is added, boric acid and chlorination is then added
Potassium forms mixture；Wherein, the ratio of the mole of boron element contained by the mole of fluorine element contained by fluorine-containing rare-earth mineral and boric acid
Value is 1: (4.8~10), the mass ratio between boric acid and potassium chloride are 1: (0.9~1.15)；
2) concentrated hydrochloric acid that mass concentration is 30% is added into reaction kettle and adjusts the acidity of mixture in kettle to 3~8N, and
Forming solid-to-liquid ratio is 1: the solidliquid mixture of (4~10)；
3) after reaction kettle heating, under conditions of 80~110 DEG C of temperature and condensing reflux, after carrying out 1~5h of Leach reaction,
It is separated by solid-liquid separation to obtain slag and feed liquid；
4) it after feed liquid is naturally cooled to 15~35 DEG C and crystallized, then is separated by solid-liquid separation, obtains thick potassium fluoborate and peracid feed liquid；
5) thick potassium fluoborate uses 1~6N chlorohydric acid pickling 1 time, then centrifugal dehydration after being washed with cold water, it is dry after, must refine
Potassium fluoborate.
Embodiment 2
A kind of fluorine-containing Rare Earth Mine defluorinate extract technology, which comprises the following steps:
1) fluorine-containing rare-earth mineral is crushed and is crossed after 100~300 meshes and reaction kettle is added, boric acid and chlorination is then added
Potassium forms mixture；Wherein, the ratio of the mole of boron element contained by the mole of fluorine element contained by fluorine-containing rare-earth mineral and boric acid
Value is 1: (4.8~10), the mass ratio between boric acid and potassium chloride are 1: (0.9~1.15)；
2) concentrated hydrochloric acid that mass concentration is 30% is added into reaction kettle and adjusts the acidity of mixture in kettle to 3~8N, and
Formation solid-to-liquid ratio be 1:(4~10) solidliquid mixture；
3) after reaction kettle heating, under conditions of 80~110 DEG C of temperature and condensing reflux, after carrying out 1~5h of Leach reaction,
It is separated by solid-liquid separation to obtain slag and feed liquid；
4) it after feed liquid is naturally cooled to 15~35 DEG C and crystallized, then is separated by solid-liquid separation, obtains thick potassium fluoborate and peracid feed liquid；
5) thick potassium fluoborate uses 1~6N chlorohydric acid pickling 1 time, then centrifugal dehydration after being washed with cold water, it is dry after, must refine
Potassium fluoborate.
6) into step 4, the fluorine-containing rare-earth mineral of identical type and granularity reduces acid in gained peracid feed liquid investment step 1
After degree, it is separated by solid-liquid separation to obtain deacidification feed liquid and solid impurity, extraction of the deacidification filtrate for rare earth element is recycled, and impurity is for walking
Reaction kettle circular treatment is added in rapid 2.
Embodiment 3
A kind of fluorine-containing Rare Earth Mine defluorinate extract technology, which comprises the following steps:
1) fluorine-containing rare-earth mineral is crushed and is crossed after 300 meshes and reaction kettle is added, boric acid and potassium chloride is then added, formed
Mixture；Wherein, the ratio of the mole of boron element contained by the mole of fluorine element contained by fluorine-containing rare-earth mineral and boric acid is 1:
4.8, the mass ratio between boric acid and potassium chloride is 1: 0.9；
2) concentrated hydrochloric acid that mass concentration is 30% is added into reaction kettle and adjusts the acidity of mixture in kettle to 3N, and is formed
The solidliquid mixture that solid-to-liquid ratio is 1: 4；
3) it after reaction kettle heating, under conditions of 80 DEG C of temperature and condensing reflux, after carrying out Leach reaction 1, is separated by solid-liquid separation
Obtain slag and feed liquid；
4) it after feed liquid is naturally cooled to 15 DEG C and crystallized, then is separated by solid-liquid separation, obtains thick potassium fluoborate and peracid feed liquid；
5) thick potassium fluoborate uses 1N chlorohydric acid pickling 1 time, then centrifugal dehydration after being washed with cold water, it is dry after, obtain purification fluorine
Potassium borate.
