CN107032376B - A method of by obtaining valuable element in alunite - Google Patents

A method of by obtaining valuable element in alunite Download PDF

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CN107032376B
CN107032376B CN201610961769.9A CN201610961769A CN107032376B CN 107032376 B CN107032376 B CN 107032376B CN 201610961769 A CN201610961769 A CN 201610961769A CN 107032376 B CN107032376 B CN 107032376B
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alunite
gained
mixed liquor
lye
sub
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CN107032376A (en
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于建国
刘程琳
罗孟杰
薛金
李平
宋兴福
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East China University of Science and Technology
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East China University of Science and Technology
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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
    • C01F7/02—Aluminium oxide; Aluminium hydroxide; Aluminates
    • C01F7/04—Preparation of alkali metal aluminates; Aluminium oxide or hydroxide therefrom
    • C01F7/14—Aluminium oxide or hydroxide from alkali metal aluminates
    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01D—COMPOUNDS OF ALKALI METALS, i.e. LITHIUM, SODIUM, POTASSIUM, RUBIDIUM, CAESIUM, OR FRANCIUM
    • C01D5/00—Sulfates or sulfites of sodium, potassium or alkali metals in general
    • C01D5/008—Preparation of potassium sulfate from alunite
    • C—CHEMISTRY; METALLURGY
    • C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
    • C22B—PRODUCTION AND REFINING OF METALS; PRETREATMENT OF RAW MATERIALS
    • C22B58/00—Obtaining gallium or indium
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
    • Y02P10/00—Technologies related to metal processing
    • Y02P10/20—Recycling

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  • Chemical & Material Sciences (AREA)
  • Organic Chemistry (AREA)
  • Engineering & Computer Science (AREA)
  • Materials Engineering (AREA)
  • Inorganic Chemistry (AREA)
  • Manufacturing & Machinery (AREA)
  • Mechanical Engineering (AREA)
  • Metallurgy (AREA)
  • Life Sciences & Earth Sciences (AREA)
  • Geology (AREA)
  • Manufacture And Refinement Of Metals (AREA)

Abstract

The present invention relates to a kind of method by obtaining valuable element in alunite, the method is to decompose alunite using sub-molten salt, to obtain valuable element (such as potassium, aluminium plus gallium).Using the method for the invention, the dissolution rate that the dissolution rate that the dissolution rate of potassium element is greater than 90%, aluminium element is greater than 60%, gallium element is greater than 50%, and element silicon dissolution rate is less than 2%.In addition, the present invention is a kind of low energy consumption and the environment amenable method by obtaining valuable element in alunite.

