CN109136536A - A kind of reduction roasting-fused salt chlorimation extracting method of low-grade niobium concentrate - Google Patents
A kind of reduction roasting-fused salt chlorimation extracting method of low-grade niobium concentrate Download PDFInfo
- Publication number
- CN109136536A CN109136536A CN201811121174.8A CN201811121174A CN109136536A CN 109136536 A CN109136536 A CN 109136536A CN 201811121174 A CN201811121174 A CN 201811121174A CN 109136536 A CN109136536 A CN 109136536A
- Authority
- CN
- China
- Prior art keywords
- fused salt
- low
- chloride
- reduction roasting
- 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
- C22B1/00—Preliminary treatment of ores or scrap
- C22B1/02—Roasting processes
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B03—SEPARATION OF SOLID MATERIALS USING LIQUIDS OR USING PNEUMATIC TABLES OR JIGS; MAGNETIC OR ELECTROSTATIC SEPARATION OF SOLID MATERIALS FROM SOLID MATERIALS OR FLUIDS; SEPARATION BY HIGH-VOLTAGE ELECTRIC FIELDS
- B03C—MAGNETIC OR ELECTROSTATIC SEPARATION OF SOLID MATERIALS FROM SOLID MATERIALS OR FLUIDS; SEPARATION BY HIGH-VOLTAGE ELECTRIC FIELDS
- B03C1/00—Magnetic separation
- B03C1/005—Pretreatment specially adapted for magnetic separation
- B03C1/015—Pretreatment specially adapted for magnetic separation by chemical treatment imparting magnetic properties to the material to be separated, e.g. roasting, reduction, oxidation
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
- C01B33/00—Silicon; Compounds thereof
- C01B33/08—Compounds containing halogen
- C01B33/107—Halogenated silanes
- C01B33/1071—Tetrachloride, trichlorosilane or silicochloroform, dichlorosilane, monochlorosilane or mixtures 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
- C22B34/00—Obtaining refractory metals
- C22B34/20—Obtaining niobium, tantalum or vanadium
- C22B34/24—Obtaining niobium or tantalum
Landscapes
- Chemical & Material Sciences (AREA)
- Engineering & Computer Science (AREA)
- Organic Chemistry (AREA)
- Metallurgy (AREA)
- Manufacturing & Machinery (AREA)
- Materials Engineering (AREA)
- Mechanical Engineering (AREA)
- Environmental & Geological Engineering (AREA)
- General Life Sciences & Earth Sciences (AREA)
- Geochemistry & Mineralogy (AREA)
- Geology (AREA)
- Life Sciences & Earth Sciences (AREA)
- General Chemical & Material Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Inorganic Chemistry (AREA)
- Manufacture And Refinement Of Metals (AREA)
Abstract
The invention discloses a kind of reduction roasting-fused salt chlorimation extracting methods of low-grade niobium concentrate, including reduction roasting；Magnetic separation separation；Fused salt chlorimation reaction, reduction roasting-fused salt chlorimation extracting method process flow of low-grade niobium concentrate of the invention is short, the impurity elements of ferrum that will affect chlorination reaction by the way of reduction roasting-magnetic separation first is separated, iron ore concentrate is obtained, the Iron grade of iron ore concentrate can do the quality raw materials of Ferrous Metallurgy 75% or more；Meet Atom economy, the separation and purification of niobium can not only be realized by chlorination reaction and subsequent refrigerated separation process, additionally it is possible to recycle associated resources from chloride dirt mud, the critical materials silicon tetrachloride for gas-phase silica is also obtained；It uses the present invention all to recycle the associated resources for being likely to become the three wastes originally with high value added product, reduces three wastes discharge amount.
Description
Technical field
The invention belongs to metallurgical technology fields, and in particular to a kind of reduction roasting-fused salt chlorimation of low-grade niobium concentrate mentions
Method is taken,
Background technique
China is maximum niobium country of consumption in the world, but concentrate product almost all required for niobium industry relies on import,
The 0.1% of the insufficient global yield of China's niobium concentrate production capacity at present, however the niobium consumption figure in China but accounts for the 26% of the whole world, and with
The continuous development of China's economic society, the demand to niobium also will be more and more, it was predicted that the demand growth with current China to niobium
Rate, until 2035, the equilibrium of supply and demand was also much not achieved in the demand of China's niobium, and therefore, China is highly dependent on niobium resource
Foreign countries, demand are far longer than supply amount, and this situation that supply falls short of demand is by long-term existence.
