CN106119522A - The extracting method of Rare Earth Mine - Google Patents
The extracting method of Rare Earth Mine Download PDFInfo
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- CN106119522A CN106119522A CN201610581401.XA CN201610581401A CN106119522A CN 106119522 A CN106119522 A CN 106119522A CN 201610581401 A CN201610581401 A CN 201610581401A CN 106119522 A CN106119522 A CN 106119522A
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- rare earth
- sulphuric acid
- roasting
- extracting method
- earth mine
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- C—CHEMISTRY; METALLURGY
- C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
- C22B—PRODUCTION AND REFINING OF METALS; PRETREATMENT OF RAW MATERIALS
- C22B3/00—Extraction of metal compounds from ores or concentrates by wet processes
- C22B3/04—Extraction of metal compounds from ores or concentrates by wet processes by leaching
- C22B3/06—Extraction of metal compounds from ores or concentrates by wet processes by leaching in inorganic acid solutions, e.g. with acids generated in situ; in inorganic salt solutions other than ammonium salt solutions
- C22B3/08—Sulfuric acid, other sulfurated acids or salts thereof
-
- C—CHEMISTRY; METALLURGY
- C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
- C22B—PRODUCTION AND REFINING OF METALS; PRETREATMENT OF RAW MATERIALS
- C22B1/00—Preliminary treatment of ores or scrap
- C22B1/02—Roasting processes
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- C—CHEMISTRY; METALLURGY
- C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
- C22B—PRODUCTION AND REFINING OF METALS; PRETREATMENT OF RAW MATERIALS
- C22B59/00—Obtaining rare earth metals
-
- 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
- C22B60/00—Obtaining metals of atomic number 87 or higher, i.e. radioactive metals
- C22B60/02—Obtaining thorium, uranium, or other actinides
- C22B60/0291—Obtaining thorium, uranium, or other actinides obtaining thorium
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
- Y02P10/00—Technologies related to metal processing
- Y02P10/20—Recycling
Abstract
The invention provides the extracting method of a kind of Rare Earth Mine.This extracting method includes: carry out roasting with sulphuric acid after Rare Earth Mine being mixed, obtain flue gas and rare earth roasted ore, roasting process includes the process using multihearth to carry out continuous roasting under different temperature sections, sulphuric acid is the sulphuric acid that concentration is more than or equal to 97wt%, and Rare Earth Mine is fluorine carbon cerium mischmetal ore deposit and/or mischmetal ore deposit.Use said extracted device that the roasting process of Rare Earth Mine can be made to carry out at a lower temperature, and at a lower temperature Rare Earth Mine is carried out roasting and is conducive to suppression sulphuric acid to decompose in a large number, thus reduce the sulfur in flue gas and the probability of fluoride mixing, and then reduce vent gas treatment cost.Rare Earth Mine is carried out at a lower temperature the productivity of pyrophosphate in the rare earth roasted ore obtained after roasting process can also reduce roasting simultaneously, and then the content advantageously reducing pyrophosphate advantageously reduces the yield of solid slag during Rare Earth Mine is extracted and improves the utilization rate of thorium element.
Description
Technical field
The present invention relates to field of rare earth metallurgy, in particular to the extracting method of a kind of Rare Earth Mine.
Background technology
China is rare earth big country, and wherein the rare earth of more than 80% is mischmetal ore deposit and fluorine carbon cerium mischmetal ore deposit.Above-mentioned rare earth
The extracting method main high-temperature sulfuric acid roasting method in ore deposit, i.e. carries out high-temperature roasting by Rare Earth Mine in the environment of sulphuric acid, is then passed through
The operations such as leaching and purification and impurity removal prepare various rare-earth products.There are some problems in this production method: temperature during (1) high-temperature roasting
Degree need to be arranged on more than 600 DEG C, this can cause sulphuric acid fast decoupled formed flue gas, and sulfureous in flue gas and fluoride mixing after relatively
Difficult, and the processing cost of tail gas is higher.(2) high-temperature roasting can cause in leached mud thorium presented in thorium pyrophosphate,
Thus level of residue is big after causing extraction, radioactivity exceeds standard, and thorium such as can not be utilized effectively at the problem.
Summary of the invention
Present invention is primarily targeted at the extracting method that a kind of Rare Earth Mine is provided, to solve existing Extraction of rare eart method
The problem that middle vent gas treatment cost is high and rare earth element utilization rate is low.
To achieve these goals, one aspect of the invention provides the extracting method of a kind of Rare Earth Mine, extracting method bag
Including: carry out roasting after Rare Earth Mine being mixed with sulphuric acid, obtain flue gas and rare earth roasted ore, roasting process includes using multihearth to exist
Carrying out the process of continuous roasting under different temperature sections, sulphuric acid is the sulphuric acid that concentration is more than or equal to 97wt%, and Rare Earth Mine is fluorine carbon
Cerium mischmetal ore deposit and/or mischmetal ore deposit, wherein, mischmetal ore deposit includes 60～68.40wt%ReO, 4～5wt%CaO, 0.94
～5wt%BaO, 4.8～8wt%Fe2O3, 0.45～5wt%SiO2, 5～6wt%P2O5, 0.18～0.21wt%ThO2With 0～
7.2wt%F.
