CN108913876A - A kind of method that Rare Earth Mine microwave decomposition-high acidic oils extract high-purity cerium - Google Patents
A kind of method that Rare Earth Mine microwave decomposition-high acidic oils extract high-purity cerium Download PDFInfo
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Abstract
The invention discloses a kind of methods that Rare Earth Mine microwave decomposition-high acidic oils extract high-purity cerium, include the following steps：1) product of roasting is made in Rare Earth Mine after oxidizing roasting；2) product of roasting leaches to obtain acidizing product through high acid environment under microwave heating condition；2) acidizing product is through filtering to get filtrate；4) filtrate obtains high-purity cerium and fluorine, thorium byproduct after multistage purification by liquid extraction.Using the technique of the high acid system leaching of microwave heating, the alkali conversion process of acid leaching residue, not highly shortened the production cycle, save a large amount of equipment, the energy and cost of investment；Leachate does not have to neutralize except iron thorium and other non-rare earth impurities, and the separation of cerium and other rare earths can be directly carried out into extraction tank, obtains high-purity cerium product.To increase substantially the rate of recovery of rare earth, rare earth yield is up to 98% or more；Using fluorine removal reducing agent, nitric acid stripping process, substep fluorine removal, except thorium can obtain the byproduct of the higher fluorine thorium of purity are being combined.
Description
Technical field
The present invention relates to Rare Earth Separation purification technique fields, and in particular to a kind of Rare Earth Mine microwave decomposition-high acidic oils mention
The method for taking high-purity cerium.
Background technique
Rare earth has the title of industrial " gold ", in military affairs, metallurgy, petrochemical industry, high skill as a kind of important strategic resource
The multiple fields such as art, agricultural can the amount of playing arrive matter change.For example, in semicon industry, throwing prepared by rare earth oxide
Light powder can be obviously improved the polishing efficiency and polishing effect of silicon wafer；In petrochemical industry, molecular sieve made by rare earth metal
Catalyst, it is active it is high, selectivity it is good, preventing from heavy metal poisoning capability is strong many advantages, such as, therefore exist replace alumina silicate catalysis
Agent is used for the application example of petroleum catalytic pyrolysis.
According to data, the rare earth reserves in China are once to occupy global 80% in nineteen ninety, are qualified dilute
Native big country.But due to exhaustive exploitation and outlet, or even smuggling, by 2011, the rare earth reserves in China were only remaining global
23%, it has slid to third place in the world.Thus, in recent years, rare earth control and the sound of protection become increasingly conspicuous, and country is
Through putting into effect relevant policies, to protect the remaining rare earth resources in China to full capacity.Faced with this situation, it manages and regulates and controls and only protect
The one aspect of rare earth resources, and how to realize the abundant refinement of rare earth element in rare earth and improve rare earth money using then becoming
Source utilization rate, another important subject for avoiding rare earth resources exhausted too early.
Sichuan Rare Earth, as an important component of China's rare earth resources, from reserves, easily exploitation property, ore product
Position, easily refinement property are said, are listed as the big high-quality rare earth resources in China two with Baotou rare earth.Sichuan Rare Earth is typical bastnaesite,
Mainly with RFCO3Form exist, wherein representated by R be mainly Ce, La.For the mineral, more than 30 coming year are successive both at home and abroad
More than ten kinds of different smelting processes are had developed, to meet the product demand of different times.By Vehicles Collected from Market to the need of rare-earth products
Consideration is asked, these techniques are able to satisfy the market demand, but still have the necessity for improving and seeking new process.For example, what mainstream used
Wet-treating bastnaesite, present in critical problem still have：How fluorine and thorium are resolved the rare-earth smelting during
Interference prevents the diffusion pollution for generating rare earth fluoride and thorium, to eliminate fluorine and thorium in extraction process to the shadow of smelting process
It rings.
Currently, domestic each producer is to used by bastnaesite when technique：Oxidizing roasting is carried out using rotary kiln, is then existed
Under the conditions of single tank is very steam-heated, rare-earth salts is refined by way of salt Ore Leaching.Under the technique, salt Ore Leaching is being used
During, quadrivalent cerium is formed by through oxidizing roasting and is reduced into three valence states and is leached simultaneously with other rare earths, then
Feed liquid is sent after neutralizing to extraction workshop section to the separation carried out between rare earth again.But in actual mechanical process, but there is acid leaching residue
The higher problem of middle content of rare earth, this is set to mainly due to the leaching condition shakiness of hydrochloric acid so that leaching rate is lower, and in feed liquid
Fluorine ion coexisted with rare earth ion, formed fluoride precipitating enter slag in.