The niobium stock number in China is very big, but is mostly complicated association type mine altogether, have economic value and few, and only Jiangxi is suitable
Spring, several places such as Koktokay, Limu, Guangxi Autonomous Region.The niobium minerals of association type is total to as raw material using China, the grade that ore dressing obtains
Only (Nb2O5) 2~15%, well below the grade (>=50%) of import niobium concentrate.Although baiyuneboite is that China is maximum
Niobium resource, reserves occupy the second in the world up to 6,600,000 tons, but due to no cost-effective technology, do not obtain exploitation benefit yet so far
With.The niobium resource reserve of 801 mines is also very big, and is also one of highest mineral deposit of current domestic head grade, but due to not having
Technology fails to develop and use so far, or even entire mine is all untapped.
With the increasingly scarcity of Mineral Resources in China, more metal intergrowth minerals will become mainstream resource, this low-grade
Niobium concentrate must have practicable extractive technique.Dchlorine metallurgy is the important branch of metallurgical method, the past due to technology,
The reasons such as equipment, metallurgy industry " talks chlorine discoloration ", to dchlorine metallurgy full of fear, but with the continuous improvement of scientific and technological level, chlorine
The spatter property for changing metallurgy, which increasingly send out, to be embodied and iron content is generally higher in low-grade niobium concentrate, and shadow is understood in a large amount of presence of iron
Ring the process sequence of entire dchlorine metallurgy.
For these reasons, the present invention is specifically proposed.
Summary of the invention
In order to solve problem above of the existing technology, the present invention provides a kind of reduction of low-grade niobium concentrate roastings
Burning-fused salt chlorimation extracting method, this method is eliminated first by the way of reduction roasting-magnetic separation influences chlorination reaction and separation
Impurity ferro element, the separation and purification of niobium can not only be realized by chlorination reaction and subsequent refrigerated separation process, moreover it is possible to
It is enough to recycle associated resources from chloride dirt mud, the critical materials silicon tetrachloride for gas-phase silica, Environmental Effect is also obtained
Benefit is good, reduces three wastes discharge amount.
To achieve the goals above, the present invention adopts the following technical scheme:
A kind of reduction roasting-fused salt chlorimation extracting method of low-grade niobium concentrate, the method include the following steps:
(1) reduction roasting: low-grade niobium concentrate is baking mixed with reducing agent, roasted ore is obtained after roasting；
(2) magnetic separation separates: the roasted ore being crushed and ground, then carries out magnetic separation, magnetic separation obtains iron ore concentrate and non-
Magnetisable material；
(3) fused salt chlorimation is reacted: solid chloride fused salt being added into Molten salt chlorination furnace, it is molten that heating obtains liquid chloride
The namagnetic substance and metallurgical coke or graphite are added in the liquid molten chloride by salt, while to liquid chlorine
It is passed through chlorine in compound fused salt and carries out fused salt chlorimation reaction, reaction generates overflow, and the overflow is carried out four sections of coolings
Separation boiling fused salt difficult in Molten salt chlorination furnace is periodically discharged, to keep fused salt liquid level stabilizing in Molten salt chlorination furnace.
Further, the low-grade niobium concentrate is 15- for the Nb2O5 and mass fraction for being 2-15% containing mass fraction
The concentrate of 50% iron.
Further, reducing agent is one of coke, coal dust and petroleum coke or a variety of, described low product in step (1)
The mass ratio of position niobium concentrate and reducing agent is 1:0.15-0.35.
Further, the temperature roasted in step (1) is 700-1300 DEG C.
Further, content >=50% of the partial size that roasted ore is ground in step (2) less than 100 mesh.
Further, the magnetic field strength of magnetic separation is 0.15-0.6T in step (2).
Further, solid chloride fused salt described in step (3) be alkali metal chloride, alkaline earth metal chloride and
One of rare earth-iron-boron is a variety of.
Further, solid chloride fused salt and namagnetic substance mass ratio are 30-40:1, nonmagnetics in step (3)
The mass ratio of matter and metallurgical coke or graphite is 1:0.1-0.35, and the quality of chlorine and the mass ratio of namagnetic substance are 2-4.5:1.
Further, the temperature that fused salt chlorimation is reacted in step (3) is 700-1000 DEG C.
Further, in step (3) in four sections of cooling separation, the isolated temperature of one section of cooling is 350-450 DEG C, two sections of drops
The temperature of temperature separation is 250-340 DEG C, and the isolated temperature of three sections of coolings is 60-240 DEG C, and the isolated temperature of four sections of coolings is -30-
50℃。
Further, the isolated high-melting-point dirt slag of one section of cooling and gaseous chloride；Two sections of coolings are isolated solid
State iron chloride and gaseous chloride；The isolated solid-state niobium chloride of three sections of coolings and gaseous chloride, four sections of coolings point
From obtaining liquid silicon tetrachloride and carbon dioxide and a small amount of unreacted chlorine mixed gas.
