CN109207746A - A kind of fused salt chlorimation extracting method of low-grade niobium concentrate - Google Patents
A kind of fused salt chlorimation extracting method of low-grade niobium concentrate Download PDFInfo
- Publication number
- CN109207746A CN109207746A CN201811121173.3A CN201811121173A CN109207746A CN 109207746 A CN109207746 A CN 109207746A CN 201811121173 A CN201811121173 A CN 201811121173A CN 109207746 A CN109207746 A CN 109207746A
- Authority
- CN
- China
- Prior art keywords
- chloride
- fused salt
- low
- rare earth
- niobium concentrate
- 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.)
- Granted
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
- C22B34/00—Obtaining refractory metals
- C22B34/20—Obtaining niobium, tantalum or vanadium
- C22B34/24—Obtaining niobium or tantalum
Landscapes
- Engineering & Computer Science (AREA)
- Chemical & Material Sciences (AREA)
- Manufacturing & Machinery (AREA)
- Materials Engineering (AREA)
- Mechanical Engineering (AREA)
- Metallurgy (AREA)
- Organic Chemistry (AREA)
- Manufacture And Refinement Of Metals (AREA)
- Inorganic Compounds Of Heavy Metals (AREA)
Abstract
The present invention provides a kind of fused salt chlorimation extracting method of low-grade niobium concentrate, the method is to extract object with low-grade niobium concentrate, it is reacted by fused salt chlorimation, obtain the chloride of niobium, silicon, iron in low-grade niobium concentrate, then by way of gradually continuous cooling, the method recovering rare earth and radioactive element that the chloride of niobium, silicon, iron is separated, and is gone out by acid or water logging.Extracting method provided by the invention meets Atom economy, excessively high temperature is avoided to cause energy waste, it avoids causing water pollution using a large amount of water, the clean and effective that can be realized low-grade niobium concentrate extracts, three kinds of rare earth chloride, iron chloride and silicon tetrachloride high value added products are obtained simultaneously, extraction efficiency is high, and obtained product purity is high, with good economic efficiency, environmental benefit and social benefit.
Description
Technical field
The invention belongs to field of metallurgy, and in particular to a kind of fused salt chlorimation extracting method of low-grade niobium concentrate.
Background technique
China is maximum niobium resources consumption state in the world, but concentrate product almost all required for niobium industry rely on into
Mouthful.According to statistics, the niobium concentrate total amount of worldwide production in 2815 is 64388 tons, and the niobium concentrate of domestic production only has 58 tons, and deficiency is complete
The 8.1% of ball yield, however the niobium resource of the same year China consumption is 16641 tons, accounts for the 26% of the whole world.Therefore, from supply and demand angle
Analysis, China are highly dependent on foreign countries to niobium resource, and demand is far longer than supply amount, and this situation that supply falls short of demand will
Long-term existence.
In fact, the niobium stock number in China is very big, but with economic value and few, be mainly distributed on Yichuan,
Several places such as Koktokay, Limu, Guangxi Autonomous Region, reserves are in several hundred tons to tons up to ten thousand etc..Although baiyuneboite is China
Maximum niobium resource, reserves occupy the second in the world up to 6,680,000 tons, but due to no cost-effective technology, do not obtain yet so far
Development and utilization.
The niobium resource in China belongs to total association type mineral deposit (such as baiyuneboite, 881 mines etc.) more, and ore dressing can only obtain product
Position (Nb2O5) 2815%, and contain the low-grade niobium concentrate of higher rare earth, iron, silicon simultaneously, well below import niobium concentrate product
Position >=58%.Since concentrate grade is low, at present using this low-grade niobium concentrate as raw material, there are no develop economical and effective so far
Metallurgical technology, for example, niobium resource metallurgical technology in baiyuneboite is researched and developed nearly 58 years, but up to the present there are no reach
To the level of commerical test.The research for the extracting method of low-grade niobium concentrate mostly uses hydrofluoric acid technique or calcining at present
The method of pickling afterwards, but these method one side extraction efficiencies are low, on the other hand there is a large amount of three waste discharge, pollute ring
Border.
Number of patent application is CN281318388543.8, and patent name is " from low-grade containing the method for extracting niobium in niobium minerals "
In disclose one kind, the richness of raw material or baiyuneboite through selecting niobium to obtain for being selected iron, rare earth, fluorite to obtain with baiyuneboite
Integrate object as raw material, (1) roasts after mixing raw material with ammonium acid fluoride, obtains roasted ore；(2) roasted ore and hydrochloric acid carry out acidleach,
Concentration of hydrochloric acid: 3.5~8.8mol/L, extraction temperature: 58~95 DEG C, extraction time: 48~128min；(3) acid leaching residue hydrogen-oxygen
Change potassium solution to decompose, the mass ratio of acid leaching residue and potassium hydroxide is 1.8 ︰ 2.588.5, decomposition temperature: 1588358 DEG C, when decomposition
Between: 588248min；(4) decomposition product leaches in water, extraction temperature: 58895 DEG C, extraction time: 388188min is filtered
To the leachate containing niobium.This method first passes through roasting, then carries out acidleach, finally obtains the aqueous solution containing niobium, and in miberal powder
Other elements do not extracted adequately, be unfavorable for economizing on resources and the energy.