In order to improve the rate of recovery of rare earth, current technology usually also needs to make its shape using the means of alkali conversion to acid leaching residue
At rare earth hydrate, rare earth is then leached again using hydrochloric acid.Although above-mentioned technique solves in current technology to a certain extent
The not high problem of rare earth yield, but still have the following problems：First, content of the thorium element in residue is still higher, does not have
There is sufficiently recycling to refine；Second, due to the presence of the rare earth fluorides such as cerium fluoride, partial size is small and surface-active is strong, and then is extracting
It takes honor and extractant effect in workshop section to generate third phase, is that extraction process can not be normally carried out；Third, due to needing to acidleach
Slag handled after its acidification leach, to obtain the high rate of recovery, must just extend process line, will cause raw and auxiliary material and
Significant wastage on the energy.
Summary of the invention
The present invention provides a kind of Rare Earth Mine microwave decomposition-high acidic oils and extracts the method for high-purity cerium, and it is an object of the present invention to provide one
Kind of process route shortization is easy to extraction and separation and the high rare earth refinement method of rare earth yield, to solve technique in prior art
The problem that road route is long, process efficiency is low and acidification is leached and extraction process is unstable.
To solve the above problems, the technical solution adopted by the present invention is as follows：
A kind of method that Rare Earth Mine microwave decomposition-high acidic oils extract high-purity cerium, includes the following steps：
1) product of roasting is made in Rare Earth Mine after oxidizing roasting；
2) product of roasting leaches to obtain acidizing product through high acid environment under microwave heating condition；
3) acidizing product is through filtering to get filtrate；
4) filtrate obtains high-purity cerium and fluorine, thorium byproduct after multistage purification by liquid extraction.
The principle and realization process of the technical program are as follows：
Firstly, it is necessary to understand existing process flow, it is as follows：
In current technology, Rare Earth Mine is subjected to pyrolytic using rotary kiln oxidizing roasting technique, then uses salt acidleach
Out, during leaching, since hydrochloric acid has a reproducibility, and by quadrivalent cerium be reduced to trivalent cerium and with other rare earths simultaneously by
It leaches.Content of rare earth in current technology slag is also higher, mainly since its unstable leaching rate of the leaching condition of hydrochloric acid is lower；
There are also being exactly that fluorine ion in feed liquid coexists with rare earth ion, fluoride precipitating is formed into slag；In addition, fluorine ion is free out
To form fluoride precipitating with trivalent cerium ion.These fluorides are that the very tiny material surface activity of some particles is very strong very
It is easy to generate emulsion with extractant effect to form third phase, be normally carried out extraction process can not.
In contrast, still using rotary kiln oxidation roasting to the process that Rare Earth Mine carries out oxidizing roasting in the technical program
Firing technique decomposes Rare Earth Mine, so that the Ce elements in Rare Earth Mine are also all oxidized to four valence states.And in order to protect
The valence state for demonstrate,proving quadrivalent cerium is constant, and the technical program uses nitric acid or sulfuric acid leaching.Since above two acid is provided with strong oxidizing property,
Therefore quadrivalent cerium will not be reduced in leaching process, to continue to keep four valence states.On this basis, free out with leaching
By complexation reaction between the good teacher's ion of department and fluorine ion come, cerium fluoro complex is formed, this is spy not available for trivalent cerium
Point.In this case, i.e., under sulfuric acid or nitric acid Leaching Systems, trivalent rare earth, quadrivalent cerium fluorine ion stable simultaneously can deposit
, so as to avoid the formation of cerous fluoride precipitating, so that 96~98% of rare earth or more high leaching rate is on the one hand realized,
On the other hand the formation of waste residue is then avoided, to improve the comprehensive utilization ratio of Rare Earth Mine.At the same time, using sulfuric acid or nitre
Acid system leaches, since quadrivalent cerium and fluorine ion will form the complex ion [CeF of cerium at this time2]2+For trivalent rare earth and quadrivalent cerium, four
The separation of valence thorium provides convenience, because the separation factor of trivalent rare earth and quadrivalent metallic ion is than point between trivalent rare earth
It is much bigger from factor.