Compared with prior art, the invention has the benefit that
(1) reduction roasting-fused salt chlorimation extracting method process flow of low-grade niobium concentrate of the invention is short, adopts first
It is separated with the impurity elements of ferrum that reduction roasting-magnetic separation mode will affect chlorination reaction, has obtained iron ore concentrate, iron ore concentrate
Grade can do the quality raw materials of Ferrous Metallurgy 75% or more；
(2) preparation method of the invention is good in economic efficiency, meets Atom economy, passes through chlorination reaction and subsequent cooling
Separation process can not only realize the separation and purification of niobium, additionally it is possible to recycle associated resources from chloride dirt mud, be also obtained
Critical materials silicon tetrachloride for gas-phase silica；
(3) preparation method environmental benefit of the invention is good, will be likely to become the associated resources of the three wastes originally using the present invention
It is all recycled with high value added product, reduces three wastes discharge amount.
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.
Reduction roasting-fused salt chlorimation extracting method process flow chart of low-grade niobium concentrate Fig. 1 of 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.
Fig. 1 is reduction roasting-fused salt chlorimation extracting method process flow chart of low-grade niobium concentrate of the invention.
Embodiment 1
It is respectively Nb that the low-grade niobium concentrate of the present embodiment, which is containing mass fraction,2O52.33%, Fe 35.86% and SiO2
The low-grade niobium concentrate of 16.53% Inner Mongol baiyuneboite is raw material, and preparation method includes the following steps:
(1) it reduction roasting: will be roasted after low-grade niobium concentrate and coal dust mixed pelletizing, low-grade niobium concentrate and coal dust
Mass ratio be 1:0.35, the temperature of roasting is 770 DEG C, and roasted ore is obtained after roasting；
(2) magnetic separation separates: the roasted ore is crushed and is ground, the partial size of grinding less than 100 mesh content >=52%,
Then magnetic separation is carried out, magnetic separation includes one roughing and once purging selection, and the intensity in roughing magnetic field is 0.3T, and scanning magnetic field strength is
0.3T, rougher concentration and scavenger concentrate obtain iron ore concentrate after merging, and rougher tailings is scanned, and scanning tailing is non-magnetic separation object
Matter, as the raw material of fused salt chlorimation reaction, after measured, the Iron grade of iron ore concentrate reaches 85.3%；
(3) fused salt chlorimation is reacted: be added potassium chloride and sodium chloride into Molten salt chlorination furnace, heating obtain liquid potassium chloride and
The namagnetic substance and metallurgical coke are added in the liquid potassium chloride and sodium chloride fused salt, together by sodium chloride fused salt
When be passed through into liquid potassium chloride and sodium chloride fused salt chlorine carry out fused salt chlorimation reaction, fused salt chlorimation reaction temperature be 700-
800 DEG C, reaction generate overflow, wherein the mass ratio of potassium chloride, sodium chloride and namagnetic substance be 20:20:1, metallurgical coke with
The mass ratio of namagnetic substance is 0.1:1, and the mass ratio of chlorine and namagnetic substance is 2.5:1, and the overflow is carried out
Four sections of coolings separate, and difficult boiling fused salt is periodically discharged in Molten salt chlorination furnace, to keep fused salt liquid level stabilizing in Molten salt chlorination furnace:
Wherein, four sections of cooling separation are as follows:
1. one section of cooling separation: fused salt chlorimation is reacted to the one section of cooling separation of overflow progress for overflowing Molten salt chlorination furnace,
Temperature is controlled at 360-400 DEG C, obtains high-melting-point dirt slag, is unreacted low-grade niobium concentrate and gaseous chloride；
2. two sections of cooling separation: the isolated gaseous chloride of one section of cooling is carried out two sections of cooling separation, control temperature
Degree obtains solid-state iron chloride and gaseous chloride at 250-305 DEG C, and after measured, the purity of iron chloride is 92.5%；
3. three sections of cooling separation: the isolated gaseous chloride of two sections of coolings is carried out three sections of cooling separation, control temperature
Degree obtains solid-state niobium chloride and gaseous chloride at 60-90 DEG C, and after measured, the purity of niobium chloride is 96.5%, niobium recycling
Rate is 83.4%；
4. four sections of cooling separation: the isolated gaseous chloride of three sections of coolings is carried out four sections of cooling separation, control temperature
Degree obtains the mixed gas of liquid silicon tetrachloride and carbon dioxide and unreacted chlorine, after measured, tetrachloro at -30-0 DEG C
The purity of SiClx is 89.9%, and the silicon rate of recovery is 89.0%.