Embodiment 4
A kind of fluorine-containing Rare Earth Mine defluorinate extract technology, which comprises the following steps:
1) reaction kettle is added after fluorine-containing rare-earth mineral being crushed and sieved with 100 mesh sieve, boric acid and potassium chloride is then added, is formed
Mixture；Wherein, the ratio of the mole of boron element contained by the mole of fluorine element contained by fluorine-containing rare-earth mineral and boric acid is 1:
10, the mass ratio between boric acid and potassium chloride is 1: 1.15；
2) concentrated hydrochloric acid that mass concentration is 30% is added into reaction kettle and adjusts the acidity of mixture in kettle to 8N, and is formed
The solidliquid mixture that solid-to-liquid ratio is 1: 10；
3) after reaction kettle heating, under conditions of 110 DEG C of temperature and condensing reflux, after carrying out Leach reaction 5h, solid-liquid point
From slag and feed liquid；
4) it after feed liquid is naturally cooled to 35 DEG C and crystallized, then is separated by solid-liquid separation, obtains thick potassium fluoborate and peracid feed liquid；
5) thick potassium fluoborate uses 6N chlorohydric acid pickling 1 time, then centrifugal dehydration after being washed with cold water, it is dry after, obtain purification fluorine
Potassium borate.
Embodiment 5
A kind of fluorine-containing Rare Earth Mine defluorinate extract technology, which comprises the following steps:
1) fluorine-containing rare-earth mineral is crushed and is crossed after 240 meshes and reaction kettle is added, boric acid and potassium chloride is then added, formed
Mixture；Wherein, the ratio of the mole of boron element contained by the mole of fluorine element contained by fluorine-containing rare-earth mineral and boric acid is 1:
6, the mass ratio between boric acid and potassium chloride is 1: 0.97；
2) concentrated hydrochloric acid that mass concentration is 30% is added into reaction kettle and adjusts the acidity of mixture in kettle to 4N, and is formed
The solidliquid mixture that solid-to-liquid ratio is 1: 5.5；
3) it after reaction kettle heating, under conditions of 88 DEG C of temperature and condensing reflux, after carrying out Leach reaction 2h, is separated by solid-liquid separation
Obtain slag and feed liquid；
4) it after feed liquid is naturally cooled to 20 DEG C and crystallized, then is separated by solid-liquid separation, obtains thick potassium fluoborate and peracid feed liquid；
5) thick potassium fluoborate uses 3N chlorohydric acid pickling 1 time, then centrifugal dehydration after being washed with cold water, it is dry after, obtain purification fluorine
Potassium borate.
Embodiment 6
A kind of fluorine-containing Rare Earth Mine defluorinate extract technology, which comprises the following steps:
1) fluorine-containing rare-earth mineral is crushed and is crossed after 120 meshes and reaction kettle is added, boric acid and potassium chloride is then added, formed
Mixture；Wherein, the ratio of the mole of boron element contained by the mole of fluorine element contained by fluorine-containing rare-earth mineral and boric acid is 1:
8.7, the mass ratio between boric acid and potassium chloride is 1: 1.1；
2) concentrated hydrochloric acid that mass concentration is 30% is added into reaction kettle and adjusts the acidity of mixture in kettle to 6N, and is formed
The solidliquid mixture that solid-to-liquid ratio is 1: 8.5；
3) after reaction kettle heating, under conditions of 104 DEG C of temperature and condensing reflux, after carrying out Leach reaction 4h, solid-liquid point
From slag and feed liquid；
4) it after feed liquid is naturally cooled to 30 DEG C and crystallized, then is separated by solid-liquid separation, obtains thick potassium fluoborate and peracid feed liquid；
5) thick potassium fluoborate uses 5N chlorohydric acid pickling 1 time, then centrifugal dehydration after being washed with cold water, it is dry after, obtain purification fluorine
Potassium borate.