Have above-mentioned it is found that the technical program is since there is no waste residue, does not need to extract by leaching waste residue again
The rare earth element precipitated in waste residue, therefore for more existing hydrochloric acid extract technology, it can be produced in the cerium series for obtaining higher purity
While product, extraction process route is greatly shortened, to be significantly compression the production and operation cost of Rare Earth Mine separating-purifying.
It is worth noting that, the steam-heated mode that uses is different from current technology leaching process, in the technical program
Used heating method is microwave heating.This method is different from traditional molten heating mechanism of acid, microwave-medium principle of heating,
Chemical raw material is once put into microwave electric field, produces the effect similar to phase mutual friction between molecule, to absorb electric field
Energy and generate heat, since microwave has stronger penetration capacity, it can be deep into sample interior, make ore central temperature rapid first
Raising achievees the purpose that decomposing ore.In other words, propagation is much more uniform than traditional heating mode, and heating efficiency also compares
The high moral of steam cycle is more.Because Rare Earth Mine fills ore by the molecular motion inside ore under the action of microwave at this time
The decomposition divided, soluble salt are easier to react with high acid solution to be dissolved to form salting liquid by high acid solution.By
In using microwave heating, the technical program greatly improves the efficiency that the high acid dissolution of ore leaches, can be at 10~30 minutes
Reach required temperature, so that time cost and heating energy consumption be greatly saved.
After completing high acidic oils, usually selects but be not limited to the progress filters pressing of frame plate type pressure filter, to filter out in Rare Earth Mine
Insoluble matter.It is emphasized that insoluble matter herein refers to solid valueless present in Rare Earth Mine and insoluble in acid
Impurity, the acid leaching residue being different from current technology are still to be recycled containing a certain amount of rare earth in the latter.Therefore, can recognize
To be generated in the technical program without acid leaching residue.
It should be noted that in the technical program, by controlling concentrated nitric acid according to the content of ore middle rare earth
Or the additional amount of sulfuric acid, gained filtrate usually have following index：
Filter liquor concentration：110~150g/L；
Filtrate acidity：5~8N/L；
Ce4+/∑CeO：100%；
Fe：By Fe2O3Meter, < 2g/L；
Th,Pb,Al：Based on each autoxidisable substance, the equal < 0.05~0.2% of weight percent；
And filtrate is clear, no mechanical admixture.
Further, the concrete technology condition of microwave heating described in step 2 is：Under microwave, 10~30min of heating is extremely
After 100~120 DEG C, 20~30min is kept the temperature.
Further, in step 2, forming high acid solution used in the high acid environment is concentrated nitric acid or sulfuric acid.It utilizes
The strong oxidizing property of concentrated nitric acid or sulfuric acid, can guarantee to leach the cerium ion in feed liquid always for four valence states, so as to avoid because
The presence of trivalent cerium and in conjunction with free fluorine ion generate precipitating.
Further, high acid environment described in step 2, condition are：The acidity of the high acid environment is 5~8mol/
L.Under high acid environment, is on the one hand conducive to the dissolution of soluble salt in Rare Earth Mine, is on the other hand then to aid in the guarantor of fluorine cerium complex ion
It holds.
Further, in step 3, acidizing product is cooled to after 75~85 DEG C row filtering again.
By the above process, content of rare earth can reach 98% of content of rare earth in tcrude ore in obtained leaching feed liquid
More than, i.e., rare-earth yield is greater than 98%, and this yield can also be further increased with rising to for Rare Earth Mine grade.
Further, the multistage extract the step of include：
A) extraction section：By filtrate through shunt extract, obtain enrichment cerium, fluorine, thorium one section of organic phase and extract cerium from raffinate；
B) fluorine removal section：Fluorine removal reducing agent is added into one section of organic phase, and after being neutralized to neutrality, after cross current solvent extraction, obtains
It arrives and two sections of water phases of two sections of organic phases and enrichment fluorine；
C) stripping section：By two sections of organic phases after nitric acid is stripped, the adjusted back extraction acid of three sections of organic phases is obtained.Acidity can be with
Obtain thorium and cerous nitrate solution
Further, in step a, used extractant is organic extractant, compositional system P204- TBP- is dilute
Release agent.