Embodiment 2
It is respectively Nb that the low-grade niobium concentrate of the present embodiment, which is containing mass fraction,2O56.07%, Fe 21.04% and SiO2
The low-grade niobium concentrate of 22.49% Inner Mongol baiyuneboite is raw material, and preparation method includes the following steps:
(1) it reduction roasting: will be roasted after low-grade niobium concentrate and coke mixed pelletizing, low-grade niobium concentrate and coke
Mass ratio be 1:0.15, the temperature of roasting is 950 DEG C, and roasted ore is obtained after roasting；
(2) magnetic separation separates: the roasted ore is crushed and is ground, the partial size of grinding less than 100 mesh content >=69%,
Then the roasted ore after grinding is subjected to magnetic separation, magnetic separation includes one roughing and once purging selection, and the intensity in roughing magnetic field is
0.15T, scanning magnetic field strength is 0.18T, and rougher concentration and scavenger concentrate obtain iron ore concentrate after merging, and rougher tailings is swept
Choosing, scanning tailing is non-magnetic separation substance, and as the raw material of fused salt chlorimation reaction, after measured, the Iron grade of iron ore concentrate reaches
95.6%；
(3) fused salt chlorimation is reacted: sodium chloride and rare earth chloride being added into Molten salt chlorination furnace, heating obtains liquid sodium chloride
With rare earth chloride fused salt, it is dilute that the namagnetic substance, metallurgical coke and graphite are added to the liquid sodium chloride and chlorination
In native fused salt, while chlorine being passed through into liquid sodium chloride and rare earth chloride fused salt and carries out fused salt chlorimation reaction, fused salt chlorimation is anti-
The temperature answered is 800-1000 DEG C, and reaction generates overflow, wherein the mass ratio of sodium chloride, rare earth chloride and namagnetic substance
For 20:10:1, the mass ratio of metallurgical coke, graphite and namagnetic substance is 0.1:0.1:1, the mass ratio of chlorine and namagnetic substance
For 2.1:1, the overflow is subjected to four sections of cooling separation, difficult boiling fused salt is periodically discharged in Molten salt chlorination furnace, to keep molten
Fused salt liquid level stabilizing in salt chlorination furnace:
Wherein, four sections of cooling separation are as follows:
1. one section of cooling separation: fused salt chlorimation is reacted to the one section of cooling separation of overflow progress for overflowing Molten salt chlorination furnace,
Temperature is controlled at 380-430 DEG C, obtains high-melting-point dirt slag, is unreacted low-grade niobium concentrate and gaseous chloride；
2. two sections of cooling separation: the isolated gaseous chloride of one section of cooling is carried out two sections of cooling separation, control temperature
Degree obtains solid-state iron chloride and gaseous chloride at 270-310 DEG C, and after measured, the purity of iron chloride is 93.3%；
3. three sections of cooling separation: the isolated gaseous chloride of two sections of coolings is carried out three sections of cooling separation, control temperature
Degree obtains solid-state niobium chloride and gaseous chloride at 120-220 DEG C, and after measured, the purity of niobium chloride is 95.5%, and niobium returns
Yield is 84.5%；
4. four sections of cooling separation: the isolated gaseous chloride of three sections of coolings is carried out four sections of cooling separation, control temperature
Degree obtains the mixed gas of liquid silicon tetrachloride and carbon dioxide and unreacted chlorine, after measured, tetrachloro at 0-15 DEG C
The purity of SiClx is 88.4%, and the silicon rate of recovery is 88.3%.