Further, roasting process includes: carry out the first roasting with sulphuric acid after Rare Earth Mine being mixed at 80～150 DEG C
Journey, roasting time is T1, obtain the first intermediate product；First intermediate product is carried out at 250～300 DEG C the second roasting
Journey, roasting time is T2, obtain the second intermediate product；And the second intermediate product is cooled at 180～220 DEG C, cool time
For T3, obtain rare earth roasted ore and flue gas, T1: T2: T3It is 1～4:1～11:1～4.
Further, Rare Earth Mine is 1:0.6～1.0 with the weight ratio of sulphuric acid.
Further, extracting method also includes that flue gas is carried out drip washing is purified the mistake of the step of flue gas, preferably drip washing
Journey includes the step that flue gas sequentially passes through sulfuric acid scrubbing and washing.
Further, extracting method also includes the process that sulphuric acid recycles, and the process that sulphuric acid recycles includes drenching
Sulphuric acid during washing reclaims, and the sulphuric acid after then reclaiming uses as the leacheate of lessivation again.
Further, sulphuric acid recycle process also include sulphuric acid feed process, sulphuric acid supply process be will reclaim after
Sulphuric acid is replenished to roasting process.
Further, during sulphuric acid supply, the weight ratio of Rare Earth Mine and sulphuric acid is 1:0.2～0.5.
Further, sulphuric acid atomization and/or the mistake of thickness of feed layer adjustment are carried out during extracting method is additionally included in roasting process
Journey.
Further, the thermal source of roasting process is fuel gas buring or is passed through hot blast；The temperature of hot blast is preferably 200～500
℃。
Further, combustion gas is preferably natural gas and/or coal gas.
Application technical scheme, it is possible to make the roasting process of Rare Earth Mine carry out at a lower temperature, and relatively
Rare Earth Mine carries out at a temperature of low roasting is conducive to suppression sulphuric acid to decompose in a large number, thus reduces the sulfur in flue gas and fluoride and mix
The probability closed, and then reduce vent gas treatment cost.Rare Earth Mine carries out roasting process simultaneously at a lower temperature can also drop
The productivity of pyrophosphate in the rare earth roasted ore obtained after low roasting, and then advantageously reduce the content beneficially fall of pyrophosphate
The yield of low Rare Earth Mine solid slag during extracting and the utilization rate of raising thorium element.
Accompanying drawing explanation
The Figure of description of the part constituting the application is used for providing a further understanding of the present invention, and the present invention shows
Meaning property embodiment and explanation thereof are used for explaining the present invention, are not intended that inappropriate limitation of the present invention.In the accompanying drawings:
Fig. 1 shows in a kind of Rare Earth Mine extracting method that a kind of typical embodiment according to the present invention provides and uses
The structural representation of Extraction of rare eart device.
Wherein, above-mentioned accompanying drawing includes the following drawings labelling:
10, roasting unit；101, the first exhanst gas outlet；102, rare earth roasted ore outlet；103, sulphuric acid supply mouth；20, cigarette
Gas washing unit；21, sulphuric acid elution device；211, the first smoke inlet；212, the second exhanst gas outlet；213, sulphuric acid outlet；
214, sulphuric acid loop head；22, water washing device；221, silicate fluoride solution storage tank；23, sulphuric acid storage tank；30, extraction unit；40, mixed
Close unit；50, heat source accommodation device.
Detailed description of the invention
It should be noted that in the case of not conflicting, the embodiment in the application and the feature in embodiment can phases
Combination mutually.Describe the present invention below with reference to the accompanying drawings and in conjunction with the embodiments in detail.
The extraction process of Rare Earth Mine generally includes the roasting process of Rare Earth Mine, fume treatment process and the leaching of rare earth element
Take process.As described by background technology, the roasting process of existing Extraction of rare eart method uses high-temperature roasting method more, this
The problem that during Rare Earth Mine can be caused to extract, vent gas treatment cost is high and rare earth element utilization rate is low.In order to solve above-mentioned technology
Problem, the invention provides the extracting method of a kind of Rare Earth Mine, and this extracting method includes: carry out after Rare Earth Mine being mixed with sulphuric acid
Roasting, obtains flue gas and rare earth roasted ore, and roasting process includes using multihearth to carry out continuous roasting under different temperature sections
Process, sulphuric acid is the sulphuric acid that concentration is more than or equal to 97wt%, and Rare Earth Mine is fluorine carbon cerium mischmetal ore deposit and/or mischmetal ore deposit, its
In, mischmetal ore deposit includes 60～68.40wt%ReO, 4～5wt%CaO, 0.94～5wt%BaO, 4.8～8wt%Fe2O3,
0.45～5wt%SiO2, 5～6wt%P2O5, 0.18～0.21wt%ThO2With 0～7.2wt%F.