Preferably, the diluent is sulfonated kerosene, 260#Any one of solvent naphtha, D-70 solvent naphtha and octanol.
Preferably, the fluorine removal reducing agent is mixed by hydrogen peroxide and acid solution；The acid solution is sulfuric acid or hydrochloric acid.
Further, in step c, the concentration of the nitric acid is 3~6mol/L.
The principle and process of above-mentioned multistage extraction are as follows：
In the technical program, extraction and separation are carried out using extraction mode is shunted using box extraction tank.Extraction section by cerium with
The complex ion of fluorine extracts into organic phase, while also having the thorium of 70-85% and 20-30% iron to be extracted into organic phase.Trivalent at this time is dilute
Soil be it is inextractable, stay in and extract cerium from raffinate.For the purity for improving cerium, 3-5 grades of washing sections can also be joined, will be pressed from both sides
Band in organic phase trivalent rare earth washing return water quite in.
Then, fluorine removal reducing agent is used using cross current solvent extraction method, in neutral conditions fluorine removal.Firstly, filtrate is adjusted to
It is neutral.Under neutrallty condition, the complex ion [CeF of cerium and fluorine2]2+It no longer keeps form complexed and then is destroyed, the tetravalence of going out of dissociating
Cerium is reduced to three valence states and fluorine ion also separate out therewith.At this point, if control condition it is bad when will generate it is borontrifluoride
Cerium precipitates influence extraction process in extraction tank and is normally carried out.The present invention be by control fluorine removal reducing agent additional amount and fluorine from
Sub- concentration realizes defluorinating process.Because fluorine removal reducing agent is controllable variable, fluorine is made by the overall control of fluorine removal reducing agent
With the complexing of metal ion in defluorinating agent, the solubility salt for forming fluoride is quantitatively discharged ion substep in water phase, thus
The generation for avoiding cerous fluoride precipitating realizes efficiently separating for fluorine ion and rare earth.Using the fluorine removal in the technical program
Technique, fluoride removing rate are greater than 98%.
Organic phase enters stripping section after fluorine removal, and cerium at this time has been three valence states, so just do not have to add reducing agent again,
Directly it is stripped with the HNO solution that concentration is 3-6mol/L.Back extraction is realized using half counter-current extraction method.The purpose is to anti-
Rare earth is concentrated extraction section, and the utilization rate for improving back extraction acid also reduces system acidity simultaneously, provides conveniently for next procedure.
Being stripped obtained water phase is cerous nitrate solution, and the fluorine content in solution remittance is less than 50ppm.The cerous nitrate send nano material
Workshop makes cerium series product, the additive as new function material.
After organic phase enters anti-iron thorium section, back extraction iron is reached using the water phase self-loopa method for improving acidity reduction flow
The purpose of thorium.Wherein, box extraction tank water phase self-circulation system is referring to patent CN201620627684.2.It is stripped the iron thorium obtained
Mixed liquor can be again by TBP-HNO3Extract liquor system extracts thorium, can obtain pure thorium nitrate crystal and ferric nitrate and produce
Product.
Organic phase (P204) regeneration washed using oxalic acid solution or weak caustic solution, make not to be stripped clean metal from
It is recovered after sub further complexing into water phase.
It extracts cerium from raffinate to deacidify through electrodialysis, restored acid can be recycled.The remaining a small amount of acid of raffinate is extracted cerium to use
Alkali neutralization is except non-rare earth impurities such as iron thorium D aluminium.Micro slag is obtained through being separated by solid-liquid separation, concentrates stockpiling.It is neutralized to extract cerium from raffinate
After filtering, lanthanum, praseodymium, neodymium separation production line are sent.
