CN107140667B - A method of utilizing lepidolite sulphuric leachate extraction aluminum sulfate, alum, rubidium sulfate and cesium sulfate - Google Patents
A method of utilizing lepidolite sulphuric leachate extraction aluminum sulfate, alum, rubidium sulfate and cesium sulfate Download PDFInfo
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- CN107140667B CN107140667B CN201710404674.1A CN201710404674A CN107140667B CN 107140667 B CN107140667 B CN 107140667B CN 201710404674 A CN201710404674 A CN 201710404674A CN 107140667 B CN107140667 B CN 107140667B
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- sulfate
- lepidolite
- alum
- sulphuric leachate
- rubidium
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- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01F—COMPOUNDS OF THE METALS BERYLLIUM, MAGNESIUM, ALUMINIUM, CALCIUM, STRONTIUM, BARIUM, RADIUM, THORIUM, OR OF THE RARE-EARTH METALS
- C01F7/00—Compounds of aluminium
- C01F7/68—Aluminium compounds containing sulfur
- C01F7/74—Sulfates
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- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01D—COMPOUNDS OF ALKALI METALS, i.e. LITHIUM, SODIUM, POTASSIUM, RUBIDIUM, CAESIUM, OR FRANCIUM
- C01D17/00—Rubidium, caesium or francium compounds
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- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01F—COMPOUNDS OF THE METALS BERYLLIUM, MAGNESIUM, ALUMINIUM, CALCIUM, STRONTIUM, BARIUM, RADIUM, THORIUM, OR OF THE RARE-EARTH METALS
- C01F7/00—Compounds of aluminium
- C01F7/68—Aluminium compounds containing sulfur
- C01F7/74—Sulfates
- C01F7/76—Double salts, i.e. compounds containing, besides aluminium and sulfate ions, only other cations, e.g. alums
- C01F7/762—Ammonium or alkali metal aluminium sulfates
Abstract
The present invention provides a kind of aluminum sulfate is extracted using lepidolite sulphuric leachate, alum, the method of rubidium sulfate and cesium sulfate, this method includes the ball milling activation of lepidolite, sulfuric acid solid phase thermal reaction, dilute sulfuric acid hot dipping carries, the step of preparation of continuous crystallisation and rubidium sulfate and cesium sulfate, aluminum sulfate is obtained successively, alum, rubidium sulfate and cesium sulfate, aluminum sulfate can be not only prepared in the preparation method simultaneously, alum, rubidium sulfate and cesium sulfate, and the aluminum sulfate and alum that can obtain extraction deacidify, washing, it is directly sold with technical grade product after drying, in addition, the preparation method step is simple, it is more to can avoid waste residue, byproduct is not easy the shortcomings of utilizing.
Description
Technical field
The present invention relates to lepidolites to extract rubidium caesium aluminium salt technical field, and in particular to a kind of to utilize lepidolite sulphuric leachate
The method for extracting aluminum sulfate, alum, rubidium sulfate and cesium sulfate.
Background technology
Lepidolite is a kind of important mineral resources, containing abundant Rare Metals Materials for example lithium, sodium, potassium, rubidium, caesium and
Aluminium etc., lepidolite are the byproducts that tantalum niobium exploitation tailing is obtained through flotation, and the chemical component of lepidolite is K { Li2-xAl1+x
[Al2xSi4-2xO10](F,OH)2(x=0~0.5)；The chemical composition change of lepidolite is larger, usually contains SiO247~60%,
Al2O322~29%, FeO8~12%, Li2O3.5~6%, F4~9%.Rich lithium end is Al-Li or Fe-Li isomorphs,
Al-Li series is restricted isomorphism, and Fe-Li series is then perfect isomorphism；Substitute K has Na (≤1.1%), Rb
(≤4.9%), Cs (≤1.9%).Jiangxi Province's Yichun lithia mica reserves are huge, are the lithium clouds for the Fia verified so far
Female mine.By produce per year 10,000 tons of battery-level lithium carbonates in terms of, the explored grade B reserves of Yichun lithia mica mine can exploit 100 years it
Long, a variety of metal values and the nonmetalloids such as Li, Na, K, Rb, Cs, Al and F, lepidolite are contained in Yichun lithia mica mine
Li in mine2O content is only second to 6~8wt.% of spodumene, K in 4~5wt.%2O content may be up to 8.5wt.%, and Rb2O
Content can reach 1.2~1.6wt.%, Cs2O content can reach 0.15~0.2wt.%, therefore lepidolite is also the rare gold of extraction
Belong to the valuable source of rubidium, caesium, there is great economic value.