Summary of the invention
For the technical problem more than solving, the present invention provides a kind of fused salt chlorimation extracting method of low-grade niobium concentrate,
It solves the problems, such as that low-grade niobium concentrate difficulty utilizes, while the associations such as recovering rare earth, iron, silicon can be provided from low-grade niobium concentrate
Source not only had an economic benefit, but also had environmental benefit.
The object of the present invention is to provide a kind of fused salt chlorimation extracting methods of low-grade niobium concentrate.
The fused salt chlorimation extracting method of the niobium concentrate of specific embodiment according to the present invention, comprising the following steps:
(1) fused salt chlorimation is reacted: molten chloride being added in reacting furnace, is heated to molten chloride fusing, then
Low-grade niobium concentrate and reducing agent is added, while being passed through chlorine, carries out fused salt chlorimation reaction, it is molten that difficult boiling in reacting furnace is periodically discharged
Salt；The temperature of the fused salt chlorimation reaction is 88881188 DEG C, and the additional amount of the chlorine is low-grade niobium concentrate weight
284.5 times, the weight ratio of the molten chloride, low-grade niobium concentrate and reducing agent is 38845:1:8.288.4；
(2) one sections of cooling separation: the product that fused salt chlorimation is reacted in step (1) is cooled to 3588588 DEG C, separation
Obtain high-melting-point chloride dirt mud and the first gaseous chloride；
(3) two sections of cooling separation: the first gaseous chloride obtained in step (2) is cooled to 2588348 DEG C, is separated
To solid-state iron chloride and the second gaseous chloride；
(4) three sections of cooling separation: the second gaseous chloride obtained in step (3) is cooled to 688248 DEG C, is separated
To solid-state niobium chloride and third gaseous chloride；
(5) four sections of cooling separation: third gaseous chloride obtained in step (4) is cooled to -38858 DEG C, is separated
To liquid silicon tetrachloride；
(6) it leaches: high-melting-point chloride dirt mud obtained in the boiling fused salt of hardly possible obtained in step (1) and step (2) is closed
And solid mixture is obtained, acid is added into solid mixture or water is leached, filters, filtrate is to contain uranium chloride, chlorine
Two or more mixed solutions in change thorium, rare earth chloride, filter residue and drying return to reacting furnace.
The fused salt chlorimation extracting method of the low-grade niobium concentrate of specific embodiment according to the present invention, it is preferable that step (1)
In, the sum of thorium anhydride and triuranium octoxide in the low-grade niobium concentrate >=8.1%, niobium pentaoxide 2815%, three oxidations
Two iron 28848%, rare earth 8.585%, silica 28858%.
The fused salt chlorimation extracting method of the low-grade niobium concentrate of specific embodiment according to the present invention, it is preferable that step (1)
In, the reducing agent is metallurgical coke and/or graphite, it is further preferred that the reducing agent is metallurgical coke and graphite, the metallurgy
Burnt and graphite weight ratio is 1:1.When there is the addition of reducing agent, the exothermal effect of chlorination reaction is significant, different reducing agents,
Different to the facilitation effect of reaction, metallurgical coke is easier to react, and the reaction rate of graphite is relatively slow, using metallurgical coke
The mixture being mixed to get with the weight ratio of graphite using 1:1 can control reaction rate as reducing agent, can make reaction process
Temperature remains in target zone, makes the steady direct motion of reaction process.
The fused salt chlorimation extracting method of the low-grade niobium concentrate of specific embodiment according to the present invention, it is preferable that step (1)
In, the molten chloride is one of alkali metal chloride, alkaline earth metal chloride and rare earth-iron-boron or a variety of.
The fused salt chlorimation extracting method of the low-grade niobium concentrate of specific embodiment according to the present invention, it is preferable that step (1)
In, the molten chloride is rare earth-iron-boron, sodium chloride and potassium chloride, the rare earth-iron-boron, sodium chloride and potassium chloride
Weight ratio is 1:1:1.Fused salt mixt using sodium chloride and potassium chloride is safer method, has low-steam pressure, high boiling
The remarkable advantages such as point, the two, which is used in mixed way, is easier to ensure that stability, and molten boiling point and sodium chloride, the potassium chloride of rare earth-iron-boron connect
Closely, it may have higher fusing point and boiling point, three use be capable of forming more stable fused salt mixt simultaneously；Low-grade niobium concentrate
In contain a small amount of rare earth, these rare earths are all the precious resources to be recycled, will not be to body so rare earth chloride is added in fused salt
System impacts；In addition, the specific gravity of low-grade niobium concentrate is larger, the biggish rare earth chloride of specific gravity is added as fused salt, Ke Yiti
Flow uniformity of the high low-grade concentrate in fused salt reaction process.
The fused salt chlorimation extracting method of the low-grade niobium concentrate of specific embodiment according to the present invention, it is preferable that step (1)
In, the molten chloride is sodium chloride and potassium chloride, and the weight ratio of the sodium chloride and potassium chloride is 5:1.Using sodium chloride
Fused salt mixt with potassium chloride is safer method, and there is remarkable advantages, the two such as low-steam pressure, higher boiling to be used in mixed way
It is easier to ensure that stability.Using the fused salt mixt of sodium chloride and potassium chloride, more simple being added thereto is a kind of more stable, and
The price of sodium chloride is lower, so the large percentage of sodium chloride, is the economy in order to improve technique.