In conclusion by adopting the above-described technical solution, the beneficial effects of the invention are as follows：
(1) using the technique of the high acid system leaching of microwave heating, the alkali conversion process of acid leaching residue, not highly shortened
Production cycle has saved a large amount of equipment, the energy and cost of investment；
(2) P is used204The extraction of-TBP- diluent system, is isolating high-purity cerium solution while obtaining fluorine byproduct；
(3) fluorine removal reducing agent is used, is combining nitric acid stripping process, substep fluorine removal can obtain the higher fluorine pair of purity
Product；
(4) leachate does not have to neutralize except iron thorium and other non-rare earth impurities, and it is dilute with other directly can to carry out cerium into extraction tank
The separation of soil, obtains high-purity cerium product, to increase substantially the rate of recovery of rare earth, through comprehensive statistics, rare earth yield is reachable
98% or more；
(5) since temperature, acidity, heating time in system etc. is controllable and is easy to regulate and control, so the skill of products obtained therefrom
Art parameter stability.
Specific embodiment
It is right combined with specific embodiments below in order to make those skilled in the art more fully understand technical solution of the present invention
The present invention is described in further detail.
Each substance title, is explained as follows involved in the present invention：
Rare Earth Mine refers to that the type exploited from Rare Earth Mine place is the natural rare earth ore of bastnaesite, typically there is master
Will group is divided into the Sichuan Rare Earth of bastnaesite, main component is beiyinte of bastnaesite etc. in Baotou rare earth, mainly contain cerium,
The rare earth elements such as lanthanum, praseodymium, neodymium, usually also containing non-rare earths such as fluorine, iron, thorium, lead, aluminium.
Nitric acid refers to containing HNO3Aqueous solution, belong to unitary inorganic strong acid, have highly acid and strong oxidizing property.Generally
It is concentrated nitric acid higher than the numerical value using 6mol/L as boundary；Wherein, Reagent grade nitric acid concentration is about 68% or so, and technical grade is dense
Concentration of nitric acid is then 98%, and usual fuming nitric aicd concentration is about 98%.
Sulfuric acid refers to containing H2SO4Aqueous solution, have highly acid, high dehydrated and strong oxidizing property.
Hydrochloric acid refers to the aqueous solution containing HCl, belongs to unitary inorganic strong acid, has highly acid, strong reducing property and volatilization
Property.
P204, Chinese is di-(2-ethylhexyl)phosphoric acid ester, chemical formula C16H35O4P is a kind of phosphoric acid class acid extract
Agent is mainly used for the extraction of rare earth, non-ferrous metal (including cobalt, nickel, gold, copper, indium etc.), electrolytic metal.
TBP, Chinese are tributyl phosphate, chemical formula C12H27O4P can be used as Extractant of Rare Earth Elements and rare earth gold
Belong to complex compound extractant.
Sulfonated kerosene refers to that common kerosene removes the kerosene product of contained unsaturated bond through concentrated sulfuric acid washing.
260#Solvent naphtha refers to that the trade mark is 260#Special kerosene type solvent.
D-70 solvent naphtha refers to that, through Porous deproteinized bone treated No. 70 solvent naphthas, boiling range is 60~70 DEG C.
Octanol, chemical formula C8H18O is a kind of colourless flammable liquid for having special odor.
Hydrogen peroxide refers to containing H2O2Aqueous solution, have strong oxidizing property.
Embodiment 1
A kind of method that Rare Earth Mine microwave decomposition-high acidic oils extract high-purity cerium, includes the following steps：
1) product of roasting is made in Rare Earth Mine after oxidizing roasting；
2) product of roasting leaches to obtain acidizing product through high acid environment under microwave heating condition；
3) acidizing product is through filtering to get filtrate；
4) filtrate obtains high-purity cerium and fluorine, thorium byproduct after multistage purification by liquid extraction.
Wherein, the concrete technology condition of microwave heating described in step 2 is：Under microwave, after 10 to 100 DEG C of heating, protect
Warm 20min；In step 2, forming high acid solution used in the high acid environment is sulfuric acid；High acid environment described in step 2,
Condition is：The acidity of the high acid environment is 5mol/L；In step 3, acidizing product is cooled to after 75 DEG C row filtering again.
