CN108273826B - A kind of complete mutually high-valued recoverying and utilizing method of lithium slag - Google Patents
A kind of complete mutually high-valued recoverying and utilizing method of lithium slag Download PDFInfo
- Publication number
- CN108273826B CN108273826B CN201810044953.6A CN201810044953A CN108273826B CN 108273826 B CN108273826 B CN 108273826B CN 201810044953 A CN201810044953 A CN 201810044953A CN 108273826 B CN108273826 B CN 108273826B
- Authority
- CN
- China
- Prior art keywords
- lithium
- slag
- lithium slag
- treatment process
- pyrophillite
- 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.)
- Active
Links
Classifications
-
- 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
- Y02W—CLIMATE CHANGE MITIGATION TECHNOLOGIES RELATED TO WASTEWATER TREATMENT OR WASTE MANAGEMENT
- Y02W30/00—Technologies for solid waste management
- Y02W30/50—Reuse, recycling or recovery technologies
- Y02W30/91—Use of waste materials as fillers for mortars or concrete
Abstract
The present invention provides a kind of complete mutually high-valued recoverying and utilizing methods of lithium slag, the lithium slag be to spodumene using sulfuric acid process through leaching lithium process mention lithium after gained slag, it includes the following steps: that (1) sizes mixing to the lithium slag, stirring, so that sulfate mineral is in dispersion suspended state in lithium slag；(2) reaction treatment is carried out using soluble carbonate salt in any order to step (1) gains and carries out wet magnetic separation processing；(3) gained slurry after step (2) processing is concentrated, is filtered and is dried, obtain glass pyrophillite raw material.The present invention is high-efficient when handling lithium slag and no three wastes generates, and realizes the leap of the high-valued recycling of lithium slag, has significant economic benefit and environmental benefit.
Description
Technical field
The invention belongs to the environmentally protective recycling fields of Industrial Solid Waste, are related to lithium slag for comprehensive and utilize field, and in particular to one
Complete mutually recycling and the high-valued method of product of kind lithium slag.
Background technique
Content of the lithium in the earth's crust is about 0.0065%, mainly with salt lake bittern, spodumene, lepidolite, petalite and
Phosphorus aluminium ore exist, be mainly distributed on Bolivia, Chile, China, Argentina, the U.S., Australia, Russia, Canada and
The states such as Serbia.
Tellurian spodumene mine is distributed mainly on Australia, Canada, Zimbabwe, the Congo, Brazil and China；Lithium
Mica Mine is distributed mainly on Zimbabwe, Canada, the U.S., Mexico and China.In China, spodumene is concentrated mainly on four
The ground such as river, Xinjiang, Henan, lepidolite are concentrated mainly on Jiangxi Province and Hunan Province.
Lithium slag, be after carrying out mentioning lithium to rich lithium resource caused by waste residue general designation.Currently, China is mainly from lithium ore
In mention lithium.China mentions lithium mainly using sodium chloride autoclaving method from lepidolite, mentions lithium from spodumene and mainly uses sulfuric acid
Method.Therefore, the lithium slag in China is predominantly by mentioning lithium by-product slag caused by above two method.
In recent years, the lithium battery industry development in China is rapid, wherein the nationalization process of critical material is also constantly accelerated,
So that the demand of related lithium product is constantly promoted.Meanwhile consequent be corresponding lithium slag output it is increasing, lithium slag band
The problem of environmental pollution come constantly shows.The best way for solving the problems, such as this is to carry out resource utilization processing to lithium slag it is made
Its available industrial products.In this respect, the prior art has carried out some trials.
102126838 A of Chinese patent CN discloses a kind of side that light building material ceramic is prepared using lepidolite extracted lithium slag
Method carries out high temperature sintering by being added after clay powder and pore creating material, can obtain light building material ceramic, product quality reaches
To the quality requirement of common light-weight aggregate high-class product as defined in GB/T 17431.2-1998.Although this method realizes lepidolite and mentions
The recycling of lithium slag, but processing added value brought by it is extremely limited, with other light building material ceramics that are used to prepare
Raw material is compared, and does not generate the effect that significant cost reduces and added value is promoted.Likewise, Chinese patent CN
There is also similar problems by 103979809 A.
《Influence of lithium slag from lepidolite on the durability of
Concrete " (doi:10.1088/1755-1315/61/1/012151) for lepidolite extracted lithium slag as cement additive
It is studied, it is found that it is able to ascend the quality of cement.
《Nanoindentation Characteristics of Cementitious Materials Containing
Lithium Slag》(DOI:10.1166/nnl.2017.2276)、《Utilization of Lithium Slag as An
Admixture in Blended Cements:Physico-mechanical and Hydration
Characteristics》(DOI:10.1007/11595-015-1113-x)、《Mechanical Properties of
Concretes Containing Super-fine Mineral Admixtures》(DOI:10.4028/
) and " Study on Preparing Aero-Concrete Using www.scientific.net/AMM.174-177.1406
Leaching Residual Slag of Lepidolite ore》(DOI:10.4028/www.scientific.net/
AMM.99-100.375) different research also has been carried out to using lithium slag as cement additive aspect.
103922626 A of Chinese patent CN provides the recoverying and utilizing method that a kind of pair of salt lake mentions lithium by-product lithium slag, is used for
Prepare concrete alkali aggregate reaction inhibitor.Concrete has been prepared by reducing the harmful components sodium chloride in lithium slag in it
The inhibitor of alkali.Likewise, this method only realizes the recycling of discarded lithium slag to a certain extent, but
Its added value does not bring biggish promotion.
Above-mentioned technology and other similar problems of the existing technology are: these technologies are only able to achieve the low value of lithium slag
Change, the recovery processing of single application.Since the production industries such as concrete material, cement, building material ceramic have been matures
Industry does not have advantage for lithium slag as the raw material for producing these products, solves at the recycling of lithium slag to can not realize very well
The problem of reason.