Description

A method of by obtaining valuable element in alunite
Technical field
The present invention relates to a kind of methods by obtaining valuable element in alunite, specifically, being related to a kind of using sub- molten Salt decomposes alunite, the method to obtain valuable element (such as potassium, aluminium plus gallium).
Background technique
Sulfate and a kind of multielement mineral resources with comprehensive utilization value of the alunite for a kind of complexity.So And alunite exceptional stability, it is difficult to be dissolved in the reagents such as water or acid under room temperature.It is therefore, existing by obtaining valuable element in alunite, High-temperature calcination first must be carried out to alunite, improve its solubility in the reagents such as water or acid.
MineEtc. reporting a kind of method using sulfuric acid and HCl treatment alunite (Hydrometallurgy, 76 (2005), 217-224).This method has main steps that: first passing through alunite to be processed Then high-temperature calcination certain time is reacted using certain density sulfuric acid and hydrochloric acid with the alunite through high-temperature roasting, phase is obtained The valuable element answered.MineEtc. thinking, calcination temperature is to influence the key factor of valuable element dissolution rate (to work as calcining Temperature is higher than 650 DEG C, and valuable element dissolution rate obviously rises；Conversely, then declining).
Obviously, in the method existing by obtaining valuable element in alunite, being to alunite progress high-temperature calcination must not The step that can lack.In this way, high energy consumption will be inevitable.
In consideration of it, there is an urgent need in the art to a kind of low energy consumption and environment amenable by obtaining valuable element in alunite Method.
Summary of the invention
It will be a kind of low energy consumption by being obtained in alunite as can decompose alunite using sub-molten salt to obtaining valuable element The method for obtaining valuable element.But the technical problem that must be solved is: how to effectively control a large amount of of silicon in alunite (Si) element Step dissolution is realized in dissolution.The present inventor it has been investigated that: when alunite and sub-molten salt are suitable in thermotonus appropriate When time, can not influence other valuable elements dissolution under the premise of, effectively control Si element a large amount of dissolutions, reach step Dissolve out purpose.
Therefore, the object of the present invention is to provide a kind of low energy consumption and environment amenable valuable by obtaining in alunite The method of element.
Described method includes following steps:
(1) alunite, sub-molten salt and water are placed in the reaction vessel with heating, temperature control and agitating device, in normal pressure And under the conditions of 30 DEG C~110 DEG C, stirs 10 minutes to 4 hours, obtain slurries；
(2) it under the conditions of normal pressure and 30 DEG C~100 DEG C, filters by step (1) resulting slurries, filter cake is washed with water, and closes And filtrate and cleaning solution, mixed liquor is obtained, desiliconization is carried out to gained mixed liquor using existing desilication method, and makes its Al/Si (ratio Value) it is greater than 500；
(3) it will be evaporated crystallization and filtering for 500~600 mixed liquor by step (2) resulting Al/Si (ratio), Gained crystal is potassium sulfate, and gained filtrate obtains the solution containing potassium aluminate after extraction recycles lye；
It in solution addition aluminium hydroxide (as crystal seed) of the gained containing potassium aluminate and filters, obtains aluminium hydroxide；Gained returns Receiving lye can be recycled (i.e. in step (1))；
(4) lye at least three times is recycled and is adsorbed that (chelate resin etc. can be selected in adsorption column, and adsorption conditions are normal Warm (20 DEG C~40 DEG C) and normal pressure (1 atmospheric pressure)), obtain gallium element；
Wherein, the mass ratio of alunite and sub-molten salt is 1:(1~5), the sub-molten salt is sodium hydroxide or/and hydroxide Potassium, it is C that extraction described in step (3), which recycles extractant selected by lye,1~C4The phenol that linear or branched alkyl group replaces, Gallium element is obtained through absorption described in step (4), used adsorption column is chelate resin, and adsorption conditions are room temperature (20 DEG C~40 DEG C) and normal pressure (1 atmospheric pressure).
Specific embodiment
In a preferred technical solution of the invention, the average particle size of alunite used is 100~400 mesh；More preferably Technical solution is: the average particle size of alunite used is 300~400 mesh.
In presently preferred technical solution, in step (1), the mass percentage concentration of sub-molten salt is preferably 20%~70%.
In a further preferred technical solution of the present invention, in step (1), stirring rate be 200 revs/min~800 turns/ Point.
In a further preferred technical solution of the present invention, in step (2), the mixing through existing desilication method desiliconization processing The Al/Si (ratio) of liquid is 500~600.
In a further preferred technical solution of the present invention, selected extractant is in step (3): methyl, ethyl, third The phenol that base, isopropyl, butyl, isobutyl group or/and tert-butyl replace, the integer that substituent group number is 1~5；
Further preferred technical solution is: selected extractant is in step (3): 2,4-DTBP, 2, 6- DI-tert-butylphenol compounds, 2- tert-butyl-4-methyl-Phenol, 2-TBP or 2,6- xylenol.
In a further preferred technical solution of the present invention, gallium element is obtained through absorption described in step (4), is used Adsorption column be SEPLITE LSC-600 resin (Xi'an Lanxiao Sci-Tech Co., Ltd.'s product).
The present invention has the advantage that
(1) method that sub-molten salt provided by the invention decomposes rich potassium alumstone ore, reaction pressure is normal pressure, and reaction temperature is 30 DEG C~110 DEG C, compared with traditional handicraft, operating condition is mild；
(2) dissolution rate of potassium element is greater than 90%, and the dissolution rate of aluminium element is greater than 60%, and the dissolution rate of gallium element is greater than 50%, and element silicon dissolution rate is less than 2%.That is present invention valuable element potassium, aluminium plus gallium in guaranteeing alunite obtains high dissolution While rate, a large amount of dissolutions of element silicon are effectively avoided, achieve the purpose that step dissolves out.