The fused salt chlorimation extracting method of the low-grade niobium concentrate of specific embodiment according to the present invention, it is preferable that step (1)
In, the molten chloride is rare earth chloride and magnesium chloride, and the weight ratio of the rare earth chloride and magnesium chloride is 3:1.For containing
There is the low-grade niobium concentrate of a certain amount of rare earth, rare earth is difficult to overflow in gaseous form in chlorination reaction process, is left on fused salt
In, so rare earth is enriched in fused salt, content is higher, when using rare earth chloride as fused salt, can guarantee dilute in fused salt
Native concentration will not reduce, and improve the recycling economy of rare earth in fused salt；A certain amount of magnesium chloride, which is added, can adjust chlorination reaction
The mobility of fused salt in the process is conducive to reaction and carries out, and the addition of magnesium chloride, itself can't be to the subsequent recovering rare earth from fused salt
Adverse effect is brought, and fused salt is done with magnesium chloride and can be improved recycling for resource, because magnesium chloride is typically derived from chlorine
The reduction electrolysis by-products of compound.
The fused salt chlorimation extracting method of the low-grade niobium concentrate of specific embodiment according to the present invention, it is preferable that step (1)
In, the molten chloride is rare earth chloride and potassium chloride, and the weight ratio of the rare earth chloride and potassium chloride is 1:183.Low product
Contain a certain amount of rare earth in the niobium concentrate of position, high-melting-point fused salt is generated after chlorination reaction, so not using rare earth chloride fused salt
Other impurities can be added into system, fused salt, which can also be recycled, is used in mixed way rare earth chloride and alkali metal chloride especially
It is the mixture that is mixed to get of the weight ratio for using rare earth chloride and potassium chloride using 1:183 as fused salt, is conducive to improve fused salt
The mobility of reaction process and the stability of vapour pressure.
The fused salt chlorimation extracting method of the low-grade niobium concentrate of specific embodiment according to the present invention, it is preferable that step (6)
In, acid is hydrochloric acid, and the concentration of hydrochloric acid is 7mol/L hereinafter, the weight ratio of hydrochloric acid and solid mixture is 286:1.The volatilization of hydrochloric acid
Property and boiling point and concentration of hydrochloric acid it is in close relations, when concentration of hydrochloric acid be higher than 7mol/L when, hydrochloric acid highly volatile, increase acid gas return
Difficulty is received, the corrosion of equipment is also increased；Liquid-solid ratio within this range, is to have combined leaching efficiency and economy, works as liquid
Gu than be lower than this value when leaching efficiency it is low, but be higher than this value when leaching efficiency variation less, will increase the treating capacity of waste water instead,
It is economical unreasonable；Extraction temperature is not strict in reaction, this reaction does not need outside heat supply, and reaction process is salt
Dissolution, and certain heat can be discharged in the process, reaction is promoted to carry out.
The invention has the benefit that
The present invention provides a kind of fused salt chlorimation extracting method of low-grade niobium concentrate, and the method is with low-grade niobium concentrate
Object is extracted, is reacted by fused salt chlorimation, obtains the chloride of niobium, silicon, iron in low-grade niobium concentrate, then by gradually continuous
The mode of cooling separates the chloride of niobium, silicon, iron, and passes through method recovering rare earth and radiation that sour or water logging goes out
Property element.Extracting method provided by the invention meets Atom economy, and excessively high temperature is avoided to cause energy waste, avoid using
A large amount of water cause water pollution, and the clean and effective that can be realized low-grade niobium concentrate extracts, at the same obtain rare earth chloride, iron chloride and
Three kinds of high value added products of silicon tetrachloride, extraction efficiency is high, and obtained product purity is high, and wherein the purity of iron chloride is 85.4%
More than, iron recovery is 87.6% or more, and the purity of niobium chloride is 87.9% or more, and the niobium rate of recovery is 86.2% or more, tetrachloro
The purity of SiClx is 86.2% or more, and the silicon rate of recovery is 86.6% or more, and the uranium thorium rate of recovery is 87.2% or more, rare earth yield
It is 84.5% or more, with good economic efficiency, environmental benefit and social benefit.
Detailed description of the invention
In order to more clearly explain the embodiment of the invention or the technical proposal in the existing technology, to embodiment or will show below
There is attached drawing needed in technical description to be briefly described, it should be apparent that, the accompanying drawings in the following description is only this
Some embodiments of invention for those of ordinary skill in the art without creative efforts, can be with
It obtains other drawings based on these drawings.
Fig. 1 is the process flow chart of the fused salt chlorimation extracting method of low-grade niobium concentrate provided by the invention.
Specific embodiment
To make the object, technical solutions and advantages of the present invention clearer, technical solution of the present invention will be carried out below
Detailed description.Obviously, described embodiments are only a part of the embodiments of the present invention, instead of all the embodiments.Base
Embodiment in the present invention, those of ordinary skill in the art are obtained all without making creative work
Other embodiment belongs to the range that the present invention is protected.