Under different temperature sections, carry out continuous roasting can accurately control the sintering temperature of Rare Earth Mine, make roasting process real
Show the purpose of continuous operations and extend roasting time.Above-mentioned both sides reason makes Rare Earth Mine progressively to decompose, thus
The roasting process that can make Rare Earth Mine is carried out continuously at a lower temperature.At a lower temperature Rare Earth Mine is carried out roasting to have
It is beneficial to suppression sulphuric acid decompose in a large number, thus reduces the sulfur in flue gas and the probability of fluoride mixing, and then reduce vent gas treatment one-tenth
This.In addition Rare Earth Mine is carried out at a lower temperature in the rare earth roasted ore obtained after roasting process can also reduce roasting burnt
Phosphatic productivity, and due to most of pyrophosphate indissoluble things, thus the content reducing pyrophosphate advantageously reduces rare earth
Ore deposit is the yield of solid slag during extracting, and also helps the productivity reducing thorium pyrophosphate simultaneously, and then is conducive to improving thorium element
Utilization rate.
In said extracted method, multihearth successively temperature is used to control to make roasting process enter at a suitable temperature
OK, so improve Extraction of rare eart efficiency.In a preferred embodiment, above-mentioned roasting process includes: by Rare Earth Mine and sulfur
Carrying out the first roasting process at 80～150 DEG C after acid mixing, roasting time is T1, obtain the first intermediate product；By in first
Between product at 250-300 DEG C, carry out the second roasting process, roasting time is T2, obtain the second intermediate product；And by second
Between product be cooled at 180～220 DEG C, cool time is T3, obtain rare earth roasted ore and flue gas, T1: T2: T3Be 1～4:1～
11:1～4.
First at 80～150 DEG C, carry out the first roasting process after Rare Earth Mine being mixed with sulphuric acid, be conducive to suppression sulphuric acid with
Rare Earth Mine reaction acutely causes material outer wrap serious, hinders the carrying out of reaction；By the first intermediate product 250～300
Carry out the second roasting process at DEG C, be conducive to the response speed accelerating sulphuric acid with Rare Earth Mine；Then by the second intermediate product cooling
To 180～220 DEG C, obtain rare earth roasted ore and flue gas.Extraction of rare eart is improved further by becoming above-mentioned roasting process to be conducive to
Efficiency.
In said extracted method, ratio therebetween can be selected to close according to the stoichiometric relationship of Rare Earth Mine with sulphuric acid
System.In a preferred embodiment, Rare Earth Mine is 1:0.6～1.0 with the weight ratio of sulphuric acid.Rare Earth Mine and the weight of sulphuric acid
Ratio is including but not limited to above-mentioned scope, and is conducive to the limited proportion of the two within the above range improving Rare Earth Mine and sulphuric acid
Reaction efficiency, thus further improve the extraction efficiency of rare earth element.
In a preferred embodiment, extracting method also includes that flue gas is carried out drip washing is purified the step of flue gas
Suddenly, the process of preferably drip washing includes the step that flue gas sequentially passes through sulfuric acid scrubbing and washing.The flue gas that roasting process is obtained
Carrying out drip washing can make the tail gas of Rare Earth Mine extraction process purify, thus to improve this feature of environmental protection.
In a preferred embodiment, extracting method also includes the process that sulphuric acid recycles, and sulphuric acid recycles
Process include reclaiming the sulphuric acid in lessivation, then will reclaim after sulphuric acid again as the drip washing of lessivation
Liquid uses.The sulphuric acid liquid discharged in sulphuric acid lessivation reclaims, and is then again used as leacheate by the sulphuric acid reclaimed,
This utilization rate being conducive to improving sulphuric acid, and then reduce the use cost of leacheate.
In a preferred embodiment, sulphuric acid recycles process and also includes that sulphuric acid feeds process, and sulphuric acid fed
Journey is that the sulphuric acid after reclaiming is replenished to roasting process.On the one hand the sulphuric acid of recovery can be carried as the bulking liquor of roasting process
On the other hand the utilization rate of high sulphuric acid, can also make the more abundant of roasting process middle rare earth ore deposit and sulfuric acid reaction, improve rare earth
The extraction efficiency of element.
In the extracting method of above-mentioned Rare Earth Mine, the supply of sulphuric acid during sulphuric acid feeds can be adjusted according to practical situation
Amount.In a preferred embodiment, during sulphuric acid supply, the weight ratio of Rare Earth Mine and sulphuric acid is 1:0.2～0.5.By sulfur
The increment of acid controls to be conducive within the above range saving sulfur on the basis of guarantee sulphuric acid acidizing effect is precisely controlled simultaneously
The consumption of acid.