To sum up, the present invention is to provide a kind of low energy consumption and environment amenable by obtaining valuable element in alunite Method.
Below by embodiment, the present invention is further elaborated, and purpose, which is only that, is best understood from the contents of the present invention.
Alunite used is the rich potassium alumstone ore obtained by after nominal group process flotation in the examples below that, wherein alunite Content is 70wt%~75wt%, and other major impurities are kaolinite, dickite and quartz.Its average particle size is 300~400 Mesh.
Valuable element dissolution rate (%) is calculated by following equation:
Embodiment 1
(1) 30g average particle size is analyzed into pure NaOH and 90ml deionization for rich potassium alumstone ore, the 90g of 100~200 mesh Water is placed in the reaction vessel with heating, temperature control and agitating device, under the conditions of normal pressure and 60 DEG C, is stirred 60 minutes, stirring Rotary speed is 400 revs/min and obtains slurries；
(2) it under the conditions of normal pressure and 50 DEG C~90 DEG C, filters by step (1) resulting slurries, filter cake is washed with water, and merges Filtrate and cleaning solution obtain mixed liquor, and the Al/Si (ratio) of gained mixed liquor is 300~340, (in detail using existing desilication method See: Yang little Xiang, " atmospheric silicon removing production technology reduces practicing for energy consumption ", [J] the energy and energy conservation, 2015, (9): 92-93, under The mixed liquor for being 300~340 to gained Al/Si (ratio) carries out desiliconization together), its Al/Si (ratio) is made to be greater than 500；
(3) mixed liquor by step (2) resulting Al/Si (ratio) greater than 500 is evaporated crystallization and filtering, gained Crystal is potassium sulfate, and gained filtrate obtains after extraction (extractant selection 2,4-DTBP) recycles lye containing aluminium The solution of sour potassium；
Aluminium hydroxide (as crystal seed) is added in solution of the gained containing potassium aluminate, has Precipitation, is filtered, obtained solid As aluminium hydroxide, gained recycling lye can be recycled (i.e. in step (1))；
(4) lye at least three times is recycled and is adsorbed that (adsorption column is SEPLITE LSC-600 resin (Xi'an indigo plant dawn Science and Technology Ltd. produces), adsorption conditions are room temperature (20 DEG C~40 DEG C) and normal pressure (1 atmospheric pressure)), gallium element can be obtained；
Through above-mentioned steps, the dissolution rate of potassium element is 95%, and the dissolution rate of aluminium is 72%, and the dissolution rate of silicon is 0.6%, gallium Dissolution rate be 51.5%.
Embodiment 2
(1) by 40g rich potassium alumstone ore, 90g analyze pure NaOH and 135ml deionized water be placed in heating, temperature control and In the reaction vessel of agitating device, under the conditions of normal pressure and 80 DEG C, stir 120 minutes, speed of agitator degree, which is 700 revs/min, to be starched Liquid；
(2) it under the conditions of normal pressure and 50 DEG C~90 DEG C, filters by step (1) resulting slurries, filter cake is washed with water, and merges Filtrate and cleaning solution obtain mixed liquor, and the Al/Si (ratio) of gained mixed liquor is 200~240, (same using existing desilication method On) desiliconization is carried out for 200~240 mixed liquor to gained Al/Si (ratio), so that its Al/Si (ratio) is greater than 500；
(3) mixed liquor by step (2) resulting Al/Si (ratio) greater than 500 is evaporated crystallization and filtering, gained Crystal is potassium sulfate, and gained filtrate is contained after extraction (extractant selects 2- tert-butyl-4-methyl-Phenol) recycling lye The solution of potassium aluminate；
Aluminium hydroxide (as crystal seed) is added in solution of the gained containing potassium aluminate, has Precipitation, is filtered, obtained solid As aluminium hydroxide, gained recycling lye can be recycled (i.e. in step (1))；
(4) lye at least three times is recycled and is adsorbed that (adsorption column is SEPLITE LSC-600 resin (Xi'an indigo plant dawn Science and Technology Ltd. produces), adsorption conditions are room temperature (20 DEG C~25 DEG C) and normal pressure (1 atmospheric pressure)), gallium element can be obtained；
Through above-mentioned steps, the dissolution rate of potassium element is 91%, and the dissolution rate of aluminium is 67%, and the dissolution rate of silicon is 1.2%, gallium Dissolution rate be 54%.
Embodiment 3
(1) 30g average particle size is analyzed pure NaOH and 60ml water and be placed in for rich potassium alumstone ore, the 90g of 100~400 mesh In reaction vessel with heating, temperature control and agitating device, under the conditions of normal pressure and 60 DEG C, stir 85 minutes, speed of agitator degree Slurries are obtained for 500 revs/min；
(2) it under the conditions of normal pressure and 50 DEG C~90 DEG C, filters by step (1) resulting slurries, filter cake is washed with water, and merges Filtrate and cleaning solution obtain mixed liquor, and the Al/Si (ratio) of gained mixed liquor is 100~150, (same using existing desilication method On) desiliconization is carried out for 100~150 mixed liquor to gained Al/Si (ratio), so that its Al/Si (ratio) is greater than 500；
(3) mixed liquor by step (2) resulting Al/Si (ratio) greater than 500 is evaporated crystallization and filtering, gained Crystal is potassium sulfate, and gained filtrate obtains after extraction (extractant selects 2,6- xylenol) recycling lye containing aluminic acid The solution of potassium；
Aluminium hydroxide (as crystal seed) is added in solution of the gained containing potassium aluminate, has Precipitation, is filtered, obtained solid As aluminium hydroxide, gained recycling lye can be recycled (i.e. in step (1))；
(4) lye at least three times is recycled and is adsorbed that (adsorption column is that adsorption column is SEPLITE LSC-600 resin (Xi'an Lanxiao Sci-Tech Co., Ltd.'s product), adsorption conditions are room temperature (20 DEG C~40 DEG C) and normal pressure (1 atmospheric pressure)), it can be obtained Gallium element；
Through above-mentioned steps, the dissolution rate of potassium element is 97%, and the dissolution rate of aluminium is 75%, and the dissolution rate of silicon is 1.5%, gallium Dissolution rate be 52.5%.
The above is only preferred implementation case of the invention, is not intended to restrict the invention, for the art Technical staff, under the premise of not departing from present inventive concept and principle, several modifications, equivalent replacement, improvement and the profit made Decorations etc., are regarded as in protection scope of the present invention.