Embodiment 1
With (the Nb containing niobium2O5) 6.87%, iron (Fe2O3) 21.84%, silicon (SiO2) 22.49%, uranium thorium (U3O8+ThO2)
8.14%, the low-grade niobium concentrate of the Inner Mongol baiyuneboite of rare earth (REO) 1.81% is raw material, utilizes technique side of the invention
Method carries out following processing step:
(1) fused salt chlorimation is reacted: solid water-free rare earth chloride 15Kg, sodium chloride 15Kg, chlorine being added into Molten salt chlorination furnace
Change potassium 15Kg, solid fused salt is melted, is added to after then mixing the low-grade niobium concentrate of 1888g with 268g metallurgical coke by heating
It is reacted in liquid fused salt, while being passed through chlorine 2288g into fused salt, fused salt chlorimation reaction temperature is 88881858 DEG C, fused salt chlorine
Change the overflow that reaction generates and carry out continuous four sections of coolings separation, fused salt is periodically discharged in furnace, keeps fused salt in Molten salt chlorination furnace
Liquid level stabilizing；
Fused salt chlorimation: being reacted the one section of cooling separation of overflow progress for overflowing Molten salt chlorination furnace by (2) one sections of cooling separation,
Controlled at 3688428 DEG C, the isolated high-melting-point chloride dirt mud of one section of cooling and the first gaseous chloride；
(3) two sections of cooling separation: the first isolated gaseous chloride of one section of cooling is subjected to two sections of cooling separation, control
Temperature processed is 2688318 DEG C, the isolated solid-state iron chloride of two sections of coolings and the second gaseous chloride, after measured, iron chloride
Purity be 95.3%, iron recovery 92.6%；
(4) three sections of cooling separation: the second isolated gaseous chloride of two sections of coolings is subjected to three sections of cooling separation, temperature
Degree is 1888288 DEG C, three sections of isolated solid-state niobium chlorides of cooling and third gaseous chlorides, after measured, niobium chloride it is pure
Degree is 92.9%, and the niobium rate of recovery is 87.2%；
(5) four sections of cooling separation: the isolated third gaseous chloride of three sections of coolings carries out four sections of cooling separation, temperature
It is -3888 DEG C, four sections of cool down isolated liquid silicon tetrachloride and carbon dioxide and a small amount of unreacted chlorine gaseous mixtures
Body, after measured, the purity of silicon tetrachloride are 88.8%, and the silicon rate of recovery is 92.1%；
(6) it leaches: difficult boiling fused salt that fused salt chlorimation reaction is periodically discharged being cooled down with one section and isolated obtains Gao Rong
It after point chloride dirt mud merges, is leached, leaches the hydrochloric acid that acid is concentration 6mol/L, it is 2:1 that liquid, which consolidates mass ratio, is filtered, filter
Liquid is mixed chlorinated uranium, chloride, re chloride, and filter residue returns to Molten salt chlorination furnace after being dried to moisture < 1%, through surveying
Fixed, the uranium thorium rate of recovery is 98.8%, rare earth yield 96.9%.
Embodiment 2
With (the Nb containing niobium2O5) 2.15%, iron (Fe2O3) 28.54%, silicon (SiO2) 25.13%, uranium thorium (U3O8+ThO2)
8.1%, the low-grade niobium concentrate of the Inner Mongol baiyuneboite of rare earth (REO) 2.86% is raw material, utilizes technique side of the invention
Method carries out following processing step:
(1) fused salt chlorimation is reacted: solid sodium chloride 25Kg, potassium chloride 5Kg being added into Molten salt chlorination furnace, heating will consolidate
Body fused salt melts, and is added to liquid fused salt after then mixing the low-grade niobium concentrate of 1888g with 188g metallurgical coke, 188g graphite powder
Middle reaction, while chlorine 3688g is passed through into fused salt, fused salt chlorimation reaction temperature is 98881188 DEG C, fused salt chlorimation reaction life
At overflow carry out continuous four sections of coolings separation, fused salt is periodically discharged in furnace, fused salt liquid level stabilizing in holding Molten salt chlorination furnace；
Fused salt chlorimation: being reacted the one section of cooling separation of overflow progress for overflowing Molten salt chlorination furnace by (2) one sections of cooling separation,
Controlled at 3888458 DEG C, the isolated high-melting-point chloride dirt mud of one section of cooling and the first gaseous chloride；
(3) two sections of cooling separation: the first isolated gaseous chloride of one section of cooling carries out two sections of cooling separation, control
Temperature is 2588298 DEG C, the isolated solid-state iron chloride of two sections of coolings and the second gaseous chloride, after measured, iron chloride
Purity is 98.9%, iron recovery 96.3%；
(4) three sections of cooling separation: the second isolated gaseous chloride of two sections of coolings carries out three sections of cooling separation, temperature
It is 888158 DEG C, the isolated solid-state niobium chloride of three sections of coolings and third gaseous chloride, after measured, the purity of niobium chloride is
95.5%, the niobium rate of recovery is 97.8%；
(5) four sections of cooling separation: the isolated third gaseous chloride of three sections of coolings carries out four sections of cooling separation, temperature
It is -15815 DEG C, four sections of cool down isolated liquid silicon tetrachloride and carbon dioxide and a small amount of unreacted chlorine gaseous mixtures
Body, after measured, the purity of silicon tetrachloride are 98.7%, and the silicon rate of recovery is 86.6%；
(6) it leaches: difficult boiling fused salt that fused salt chlorimation reaction is periodically discharged being cooled down with one section and isolated obtains Gao Rong
It after point chloride dirt mud merges, is leached, leaches the hydrochloric acid that acid is concentration 2mol/L, it is 4:1 that liquid, which consolidates mass ratio, is filtered, filter
Liquid is mixed chlorinated uranium, chloride, re chloride, and filter residue returns to Molten salt chlorination furnace after being dried to moisture < 1%, through surveying
Fixed, the uranium thorium rate of recovery is 92.3%, rare earth yield 94.8%.