It solves lithium slag and recycles to be worth there are mainly two types of low methods, one is the method for comprehensive utilization of research lithium slag,
So that lithium slag is after treatment, various pieces are effectively utilized；Another kind is so that lithium slag becomes after treatment has
Emulative high-value product.
103789553 A of Chinese patent CN provides a kind of lepidolite ore phase reconstruction and proposes the method that lithium slag for comprehensive utilizes, and leads to
Countercurrent flotation is carried out again after crossing acid adding plus base extraction, can obtain calcium chloride, rich aluminium slag, aluminosilicate and fluorite concentrate.It should
Although technology can obtain multiple product, for other acquisition modes of its product, do not have equally obvious excellent
Gesture.Meanwhile the technology needs to use a large amount of acid-base solution, and is difficult to realize the recycling of acid-base solution, be easy to cause dirt
Dye problem, so that recycling lithium slag cannot be realized to avoid the original idea of pollution.
103601230 A of Chinese patent CN provides a kind of method that lithium slag for comprehensive utilizes production industrial chemicals, this method
Discharge gas is absorbed using ammonium hydroxide, reduces exhaust emission, while liquid reduces the pollution of waste water without direct emission.
The patent obtains calcium chloride, ammonium fluoride, white carbon black, aluminium salt and ammonium sulfate by multiple steps.With 103789553 A phase of CN
Than, the patent in terms of reducing water, gas and slag discharge, certain progress is achieved, but its products obtained therefrom and other common systems
In comparison Preparation Method, does not have clear superiority equally.In addition, the patent is same unavoidable using a large amount of acid solution, together
Sample is also difficult to realize the recycling of acid solution, and safety and blowdown the control aspect of operation face problem, keeps it same difficult
To promote and apply.
The targeted lithium slag of above-mentioned patent is to carry out mentioning lithium to lepidolite or salt lake mentions the resulting by-product slag of lithium.
Currently, China for how to handle mentioned from spodumene lithium slag caused by lithium further investigation it is less.Due to
When refining lithium carbonate from spodumene using sulfuric acid process, about it is discharged therefore how 8~10 tons of lithium slags are handled when producing 1 ton of lithium salts
This kind of lithium slag becomes urgent problem to be solved.But, people fail to the research of this respect also still in the more preliminary stage
Realize that the high-valued and green high-efficient of lithium slag utilizes processing.
" source of lithium slag and the impervious Exploration of Mechanism of the enhancing of lithium dreg concrete " (Sichuan non-ferrous metal 04 phase in 2000) mentions
It has supplied using lithium slag as the technology of the reinforcing agent of concrete and the additive of cement.But, due to the supply side structure in China
Property reform have the requirement of " three go a drop one to mend " for cement industry so that the lithium slag is as cement additive using will
It is limited.In addition, using lithium slag as the method for cement additive, it is also very limited for the value promotion of lithium slag.
Chinese patent CN1112335C provides a kind of utilize to spodumene using caused by acid system production lithium carbonate
Waste residue prepares the technology of gypsum reinforcing agent.106082739 A of Chinese patent CN provides a kind of utilize to spodumene using acid system
Technology of the drying products therefrom as cement admixture is carried out after mixing with waste residue caused by alkaline process production lithium carbonate.China
1090597 C of patent CN discloses the method using acid lithium slag manufacture glaze for glazed tile.But, these technologies are for lithium slag
Economic value promoted limitation.
101624191 B of Chinese patent CN provides the method for preparing 13X molecular sieve as raw material using lithium slag, this method institute
The product market price of acquisition is higher, so that the added value of the recycling working process of lithium slag is increased dramatically.But, this method
It needs to be added base reagent and carries out high temperature alkali fuse, energy consumption is higher, while also needing to carry out wastewater treatment, and industrial application is limited." lithium
Slag synthesize NaX molecular sieve structure characterization and characterization of adsorption research ", " Synthesis and characterization of
Zeolite X from lithium slag " (DOI:10.1016/j.clay.2012.02.017) and " Structural
characterization ofNaX zeolite synthesisedby solution-hydrothermal methord
From Lithium slag " it is also studied accordingly in this respect.
Therefore, the processing problem of mentioning in lithium industry in China, generated lithium slag is still not well solved.Such as
On the basis of the economic value added for where promoting the recycling processing of lithium slag, moreover it is possible to which the maximized generation for reducing pollution is that solve should
The key of problem.
Pyrophillite micro mist is the important source material for preparing glass, is by obtaining after being crushed to pyrophyllite deposit.Mesh
Before, when preparing glass, need to be added spodumene to reduce the temperature and melt viscosity when glass melting, improve glass density and
Finish improves intensity, ductility, corrosion resistance and the heat-resisting shock property of product.According to one of the world's largest glass fibre factory
Applicable cases research of the Johns Manvile company of the U.S. for spodumene, be added when producing glass spodumene have it is as follows
Advantage: reduce cost: after spodumene is added, the melt flow ability in platinum alloy smelting furnace improves 6.5%；Improve the nature of glass
Amount: 20-30% can be improved in anti-hydrolysis ability, and 30-35% can be improved in acid-proof ability；Environmental-protection function: it reduces fluorine dosage and reaches 20-
30%.However, the price continuous rise of spodumene, so that the production cost of glass is high, the sector and other is limited
The application development of relevant industries.
In conclusion being connected existing if a kind of method can be found and proposing lithium industrial system, so that using sulfuric acid process pair is used
Spodumene mentions slag obtained by lithium to produce and be used to prepare the pyrophillite micro mist of glass and solve that this valuable raw material of spodumene need to be added
Problem, it will greatly facilitate the development of lithium Slag treatment industry.Meanwhile if the technology is able to achieve no waste water and gas discharge, and
After processing, each section of lithium slag can obtain efficiently using to realize and generate without solid waste, and one action is solved lithium Slag treatment industry
In great main bugbear.
