CN109437264A - A method of aluminium oxide is prepared from mentioning in lithium waste residue - Google Patents
A method of aluminium oxide is prepared from mentioning in lithium waste residue Download PDFInfo
- Publication number
- CN109437264A CN109437264A CN201811485391.5A CN201811485391A CN109437264A CN 109437264 A CN109437264 A CN 109437264A CN 201811485391 A CN201811485391 A CN 201811485391A CN 109437264 A CN109437264 A CN 109437264A
- Authority
- CN
- China
- Prior art keywords
- lithium
- aluminium oxide
- waste residue
- proposing
- preparing
- 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.)
- Pending
Links
Classifications
-
- 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
- C01F7/02—Aluminium oxide; Aluminium hydroxide; Aluminates
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
- C01P2006/00—Physical properties of inorganic compounds
- C01P2006/80—Compositional purity
Abstract
The invention discloses a kind of from proposing the method for preparing aluminium oxide in lithium waste residue, specifically the lithium ore after smashing and grinding is immersed in hydrochloric acid, stirring is warming up to 80 ~ 100 DEG C of acidleach 4 ~ 8 hours, heat filtering after hydrogen chloride is distilled off, filtrate is cooled to room temperature, the aluminium hydroxide filter residue being obtained by filtration after the alkaline maturing agent adjusting pH value of addition to 6 ~ 7, still aging 1 ~ 3 hour, filter residue is washed, 100 ~ 110 DEG C drying, 1000 ~ 1200 DEG C high-temperature calcination 1 ~ 1.5 hour, pulverization process obtains α-Al2O3Powder.This method process flow is simple to operation, while the resources circulation for realizing waste residue recycles, energy conservation and environmental protection；Aluminium oxide purity is greater than 98.5%, can be satisfied with and prepare metallic aluminium, manufactures the application requirement or the further production after purification for integrated circuit board base etc. of various refractory materials.
Description
Technical field
The invention belongs to the separation and purification fields of inorganic material, and in particular to a kind of to prepare aluminium oxide from mentioning in lithium waste residue
Method.
Background technique
In recent years, with the extensive use of lithium ion battery and the rise of power vehicle industry and development, as synthesis lithium
The demand of the lithium carbonate of ion battery positive electrode increases year by year.Lithium carbonate is mainly by mentioning lithium leachate or salt lake from ore
It is prepared in brine by purifying process.Wherein, the process of lithium carbonate is prepared by extraction containing lithium ore, can be generated largely containing aluminium
Waste residue, storage take up a large area and seriously pollute environment, constitute dual harm to ecology and environment, therefore carry out Aluminiferous waste slag
Comprehensive utilization have Great significance.Meanwhile as rapid growth, the various mineral resources of social industry are increasingly in short supply,
The price of bauxite also rises steadily, and has seriously affected the sound development of aluminum i ndustry.From national economic development growth trend
From the point of view of, China will constantly increase the demand of aluminium product, and the insufficient contradiction of alumina resource provisioning can be protruded more.Therefore, it opens
The technology of non-bauxitic resource production aluminium oxide is opened up, thoroughly solve the insufficient contradiction of bauxite resource becomes research heat again
Point.The characteristics of non-bauxitic resource is that the content of silica is higher, and silica does not almost dissolve in acid, therefore selects acid system
The desiliconization problem that can reasonably avoid alkaline process from producing.
Have now been found that lithium minerals and mine containing lithium there are more than 150 kinds in nature, wherein the Independent Mineral of lithium there are more than 30 kinds, makees
It is mainly spodumene (Li to produce the raw mineral materials of lithium2O·Al2O3·4SiO2, contain Li2O 5.8% ~ 8.1%), lepidolite
(KL1.5iAl1.5〔AlSi3O10〕(F,OH)2, contain Li2O 3.2% ~ 6.45%), montebrasite ((LiAl (PO4) (OHF), contain Li2O
7.1% ~ 10.1%), petalite (H4AlLiO10Si4Containing Li2O2.9% ~ 4.8%) and zinnwaldite (containing Li2O 1.1% ~ 5%),
In preceding 3 mineral it is mostly important, the content of aluminium element or even aluminium mostly rich in will be far longer than lithium in these mineral
Content, therefore contain the largely aluminium for utilizing in mentioning lithium waste residue, it would be highly desirable to people go to develop.