Embodiment 3
With (the Nb containing niobium2O5) 18.18%, iron (Fe2O3) 28.49%, silicon (SiO2) 18.97%, uranium thorium (U3O8+ThO2)
8.67%, 881 mine of the Inner Mongol of rare earth (REO) 5.84% carries out following technique step using process of the invention for raw material
It is rapid:
(1) fused salt chlorimation is reacted: solid chlorine rare earth 38Kg, magnesium chloride 18Kg are added into Molten salt chlorination furnace, heats, it will
Solid fused salt melts, and is added in liquid fused salt and reacts after then mixing the low-grade niobium concentrate of 1888g with 398g graphite powder, together
When be passed through chlorine 4488g into fused salt, fused salt chlorimation reaction temperature is 188881188 DEG C, the spilling that fused salt chlorimation reaction generates
Object carries out continuous four sections of coolings separation, and fused salt is periodically discharged in furnace, keeps fused salt liquid level stabilizing in Molten salt chlorination furnace；
Fused salt chlorimation: being reacted the one section of cooling separation of overflow progress for overflowing Molten salt chlorination furnace by (2) one sections of cooling separation,
Controlled at 3588588 DEG C, the isolated high-melting-point chloride dirt mud of one section of cooling and the first gaseous chloride；
(3) two sections of cooling separation: the first isolated gaseous chloride of one section of cooling carries out two sections of cooling separation, control
Temperature is 2788388 DEG C, the isolated solid-state iron chloride of two sections of coolings and the second gaseous chloride, after measured, iron chloride
Purity is 91.1%, iron recovery 87.6%；
(4) three sections of cooling separation: the second isolated gaseous chloride of two sections of coolings carries out three sections of cooling separation, temperature
It is 688248 DEG C, the isolated solid-state niobium chloride of three sections of coolings and third gaseous chloride, after measured, the purity of niobium chloride is
91.4%, the niobium rate of recovery is 98.8%；
(5) four sections of cooling separation: the isolated third gaseous chloride of three sections of coolings carries out four sections of cooling separation, temperature
It is 15858 DEG C, four sections of cool down isolated liquid silicon tetrachloride and carbon dioxide and a small amount of unreacted chlorine gaseous mixtures
Body, after measured, the purity of silicon tetrachloride are 89.9%, and the silicon rate of recovery is 92.3%；
(6) it leaches: difficult boiling fused salt that fused salt chlorimation reaction is periodically discharged being cooled down with one section and isolated obtains Gao Rong
It after point chloride dirt mud merges, is leached, leaching the solvent used is water, and it is 6:1 that liquid, which consolidates mass ratio, and filtering, filtrate is mixed
Uranium chloride, chloride, re chloride are closed, filter residue returns to Molten salt chlorination furnace after being dried to moisture < 1%, after measured, uranium thorium
The rate of recovery is 98.9%, rare earth yield 92.2%.
Embodiment 4
With (the Nb containing niobium2O5) 14.12%, iron (Fe2O3) 38.95%, silicon (SiO2) 12.46%, uranium thorium (U3O8+ThO2)
1.39%, 881 mine of the Inner Mongol of rare earth (REO) 3.99% carries out following technique step using process of the invention for raw material
It is rapid:
(1) fused salt chlorimation is reacted: solid chlorine rare earth 48Kg being added into Molten salt chlorination furnace, solid fused salt is melted in heating
Change, then will be added in liquid fused salt after the mixing of the low-grade niobium concentrate of 1888g and 328g metallurgical coke and react, while to fused salt
In be passed through chlorine 3888g, fused salt chlorimation reaction temperature is 85881858 DEG C, and the overflow that fused salt chlorimation reaction generates carries out continuous
Four sections of coolings separate, and fused salt is periodically discharged in furnace, keep fused salt liquid level stabilizing in Molten salt chlorination furnace；
Fused salt chlorimation: being reacted the one section of cooling separation of overflow progress for overflowing Molten salt chlorination furnace by (2) one sections of cooling separation,
Controlled at 3788478 DEG C, the isolated high-melting-point chloride dirt mud of one section of cooling and the first gaseous chloride；
(3) two sections of cooling separation: the first isolated gaseous chloride of one section of cooling carries out two sections of cooling separation, control
Temperature is 2588348 DEG C, the isolated solid-state iron chloride of two sections of coolings and the second gaseous chloride, after measured, iron chloride
Purity is 85.4%, iron recovery 95.9%；
(4) three sections of cooling separation: the second isolated gaseous chloride of two sections of coolings carries out three sections of cooling separation, temperature
It is 1588248 DEG C, the isolated solid-state niobium chloride of three sections of coolings and third gaseous chloride, after measured, the purity of niobium chloride
It is 87.9%, the niobium rate of recovery is 86.2%；
(5) four sections of cooling separation: the isolated third gaseous chloride of three sections of coolings carries out four sections of cooling separation, temperature
It is 8838 DEG C, four sections of cool down isolated liquid silicon tetrachloride and carbon dioxide and a small amount of unreacted chlorine mixed gas,
After measured, the purity of silicon tetrachloride is 95.4%, and the silicon rate of recovery is 89.9%；
(6) it leaches: difficult boiling fused salt that fused salt chlorimation reaction is periodically discharged being cooled down with one section and isolated obtains Gao Rong
It after point chloride dirt mud merges, is leached, leaches the hydrochloric acid that acid concentration is 1mol/L, it is 5:1 that liquid, which consolidates mass ratio, is filtered, filter
Liquid is mixed chlorinated uranium, chloride, re chloride, and filter residue returns to Molten salt chlorination furnace after being dried to moisture < 1%, through surveying
Fixed, the uranium thorium rate of recovery is 89.9%, rare earth yield 91.6%.