The excellent photoelectric characteristic and its chemical activity of rubidium and caesium have unique purposes in each technical field, non-other
Metallic element can replace.Currently, rubidium and the caesium overwhelming majority are used for developmental research field, can be used as manufacture photoelectric tube and
The photoelectric cathode materials of photomultiplier, therefore can be widely applied to photoelectric instrument and electron ray instrument, automatically control, luminosity
, spectral measurement, film, TV, radar and facsimile telegraph technology and laser technology etc. have light wave range wide, spirit
Sensitivity is high and the features such as stabilization.In addition, rubidium and caesium can be also used for electric light source, laser technology, fluorescent material and power supply etc..
Therefore, Cong Fuhan rubidiums are researched and developed, the lepidolite extraction rubidium cesium salt of caesium is of great significance.
The method that the lithium salts such as lithium carbonate and lithium sulfate are prepared from lepidolite is disclosed by the prior art, but so far not yet
It was found that the method for extracting aluminum sulfate, alum, rubidium sulfate and cesium sulfate simultaneously from lepidolite.
Invention content
The technical problem to be solved by the present invention is to not yet find from lepidolite while extracting in the prior art aluminum sulfate,
The method of alum, rubidium sulfate and cesium sulfate, and then a kind of utilization lepidolite sulphuric leachate extraction aluminum sulfate of offer, sulfuric acid
The method of aluminium potassium, rubidium sulfate and cesium sulfate.
For this purpose, the present invention realizes that the technical solution of above-mentioned purpose is：
A method of using lepidolite sulphuric leachate extraction aluminum sulfate, alum, rubidium sulfate and cesium sulfate, including
Following steps：
(1) the ball milling activation of lepidolite
Lepidolite is subjected to ball milling and removes iron, obtains lepidolite powder, it is spare；
(2) sulfuric acid solid phase thermal reaction
The concentrated sulfuric acid solution that the lepidolite powder obtained in step (1) and mass concentration are 92~97% is mixed to get mixed
Material is closed, mixture ball is then obtained into pellet, then pellet is heated to 200~400 DEG C, and keep the temperature lower insulation reaction 5 herein
~7h, the gas generated in heating process are passed through in limewash；
(3) dilute sulfuric acid hot dipping carries
Pellet after 5~7h of insulation reaction in step (2) is crushed and mixed for 10~15% sulfuric acid solutions with mass concentration
Hot dipping being carried out at 90~98 DEG C after closing uniformly and proposing reaction, the slurries obtained in reaction are separated by solid-liquid separation rapidly to obtain the leaching of lepidolite sulfuric acid
Go out liquid, and leachate is kept the temperature at 95 DEG C；
(4) continuous crystallisation
Ultra-fine alum powder crystal is added in the lepidolite sulphuric leachate that temperature into step (3) is 95 DEG C, and will be described
Lepidolite sulphuric leachate is gradually cooled to 80 DEG C, obtains the salt-mixture of aluminium rubidium sulfate, aluminium cesium sulfate and alum；
Ultra-fine potassium sulfate powder crystal will be added in the above-mentioned lepidolite sulphuric leachate for being cooled to 80 DEG C, and continues to be cooled to 65
DEG C, obtain aluminum sulfate sylvite；
The mixing of potassium sulfate, aluminum sulfate and aluminium hydroxide will be added in the above-mentioned lepidolite sulphuric leachate for being cooled to 65 DEG C
Object, and continue to be cooled to 35 DEG C, obtain aluminum sulfate salt；
(5) preparation of rubidium sulfate and cesium sulfate
By the salt-mixture of the aluminium rubidium sulfate, aluminium cesium sulfate and the alum that are obtained in step (4), use t-BAMAP for extraction
Agent is taken, for diluent, using hydrochloric acid, sulfuric acid or carbon dioxide as back washing agent, to be adopted in sulfonated kerosene, dimethylbenzene and/or diethylbenzene
With Pyatyi cocurrent extraction, rubidium sulfate and cesium sulfate are obtained.
In step (1), lepidolite is carried out to be milled to 100~400 mesh.
In step (2), the mass ratio for the concentrated sulfuric acid solution that the lepidolite powder is 92~97% with the mass concentration
It is 1~2：1.
In step (3), the mass ratio for the sulfuric acid solution that the pellet is 10~15% with the mass concentration is 1：1~2.
In step (4), potassium sulfate, aluminum sulfate and hydroxide in the mixture of the potassium sulfate, aluminum sulfate and aluminium hydroxide
The molar ratio of aluminium is 1~2：10：10.