Said extracted method is additionally included in roasting process and carries out sulphuric acid atomization and/or the process of thickness of feed layer adjustment.
In said extracted method, roasting thermal source supply mode commonly used in the art can be selected.Preferably implement in one
In mode, the thermal source of roasting process is fuel gas buring or is passed through hot blast.In combustion process combustion gas be preferably natural gas, coal gas or its
His fuel gas.Hot blast temperature is preferably 200～500 DEG C.
The leaching process of the application rare earth elements uses the leach extraction method that this area is conventional.
In order to solve above-mentioned technical problem, the invention provides the extraction element of a kind of Rare Earth Mine, as it is shown in figure 1, this carries
Fetching is put and is included that roasting unit 10, roasting unit 10 are provided with sulphuric acid entrance and Rare Earth Mine entrance, and above-mentioned roasting unit 10 has
The multiple burner hearths being sequentially connected and the temperature monitor controlling each hearth roasting temperature, be provided with sulphuric acid entrance and Rare Earth Mine enters
The burner hearth of mouth is initial burner hearth, and above-mentioned Rare Earth Mine is fluorine carbon cerium mischmetal ore deposit and/or mischmetal ore deposit, and wherein mischmetal ore deposit includes
60～68.40wt%ReO, 4～5wt%CaO, 0.94～5wt%BaO, 4.8～8wt%Fe2O3, 0.45～5wt%SiO2, 5
～6wt%P2O5, 0.18～0.21wt%ThO2With 0～7.2wt%F.
Above-mentioned Extraction of rare eart device carries out roasting process by multihearth, and this can accurately control the roasting temperature of Rare Earth Mine
Degree, makes Rare Earth Mine roasting in multiple burner hearths of multihearth realize continuous operations, and can time of conservative control roasting
To reach purpose Rare Earth Mine progressively decomposed.The reason of these two aspects makes the roasting process of Rare Earth Mine can be in relatively low temperature
Carry out under degree.Rare Earth Mine carries out roasting at a lower temperature is conducive to suppression sulphuric acid to decompose in a large number, thus reduces in flue gas
Sulfur and fluoride mixing probability, and then reduce vent gas treatment cost.In addition Rare Earth Mine is roasted at a lower temperature
The productivity of pyrophosphate in the rare earth roasted ore that burning process obtains after can also reducing roasting, and owing to most of pyrophosphates are difficult
Molten thing, thus the content reducing pyrophosphate advantageously reduces the yield of solid slag during Rare Earth Mine is extracted, and also helps simultaneously
Reduce the productivity of thorium pyrophosphate, and then be conducive to improving the utilization rate of thorium element.
In a preferred embodiment, roasting unit 10 is multihearth.Use above-mentioned Rare Earth Mine extraction element to dilute
Tu Kuang carries out roasting can not only make above-mentioned roasting process carry out reducing the processing cost of tail gas at a lower temperature, additionally it is possible to
Improve the added economic value of extraction element.Under normal circumstances, multihearth can be adjusted according to the weight of Rare Earth Mine and kind
The quantity of burner hearth.The most described multihearth is provided with the 6～19 layers of burner hearth being sequentially connected.The number of multihearth burner hearth is controlled
In above-mentioned scope, be conducive to reducing the volume of extraction element in controlled scope.
Sintering temperature and roasting time have large effect to the leaching rate of rare earth element.Preferably, every layer of burner hearth stove
Temperature range is 40～300 DEG C, and every layer of sintering temperature fluctuation range is ± 20 DEG C.The total continuous roasting time of Rare Earth Mine is preferably
8～12h.This is advantageously implemented the leaching of thorium, makes rare earth element leaching rate ＞ 95wt%, advantageously reduces the radiation of slag simultaneously
Property, it is achieved harmless treatment.Every layer of multiple hearth furnace temperature is constant in roasting process, and temperature is deteriorated less than ± 20 DEG C.
With above-mentioned Rare Earth Mine extraction element, Rare Earth Mine is carried out roasting and can make above-mentioned roasting process at a lower temperature
Carry out, and then reduce the processing cost of tail gas.In a preferred embodiment, as it is shown in figure 1, roasting unit 10 also sets up
Having the first exhanst gas outlet 101, the burner hearth with the first exhanst gas outlet is end burner hearth, and extraction element also includes washing smoke unit
20, washing smoke unit 20 is connected by the first flue gas delivery pipe road with the first exhanst gas outlet 101.Roasting unit 10 drenches with flue gas
Wash unit 20 and baking tail gases can be carried out drip washing, to improve Rare Earth Mine extraction element by the first flue gas delivery pipe road is connected
The feature of environmental protection.