Embodiment 5
With (the Nb containing niobium2O5) 8.96%, iron (Fe2O3) 26.82%, silicon (SiO2) 21.88%, uranium thorium (U3O8+ThO2)
1.12%, 881 mine of the Inner Mongol of rare earth (REO) 7.77% carries out following technique step using process of the invention for raw material
It is rapid:
(1) fused salt chlorimation is reacted: solid chlorine rare earth 28Kg, potassium chloride 28Kg are added into Molten salt chlorination furnace, heats, it will
Solid fused salt melts, and is added in liquid fused salt and reacts after then mixing the low-grade niobium concentrate of 1888g with 288g metallurgical coke,
Chlorine 4288g is passed through into fused salt simultaneously, fused salt chlorimation reaction temperature is 85881888 DEG C, the spilling that fused salt chlorimation reaction generates
Object carries out continuous four sections of coolings separation, and fused salt is periodically discharged in furnace, keeps fused salt liquid level stabilizing in Molten salt chlorination furnace；
Fused salt chlorimation: being reacted the one section of cooling separation of overflow progress for overflowing Molten salt chlorination furnace by (2) one sections of cooling separation,
Controlled at 3588458 DEG C, the isolated high-melting-point chloride dirt mud of one section of cooling and the first gaseous chloride；
(3) two sections of cooling separation: the first isolated gaseous chloride of one section of cooling carries out two sections of cooling separation, control
Temperature is 2888328 DEG C, the isolated solid-state iron chloride of two sections of coolings and the second gaseous chloride, after measured, iron chloride
Purity is 88.2%, iron recovery 92.8%；
(4) three sections of cooling separation: the second isolated gaseous chloride of two sections of coolings carries out three sections of cooling separation, temperature
It is 1888238 DEG C, the isolated solid-state niobium chloride of three sections of coolings and third gaseous chloride, after measured, the purity of niobium chloride
It is 96.6%, the niobium rate of recovery is 89.9%；
(5) four sections of cooling separation: the isolated third gaseous chloride of three sections of coolings carries out four sections of cooling separation, temperature
It is -28828 DEG C, four sections of cool down isolated liquid silicon tetrachloride and carbon dioxide and a small amount of unreacted chlorine gaseous mixtures
Body, after measured, the purity of silicon tetrachloride are 86.2%, and the silicon rate of recovery is 99.1%；
(6) it leaches: difficult boiling fused salt that fused salt chlorimation reaction is periodically discharged being cooled down with one section and isolated obtains Gao Rong
It after point chloride dirt mud merging, being leached, leaches the hydrochloric acid that acid is concentration 3mol/L, it is 4.5:1 that liquid, which consolidates mass ratio, it filters,
Filtrate is mixed chlorinated uranium, chloride, re chloride, and filter residue returns to Molten salt chlorination furnace after being dried to moisture < 1%, through surveying
Fixed, the uranium thorium rate of recovery is 87.2%, rare earth yield 92.8%.
Embodiment 6
With (the Nb containing niobium2O5) 2.84%, iron (Fe2O3) 28.68%, silicon (SiO2) 7.21%, uranium thorium (U3O8+ThO2)
1.88%, 881 mine of the Inner Mongol of rare earth (REO) 5.22% carries out following technique step using process of the invention for raw material
It is rapid:
(1) fused salt chlorimation is reacted: solid chlorine rare earth 18Kg, potassium chloride 38Kg are added into Molten salt chlorination furnace, heats, it will
Solid fused salt melts, and is added in liquid fused salt and reacts after then mixing the low-grade niobium concentrate of 1888g with 488g metallurgical coke,
Be passed through chlorine 4588g into fused salt simultaneously, fused salt chlorimation reaction temperature is 888 DEG C, the overflow that fused salt chlorimation reaction generates into
The continuous four sections of coolings of row separate, and fused salt is periodically discharged in furnace, keep fused salt liquid level stabilizing in Molten salt chlorination furnace；
Fused salt chlorimation: being reacted the one section of cooling separation of overflow progress for overflowing Molten salt chlorination furnace by (2) one sections of cooling separation,
Controlled at 3588458 DEG C, the isolated high-melting-point chloride dirt mud of one section of cooling and the first gaseous chloride；
(3) two sections of cooling separation: the first isolated gaseous chloride of one section of cooling carries out two sections of cooling separation, control
Temperature is 2888328 DEG C, the isolated solid-state iron chloride of two sections of coolings and the second gaseous chloride, after measured, iron chloride
Purity is 88.2%, iron recovery 92.8%；
(4) three sections of cooling separation: the second isolated gaseous chloride of two sections of coolings carries out three sections of cooling separation, temperature
It is 1888238 DEG C, the isolated solid-state niobium chloride of three sections of coolings and third gaseous chloride, after measured, the purity of niobium chloride
It is 96.6%, the niobium rate of recovery is 89.9%；
(5) four sections of cooling separation: the isolated third gaseous chloride of three sections of coolings carries out four sections of cooling separation, temperature
It is -28828 DEG C, four sections of cool down isolated liquid silicon tetrachloride and carbon dioxide and a small amount of unreacted chlorine gaseous mixtures
Body, after measured, the purity of silicon tetrachloride are 86.2%, and the silicon rate of recovery is 99.1%；
(6) it leaches: difficult boiling fused salt that fused salt chlorimation reaction is periodically discharged being cooled down with one section and isolated obtains Gao Rong
It after point chloride dirt mud merging, being leached, leaches the hydrochloric acid that acid is concentration 7mol/L, it is 4.5:1 that liquid, which consolidates mass ratio, it filters,
Filtrate is mixed chlorinated uranium, chloride, re chloride, and filter residue returns to Molten salt chlorination furnace after being dried to moisture < 1%, through surveying
Fixed, the uranium thorium rate of recovery is 87.2%, rare earth yield 84.5%.