Summary of the invention
In view of the deficiencies of the prior art and technical need, the purpose of the present invention is to provide a kind of the complete mutually high-valued of lithium slag
Recoverying and utilizing method, the lithium slag be to spodumene using sulfuric acid process through leaching lithium process mention lithium after gained slag, which is characterized in that
Described method includes following steps:
(1) it sizes mixing, stirs to the lithium slag, so that sulfate mineral is in dispersion suspended state in lithium slag；
(2) B treatment process is carried out using first progress A treatment process to step (1) gains again, or first carries out B processing
The mode that process carries out A treatment process again is handled:
The A treatment process are as follows: soluble carbonate salt is added and is reacted, controlling the pH in slurry is 7~14, so that material
The sulfur content of slag phase in slurry is no more than 0.5%；
The B treatment process are as follows: under conditions of 0.5~2.0T of magnetic field strength, handled using wet-type magnetic separation method,
So that the content of the di-iron trioxide in slurry obtained by magnetic separation is no more than 0.5%；
(3) gained slurry after step (2) processing is concentrated, is filtered and is dried, obtain glass pyrophillite raw material；
The soluble carbonate salt includes Na2CO3、Li2CO3、(NH4)2CO3、NH4HCO3At least one of；
Tailings obtained by magnetic separation is used as construction material in step (2), and the construction material includes cement admixture or system
Brick raw material；
Wet magnetic separation of the resulting filtrate recycle of filtering in the leaching lithium process or the B treatment process in step (3)；
The glass pyrophillite raw material contain the whole components for being used to prepare the pyrophillite of glass and content be 0.1~
1% lithia.
Grope by long-term, the pleasantly surprised discovery of invention of the invention passes through the A treatment process and B by any order
After treatment process, so that it may easily obtain glass pyrophillite raw material of the present invention, and the tailings of magnetic separation can be made
For raw material of building materials such as the cement admixture or brick-making raw materials.
For the present invention, as long as after sulfuric acid process carries out leaching lithium process to spodumene resulting lithium slag, it is suitable
For the present invention.That is, whether for be which kind of spodumene using which kind of specific leaching resulting tailings of lithium process, all
It is to be suitable for the invention.
The technique for mentioning lithium (lithium salts such as production lithium carbonate) to spodumene for sulfuric acid process, can be with reference to " synthesis of lithium slag is returned
Receive and utilize " (" Xinjiang non-ferrous metal ", 2014, the 4th phase) and " source of lithium slag and the impervious Discussion of Mechanism of the enhancing of lithium dreg concrete
Beg for " record in (" Sichuan non-ferrous metal, 2000, the 4th phase ").It is worth noting that above-mentioned two reports are used only for pair
Lithium slag of the present invention and the understanding for leaching process, are not limitation of the present invention.
Compared with prior art, the present invention realizes the interior circulation to the waste liquid generated during lithium Slag treatment, in step
The resulting filtrate of filtering can largely be back to during the wet magnetic separation in the B treatment process in step (3), small part
It can be back to the leaching lithium process, substantially carried out the zero-emission of waste water.When entire invention process flow is out of service,
Filtrate therein can store, and be arranged after can also carrying out relevant wastewater treatment process for next lithium Slag treatment
It puts.
The present invention can make what lithium slag became glass this high value industrial product to prepare raw material, be greatly improved
The added value that lithium slag recycles.Importantly, for existing glass production pyrophillite micro mist, institute of the present invention
The lithia for being also 0.1~1.0% containing content in the glass pyrophillite raw material obtained, so that being saved when producing glass
The usage amount of expensive spodumene.It is understandable to be, since production technology of the present invention is environmentally protective and can get and is used for
Prepare the pyrophillite raw material of glass, the present invention for the recycling industry of lithium slag, undoubtedly hewed out " it is energy saving, water-saving,
The production of environmental protection, high benefit " and application approach.
For ease of description and by the present invention resulting glass pyrophillite raw material and the existing glass that is used to prepare
Pyrophillite micro mist distinguishes, and resulting glass pyrophillite raw material is referred to as " lithium matter pyrophillite " by the present invention, with more than you know
Show the wherein lithia containing 0.1~1.0%.It shall also be appreciated that the oxidation in lithium matter pyrophillite described in the present invention
Lithium does not imply that pure zirconia lithium powder, and refers to the lithia ingredient in lithium matter pyrophillite of the present invention, specifically with siliceous oxidation
The form of lithium exists.
It is important to note that core of the invention is, by technique of the invention, quality can be easily obtained
Excellent glass pyrophillite raw material, and any waste water and solid waste will not be generated.
It is noted that the full solid formation utilization during lithium Slag treatment may be implemented in the present invention.Magnetic separation in step (2)
Tailings can be used as the construction materials such as the cement admixture or brick-making raw material.In addition, the present invention is during lithium Slag treatment
The liquid phase of generation also may be implemented to be recycled.
Therefore, no waste liquid, the effect without exhaust gas and without solid waste discharge may be implemented in the present invention, truly realizes
Lithium slag high price value utilization, complete utilization and non-waste-emission purpose.
The characteristics of according to lithium process is proposed, carries out during mentioning lithium and generating by-product lithium slag, needs to press lithium slag
Filter be easy to cause sulfate mineral agglomeration cohesive mass therein.Therefore, when the sulphur in lithium slag is (with S03Meter, ingredient are mainly
Refer to calcium sulfate mineral) too high levels when, in step (1), dispersing agent, which can be added, makes sulfate mineral be easier to disperse.It is general and
Speech, when the sulfur content in lithium slag is (with S03Meter) be more than or equal to 1% when, be easy to agglomerate reunion.Agglomeration adherency of the present invention group
It is poly-, refer to that sulfate mineral is adhered in other mineral and generates agglomeration.