In above-mentioned Extraction of rare eart device, washing smoke unit 20 can use elution device commonly used in the art.In one
In preferred embodiment, as it is shown in figure 1, washing smoke unit 20 includes sulphuric acid elution device 21 and water washing device 22.Sulphuric acid
Elution device 21, is provided with the first smoke inlet 211 and the second exhanst gas outlet 212, and the first smoke inlet 211 goes out with the first flue gas
Mouth 101 is connected by the first flue gas delivery pipe road；And preferred water washing device 22, water washing device 22 is logical with the second exhanst gas outlet 212
Cross the second flue gas pipeline to be connected.Washing smoke unit 20 arranges two-stage elution device and is conducive to improving the drip washing effect of flue gas.On
The flue gas stating roasting process generation can remove the trace flue dust in flue gas after the washing of persulfuric acid elution device 21, drenches simultaneously
During washing, sulphuric acid can also be preheated by flue gas.Flue gas after sulphuric acid elution device 21 washs enters back into water washing device and washs
Can obtain silicate fluoride solution, this can lay in as fluorine industrial chemicals, and then the Rare Earth Mine improving the application offer carries
The economy that fetching is put.Above-mentioned water washing device 22 is preferably horizontal scrubber, uses the washing of industry water multi-stage spray.Make actual
During with, above-mentioned water washing device 22 preferably comprises silicate fluoride solution storage tank 221, this silicate fluoride solution storage tank 221 and washing dress
Put 22 to be connected by silicate fluoride solution transfer pipeline.
In a preferred embodiment, as it is shown in figure 1, sulphuric acid elution device 21 is additionally provided with sulphuric acid outlet 213 Hes
Sulphuric acid loop head 214, washing smoke unit 20 also includes that sulphuric acid storage tank 23, sulphuric acid outlet 213 pass through sulfur with sulphuric acid storage tank 23
Acid output pipe is connected, and sulphuric acid loop head 214 is connected with sulphuric acid circulation line with sulphuric acid storage tank 23.Sulphuric acid lessivation is arranged
The sulphuric acid liquid gone out enters sulphuric acid storage tank 23 from sulphuric acid outlet 213 and is collected, and then the sulphuric acid in sulphuric acid storage tank 23 is passed through sulfur
Acid circulation line uses as leacheate sending sulphuric acid elution device 21 back to, this utilization rate being conducive to improving sulphuric acid, reduces pouring
The use cost of washing liquid.
In a preferred embodiment, as it is shown in figure 1, roasting unit 10 is additionally provided with sulphuric acid supply mouth 103, arrange
On burner hearth, and above-mentioned burner hearth does not comprise initial burner hearth, and sulphuric acid supply mouth 103 feeds pipeline phase with sulphuric acid storage tank 23 by sulphuric acid
Even.Due to loss or the parcel of acid, and the mixing of acid is uneven etc., causes Rare Earth Mine reaction insufficient.Thus sulphuric acid is set
Supply mouth 103 is conducive to carrying out secondary supplement sulphuric acid to roasting unit 10 as required.And sulphuric acid is fed mouth 103 and stores up with sulphuric acid
Groove 23 is communicated with beneficially further with the sulphuric acid leacheate in sulphuric acid elution device 21, improves its utilization rate.
In a preferred embodiment, roasting unit 10 arranges sulfuric acid mist gasifying device, is arranged at inside burner hearth,
And be connected with sulphuric acid entrance and sulphuric acid supply mouth；And/or roasting unit 10 is additionally provided with adjustable automatic cleaning rake arms device, if
It is placed in inside burner hearth, the height of Rare Earth Mine in regulating burner hearth.Sulfuric acid mist gasifying device is preferably provided with 2～3 spray guns, more preferably
Ground spray gun is uniformly laid on every layer multi-layer stove.This is conducive to making roasting process more abundant, and then improves roasting conversion rate.Spray
Entering acid amount with Rare Earth Mine generally according to weight ratio 0.2～0.5:1, concrete operations can also be according to each layer Rare Earth Mine roasting sampling knot
Fruit determines.
Bottom multiple hearth furnace axis be provided with adjustable automatically clear up rake arms device can by adjust rake arms elevating control
Thickness of feed layer in burner hearth.This is conducive to promoting that sulphuric acid contacts with the bed of material further, thus improves the decomposition effect of Rare Earth Mine further
Rate.
In actual use, it is preferable that the exhanst gas outlet of multihearth is arranged on furnace roof or top layer 1～the sidewall of 5 layers
On.During this is conducive to sulfur acid acid mist air-flow to rise in multihearth, the preheating of last layer material or offer sulphuric acid are mended
Fill.
At actual roasting process, the sintering temperature of Rare Earth Mine and roasting time are important control parameters, and sintering temperature is permissible
Controlling multiple hearth furnace each layer sintering temperature by fuel gas buring in multihearth and fire door cold blast rate, roasting time can pass through multiple hearth furnace
Regulation and the multiple hearth furnace number of plies of axis rotating speed are controlled.