The above description is merely a specific embodiment, but scope of protection of the present invention is not limited thereto, any
Those familiar with the art in the technical scope disclosed by the present invention, can easily think of the change or the replacement, and should all contain
Lid is within protection scope of the present invention.Therefore, protection scope of the present invention should be based on the protection scope of the described claims.
Claims (10)
1. a kind of fused salt chlorimation extracting method of low-grade niobium concentrate, which comprises the following steps:
(1) fused salt chlorimation is reacted: molten chloride being added in reacting furnace, molten chloride fusing is heated to, is then added
Low-grade niobium concentrate and reducing agent, while it being passed through chlorine, fused salt chlorimation reaction is carried out, difficult boiling fused salt in reacting furnace is periodically discharged；
The temperature of the fused salt chlorimation reaction is 88881188 DEG C, and the additional amount of the chlorine is the 284.5 of low-grade niobium concentrate weight
Times, the weight ratio of the molten chloride, low-grade niobium concentrate and reducing agent is 38845:1:8.288.4；
(2) one sections of coolings separation: being cooled to 3588588 DEG C for the product that fused salt chlorimation is reacted in step (1), isolated
High-melting-point chloride dirt mud and the first gaseous chloride；
(3) two sections of coolings separation: being cooled to 2588348 DEG C for the first gaseous chloride obtained in step (2), isolated solid
State iron chloride and the second gaseous chloride；
(4) three sections of coolings separation: being cooled to 688248 DEG C for the second gaseous chloride obtained in step (3), isolated solid
State niobium chloride and third gaseous chloride；
(5) four sections of cooling separation: third gaseous chloride obtained in step (4) is cooled to -38858 DEG C, isolated liquid
State silicon tetrachloride；
(6) it leaches: the boiling fused salt of hardly possible obtained in step (1) being merged with high-melting-point chloride dirt mud obtained in step (2), is obtained
To solid mixture, acid is added into solid mixture or water is leached, filter, filtrate be containing uranium chloride, chloride,
Two or more mixed solutions in rare earth chloride, filter residue and drying return to reacting furnace.
2. the fused salt chlorimation extracting method of low-grade niobium concentrate according to claim 1, which is characterized in that in step (1),
The sum of thorium anhydride and triuranium octoxide in the low-grade niobium concentrate >=8.1%, niobium pentaoxide 2815%, di-iron trioxide
28848%, rare earth 8.585%, silica 28858%.
3. the fused salt chlorimation extracting method of low-grade niobium concentrate according to claim 1, which is characterized in that in step (1),
The reducing agent is metallurgical coke and/or graphite.
4. the fused salt chlorimation extracting method of low-grade niobium concentrate according to claim 3, which is characterized in that in step (1),
The reducing agent is metallurgical coke and graphite, and the weight ratio of the metallurgical coke and graphite is 1:1.
5. the fused salt chlorimation extracting method of low-grade niobium concentrate according to claim 1, which is characterized in that in step (1),
The molten chloride is one of alkali metal chloride, alkaline earth metal chloride and rare earth-iron-boron or a variety of.
6. the fused salt chlorimation extracting method of low-grade niobium concentrate according to claim 5, which is characterized in that in step (1),
The molten chloride is rare earth-iron-boron, sodium chloride and potassium chloride, the weight of the rare earth-iron-boron, sodium chloride and potassium chloride
Than for 1:1:1.
7. the fused salt chlorimation extracting method of low-grade niobium concentrate according to claim 1, which is characterized in that in step (1),
The molten chloride is sodium chloride and potassium chloride, and the weight ratio of the sodium chloride and potassium chloride is 5:1.
8. the fused salt chlorimation extracting method of low-grade niobium concentrate according to claim 1, which is characterized in that in step (1),
The molten chloride is rare earth chloride and magnesium chloride, and the weight ratio of the rare earth chloride and magnesium chloride is 3:1.
9. the fused salt chlorimation extracting method of low-grade niobium concentrate according to claim 1, which is characterized in that in step (1),
The molten chloride is rare earth chloride and potassium chloride, and the weight ratio of the rare earth chloride and potassium chloride is 1:183.