In the present invention, the purpose that dispersing agent is added is that the sulfate mineral of lithium slag is made to be in homogeneously dispersed state, drops
Adhering to other mineral for protosulfate mineral, causes to reunite.As long as that is, can play the role of it is this, no matter use what
Kind dispersing agent, is suitable for the invention.
Especially it should be pointed out that being added with the examination that the purpose of cohesive mass of above-mentioned reduction sulfate mineral can be achieved
On the basis of agent, the preparation for dispersing other mineral in lithium slag can also be added in those skilled in the art.Therefore, institute of the present invention
Addition is not precluded in " dispersing agent " stated, and these are used to disperse the preparation of other mineral.
In the present invention, " the dispersion suspended state " refers to that the sulfate mineral in lithium slag is in dispersion suspension
State does not imply that lithium slag generally in dispersion suspended state, is also not specific under any micro-scale sulfate mineral without group
Poly- phenomenon is carried out as long as being conducive to subsequent handling.
Under normal circumstances, the additive amount of the dispersing agent is 0.1~2Kg/t lithium slag.
Phosphate of the present invention can be calgon, hexa metaphosphoric acid lithium etc., the copolymerization of organic acid binary low molecule
Object can be tripolyphosphate, tannin, lignosulphonates etc., organic acid ternary low molecule copolymer can be sodium allylsulfonate,
The product of maleic anhydride, acrylic acid ternary free radicals copolymerization reaction.
The purpose of step (2) of the invention is so that the sulfur content of slag phase is not higher than 0.5%, Fe2O3Content, which is down to, not to be surpassed
Cross 0.5%.It realizes that principle based on this effect is: in A treatment process, will mainly generate following reaction: CaSO4+
CO3 2-=CaCO3+SO4 2-, which can convert the very low indissoluble of solubility coefficient for the slightly soluble compound calcium sulfate of lithium slag
Compound calcium carbonate, to realize the purpose of lithium slag desulfurization.The present invention passes through the spy largely tested to lithium slag of the present invention
Point is found after being groped, this reaction can be made to obtain to lithium slag of the present invention addition soluble carbonate salt relatively good
It carries out, in conventional reaction condition and can reach good effect in the reaction time, so that the sulphur of the slag phase in slurry contains
Amount is no more than 0.5%.In B treatment process, wet magnetic separation processing realizes ferrotitanium mineral etc magnetic material by the magnetic field mode of magnetization
The poly- flocculation of matter group, is separated high-melting-point mineral with target minreal using the difference of magnetic mineral, realizes the dyeing mine such as removal ferrotitanium
It is miscellaneous that object achievees the purpose that upgrading is dropped.
Preferably, the soluble carbonate salt is Na2CO3、Li2CO3At least one of.
Preferably, in the A treatment process of step (2), the molar ratio of carbonate and the sulphur in lithium slag is 1.00~1.50.
Preferably, in the A treatment process of step (2), when carrying out the reaction, the reaction time is 5~120min, reaction temperature
Degree is 5~95 DEG C；And/or the liquid-solid ratio of slurry is 1.5~5.0.
When carrying out the magnetic separation, a magnetic separation is at least carried out, it is preferred to use one slightly sweeps technique；When magnetic separation, magnetic field strength
Preferably 1.2-2.0T.
When the magnetic separation process slightly swept using one, ferric oxide content can be made to be down to 0.4%, titanium dioxide is not
More than 0.15%.When magnetic field strength is 1.2~2.0T, effect is best.
Under normal circumstances, the sulfur content in lithium slag is (with SO3Meter) it is not higher than 12%.The present invention only refers to that the present invention is suitable
In the processing of resulting lithium slag under normal circumstances, but this does not imply that the present invention is unsuitable for sulfur content (with SO3Meter) it is higher than
12% lithium slag is handled.When the sulfur content in lithium slag is (with SO3Meter) be not higher than 3% when, the present invention is easier to carry out.
Such as not special explanation is that water is added to lithium slag to size mixing when carrying out of the present invention size mixing.The present invention
There is no limit for pH value and mineral content for water used.Preferably, when sizing mixing described in progress, percentage meter by weight, mine
Starching concentration is 10~65%, it is contemplated that the factor of water flow dynamic balancing and water circulation, preferred pulp density are 30~60%.In benefit
When with Production By Sulfuric Acid Process lithium carbonate, technique liquid amount balance is the critical issue for solving the lithium rate of recovery, can be by mine in actual work
Slurry concentration be adjusted to soak lithium process in liquid-solid ratio it is consistent, to guarantee the closed circulation of water balance and ADSORPTION STATE lithium, so that this hair
It is bright lithium operation be mentioned with spodumene for the treatment process of lithium slag to realize optimal be connected.
Optionally, in step (3), when carrying out the drying, using expansion drying method or fluidized bed drying, drying temperature
It is 100~190 DEG C.
To those skilled in the art, above-mentioned dry it can be appreciated that common drying mode may be adapted to the present invention
Dry mode is only optional two ways.
Under normal circumstances, the sulfate concentration in rate-determining steps (3) in the resulting filtrate of filtering is no more than 50g/L.Work as filter
When sulfate concentration in liquid is more than 50g/L, water can be added thereto, it, can also be right in order to be back to the leaching lithium process
It carries out crystallization treatment, obtains crystalline sulfuric acid salt.