Embodiment 7
A kind of fluorine-containing Rare Earth Mine defluorinate extract technology, which comprises the following steps:
1) fluorine-containing rare-earth mineral is crushed and is crossed after 180 meshes and reaction kettle is added, boric acid and potassium chloride is then added, formed
Mixture；Wherein, the ratio of the mole of boron element contained by the mole of fluorine element contained by fluorine-containing rare-earth mineral and boric acid is 1:
7.4, the mass ratio between boric acid and potassium chloride is 1: 1.04；
2) concentrated hydrochloric acid that mass concentration is 30% is added into reaction kettle and adjusts the acidity of mixture in kettle to 5N, and is formed
The solidliquid mixture that solid-to-liquid ratio is 1: 7；
3) it after reaction kettle heating, under conditions of 96 DEG C of temperature and condensing reflux, after carrying out Leach reaction 3h, is separated by solid-liquid separation
Obtain slag and feed liquid；
4) it after feed liquid is naturally cooled to 25 DEG C and crystallized, then is separated by solid-liquid separation, obtains thick potassium fluoborate and peracid feed liquid；
5) thick potassium fluoborate uses 4N chlorohydric acid pickling 1 time, then centrifugal dehydration after being washed with cold water, it is dry after, obtain purification fluorine
Potassium borate.
Test example 1
Mianning bastnaesite (RE0:70%；F:8% it) is crushed to after 180 mesh are sieved entirely, weighs 200 grams and be placed in 2000 milliliters
In three-necked flask, 19.5 grams of boric acid, 17.5 grams of potassium chloride are weighed, 200 milliliters of water are added, 30% hydrochloric acid is added and adjusts reaction system
H+Content is 4N.85 DEG C isothermal reaction 4 hours, be separated by solid-liquid separation after the reaction was completed, residue carried out to wash dry inspection.Feed liquid is cold
But it to filtering crystals after 15 DEG C, then washed once using 4N hydrochloric acid, cold water washed once, inspection after drying.
Testing inspection result is as follows:
Residue: F content: 0.045%；REO:2.3%；Quality is 20 grams；
Potassium fluoborate purity: 98.5%；
REO leaching rate: 99.67%；
Defluorinate rate: 99.94%.
Test example 2
Dechang bastnaesite (RE0:66%；F content: 10.5%) it is crushed to after 200 mesh are sieved entirely, weighs 200 grams and be placed in
In 2000 milliliters of three-necked flasks, 27 grams of boric acid, 24.3 grams of potassium chloride are weighed, 200 milliliters of water are added, 30% hydrochloric acid is added and adjusts instead
Answer system H+Content is 3N.80 DEG C isothermal reaction 3 hours, be separated by solid-liquid separation after the reaction was completed, residue carried out to wash dry inspection.
Then filtering crystals after feed liquid is cooled to 15 DEG C washed once using 4N hydrochloric acid, cold water washed once, inspection after drying.
Testing inspection result is as follows:
Residue: F content: 0.089%；REO:4.25%；Quality is 28 grams；
Potassium fluoborate purity: 98.32%；
REO leaching rate: 99.1%；
Defluorinate rate: 99.88%.
Test example 3
U.S. awns court of a feudal ruler Paasche mine (RE0:50%；F content: 4.3%；Wherein phosphoric acid content of rare earth 4.8%) it is crushed to 200 mesh
200 grams are weighed after full sieving to be placed in 2000 milliliters of three-necked flasks, weighs 12 grams of boric acid, 10.8 grams of potassium chloride, are added 200 milliliters
Water is added 30% hydrochloric acid and adjusts reaction system H+Content is 5N.85 DEG C isothermal reaction 2 hours, be separated by solid-liquid separation after the reaction was completed, it is right
Residue carries out washing dry inspection.Then filtering crystals after feed liquid is cooled to 15 DEG C washed once using 4N hydrochloric acid, cold water washing
Once, inspection after drying.
Testing inspection result is as follows:
Residue: F content: 0.035%；REO 32.7%；Quality is 17 grams；
Potassium fluoborate purity: 98.42%
REO leaching rate: 94.44% (wherein, non-phosphorus acid rare earth leaching rate: 99.2%)
Defluorinate rate: 99.94%
Test example 4
Dechang bastnaesite (RE0:66%；F content: 10.5%) it is crushed to and weighs 2000 grams after 200 mesh are sieved entirely and be placed in
In 20 liters of reaction kettles, 270 grams of boric acid, 250 grams of potassium chloride are weighed, 2 liters of water are added, 30% hydrochloric acid is added and adjusts reaction system H+Contain
Amount is 6N.88 DEG C isothermal reaction 2 hours, be separated by solid-liquid separation after the reaction was completed, residue carried out to wash dry inspection.Feed liquid is cooled to
Then filtering crystals after 15 DEG C washed once using 4N hydrochloric acid, cold water washed once, inspection after drying.