In a preferred embodiment, as it is shown in figure 1, roasting unit 10 is provided with rare earth roasted ore outlet 102, on
Stating extraction element and also include extracting unit 30, extraction unit 30 is connected with rare earth roasted ore outlet 102.The application rare earth elements
Leaching process extraction unit 30 in carry out, this extraction unit 30 uses leaching device commonly used in the art.
In a preferred embodiment, as it is shown in figure 1, Rare Earth Mine extraction element is additionally provided with mixed cell 40, should
Mixed cell 40 is provided with sulphuric acid entrance, Rare Earth Mine entrance and compound outlet, and compound outlet enters with the raw material of roasting unit
Mouth is connected by feedstock transportation pipeline.Arrange mixed cell can by roasting raw material mix homogeneously before roasting process, thus
Be conducive to making the most abundant of roasting process middle rare earth ore deposit.
The preferably material of the body of heater of multihearth includes but not limited to that steel lining graphite, steel lining politef and steel lining are acidproof
One or more in brick.Above-mentioned material has good heat resistance, uses above-mentioned material favourable as the body of heater of multihearth
In the heat resistance of raising multihearth, thus adapt to the temperature requirements of roasting in various degree.
In a preferred embodiment, as it is shown in figure 1, extraction element also includes heat source accommodation device 50, this thermal source
Feeding mechanism is fuel gas supply equipment, and each burner hearth is respectively arranged with gas nozzle, and gas nozzle passes through with heat source accommodation device 50
Thermal source transfer pipeline is connected.The fuel gas buring liberated heat in heat source accommodation device 50 is utilized to provide heat for roasting unit 10
Source.Preferably, gas nozzle is symmetrical arranged；The more preferably number of gas nozzle is 2～4.This is conducive to making Rare Earth Mine in roasting
Decompose more thorough during burning.In combustion process, fuel is preferably natural gas, coal gas or other fuel gas.
In a preferred embodiment, said extracted device also includes heat source accommodation device 50, and this thermal source supply fills
Being set to hot-air supplying equipment, each burner hearth is respectively arranged with hot-air mouth, and hot-air mouth and heat source accommodation device 50 are by thermal source conveying pipe
Road is connected.Use hot air technique device to provide roasting unit 10 to provide thermal source for the application, be conducive to avoiding naked light to occur, thus
Improve the safety of device.Preferably, hot-air mouth is symmetrical arranged；The more preferably number of hot-air mouth is 2～4.This be conducive to into
One step improves Rare Earth Mine resolution ratio in roasting process.
Being described in further detail the present invention below in conjunction with specific embodiment, these embodiments are it is not intended that limit this
Invent scope required for protection.
Embodiment 1 to 4 and comparative example 1 middle rare earth ore deposit consist of 60～68.40wt%ReO, 4～5wt%CaO, 0.94
～5wt%BaO, 4.8～8wt%Fe2O3, 0.45～5wt%SiO2, 5～6wt%P2O5, 0.18～0.21wt%ThO2With 0～
7.2wt%F；The method of testing of rare earth element leaching experiment is: GB/T18114.1-2010 Rare Earth Mine chemical analysis method the 1st
Point: the gravimetry method of total amount of the rare earth oxide.
Embodiment 1 to 4 uses the rare earth element in extraction element Extraction of rare earth ore deposit as shown in Figure 1.
Embodiment 1
Take after 500kg Rare Earth Mine mixes according to weight ratio 1:0.8 with sulphuric acid, be continuously added to roasting unit 10 (multihearth)
In, obtain rare earth roasted ore.In multihearth, the sintering temperature of each layer is shown in Table 1.
Table 1
| The multiple hearth furnace number of plies | 1 | 2 | 3 | 4 | 5 | 6 | 7 | 8 | 9 | 10 |
| Sintering temperature | 80 | 80 | 150 | 150 | 250 | 250 | 250 | 300 | 250 | 200 |
During whole, each layer roasting time is identical, and roasting total time is 6h, carries out sulphuric acid benefit at the 4th, 5,6,7 layers
Giving, the increment of sulphuric acid is about the 30wt% of the Rare Earth Mine amount added.
Baking flue gas is through the sulfuric acid scrubbing of persulfuric acid elution device 21 and the repeatedly water of water washing device 22 (horizontal scrubber)
Wash, obtain hydrofluoric acid solution, about hexafluosilicic acid concentration 10.2wt%.In tail gas, Oil repellent is less than 2mg/Nm3, meet country's waste gas
Discharge standard.
Rare earth roasted ore goes out checking through water logging, and rare earth leaching rate is 96.2wt%, and thorium leaching rate is 84.2wt%, and slag is put
The radioactivity requirement of penetrating property specific activity 1554Bq/Kg, slightly above national standard 1000Bq/Kg.
Embodiment 2
Take after 500kg Rare Earth Mine mixes according to weight ratio 1:1 with sulphuric acid, be continuously added in roasting unit 10 (multihearth),
Obtain rare earth roasted ore.In multihearth, the sintering temperature of each layer is shown in Table 2.