Currently, the method at home and abroad handling lithium ore mostly uses vitriol lixiviation roasting to propose lithium technique.Chinese patent
A kind of method of Production By Sulfuric Acid Process battery-level lithium carbonate is disclosed in CN1267636A, is that lithium concentrate is subjected to transition roasting, acid
Change roasting, leaching, purified treatment, concentration, sinker processing, cleaning, be dried, crushing, pack be process.Canada
Patent CA2786317A1 describes a kind of method for manufacturing lithium carbonate, is by spodumene mine or concentrate calcining transformation, high temperature
It is lower to precipitate deliming with extraction, removing impurity by means of precipitation, addition sodium carbonate in sulfuric acid acidification, water, it is further removed through ion exchange remaining
Calcium, magnesium and other remaining polyvalent cations, purifying go to lithium carbonate settling step, sodium carbonate, the lithium carbonate precipitated are added
With sulfuric acid mother liquid of sodium.In contrast, the volatility and corrosivity of sulfuric acid are smaller, so the research to sulfuric acid process is relatively more.But
It is that wherein aluminium exists in the form of aluminium alum, and is recycled mostly in the form of aluminium hydroxide, and the per molecule sulfuric acid that vitriol lixiviation goes out
Aluminium generally has 18 ~ 24 crystallizations water, and the mass fraction of aluminium oxide is low, and energy consumption is big when calcining this crystallized product and easily melts, and
And it is also easy to produce the exhaust gas of sulfur-containing oxide, higher cost.
For aluminium oxide there are many allomorphism, the variant that root is crossed according to research reports has more than ten kinds.In these variants, mainly
There are 3 kinds, i.e. α-Al2O3、β-Al2O3With γ-Al2O3.Alpha-type aluminum oxide is a kind of most stable of clear crystal powder, is had than table
Area is big, fusing point is high, thermal stability is fabulous, hardness is high, water absorption rate is low, electrical insulation capability is good and acid-alkali-corrosive-resisting etc. is many excellent
Point is often widely used in insulating materials, microelectronic substrate, structural material and catalyst carrier.
Summary of the invention
To realize the reasonable recycling for mentioning lithium process Aluminiferous waste slag, meet the development need of existing aluminum oxide industry synthetic technology
It asks, the present invention provides a kind of from proposing the method for preparing aluminium oxide in lithium waste residue.
A method of aluminium oxide is prepared from mentioning in lithium waste residue, which comprises the following steps:
(1) lithium ore after smashing and grinding is immersed in hydrochloric acid, stirring is warming up to 80 ~ 100 DEG C of acidleach 4 ~ 8 hours, is distilled off
Heat filtering after hydrogen chloride；
(2) filtrate obtained in step (1) is cooled to room temperature, and alkaline maturing agent is added and adjusts pH value to 6 ~ 7, still aging 1 ~ 3
Aluminium hydroxide filter residue is filtered to obtain after hour；
(3) aluminium hydroxide filter residue is washed, 100 ~ 110 DEG C drying, 1000 ~ 1200 DEG C high-temperature calcination 1 ~ 1.5 hour, powder
It is broken to handle to obtain technical grade α-Al2O3Powder.
Preferably, Al in the lithium ore2O3Mass content be 15 ~ 45%.
Preferably, the mass fraction of hydrochloric acid is 15 ~ 30% in the step (1), 3 ~ 8:1 of mass ratio of hydrochloric acid and lithium ore；
It is highly preferred that hydrochloric acid and the mass ratio of lithium ore are 4 ~ 6:1 in step (1).
Preferably, heat filtering temperature is 50 ~ 100 DEG C in step (1)；It is highly preferred that heat filtering temperature is 60 in step (1)
~80℃。
Preferably, alkaline maturing agent described in step (2) is the ammonium hydroxide that mass fraction is 20 ~ 30%.
Preferably, the filtrate being obtained by filtration in step (2) is used to prepare lithium carbonate.
Preferably, the filtering in step (1) and step (2) uses negative pressure leaching or filters pressing mode.
It is a kind of using from mention the aluminium oxide that the method that aluminium oxide is prepared in lithium waste residue is prepared can be used for preparing metallic aluminium,
Production after manufacturing various refractory materials or further purifying for integrated circuit board base etc..