Embodiment 3
It is respectively Nb that the low-grade niobium concentrate of the present embodiment, which is containing mass fraction,2O514.65%, Fe 8.89% and SiO2
The low-grade niobium concentrate of 25.86% Inner Mongol baiyuneboite is raw material, and preparation method includes the following steps:
(1) it reduction roasting: will be roasted after low-grade niobium concentrate and petroleum coke mixed pelletizing, low-grade niobium concentrate and stone
The mass ratio of oil coke is 1:0.15, and the temperature of roasting is 1150 DEG C, and roasted ore is obtained after roasting；
(2) magnetic separation separates: the roasted ore is crushed and is ground, the partial size of grinding less than 100 mesh content >=60%,
Then the roasted ore after grinding is subjected to magnetic separation, magnetic separation includes one roughing and once purging selection, and the intensity in roughing magnetic field is
0.35T, scanning magnetic field strength is 0.38T, and rougher concentration and scavenger concentrate obtain iron ore concentrate after merging, and rougher tailings is swept
Choosing, scanning tailing is non-magnetic separation substance, and as the raw material of fused salt chlorimation reaction, after measured, the Iron grade of iron ore concentrate reaches
88.6%；
(3) fused salt chlorimation is reacted: potassium chloride and rare earth chloride being added into Molten salt chlorination furnace, heating obtains liquid potassium chloride
With rare earth chloride fused salt, the namagnetic substance and metallurgical coke are added to the liquid potassium chloride and rare earth chloride fused salt
In, while being passed through chlorine into liquid potassium chloride and rare earth chloride fused salt and carrying out fused salt chlorimation reaction, the temperature of fused salt chlorimation reaction
Degree is 760-940 DEG C, and reaction generates overflow, wherein the mass ratio of potassium chloride, rare earth chloride and namagnetic substance is 20:10:
1, the mass ratio of metallurgical coke and namagnetic substance is 0.32:1, and the mass ratio of chlorine and non-magnetic separation substance is 4.5:1, will be described
Overflow carries out four sections of cooling separation, and difficult boiling fused salt is periodically discharged in Molten salt chlorination furnace, to keep liquid fused salt in Molten salt chlorination furnace
Stablize in face:
Wherein, four sections of cooling separation are as follows:
1. one section of cooling separation: fused salt chlorimation is reacted to the one section of cooling separation of overflow progress for overflowing Molten salt chlorination furnace,
Temperature is controlled at 350-420 DEG C, obtains high-melting-point dirt slag, is unreacted low-grade niobium concentrate and gaseous chloride；
2. two sections of cooling separation: the isolated gaseous chloride of one section of cooling is carried out two sections of cooling separation, control temperature
Degree obtains solid-state iron chloride and gaseous chloride at 270-310 DEG C, and after measured, the purity of iron chloride is 95.9%；
3. three sections of cooling separation: the isolated gaseous chloride of two sections of coolings is carried out three sections of cooling separation, control temperature
Degree obtains solid-state niobium chloride and gaseous chloride at 100-240 DEG C, and after measured, the purity of niobium chloride is 90.5%, and niobium returns
Yield is 84.5%；
4. four sections of cooling separation: the isolated gaseous chloride of three sections of coolings is carried out four sections of cooling separation, control temperature
Degree obtains the mixed gas of liquid silicon tetrachloride and carbon dioxide and unreacted chlorine, after measured, four at -15-15 DEG C
The purity of silicon chloride is 90.6%, and the silicon rate of recovery is 87.5%.
Embodiment 4
It is respectively Nb that the low-grade niobium concentrate of the present embodiment, which is containing mass fraction,2O510.98% He of 10.04%, Fe
SiO2The low-grade niobium concentrate of 20.88% Inner Mongol baiyuneboite is raw material, and preparation method includes the following steps:
(1) it reduction roasting: will be roasted after low-grade niobium concentrate and coke, coal dust mixed pelletizing, low-grade niobium concentrate
Mass ratio with coke, coal dust is 1:0.1:0.1, and the temperature of roasting is 1300 DEG C, and roasted ore is obtained after roasting；
(2) magnetic separation separates: the roasted ore is crushed and is ground, the partial size of grinding less than 100 mesh content >=81%,
Then the roasted ore after grinding being subjected to magnetic separation, magnetic separation includes one roughing and once purging selection, and the intensity in roughing magnetic field is 0.5T,
Scanning magnetic field strength is 0.3T, and rougher concentration and scavenger concentrate obtain iron ore concentrate after merging, and rougher tailings is scanned, and tail is scanned
Mine is non-magnetic separation substance, and as the raw material of fused salt chlorimation reaction, after measured, the Iron grade of iron ore concentrate reaches 90.6%；
(3) fused salt chlorimation is reacted: be added magnesium chloride and potassium chloride into Molten salt chlorination furnace, heating obtain liquid magnesium chloride and
The namagnetic substance, metallurgical coke and graphite are added to the liquid magnesium chloride and potassium chloride fused salt by potassium chloride fused salt
In, while being passed through chlorine into liquid magnesium chloride and potassium chloride fused salt and carrying out fused salt chlorimation reaction, the temperature of fused salt chlorimation reaction
It is 900-1000 DEG C, reaction generates overflow, wherein the mass ratio of magnesium chloride, potassium chloride and namagnetic substance is 20:10:1,
The mass ratio of metallurgical coke, graphite and namagnetic substance is 0.1:0.1:1, and the mass ratio of chlorine and namagnetic substance is 2.1:1, will
The overflow carries out four sections of cooling separation, and difficult boiling fused salt is periodically discharged in Molten salt chlorination furnace, to keep in Molten salt chlorination furnace
Fused salt liquid level stabilizing:
Wherein, four sections of cooling separation are as follows:
1. one section of cooling separation: fused salt chlorimation is reacted to the one section of cooling separation of overflow progress for overflowing Molten salt chlorination furnace,
Temperature is controlled at 360-400 DEG C, obtains high-melting-point dirt slag, is unreacted low-grade niobium concentrate and gaseous chloride；
2. two sections of cooling separation: the isolated gaseous chloride of one section of cooling is carried out two sections of cooling separation, control temperature
Degree obtains solid-state iron chloride and gaseous chloride at 260-335 DEG C, and after measured, the purity of iron chloride is 96.0%；
3. three sections of cooling separation: the isolated gaseous chloride of two sections of coolings is carried out three sections of cooling separation, control temperature
Degree obtains solid-state niobium chloride and gaseous chloride at 60-75 DEG C, and after measured, the purity of niobium chloride is 93.3%, niobium recycling
Rate is 80.7%；
4. four sections of cooling separation: the isolated gaseous chloride of three sections of coolings is carried out four sections of cooling separation, control temperature
Degree obtains the mixed gas of liquid silicon tetrachloride and carbon dioxide and unreacted chlorine, after measured, four at -25-50 DEG C
The purity of silicon chloride is 91.1%, and the silicon rate of recovery is 82.6%.