Beneficial effects of the present invention:
1, the present invention realizes the processing of the higher value application to lithium slag, solids product complete utilization, solves lithium Slag treatment
Present in great difficult problem；
2, the present invention can obtain the pyrophillite raw material for being used to prepare glass-lithium matter pyrophillite with high value, first
Degree realizes the leap by lithium slag to the preparation high value raw material of industry；Glass is prepared compared to using existing pyrophillite micro mist and spodumene
For fibre, lithium matter pyrophillite of the present invention has the speciality of pyrophillite micro mist and spodumene concurrently, significantly reduces being produced into for glass
This；
3, the present invention realizes the full solid product utilization during lithium Slag treatment, on the basis for producing lithium matter pyrophillite
On, other solid products can directly carry out industrial utilization, further improve the economic value of lithium slag recovery processing；
4, the zero-emission of pollution exhaust gas and solid waste, the basic zero-emission for realizing waste liquid may be implemented in the present invention, has good
Good social benefit and environmental benefit；
5, the present invention can also propose the realization of lithium technique with sulfuric acid process and be connected, while promoting glass-fiber industry development, greatly
Alleviate the problem that spodumene proposes lithium industry environmental protection production.Substantially, the present invention is to be realized for the first time to glass production industry, mentioned
The organic combination of lithium industry and lithium slag fixed-end forces industry has high application prospect.
Detailed description of the invention
Fig. 1 is process flow diagram of the present invention to lithium slag；In figure, described is not limited to pure water or industry life " with water "
Fisheries water, according to the understanding of the present invention comprising the feed liquid and additional water that the present invention generates.
Specific embodiment
The present invention is specifically described below by embodiment, it is necessary to which indicated herein is that following embodiment is only used
It is further detailed in the present invention, should not be understood as limiting the scope of the invention, which is skilled in technique
Some nonessential modifications and adaptations that personnel are made according to foregoing invention content, still fall within protection scope of the present invention.
The present invention is using the tailings product that lithium slag is that certain domestic Ti Li enterprise spodumene sulfuric acid process soaks lithium process.
In following embodiments, " SO3" refer to SO3The sulfur content of meter.
Embodiment 1
Lithium slag caused by lithium carbonate is prepared using sulfuric acid process for spodumene for Sichuan spodumene Ti Li enterprise
(Li2O 0.3%, SO36.58%, Fe2O31.8%, SiO262%, Al2O321%), water is added to size mixing, pulp density 40%, and add
Enter 1000 g tons of lithium slags of dispersing agent sodium metasilicate；Sodium carbonate (87.5kg/t lithium slag) is added to ore pulp and carries out desulphurization reaction, controls pH
9.2, room temperature of sizing mixing leaches 100min；Desulfurization slurry enters Wet-type strong magnetic separator, and high intensity magnetic separation slightly sweeps technique using one, slightly
Selected control magnetic field strength is 1.2T, and scanning control magnetic field strength is 1.5T, obtains magnetic separation slurry and magnetic separation tailings；Magnetic separation is then right
Gained magnetic separation slurry is concentrated, is filtered and is dried, and glass lithium matter pyrophillite product is obtained.It filters resulting filtrate and passes through water
Balanced flow regulates and controls the filtrate recycle of 15% (v/v) in desulphurization reaction；Regulate and control the filtrate of 15% (v/v) and is returned with substituting industrial water
For propose the leaching lithium process in lithium to spodumene using sulfuric acid process, the leaching rate 99.3% of acquisition reaches spodumene sulfuric acid
The production target of method leaching lithium.Regulate and control the filtrate recycle of 70% (v/v) in wet magnetic separation；The filtrate equivalent of regulation and 15% (v/v)
New water for product wash, realize system plumbing balanced recycle.Specific product parameter is shown in Table 1.
Table 1
Note: the market price of cement blending agent obtained by the present embodiment is about 50 yuan/ton.
" a " in table is referred in " building material mineral products " (Wang Suli writes, Chemical Industry Press, 2014.P253.)
The quality standard of " glass raw material " project in " quality requirement of the table 5-11 every profession and trade to pyrophillite ".Lithium matter obtained by the present embodiment
Pyrophillite, other than containing lithia, remaining ingredient reaches quality standard requirement.
The production cost of the resulting lithium matter pyrophillite of the present invention is 310 yuan/ton, and prepare the pyrophillite micro mist of glass
Market price is 620 yuan/ton.When preparing glass using lithium matter pyrophillite, using glass of the present invention with pyrophillite raw material without adding
Enter spodumene, can significantly reduce the preparation cost of glass.Since gained glass pyrophillite raw material (lithium matter pyrophillite) contains
Lithium prepares glass pyrophillite micro mist better than commercially available, and the potential market estimated is worth at least at 1000 yuan/ton, realizes lithium
The higher value application that slag recycles.
Embodiment 2
Lithium slag caused by lithium carbonate is prepared using sulfuric acid process for spodumene for Sichuan spodumene Ti Li enterprise
(Li2O 0.5%, SO311.05%, Fe2O30.85%, SiO255%, Al2O321%), water is added to size mixing, pulp density 50%, and
1500 g tons of lithium slags of dispersing agent sodium metasilicate are added；Ore pulp enters Wet-type strong magnetic separator, and high intensity magnetic separation slightly sweeps work using one
Skill, it is 1.3T that roughing, which controls magnetic field strength, and scanning control magnetic field strength is 1.5T, obtains magnetic separation slurry and magnetic separation tailings；Xiang Ci
Ore dressing slurry is added sodium carbonate (148kg/t lithium slag) and is reacted, and controls pH 10.5, and room temperature of sizing mixing leaches 90min；Then to institute
It obtains desulfurization slurry to be concentrated, filtered and dried, obtains glass lithium matter pyrophillite product.It filters resulting filtrate and passes through level
The filtrate recycle of weighing apparatus flow control 68% (v/v) is in wet magnetic separation；The filtrate recycle for regulating and controlling 12% (v/v) is converted in hybrid reaction
Desulfurization process；The filtrate recycle of 20% (v/v) of regulation recycles after crystalline sulfuric acid salt；The filtrate of regulation and 20% (v/v)
The new water of equivalent is washed for product, realizes system plumbing balanced recycle.Specific product parameter is shown in Table 2.