The present invention extracts the waste residue that lithium carbonate generates using hydrochloric acid acidleach dissolution lithium ore and prepares technical grade aluminium oxide, technique
Process is simple, is rationally utilized and mentions lithium slag, turns waste into wealth, and the resulting filter residue main component of heat filtering is dioxy in step (1)
SiClx, can be used as sandstone and paves the way directly to use or be further processed and prepare high-purity silicon dioxide, be obtained by filtration in step (2)
Filtrate is used to prepare lithium carbonate in filtrate.
Beneficial effect
The present invention mentions the waste residue generated after lithium using hydrochloric acid acidleach dissolution lithium ore and prepares aluminium oxide, and process flow is simple, safe
It is easy to operate, while α-Al2O3For the rate of recovery up to 95%, purity is greater than 98.5%, realizes the cycling and reutilization of resource, turns waste into wealth,
Energy conservation and environmental protection.
Specific embodiment
In order to further illustrate essentiality content of the invention, it is illustrated in connection with specific embodiments, needs to explain
, the content of present invention includes but are not limited to following embodiment.
Lithium ore main component (wt%) used in the embodiment of the present invention is as shown in table 1 below:
Embodiment 1
(1) the lithium ore 1000g after smashing and grinding is immersed in the hydrochloric acid that 4000g mass fraction is 30%, stirring is warming up to 90
DEG C acidleach 4 hours, 80 DEG C of 2825g that filter to get filtrate were cooled to after hydrogen chloride is distilled off；
(2) filtrate in step (1) is cooled to room temperature, ammonia water conditioning system pH value that mass fraction is 25% is added to 6 ~ 6.5,
Aluminium hydroxide filter residue 254g is filtered to obtain after still aging 2 hours, is isolated filtrate and is used to prepare lithium carbonate；
(3) solable matters such as sodium, the potassium of washing removing adsorption, 100 ~ 110 DEG C of bakings are carried out to the filter residue of aluminium hydroxide
It is dry, 1000 DEG C high-temperature calcination 1.5 hours, pulverization process obtains α-Al2O3Powder 149.27g, product yield 92.08%, α-Al2O3
Purity is 98.58%.
ICP tests and analyzes α-Al obtained in step (3)2O3Impurity, wherein iron is (with Fe2O3Meter) content be 0.018%, sodium
(with Na2O meter) content be 0.05%, calcium (in terms of CaO) content be 0.0015%, magnesium (in terms of MgO) content be 0.0007%, other
It is not detected, calcination loss 1.03%.
Embodiment 2
(1) the lithium ore 1000g after smashing and grinding is immersed in the hydrochloric acid that 6000g mass fraction is 30%, stirring is warming up to 80
DEG C acidleach 6 hours, 60 DEG C of 2752g that filter to get filtrate were cooled to after hydrogen chloride is distilled off；
(2) filtrate in step (1) is cooled to room temperature, ammonia water conditioning system pH value that mass fraction is 20% is added to 6.5 ~ 7,
Aluminium hydroxide filter residue 262g is filtered to obtain after still aging 2 hours, is isolated filtrate and is used to prepare lithium carbonate；
(3) solable matters such as sodium, the potassium of washing removing adsorption, 100 ~ 110 DEG C of bakings are carried out to the filter residue of aluminium hydroxide
It is dry, 1100 DEG C high-temperature calcination 1.5 hours, pulverization process obtains α-Al2O3Powder 154.86g, product yield 93.54%, α-Al2O3
Purity is 98.72%.
ICP tests and analyzes α-Al obtained in step (3)2O3Impurity, wherein iron is (with Fe2O3Meter) content be 0.023%, sodium
(with Na2O meter) content be 0.03%, calcium (in terms of CaO) content be 0.0009%, magnesium (in terms of MgO) content be 0.0005%, other
It is not detected, calcination loss 0.57%.
Embodiment 3
(1) the lithium ore 1000g after smashing and grinding is immersed in the hydrochloric acid that 5000g mass fraction is 30%, stirring is warming up to 100
DEG C acidleach 8 hours, 65 DEG C of 2748g that filter to get filtrate were cooled to after hydrogen chloride is distilled off；
(2) filtrate in step (1) is cooled to room temperature, ammonia water conditioning system pH value that mass fraction is 30% is added to 6.5 ~ 7,
Aluminium hydroxide filter residue 273g is filtered to obtain after still aging 3 hours, is isolated filtrate and is used to prepare lithium carbonate；
(3) solable matters such as sodium, potassium that washing removes adsorption are carried out to aluminium hydroxide filter residue, 100 ~ 110 DEG C of drying,
1200 DEG C high-temperature calcination 1 hour, pulverization process obtains α-Al2O3Powder 166.13g, product yield 95.21%, α-Al2O3Purity
It is 98.87%.