The multistage extract the step of include：
A) extraction section：By filtrate through shunt extract, obtain enrichment cerium, fluorine, thorium one section of organic phase and extract cerium from raffinate；
B) fluorine removal section：Fluorine removal reducing agent is added into one section of organic phase, and after being neutralized to neutrality, after cross current solvent extraction, obtains
It arrives and two sections of water phases of two sections of organic phases and enrichment fluorine；
C) stripping section：By two sections of organic phases after nitric acid is stripped, three sections of organic phases are obtained, being adjusted out mouth acidity can be with
Obtain thorium and cerous nitrate solution；
In multistage extraction process, in step a, used extractant is organic extractant, compositional system P204-
TBP- sulfonated kerosene；In step b, the fluorine removal reducing agent is mixed by hydrogen peroxide and sulfuric acid；In step c, the nitric acid
Concentration is 3mol/L.
The product and its characteristic parameter part following table of each step of the present embodiment：
Embodiment 2
A kind of method that Rare Earth Mine microwave decomposition-high acidic oils extract high-purity cerium, includes the following steps：
1) product of roasting is made in Rare Earth Mine after oxidizing roasting；
2) product of roasting leaches to obtain acidizing product through high acid environment under microwave heating condition；
3) acidizing product is through filtering to get filtrate；
4) filtrate obtains high-purity cerium and fluorine, thorium byproduct after multistage purification by liquid extraction.
Wherein, the concrete technology condition of microwave heating described in step 2 is：Under microwave, after 15min to 110 DEG C of heating,
Keep the temperature 25min；In step 2, forming high acid solution used in the high acid environment is concentrated nitric acid；Peracid ring described in step 2
Border, condition are：The acidity of the high acid environment is 6.5mol/L；In step 3, acidizing product was gone again after being cooled to 80 DEG C
Filter.
The multistage extract the step of include：
A) extraction section：By filtrate through shunt extract, obtain enrichment cerium, fluorine, thorium one section of organic phase and extract cerium from raffinate；
B) fluorine removal section：Fluorine removal reducing agent is added into one section of organic phase, and after being neutralized to neutrality, after cross current solvent extraction, obtains
It arrives and two sections of water phases of two sections of organic phases and enrichment fluorine；
C) stripping section：By two sections of organic phases after nitric acid is stripped, obtain three sections it is organic, it is mutually adjusted go out mouth acidity can obtain
To thorium and cerous nitrate solution
In multistage extraction process, in step a, used extractant is organic extractant, compositional system P204-
TBP-260#Solvent naphtha；In step b, the fluorine removal reducing agent is by hydrogen peroxide and hydrochloric acid；In step c, the concentration of the nitric acid is
4.5mol/L。
The product and its characteristic parameter part following table of each step of the present embodiment：
Embodiment 3
A kind of method that Rare Earth Mine microwave decomposition-high acidic oils extract high-purity cerium, includes the following steps：
1) product of roasting is made in Rare Earth Mine after oxidizing roasting；
2) product of roasting leaches to obtain acidizing product through high acid environment under microwave heating condition；
3) acidizing product is through filtering to get filtrate；
4) filtrate obtains high-purity cerium and fluorine, thorium byproduct after multistage purification by liquid extraction.
Wherein, the concrete technology condition of microwave heating described in step 2 is：Under microwave, after 30min to 120 DEG C of heating,
Keep the temperature 30min；In step 2, forming high acid solution used in the high acid environment is concentrated nitric acid；Peracid ring described in step 2
Border, condition are：The acidity of the high acid environment is 8mol/L；In step 3, acidizing product is cooled to after 85 DEG C row filtering again.
The multistage extract the step of include：
A) extraction section：By filtrate through shunt extract, obtain enrichment cerium, fluorine, thorium one section of organic phase and extract cerium from raffinate；
B) fluorine removal section：Fluorine removal reducing agent is added into one section of organic phase, and after being neutralized to neutrality, after cross current solvent extraction, obtains
It arrives and two sections of water phases of two sections of organic phases and enrichment fluorine；
C) stripping section：By two sections of organic phases after nitric acid is stripped, three sections of organic phases are obtained, adjusted mouth acidity out can obtain
To thorium and cerous nitrate solution
In multistage extraction process, in step a, used extractant is organic extractant, compositional system P204-
TBP- (D-70 solvent naphtha)；In step b, the fluorine removal reducing agent is made of hydrogen peroxide and mixed in hydrochloric acid；In step c, the nitre
The concentration of acid is 6mol/L.