In step (4), lepidolite sulphuric leachate and the mass ratio of ultra-fine alum powder crystal that the temperature is 95 DEG C are
10000~20000：1.
In step (4), lepidolite sulphuric leachate and the mass ratio of ultra-fine potassium sulfate powder crystal that the temperature is 80 DEG C are
10000~20000：1.
In step (4), lepidolite sulphuric leachate and potassium sulfate, aluminum sulfate and aluminium hydroxide that the temperature is 65 DEG C
The mass ratio of mixture is 100~200：1.
In step (2), the mass concentration of concentrated sulfuric acid solution is 95%.
In step (2), heating temperature is 300 DEG C, and keeps the temperature lower insulation reaction 7h herein.
Compared with prior art, above-mentioned technical proposal of the invention has the following advantages that：
1, of the present invention to utilize lepidolite sulphuric leachate extraction aluminum sulfate, alum, rubidium sulfate and cesium sulfate
Method, first lepidolite ball milling is activated, lepidolite powder and the concentrated sulfuric acid solution after ball milling are then mixed to get mixture,
Mixture ball is then obtained into pellet, and pellet is heated, the gas generated in heating process is passed through in limewash；It will heating
Rear pellet crushes and is that 10~15% sulfuric acid solutions carry out hot dipping and carry react after mixing with mass concentration, will must in reaction
To slurries be separated by solid-liquid separation to obtain lepidolite sulphuric leachate rapidly, and leachate is kept the temperature at 95 DEG C；It is 95 through temperature
DEG C lepidolite sulphuric leachate in ultra-fine alum powder crystal is added, and the lepidolite sulphuric leachate is gradually cooled to 80
DEG C, obtain the salt-mixture of aluminium rubidium sulfate, aluminium cesium sulfate and alum；It will be cooled in 80 DEG C of lepidolite sulphuric leachate and add
It is brilliant to enter ultra-fine kalium slfuricum powder, and continues to be cooled to 65 DEG C, obtains aluminum sulfate sylvite；65 DEG C of lepidolite sulfuric acid leaching will be cooled to
The mixture of potassium sulfate, aluminum sulfate and aluminium hydroxide is added in liquid, and continues to be cooled to 35 DEG C, obtains aluminum sulfate salt, thus originally
Invention the method can simultaneously be extracted with lepidolite sulphuric leachate and obtain aluminum sulfate, alum, rubidium sulfate and cesium sulfate,
And the salt-mixture fractional extraction of obtained aluminium rubidium sulfate, aluminium cesium sulfate and alum can be detached and rubidium cesium salt is prepared；
Aluminum sulfate and alum that extraction obtains are deacidified, washed, can be sold with technical grade product after drying.In addition, of the invention
The method using lepidolite sulphuric leachate extraction aluminum sulfate, alum, rubidium sulfate and cesium sulfate can avoid waste residue
The shortcomings of more, byproduct is not easy to utilize.
Description of the drawings
It, below will be to specific in order to illustrate more clearly of the specific embodiment of the invention or technical solution in the prior art
Embodiment or attached drawing needed to be used in the description of the prior art are briefly described, it should be apparent that, in being described below
Attached drawing is some embodiments of the present invention, for those of ordinary skill in the art, before not making the creative labor
It puts, other drawings may also be obtained based on these drawings.
Fig. 1 is the work for the method that aluminum sulfate, alum, rubidium sulfate and cesium sulfate are extracted using lepidolite sulphuric leachate
Skill flow chart.
Specific implementation mode
Technical scheme of the present invention will be clearly and completely described below, it is clear that described embodiment is this hair
Bright a part of the embodiment, instead of all the embodiments.Based on the embodiments of the present invention, those of ordinary skill in the art are not having
There is the every other embodiment obtained under the premise of making creative work, shall fall within the protection scope of the present invention.In addition, below
Involved technical characteristic as long as they do not conflict with each other can be mutual in described different embodiments of the present invention
In conjunction with.