Testing inspection result is as follows:
Residue: F content: 0.095%；REO:3.8%；Quality is 180 grams；
Potassium fluoborate purity: 98.75%；
REO leaching rate: 99.48%；
Defluorinate rate: 99.92%.
Test example 5
Baotou rare earth ore concentrate (RE0:60%；F content: 7.2%) it is crushed to and weighs 2000 grams after 280 mesh are sieved entirely and be placed in 20
It rises in reaction kettle, weighs 593 grams of boric acid, 534 grams of potassium chloride, 580 milliliters of water are added, 30% hydrochloric acid is added and adjusts reaction system H+
Content is 8N.110 DEG C isothermal reaction 1 hour, be separated by solid-liquid separation after the reaction was completed, residue carried out to wash dry inspection.Feed liquid is cold
But it to filtering crystals after 25 DEG C, then washed once using 2N hydrochloric acid, cold water washed once, inspection after drying.
Testing inspection result is as follows:
Residue: F content: 0.065%；REO:5.4%；Quality is 160 grams；
Potassium fluoborate purity: 98.26%；
REO leaching rate: 99.28%；
Defluorinate rate: 99.93%.
Test example 6
Shandong bastnasite (RE0:59.7%；F content: 6.2%) it is crushed to and weighs 2000 grams after 300 mesh are sieved entirely and set
In 20 liters of reaction kettles, 926 grams of boric acid, 1065 grams of potassium chloride are weighed, 1 liter of water is added, 30% hydrochloric acid is added and adjusts reaction system H+Content is 4N.96 DEG C isothermal reaction 5 hours, be separated by solid-liquid separation after the reaction was completed, residue carried out to wash dry inspection.Feed liquid is cold
But it to filtering crystals after 35 DEG C, then washed once using 6N hydrochloric acid, cold water washed once, inspection after drying.
Testing inspection result is as follows:
Residue: F content: 0.085%；REO:4.6%；Quality is 200 grams；
Potassium fluoborate purity: 98.58%；
REO leaching rate: 99.23%；
Defluorinate rate: 99.81%.
The specific embodiment of the application above described embodiment only expresses, the description thereof is more specific and detailed, but simultaneously
The limitation to the application protection scope therefore cannot be interpreted as.It should be pointed out that for those of ordinary skill in the art
For, under the premise of not departing from technical scheme design, various modifications and improvements can be made, these belong to this
The protection scope of application.
Claims (10)
1. a kind of fluorine-containing Rare Earth Mine defluorinate extract technology, which comprises the following steps:
1) reaction kettle is added after crushing fluorine-containing rare-earth mineral, boric acid and potassium chloride is then added, forms mixture；
2) concentrated hydrochloric acid is added into reaction kettle and adjusts the acidity of mixture in kettle to 3~8N, and forming solid-to-liquid ratio is 1: (4~10)
Solidliquid mixture；
3) after reaction kettle heating, after carrying out 1~5h of Leach reaction under conditions of 80~110 DEG C, slag and material are separated by solid-liquid separation to obtain
Liquid；
4) feed liquid is after crystallisation by cooling, then is separated by solid-liquid separation, and obtains thick potassium fluoborate and peracid feed liquid；
5) thick potassium fluoborate obtains purification potassium fluoborate successively after pickling, washing, centrifugal dehydration, drying.
2. a kind of fluorine-containing Rare Earth Mine defluorinate extract technology according to claim 1, it is characterised in that: fluorine-containing dilute in step 1
Native mineral are rear after crushing to cross the use of 100~300 meshes.
3. a kind of fluorine-containing Rare Earth Mine defluorinate extract technology according to claim 1, it is characterised in that: fluorine-containing dilute in step 1
The ratio of the mole of boron element contained by the mole and boric acid of fluorine element contained by native mineral is 1: (4.8~10).
4. a kind of fluorine-containing Rare Earth Mine defluorinate extract technology according to claim 1, it is characterised in that: in step 1, boric acid with
Mass ratio between potassium chloride is 1: (0.9~1.15).