Claims (8)

1. a kind of method by obtaining valuable element in alunite comprising following steps:
(1) alunite, sub-molten salt and water are placed in the reaction vessel with heating, temperature control and agitating device, in normal pressure and 30 DEG C~110 DEG C under the conditions of, stir 10 minutes to 4 hours, obtain slurries；
(2) it under the conditions of normal pressure and 30 DEG C~100 DEG C, filters by step (1) resulting slurries, filter cake is washed with water, and merges filter Liquid and cleaning solution, obtain mixed liquor, carry out desiliconization to gained mixed liquor using existing desilication method, and be greater than its Al/Si ratio 500；
(3) mixed liquor by the resulting Al/Si ratio of step (2) greater than 500 is evaporated crystallization and filtering, gained crystal is Potassium sulfate, gained filtrate obtain the solution containing potassium aluminate after extraction recycles lye；
Gained containing potassium aluminate solution addition aluminium hydroxide, have Precipitation, filter, obtained solid is aluminium hydroxide, institute Lye, which must be recycled, can be recycled；With
(4) lye being recycled at least three times is adsorbed, and gallium element is obtained；
Wherein, the mass ratio of alunite and sub-molten salt be 1: (1~5), the sub-molten salt be sodium hydroxide or/and potassium hydroxide, It is C that extraction described in step (3), which recycles extractant selected by lye,1~C4The phenol that linear or branched alkyl group replaces, step (4) obtain gallium element through absorption described in, used adsorption column is chelate resin, adsorption conditions be 20 DEG C~40 DEG C and 1 atmospheric pressure.
2. the method as described in claim 1, which is characterized in that wherein the average particle size of alunite used is 100~400 mesh.
3. method according to claim 2, which is characterized in that wherein the average particle size of the alunite is 300~400 mesh.
4. the method as described in claim 1, which is characterized in that in step (1) mass percentage concentration of sub-molten salt be 20%~ 70%.
5. the method as described in claim 1, which is characterized in that stirring rate is 200 revs/min~800 revs/min in step (1).
6. the method as described in claim 1, which is characterized in that in step (2), the Al/Si ratio of the mixed liquor through desiliconization processing Value is 500~600.
7. the method as described in any one of claim 1~6, which is characterized in that extraction described in step (3) recycles alkali Extractant selected by liquid is: the phenol that methyl, ethyl, propyl, isopropyl, butyl, isobutyl group or/and tert-butyl replace takes The integer for being 1~5 for base number.
8. the method for claim 7, which is characterized in that wherein selected extractant is: 2,4-DTBP, 2,6- DI-tert-butylphenol compounds, 2- tert-butyl-4-methyl-Phenol, 2-TBP or 2,6- xylenol.
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