Embodiment 1
As shown in Figure 1, provided in this embodiment utilize lepidolite sulphuric leachate extraction aluminum sulfate, alum, sulfuric acid
The method of rubidium and cesium sulfate, includes the following steps：
(1) the ball milling activation of lepidolite
Lepidolite is carried out to be milled to 200 mesh, is used in combination magnetic separator de-ironing to remove iron therein, obtains lepidolite powder, it is spare；
(2) sulfuric acid solid phase thermal reaction
The lepidolite powder obtained in step (1) is mixed to get with the concentrated sulfuric acid solution that mass concentration is 95% and is mixed
Mixture ball is then obtained pellet, then pellet is heated to 300 DEG C by material, and keeps the temperature lower insulation reaction 6h herein, heated
The gas generated in journey is passed through in limewash；
Wherein, the mass ratio for the concentrated sulfuric acid solution that lepidolite powder is 95% with mass concentration is 1.2：1；
(3) dilute sulfuric acid hot dipping carries
By after insulation reaction 6h in step (2) pellet crush and with mass concentration be 13% sulfuric acid solution after mixing
Hot dipping is carried out at 95 DEG C and proposes reaction, the slurries obtained in reaction is separated by solid-liquid separation rapidly to obtain lepidolite sulphuric leachate, and will leaching
Go out liquid to be kept the temperature at 95 DEG C；
Wherein, the mass ratio for the sulfuric acid solution that pellet is 13% with mass concentration is 1：1.5；
(4) continuous crystallisation
Ultra-fine alum powder crystal is added in the lepidolite sulphuric leachate that temperature into step (3) is 95 DEG C, and will be described
Lepidolite sulphuric leachate is gradually cooled to 80 DEG C, and salt is precipitated, and is detected through Atomic absorption detection method, and the salt of precipitation is aluminum sulfate
The salt-mixture of rubidium, aluminium cesium sulfate and alum, and through complexometry it is found that the content of aluminium rubidium sulfate is in salt-mixture
60%, the content of aluminium cesium sulfate is 30%, the matter for the lepidolite sulphuric leachate and ultra-fine alum powder crystal that the temperature is 95 DEG C
Amount is than being 15000：1；
Ultra-fine potassium sulfate powder crystal will be added in the above-mentioned lepidolite sulphuric leachate for being cooled to 80 DEG C, and continues to be cooled to 65
DEG C, salt is precipitated again, is detected through Atomic absorption detection method, the salt of precipitation is aluminum sulfate sylvite, and through complexometry it is found that sulphur
The content of sour aluminium potassium is 95%, and the mass ratio of the lepidolite sulphuric leachate that the temperature is 80 DEG C and ultra-fine potassium sulfate powder crystal is
15000：1；
The mixing of potassium sulfate, aluminum sulfate and aluminium hydroxide will be added in the above-mentioned lepidolite sulphuric leachate for being cooled to 65 DEG C
Object, and continue to be cooled to 35 DEG C, salt is precipitated again, is detected through Atomic absorption detection method, the salt of precipitation is aluminum sulfate salt, and through matching
Position titration is it is found that the content of aluminum sulfate salt is 90%, sulfuric acid in the mixture of the potassium sulfate, aluminum sulfate and aluminium hydroxide
The molar ratio of potassium, aluminum sulfate and aluminium hydroxide is 1.5：10：10, the lepidolite sulphuric leachate and sulfuric acid that the temperature is 65 DEG C
The mass ratio of the mixture of potassium, aluminum sulfate and aluminium hydroxide is 150：1.
(5) preparation of rubidium sulfate and cesium sulfate
By the salt-mixture of the aluminium rubidium sulfate, aluminium cesium sulfate and the alum that are obtained in step (4), use t-BAMAP for extraction
Agent is taken, for diluent, using hydrochloric acid, sulfuric acid or carbon dioxide as back washing agent, to be adopted in sulfonated kerosene, dimethylbenzene and/or diethylbenzene
With Pyatyi cocurrent extraction, rubidium sulfate and cesium sulfate are obtained.