Table 2
| The multiple hearth furnace number of plies | 1 | 2 | 3 | 4 | 5 | 6 | 7 | 8 | 9 | 10 |
| Sintering temperature | 80 | 100 | 150 | 250 | 250 | 250 | 280 | 300 | 250 | 200 |
During whole, each layer roasting time is identical, and roasting total time is 10h, carries out sulphuric acid at the 3rd, 4,5,6,7 layers
Supply, the increment of sulphuric acid is about the 30wt% of the Rare Earth Mine amount added.
Baking flue gas is through the sulfuric acid scrubbing of persulfuric acid elution device 21 and the repeatedly water of water washing device 22 (horizontal scrubber)
Wash, obtain hydrofluoric acid solution, about hexafluosilicic acid concentration 11wt%.In tail gas, Oil repellent is less than 2mg/Nm3, meet country waste gas row
Put standard.
Rare earth roasted ore goes out checking through water logging, and rare earth leaching rate is 97.6wt%, and thorium leaching rate is 95.3wt%, and slag is put
Penetrating property specific activity is 468Bq/Kg, meets national standard requirement.
Embodiment 3
On the basis of embodiment 2, maintain other reaction conditions constant, by Rare Earth Mine with sulphuric acid according to weight ratio 1:0.3
Mixing is continuously added in multihearth.
Rare earth roasted ore goes out checking through water logging, and rare earth leaching rate is 66wt%, and thorium leaching rate is 63.7wt%, and slag radiates
Property specific activity is 3625Bq/Kg.
Embodiment 4
Take after 500kg Rare Earth Mine mixes according to weight ratio 1:1 with sulphuric acid, be continuously added in roasting unit 10 (multihearth),
Obtain rare earth roasted ore.In multihearth, the sintering temperature of each layer is shown in Table 3.
Table 3
| The multiple hearth furnace number of plies | 1 | 2 | 3 | 4 | 5 | 6 | 7 | 8 | 9 | 10 |
| Sintering temperature | 50 | 50 | 120 | 120 | 180 | 180 | 200 | 220 | 1200 | 80 |
During whole, each layer roasting time is identical, and roasting total time is 4h, carries out sulphuric acid benefit at the 3rd, 4,5,6,7 layers
Giving, the increment of sulphuric acid is about the 30wt% of the Rare Earth Mine amount added.
Rare earth roasted ore goes out checking through water logging, and rare earth leaching rate is 72wt%, and thorium leaching rate is 68wt%, slag radioactivity
Specific activity is 3172Bq/Kg.
Comparative example 1
Above-mentioned Rare Earth Mine and sulphuric acid are carried out roasting by the weight ratio of 1:1.3～1.4 in rotary kiln, obtains tail gas and dilute
Soil roasted ore, sintering temperature is 700 DEG C, and roasting time is 2h.
After roasting, rare earth leaching rate ＞ 95%, thorium is presented in thorium pyrophosphate in slag, and slag is radioactivity slag；Roasting
Tail gas contains a large amount of SO2, fluoride etc., it is difficult to process.Tail gas uses multi-level water washing, adds oxidant by sulfurous in aqueous solution
Acid group is converted into sulfate radical, and then evaporation and concentration obtains the sulphuric acid return roasting use of more than 70%, the low-concentration hydrogen evaporated
Fluorspar acid solution waste water processes or produces other products.
As can be seen from the above description, the above embodiments of the present invention achieve following technique effect:
By data in comparing embodiment 1 to 3 and comparative example 1, use in the method Extraction of rare earth that the application provides
Element, sintering temperature is greatly reduced, and the tail gas of roasting is also purified, it is often more important that achieve the serialization to Rare Earth Mine
Operation.By data in comparing embodiment 1,2 and 4, temperature and the roasting time in stage each in multihearth are controlled one
Be conducive to improving the leaching rate of Rare Earth Mine rare earth elements in the range of Ding；Comparing embodiment 2 and 3 understands simultaneously, when Rare Earth Mine with
When the weight ratio of sulphuric acid is less than 0.6, Rare Earth Mine only part is decomposed, thus causes the leaching rate of rare earth element substantially to reduce.
The foregoing is only the preferred embodiments of the present invention, be not limited to the present invention, for the skill of this area
For art personnel, the present invention can have various modifications and variations.All within the spirit and principles in the present invention, that is made any repaiies
Change, equivalent, improvement etc., should be included within the scope of the present invention.