The product and its characteristic parameter part following table of each step of the present embodiment：
| Step | Product | Yield/% | Purity/% |
| High acidic oils | Acidizing product | 98 (rare earth leaching rates) | / |
| Fluorine removal section | Two sections of organic phases | 0.001 (fluorine residue amount) | / |
| Stripping section | Cerous nitrate solution | 99.0 | 99.999 |
Embodiment 4
A kind of method that Rare Earth Mine microwave decomposition-high acidic oils extract high-purity cerium, includes the following steps：
1) product of roasting is made in Rare Earth Mine after oxidizing roasting；
2) product of roasting leaches to obtain acidizing product through high acid environment under microwave heating condition；
3) acidizing product is through filtering to get filtrate；
4) filtrate obtains high-purity cerium and fluorine byproduct after multistage purification by liquid extraction.
Wherein, the concrete technology condition of microwave heating described in step 2 is：Under microwave, after 30min to 120 DEG C of heating,
Keep the temperature 30min；In step 2, forming high acid solution used in the high acid environment is concentrated nitric acid；Peracid ring described in step 2
Border, condition are：The acidity of the high acid environment is 8mol/L；In step 3, acidizing product is cooled to after 85 DEG C row filtering again.
The multistage extract the step of include：
A) extraction section：By filtrate through shunt extract, obtain enrichment cerium, fluorine, thorium one section of organic phase and extract cerium from raffinate；
B) fluorine removal section：Fluorine removal reducing agent is added into one section of organic phase, and after being neutralized to neutrality, after cross current solvent extraction, obtains
It arrives and two sections of water phases of two sections of organic phases and enrichment fluorine；
C) stripping section：By two sections of organic phases after nitric acid is stripped, three sections of organic phases and cerous nitrate solution are obtained
In multistage extraction process, in step a, used extractant is organic extractant, compositional system P204-
TBP- octanol；In step b, the fluorine removal reducing agent is made of hydrogen peroxide and mixed in hydrochloric acid；In step c, the concentration of the nitric acid
For 6mol/L.
The product and its characteristic parameter part following table of each step of the present embodiment：
Embodiment 5
A kind of method that Rare Earth Mine microwave decomposition-high acidic oils extract high-purity cerium, includes the following steps：
1) product of roasting is made in Rare Earth Mine after oxidizing roasting；
2) product of roasting leaches to obtain acidizing product through high acid environment under microwave heating condition；
3) acidizing product is through filtering to get filtrate；
4) filtrate obtains high-purity cerium and fluorine byproduct after multistage purification by liquid extraction.
Wherein, the concrete technology condition of microwave heating described in step 2 is：Under microwave, after 15min to 110 DEG C of heating,
Keep the temperature 25min；In step 2, forming high acid solution used in the high acid environment is concentrated nitric acid；Peracid ring described in step 2
Border, condition are：The acidity of the high acid environment is 6.5mol/L；In step 3, acidizing product was gone again after being cooled to 80 DEG C
Filter.
The multistage extract the step of include：
A) extraction section：By filtrate through shunt extract, obtain enrichment cerium, fluorine, thorium one section of organic phase and extract cerium from raffinate；
B) fluorine removal section：Fluorine removal reducing agent is added into one section of organic phase, and after being neutralized to neutrality, after cross current solvent extraction, obtains
It arrives and two sections of water phases of two sections of organic phases and enrichment fluorine；
C) stripping section：By two sections of organic phases after nitric acid is stripped, obtain three sections of organic phases it is adjusted go out mouth acidity after can be with
Obtain thorium and cerous nitrate solution
E) anti-iron thorium section：Three sections of organic phases are obtained into four sections of organic phases and iron thorium mixed liquor through water phase self-loopa method；Institute
It obtains iron thorium mixed liquor and isolates thorium through TBP-HNO3 purification by liquid extraction, to obtain thorium nitrate crystal and iron nitrate solution.
F) organic phase regenerates：By four sections of organic phases after oxalic acid solution or weak caustic solution washing, removing metal ion is obtained
Regeneration organic phase, realize recycling for organic phase.
In multistage extraction process,
In step a, used extractant is organic extractant, compositional system P204-TBP-260#Solvent naphtha.