Embodiment 2
It is provided in this embodiment to utilize lepidolite sulphuric leachate extraction aluminum sulfate, alum, rubidium sulfate and cesium sulfate
Method, include the following steps：
(1) the ball milling activation of lepidolite
Lepidolite is carried out to be milled to 100 mesh, is used in combination magnetic separator de-ironing to remove iron therein, obtains lepidolite powder, it is spare；
(2) sulfuric acid solid phase thermal reaction
The lepidolite powder obtained in step (1) is mixed to get with the concentrated sulfuric acid solution that mass concentration is 97% and is mixed
Mixture ball is then obtained pellet, then pellet is heated to 350 DEG C by material, and keeps the temperature lower insulation reaction 6h herein, heated
The gas generated in journey is passed through in limewash；
Wherein, the mass ratio for the concentrated sulfuric acid solution that lepidolite powder is 97% with mass concentration is 1.1：1；
(3) dilute sulfuric acid hot dipping carries
By after insulation reaction 7h in step (2) pellet crush and with mass concentration be 10% sulfuric acid solution after mixing
Hot dipping is carried out at 98 DEG C and proposes reaction, the slurries obtained in reaction is separated by solid-liquid separation rapidly to obtain lepidolite sulphuric leachate, and will leaching
Go out liquid to be kept the temperature at 95 DEG C；
Wherein, the mass ratio for the sulfuric acid solution that pellet is 10% with mass concentration is 1：1；
(4) continuous crystallisation
Ultra-fine alum powder crystal is added in the lepidolite sulphuric leachate that temperature into step (3) is 95 DEG C, and will be described
Lepidolite sulphuric leachate is gradually cooled to 80 DEG C, and salt is precipitated, through Atomic absorption detection method it is found that the salt being precipitated is aluminum sulfate
The salt-mixture of rubidium, aluminium cesium sulfate and alum, and through complexometry it is found that the content of aluminium rubidium sulfate is in the salt-mixture
60%, the content of aluminium cesium sulfate is 30%, the matter for the lepidolite sulphuric leachate and ultra-fine alum powder crystal that the temperature is 95 DEG C
Amount is than being 20000：1；
Ultra-fine potassium sulfate powder crystal will be added in the above-mentioned lepidolite sulphuric leachate for being cooled to 80 DEG C, and continues to be cooled to 65
DEG C, salt is precipitated again, through Atomic absorption detection method it is found that the salt being precipitated is aluminum sulfate sylvite, and through complexometry it is found that sulphur
The content of sour aluminium sylvite is 85%, the mass ratio for the lepidolite sulphuric leachate and ultra-fine potassium sulfate powder crystal that the temperature is 80 DEG C
It is 10000：1；
The mixing of potassium sulfate, aluminum sulfate and aluminium hydroxide will be added in the above-mentioned lepidolite sulphuric leachate for being cooled to 65 DEG C
Object, and continue to be cooled to 35 DEG C, salt is precipitated again, through Atomic absorption detection method it is found that the salt being precipitated is aluminum sulfate salt, and through matching
Position titration is it is found that the content of aluminum sulfate salt is 90%, sulfuric acid in the mixture of the potassium sulfate, aluminum sulfate and aluminium hydroxide
The molar ratio of potassium, aluminum sulfate and aluminium hydroxide is 1：10：10, the lepidolite sulphuric leachate and sulfuric acid that the temperature is 65 DEG C
The mass ratio of the mixture of potassium, aluminum sulfate and aluminium hydroxide is 200：1.
(5) preparation of rubidium sulfate and cesium sulfate
By the salt-mixture of the aluminium rubidium sulfate, aluminium cesium sulfate and the alum that are obtained in step (4), use t-BAMAP for extraction
Agent is taken, for diluent, using hydrochloric acid, sulfuric acid or carbon dioxide as back washing agent, to be adopted in sulfonated kerosene, dimethylbenzene and/or diethylbenzene
With Pyatyi cocurrent extraction, rubidium sulfate and cesium sulfate are obtained.
Embodiment 3
It is provided in this embodiment to utilize lepidolite sulphuric leachate extraction aluminum sulfate, alum, rubidium sulfate and cesium sulfate
Method, include the following steps：
(1) the ball milling activation of lepidolite
Lepidolite is carried out to be milled to 400 mesh, is used in combination magnetic separator de-ironing to remove iron therein, obtains lepidolite powder, it is spare；
(2) sulfuric acid solid phase thermal reaction
The lepidolite powder obtained in step (1) is mixed to get with the concentrated sulfuric acid solution that mass concentration is 92% and is mixed
Mixture ball is then obtained pellet, then pellet is heated to 400 DEG C by material, and keeps the temperature lower insulation reaction 5h herein, heated
The gas generated in journey is passed through in limewash；
Wherein, the mass ratio for the concentrated sulfuric acid solution that lepidolite powder is 92% with mass concentration is 1.05：1；
(3) dilute sulfuric acid hot dipping carries
By after insulation reaction 5h in step (2) pellet crush and with mass concentration be 15% sulfuric acid solution after mixing
Hot dipping is carried out at 90 DEG C and proposes reaction, the slurries obtained in reaction is separated by solid-liquid separation rapidly to obtain lepidolite sulphuric leachate, and will leaching
Go out liquid to be kept the temperature at 95 DEG C；