Embodiment 5
It is respectively Nb that the low-grade niobium concentrate of the present embodiment, which is containing mass fraction,2O512.81% He of 4.33%, Fe
SiO2The low-grade niobium concentrate of 28.00% Inner Mongol baiyuneboite is raw material, and preparation method includes the following steps:
(1) it reduction roasting: will be roasted after low-grade niobium concentrate and coke, coal dust mixed pelletizing, low-grade niobium concentrate
Mass ratio with coke, coal dust is 1:0.15:0.01, and the temperature of roasting is 850 DEG C, and roasted ore is obtained after roasting；
(2) magnetic separation separates: the roasted ore is crushed and is ground, the partial size of grinding less than 100 mesh content >=96%,
Then the roasted ore after grinding is subjected to magnetic separation, magnetic separation includes one roughing and once purging selection, and the intensity in roughing magnetic field is
0.16T, scanning magnetic field strength is 0.27T, and rougher concentration and scavenger concentrate obtain iron ore concentrate after merging, and rougher tailings is swept
Choosing, scanning tailing is non-magnetic separation substance, and as the raw material of fused salt chlorimation reaction, after measured, the Iron grade of iron ore concentrate reaches
80.7%；
(3) fused salt chlorimation is reacted: rare earth chloride is added into Molten salt chlorination furnace, heating obtains liquid chlorination rare earth molten salt,
The namagnetic substance, metallurgical coke and graphite are added in the liquid chlorination rare earth molten salt, while to liquid chlorination
It is passed through chlorine in rare earth molten salt and carries out fused salt chlorimation reaction, the temperature of fused salt chlorimation reaction is 700-950 DEG C, and reaction, which generates, overflows
Object, wherein the mass ratio of rare earth chloride and namagnetic substance is 40:1, and the mass ratio of metallurgical coke, graphite and namagnetic substance is
The mass ratio of 0.2:0.1:1, chlorine and namagnetic substance is 4.2:1, and the overflow is carried out four sections of cooling separation, fused salt
Difficult boiling fused salt is periodically discharged in chlorination furnace, to keep fused salt liquid level stabilizing in Molten salt chlorination furnace:
Wherein, four sections of cooling separation are as follows:
1. one section of cooling separation: fused salt chlorimation is reacted to the one section of cooling separation of overflow progress for overflowing Molten salt chlorination furnace,
Temperature is controlled at 390-450 DEG C, obtains high-melting-point dirt slag, is unreacted low-grade niobium concentrate and gaseous chloride；
2. two sections of cooling separation: the isolated gaseous chloride of one section of cooling is carried out two sections of cooling separation, control temperature
Degree obtains solid-state iron chloride and gaseous chloride at 285-330 DEG C, and after measured, the purity of iron chloride is 89.9%；
3. three sections of cooling separation: the isolated gaseous chloride of two sections of coolings is carried out three sections of cooling separation, control temperature
Degree obtains solid-state niobium chloride and gaseous chloride at 75-93 DEG C, and after measured, the purity of niobium chloride is 90.2%, niobium recycling
Rate is 86.2%；
4. four sections of cooling separation: the isolated gaseous chloride of three sections of coolings is carried out four sections of cooling separation, control temperature
Degree obtains the mixed gas of liquid silicon tetrachloride and carbon dioxide and unreacted chlorine, after measured, tetrachloro at 15-50 DEG C
The purity of SiClx is 92.7%, and the silicon rate of recovery is 80.9%.