ICP tests and analyzes α-Al obtained in step (3)2O3Impurity, wherein iron is (with Fe2O3Meter) content be 0.012%, sodium
(with Na2O meter) content be 0.017%, calcium (in terms of CaO) content be 0.0004%, magnesium (in terms of MgO) content be 0.0005%, other
It is not detected, calcination loss 0.34%.
Claims (10)
1. a kind of from proposing the method for preparing aluminium oxide in lithium waste residue, which comprises the following steps:
(1) lithium ore after smashing and grinding is immersed in hydrochloric acid, stirring is warming up to 80 ~ 100 DEG C of acidleach 4 ~ 8 hours, is distilled off
Heat filtering after hydrogen chloride；
(2) filtrate obtained in step (1) is cooled to room temperature, and alkaline maturing agent is added and adjusts pH value to 6 ~ 7, still aging 1 ~ 3
Aluminium hydroxide filter residue is filtered to obtain after hour；
(3) aluminium hydroxide filter residue is washed, 100 ~ 110 DEG C drying, 1000 ~ 1200 DEG C high-temperature calcination 1 ~ 1.5 hour, powder
It is broken to handle to obtain α-Al2O3Powder.
2. a kind of from proposing the method for preparing aluminium oxide in lithium waste residue according to claim 1, which is characterized in that the lithium ore
Middle Al2O3Mass content be 15 ~ 45%.
3. according to claim 1 a kind of from proposing the method for preparing aluminium oxide in lithium waste residue, which is characterized in that step (1)
The mass fraction of middle hydrochloric acid is 15 ~ 30%, 3 ~ 8:1 of mass ratio of hydrochloric acid and lithium ore.
4. according to claim 3 a kind of from proposing the method for preparing aluminium oxide in lithium waste residue, which is characterized in that step (1)
Middle hydrochloric acid and the mass ratio of lithium ore are 4 ~ 6:1.
5. according to claim 1 a kind of from proposing the method for preparing aluminium oxide in lithium waste residue, which is characterized in that step (1)
Middle heat filtering temperature is 50 ~ 100 DEG C.
6. according to claim 5 a kind of from proposing the method for preparing aluminium oxide in lithium waste residue, which is characterized in that step (1)
Middle heat filtering temperature is 60 ~ 80 DEG C.
7. according to claim 1 a kind of from proposing the method for preparing aluminium oxide in lithium waste residue, which is characterized in that step (2)
Described in alkaline maturing agent be ammonium hydroxide that mass fraction is 20 ~ 30%.
8. according to claim 1 a kind of from proposing the method for preparing aluminium oxide in lithium waste residue, which is characterized in that the step
(2) filtrate being obtained by filtration in is used to prepare lithium carbonate.
9. according to claim 1 a kind of from proposing the method for preparing aluminium oxide in lithium waste residue, which is characterized in that the step
Suddenly it filters in (1) and step (2) using negative pressure leaching or filters pressing mode.