Wherein, the mass ratio for the sulfuric acid solution that pellet is 15% with mass concentration is 1：2；
(4) continuous crystallisation
Ultra-fine alum powder crystal is added in the lepidolite sulphuric leachate that temperature into step (3) is 95 DEG C, and will be described
Lepidolite sulphuric leachate is gradually cooled to 80 DEG C, and salt is precipitated, through Atomic absorption detection method it is found that be precipitated be aluminium rubidium sulfate,
The salt-mixture of aluminium cesium sulfate and alum, and through complexometry it is found that in the salt-mixture aluminium rubidium sulfate content be 60%,
The content of aluminium cesium sulfate is 30%, and the mass ratio of the lepidolite sulphuric leachate that the temperature is 95 DEG C and ultra-fine alum powder crystal is
10000：1；
Ultra-fine potassium sulfate powder crystal will be added in the above-mentioned lepidolite sulphuric leachate for being cooled to 80 DEG C, and continues to be cooled to 65
DEG C, salt is precipitated again, through Atomic absorption detection method it is found that is be precipitated is aluminum sulfate sylvite, and through complexometry it is found that sulfuric acid
The content of aluminium potassium is 95%, and the mass ratio of the lepidolite sulphuric leachate that the temperature is 80 DEG C and ultra-fine potassium sulfate powder crystal is
20000：1；
The mixing of potassium sulfate, aluminum sulfate and aluminium hydroxide will be added in the above-mentioned lepidolite sulphuric leachate for being cooled to 65 DEG C
Object, and continue to be cooled to 35 DEG C, salt is precipitated again, through Atomic absorption detection method it is found that obtaining aluminum sulfate salt, is examined through Atomic absorption
Survey method it is found that the content of gained aluminum sulfate is 90%, potassium sulfate in the mixture of the potassium sulfate, aluminum sulfate and aluminium hydroxide,
The molar ratio of aluminum sulfate and aluminium hydroxide is 2：10：10, the lepidolite sulphuric leachate and potassium sulfate, sulphur that the temperature is 65 DEG C
The mass ratio of the mixture of sour aluminium and aluminium hydroxide is 100：1.
(5) preparation of rubidium sulfate and cesium sulfate
By the salt-mixture of the aluminium rubidium sulfate, aluminium cesium sulfate and the alum that are obtained in step (4), use t-BAMAP for extraction
Agent is taken, for diluent, using hydrochloric acid, sulfuric acid or carbon dioxide as back washing agent, to be adopted in sulfonated kerosene, dimethylbenzene and/or diethylbenzene
With Pyatyi cocurrent extraction, rubidium sulfate and cesium sulfate are obtained.
Obviously, the above embodiments are merely examples for clarifying the description, and does not limit the embodiments.It is right
For those of ordinary skill in the art, can also make on the basis of the above description it is other it is various forms of variation or
It changes.There is no necessity and possibility to exhaust all the enbodiments.And it is extended from this it is obvious variation or
It changes still within the protection scope of the invention.
Claims (25)
1. a kind of method using lepidolite sulphuric leachate extraction aluminum sulfate, alum, rubidium sulfate and cesium sulfate, including such as
Lower step：
(1) the ball milling activation of lepidolite
Lepidolite is subjected to ball milling and removes iron, obtains lepidolite powder, it is spare；
(2) sulfuric acid solid phase thermal reaction
The lepidolite powder obtained in step (1) is mixed to get with the concentrated sulfuric acid solution that mass concentration is 92~97% and is mixed
Mixture ball is then obtained pellet by material, then pellet is heated to 200~400 DEG C, and keep the temperature herein lower insulation reaction 5~
7h, the gas generated in heating process are passed through in limewash；
(3) dilute sulfuric acid hot dipping carries
Pellet after 5~7h of insulation reaction in step (2) is crushed and is that 10~15% sulfuric acid solutions mix with mass concentration
Hot dipping being carried out at 90~98 DEG C after even and proposing reaction, the slurries obtained in reaction are separated by solid-liquid separation rapidly to obtain lepidolite sulfuric acid leaching
Liquid, and leachate is kept the temperature at 95 DEG C；
(4) continuous crystallisation
It is added ultra-fine alum powder crystal in the lepidolite sulphuric leachate that temperature into step (3) is 95 DEG C, and by the lithium cloud
Female sulphuric leachate is gradually cooled to 80 DEG C, obtains the salt-mixture of aluminium rubidium sulfate, aluminium cesium sulfate and alum；
Ultra-fine potassium sulfate powder crystal will be added in the above-mentioned lepidolite sulphuric leachate for being cooled to 80 DEG C, and continues to be cooled to 65 DEG C,
Obtain aluminum sulfate sylvite；
The mixture of potassium sulfate, aluminum sulfate and aluminium hydroxide will be added in the above-mentioned lepidolite sulphuric leachate for being cooled to 65 DEG C,
And continue to be cooled to 35 DEG C, obtain aluminum sulfate salt；
(5) preparation of rubidium sulfate and cesium sulfate
By the salt-mixture of the aluminium rubidium sulfate, aluminium cesium sulfate and the alum that are obtained in step (4), use t-BAMAP for extractant,
With in sulfonated kerosene, dimethylbenzene and/or diethylbenzene for diluent, using hydrochloric acid, sulfuric acid or carbon dioxide as back washing agent, using Pyatyi
Cocurrent extraction obtains rubidium sulfate and cesium sulfate.