10. the fused salt chlorimation extracting method of low-grade niobium concentrate according to claim 1, which is characterized in that step (6)
In, acid is hydrochloric acid, and the concentration of hydrochloric acid is 7mol/L hereinafter, the weight ratio of hydrochloric acid and solid mixture is 286:1.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201811121173.3A CN109207746B (en) | 2018-09-25 | 2018-09-25 | Molten salt chlorination extraction method of low-grade niobium concentrate |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201811121173.3A CN109207746B (en) | 2018-09-25 | 2018-09-25 | Molten salt chlorination extraction method of low-grade niobium concentrate |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN109207746A true CN109207746A (en) | 2019-01-15 |
| CN109207746B CN109207746B (en) | 2020-12-01 |
Family
ID=64981500
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN201811121173.3A Expired - Fee Related CN109207746B (en) | 2018-09-25 | 2018-09-25 | Molten salt chlorination extraction method of low-grade niobium concentrate |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN109207746B (en) |
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN112723393A (en) * | 2021-01-04 | 2021-04-30 | 湖南省华京粉体材料有限公司 | Method for preparing high-purity tantalum/niobium pentachloride and lithium chloride from waste tantalum/lithium niobate |
Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US2789880A (en) * | 1954-09-23 | 1957-04-23 | Wallace W Beaver | Selective chlorination of beryl |
| CN105154659A (en) * | 2015-10-18 | 2015-12-16 | 内蒙古科技大学 | Method for synchronously extracting iron and niobium from Bayan Obo low-grade ores |
-
2018
- 2018-09-25 CN CN201811121173.3A patent/CN109207746B/en not_active Expired - Fee Related
Patent Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US2789880A (en) * | 1954-09-23 | 1957-04-23 | Wallace W Beaver | Selective chlorination of beryl |
| CN105154659A (en) * | 2015-10-18 | 2015-12-16 | 内蒙古科技大学 | Method for synchronously extracting iron and niobium from Bayan Obo low-grade ores |
Non-Patent Citations (4)
| Title |
|---|
| 中国有色金属工业协会主编: "《有色金属系列丛书 中国铌业》", 30 June 2015, 北京：冶金工业出版社 * |
| 杨靖中主编: "《冶金环保知识问答》", 31 December 1988, 北京：冶金工业出版社 * |
| 邱竹贤主编: "《高等学校教学用书 有色金属冶金学》", 31 May 1988, 北京：冶金工业出版社 * |
| 黄礼煌编著: "《稀土提取技术》", 30 June 2006, 北京：冶金工业出版社 * |
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN112723393A (en) * | 2021-01-04 | 2021-04-30 | 湖南省华京粉体材料有限公司 | Method for preparing high-purity tantalum/niobium pentachloride and lithium chloride from waste tantalum/lithium niobate |
| CN112723393B (en) * | 2021-01-04 | 2023-09-26 | 湖南省华京粉体材料有限公司 | Method for preparing high-purity tantalum pentachloride/niobium and lithium chloride from waste tantalum/lithium niobate |
Also Published As
| Publication number | Publication date |
|---|---|
| CN109207746B (en) | 2020-12-01 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| Jamrack | Rare Metal Extraction by Chemical Engineering Techniques: International Series of Monographs on Chemical Engineering | |
| Zhang et al. | A literature review of titanium metallurgical processes | |
| CN102277483B (en) | Method for preparing rare earth chloride by using Baiyunebo rare earth concentrate | |
| CN109207744B (en) | Molten salt chlorination extraction method of multi-metal bulk concentrate | |
| CN105039725A (en) | Method for recycling rare earth elements from rare earth electrolytic slag | |
| CN103361495A (en) | Method for extracting niobium from Bayan Obo mine tailing | |
| CN109706312A (en) | A method of vanadic anhydride and chemical electrode manganese dioxide are prepared simultaneously using vanadium chromium slag and low-grade pyrolusite | |
| CN109593974A (en) | A method of extracting lithium from lithium mine | |
| CN108531718A (en) | A method of producing chrome green using tailings in vanadium extraction | |
| US20030129113A1 (en) | Upgrading titaniferous materials | |
| CN104878200B (en) | The method that magnesiothermic reduction ilmenite prepares ferro-titanium in cryolite fused salt medium | |
| CN110468285A (en) | A kind of Ti-containing slag produces TiO2The method of powder | |
| CN109207746A (en) | A kind of fused salt chlorimation extracting method of low-grade niobium concentrate | |
| CN104874590A (en) | Resource processing method of chlorination waste residue | |
| CN108165741A (en) | A kind of method that full acid system leaches metallic element in vanadium titano-magnetite | |
| CN108975359B (en) | Fused salt chlorination extraction method for rare earth beryllium silicate ore | |
| CN110453093B (en) | Method for selectively leaching titanium from titanium-containing slag | |
| CN106756129A (en) | A kind of method that uranium is extracted from stone containing betafite | |
| Habashi | Ilmenite for pigment and metal production | |
| CN109252057B (en) | Molten salt chlorination extraction method of low-grade zirconium concentrate | |
| CN109097558A (en) | A kind of reduction roasting-fused salt chlorimation extracting method of more metal composite concentrate | |
| US3227545A (en) | Metallurgical process | |
| CN109182782A (en) | A kind of fluidizing chlorination extracting method of niobium tantalum concentrate | |
| CN109136536B (en) | Reduction roasting-molten salt chlorination extraction method of low-grade niobium concentrate | |
| CN105506286B (en) | A kind of high ferro bone coal cures leachate pretreating process |
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 | ||
| GR01 | Patent grant | ||
| GR01 | Patent grant | ||
| CF01 | Termination of patent right due to non-payment of annual fee |
Granted publication date: 20201201 Termination date: 20210925 |
|
| CF01 | Termination of patent right due to non-payment of annual fee |