Table 2
Note: the market price of cement blending agent obtained by the present embodiment is about 50 yuan/ton.
" a " in table is referred in " building material mineral products " (Wang Suli writes, Chemical Industry Press, 2014.P253.)
The quality standard of " glass raw material " project in " quality requirement of the table 5-11 every profession and trade to pyrophillite ".Lithium matter obtained by the present embodiment
Pyrophillite, other than containing lithia, remaining ingredient reaches quality standard requirement.
The production cost of the resulting lithium matter pyrophillite of the present invention is 425 yuan/ton, and prepare the pyrophillite micro mist of glass
Market price is 620 yuan/ton.When preparing glass using lithium matter pyrophillite, using glass of the present invention with pyrophillite raw material without adding
Enter spodumene, can significantly reduce the preparation cost of glass.Since gained glass pyrophillite raw material (lithium matter pyrophillite) contains
Lithium prepares glass pyrophillite micro mist better than commercially available, and the market price estimated realizes the recycling of lithium slag at least at 1000 yuan/ton
The higher value application utilized.
Embodiment 3
For lithium slag (Li caused by the spodumene Ti Li enterprise of Jiangsu2O 0.27%, SO31.92%,
Fe2O31.13%, SiO267%, Al2O323%) it, is sized mixing by mortar pump water adding and squeezes into agitator, control pulp density 30%,
And 1000 g tons of lithium slags of dispersing agent sodium metasilicate are added；Sodium carbonate (27kg/t lithium slag) is added to ore pulp and carries out desulphurization reaction, control
PH 11.2, room temperature of sizing mixing leach 60min；Desulfurization slurry enters Wet-type strong magnetic separator, and high intensity magnetic separation slightly sweeps work using one
Skill, it is 1.5T that roughing, which controls magnetic field strength, and scanning control magnetic field strength is 1.8T, obtains magnetic separation slurry and magnetic separation tailings；Magnetic separation
Then gained magnetic separation slurry is concentrated, is filtered and is dried, obtain glass lithium matter pyrophillite product.Filter resulting filtrate
Desulfurization process is converted in hybrid reaction by the filtrate recycle of water balance flow control 10% (v/v)；Regulate and control the filter of 10% (v/v)
Liquid is back to substitute industrial water and propose leaching lithium process in lithium, the leaching rate of acquisition to spodumene using sulfuric acid process
98.3%, reach the production target of spodumene sulfuric acid process leaching lithium.Regulate and control the filtrate recycle of 80% (v/v) in wet magnetic separation；Regulation
It is washed with the new water of the filtrate equivalent of 10% (v/v) for product, realizes system plumbing balanced recycle.Specific product parameter is shown in
Table 3.
Table 3
Note: the market price of cement admixture obtained by the present embodiment is about 50 yuan/ton.
" a " in table is referred in " building material mineral products " (Wang Suli writes, Chemical Industry Press, 2014.P253.)
The quality standard of " glass raw material " project in " quality requirement of the table 5-11 every profession and trade to pyrophillite ".Lithium matter obtained by the present embodiment
Pyrophillite, other than containing lithia, remaining ingredient reaches quality standard requirement.
The production cost of the resulting lithium matter pyrophillite of the present invention is 185 yuan/ton, and prepare the pyrophillite micro mist of glass
Market price is 620 yuan/ton.When preparing glass using lithium matter pyrophillite, using glass of the present invention with pyrophillite raw material without adding
Enter spodumene, can significantly reduce the preparation cost of glass.Since gained glass pyrophillite raw material (lithium matter pyrophillite) contains
Lithium prepares glass pyrophillite micro mist better than commercially available, estimates market potential value at least at 1000 yuan/ton, realizes lithium
The higher value application that slag recycles
Embodiment 4
Other than dispersing agent is calgon, remaining is consistent with embodiment 1.The product of gained glass lithium matter pyrophillite
Matter reaches quality standard described in embodiment 1, and glass is 87.58% (based on butt) with lithium matter pyrophillite yield.
Embodiment 5
In addition to activator is sodium carbonate sinker mother liquor, that is, Li2CO3And Na2CO3Mixed liquor (Li2CO37.2g/L
Na2CO3Except 250g/L), remaining is consistent with embodiment 3.The quality of gained glass lithium matter pyrophillite reaches described in embodiment 3
Quality standard, glass with lithium matter pyrophillite yield be 86.8% (based on butt).
Embodiment 6
In addition to activator is NH4CO3Except, remaining is consistent with embodiment 2.Gained glass is reached with the quality of lithium matter pyrophillite
To quality standard as described in example 2, glass is 89.78% (based on butt) with lithium matter pyrophillite.
Embodiment 7
Other than magnetic field strength is 2.0T, remaining is consistent with embodiment 3.Gained glass is reached with the quality of lithium matter pyrophillite
To quality standard as described in example 2, glass is 86.78% (based on butt) with lithium matter pyrophillite.