2. according to claim 1 utilize lepidolite sulphuric leachate extraction aluminum sulfate, alum, rubidium sulfate and sulfuric acid
The method of caesium, which is characterized in that
In step (1), lepidolite is carried out to be milled to 100~400 mesh.
3. it is according to claim 1 or 2 using lepidolite sulphuric leachate extraction aluminum sulfate, alum, rubidium sulfate and
The method of cesium sulfate, which is characterized in that
In step (2), the mass ratio of the concentrated sulfuric acid solution that the lepidolite powder and the mass concentration are 92~97% is 1~
2：1.
4. according to claim 3 utilize lepidolite sulphuric leachate extraction aluminum sulfate, alum, rubidium sulfate and sulfuric acid
The method of caesium, which is characterized in that
In step (3), the mass ratio for the sulfuric acid solution that the pellet is 10~15% with the mass concentration is 1：1~2.
5. according to claim 4 utilize lepidolite sulphuric leachate extraction aluminum sulfate, alum, rubidium sulfate and sulfuric acid
The method of caesium, which is characterized in that
In step (4), potassium sulfate in the mixture of the potassium sulfate, aluminum sulfate and aluminium hydroxide, aluminum sulfate and aluminium hydroxide
Molar ratio is 1~2：10：10.
6. according to claim 5 utilize lepidolite sulphuric leachate extraction aluminum sulfate, alum, rubidium sulfate and sulfuric acid
The method of caesium, which is characterized in that
In step (4), the mass ratio of lepidolite sulphuric leachate that the temperature is 95 DEG C and ultra-fine alum powder crystal is 10000~
20000：1.
7. according to claim 6 utilize lepidolite sulphuric leachate extraction aluminum sulfate, alum, rubidium sulfate and sulfuric acid
The method of caesium, which is characterized in that
In step (4), lepidolite sulphuric leachate and the mass ratio of ultra-fine potassium sulfate powder crystal that the temperature is 80 DEG C are 10000
~20000：1.
8. according to claim 7 utilize lepidolite sulphuric leachate extraction aluminum sulfate, alum, rubidium sulfate and sulfuric acid
The method of caesium, which is characterized in that
In step (4), the mixing of lepidolite sulphuric leachate and potassium sulfate, aluminum sulfate and aluminium hydroxide that the temperature is 65 DEG C
The mass ratio of object is 100~200：1.
9. according to claim 1 utilize lepidolite sulphuric leachate extraction aluminum sulfate, alum, rubidium sulfate and sulfuric acid
The method of caesium, which is characterized in that
In step (2), the mass concentration of concentrated sulfuric acid solution is 95%.
10. according to claim 1 utilize lepidolite sulphuric leachate extraction aluminum sulfate, alum, rubidium sulfate and sulphur
The method of sour caesium, which is characterized in that
In step (2), heating temperature is 300 DEG C, and keeps the temperature lower insulation reaction 7h herein.
11. it is according to claim 1 or 2 using lepidolite sulphuric leachate extraction aluminum sulfate, alum, rubidium sulfate and
The method of cesium sulfate, which is characterized in that
In step (3), the mass ratio for the sulfuric acid solution that the pellet is 10~15% with the mass concentration is 1：1~2.
12. it is according to claim 1 or 2 using lepidolite sulphuric leachate extraction aluminum sulfate, alum, rubidium sulfate and
The method of cesium sulfate, which is characterized in that
In step (4), potassium sulfate in the mixture of the potassium sulfate, aluminum sulfate and aluminium hydroxide, aluminum sulfate and aluminium hydroxide
Molar ratio is 1~2：10：10.
13. according to claim 3 utilize lepidolite sulphuric leachate extraction aluminum sulfate, alum, rubidium sulfate and sulphur
The method of sour caesium, which is characterized in that
In step (4), potassium sulfate in the mixture of the potassium sulfate, aluminum sulfate and aluminium hydroxide, aluminum sulfate and aluminium hydroxide
Molar ratio is 1~2：10：10.
14. it is according to claim 1 or 2 using lepidolite sulphuric leachate extraction aluminum sulfate, alum, rubidium sulfate and
The method of cesium sulfate, which is characterized in that
In step (4), the mass ratio of lepidolite sulphuric leachate that the temperature is 95 DEG C and ultra-fine alum powder crystal is 10000~
20000：1.