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 reduction roasting-fused salt chlorimation extracting method of low-grade niobium concentrate, which is characterized in that the method, including
Following steps:
(1) reduction roasting: low-grade niobium concentrate is baking mixed with reducing agent, roasted ore is obtained after roasting；
(2) magnetic separation separates: the roasted ore being crushed and ground, then carries out magnetic separation, magnetic separation obtains iron ore concentrate and non magnetic
Substance；
(3) fused salt chlorimation is reacted: solid chloride fused salt is added into Molten salt chlorination furnace, heating obtains liquid molten chloride,
The namagnetic substance and metallurgical coke or graphite are added in the liquid molten chloride, while to liquid chloride
It is passed through chlorine in fused salt and carries out fused salt chlorimation reaction, reaction generates overflow, the overflow is subjected to four sections of cooling separation,
Boiling fused salt difficult in Molten salt chlorination furnace is periodically discharged, to keep fused salt liquid level stabilizing in Molten salt chlorination furnace.
2. a kind of reduction roasting-fused salt chlorimation extracting method of low-grade niobium concentrate according to claim 1, feature exist
In the low-grade niobium concentrate is the Nb for being 2-15% containing mass fraction2O5It is the concentrate of 15-50% iron with mass fraction.
3. a kind of reduction roasting-fused salt chlorimation extracting method of low-grade niobium concentrate according to claim 1 or 2, special
Sign is, reducing agent is one of coke, coal dust and petroleum coke or a variety of in step (1), the low-grade niobium concentrate with
The mass ratio of reducing agent is 1:0.15-0.35.
4. a kind of reduction roasting-fused salt chlorimation extraction side of low-grade niobium concentrate according to claim 1 to 3
Method, which is characterized in that the temperature roasted in step (1) is 700-1300 DEG C.
5. a kind of reduction roasting-fused salt chlorimation extracting method of low-grade niobium concentrate according to claim 1, feature exist
In content >=50% of the partial size that roasted ore is ground in step (2) less than 100 mesh.
6. a kind of reduction roasting-fused salt chlorimation extracting method of low-grade niobium concentrate according to claim 1 or 5, special
Sign is that the magnetic field strength of magnetic separation is 0.15-0.6T in step (2).
7. a kind of reduction roasting-fused salt chlorimation extracting method of low-grade niobium concentrate according to claim 1, feature exist
In solid chloride fused salt described in step (3) is in alkali metal chloride, alkaline earth metal chloride and rare earth-iron-boron
It is one or more.
8. a kind of reduction roasting-fused salt chlorimation extracting method of low-grade niobium concentrate according to claim 7, feature exist
In solid chloride fused salt and namagnetic substance mass ratio are 30-40:1, namagnetic substance and metallurgical coke or stone in step (3)
The mass ratio of ink is 1:0.1-0.35, and the quality of chlorine and the mass ratio of namagnetic substance are 2-4.5:1.
9. a kind of reduction roasting-fused salt chlorimation extracting method of low-grade niobium concentrate according to claim 1, feature exist
In the temperature that fused salt chlorimation is reacted in step (3) is 700-1000 DEG C.
10. a kind of reduction roasting-fused salt chlorimation extracting method of low-grade niobium concentrate according to claim 1, feature
It is, in step (3) in four sections of cooling separation, the isolated temperature of one section of cooling is 350-450 DEG C, the isolated temperature of two sections of coolings
It is 250-340 DEG C, the isolated temperature of three sections of coolings is 60-240 DEG C, and the isolated temperature of four sections of coolings is -30-50 DEG C.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201811121174.8A CN109136536B (en) | 2018-09-25 | 2018-09-25 | Reduction roasting-molten salt chlorination extraction method of low-grade niobium concentrate |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201811121174.8A CN109136536B (en) | 2018-09-25 | 2018-09-25 | Reduction roasting-molten salt chlorination extraction method of low-grade niobium concentrate |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN109136536A true CN109136536A (en) | 2019-01-04 |
| CN109136536B CN109136536B (en) | 2020-05-22 |
Family
ID=64812465
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN201811121174.8A Expired - Fee Related CN109136536B (en) | 2018-09-25 | 2018-09-25 | Reduction roasting-molten salt chlorination extraction method of low-grade niobium concentrate |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN109136536B (en) |
Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPS52128818A (en) * | 1976-04-07 | 1977-10-28 | Awamura Kinzoku Kougiyou Kk | Tin removing from niobium ore containing tin |