In step a, gained extracts cerium from raffinate and deacidifies by electrodialysis, and obtained nitric acid solution is recycled to recycle, and obtains
To deacidification after extract cerium from raffinate after the non-rare earth impurities such as alkali neutralization and iron thorium aluminium lead, be used for lanthanum.The separation of praseodymium, neodymium, with
Realize the complete purification & isolation of each rare earth element in Rare Earth Mine.Wherein, the obtained nitric acid rate of recovery of electroosmose process can reach
80%, the cyclic utilization rate of acid solution can be significantly improved.
In step b, the fluorine removal reducing agent is by hydrogen peroxide and hydrochloric acid.
In step c, the concentration of the nitric acid is 4.5mol/L.
The product and its characteristic parameter part following table of each step of the present embodiment：
The above is only the preferred embodiment of the present invention, it is noted that above-mentioned preferred embodiment is not construed as pair
Limitation of the invention, protection scope of the present invention should be defined by the scope defined by the claims..For the art
For those of ordinary skill, without departing from the spirit and scope of the present invention, several improvements and modifications can also be made, these change
It also should be regarded as protection scope of the present invention into retouching.
Claims (10)
1. a kind of method that Rare Earth Mine microwave decomposition-high acidic oils extract high-purity cerium, which is characterized in that include the following steps：
1) product of roasting is made in Rare Earth Mine after oxidizing roasting；
2) product of roasting leaches to obtain acidizing product through high acid environment under microwave heating condition；
3) acidizing product is through filtering to get filtrate；
4) filtrate obtains high-purity cerium and fluorine, thorium byproduct after multistage purification by liquid extraction.
2. the method that a kind of Rare Earth Mine microwave decomposition-high acidic oils according to claim 1 extract high-purity cerium, feature exist
In the concrete technology condition of microwave heating described in step 2 is：Under microwave, after 10~30min to 100~120 DEG C of heating,
Keep the temperature 20~30min.
3. the method that a kind of Rare Earth Mine microwave decomposition-high acidic oils according to claim 1 extract high-purity cerium, feature exist
In in step 2, forming high acid solution used in the high acid environment is concentrated nitric acid or sulfuric acid.
4. the method that a kind of Rare Earth Mine microwave decomposition-high acidic oils according to claim 3 extract high-purity cerium, feature exist
In, high acid environment described in step 2, condition is：The acidity of the high acid environment is 5~8mol/L.
5. the method that a kind of Rare Earth Mine microwave decomposition-high acidic oils according to claim 1 extract high-purity cerium, feature exist
In：In step 3, acidizing product is cooled to after 75~85 DEG C row filtering again.
6. the method that a kind of Rare Earth Mine microwave decomposition-high acidic oils according to claim 1 extract high-purity cerium, feature exist
Include in the step of, the multistage extracts：
A) extraction section：By filtrate through shunt extract, obtain enrichment cerium, fluorine, thorium one section of organic phase and extract cerium from raffinate；
B) fluorine removal section：Fluorine removal reducing agent is added into one section of organic phase, and after being neutralized to neutrality, after cross current solvent extraction, obtain and
Two sections of water phases of two sections of organic phases and enrichment fluorine；
C) stripping section：By two sections of organic phases after nitric acid is stripped, three sections of organic phases and cerous nitrate solution are obtained.
7. the method that a kind of Rare Earth Mine microwave decomposition-high acidic oils according to claim 6 extract high-purity cerium, feature exist
In：In step a, used extractant is organic extractant, compositional system P204- TBP- diluent.
8. the method that a kind of Rare Earth Mine microwave decomposition-high acidic oils according to claim 7 extract high-purity cerium, feature exist
In；The diluent is sulfonated kerosene, 260#Any one of solvent naphtha, D-70 solvent naphtha and octanol.
9. the method that a kind of Rare Earth Mine microwave decomposition-high acidic oils according to claim 7 extract high-purity cerium, feature exist
In：The fluorine removal reducing agent is mixed by hydrogen peroxide and acid solution；The acid solution is sulfuric acid or hydrochloric acid.
10. the method that a kind of Rare Earth Mine microwave decomposition-high acidic oils according to claim 6 extract high-purity cerium, feature
It is：In step c, the concentration of the nitric acid is 3~6mol/L.
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| CN113073195A (en) * | 2021-03-19 | 2021-07-06 | 四川师范大学 | Microwave chemical method for completely extracting fluorine and rare earth in bastnaesite concentrate |
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