15. according to claim 3 utilize lepidolite sulphuric leachate extraction aluminum sulfate, alum, rubidium sulfate and sulphur
The method of sour caesium, which is characterized in that
In step (4), the mass ratio of lepidolite sulphuric leachate that the temperature is 95 DEG C and ultra-fine alum powder crystal is 10000~
20000：1.
16. according to claim 4 utilize lepidolite sulphuric leachate extraction aluminum sulfate, alum, rubidium sulfate and sulphur
The method of sour caesium, which is characterized in that
In step (4), the mass ratio of lepidolite sulphuric leachate that the temperature is 95 DEG C and ultra-fine alum powder crystal is 10000~
20000：1.
17. it is according to claim 1 or 2 using lepidolite sulphuric leachate extraction aluminum sulfate, alum, rubidium sulfate and
The method of cesium sulfate, which is characterized in that
In step (4), lepidolite sulphuric leachate and the mass ratio of ultra-fine potassium sulfate powder crystal that the temperature is 80 DEG C are 10000
~20000：1.
18. according to claim 3 utilize lepidolite sulphuric leachate extraction aluminum sulfate, alum, rubidium sulfate and sulphur
The method of sour caesium, which is characterized in that
In step (4), lepidolite sulphuric leachate and the mass ratio of ultra-fine potassium sulfate powder crystal that the temperature is 80 DEG C are 10000
~20000：1.
19. according to claim 4 utilize lepidolite sulphuric leachate extraction aluminum sulfate, alum, rubidium sulfate and sulphur
The method of sour caesium, which is characterized in that
In step (4), lepidolite sulphuric leachate and the mass ratio of ultra-fine potassium sulfate powder crystal that the temperature is 80 DEG C are 10000
~20000：1.
20. according to claim 5 utilize lepidolite sulphuric leachate extraction aluminum sulfate, alum, rubidium sulfate and sulphur
The method of sour caesium, which is characterized in that
In step (4), lepidolite sulphuric leachate and the mass ratio of ultra-fine potassium sulfate powder crystal that the temperature is 80 DEG C are 10000
~20000：1.
21. it is according to claim 1 or 2 using lepidolite sulphuric leachate extraction aluminum sulfate, alum, rubidium sulfate and
The method of cesium sulfate, which is characterized in that
In step (4), the mixing of lepidolite sulphuric leachate and potassium sulfate, aluminum sulfate and aluminium hydroxide that the temperature is 65 DEG C
The mass ratio of object is 100~200：1.
22. according to claim 3 utilize lepidolite sulphuric leachate extraction aluminum sulfate, alum, rubidium sulfate and sulphur
The method of sour caesium, which is characterized in that
In step (4), the mixing of lepidolite sulphuric leachate and potassium sulfate, aluminum sulfate and aluminium hydroxide that the temperature is 65 DEG C
The mass ratio of object is 100~200：1.
23. according to claim 4 utilize lepidolite sulphuric leachate extraction aluminum sulfate, alum, rubidium sulfate and sulphur
The method of sour caesium, which is characterized in that
In step (4), the mixing of lepidolite sulphuric leachate and potassium sulfate, aluminum sulfate and aluminium hydroxide that the temperature is 65 DEG C
The mass ratio of object is 100~200：1.
24. according to claim 5 utilize lepidolite sulphuric leachate extraction aluminum sulfate, alum, rubidium sulfate and sulphur
The method of sour caesium, which is characterized in that
In step (4), the mixing of lepidolite sulphuric leachate and potassium sulfate, aluminum sulfate and aluminium hydroxide that the temperature is 65 DEG C
The mass ratio of object is 100~200：1.
25. according to claim 6 utilize lepidolite sulphuric leachate extraction aluminum sulfate, alum, rubidium sulfate and sulphur
The method of sour caesium, which is characterized in that
In step (4), the mixing of lepidolite sulphuric leachate and potassium sulfate, aluminum sulfate and aluminium hydroxide that the temperature is 65 DEG C
The mass ratio of object is 100~200：1.
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| CN111996392B (en) * | 2020-07-22 | 2022-07-15 | 中国地质科学院郑州矿产综合利用研究所 | Method for extracting cesium and rubidium from lepidolite |
| CN112645363A (en) * | 2020-12-31 | 2021-04-13 | 江西南氏锂电新材料有限公司 | Method for preparing battery-grade lithium carbonate by taking lepidolite as raw material |
| CN112624161B (en) * | 2020-12-31 | 2022-11-01 | 江西南氏锂电新材料有限公司 | Method for preparing lithium carbonate by extracting lithium from mechanically activated lepidolite |
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