5. a kind of fluorine-containing Rare Earth Mine defluorinate extract technology according to claim 1, it is characterised in that: in step 2, concentrated hydrochloric acid
Mass concentration be 30%.
6. a kind of fluorine-containing Rare Earth Mine defluorinate extract technology according to claim 1, it is characterised in that: in step 3, leach anti-
That answers carries out also while under conditions of being condensed back.
7. a kind of fluorine-containing Rare Earth Mine defluorinate extract technology according to claim 1, it is characterised in that: in step 4, cooling knot
Brilliant process is specifically, naturally cool to 15~35 DEG C for feed liquid.
8. a kind of fluorine-containing Rare Earth Mine defluorinate extract technology according to claim 1, it is characterised in that: in step 5, to thick fluorine
It when potassium borate carries out pickling, is carried out using 1~6N hydrochloric acid, and washing times are 1 time.
9. a kind of fluorine-containing Rare Earth Mine defluorinate extract technology according to claim 5, it is characterised in that: in step 5, to thick fluorine
When potassium borate is washed, carried out using cold water.
10. a kind of fluorine-containing Rare Earth Mine defluorinate extract technology according to claim 1, which is characterized in that further include step 6；
The step 6 specifically: after gained peracid feed liquid reduces acidity by way of soaking mine again in step 4, through being separated by solid-liquid separation
Deacidification feed liquid and solid impurity are obtained, extraction of the deacidification filtrate for rare earth element is recycled, and impurity is for being added reaction kettle in step 2
Circular treatment.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201811272683.0A CN109112305A (en) | 2018-10-29 | 2018-10-29 | A kind of fluorine-containing Rare Earth Mine defluorinate extract technology |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201811272683.0A CN109112305A (en) | 2018-10-29 | 2018-10-29 | A kind of fluorine-containing Rare Earth Mine defluorinate extract technology |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| CN109112305A true CN109112305A (en) | 2019-01-01 |
Family
ID=64854509
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN201811272683.0A Pending CN109112305A (en) | 2018-10-29 | 2018-10-29 | A kind of fluorine-containing Rare Earth Mine defluorinate extract technology |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN109112305A (en) |
Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN110510625A (en) * | 2019-09-20 | 2019-11-29 | 四川师范大学 | The method and potassium fluoborate of the fluorine-containing aqueous slkali separation fluorine of bastnaesite and application |
| CN113800564A (en) * | 2021-08-27 | 2021-12-17 | 稀美资源(广东)有限公司 | Preparation method of niobium oxide and tantalum oxide |
| CN115181854A (en) * | 2022-07-18 | 2022-10-14 | 乐山盛和稀土有限公司 | Double-acid leaching method for fluorine-containing rare earth ore |
| CN115259204A (en) * | 2022-07-28 | 2022-11-01 | 中国科学院长春应用化学研究所 | Clean metallurgical process method for synchronously recycling cerium and fluorine to treat bastnaesite |
Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102874756A (en) * | 2012-09-24 | 2013-01-16 | 巨化集团技术中心 | Method for removing hydrogen fluoride from hydrogen chloride gas |
| CN105731482A (en) * | 2016-01-15 | 2016-07-06 | 江苏新泰材料科技股份有限公司 | Method for preparing potassium fluoborate from fluorine-containing wastewater |
| CN106882768A (en) * | 2017-03-03 | 2017-06-23 | 巨化集团技术中心 | A kind of method of fluorine-containing hydrochloric acid defluorinate |
-
2018
- 2018-10-29 CN CN201811272683.0A patent/CN109112305A/en active Pending
Patent Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102874756A (en) * | 2012-09-24 | 2013-01-16 | 巨化集团技术中心 | Method for removing hydrogen fluoride from hydrogen chloride gas |
| CN105731482A (en) * | 2016-01-15 | 2016-07-06 | 江苏新泰材料科技股份有限公司 | Method for preparing potassium fluoborate from fluorine-containing wastewater |
| CN106882768A (en) * | 2017-03-03 | 2017-06-23 | 巨化集团技术中心 | A kind of method of fluorine-containing hydrochloric acid defluorinate |
Cited By (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN110510625A (en) * | 2019-09-20 | 2019-11-29 | 四川师范大学 | The method and potassium fluoborate of the fluorine-containing aqueous slkali separation fluorine of bastnaesite and application |