Claims (15)
1. a kind of complete mutually high-valued recoverying and utilizing method of lithium slag, the lithium slag is using sulfuric acid process to spodumene through soaking lithium process
Mention gained slag after lithium, which is characterized in that described method includes following steps:
(1) it sizes mixing, stirs to the lithium slag, so that sulfate mineral is in dispersion suspended state in lithium slag；
(2) B treatment process is carried out using first progress A treatment process to step (1) gains again, or first carries out B treatment process
The mode for carrying out A treatment process again is handled:
The A treatment process are as follows: soluble carbonate salt is added and is reacted, controlling the pH in slurry is 7 ~ 14, so that in slurry
Slag phase sulfur content be no more than 0.5%；
The B treatment process are as follows: under conditions of 0.5 ~ 2.0T of magnetic field strength, handled using wet-type magnetic separation method, so that
The content of di-iron trioxide in slurry obtained by magnetic separation is no more than 0.5%；
(3) gained slurry after step (2) processing is concentrated, is filtered and is dried, obtain glass pyrophillite raw material；
The soluble carbonate salt includes Na2CO3、Li2CO3, (NH4)2 CO3、NH4HCO3At least one of；
Tailings obtained by magnetic separation is used as construction material in step (2), and the construction material includes that cement admixture or brickmaking are former
Material；
Wet magnetic separation of the resulting filtrate recycle of filtering in the leaching lithium process or the B treatment process in step (3)；
The glass pyrophillite raw material contains the oxygen that the whole components for being used to prepare the pyrophillite of glass and content are 0.1 ~ 1%
Change lithium.
2. the method according to claim 1, wherein the sulfur content in the lithium slag is not higher than 12%.
3. the method according to claim 1, wherein the sulfur content in the lithium slag is not higher than 3%.
4. carrying out step the method according to claim 1, wherein sulfur content is more than or equal to 1% in the lithium slag
(1) when sizing mixing described in, appropriate dispersing agent is added；The dispersing agent includes that silicate, phosphate, organic acid binary or ternary are low
At least one of molecule copolymer.
5. according to the method described in claim 4, it is characterized in that, the additive amount of the dispersing agent is 0.1 ~ 2 kg/t lithium slag.
6. according to claim 1, method described in 4 or 5, which is characterized in that in step (1), when sizing mixing described in progress, by weight
Percentage meter, pulp density are 10~65%.
7. according to the method described in claim 6, it is characterized in that, in step (1), when sizing mixing described in progress, percentage by weight
Meter, pulp density are 30~60%.
8. the method according to claim 1, wherein the soluble carbonate salt is Na2CO3、Li2CO3In at least
It is a kind of.
9. the method according to claim 1, wherein in the A treatment process of step (2), in carbonate and lithium slag
Sulphur molar ratio be 1.00 ~ 1.50.
10. according to claim 1 or method described in 9, which is characterized in that in the A treatment process of step (2), carry out described anti-
At once, the reaction time is 5 ~ 120min, and reaction temperature is 5 ~ 95 DEG C；And/or the liquid-solid ratio of slurry is 1.5 ~ 5.0.
11. the method according to claim 1, wherein carrying out the wet type magnetic in the B treatment process of step (2)
When selecting, a magnetic separation is at least carried out.
12. according to the method for claim 11, which is characterized in that in the B treatment process of step (2), carry out the wet type
When magnetic separation, technique is slightly swept using one.
13. method according to claim 11 or 12, which is characterized in that when carrying out wet magnetic separation, magnetic field strength 1.2-
2.0T。
14. the method according to claim 1, wherein when carrying out the drying, being done using flash distillation in step (3)
Dry method or fluidized bed drying, drying temperature are 100 ~ 190 DEG C.
15. the method according to claim 1, wherein the sulfuric acid in rate-determining steps (3) in the resulting filtrate of filtering
Salinity is no more than 50g/L.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201810044953.6A CN108273826B (en) | 2018-01-17 | 2018-01-17 | A kind of complete mutually high-valued recoverying and utilizing method of lithium slag |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201810044953.6A CN108273826B (en) | 2018-01-17 | 2018-01-17 | A kind of complete mutually high-valued recoverying and utilizing method of lithium slag |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN108273826A CN108273826A (en) | 2018-07-13 |
| CN108273826B true CN108273826B (en) | 2018-12-11 |
Family
ID=62803986
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN201810044953.6A Active CN108273826B (en) | 2018-01-17 | 2018-01-17 | A kind of complete mutually high-valued recoverying and utilizing method of lithium slag |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN108273826B (en) |
Families Citing this family (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN110015855B (en) * | 2019-04-01 | 2021-03-30 | 中国地质科学院郑州矿产综合利用研究所 | Treatment method of lithium slag |
| CN111410202B (en) * | 2020-03-27 | 2023-07-21 | 中山市清融嘉创能源科技有限责任公司 | Method for preparing pyrophyllite from spodumene lithium extraction waste residues |
| CN111607254A (en) * | 2020-05-18 | 2020-09-01 | 安徽齐鑫新材料科技有限公司 | Preparation method for filling rubber and plastic by using lithium slag |
| CN114226413B (en) * | 2020-09-09 | 2023-06-16 | 天齐鑫隆科技(成都)有限公司 | Comprehensive treatment process of lithium slag |
| CN114031090B (en) * | 2021-11-18 | 2023-07-18 | 中山市清融嘉创能源科技有限责任公司 | Method for preparing beta-spodumene from brine with high magnesium-lithium ratio |
| CN113976309B (en) * | 2021-12-01 | 2022-06-07 | 天齐创锂科技(深圳)有限公司 | Method for comprehensively recovering lithium, tantalum-niobium, silicon-aluminum micro powder, iron ore concentrate and gypsum from lithium slag |