Claims (10)
1. the extracting method of a Rare Earth Mine, it is characterised in that described extracting method includes:
Carrying out roasting after described Rare Earth Mine being mixed with sulphuric acid, obtain flue gas and rare earth roasted ore, described roasting process includes making
With multihearth, described Rare Earth Mine is carried out successively from the mixture of sulphuric acid under different temperature sections the process of continuous roasting, described
Sulphuric acid is the sulphuric acid that concentration is more than or equal to 97wt%, and described Rare Earth Mine is fluorine carbon cerium mischmetal ore deposit and/or mischmetal ore deposit,
Wherein, described mischmetal ore deposit include 60～68.40wt%ReO, 4～5wt%CaO, 0.94～5wt%BaO, 4.8～
8wt%Fe2O3, 0.45～5wt%SiO2, 5～6wt%P2O5, 0.18～0.21wt%ThO2With 0～7.2wt%F.
Extracting method the most according to claim 1, it is characterised in that described roasting process includes:
Carrying out the first roasting process with sulphuric acid after described Rare Earth Mine being mixed at 80～150 DEG C, roasting time is T1, obtain
One intermediate product；
Described first intermediate product is carried out at 250～300 DEG C the second roasting process, and roasting time is T2, obtain in the middle of second
Product；And
Being cooled at 180～220 DEG C by described second intermediate product, cool time is T3, obtain described rare earth roasted ore and described
Flue gas, T1: T2: T3It is 1～4:1～11:1～4.
Extracting method the most according to claim 1 and 2, it is characterised in that described Rare Earth Mine and the weight ratio of described sulphuric acid
For 1:0.6～1.0.
Extracting method the most according to claim 1, it is characterised in that described extracting method also includes carrying out described flue gas
Drip washing is purified the step of flue gas, and the process of the most described drip washing includes described flue gas is sequentially passed through sulfuric acid scrubbing and washing
Step.
Extracting method the most according to claim 4, it is characterised in that described extracting method also includes what sulphuric acid recycled
Process, the process that described sulphuric acid recycles includes reclaiming the sulphuric acid in described lessivation, after then reclaiming
Described sulphuric acid leacheate as described lessivation again uses.
Extracting method the most according to claim 5, it is characterised in that described sulphuric acid recycles process and also includes that sulphuric acid is mended
To process, described sulphuric acid supply process be by described recovery after sulphuric acid be replenished to described roasting process.
Extracting method the most according to claim 6, it is characterised in that described Rare Earth Mine and institute during the supply of described sulphuric acid
The weight ratio stating sulphuric acid is 1:0.2～0.5.
Extracting method the most according to any one of claim 1 to 7, it is characterised in that described extracting method is additionally included in
Roasting process carries out sulphuric acid atomization and/or the process of thickness of feed layer adjustment.
Extracting method the most according to claim 1, it is characterised in that the thermal source of described roasting process is fuel gas buring or logical
Enter hot blast；The temperature of described hot blast is preferably 200～500 DEG C.
Extracting method the most according to claim 9, it is characterised in that described combustion gas is preferably natural gas and/or coal gas.
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| CN106756128A (en) * | 2016-12-10 | 2017-05-31 | 包头稀土研究院 | A kind of method that low acid consumption mixed rare earth concentrates concentrated sulfuric acid is decomposed |
| CN108950188A (en) * | 2018-05-25 | 2018-12-07 | 包头稀土研究院 | The method of concentrated sulfuric acid low-temperature bake phosphorous rare earth ore concentrate step by step arithmetic phosphorus and rare earth |
| CN113387391A (en) * | 2021-07-30 | 2021-09-14 | 广西埃索凯新材料科技有限公司 | Manganese sulfate production system based on manganese oxide ore |
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| CN201952466U (en) * | 2011-01-06 | 2011-08-31 | 中冶东方工程技术有限公司 | Multistage serial-connection roasting equipment |
| CN104962762A (en) * | 2015-07-22 | 2015-10-07 | 中国恩菲工程技术有限公司 | Processing method of fine bastnaesite |
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| CN1667139A (en) * | 2004-03-08 | 2005-09-14 | 中国有色工程设计研究总院 | Mixed rare earth concentrate decomposition method |
| CN1807253A (en) * | 2006-01-18 | 2006-07-26 | 朴钟殷 | Method for treating tail gas and waste water from rare earth finished ore acid method burning process |
| CN2883396Y (en) * | 2006-02-21 | 2007-03-28 | 王鸿儒 | Novel environment protective roasting furnace for sulfuric acid resolving rare-earth ore |
| CN201952466U (en) * | 2011-01-06 | 2011-08-31 | 中冶东方工程技术有限公司 | Multistage serial-connection roasting equipment |
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| CN106756128A (en) * | 2016-12-10 | 2017-05-31 | 包头稀土研究院 | A kind of method that low acid consumption mixed rare earth concentrates concentrated sulfuric acid is decomposed |
| CN108950188A (en) * | 2018-05-25 | 2018-12-07 | 包头稀土研究院 | The method of concentrated sulfuric acid low-temperature bake phosphorous rare earth ore concentrate step by step arithmetic phosphorus and rare earth |
| CN113387391A (en) * | 2021-07-30 | 2021-09-14 | 广西埃索凯新材料科技有限公司 | Manganese sulfate production system based on manganese oxide ore |
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