| CN110510625B (en) * | 2019-09-20 | 2022-11-01 | 四川师范大学 | Method for separating fluorine from bastnaesite fluorine-containing alkali solution, potassium fluoborate and application |
| CN113800564A (en) * | 2021-08-27 | 2021-12-17 | 稀美资源(广东)有限公司 | Preparation method of niobium oxide and tantalum oxide |
| CN115181854A (en) * | 2022-07-18 | 2022-10-14 | 乐山盛和稀土有限公司 | Double-acid leaching method for fluorine-containing rare earth ore |
| CN115181854B (en) * | 2022-07-18 | 2023-08-18 | 乐山盛和稀土有限公司 | Double acid leaching method for fluorine-containing rare earth ore |
| CN115259204A (en) * | 2022-07-28 | 2022-11-01 | 中国科学院长春应用化学研究所 | Clean metallurgical process method for synchronously recycling cerium and fluorine to treat bastnaesite |
| CN115259204B (en) * | 2022-07-28 | 2023-08-04 | 中国科学院长春应用化学研究所 | Clean metallurgical process method for synchronously recycling cerium fluoride to treat bastnaesite |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN109112305A (en) | A kind of fluorine-containing Rare Earth Mine defluorinate extract technology | |
| CN111137908B (en) | System method for extracting lithium-containing brine from lepidolite and manufacturing lithium salt | |
| CN113428882B (en) | Method for preparing battery-grade lithium carbonate from spodumene | |
| CN107500318B (en) | The method of lithium carbonate is extracted from aluminium oxide factory sodium aluminate solution | |
| CN109930174A (en) | The method that aluminium electrolyte takes off lithium purification and recycling lithium | |
| CN105925819B (en) | Utilize the method for elemental lithium in acidizing fired lixiviation process synthetical recovery aluminium electrolyte | |
| CN103320626A (en) | Method and system for recovering lithium, rubidium and/or cesium from lepidolite | |
| CN102897810B (en) | Method for producing aluminum oxide by using fly ash | |
| CN103103349B (en) | Method for decomposing bayan obo rare earth ore concentrate by acid and alkali combination at low temperature | |
| CN104495880A (en) | Method for preparing lithium chloride and byproducts of lithium chloride from lepidolite | |
| CN102139894A (en) | Novel method for preparing battery grade lithium carbonate by using tantalum niobium tailings lithium mica | |
| CN110510642A (en) | A kind of method that low-grade α spodumene economy mentions lithium | |
| CN115321563B (en) | Method for producing battery grade lithium carbonate by nitric acid pressure leaching of lithium stilbite | |
| CN103351010B (en) | Preparation process of battery-grade lithium carbonate | |
| CN102230081A (en) | Acid leaching method for extracting potassium, aluminum and silicon elements from potassium feldspar | |
| CN109437255A (en) | A method of extracting lithium salts from lithium ore | |
| CN113981232A (en) | Method for directly leaching and recovering lithium element in aluminum electrolyte waste residue by using aluminum sulfate | |
| CN103014317A (en) | Method for extracting lithium salt from lepidolite | |
| CN109179457A (en) | The extracting method of lithium in a kind of waste slag of electrolytic aluminium | |
| CN104404243A (en) | Method for low-temperature decomposition of low-grade Weishan rare earth ore concentrate through acid-alkali combination | |
| CN109536746A (en) | A kind of method that the pulp of low calcium high-grade mixed rare earth concentrates circulation is decomposed | |
| CN102952951A (en) | Method for extracting tantalum and niobium and producing potassium fluosilicate from tungsten smelting slag | |
| CN106586992B (en) | A kind of technique of the recycling of mixed rare earth concentrates liquid alkaline Decomposition-Synthesis fluorine and phosphorus | |
| CN105330344B (en) | A kind of preparation method for extracting potassium sulfate from blast furnace process gas ash | |
| CN106636615B (en) | The mica treatment process of lithium carbonate is prepared using lepidolite |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| PB01 | Publication | ||
| PB01 | Publication | ||
| SE01 | Entry into force of request for substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| RJ01 | Rejection of invention patent application after publication | ||
| RJ01 | Rejection of invention patent application after publication |
Application publication date: 20190101 |