| CN114643271A (en) * | 2022-03-25 | 2022-06-21 | 珠海广隆新材料科技有限公司 | Solid waste lithium slag and treatment method and application thereof |
Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102126838A (en) * | 2010-12-09 | 2011-07-20 | 江西赣锋锂业股份有限公司 | Method for preparing light building material ceramsites by using lithium extraction slag of lithium mica |
| CN103601230A (en) * | 2013-11-01 | 2014-02-26 | 青岛星火化工技术有限公司 | Method for production of chemical raw materials by comprehensive utilization of lithium slag |
| CN103789553A (en) * | 2013-11-28 | 2014-05-14 | 中南大学 | Method for comprehensively utilizing lepidolite mineralogical reconstruction lithium-extraction slags |
| CN103922626A (en) * | 2014-04-15 | 2014-07-16 | 中国科学院青海盐湖研究所 | Treating method for byproduct lithium residue of salt lake lithium extraction, concrete alkali-aggregate reaction inhibitor and application thereof |
-
2018
- 2018-01-17 CN CN201810044953.6A patent/CN108273826B/en active Active
Patent Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102126838A (en) * | 2010-12-09 | 2011-07-20 | 江西赣锋锂业股份有限公司 | Method for preparing light building material ceramsites by using lithium extraction slag of lithium mica |
| CN103601230A (en) * | 2013-11-01 | 2014-02-26 | 青岛星火化工技术有限公司 | Method for production of chemical raw materials by comprehensive utilization of lithium slag |
| CN103789553A (en) * | 2013-11-28 | 2014-05-14 | 中南大学 | Method for comprehensively utilizing lepidolite mineralogical reconstruction lithium-extraction slags |
| CN103922626A (en) * | 2014-04-15 | 2014-07-16 | 中国科学院青海盐湖研究所 | Treating method for byproduct lithium residue of salt lake lithium extraction, concrete alkali-aggregate reaction inhibitor and application thereof |
Also Published As
| Publication number | Publication date |
|---|---|
| CN108273826A (en) | 2018-07-13 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN108147658B (en) | A kind of high-valued method of comprehensive utilization of lithium slag | |
| CN108273826B (en) | A kind of complete mutually high-valued recoverying and utilizing method of lithium slag | |
| WO2021168995A1 (en) | Red mud-based sewage treatment agent, preparation method therefor, red mud-based ceramsite concrete, preparation method for same, and applications thereof | |
| CN105274622B (en) | The method for preparing magnesium hydroxide crystal whisker and calcium sulfate as raw material using phosphorus tailing | |
| CN100445232C (en) | Mine debris steamed brick and its production method | |
| CN104150794B (en) | A kind of preparation method of iron tailings portland cement | |
| CN105777008A (en) | Autoclaving-free prestressed high-strength tube pile concrete and tube pile manufacturing method | |
| CN105314955B (en) | A kind of filling in mine material | |
| CN108623196A (en) | A kind of lime excitation large dosage industrial residue low-carbon cement and preparation method thereof | |
| CN109987892A (en) | One kind is based on flyash-iron tailings geo-polymer fibre reinforced materials and preparation method thereof | |
| CN108658131A (en) | A kind of iron oxide red and gypsum plaster and preparation method thereof based on titanium gypsum | |
| CN108584994A (en) | A kind of method of lepidolite calcined by rotary kiln lithium carbonate | |
| CN108726926A (en) | A kind of method of red mud and bauxite grown place polymer cement mortar | |
| CN114772986A (en) | Method for improving quality of household garbage incineration fly ash and preparing geopolymer | |
| CN107555818A (en) | A kind of cement with little clinker and preparation method | |
| CN101543829B (en) | Comprehensive utilization method for recycling manganous carbonate slag | |
| CN106810094B (en) | The system and method for cement joint production sulphur is prepared using municipal waste and Industrial Solid Waste | |
| CN114212799B (en) | Fly ash pretreatment method for molecular sieve preparation | |
| CN102838299A (en) | Method for producing cement by electrolytic manganese residue and red mud | |
| CN101543830B (en) | Comprehensive utilization method for recycling manganese oxide slag | |
| CN108218269A (en) | A kind of ferronickel refuse lac gel material and its preparation process | |
| CN107902966A (en) | A kind of unburned red mud porcelain granule mixture and preparation method thereof | |
| CN113213498B (en) | Cement-based material carbonization recycling method and calcium carbonate whisker material | |
| CN106044784A (en) | Method for producing high-purity silicon dioxide by utilizing flyash | |
| CN111747665B (en) | Manufacturing process of finished cement added with Bayer process red mud |
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 | ||
| TA01 | Transfer of patent application right | ||
| TA01 | Transfer of patent application right |
Effective date of registration: 20180718 Address after: 610000 1, 193, 195, 197, three sections of Huayang Road, Huayang street, Tianfu New District, Chengdu, Sichuan Applicant after: CHENGDU LYULI ENVIRONMENTAL PROTECTION TECHNOLOGY Co.,Ltd. Address before: 610000 12, 2 Building 2, unit 2, 67 West Pier Street, Jinjiang District, Chengdu, Sichuan. Applicant before: Tax Xin |
|
| GR01 | Patent grant | ||
| GR01 | Patent grant | ||
| TR01 | Transfer of patent right | ||
| TR01 | Transfer of patent right |
Effective date of registration: 20211202 Address after: 621600 No. 16, Xiling Avenue, Yanting Economic Development Zone, Mianyang City, Sichuan Province Patentee after: Yanting Youli New Material Technology Co.,Ltd. Address before: 610000 1, 193, 195, 197, three sections of Huayang Road, Huayang street, Tianfu New District, Chengdu, Sichuan Patentee before: CHENGDU LYULI ENVIRONMENTAL PROTECTION TECHNOLOGY Co.,Ltd. |
|
| TR01 | Transfer of patent right | ||
| TR01 | Transfer of patent right |
Effective date of registration: 20230417 Address after: No.12 Wenhua Road, Jiancha street, Tianfu New District, Chengdu, Sichuan 610000 Patentee after: Tianqi Xinlong Technology (Chengdu) Co.,Ltd. Address before: 621600 No. 16, Xiling Avenue, Yanting Economic Development Zone, Mianyang City, Sichuan Province Patentee before: Yanting Youli New Material Technology Co.,Ltd. |