| CN102872968A (en) * | 2012-09-18 | 2013-01-16 | 镇康县金宏矿业有限公司 | Ore dressing method for separating ferrocolumbium |
| CN102994738A (en) * | 2012-12-06 | 2013-03-27 | 内蒙古科技大学 | Method for preparing niobium-enriched ore by employing X-fluorescence sorting-microwave carbon thermal reduction |
| CN104894363A (en) * | 2015-06-24 | 2015-09-09 | 东北大学 | Method for using low-grade niobium concentrate to produce niobium-iron alloy and rare earth double sulfate salt |
| 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 CN201811121174.8A patent/CN109136536B/en not_active Expired - Fee Related
Patent Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPS52128818A (en) * | 1976-04-07 | 1977-10-28 | Awamura Kinzoku Kougiyou Kk | Tin removing from niobium ore containing tin |
| CN102872968A (en) * | 2012-09-18 | 2013-01-16 | 镇康县金宏矿业有限公司 | Ore dressing method for separating ferrocolumbium |
| CN102994738A (en) * | 2012-12-06 | 2013-03-27 | 内蒙古科技大学 | Method for preparing niobium-enriched ore by employing X-fluorescence sorting-microwave carbon thermal reduction |
| CN104894363A (en) * | 2015-06-24 | 2015-09-09 | 东北大学 | Method for using low-grade niobium concentrate to produce niobium-iron alloy and rare earth double sulfate salt |
| 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 |
Also Published As
| Publication number | Publication date |
|---|---|
| CN109136536B (en) | 2020-05-22 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN101418370B (en) | Novel industrialization method for comprehensive utilization of vanadium ferrotitanium ore concentrate | |
| CN108998662A (en) | A method of high efficiente callback iron, scandium, aluminium from brown iron type nickel laterite ore | |
| CN101824502B (en) | Reduction roasting magnetic separation process of low-grade raw iron ores | |
| CN101792852B (en) | Processing for recovering low-grade molybdenum oxide concentrate through wet process | |
| CN103966435B (en) | Alkali leaching, pickling and magnetic separation is utilized to select the method for v-ti magnetite concentrate again | |
| CN109207744A (en) | A kind of fused salt chlorimation extracting method of Complex metal bulk concentrates | |
| CN101418359A (en) | Method for extracting iron and high grade ferro-nickel alloy from laterite nickle mine | |
| CN103952533B (en) | Calcining, alkali leaching and desliming is utilized to select the method for v-ti magnetite concentrate again | |
| CN104878200A (en) | Method for preparing ferrotitanium alloy from ilmenite by virtue of magnesiothermic reduction in cryolite fused salt medium | |
| CN103977880B (en) | Method for recleaning of vanadium-titanium magnetite concentrates by utilizing alkaline leaching, desliming and magnetic-gravity combined separation | |
| CN109136536A (en) | A kind of reduction roasting-fused salt chlorimation extracting method of low-grade niobium concentrate | |
| CN103952532B (en) | Utilize the method that alkali soaks, v-ti magnetite concentrate is selected in classification again | |
| CN104313335B (en) | Ferroalloy manganese dirt ash wet separation Application way | |
| CN103602837A (en) | Method for collecting scandium oxide from anatase associated scandium mineral | |
| CN109207746A (en) | A kind of fused salt chlorimation extracting method of low-grade niobium concentrate | |
| CN103966436B (en) | Utilize the method that alkali soaks, v-ti magnetite concentrate is selected in desliming again | |
| CN103949335A (en) | Method for recleaning of vanadium-titanium magnetite concentrate by using alkaline leaching, grading and magnetic separation | |
| CN103966423A (en) | Method for re-concentrating vanadium-titanium magnetite concentrate through alkaline leaching, acid pickling and re-selection | |
| CN109182782A (en) | A kind of fluidizing chlorination extracting method of niobium tantalum concentrate | |
| CN109097558A (en) | A kind of reduction roasting-fused salt chlorimation extracting method of more metal composite concentrate | |
| CN103962226A (en) | Method for recleaning of vanadium-titanium magnetite concentrates through calcination, alkaline leaching, acid pickling and combination of magnetic separation and gravity concentration | |
| CN103962228B (en) | Utilize calcining, alkali leaching, classification and heavily select the method selecting v-ti magnetite concentrate again | |
| CN103962220B (en) | Alkali leaching, pickling, desliming and heavy magnetic associating is utilized to select v-ti magnetite concentrate method again | |
| CN109252057A (en) | A kind of fused salt chlorimation extracting method of low-grade zircon concentrate | |
| CN103962218B (en) | Utilize calcining, alkali leaching, desliming and heavily select the method selecting v-ti magnetite concentrate again |
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: 20200522 Termination date: 20210925 |
|
| CF01 | Termination of patent right due to non-payment of annual fee |