10. a kind of aluminium oxide using the preparation of method described in claim 1 ~ 9 is preparing metallic aluminium, the various refractory materials of manufacture
Or the further application after purification on production integrated circuit board base.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201811485391.5A CN109437264A (en) | 2018-12-06 | 2018-12-06 | A method of aluminium oxide is prepared from mentioning in lithium waste residue |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201811485391.5A CN109437264A (en) | 2018-12-06 | 2018-12-06 | A method of aluminium oxide is prepared from mentioning in lithium waste residue |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| CN109437264A true CN109437264A (en) | 2019-03-08 |
Family
ID=65557343
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN201811485391.5A Pending CN109437264A (en) | 2018-12-06 | 2018-12-06 | A method of aluminium oxide is prepared from mentioning in lithium waste residue |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN109437264A (en) |
Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN111569828A (en) * | 2020-03-06 | 2020-08-25 | 伊犁师范大学 | Resource utilization method for lavender essential oil distillation waste residues and preparation of porous biochar |
| CN114988484A (en) * | 2022-05-16 | 2022-09-02 | 安徽大学绿色产业创新研究院 | Gypsum tailing treatment method of solid lithium ore neutralization process |
| CN115448318A (en) * | 2022-09-13 | 2022-12-09 | 湖南绿脉环保科技股份有限公司 | Comprehensive recycling method for extracting silicon and aluminum from lithium slag |
Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN103789553A (en) * | 2013-11-28 | 2014-05-14 | 中南大学 | Method for comprehensively utilizing lepidolite mineralogical reconstruction lithium-extraction slags |
| CN107454916A (en) * | 2015-01-27 | 2017-12-08 | 里德先进材料有限公司 | The processing of lithium-containing materials including HCl injections |
-
2018
- 2018-12-06 CN CN201811485391.5A patent/CN109437264A/en active Pending
Patent Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN103789553A (en) * | 2013-11-28 | 2014-05-14 | 中南大学 | Method for comprehensively utilizing lepidolite mineralogical reconstruction lithium-extraction slags |
| CN107454916A (en) * | 2015-01-27 | 2017-12-08 | 里德先进材料有限公司 | The processing of lithium-containing materials including HCl injections |
Non-Patent Citations (1)
| Title |
|---|
| 张霞等: "《无机化学》", 31 August 2015 * |
Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN111569828A (en) * | 2020-03-06 | 2020-08-25 | 伊犁师范大学 | Resource utilization method for lavender essential oil distillation waste residues and preparation of porous biochar |
| CN114988484A (en) * | 2022-05-16 | 2022-09-02 | 安徽大学绿色产业创新研究院 | Gypsum tailing treatment method of solid lithium ore neutralization process |
| CN115448318A (en) * | 2022-09-13 | 2022-12-09 | 湖南绿脉环保科技股份有限公司 | Comprehensive recycling method for extracting silicon and aluminum from lithium slag |
| CN115448318B (en) * | 2022-09-13 | 2024-01-26 | 湖南绿脉环保科技股份有限公司 | Comprehensive recycling method for extracting silicon aluminum from lithium slag |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN104495899B (en) | A kind of carbide slag and flyash work in coordination with the method for recycling | |
| CN102424391B (en) | Method for comprehensive utilization of aluminum-containing material | |
| CN103145161B (en) | Method for preparing pseudo-boehmite co-preparation white carbon black by coal gangue | |
| CN103693665B (en) | A kind of coal ash for manufacturing is for the method for high purity aluminium oxide | |
| CN102897810B (en) | Method for producing aluminum oxide by using fly ash | |
| CN109437264A (en) | A method of aluminium oxide is prepared from mentioning in lithium waste residue | |
| CN103614547A (en) | Method for separating iron, aluminum and silicon from diasporic bauxite | |
| CN109777960A (en) | A method of separating and recovering lithium, aluminium from flyash | |
| CN109384254B (en) | Method for preparing crystalline aluminum chloride and white carbon black from fly ash or coal gangue | |
| WO2013143335A1 (en) | Method for extracting aluminium oxide in fly ash by alkaline process | |
| CN103241754A (en) | Production method of high-purity aluminum oxide | |
| CN105439156A (en) | Method for preparing rubber and plastics filler by use of microsilica and carbide slag | |
| CN108866678A (en) | A method of continuous alumina fiber is prepared by gangue | |
| CN108946772A (en) | A method of pure Lithium Carbonate is prepared by lithium ore | |
| CN102502722A (en) | Preparation method of high-purity magnesium oxide | |
| CN103708480A (en) | Method for preparing microcrystalline mullite from fly ash | |
| CN109336123A (en) | A method of using coal ash for manufacturing for soluble glass of high modulus | |
| CN101100304A (en) | Method for preparing aluminum oxide from low aluminum-silicon ratio aluminum-containing mineral | |
| CN105060326B (en) | The technique that AZS solid wastes prepare sodium metaaluminate | |
| CN101913633B (en) | Extraction technology of alumina and potassium sulfate from alunite by using hot-pressing leaching process | |
| CN106348319A (en) | Method for utilizing serpentine for preparing high-purity magnesium oxide | |
| Lin et al. | Aluminium hydroxide ultrafine powder extracted from fly ash | |
| CN103738989B (en) | A kind of middle-low bauxite produces the method for aluminum oxide | |
| CN111592017A (en) | Method for preparing battery-grade lithium chloride by pressing and soaking spodumene | |
| CN103011278A (en) | Process for hydrothermally preparing zirconium oxychloride with low alkali consumption |
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 | ||
| RJ01 | Rejection of invention patent application after publication |
Application publication date: 20190308 |
|
| RJ01 | Rejection of invention patent application after publication |